Low-melting-point medium-aluminum glass as well as preparation method and application thereof

Abstract

The invention provides low-melting-point medium aluminum glass and a preparation method and application thereof.The low-melting-point medium aluminum glass is prepared by adopting a silicon source, a fluxing agent, albite, potassium carbonate, dolomite, calcite and an auxiliary as raw materials and conducting proper weight proportioning, and during preparation, the raw materials are fully and evenly mixed and subjected to high-temperature melting treatment; and then forming treatment and annealing treatment are performed in sequence to finally prepare the low-melting-point medium-aluminum glass, and the low-melting-point medium-aluminum glass has excellent mechanical strength, hardness, chemical stability and ion exchange depth at the same time. In conclusion, the ore raw materials are adopted to replace chemical raw materials, so that the production cost of the medium-aluminum glass is greatly reduced on the premise of meeting the mechanical property, hardness, chemical stability, high transparency and ion exchange depth of the medium-aluminum glass, and the requirements of industrial production are better met. Detection data shows that the bending strength of the low-melting-point medium-aluminum glass reaches up to 776 MPa, the Vickers hardness reaches up to 660 HV, and the low-melting-point medium-aluminum glass can be applied to display devices with higher requirements for glass performance.

Description

[0001] The invention belongs to the technical field of glass, and in particular relates to a low-melting-point medium-aluminum glass and a preparation method and application thereof. Background Art

[0002] At present, with the development of national economy, people's living standards are constantly improving, and automobiles and electronic glass are constantly developing. Flat glass will be a common glass. People will pay more and more attention to defects such as thickness difference and ripples in glass. Ordinary glass will be difficult to meet the requirements of automobile glass and electronic glass. Solving defects such as thickness difference and ripples is the key to solving the secondary processing rate of glass.

[0003] Cover glass is mainly used for the outermost layer of the touch screen, also known as strengthened optical glass, glass window, strengthened mobile phone lens, etc. The main raw material of the product is ultra-thin flat glass, which has the functions of anti-impact, scratch-resistant, oil-resistant, anti-fingerprint, and enhanced light transmittance after being processed by cutting, CNC carving, thinning, strengthening, coating, printing and other processes.

[0004] Chinese patent document CN116514391A discloses a method for preparing medium aluminum glass (cover glass), specifically: a mixture containing a composition for medium aluminum glass is subjected to melting treatment, forming treatment and annealing treatment in sequence; based on the total weight of the composition, the composition contains 68-74wt% SiO2, 5.2-8.0wt% Al2O3, 7.5-10wt% CaO, 3.5-6wt% MgO and 12-14.5wt% Na2O; and the amount of Al2O3 used M1 and the amount of CaO used M2 satisfy formula (1): Formula (1): 13wt%≤M1+M2≤16wt%; wherein the amount of Fe2O3 introduced is not higher than 100ppm. According to the above records, the raw materials for preparing medium aluminum glass in the above method are mainly chemical raw materials, and the cost of chemical raw materials is high, resulting in increased production costs. Therefore, on the premise of meeting the mechanical properties, hardness, chemical stability, high transmittance and ion exchange depth of medium aluminum glass, how to reduce the production cost of medium aluminum glass and make it have a wider application is of great significance to the development of medium aluminum glass. Summary of the invention

[0005] In order to solve the above problems, the present invention provides a low melting point aluminum glass and a preparation method and application thereof. The present invention uses ore raw materials to replace chemical raw materials, thereby significantly reducing the production cost of aluminum glass while meeting the mechanical properties, hardness, chemical stability, high permeability and ion exchange depth of aluminum glass.

[0006] The technical solution of the present invention is:

[0007] A low melting point aluminum glass, wherein the low melting point aluminum glass is made from the following raw materials:

[0008] Silicon source, 407.50-434.50 parts by weight;

[0009] Flux, 160.00-166.00 parts by weight;

[0010] Sodium feldspar, 218.00-242.50 parts by weight;

[0011] Potassium carbonate, 0.40-2.95 parts by weight;

[0012] Dolomite, 155.60-163.25 parts by weight;

[0013] Calcite, 15.35-16.55 parts by weight;

[0014] Auxiliary agent, 5.20-6.30 parts by weight.

[0015] It is further preferred that the low melting point aluminum glass is made from the following raw materials:

[0016] Silicon source, 434.50 parts by weight;

[0017] Flux, 166.00 parts by weight;

[0018] Sodium feldspar, 218.00 parts by weight;

[0019] Potassium carbonate, 2.40 parts by weight;

[0020] Dolomite, 160.5 parts by weight;

[0021] Calcite, 15.35 parts by weight;

[0022] Auxiliary agent, 5.75 parts by weight.

