Chemically-corrosion-resistant functional glass cover plate and preparation method thereof

Abstract

The application belongs to the technical field of functional glass materials, and discloses a chemical corrosion resistant functional glass cover plate and a preparation method thereof. The glass cover plate is obtained by melting and forming a glass batch containing aluminum silicate base glass raw materials and pre-reaction type fluorine-zirconium-lanthanum-silicon-aluminum composite raw materials; the composite raw materials are prepared by complexation, co-precipitation or co-gelation, drying and low-temperature heat treatment of a zirconium source, a lanthanum source, a fluorine source, a silicon source and an aluminum source, and are in an amorphous state or a low-crystallization state. The method can reduce fluorine volatilization, local enrichment of raw materials, bubbles, stripes and crystallization defects, and improve the chemical corrosion resistance, light transmittance stability and mechanical property consistency of the glass cover plate.

Description

Technical Field

[0001] This invention belongs to the field of functional glass materials technology, specifically relating to a chemically resistant functional glass cover and its preparation method. Background Technology

[0002] Glass covers are widely used in mobile phones, tablets, automotive displays, smart wearable devices, medical display devices, industrial control panels, and outdoor smart terminals. With increasingly complex operating environments, glass covers not only need high light transmittance, low haze, good mechanical strength, and chemical fortification compatibility, but also need to maintain stable appearance and performance under the influence of media such as acids, alkalis, salt spray, sweat, alcohol, cleaning agents, and disinfectants.

[0003] Existing functional glass covers mostly utilize aluminosilicate glass systems, improving their chemical corrosion resistance, mechanical properties, and melting performance by adjusting the proportions of silica, alumina, alkali metal oxides, and alkaline earth metal oxides, or by adding modifying components such as zirconium dioxide, lanthanum oxide, lanthanum fluoride, zirconium tetrafluoride, silica, and alumina. However, current technologies typically involve weighing and mechanically mixing these individual raw materials before adding them to the glass batch. Because zirconium sources like zirconium dioxide have high melting points and low reactivity, they are prone to localized agglomeration or incomplete melting during the melting process. When lanthanum and fluorine sources are added separately, localized enrichment of lanthanum and fluorine, fluorine volatilization, bubbles, streaks, or crystallization defects can easily occur, thus affecting the glass cover's light transmittance, haze, and corrosion resistance stability. Furthermore, fluorine-containing raw materials are prone to volatilization loss during high-temperature melting, leading to fluctuations in glass composition and affecting batch stability. Simply increasing the content of corrosion-resistant components may increase melting difficulty and even cause optical defects or a decrease in mechanical properties. Summary of the Invention

[0004] To address the shortcomings mentioned in the background art, the present invention aims to provide a chemically resistant functional glass cover and its preparation method. The glass cover is obtained by melting and molding an aluminosilicate base glass raw material and a pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material. The composite raw material is pre-reacted from a zirconium source, a lanthanum source, a fluorine source, a silicon source, and an aluminum source, which can reduce fluorine volatilization, local enrichment, and melting defects, and improve the corrosion resistance, light transmittance stability, and mechanical properties of the glass cover.

[0005] The objective of this invention can be achieved through the following technical solutions: A chemically resistant functional glass cover plate is obtained by melting and molding a glass batch, wherein the glass batch includes aluminosilicate base glass raw material and pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material; Based on a total oxide content of 100 parts by weight of the aluminosilicate base glass raw material, the aluminosilicate base glass raw material includes 58-70 parts of silicon dioxide, 10-20 parts of aluminum oxide, 6-13 parts of sodium oxide, 0-5 parts of potassium oxide, 0-5 parts of lithium oxide, 2-8 parts of magnesium oxide, 0-4 parts of calcium oxide, 0-5 parts of boron oxide, and 0-1 parts of clarifying auxiliary components. Based on 100 parts by weight of the total oxide content of the aluminosilicate base glass raw material, the amount of the pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material added is 0.3-5 parts; based on 100 parts by weight of the dry basis of the pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material, the pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material includes 35-55 parts of zirconium dioxide equivalent component, 8-20 parts of lanthanum oxide equivalent component, 5-15 parts of fluorine element, 15-35 parts of silicon dioxide and 3-12 parts of aluminum oxide; The pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material is prepared by complexation co-precipitation pre-reaction or complexation co-gel pre-reaction of zirconium source, lanthanum source, fluorine source, silicon source and aluminum source.

