A strengthened glass composition and method of making and use thereof

Abstract

This invention relates to the field of glass technology, specifically to a strengthened glass composition, its preparation method, and its applications. The strengthened glass composition provided by this invention comprises, by mass percentage: 0.1-5% hydrogen chloride, 0.1-2% ammonium bifluoride, 1% citric acid, 2% sodium gluconate, 1% corrosion inhibitor, and the balance water. The strengthened glass composition obtained by using the components in the specific mass percentages of this invention exhibits a synergistic effect, significantly improving glass strength without causing numerous scratches on the glass surface. After treating chemically strengthened glass, the strengthened glass composition of this invention corrodes away sharp microcracks and areas with high tensile stress thresholds on the glass surface, thereby improving the glass strength.

Description

Technical Field

[0001] This invention relates to the field of glass technology, and more specifically to a strengthened glass composition, its preparation method, and its application. Background Technology

[0002] Surface decorative glass is widely used in the 3C (computer, communication, and consumer electronics) industry, especially as cover glass for LCD and OLED displays. End consumers have high demands for screen reliability when using electronic products, and this reliability is a crucial indicator of a product's market competitiveness. For example, whether the glass possesses sufficient strength to maintain its integrity during normal use or accidental drops or impacts is also an important aspect of product quality.

[0003] There are many ways to evaluate the strength and reliability of cover glass. Commonly used methods that can simulate the breakage of end customers by dropping the glass include four-point bending, drop ball test and ring-to-ring compression test. Among them, drop ball test is the most commonly used and also the most demanding strength test method.

[0004] Glass fractures in a typical brittle material manner, and the most basic fracture theory follows the microcrack propagation theory. Ion exchange, a common method in chemical strengthening, is used to reduce microcracks and thus improve glass strength. A specific ratio of potassium nitrate / sodium nitrate is placed in a high-temperature environment of 300-500℃ to form a molten liquid. Cleaned and dried aluminized sodium glass is then immersed in this liquid. After a period of time, the aluminized sodium glass is removed, cooled, and cleaned, resulting in chemically strengthened aluminized sodium glass. However, even after chemical strengthening, the glass surface still exhibits numerous microcracks or stress concentration defects, leading to relatively low glass strength.

[0005] In chemical strengthening, potassium nitrate replaces sodium ions in the glass, forming a compressive stress layer on the glass surface. This layer prevents sharp microcracks from propagating through the glass or increases the tensile stress threshold required for microcrack propagation, thus improving the glass's strength. Furthermore, the fewer sharp microcracks on the glass surface, the higher the average strength of the glass. However, chemically strengthened glass is still relatively fragile because the microcracks on the glass surface are not adequately addressed. Further research into the glass manufacturing process reveals that microcracks originate from two main causes: firstly, the polishing process before chemical strengthening (ion exchange) fails to completely remove surface or shallow surface cracks; secondly, the pH of the molten potassium nitrate or sodium nitrate used in the chemical strengthening process is not neutral, leading to surface corrosion and subsequently widening existing fine cracks or creating new microcracks.

[0006] Faced with the problem that the strength of chemically strengthened glass is still relatively low, consumer electronics manufacturers are not only actively improving polishing processes and chemical strengthening techniques, but also actively seeking a method to improve microcracks in chemically strengthened glass, thereby further improving its strength. Summary of the Invention

[0007] To address the problem of low strength in chemically strengthened glass in existing technologies, this invention provides a strengthened glass composition, a preparation method, and its applications.

[0008] To achieve the above-mentioned technical objectives, the present invention provides a reinforced glass composition comprising, by mass percentage: 0.1-5% hydrogen chloride, 0.1-2% ammonium bifluoride, 1% citric acid, 2% sodium gluconate, 1% corrosion inhibitor, and the balance being water.

[0009] The tempered glass composition comprises, by mass percentage, 0.1-4% hydrogen chloride, 0.1-2% ammonium bifluoride, 1% citric acid, 2% sodium gluconate, 1% corrosion inhibitor, and the balance being water.

