Aluminosilicate glass, preparation method thereof and glass product

Abstract

The invention relates to aluminosilicate glass, a preparation method thereof and a glass product. The aluminosilicate glass is prepared from the following raw materials in percentage by mass: 58 percent to 63 percent of SiO2, 12 percent to 16 percent of Al2O3, 11 percent to 14.5 percent of Na2O, 3 percent to 6 percent of K2O, 2 percent to 5 percent of MgO, 1.4 percent to 3 percent of ZrO2 and 0.5 percent to 3.5 percent of B2O3. The preparation raw materials of the aluminosilicate glass comprise specific components with a specific proportioning relation, all the components are coordinated and matched to endow the aluminosilicate glass with good stress relaxation resistance and mechanical properties, and the service life of fused salt can be prolonged.

Description

Technical Field

[0001] The present application relates to the technical field of glass production, and in particular to an aluminosilicate glass and a preparation method thereof, and a glass product. Background Art

[0002] For the application scenarios of aluminosilicate glass on the market, in order to give full play to the advantages of aluminosilicate glass, it needs to be chemically strengthened. In terms of processing cost, process complexity and adaptability of glass composition, a one-time strengthening process is the mainstream, so that aluminosilicate glass can obtain a significant improvement in mechanical properties to meet more demanding needs. After chemical strengthening, the mechanical properties of aluminosilicate glass will be greatly improved, while the increase of ordinary soda-lime glass is relatively small, and the intrinsic strength of aluminosilicate glass is also higher than that of soda-lime glass, which further widens the gap in mechanical properties between the two after strengthening. This makes aluminosilicate glass applicable to some scenarios with high requirements for mechanical properties, or high-end products, thus giving it a higher value.

[0003] However, in the process of chemical strengthening, with the continuous use of molten salt, the Na in the glass + ions enter the molten salt, making the Na + The content gradually increases, and the molten salt changes from pure KNO3 molten salt to a mixed molten salt of KNO3 and NaNO3. This results in the Na in the glass and molten salt + As the difference in content decreases, it will affect the glass's ability to resist relaxation, and when stress relaxation reaches a certain level, it will ultimately affect the glass's strengthening properties.

[0004] Therefore, how to improve the glass's ability to resist stress relaxation and mechanical properties has become an urgent problem to be solved. Summary of the invention

[0005] Based on this, the present application provides an aluminosilicate glass and a preparation method and glass products thereof. The aluminosilicate glass has good chemical strengthening properties and strength, and the aluminosilicate glass obtained after strengthening treatment has good resistance to stress relaxation and mechanical properties, and can extend the service life of molten salt.

[0006] In a first aspect, the present application provides an aluminosilicate glass. The raw materials for preparing the aluminosilicate glass include, by mass percentage: 58%~63% SiO2, 12%~16% Al2O3, 11%~14.5% Na2O, 3%~6% K2O, 2%~5% MgO, 1.4%~3% ZrO2, and 0.5%~3.5% B2O3.

[0007] The raw materials for preparing the aluminosilicate glass of the present application include specific components with specific proportions, wherein SiO2 can improve the mechanical strength, chemical stability and thermal stability of the glass, Al2O3 can improve the strength and strengthening performance of the glass, MgO can reduce the viscosity of the glass at high temperatures and promote the melting and clarification of the glass; K2O and Na2O can significantly improve the solubility of the glass and improve the strength of the glass, B2O3 can reduce the high-temperature viscosity of the glass, and ZrO2 can improve the weather resistance of the glass and can increase the CS value by reducing the thermal expansion coefficient of the glass; the components, through the coordinated cooperation of a specific proportion, give the aluminosilicate glass better resistance to stress relaxation and mechanical properties, and can extend the service life of the molten salt.

[0008] Furthermore, the preparation process of the aluminosilicate glass is simple and easy to implement, and the prepared aluminosilicate glass can adapt to existing production processes.

[0009] In some embodiments, the aluminosilicate glass satisfies μ of 0.922 to 0.979; wherein μ is the glass stress relaxation resistance index, which satisfies the following formula: μ=0.1×[ln(SiO2+1.5ZrO2)+ln(Al2O3-0.2Na2O+0.3K2O-0.2MgO-0.3B2O3)+ln(Al2O3+0.2Na2O-0.1K2O+0.4MgO+0.3B2O3)];

[0010] Each oxide in the above formula represents its mass percentage in the aluminosilicate glass multiplied by 100.