[0006] More preferably, the pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material is an amorphous powder or a low-crystallization powder, and each individual composite raw material particle of the pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material contains zirconium, lanthanum, fluorine, silicon and aluminum simultaneously.

[0007] More preferably, the pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material has a D50 of 0.2-2.0 μm, a D90 of no more than 5.0 μm, and a moisture content of no more than 0.5%.

[0008] More preferably, the zirconium source is selected from one or more of zirconium oxynitrate, zirconium oxychloride, and zirconium acetate; the lanthanum source is selected from one or more of lanthanum nitrate hexahydrate, lanthanum chloride heptahydrate, lanthanum acetate hydrate, and lanthanum salt solution obtained by dissolving lanthanum oxide in nitric acid or acetic acid; the fluorine source is selected from one or two of ammonium fluoride and ammonium bifluoride; the silicon source is selected from one or two of tetraethyl orthosilicate and silica sol; and the aluminum source is selected from one or more of aluminum nitrate nonahydrate, aluminum isopropoxide, aluminum sol, and boehmite.

[0009] More preferably, the clarifying auxiliary component is introduced from a clarifying auxiliary agent raw material, which is selected from one or more of tin oxide, cerium oxide, sodium nitrate, potassium nitrate, and sodium sulfate; based on 100 parts by weight of the final converted total oxide of the functional glass cover, the functional glass cover includes 0.2-2.5 parts of zirconium dioxide, 0.05-1.0 parts of lanthanum oxide, and 0.1-1.5 parts of fluorine.

[0010] A method for preparing a chemically resistant functional glass cover includes the following steps: S1. Zirconium source is added to solvent, complexing agent is added and stirred, lanthanum source, fluorine source, silicon source and aluminum source are added in sequence, pH is adjusted and aging is carried out, and pre-reactive fluorine-zirconium-lanthanum-silicon-aluminum composite raw material is obtained after solid-liquid separation, washing, drying, low temperature heat treatment and pulverization. S2. Mix the aluminosilicate base glass raw material with the pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material to obtain a glass batch material; S3. The glass batch is melted, clarified, homogenized and shaped to obtain a glass substrate; S4. Anneal, cut, grind, polish and chemically strengthen the glass substrate to obtain a chemically resistant functional glass cover.

[0011] More preferably, in step S1, the solvent is water, ethanol, or a mixture of water and ethanol; the complexing agent is selected from one or more of citric acid, tartaric acid, acetylacetone, and disodium EDTA; after adding the zirconium source to the solvent and the complexing agent, the pH of the system is adjusted to 2.0-3.5.

[0012] More preferably, in step S1, the amount of lanthanum source added is 0.05-0.35:1 based on the molar ratio of lanthanum to zirconium; the amount of fluorine source added is 1.0-3.5:1 based on the total molar ratio of fluorine to zirconium and lanthanum; after adding silicon and aluminum sources, the pH of the system is adjusted to 4.5-6.5; the aging temperature is 50-80℃, and the aging time is 2-8h; the drying temperature is 80-120℃; the low-temperature heat treatment temperature is 350-650℃, and the low-temperature heat treatment time is 1-4h.

[0013] More preferably, in step S3, the melting temperature of the glass batch is 1500-1650℃, the melting time is 4-8 h, the clarification temperature is 1550-1600℃, and the clarification time is 1-3 h; in step S4, the chemical strengthening uses potassium nitrate molten salt or a mixed molten salt of potassium nitrate and sodium nitrate, the strengthening temperature is 380-450℃, and the strengthening time is 2-8 h.

