High-strength corrosion-resistant aluminum-silicon glass and method for preparing the same

Abstract

This invention relates to the field of aluminosilicate glass technology, and discloses a high-strength corrosion-resistant aluminosilicate glass and its preparation method. The preparation method includes the following steps: ultrasonically dispersing fluorinated POSS-modified graphene oxide in deionized water to obtain a graphene dispersion; adding tetraethyl orthosilicate to ethanol and stirring evenly, adding hydrochloric acid, heating to 30-31℃ and stirring for 24 hours to obtain a tetraethyl orthosilicate hydrolysate; placing fluorinated POSS-modified graphene oxide, graphene dispersion, and tetraethyl orthosilicate hydrolysate at 30-31℃ and stirring for 7-8 hours to obtain a coating solution; ultrasonically treating LAS glass sequentially in ethanol, acetone, and deionized water for 15-30 minutes, and setting aside; spin-coating the coating solution onto the surface of the LAS glass, heating to 100-101℃ and holding for 1-1.5 hours under a nitrogen atmosphere, continuing to heat to 550-650℃ and holding for 2-2.5 hours, and cooling to room temperature to obtain high-strength corrosion-resistant aluminosilicate glass.

Description

Technical Field

[0001] This invention relates to the field of aluminosilicate glass technology, specifically to a high-strength corrosion-resistant aluminosilicate glass and its preparation method. Background Technology

[0002] Silicon glass is a material with excellent physical and chemical properties, widely used in electronic information product cover plates, aerospace transparent devices, and observation windows in ships, special vehicles, and deep-sea probes. This type of glass is favored for its low coefficient of thermal expansion and good mechanical properties, especially in high-temperature or extreme environments. However, aluminosilicate glass is susceptible to corrosion in acidic and alkaline environments, particularly glasses containing high concentrations of alkali metal ions (such as Li+), where corrosion is more pronounced. This corrosion typically manifests as surface haziness, powdering, and pitting, severely affecting the glass's optical performance and aesthetics, and potentially reducing its mechanical strength, thus impacting its lifespan and safety.

[0003] The corrosion mechanism of aluminosilicate glass is mainly caused by ion exchange between H+ or OH- and alkali metal ions (such as Na+, K+) in the glass. When the glass is exposed to water or acidic environments, H+ or H3O+ in the solution penetrates into the glass structure and exchanges with alkali metal ions to form Si-OH groups. These groups further hydrolyze, breaking the Si-O-Si bonds to generate non-bridging oxygen Si-OH, ultimately forming silicic acid and OH-. In alkaline environments, OH- attacks the Si-O bonds on the glass surface, causing the silicon-oxygen network structure to be destroyed, generating silicate ions. These ions combine with cations on the glass surface to form silicates, which eventually dissolve in the alkaline solution.

[0004] Due to the corrosion problem of aluminosilicate glass, researchers have proposed various methods to improve its corrosion resistance. One common method is to add corrosion-resistant additives during the glass forming process. These additives can significantly improve the glass's resistance to chemical attack. For example, by adding certain oxides or fluorides, the stability of the glass network can be enhanced, thereby reducing corrosion. Another method is to apply a coating to the glass surface, forming a protective coating to isolate it from corrosive media. For example, coating a MgF2 protective film on a phosphate glass filter can effectively improve its corrosion resistance in tropical marine environments.

[0005] Furthermore, optimizing the chemical composition of glass can also improve its corrosion resistance. For example, reducing the content of alkali metal and alkaline earth metal ions in glass, or increasing the SiO2 content, helps to enhance the chemical stability of glass. Studies have shown that the higher the SiO2 content in glass, the more stable its structure and the stronger its resistance to acidic and alkaline media. On the other hand, improving the density and homogeneity of glass, and reducing the presence of internal defects and microcracks, also helps to improve its corrosion resistance.

[0006] Therefore, inventing a high-strength, corrosion-resistant aluminosilicate glass is of great significance. Summary of the Invention

[0007] The purpose of this invention is to provide a high-strength, corrosion-resistant aluminosilicate glass and its preparation method, so as to solve the problems mentioned in the background art.

[0008] To solve the above-mentioned technical problems, the present invention provides the following technical solution:

[0009] A method for preparing high-strength, corrosion-resistant aluminosilicate glass includes the following steps:

[0010] S1: Sonicate the LAS glass sequentially in ethanol, acetone and deionized water for 15-30 minutes, and set aside.

[0011] Step (1): Octamethylcyclotetrasiloxane, γ-chloropropylmethyldiethoxysilane, and γ-mercaptopropyltriethoxysilane were added to a reaction vessel and stirred until homogeneous. Concentrated sulfuric acid was added, and the mixture was heated to 60-65°C and reacted for 6-8 hours. The mixture was then extracted with deionized water and dichloromethane. This process was repeated three times to remove the aqueous phase. The organic phase was then heated to 40-45°C and the solvent was removed by rotary evaporation to obtain mercaptochloropropyl polysiloxane.