[0011] In some of the embodiments, the aluminosilicate glass includes the following components, by mass percentage: 58.2%~62.8% SiO2, 12.5%~15.2% Al2O3, 11.8%~14% Na2O, 3.5%~5.5% K2O, 2.5%~4.6% MgO, 1.7%~2.6% ZrO2, and 1%~3% B2O3.

[0012] In a second aspect, the present application provides a method for preparing aluminosilicate glass, comprising the following steps:

[0013] Providing raw materials according to the above-mentioned composition of aluminosilicate glass;

[0014] After the raw materials are mixed, melting treatment, molding treatment, annealing treatment and chemical strengthening treatment are sequentially performed.

[0015] In some embodiments, the melting process comprises the following steps: subjecting the mixed raw materials to a first melting process to obtain a first molten glass liquid; the temperature of the first melting process is 1600° C. to 1650° C.;

[0016] The first molten glass liquid is subjected to a second melting treatment to obtain a second molten glass liquid; the temperature of the second melting treatment is 1550° C. to 1620° C., wherein the temperature of the second melting treatment is lower than the temperature of the first melting treatment.

[0017] In some embodiments, the first melting treatment time is 5h~8h,

[0018] And / or; the time of the second melting treatment is 1h~2.5h.

[0019] In some embodiments, the annealing treatment is performed at a temperature of 700°C to 760°C.

[0020] In some of the embodiments, the step of chemical strengthening treatment includes: placing the product after the annealing treatment in a molten salt containing KNO3 for chemical strengthening treatment.

[0021] In some embodiments, at least one of the following conditions (1) to (2) is satisfied:

[0022] (1) The temperature of the molten salt is 425°C to 435°C;

[0023] (2) The time of the chemical strengthening treatment is 2.85h~3.15h.

[0024] In a third aspect, the present application provides a glass product, wherein the glass product comprises the above-mentioned aluminosilicate glass or aluminosilicate glass prepared by the above-mentioned method for preparing aluminosilicate glass. DETAILED DESCRIPTION

[0025] In order to make the above-mentioned purposes, features and advantages of the present application more obvious and easy to understand, the specific implementation methods of the present application are described in detail below.

[0026] However, the present application can be implemented in many other ways different from those described herein, and those skilled in the art can make similar improvements without violating the connotation of the present application, so the present application is not limited by the specific embodiments disclosed below.

[0027] In the description of this application, the meaning of "plurality" is at least two, such as two, three, etc., unless otherwise clearly and specifically limited. "At least one" used in this application refers to any one, any two, or any two or more of the listed items. "Above a certain number" used in this application should be understood as a certain number and a range greater than a certain number.

[0028] The terms "and / or", "or / and", and "and / or" used in this application have an optional scope including any one of two or more related listed items, and also include any and all combinations of the related listed items, said any and all combinations including any combination of any two related listed items, any more related listed items, or all related listed items.

[0029] Where “including,” “having,” and “comprising” are used as described herein, it is intended to cover a non-exclusive inclusion, and another component may be added unless an explicit limiting term is used, such as “only,” “consisting of,” etc. Unless mentioned otherwise, a term in the singular form may include a plural form and shall not be construed as being one in number.

[0030] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art to which this application belongs. The terms used herein in the specification of this application are only for the purpose of describing specific embodiments and are not intended to limit this application.

[0031] As shown in the background technology, in the traditional technology, Na + The increase in content will cause K to enter the glass + The “crowding effect” is reduced, which will lead to a significant reduction in CS, while K + The depth of diffusion is not affected at all, so the DOL is less affected. That is, the main problem with older molten salts is the reduction of CS.

[0032] Generally speaking, high-end tempered glass manufacturers with large processing volumes have relatively high requirements for tempering efficiency, tempering performance, and tempering yield. After using old salt for a period of time, tempering often cannot achieve the performance comparable to that of new salt. At this time, it is necessary to replace it with a new molten salt. Generally speaking, when the Na in the molten salt is + When the concentration reaches 2000ppm, due to the attenuation of the CS value, the mechanical properties will be reduced to less than 90% of the new salt-strengthened sample. This is unacceptable for high-end manufacturers. At this time, new salt needs to be replaced. The specific replacement frequency depends on the performance requirements and the processing volume of the manufacturer. Replacement every 3-4 months is a typical frequency.

[0033] However, the raw material cost of replacing molten salt is high, while the recycling value of waste molten salt is low, and the treatment will also incur costs, and there is also potential environmental pollution problems; the downtime cycle for replacing new salt is long and the volume is large, which affects production efficiency. At the same time, the relatively high frequency of salt change also increases certain safety operation risks.