[0014] The beneficial effects of this invention are: This invention introduces a pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite material into aluminosilicate glass raw materials, enabling zirconium, lanthanum, fluorine, silicon, and aluminum to form a particle-scale composite distribution before entering the glass melting system. Because this composite material is prepared through complexation, co-precipitation or co-gelation, drying, and low-temperature heat treatment, and exists in an amorphous or low-crystallinity state, it exhibits good reactivity and dispersion uniformity during glass melting. This reduces the agglomeration of refractory zirconium sources, local enrichment of lanthanum and fluorine, and compositional fluctuations caused by high-temperature volatilization of fluorine, thereby reducing the generation of bubbles, streaks, and crystallization defects. The zirconium component helps enhance the stability of the glass network, the lanthanum component helps regulate the distribution of fluorine-containing components, an appropriate amount of fluorine component can improve the component reaction and homogenization effect during melting, and the silicon-aluminum component improves the compatibility of the composite material with the aluminosilicate glass system. Therefore, this invention can improve the melting uniformity and structural stability of glass cover materials from the raw material end, reduce the risk of alkali metal ion precipitation, surface fogging and quality loss under the action of corrosive media, and enable the obtained glass cover to maintain good chemical corrosion resistance in environments such as acid, alkali, salt spray, sweat, alcohol, cleaning agents and disinfectants. Attached Figure Description

[0015] The invention will now be further described with reference to the accompanying drawings.

[0016] Figure 1 A bar chart comparing the fluoride retention rates of the glass cover plates in the examples and comparative examples; Figure 2 The bar chart shows the comparison of the mass loss rates due to acid corrosion and alkali corrosion of the glass cover plates in the examples and comparative examples. Detailed Implementation

[0017] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0018] Example 1 A method for preparing a chemically resistant functional glass cover includes the following steps: S1. Take 175g of zirconium oxynitrate solution and add it to 300g of deionized water, wherein the zirconium oxynitrate solution has a mass content of 20% based on zirconium dioxide. Add 59.7g of citric acid monohydrate, adjust the pH to 2.0, and stir to form a zirconium complex solution. Then add 31.9g of lanthanum nitrate hexahydrate to the zirconium complex solution and stir at 50℃ for 40min. Then add ammonium fluoride solution prepared by dissolving 15.6g of ammonium fluoride in 100g of deionized water and continue stirring for 60min. Mix 121.4g of tetraethyl orthosilicate, 350g of anhydrous ethanol and 200g of deionized water and adjust the pH to 2.5. After hydrolyzing for 45min, add it to the above system. Then add 73.6g of aluminum nitrate nonahydrate, adjust the pH to 4.5, and age at 50℃ for 2h to obtain the fluorine-zirconium-lanthanum-silicon-aluminum composite precursor slurry. The composite precursor slurry was subjected to solid-liquid separation, washing, drying at 80℃ for 12 hours, low-temperature heat treatment at 350℃ for 1 hour, and pulverization and classification to obtain a pre-reactive fluorine-zirconium-lanthanum-silicon-aluminum composite raw material. Testing showed that the pre-reactive fluorine-zirconium-lanthanum-silicon-aluminum composite raw material obtained in Example 1 had a D50 of 0.2 μm, a D90 of 4.2 μm, and a moisture content of 0.45%.

[0019] S2. Take 700g of quartz sand, 100g of alumina, 222.3g of sodium carbonate, 20g of magnesium oxide, 71.4g of calcium carbonate and 10g of tin oxide, and add 3g of pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material. Mix for 45 minutes to obtain glass batch material.

[0020] S3. The glass batch is placed in a platinum crucible, melted at 1500°C for 4 hours, clarified and homogenized at 1550°C for 1 hour, cast and annealed at 580°C for 2 hours, and then cooled to obtain a glass substrate.

[0021] S4. Cut, grind, grind and polish the glass substrate to obtain a glass cover plate substrate; place the glass cover plate substrate in potassium nitrate molten salt at 380℃ for chemical strengthening for 2 hours, clean and dry to obtain a chemically resistant functional glass cover plate.