[0010] The tempered glass composition comprises, by mass percentage, 1-4% hydrogen chloride, 1-2% ammonium bifluoride, 0.5-1% citric acid, 1-2% sodium gluconate, 0.5-1% corrosion inhibitor, and the balance being water; preferably, the tempered glass composition comprises, by mass percentage, 2% hydrogen chloride, 1% ammonium bifluoride, 0.5% citric acid, 2% sodium gluconate, 0.5% corrosion inhibitor, and 94% water.

[0011] The corrosion inhibitor is selected from one or more of nitrite, polyphosphate, sulfonated lignin, polyaspartic acid, sodium citrate, and borate.

[0012] The present invention also provides a method for preparing a reinforced glass composition, comprising taking each component according to the above-mentioned mass, mixing them, and thus obtaining the composition.

[0013] The mixing process involves dissolving ammonium fluoride, citric acid, sodium gluconate, and a corrosion inhibitor in water to obtain a solution; then mixing this solution with a solution containing hydrogen chloride and adding water in a measured amount to obtain the final product.

[0014] The process of dissolving in water or mixing with a solution containing hydrogen chloride further includes a stirring step; preferably, the stirring time is 10-15 minutes.

[0015] The present invention also provides the application of a strengthened glass composition or a method for preparing a strengthened glass composition in glass strengthening.

[0016] The present invention also provides a glass strengthening method, comprising immersing chemically strengthened glass in a glass strengthening composition or a glass strengthening composition prepared by a method thereof.

[0017] Furthermore, in the tempered glass composition, the immersion time is 20-40 seconds and the temperature is 20-30°C.

[0018] The chemical strengthening treatment involves placing the glass in a molten alkali salt; preferably, the alkali salt includes one or more of potassium nitrate and sodium nitrate, and the ambient temperature of the chemical strengthening treatment is 350-450°C.

[0019] Furthermore, the alkali salt contains 0.6-40 wt% sodium nitrate and 60-99.4 wt% potassium nitrate.

[0020] The technical solution of the present invention has the following beneficial effects:

[0021] (1) The present invention provides a tempered glass composition comprising, by mass percentage: 0.1-5% hydrogen chloride, 0.1-2% ammonium bifluoride, 1% citric acid, 2% sodium gluconate, 1% corrosion inhibitor, and the balance water. The tempered glass composition obtained by using the components of the present invention in specific mass percentages can exert a synergistic effect, significantly improving the strength of the glass without generating numerous scratches on the glass surface. After treating chemically strengthened glass with the tempered glass composition of the present invention, sharp microcracks and areas with high tensile stress thresholds on the glass surface are corroded away, thereby improving the glass strength. Hydrogen chloride provides an acidic environment, and ammonium bifluoride, under acidic conditions, helps eliminate sharp microcracks or stress concentration points on the glass surface. Citric acid can also slightly corrode microcracks on the glass surface and has a certain acid-releasing effect. At the same time, under acidic conditions, when citric acid and fluoride ions corrode the glass together, they produce a very small amount of viscous corrosion product that remains on the glass surface. After drying, this residue will cover subsurface defects in the glass, thereby weakening the microcracks. Sodium gluconate slows down the corrosion rate of fluoride on the glass, preventing excessively rapid corrosion that could cause numerous scratches on the glass surface. The corrosion inhibitor increases the corrosion resistance of the glass strengthening composition.

[0022] (2) The present invention provides a tempered glass composition comprising, by mass percentage, 0.1-5% hydrogen chloride, 0.1-2% ammonium bifluoride, greater than 0 and less than or equal to 1% citric acid, greater than 0 and less than or equal to 2% sodium gluconate, greater than 0 and less than or equal to 1% corrosion inhibitor, and the balance being water; preferably, the tempered glass composition comprises, by mass percentage, 0.1-4% hydrogen chloride, 0.1-2% ammonium bifluoride, greater than 0 and less than or equal to 1% citric acid, greater than 0 and less than or equal to 2% sodium gluconate, and greater than 0 and less than 1% corrosion inhibitor, and the balance being water. The composition comprises, by mass percentage, 1-4% hydrogen chloride, 1-2% ammonium bifluoride, 0.5-1% citric acid, 1-2% sodium gluconate, 0.5-1% corrosion inhibitor, and the balance being water; more preferably, the composition comprises, by mass percentage, 2% hydrogen chloride, 1% ammonium bifluoride, 0.5% citric acid, 2% sodium gluconate, 0.5% corrosion inhibitor, and 94% water. By optimizing the mass percentage of substances in the composition, the strength of the glass is further improved.