[0034] Based on this, one embodiment of the present application provides an aluminosilicate glass, which includes the following components in mass percentage: 58%~63% SiO2, 12%~16% Al2O3, 11%~14.5% Na2O, 3%~6% K2O, 2%~5% MgO, 1.4%~3% ZrO2, and 0.5%~3.5% B2O3.

[0035] The raw materials for preparing the aluminosilicate glass of the present application include specific components with specific proportions, wherein SiO2 can improve the mechanical strength, chemical stability and thermal stability of the glass, Al2O3 can improve the strength and strengthening performance of the glass, MgO can reduce the viscosity of the glass at high temperatures and promote the melting and clarification of the glass; K2O and Na2O can significantly improve the solubility of the glass and improve the strength of the glass, B2O3 can reduce the high-temperature viscosity of the glass, and ZrO2 can improve the weather resistance of the glass and can increase the CS value by reducing the thermal expansion coefficient of the glass; the components, through the coordinated cooperation of a specific proportion, give the aluminosilicate glass better resistance to stress relaxation and mechanical properties, and can extend the service life of the molten salt.

[0036] It is understood that when a numerical range is disclosed herein, the above range is considered continuous and includes the minimum and maximum values ​​of the range, as well as every value between such minimum and maximum values. Further, when a range refers to an integer, every integer between the minimum and maximum values ​​of the range is included. In addition, when multiple ranges are provided to describe features or characteristics, the ranges can be combined. In other words, unless otherwise indicated, all ranges disclosed herein should be understood to include any and all subranges included therein.

[0037] Silicon dioxide (SiO2) is the main component of the glass skeleton and is necessary. It also improves the strength of the glass, but increases the viscosity of the glass. If the mass percentage of SiO2 is less than 58%, the glass forming performance is poor, and the strength and weather resistance are insufficient; if it exceeds 63%, the melting property of the glass deteriorates.

[0038] It should be noted that the value range of SiO2 is "58%~63%", that is, the minimum and maximum values ​​in the range of 58%~63%, and every value between the minimum and maximum values. Specific examples include but are not limited to the point values ​​in the embodiment and the following point values: 58%, 58.1%, 58.2%, 58.3%, 58.4%, 58.5%, 58.6%, 58.7%, 58.8%, 58.9%, 59%, 59.1%, 59.2%, 59.3%, 59.4%, 59.5%, 59.6%, 59.7%, 59.8%, 59.9%, 60%, 60.1%, 60.2%, 60.3%, 60.4%, 60.5%, 60.6%, 60.7%, 60.8%, 60.9%, 61.1%, 61.2%, 61.3%, 61.4%, 61.5%, 61.6%, 61.7%, 61.8%, 61.9%, 61.1%, 61. 1%, 61.1%, 61.2%, 61.3%, 61.4%, 61.5%, 61.6%, 61.7%, 61.8%, 61.9%, 62%, 62.1%, 62.2%, 62.3%, 62.4%, 62.5%, 62.6%, 62.7%, 62.8%, 62.9% or 63%; or a range composed of any two of these values, more preferably 58.2% to 62.8% SiO2, further preferably 59% to 62.3% SiO2, and most preferably 60.5% to 61.2% SiO2.

[0039] Alumina (Al2O3) can improve the strength and strengthening properties of glass, but it will increase the viscosity of the glass and make it more difficult to clarify. It is a necessary component. If its content is less than 12%, the strength and strengthening properties of the glass are insufficient. If it is higher than 16%, the viscosity of the glass is too high and it is difficult to clarify, and the melting quality is reduced.

[0040] The value range of Al2O3 is "12%~16%", that is, the minimum and maximum values ​​in the range of 12%~16%, and every value between the minimum and maximum values. Specific examples include, but are not limited to, the point values ​​in the embodiments and the following point values: 12%, 12.1%, 12.2%, 12.3%, 12.4%, 12.5%, 12.6%, 12.7%, 12.8%, 12.9%, 13%, 13.1%, 13.2%, 13.3%, 13.4%, 13.5%, 13.6%, 13.7%, 13.8%, 13.9%, 14%, 14.1%, 14.2%, 14.3%, 14.4%, 14.5 %, 14.6%, 14.7%, 14.8%, 14.9%, 15%, 15.1%, 15.2%, 15.3%, 15.4%, 15.5%, 15.6%, 15.7%, 15.8%, 15.9% or 16%; or a range composed of any two of these values, more preferably 12.5% ​​to 15.2% Al2O3, further preferably 13% to 14.7% Al2O3, and most preferably 13.7% to 14.5% Al2O3.