[0022] Example 2 A method for preparing a chemically resistant functional glass cover includes the following steps: S1. Add 275g of zirconium oxynitrate solution to 300g of deionized water. The zirconium oxynitrate solution has a mass content of 20% based on zirconium dioxide. Add 93.9g of citric acid monohydrate, adjust the pH to 3.5, and stir to form a zirconium complex solution. Add 47.9g of lanthanum nitrate hexahydrate to the zirconium complex solution and stir at 70℃ for 60min. Then add an ammonium fluoride solution prepared by 13.5g of ammonium bifluoride and 100g of deionized water, and continue stirring for 120min. Mix 52.0g of tetraethyl orthosilicate, 300g of anhydrous ethanol, and 200g of deionized water and adjust the pH to 2.5. After hydrolysis for 45min, add the mixture to the above system. Then add 22.1g of aluminum nitrate nonahydrate, adjust the pH to 6.5, and age at 80℃ for 8h to obtain a fluorine-zirconium-lanthanum-silicon-aluminum composite precursor slurry. The composite precursor slurry was subjected to solid-liquid separation, washing, drying at 120℃ for 12 h, low-temperature heat treatment at 650℃ for 4 h, and pulverization and classification to obtain a pre-reactive fluorine-zirconium-lanthanum-silicon-aluminum composite raw material. Testing showed that the pre-reactive fluorine-zirconium-lanthanum-silicon-aluminum composite raw material obtained in Example 2 had a D50 of 2.0 μm, a D90 of 5.0 μm, and a moisture content of 0.50%.

[0023] S2. Weigh 580g of quartz sand, 200g of alumina, 102.6g of sodium carbonate, 73.4g of potassium carbonate, 123.6g of lithium carbonate, 20g of magnesium oxide and 71.4g of calcium carbonate, and add 50g of pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material. Mix for 45 minutes to obtain glass batch material.

[0024] S3. Place the glass batch in a platinum crucible and melt it at 1650℃ for 8 hours, then clarify and homogenize it at 1600℃ for 3 hours to obtain a clarified glass melt. Then pour the clarified glass melt into a preheated mold to form a glass preform; place the glass preform in an annealing furnace and anneal it at 600℃ for 2 hours, then cool it to room temperature in the furnace to obtain a glass substrate.

[0025] S4. Cut, grind, polish, and grind the glass substrate to obtain a glass cover substrate. Place the glass cover substrate in a mixed molten salt of potassium nitrate and sodium nitrate at 450℃ for chemical strengthening for 8 hours. After removal, wash with deionized water and dry to obtain a chemically resistant functional glass cover.

[0026] Example 3 A method for preparing a chemically resistant functional glass cover includes the following steps: S1. Add 225g of zirconium oxynitrate solution (calculated as zirconium dioxide, mass content) to 300g of deionized water. Add 76.8g of citric acid monohydrate, stir for 30min, and adjust the pH of the system to 2.75 with dilute nitric acid or dilute ammonia to obtain a zirconium complex solution. Add 37.2g of lanthanum nitrate hexahydrate to the zirconium complex solution, and stir at 60℃ for 50min to obtain a zirconium-lanthanum mixture. Dissolve 19.5g of ammonium fluoride in 100g of deionized water to obtain an ammonium fluoride solution. Add the ammonium fluoride solution dropwise to the zirconium-lanthanum mixture over 30min. After the addition is complete, continue stirring at 60℃ for 90min to obtain a composite dispersion containing zirconium, lanthanum, and fluorine. Separately, mix 81.5g of tetraethyl orthosilicate, 320g of anhydrous ethanol, and 200g of deionized water, adjust the pH to 2.5 with dilute nitric acid, and stir for 45min to obtain a hydrolyzed silicon source solution. A hydrolyzed silicon source solution was added to a composite dispersion containing zirconium, lanthanum, and fluorine, followed by the addition of 55.2 g of aluminum nitrate nonahydrate. After stirring for 30 min, the pH of the system was adjusted to 5.5 with dilute ammonia. The mixture was then aged at 65 °C for 5 h to obtain a fluorine-zirconium-lanthanum-silicon-aluminum composite precursor slurry. The fluorine-zirconium-lanthanum-silicon-aluminum composite precursor slurry was then subjected to solid-liquid separation. The obtained solid was washed with deionized water until the pH of the filtrate reached 7, and then dried at 100 °C for 12 h. The dried material was then subjected to low-temperature heat treatment at 500 °C for 2.5 h, cooled, pulverized, and classified to obtain a pre-reactive fluorine-zirconium-lanthanum-silicon-aluminum composite raw material. The pre-reactive fluorine-zirconium-lanthanum-silicon-aluminum composite raw material prepared in Example 3 had a D50 of 0.8 μm, a D90 of 4.6 μm, and a water content of 0.38%.