[0023] (3) The present invention provides a glass strengthening composition and preparation method and its application. The glass strengthening composition is a composite solvent. In addition to significantly improving the strength of the glass, it can also avoid the large number of scratches on the glass surface caused by single acid treatment or alkaline treatment. It has very practical market value. Secondly, the preparation method is simple and can be applied to large-scale production. Attached Figure Description

[0024] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0025] Figure 1 This is a diagram of the ball-dropping test method in Experiment Example 1 of the present invention; where a is ball-dropping test method 1 and b is ball-dropping test method 2.

[0026] Figure label:

[0027] 1. Steel ball; 2. Silicone skin; 3. Glass; 4. Bakelite; 5. Bakelite base. Detailed Implementation

[0028] The following embodiments are provided to better understand the present invention and are not limited to the preferred embodiments described. They do not constitute a limitation on the content and scope of protection of the present invention. Any product that is the same as or similar to the present invention, derived by any person under the guidance of the present invention or by combining the features of the present invention with other prior art, falls within the protection scope of the present invention.

[0029] For experiments not specifically described in the examples, the procedures and conditions should be followed according to the conventional experimental procedures described in the literature in this field. Reagents or instruments whose manufacturers are not specified are all commercially available conventional reagent products. Corning glass, model GG5 or GG3.

[0030] Example 1

[0031] This embodiment provides a reinforced glass composition, the composition of which and the amount of raw materials are shown in Table 1.

[0032] Table 1. Composition and Raw Material Amounts of Reinforced Glass Composition

[0033] composition ammonium hydrogen fluoride Citric acid Sodium gluconate Sodium citrate hydrogen chloride Mass percentage (%) 1 0.5 1 0.5 1 raw material ammonium hydrogen fluoride Citric acid Sodium gluconate Sodium citrate 37% concentrated hydrochloric acid Dosage (g) 10 5 10 5 27

[0034] Prepare according to the following method:

[0035] According to the table above, weigh ammonium bifluoride, citric acid, sodium gluconate, and sodium citrate into a beaker, add 500g of water and stir for 10 minutes to obtain a solution; add concentrated hydrochloric acid to the solution and mix, stir for 10 minutes, add water quantitatively until the total mass of the reinforced glass composition is 1000g, stir for 10 minutes, and the final product is obtained.

[0036] Example 2

[0037] This embodiment provides a reinforced glass composition, the composition of which and the amount of raw materials are shown in Table 2. The preparation method is the same as in Example 1.

[0038] Table 2. Composition and Raw Material Amount of Reinforced Glass Composition

[0039] composition ammonium hydrogen fluoride Citric acid Sodium gluconate Sodium citrate hydrogen chloride Mass percentage (%) 1 0.5 2 0.5 2 raw material ammonium hydrogen fluoride Citric acid Sodium gluconate Sodium citrate 37% concentrated hydrochloric acid Dosage (g) 10 5 20 5 54

[0040] Example 3

[0041] This embodiment provides a reinforced glass composition, the composition of which and the amount of raw materials are shown in Table 3. The preparation method is the same as in Example 1.

[0042] Table 3. Composition and Raw Material Amount of Reinforced Glass Composition

[0043] composition ammonium hydrogen fluoride Citric acid Sodium gluconate Sodium citrate hydrogen chloride Quality percentage (%) 2 1 2 1 4 raw material ammonium hydrogen fluoride Citric acid Sodium gluconate Sodium citrate 37% concentrated hydrochloric acid Dosage (g) 20 10 20 10 108

[0044] Example 4

[0045] This embodiment provides a reinforced glass composition, the composition of which and the amount of raw materials are shown in Table 4. The preparation method is the same as in Example 1.