[0041] Sodium oxide (Na2O) can significantly improve the melting property of glass and is a necessary component, but it will reduce the chemical stability of glass and increase the thermal expansion coefficient. If the mass percentage is less than 11%, the melting property of glass will be poor. In addition, too low sodium oxide content will lead to Na + Concentration and Na in molten salt + As the concentration difference decreases, the glass's adaptability to old salt deteriorates; if it is higher than 14.5%, the glass's thermal expansion coefficient is too large and the processing yield is reduced.

[0042] Potassium oxide (K2O) is an essential component that can improve the fusibility of glass. It can work together with sodium oxide to produce a "mixed alkali effect", improve the strength of glass, and increase the DOL value of glass after strengthening. If the mass percentage is less than 3%, the fusibility of the glass is poor; if it is higher than 6%, the thermal expansion coefficient of the glass is too large.

[0043] The value range of Na2O is "11%~14.5%", that is, it can take the minimum and maximum values ​​in the range of 11%~14.5%, as well as every value between this minimum and maximum value. Specific examples include, but are not limited to, the point values ​​in the embodiments and the following point values: 11%, 11.1%, 11.2%, 11.3%, 11.4%, 11.5%, 11.6%, 11.7%, 11.8%, 11.9%, 12%, 12.1%, 12.2%, 12.3%, 12.4%, 12.5%, 12.6%, 12.7%, 12.8%, 12.9%, 13%, 13.1%, 13.2%, 13.3%, 13.4%, 13.5%, 13.6%, 13.7%, 13.8%, 13.9%, 14%, 14.1%, 14.2%, 14.3%, 14.4% or 14.5%; or a range composed of any two of these values, more preferably 11.8% to 14% Na2O, further preferably 12.3% to 13.5% Na2O, and most preferably 12.8% to 13.3% Na2O.

[0044] The value range of K2O is "3%~6%", that is, the minimum and maximum values ​​in the range of 3%~6%, and every value between the minimum and maximum values. Specific examples include, but are not limited to, the point values ​​in the embodiments and the following point values: 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9% or 6%; or a range consisting of any two of these values, more preferably 3.5%~5.5% K2O, further preferably 4%~5% K2O, and most preferably 4.2%~4.8% K2O.

[0045] Magnesium oxide (MgO) can reduce the viscosity of glass at high temperatures, promote the melting and clarification of glass, reduce the thermal expansion coefficient of glass, increase the CS value, but reduce the DOL value. It is a necessary component. If the mass fraction of MgO is less than 2%, the meltability of the glass will deteriorate, and the thermal expansion coefficient will increase, resulting in insufficient CS. If the mass fraction of MgO is higher than 5%, the DOL value of the glass will decrease, and it will be difficult to achieve the ideal strengthening performance.

[0046] The value range of MgO is "2%~5%", that is, the minimum and maximum values ​​of the range of 2%~5%, and each value between the minimum and maximum values. Specific examples include, but are not limited to, the point values ​​in the embodiments and the following point values: 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9% or 5%; or a range composed of any two of these values, more preferably 2.5%~4.6% MgO, further preferably 3%~4.2% MgO, and most preferably 3.2%~4% MgO.

[0047] Zirconium oxide (ZrO2) can improve the weather resistance of glass and increase the CS value by reducing the thermal expansion coefficient of glass, but it will increase the viscosity of the glass and is a necessary component; if the mass percentage is lower than 1.4%, the CS value of the glass is insufficient; if the mass percentage is higher than 3%, the solubility of the glass deteriorates.

[0048] The value range of ZrO2 is "1.4%~3%", that is, the minimum and maximum values ​​in the range of 1.4%~3%, and every value between the minimum and maximum values. Specific examples include, but are not limited to, the point values ​​in the embodiments and the following point values: 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9% or 3%; or a range composed of any two of these values, more preferably 1.7%~2.6% ZrO2, further preferably 1.9%~2.4% ZrO2, and most preferably 2%~2.3% ZrO2.

[0049] Boron oxide (B2O3) can reduce the high temperature viscosity of glass and reduce the thermal expansion coefficient of glass, thereby increasing the CS value, but it will reduce the DOL value. It is a necessary component. If the mass percentage is lower than 0.5%, the glass's meltability will deteriorate and the thermal expansion coefficient will increase, resulting in insufficient CS. If the mass percentage is higher than 3.5%, the glass will be difficult to homogenize, the quality will be reduced, and the DOL value will be reduced.

[0050] The value range of B2O3 is "0.5%~3.5%", that is, the minimum and maximum values ​​of the range of 0.5%~3.5%, and every value between the minimum and maximum values. Specific examples include, but are not limited to, the point values ​​in the embodiments and the following point values: 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%; or a range composed of any two of these values, more preferably 1%~3%, further preferably 1.5%~2.5%, and most preferably 1.8%~2.2%.