[0027] S2. Take 605g of quartz sand, 150g of alumina, 162.5g of sodium carbonate, 36.7g of potassium carbonate, 61.8g of lithium carbonate, 50g of magnesium oxide, 35.7g of calcium carbonate, 44.4g of boric acid, and 5g of tin oxide, and weigh out 26.5g of pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material. Add the above raw materials to a mixer and mix for 45 minutes to obtain the glass batch.

[0028] S3. Place the glass batch obtained in step S2 into a platinum crucible and melt it at 1575°C for 6 hours, then clarify and homogenize it at 1575°C for 2 hours to obtain a clarified glass melt. Pour the clarified glass melt into a preheated mold to form a glass preform; place the glass preform in an annealing furnace and anneal it at 590°C for 2 hours, then cool it to room temperature in the furnace to obtain a glass substrate.

[0029] S4. Cut, grind, polish, and grind the glass substrate obtained in step S3 to obtain a glass cover substrate. Place the glass cover substrate in potassium nitrate molten salt at 415℃ for chemical strengthening for 5 hours, then remove it, wash it with deionized water, and dry it to obtain a chemically resistant functional glass cover.

[0030] Comparative Example 1: No pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material prepared S1. Add 45g zirconium dioxide, 14g lanthanum oxide, 19.5g ammonium fluoride, 23.5g silicon dioxide and 7.5g alumina to a mixer and mix for 45 minutes to obtain mechanically mixed fluorine-zirconium-lanthanum-silicon-aluminum raw materials.

[0031] S2. Weigh 605g of quartz sand, 150g of alumina, 162.5g of sodium carbonate, 36.7g of potassium carbonate, 61.8g of lithium carbonate, 50g of magnesium oxide, 35.7g of calcium carbonate, 44.4g of boric acid, and 5g of tin oxide, and weigh 29.0g of the mechanically mixed fluorine-zirconium-lanthanum-silicon-aluminum raw material obtained in step S1. Add the above raw materials to a mixer and mix for 45 minutes to obtain the glass batch.

[0032] S3. Place the glass batch obtained in step S2 into a platinum crucible and melt it at 1575°C for 6 hours, then clarify it at 1575°C for 2 hours to obtain a clarified glass melt. Pour the clarified glass melt into a preheated mold to form a glass preform; place the glass preform in an annealing furnace and anneal it at 590°C for 2 hours, then cool it to room temperature in the furnace to obtain a glass substrate.

[0033] S4. The glass substrate obtained in step S3 is cut, edged, ground, and polished to obtain a glass cover substrate. The glass cover substrate is chemically strengthened in potassium nitrate molten salt at 415℃ for 5 hours, then removed, washed with deionized water, and dried to obtain the glass cover of Comparative Example 1.

[0034] Comparative Example 2: In this comparative example, a pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material was first prepared, and then calcined at 900℃ for 2 hours to transform it into a strongly crystallized fluorine-zirconium-lanthanum-silicon-aluminum composite raw material. S1. Prepare a pre-reactive fluorine-zirconium-lanthanum-silicon-aluminum composite raw material according to the method in step S1 of Example 3. Place the prepared pre-reactive fluorine-zirconium-lanthanum-silicon-aluminum composite raw material in a muffle furnace and calcine it at 900°C for 2 hours. After cooling, pulverize and classify it to obtain a highly crystalline fluorine-zirconium-lanthanum-silicon-aluminum composite raw material. Perform composition testing on the calcined highly crystalline fluorine-zirconium-lanthanum-silicon-aluminum composite raw material and adjust its weighing amount according to the test results so that the zirconium dioxide equivalent component, lanthanum oxide equivalent component, and fluorine element introduced are the same as in Example 3.