[0046] Table 4. Composition and Raw Material Amount of Reinforced Glass Composition

[0047] composition ammonium hydrogen fluoride Citric acid Sodium gluconate Sodium citrate hydrogen chloride Quality percentage (%) 2 1 2 1 5 raw material ammonium hydrogen fluoride Citric acid Sodium gluconate Sodium citrate 37% concentrated hydrochloric acid Dosage (g) 20 10 20 10 135

[0048] Comparative Example 1

[0049] This comparative example provides a reinforced glass composition, which differs from Example 1 in that the reinforced glass composition is water.

[0050] Comparative Example 2

[0051] This comparative example provides a reinforced glass composition using a 6% aqua regia solution. Preparation: Concentrated hydrochloric acid (37 wt%) and concentrated nitric acid (65 wt%) are mixed in a volume ratio of 3:1 to obtain aqua regia. 60 g of the aqua regia is taken, and water is added quantitatively until the total mass of the reinforced glass composition is 1000 g. The mixture is stirred for 10 min to obtain a 6% aqua regia solution.

[0052] Comparative Example 3

[0053] This comparative example provides a tempered glass composition using a 6% hydrofluoric acid solution. Preparation method: Take 120g of hydrofluoric acid (50% concentration), add water to a measured amount until the total mass of the tempered glass composition is 1000g, stir for 10 minutes, and the mixture is ready.

[0054] Comparative Example 4

[0055] This comparative example provides a tempered glass composition using a 6% citric acid solution. Preparation method: Take 60g of citric acid, add 500g of water and stir for 10 minutes to obtain a solution; add water quantitatively until the total mass of the tempered glass composition is 1000g, stir for 10 minutes, and the final product is obtained.

[0056] Comparative Example 5

[0057] This comparative example provides a tempered glass composition using a 6% phosphoric acid solution. Preparation method: Take 71g of phosphoric acid (85% concentration), add water to a measured amount until the total mass of the tempered glass composition is 1000g, stir for 10 minutes, and the result is obtained.

[0058] Comparative Example 6

[0059] This comparative example provides a tempered glass composition using a 6% sulfuric acid solution. Preparation method: Take 61g of concentrated sulfuric acid (98% concentration), add water quantitatively until the total mass of the tempered glass composition is 1000g, stir for 10 minutes, and the product is obtained.

[0060] Comparative Example 7

[0061] This comparative example provides a tempered glass composition using a 6% potassium hydroxide solution. Preparation method: Take 60g of potassium hydroxide, add 500g of water and stir for 10 minutes to obtain a solution; add water quantitatively until the total mass of the tempered glass composition is 1000g, stir for 10 minutes, and the final product is obtained.

[0062] Comparative Example 8

[0063] This comparative example provides a strengthened glass composition, the composition of which and the amounts of raw materials are shown in Table 5. The preparation method is the same as in Example 1.

[0064] Table 5. Composition and Raw Material Amounts of Reinforced Glass Compositions

[0065] composition ammonium hydrogen fluoride Citric acid Sodium gluconate Sodium citrate hydrogen chloride Mass percentage (%) 3 2 2 1 6 raw material ammonium hydrogen fluoride Citric acid Sodium gluconate Sodium citrate 37% concentrated hydrochloric acid Dosage (g) 30 20 20 10 162

[0066] Experimental Example 1

[0067] The tempered glass compositions provided in the examples and comparative examples were used to strengthen the glass according to the following method to obtain tempered glass. Drop ball tests were then performed on each group of tempered glass. The specific method is as follows:

[0068] Preparation of chemically strengthened glass: (1) Treatment method of GG5 type glass: Mix 62wt% potassium nitrate and 38wt% sodium nitrate and melt in a furnace at 380℃ for 24 hours as the molten liquid for the first chemical strengthening. Preheat the cleaned and dried Corning glass (type GG5) in a furnace at 380℃ for 60min, and then quickly put it into the molten liquid for the first chemical strengthening. After 100min, take out the glass and cool it quickly to 25℃. Then clean the glass to remove the surface residue and dry it. After preheating it at 380℃ for 60min, quickly put it into the molten liquid for the second chemical strengthening containing 91wt% potassium nitrate and 9wt% sodium nitrate. After 30min, take out the glass and cool it to 25℃. Clean it to obtain the chemically strengthened glass. (2) Processing method of GG3 glass: 99.33 wt% potassium nitrate and 0.67 wt% sodium nitrate are placed in a furnace at 410°C and melted for 24 hours as the chemical strengthening melt. After cleaning and drying, Corning glass (model GG3) is placed in a furnace at 400°C and preheated for 60 minutes. Then, it is quickly immersed in the above chemical strengthening melt. After 9 hours, the glass is taken out, cooled to 25°C, and cleaned to obtain the chemically strengthened glass.

[0069] Method for treating glass with tempered glass composition: (1) Soak the chemically strengthened glass in water for 30 minutes and then dry the water stains on the glass surface at 22°C; (2) Randomly group the dried glass and quickly and completely immerse it in the tempered glass compositions of each example and comparative example. The immersion time and temperature are shown in Table 6. After taking it out for 30 seconds, use a flat plate washer to clean the glass surface with pure water as the cleaning agent. After taking out the glass, dry the water stains on the glass surface at 22°C to obtain tempered glass.

[0070] Drop ball test method 1: The test is conducted according to the national standard GB / T39814-2021 "Test Method for Impact Strength of Ultra-thin Glass - Drop Ball Impact Method". The glass 3 is fixed between the silicone skin 2 and the bakelite 4, with the bakelite 4 positioned on the bakelite base 5. During the test, the steel ball 1 is adjusted as follows: Figure 1 As shown in a.

[0071] Drop ball test method 2: The test is conducted in accordance with the national standard GB / T39814-2021 "Test Method for Impact Resistance of Ultra-thin Glass - Drop Ball Impact Method". ， Place both ends of glass 3 onto bakelite 4, with bakelite 4 positioned on bakelite base 5. During testing, adjust steel ball 1 as follows: Figure 1 As shown in b.

[0072] The steel ball 1 has a mass of 130g. During the test, the distance between the bottom of the steel ball 1 and the upper surface of the glass 3 was adjusted. The distance difference was 5cm each time. The ball drop test was carried out at 9 drop points on the glass. The test was carried out on 10 pieces of tempered glass treated with the same tempered glass composition. The drop height was recorded as the distance between the bottom of the steel ball and the upper surface of the sample. The drop height was the minimum value of multiple measurement results.

[0073] The types of tempered glass, immersion temperatures, immersion times, and drop ball test results involved in the drop ball test are shown in Table 6 below. The drop ball heights of Examples 1-4 are greater than those of Comparative Examples 1-8. Therefore, the tempered glass composition prepared in this invention significantly improves the strength of the glass after chemically strengthened glass treatment. Compared with Examples 1-4, the tempered glass treated in Example 2 has the best strength.

[0074] Table 6. Ball Drop Test Results

[0075] sample Glass type Immersion temperature ℃ Soaking time (s) Testing methods Drop ball height (cm) Example 1 GG5 22 30 Method 1 80 Example 2 GG5 22 30 Method 1 90 Example 3 GG5 22 30 Method 1 85 Example 4 GG5 22 30 Method 1 80 Comparative Example 1 GG5 22 30 Method 1 15 Comparative Example 2 GG5 22 30 Method 1 30 Comparative Example 3 GG5 22 30 Method 1 35 Comparative Example 4 GG5 40 30 Method 1 25 Comparative Example 5 GG5 40 30 Method 1 25 Comparative Example 6 GG5 22 30 Method 1 30 Comparative Example 7 GG5 60 180 Method 1 30 Comparative Example 8 GG5 22 30 Method 1 70 Example 1 GG3 22 30 Method 2 50 Example 2 GG3 22 30 Method 2 55 Example 3 GG3 22 30 Method 2 50 Example 4 GG3 22 30 Method 2 50 Comparative Example 1 GG3 22 30 Method 2 10 Comparative Example 2 GG3 22 30 Method 2 20 Comparative Example 3 GG3 22 60 Method 2 30 Comparative Example 3 GG3 22 30 Method 2 20 Comparative Example 4 GG3 40 30 Method 2 15 Comparative Example 5 GG3 40 30 Method 2 25 Comparative Example 6 GG3 22 30 Method 2 25 Comparative Example 7 GG3 60 180 Method 2 20 Comparative Example 8 GG3 22 30 Method 2 35