[0051] In some embodiments, the aluminosilicate glass satisfies μ of 0.922 to 0.979; wherein μ is the stress relaxation resistance index of the glass, and satisfies the following formula: μ=0.1×[ln(SiO2+1.5ZrO2)+ln(Al2O3-0.2Na2O+0.3K2O-0.2MgO-0.3B2O3)+ln(Al2O3+0.2Na2O-0.1K2O+0.4MgO+0.3B2O3)];

[0052] Each oxide in the above formula represents its mass percentage in the aluminosilicate glass multiplied by 100.

[0053] The adaptability of glass to old salt can be measured by the relaxation index μ. The larger the μ, the smaller the attenuation of the glass when it is strengthened under old salt and its CS value relative to the CS value of new salt.

[0054] In glass, when the content of silicon dioxide (SiO2) and zirconium oxide (ZrO2) increases, the glass structure becomes denser and the ability to resist stress relaxation is enhanced; when the content of aluminum oxide (Al2O3) increases, the glass can obtain more sufficient ion exchange and higher basic stress under the condition of unchanged strengthening process, which is also conducive to resisting stress relaxation; the ability to resist stress relaxation is positively correlated with the content of the above three components, which is reflected in the fact that the coefficient is a positive number in the calculation formula.

[0055] Sodium oxide (Na2O) is a raw material for ion exchange. On the other hand, it will lead to an excessive expansion coefficient, a decrease in CS, and a weakened ability to resist stress relaxation; potassium oxide (K2O) can increase the DOL after strengthening, but on the other hand it will lead to a decrease in CS, affecting the stress relaxation ability; magnesium oxide (MgO) and boron oxide (B2O3) will reduce the DOL after strengthening, but will increase CS, thereby improving the ability to resist stress relaxation. The ability to resist stress relaxation is more complicated with the content of the above four components, and includes both positive and negative correlations, which are reflected in the fact that they appear twice in the calculation formula, with one positive and one negative coefficient.

[0056] In the present application, μ is 0.922~0.979. If μ is less than 0.922, the anti-relaxation ability of the glass is insufficient, and the CS will still relax to a large extent after being strengthened in old salt. If μ is 0.979, there is almost no negative impact on the glass.

[0057] In some of the embodiments, the aluminosilicate glass includes the following components, measured by mass percentage: 58.2%~62.8% SiO2, 12.5%~15.2% Al2O3, 11.8%~14% Na2O, 3.5%~5.5% K2O, 2.5%~4.6% MgO, 1.7%~2.6% ZrO2, and 1%~3% B2O3.

[0058] In some of the embodiments, the aluminosilicate glass comprises the following components, by mass percentage: 58% SiO2, 16% Al2O3, 11% Na2O, 6% K2O, 5% MgO, 3% ZrO2, and 1% B2O3.

[0059] An embodiment of the present application further provides a method for preparing aluminosilicate glass, comprising steps S10 to S20.

[0060] Step S10: providing raw materials according to the above-mentioned composition of aluminosilicate glass.

[0061] Step S20: After mixing the above raw materials, sequentially perform melting treatment, molding treatment, annealing treatment and chemical strengthening treatment.

[0062] Specifically, the above-mentioned melting process includes step a to step b.

[0063] Step a: subjecting the mixed raw materials to a first melting treatment to obtain a first molten glass liquid; the temperature of the first melting treatment is 1600°C to 1650°C.

[0064] Step b: subjecting the first molten glass liquid to a second melting treatment to obtain a second molten glass liquid; the temperature of the second melting treatment is 1550° C. to 1620° C., wherein the temperature of the second melting treatment is lower than the temperature of the first melting treatment.

[0065] In some embodiments, the first melting treatment is performed for 5 to 8 hours.

[0066] In some embodiments, the second melting treatment is performed for 1 h to 2.5 h.

[0067] In some embodiments, the annealing treatment is performed at a temperature of 700° C. to 760° C.

[0068] In some of the embodiments, the chemical strengthening treatment step includes: placing the product after the annealing treatment in a molten salt containing KNO3 for chemical strengthening treatment.

[0069] In some of the embodiments, the temperature of the molten salt is 425°C-435°C.