[0035] S2. Weigh 605g of quartz sand, 150g of alumina, 162.5g of sodium carbonate, 36.7g of potassium carbonate, 61.8g of lithium carbonate, 50g of magnesium oxide, 35.7g of calcium carbonate, 44.4g of boric acid, and 5g of tin oxide. Based on the measured composition after calcination, weigh the highly crystalline fluorine-zirconium-lanthanum-silicon-aluminum composite raw material obtained in step S1, ensuring that the introduced zirconium dioxide equivalent composition, lanthanum oxide equivalent composition, and fluorine element are the same as in Example 3. Add the above raw materials to a mixer and mix for 45 minutes to obtain the glass batch.

[0036] S3. Place the glass batch obtained in step S2 into a platinum crucible and melt it at 1575°C for 6 hours, then clarify it at 1575°C for 2 hours to obtain clarified glass melt. Pour the clarified glass melt into a preheated mold to form a glass preform; then place the glass preform in an annealing furnace and anneal it at 590°C for 2 hours, and then cool it to room temperature with the furnace to obtain a glass substrate.

[0037] S4. The glass substrate obtained in step S3 is cut, edge-ground, ground, and polished to obtain a glass cover plate substrate. The glass cover plate substrate is chemically strengthened in potassium nitrate molten salt at 415℃ for 5 hours, then removed, washed with deionized water, and dried to obtain the glass cover plate of Comparative Example 2.

[0038] Performance testing The glass covers prepared in Examples 1-3 and Comparative Examples 1-2 were subjected to performance tests. All test samples were processed to the same thickness and were cleaned and dried with deionized water and ethanol before testing.

[0039] Fluorine Retention Rate Test: The theoretically introduced fluorine mass in the glass batch was calculated, and the actual fluorine content in the fused glass sample was determined. Glass samples were crushed and ground before sampling. The samples were treated using alkali fusion decomposition or high-temperature combustion water absorption methods, and then the fluorine content was determined using ion chromatography or fluoride ion selective electrode method. The fluorine retention rate was calculated using the following formula: Fluorine Retention Rate / % = (Measured fluorine mass in fused glass / Theoretically introduced fluorine mass in glass batch) × 100%; where the measured fluorine mass in fused glass was calculated based on the mass of the fused glass and the measured fluorine mass fraction in the glass. Each sample group was tested in triplicate, and the average value was taken.

[0040] Bubble count test: The glass cover plate was cut into 50mm×50mm samples and polished to a thickness of 1.0mm. The bubbles inside the samples were observed under transmitted light using an optical microscope. Five fields of view were randomly selected for each sample, with each field of view having an area of ​​1cm². The number of bubbles with a diameter greater than 50μm was counted, and the number of bubbles per unit area was calculated, with the unit being bubbles / cm².

[0041] Visible light transmittance test: The glass cover sample was processed into test pieces of the same thickness. After cleaning and drying, the transmittance in the range of 380-780nm was measured using a UV-Vis spectrophotometer. The transmittance at 550nm was taken as the evaluation value of visible light transmittance. Three pieces were tested for each group of samples, and the average value was taken.

[0042] Haze test: The haze of the glass cover samples was measured using a haze meter. Before testing, the sample surface was cleaned and dried, and the sample thickness was kept consistent. Three samples were tested in each group, and the average value was taken.

[0043] Accelerated acid corrosion mass loss rate test: Cut the glass cover plate sample into 30mm×30mm test pieces, clean and dry them, and weigh the initial mass m0. Immerse the sample completely in a 5wt% hydrochloric acid solution and keep it at 60℃ for 24 hours. After removing the sample, rinse it with deionized water, dry it, and weigh the mass m1 after corrosion. Acid corrosion mass loss rate / % = (m0-m1) / m0×100%. Three pieces of each group of samples were tested in parallel, and the average value was taken.