[0023] The silicon source is quartz sand. By using quartz sand to introduce SiO2, it is used as a glass network former and is the "skeleton" of the glass. When its content is too low, the chemical stability of the obtained glass substrate, especially the acid resistance, becomes poor; when the content is too high, the high-temperature viscosity of the obtained glass substrate increases greatly, making the meltability of the glass component poor. Therefore, the content of quartz sand is limited to 40-50wt% in the present invention.

[0024] The flux is sodium carbonate. Sodium carbonate is used to introduce Na2O, which can greatly reduce the viscosity of glass liquid. It is a flux for making glass and has a great influence on the formation of glass and the clarification process of glass liquid. However, if the content is too much, the chemical stability, thermal stability and mechanical strength of the glass will be greatly reduced, and the glass will be easily moldy and the production cost of the glass will increase. Therefore, the present invention limits the content of sodium carbonate to 10-20wt%.

[0025] Albite introduces Al2O3, which is an intermediate oxide of glass. When its content is too low, the glass is prone to crystallization; when its content is too high, the viscosity of the glass liquid is high and a higher melting temperature is required. Therefore, the content of albite is limited to 20-30wt% in the present invention.

[0026] Potassium carbonate introduces K2O, which can reduce the melting point, viscosity and surface tension of glass, making the glass melt faster during heating. It can also reduce the crystallization tendency of glass, improve the optical properties of glass, adjust the color and corrosion resistance. Therefore, the present invention limits the content of potassium carbonate to 0.5-5wt%.

[0027] Dolomite introduces MgO, which can improve the chemical stability and mechanical strength of glass and reduce the crystallization tendency of glass. MgO has a complex effect on the viscosity of glass. When the temperature is higher than 1200°C, it will reduce the viscosity of glass liquid, and between 1200-900°C, it tends to increase the viscosity of glass liquid. Below 900°C, it will reduce the viscosity of glass. The MgO content in glass should not be too large. Therefore, the present invention limits the content of dolomite to 10-20wt%.

[0028] Calcite introduces CaO, which can accelerate the melting and clarification process of glass. Too high a content of CaO will cause the glass to crystallize. The content of CaO in the glass should not be too high. If it is greater than 10%, it will increase the brittleness of the glass. Therefore, the present invention limits the content of calcite to 10-20wt%.

[0029] The auxiliary agent is a mixture of sodium sulfate and carbon powder in a mass ratio of (5-6): (0.2-0.3). In the glass manufacturing process, sodium sulfate plays a role in increasing the transparency of glass, making the glass more transparent; it can also improve the physical properties of glass and enhance the hardness and strength of glass; carbon powder has multiple functions in glass production, including: as a flux, it can promote the melting of glass; as a toner, it can change the color and transparency of glass; as a conductive agent, it can improve the conductivity of glass; as a reinforcing agent, it can increase the strength and hardness of glass; as a stabilizer, it can improve the heat resistance and acid and alkali resistance of glass. The addition of carbon powder not only improves the physical and chemical properties of glass, but also broadens the application field of glass, providing more choices and possibilities for the low-melting-point medium-aluminum glass product of the present invention.

[0030] It should be noted that the obtained low-melting-point medium-aluminum glass product contains a certain amount of Fe2O3. The amount of Fe2O3 introduced refers to the amount introduced in the raw materials and the preparation process. The purpose is to improve the index requirements of the raw materials and strengthen the production process management. Fe2O3 is an impurity that will color the glass. FeO will make the glass appear cyan, and Fe2O3 will make the glass appear yellow-green. Fe3O4 will make the glass appear green. Fe2O3 and FeO are usually present in glass. The glass studied in the present invention is cyan glass, and the color requirement is not high. Therefore, the present invention sets the content of Fe2O3 to be less than 900ppm.

[0031] The low-melting-point aluminum glass product contains 68-72% SiO2, 4-13% Al2O3, 5.0-8.0% CaO, 3.0-6.0% MgO, 0-1.0% K2O, 10-15% Na2O, and ≤0.09% Fe2O3, based on the total weight of the low-melting-point aluminum glass. The amount of Fe2O3 introduced is not higher than 900ppm. The aluminum glass has the following properties: bending strength is not lower than 650MPa, Vickers hardness is not lower than 600HV, visible light transmittance is greater than 91.5%, and ion exchange depth is 9-11μm.