[0070] The temperature of the molten salt ranges from "425°C to 435°C", that is, the minimum and maximum values ​​of the range of 425°C to 435°C, and every value between the minimum and maximum values. Specific examples include, but are not limited to, the point values ​​in the embodiments and the following point values: 425°C, 425.5°C, 426°C, 426.5°C, 427°C, 427.5°C, 428°C, 428.5°C, 429°C, 429.5°C, 430°C, 430.5°C, 431°C, 431.5°C, 432°C, 432.5°C, 433°C, 433.5°C, 434°C, 434.5°C or 435°C; or a range consisting of any two of these values, for example, 425°C to 430°C.

[0071] In some embodiments, the chemical strengthening treatment time is 2.85h~3.15h.

[0072] The range of the time of the chemical strengthening treatment is "2.85h~3.15h", that is, the minimum and maximum values ​​of the range of 2.85h~3.15h, and each value between the minimum and maximum values. Specific examples include but are not limited to the point values ​​in the embodiment and the following point values: 2.85h, 2.9h, 2.95h, 3h, 3.05h, 3.1h or 3.15h; or a range consisting of any two of these values, as an example, 2.8h~3h.

[0073] The preparation process of the aluminosilicate glass is simple and easy to implement, and the prepared aluminosilicate glass can adapt to the existing production process.

[0074] One embodiment of the present application further provides a glass product, wherein the glass product comprises the aluminosilicate glass or is prepared by the preparation method of the aluminosilicate glass.

[0075] When the aluminosilicate glass and the preparation method thereof are used to prepare glass products, the stress relaxation resistance and mechanical properties of the glass can be improved.

[0076] In some embodiments, the glass products include but are not limited to mobile phones, tablets or car display covers, protective films, etc.

[0077] In order to make the purpose and advantages of the present application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

[0078] Example 1

[0079] (1) Raw materials: According to the glass component formula shown in Table 1, the required raw materials are accurately weighed and mixed uniformly to obtain a mixture.

[0080] (2) Melting: Place the mixed raw materials in a platinum crucible, place the platinum crucible in a lifting furnace, heat to 1650°C, keep warm for 8 hours, then reduce to 1620°C, and keep warm for another 2 hours to obtain a molten liquid.

[0081] (3) Molding: The molten liquid is poured into a rectangular graphite mold that has been heated to 450°C. After it hardens, a molded glass product is obtained.

[0082] (4) Annealing: The formed glass products are placed in an annealing furnace heated to 740°C, kept at that temperature for 6 hours, and then cooled to room temperature.

[0083] (4) Processing: Cut the glass products into thin slices, grind and polish both sides, and the size of the polished glass is 50mm×50mm×1.1mm; the polished glass samples are CNC-processed into 2D glass sheets.

[0084] (6) The glass sheets are chemically strengthened by two methods:

[0085] The first method: chemically strengthen the processed glass sheet in pure potassium nitrate molten salt at a temperature of 435°C and a time of 2.85h to obtain a glass sample; the prepared glass sample is tested for physical and chemical properties, and the tested stress values ​​are recorded as CS0 and DOL0, and the Vickers hardness and ROR strength are tested to obtain the corresponding V0 and R0 values.

[0086] The second method: the processed glass pieces were strengthened in a mixed molten salt of KNO3:NaNO3=98:2 under the same strengthening process, the chemical strengthening temperature was 435℃, and the chemical strengthening time was 2.85h to obtain glass samples; the obtained glass samples were tested for physical and chemical properties, and the stress values ​​of the tests were recorded as CS2 and DOL2. DOL2 is basically consistent with DOL0, and the difference is within the test error range. + The Vickers hardness and ROR strength tests were performed on the strengthened samples (with a concentration of about 5200ppm) to obtain the corresponding V2 and R2 values.

[0087] The following is a specific performance test.

[0088] 1. Surface compressive stress (CS) and stress layer depth (DOL) test: After strengthening, wash and dry the glass, and use FSM-6000LE birefringence stress meter to test the surface stress value CS and stress layer depth DOL of the strengthened glass according to the standard GB / T18144-2008. The photoelastic coefficient used in the test is 27.8nm / (cm·MPa) and the refractive index is 1.52.

[0089] 2. Vickers hardness test of glass surface: Use Falcon 400 Vickers hardness tester to test the hardness of the above samples, use 200gf test force, keep single point test time for 10~15S, measure 10 points of the sample, test to get HV hardness value, and take the average value.

[0090] 3. Glass bending strength test: Use PT-307A bending strength tester to perform ROR ring compression test on the above samples. Use test mold with upper ring diameter of φ16mm and lower ring diameter of φ32mm. Ring compression test method is selected for testing. 10 pieces are grouped together. Test the ROR strength data and take the average value.

[0091] Among them, V=V2 / V0 and R=R2 / R0 are used to evaluate the degree of mechanical property attenuation.