[0044] Accelerated Alkali Corrosion Mass Loss Rate Test: Cut the glass cover plate sample into 30mm × 30mm test pieces, clean and dry them, and weigh the initial mass m0. Immerse the sample completely in a 5wt% sodium hydroxide solution and maintain it at 60℃ for 24 hours. After removing the sample, rinse it with deionized water, dry it, and weigh the mass m1 after corrosion. Alkali corrosion mass loss rate / % = (m0 - m1) / m0 × 100%. Three pieces of each group of samples were tested in parallel, and the average value was taken.

[0045] The test results are shown in Table 1 below.

[0046] Table 1 Performance analysis results of different glass cover samples

[0047] As shown in Table 1, the fluorine retention rates of Examples 1-3 were 82.6%, 85.4%, and 88.7%, respectively, all significantly higher than those of Comparative Example 1 (63.5%) and Comparative Example 2 (71.2%). This indicates that the volatilization loss of fluorine during glass melting was effectively reduced after using the pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material. The bubble count of Examples 1-3 was 2.2-3.8 bubbles / cm², significantly lower than that of Comparative Example 1 (8.9 bubbles / cm²) and Comparative Example 2 (6.7 bubbles / cm²), indicating that the composite raw material can improve the dispersion uniformity of fluorine-containing and corrosion-resistant components and reduce melting defects. In terms of optical performance, the transmittance at 550nm of Examples 1-3 was all above 91%, and the haze was all below 0.40%, while Comparative Example 1 and Comparative Example 2 had lower transmittance and higher haze, indicating that the present invention can maintain good transparency and low scattering characteristics while improving corrosion resistance. Regarding corrosion resistance, the acid corrosion mass loss rate and alkali corrosion mass loss rate of Example 3 were 0.021% and 0.033%, respectively, both lower than those of Comparative Example 1 and Comparative Example 2, indicating that the stability of the glass network and its resistance to acid and alkali corrosion were improved. Example 3 showed superior performance compared to Comparative Example 1, proving that the effect of this invention does not stem from a simple mechanical mixing of zirconium, lanthanum, fluorine, silicon, and aluminum, but rather from the particle-scale composite distribution of the pre-reactive composite raw materials. Example 3 was superior to Comparative Example 2, indicating that maintaining the composite raw materials in an amorphous or low-crystallinity state is beneficial for improving melting reactivity and compositional uniformity.

[0048] In the description of this specification, references to terms such as "an embodiment," "example," "specific example," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment or example is included in at least one embodiment or example of the invention. In this specification, illustrative expressions of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments or examples.

[0049] The foregoing has shown and described the basic principles, main features, and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited to the above embodiments. The embodiments and descriptions in the specification are merely illustrative of the principles of the invention. Various changes and modifications can be made to the invention without departing from its spirit and scope, and all such changes and modifications fall within the scope of the claimed invention.

Claims

1. A functional glass cover plate resistant to chemical corrosion, characterized in that, The functional glass cover is made by melting and molding a glass batch, which includes aluminosilicate base glass raw material and pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material. Based on a total oxide content of 100 parts by weight of the aluminosilicate base glass raw material, the aluminosilicate base glass raw material includes 58-70 parts of silicon dioxide, 10-20 parts of aluminum oxide, 6-13 parts of sodium oxide, 0-5 parts of potassium oxide, 0-5 parts of lithium oxide, 2-8 parts of magnesium oxide, 0-4 parts of calcium oxide, 0-5 parts of boron oxide, and 0-1 parts of clarifying auxiliary components. Based on 100 parts by weight of the total oxide content of the aluminosilicate base glass raw material, the amount of the pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material added is 0.3-5 parts; based on 100 parts by weight of the dry basis of the pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material, the pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material includes 35-55 parts of zirconium dioxide equivalent component, 8-20 parts of lanthanum oxide equivalent component, 5-15 parts of fluorine element, 15-35 parts of silicon dioxide and 3-12 parts of aluminum oxide; The pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material is prepared by complexation co-precipitation pre-reaction or complexation co-gel pre-reaction of zirconium source, lanthanum source, fluorine source, silicon source and aluminum source.