[0032] The method for preparing the low-melting-point medium-aluminum glass comprises the following specific steps:

[0033] (1) taking various raw materials, stirring and mixing them thoroughly, and then subjecting them to high-temperature melting treatment in an oxygen atmosphere to obtain a first material;

[0034] (2) forming the first material to obtain a second material;

[0035] (3) Annealing the second material to obtain the medium aluminum glass.

[0036] In step (1), the high temperature melting treatment is controlled at a temperature of 1450-1650°C for 6-10 hours. Preferably, the high temperature melting treatment is controlled at a temperature of 1500°C for 8 hours.

[0037] In step (2), the molding process is controlled under the following conditions: temperature is 800-1200° C., and time is 0.5-4 h. Preferably, the molding process is controlled under the following conditions: temperature is 950° C., and time is 1 h.

[0038] In step (3), the annealing treatment is controlled at a temperature of 450-600°C for a time of 10-30 minutes. Preferably, the annealing treatment is controlled at a temperature of 500°C for a time of 20 minutes.

[0039] The application of the low melting point medium aluminum glass in display devices.

[0040] The beneficial effects of the present invention are:

[0041] The present invention provides a low-melting-point medium-aluminum glass, the raw material components include a silicon source, a flux, albite, potassium carbonate, dolomite, calcite, and an auxiliary agent in an appropriate weight ratio. During preparation, the raw materials are first fully mixed and evenly melted at high temperature, and then molded and annealed in sequence. The low-melting-point medium-aluminum glass finally prepared has excellent mechanical strength, hardness, chemical stability, and ion exchange depth. In summary, the present application adopts ore raw materials to replace chemical raw materials, thereby achieving a significant reduction in the production cost of medium-aluminum glass while meeting the mechanical properties, hardness, chemical stability, high transmittance, and ion exchange depth of the medium-aluminum glass, and better meeting the requirements of industrialized production. Test data show that the bending strength of the low-melting-point medium-aluminum glass of the present invention is as high as 776MPa and the Vickers hardness is as high as 660HV, which can be used in display devices with higher requirements for glass performance. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative work.

[0043] Figure 1 Shown is a flow chart for preparing the low-melting-point medium-aluminum glass described in Example 1 of the present invention. DETAILED DESCRIPTION

[0044] To make the purpose, technical solution and advantages of the present invention clearer, the technical solution of the present invention will be described in detail below. Obviously, the described embodiments are only part of the embodiments of the present invention, rather than all of the embodiments. Based on the embodiments of the present invention, all other implementation methods obtained by ordinary technicians in this field without creative work belong to the scope of protection of the present invention.

[0045] The above technical solution is described in detail below in conjunction with specific embodiments.

[0046] In the following embodiments, the performance testing methods involved are as follows:

[0047] Visible light transmittance (%): tested using an ultraviolet spectrophotometer (model: UV-2600i, manufacturer: Shimadzu), the test sample thickness is 0.7 mm;

[0048] Bending strength: tested using a universal testing machine (manufacturer: Beidou Precision Instruments, model: PT-605A);

[0049] Ion exchange depth: chemically strengthened at 420°C for 4 hours, tested using a stress tester (manufacturer: Orihara, model: FSM-6000X);

[0050] Vickers hardness: tested in accordance with GB / T 16534-2009 standard.

[0051] Chemical resistance: The weight loss method is used to detect the amount of corrosion of the glass in 10wt% hydrofluoric acid solution, 5wt% hydrochloric acid solution, and 5wt% sodium hydroxide solution. The test conditions include: placing the defect-free glass in the HF acid solution of the above concentration at 20°C and corroding it for 20 minutes under a shaking state; placing the defect-free glass in the HCl acid solution of the above concentration at 95±5°C and corroding it for 24 hours under a shaking state; placing the defect-free glass in the sodium hydroxide solution of the above concentration at 95±5°C and corroding it for 6 hours under a shaking state; calculating the corrosion amount,

[0052] The calculation formula is:

[0053]

[0054] Erosion amount: mg / cm 2 , the smaller the value, the stronger the chemical resistance;

[0055] M: weight of the sample before and after erosion, mg;

[0056] S: sample surface area, cm 2 ;

[0057] Detection of the amount of Fe2O3 introduced: An X-ray fluorescence spectrometer was used for detection (manufacturer: Shimadzu, model: XRF-1800).

[0058] The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, etc. used in the following examples are all commercially available unless otherwise specified.

[0059] In the following examples, 1 part by weight represents 1 g.