[0092] Specifically, V can be calculated by the following formula:

[0093] V=exp((CS2-CS0) / CS0).

[0094] R can be calculated by the following formula:

[0095] R=0.2×(3.5μ+1.5μ 3 ).

[0096] In the above formula, the units of CS0 and CS2 are both MPa, and the units of DOL0 and DOL2 are μm. The units are not substituted in the calculation.

[0097] Embodiments 2 to 28

[0098] The preparation methods of the aluminosilicate glasses of Examples 2 to 28 are substantially the same as those of Example 1, and the only differences are the components and parameters in Tables 1 to 4.

[0099] Other conditions and parameters are the same as those in Example 1. Please see Tables 1 to 4 for specific test results.

[0100] Comparative Examples 1 to 5

[0101] The preparation methods of the aluminosilicate glasses of Comparative Examples 1 to 5 are substantially the same as those of Example 17, except that the raw material formulas of the glasses in Comparative Examples 1 to 5 are different.

[0102] Other conditions and parameters are the same as those in Example 17. Please see Table 4 for specific test results.

[0103] Table 1

[0104]

[0105] Table 2

[0106]

[0107] Table 3

[0108]

[0109] Table 4

[0110]

[0111] In Tables 1 to 4, Examples 1 to 28 are all cases that meet the requirements of this application. From the test results, it can be seen that after being strengthened with old salt, the mechanical properties of the glass of this application can reach about 93% of the new salt strengthened sample, which is a relatively ideal level. For the glass of this application, V2 is preferably 602kgf / mm 2 In the present application, the preferred range of V is 0.909 to 0.974, and the preferred range of R is 0.881 to 0.966.

[0112] Example 25 is almost the same as Example 17, with the main difference being that the strengthening process used in Example 25 is 3.5 h. At the specified temperature, the strengthening time is too long, resulting in obvious relaxation of stress and decreased anti-relaxation ability. CS2 / CS0 only reaches 0.875, V is 0.869, and R is 0.860.

[0113] Example 26 is almost the same as Example 17, with the main difference being that the strengthening process used in Example 26 is 2.4 h, which is lower than the preferred range of the present application. This results in insufficient ion exchange and insufficient anti-relaxation ability, with CS2 / CS0 only reaching 0.868, and V and R being 0.863 and 0.857, respectively.

[0114] Example 27 is almost the same as Example 17, with the main difference being that the strengthening process used in Example 27 is 450°C. Within the specified time, the strengthening temperature is too high, resulting in obvious relaxation of stress and decreased anti-relaxation ability. CS2 / CS0 only reaches 0.882, V is 0.877, and R is 0.869.

[0115] Example 28 is almost the same as Example 17, with the main difference being that the strengthening process used in Example 28 is at a temperature of 410°C, which is lower than the preferred range of the present application. This results in insufficient ion exchange and insufficient anti-relaxation ability, with CS2 / CS0 only reaching 0.871, and V and R being 0.866 and 0.860, respectively.

[0116] The composition of Comparative Example 1 meets the requirements of the present application, but its anti-relaxation index μ is relatively low, only 0.913, which is lower than 0.922 required by the present application, and CS2 / CS0 only reaches 0.880, indicating that CS relaxation is more serious; V is 0.875, and R is 0.856, which are significantly lower than the embodiments of the present application.

[0117] Comparative Example 2 is almost the same as Example 1, with the main difference being that the mass percentage of MgO in Comparative Example 2 is higher than 5%, and CS2 / CS0 is only 0.867, indicating that CS relaxation is more serious; V and R are 0.862 and 0.843, respectively, which are lower than the requirements of this application.

[0118] Comparative Example 3 is almost the same as Example 12, with the main difference being that the mass percentage of Al2O3 in Comparative Example 3 is lower than 12%, and CS2 / CS0 is only 0.855, indicating that CS relaxation is more serious; V is 0.849, and R is 0.830, which are lower than those in the present application.

[0119] Comparative Example 4 is almost the same as Example 7, with the main difference being that the mass percentage of B2O3 in Comparative Example 4 is higher than 3.5%. At this time, the contribution of B2O3 to stress relaxation is negative, and CS2 / CS0 only reaches 0.860, indicating that CS relaxation is more serious; V and R are 0.853 and 0.836, respectively, which are also lower than those of the embodiments of the present application.

[0120] Comparative Example 5 is almost the same as Example 1, with the main difference being that the mass percentage of ZrO2 in Comparative Example 5 is lower than 1.4%. At this time, the glass structure is relatively loose and the ability to resist stress relaxation is relatively poor. CS2 / CS0 only reaches 0.865, indicating that CS relaxation is relatively serious. V and R are 0.860 and 0.852, respectively, which are also lower than those of the examples of the present application.