2. The chemically resistant functional glass cover plate according to claim 1, characterized in that, The pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material is an amorphous powder or a low-crystallization powder, and each individual composite raw material particle of the pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material contains zirconium, lanthanum, fluorine, silicon and aluminum simultaneously.

3. The chemically resistant functional glass cover plate according to claim 1, characterized in that, The pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material has a D50 of 0.2-2.0 μm, a D90 of no more than 5.0 μm, and a moisture content of no more than 0.5%.

4. The chemically resistant functional glass cover plate according to claim 1, characterized in that, The zirconium source is selected from one or more of zirconium oxynitrate, zirconium oxychloride, and zirconium acetate; the lanthanum source is selected from one or more of lanthanum hexahydrate, lanthanum heptahydrate, lanthanum acetate hydrate, and lanthanum salt solution obtained by dissolving lanthanum oxide in nitric acid or acetic acid; the fluorine source is selected from one or two of ammonium fluoride and ammonium bifluoride; the silicon source is selected from one or two of tetraethyl orthosilicate and silica sol; and the aluminum source is selected from one or more of aluminum nonahydrate, aluminum isopropoxide, aluminum sol, and boehmite.

5. The chemically resistant functional glass cover plate according to claim 1, characterized in that, The clarifying auxiliary component is introduced from the clarifying auxiliary agent raw material, which is selected from one or more of tin oxide, cerium oxide, sodium nitrate, potassium nitrate and sodium sulfate; based on 100 parts by weight of the final converted total oxide of the functional glass cover, the functional glass cover includes 0.2-2.5 parts of zirconium dioxide, 0.05-1.0 parts of lanthanum oxide, and 0.1-1.5 parts of fluorine.

6. A method for preparing a chemically resistant functional glass cover according to any one of claims 1-5, characterized in that, Includes the following steps: S1. Zirconium source is added to solvent, complexing agent is added and stirred, lanthanum source, fluorine source, silicon source and aluminum source are added in sequence, pH is adjusted and aging is carried out, and pre-reactive fluorine-zirconium-lanthanum-silicon-aluminum composite raw material is obtained after solid-liquid separation, washing, drying, low temperature heat treatment and pulverization. S2. Mix the aluminosilicate base glass raw material with the pre-reacted fluorine-zirconium-lanthanum-silicon-aluminum composite raw material to obtain a glass batch material; S3. The glass batch is melted, clarified, homogenized and shaped to obtain a glass substrate; S4. Anneal, cut, grind, polish and chemically strengthen the glass substrate to obtain a chemically resistant functional glass cover.

7. The preparation method according to claim 6, characterized in that, In step S1, the solvent is water, ethanol, or a mixture of water and ethanol; the complexing agent is selected from one or more of citric acid, tartaric acid, acetylacetone, and disodium EDTA; after adding the zirconium source to the solvent and the complexing agent, the pH of the system is adjusted to 2.0-3.

5.

8. The preparation method according to claim 6, characterized in that, In step S1, the amount of lanthanum source added is 0.05-0.35:1 based on the molar ratio of lanthanum to zirconium; the amount of fluorine source added is 1.0-3.5:1 based on the total molar ratio of fluorine to zirconium and lanthanum; after adding silicon and aluminum sources, the pH of the system is adjusted to 4.5-6.5; the aging temperature is 50-80℃, and the aging time is 2-8h; the drying temperature is 80-120℃; the low-temperature heat treatment temperature is 350-650℃, and the low-temperature heat treatment time is 1-4h.

9. The preparation method according to claim 6, characterized in that, In step S3, the melting temperature of the glass batch is 1500-1650℃, the melting time is 4-8 h, the clarification temperature is 1550-1600℃, and the clarification time is 1-3 h; in step S4, the chemical strengthening uses potassium nitrate molten salt or a mixed molten salt of potassium nitrate and sodium nitrate, the strengthening temperature is 380-450℃, and the strengthening time is 2-8 h.

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