[0060] Example 1

[0061] This embodiment provides a low melting point aluminum glass, the raw material ratio of which is in accordance with the formula in Table 1 and is prepared according to the following method, the specific steps of which include:

[0062] (1) stirring and mixing the raw material components of the medium aluminum glass, placing the mixture in a platinum crucible, and subjecting the mixture to a high-temperature melting treatment in an oxygen atmosphere to obtain a first material; the melting treatment conditions are: a temperature of 1500° C. and a time of 8 hours;

[0063] (2) pouring the first material into a mold for molding to obtain a second material; the molding process is performed under the conditions of: temperature of 950° C. and time of 1 hour.

[0064] (3) Annealing the second material to obtain the medium aluminum glass, wherein the annealing conditions are: temperature of 500° C. and time of 20 min.

[0065] Unless otherwise specified, the remaining examples are carried out using a process similar to that of Example 1, except that the formulas used in the examples are different, as shown in Table 1. The composition of the products obtained in the examples is shown in Table 2.

[0066] Table 1 - Specific raw material dosage of different examples

[0067]

[0068] Table 2 - Composition of the products obtained from different examples

[0069]

[0070] The components of the product in the prior art were determined as a comparative product, see Table 3 for details.

[0071] Table 3 - Composition of different comparative examples

[0072]

[0073]

[0074] The above-mentioned test method was used to measure the performance of the medium aluminum glass obtained in each embodiment and comparative example. The specific results are shown in Table 4.

[0075] Table 4 - Performance test data of the medium aluminum glass obtained in each embodiment and comparative example

[0076]

[0077] It can be seen from the results in Table 4 that the performance of the medium aluminum glass provided by the present invention meets the requirements of the 1JC / T2130-2012 performance standard for mobile electronic product screen cover glass, that is, the medium aluminum glass of the present invention can meet the various mechanical properties, hardness, chemical stability, high transmittance and ion exchange depth required of the cover glass in the display device while greatly reducing the production cost.

[0078] The above is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any person skilled in the art can easily think of changes or substitutions within the technical scope disclosed by the present invention, which should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the protection scope of the claims.

Claims

1. A low melting point aluminum glass, characterized in that: The low melting point aluminum glass is prepared using the following raw materials: Silicon source, 407.50-434.50 parts by weight; Flux, 160.00-166.00 parts by weight; Sodium feldspar, 218.00-242.50 parts by weight; Potassium carbonate, 0.40-2.95 parts by weight; Dolomite, 155.60-163.25 parts by weight; Calcite, 15.35-16.55 parts by weight; Auxiliary agent, 5.20-6.30 parts by weight.

2. The low melting point aluminum glass according to claim 1, characterized in that: The low melting point aluminum glass is prepared using the following raw materials: Silicon source, 434.50 parts by weight; Flux, 166.00 parts by weight; Sodium feldspar, 218.00 parts by weight; Potassium carbonate, 2.40 parts by weight; Dolomite, 160.5 parts by weight; Calcite, 15.35 parts by weight; Auxiliary agent, 5.75 parts by weight.

3. The low melting point medium aluminum glass according to claim 1 or 2, characterized in that: The silicon source is quartz sand.

4. The low melting point aluminum glass according to claim 1 or 2, characterized in that: The flux is sodium carbonate.

5. The low melting point aluminum glass according to claim 1 or 2, characterized in that: The auxiliary agent is a mixture of sodium sulphate and carbon powder in a mass ratio of (5-6):(0.2-0.3).

6. A method for preparing the low-melting-point medium-aluminum glass according to any one of claims 1 to 5, characterized in that: The specific operations are: (1) taking various raw materials, stirring and mixing them thoroughly, and then subjecting them to high-temperature melting treatment in an oxygen atmosphere to obtain a first material; (2) forming the first material to obtain a second material; (3) Annealing the second material to obtain the medium aluminum glass.

7. The method for preparing low-melting-point medium-aluminum glass according to claim 6, characterized in that: In step (1), the conditions of the high temperature melting treatment are controlled as follows: temperature is 1450-1650°C and time is 6-10h.

8. The method for preparing low-melting-point medium-aluminum glass according to claim 6, characterized in that: In step (2), the molding treatment conditions are controlled as follows: temperature is 800-1200° C., and time is 0.5-4 h.

9. The method for preparing low-melting-point medium-aluminum glass according to claim 6, characterized in that: In step (3), the annealing treatment conditions are controlled as follows: temperature is 450-600° C., and time is 10-30 min.

10. Use of the low-melting-point medium-aluminum glass according to any one of claims 1 to 5 or the low-melting-point medium-aluminum glass prepared by the method according to any one of claims 6 to 9 in display devices.

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