[0121] This application has deeply optimized the composition of glass and adapted it with an accurate strengthening process to maintain performance comparable to that of new salt, greatly extending the service life of molten salt, which not only reduces the cost of raw materials, but also improves production efficiency and reduces safety risks. The mechanical properties of glass can also be predicted based on parameters such as the composition of the glass and the strengthening process, which has a guiding role and is convenient for formula and process optimization when there are specific needs. Through the results of this application, the Na in molten salt can be predicted. + The allowable concentration value has been increased from 2000ppm to 5200ppm. According to general industry rules, it is estimated that the life of the molten salt will be increased by about 6 months.

[0122] Compared with the aluminosilicate glass prepared in the comparative example, the aluminosilicate glass prepared according to the technical solution of the present application has better stress relaxation resistance and mechanical properties, can extend the service life of the molten salt, and can meet the practical application of the product.

[0123] The technical features of the above-described embodiments may be arbitrarily combined. To make the description concise, not all possible combinations of the technical features in the above-described embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0124] The above-described embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be construed as limiting the scope of the patent application. It should be pointed out that, for a person of ordinary skill in the art, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application. Therefore, the protection scope of the patent application shall be subject to the attached claims, and the description may be used to interpret the content of the claims.

Claims

1. An aluminosilicate glass, characterized in that: The aluminosilicate glass includes the following components in percentage by mass: 58% to 63% SiO2, 12% to 16% Al2O3, 11% to 14.5% Na2O, 3% to 6% K2O, 2% to 5% MgO, 1.4% to 3% ZrO2, and 0.5% to 3.5% B2O3.

2. The aluminosilicate glass according to claim 1, characterized in that: The aluminosilicate glass satisfies μ of 0.922 to 0.979; wherein μ is the glass stress relaxation resistance index, and satisfies the following formula: μ=0.1×[ln(SiO2+1.5ZrO2)+ln(Al2O3-0.2Na2O+0.3K2O-0.2MgO-0.3B2O3)+ln(Al2O3+0.2Na2O-0.1K2O+0.4MgO+0.3B2O3)]; Each oxide in the above formula represents its mass percentage in the aluminosilicate glass multiplied by 100.

3. The aluminosilicate glass according to claim 1, characterized in that: The aluminosilicate glass includes the following components in percentage by mass: 58.2% to 62.8% SiO2, 12.5% ​​to 15.2% Al2O3, 11.8% to 14% Na2O, 3.5% to 5.5% K2O, 2.5% to 4.6% MgO, 1.7% to 2.6% ZrO2, and 1% to 3% B2O3.

4. A method for preparing aluminosilicate glass, characterized in that: The steps include: Providing raw materials according to the components of the aluminosilicate glass according to any one of claims 1 to 3; After the raw materials are mixed, melting treatment, molding treatment, annealing treatment and chemical strengthening treatment are sequentially performed.

5. The method for preparing aluminosilicate glass according to claim 4, characterized in that: The melting process comprises the following steps: performing a first melting process on the mixed raw materials to obtain a first molten glass liquid; the temperature of the first melting process is 1600° C. to 1650° C.; The first molten glass liquid is subjected to a second melting treatment to obtain a second molten glass liquid; the temperature of the second melting treatment is 1550° C. to 1620° C., wherein the temperature of the second melting treatment is lower than the temperature of the first melting treatment.

6. The method for preparing aluminosilicate glass according to claim 5, characterized in that: The first melting treatment time is 5h~8h, And / or; the time of the second melting treatment is 1h~2.5h.

7. The method for preparing aluminosilicate glass according to any one of claims 4 to 6, characterized in that: The annealing treatment is performed at a temperature of 700°C to 760°C.

8. The method for preparing aluminosilicate glass according to any one of claims 4 to 6, characterized in that: The step of chemical strengthening treatment includes: placing the product after the annealing treatment in a molten salt containing KNO3 for chemical strengthening treatment.

9. The method for preparing aluminosilicate glass according to claim 8, characterized in that: Satisfy at least one of the following conditions (1) to (2): (1) The temperature of the molten salt is 425°C to 435°C; (2) The time of the chemical strengthening treatment is 2.85h~3.15h.

10. A glass product, characterized in that: The glass product comprises the aluminosilicate glass according to any one of claims 1 to 3 or the aluminosilicate glass prepared by the method for preparing the aluminosilicate glass according to any one of claims 4 to 9.

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