[0076] Experiment Example 2

[0077] The glass samples from the various examples and comparative examples in Experimental Example 1 were observed before and after treatment with the strengthened glass compositions. Surface compressive stress and glass thickness were tested on the glass samples from the various examples in Experimental Example 1 before and after treatment with the strengthened glass compositions. Surface compressive stress was tested using a Mitsutoyo FSM-6000LE, and thickness was measured using a micrometer.

[0078] The test results are shown in Table 7 below. The glass surfaces treated with the tempered glass compositions of Examples 1-4 showed no unacceptable scratches, especially Examples 1-3, which showed no visible scratches. In contrast, Comparative Examples 2 (GG5 model) and 3 (GG3 model) showed unacceptable scratches on their glass surfaces, while Comparative Example 8 (GG5 model) showed more obvious unacceptable scratches. This indicates that the tempered glass compositions of Examples 1-4 strengthen the glass without damaging it. Furthermore, the surface compressive stress and glass thickness variations in Examples 1-4 were small, meeting production requirements.

[0079] Table 7 Test Results

[0080]

[0081] Note: / , The surface of the tempered glass is free of scratches.

[0082] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A strengthened glass composition, characterized by, The reinforced glass composition comprises, by mass percentage, 1-4% hydrogen chloride, 1-2% ammonium bifluoride, 0.5-1% citric acid, 1-2% sodium gluconate, 0.5-1% corrosion inhibitor, and the balance being water.

2. The strengthened glass composition according to claim 1, characterized in that, The reinforced glass composition comprises, by mass percentage, 2% hydrogen chloride, 1% ammonium bifluoride, 0.5% citric acid, 2% sodium gluconate, 0.5% corrosion inhibitor, and 94% water.

3. The reinforced glass composition according to claim 1 or 2, characterized in that, The corrosion inhibitor is selected from one or more of nitrite, polyphosphate, sulfonated lignin, polyaspartic acid, sodium citrate, and borate.

4. A method of producing the strengthened glass composition according to any one of claims 1 to 3, characterized by, This involves taking the components according to the above-mentioned mass, mixing them, and then obtaining the final product.

5. The method of making a strengthened glass composition according to claim 4, wherein, The mixing process involves dissolving ammonium fluoride, citric acid, sodium gluconate, and a corrosion inhibitor in water to obtain a solution; then mixing this solution with a solution containing hydrogen chloride and adding water in a measured amount to obtain the final product.

6. The method of making a strengthened glass composition according to claim 5, wherein, The process of dissolving in water or mixing with a solution containing hydrogen chloride also includes a stirring step.

7. The method of making a strengthened glass composition according to claim 6, wherein, The stirring time is 10-15 minutes.

8. The application of a reinforced glass composition prepared by any of the methods described in claims 1-3 or 4-7 in glass strengthening.

9. A glass strengthening method characterized by, This includes immersing chemically strengthened glass in a strengthened glass composition prepared by any of the methods described in claims 1-3 or any of the methods described in claims 4-7.

10. The glass strengthening method according to claim 9, wherein, The chemical strengthening treatment involves placing the glass in molten alkali salt.

11. The glass strengthening method according to claim 10, wherein, The alkaline salt includes one or more of potassium nitrate and sodium nitrate; And / or, the ambient temperature for the chemical enhancement treatment is 350-450°C.

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