[0012] Furthermore, in the mercaptochloropropyl polysiloxane, the molar ratio of octamethylcyclotetrasiloxane: γ-chloropropylmethyldiethoxysilane: γ-mercaptopropyltriethoxysilane: concentrated sulfuric acid is 3.5:(2-4):(1-3):3.5;

[0013] Step (2): Add sodium iodide to acetone and stir evenly. Add mercaptochloropropyl polysiloxane and heat to 70-75℃ and reflux for 48-50h. Filter and heat the filtrate to 60-65℃ to remove the solvent by rotary evaporation. Extract the residue with diethyl ether and heat to 35-37℃ to remove the diethyl ether by rotary evaporation to obtain mercaptoiodopropyl polysiloxane.

[0014] Furthermore, in the mercaptoiodopropyl polysiloxane, the mass ratio of mercaptochloropropyl polysiloxane to sodium iodide is 4:(0.8-1);

[0015] Step (3): Add mercaptoiodopropyl polysiloxane to tetrahydrofuran, add triethylamine, heat to 40-45℃ and stir to react for 72-74h, heat to 60-65℃ to remove solvent by rotary evaporation, wash with ethanol, and dry at 60-65℃ to obtain mercapto quaternary ammonium salt polysiloxane.

[0016] Furthermore, in the mercaptoquaternary ammonium salt polysiloxane, the mass ratio of mercaptoiodopropyl polysiloxane to triethylamine is 9:(4-5);

[0017] S2: Graphene oxide is ultrasonically dispersed in deionized water, 0.1M sodium hydroxide is added to adjust the pH to 7.5-8, a chloroform solution of mercaptoquaternary ammonium salt polysiloxane is added, and ultrasonic dispersion is carried out for 30-45 minutes to obtain modified graphene oxide.

[0018] Furthermore, in the modified graphene oxide, the mass ratio of graphene oxide to mercapto quaternary ammonium salt polysiloxane is 0.002:(0.15-0.3);

[0019] S3: Modified graphene oxide was added to a dichloromethane solution of 8-methacrylic acid POSS and 0.15-0.2wt% 2-hydroxy-2-methylacetophenone, irradiated with ultraviolet light for 40-45 min, washed with ethanol, and dried at 60-65℃ to obtain POSS-modified graphene oxide; POSS-modified graphene oxide and azobisisobutyronitrile were added to HFO, heated to 85-87℃ under a nitrogen atmosphere, 2-(perfluorooctyl)ethyl methacrylate, azobisisobutyronitrile, and HFO were added, and the reaction was maintained at this temperature for 1-2 h, washed with ethanol, and dried at 60-65℃ to obtain fluorinated POSS-modified graphene oxide;

[0020] Furthermore, in the POSS-modified graphene oxide, the mass ratio of modified graphene oxide to 8-methylallyl POSS is 1:(40-50); in the fluorinated POSS-modified graphene oxide, the mass ratio of POSS-modified graphene oxide to 2-(perfluorooctyl)ethyl methacrylate is (0.15-0.2):(6-8).

[0021] Furthermore, the HFO is 1H,1H,5H-octafluoropentyl-1,1,2,2-tetrafluoroethyl ether.

[0022] S4: Fluorinated POSS-modified graphene oxide is ultrasonically dispersed in deionized water to obtain a graphene dispersion; tetraethyl orthosilicate is added to ethanol and stirred evenly, hydrochloric acid is added, and the mixture is heated to 30-31℃ and stirred for 24 hours to obtain a tetraethyl orthosilicate hydrolysate; the fluorinated POSS-modified graphene oxide, graphene dispersion, and tetraethyl orthosilicate hydrolysate are placed at 30-31℃ and stirred for 7-8 hours to obtain a coating solution;

[0023] Furthermore, the concentration of the graphene dispersion is 0.003-0.005 g / mL; the concentration of the hydrochloric acid is 1.3 M; in the tetraethyl orthosilicate hydrolysate solution, the volume ratio of tetraethyl orthosilicate:ethanol:hydrochloric acid is (3.5-3.75):5:(1.25-1.5); in the coating solution, 15 mL of graphene dispersion and 10 mL of tetraethyl orthosilicate hydrolysate are added for every 0.05 g of fluorinated POSS modified graphene oxide.

[0024] S5: Spin-coat the coating solution onto the LAS glass surface, heat to 100-101℃ and hold for 1-1.5h in a nitrogen atmosphere, continue heating to 550-650℃ and hold for 2-2.5h, then cool to room temperature to obtain high-strength corrosion-resistant aluminosilicate glass.

[0025] Furthermore, the coating solution has a thickness of 3-5 μm; the heating rate during the heating process is 2 °C / min.

[0026] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0027] This invention uses octamethylcyclotetrasiloxane, γ-chloropropylmethyldiethoxysilane, and γ-mercaptopropyltriethoxysilane as silane monomer raw materials to prepare linear polysilanes containing mercapto and chloropropyl side chain structures. These polysilanes are then subjected to sodium iodide and triethylamine substitution and quaternization reactions to obtain mercapto quaternary ammonium salt polysiloxanes. Finally, these polysiloxanes are ion-substituted with weakly basic graphene oxide and grafted onto the surface of graphene oxide to prepare modified graphene oxide. On the one hand, it improves the dispersibility of graphene oxide in the subsequent coating solution component tetraethyl orthosilicate, avoiding agglomeration problems. On the other hand, it utilizes the two-dimensional sheet structure of graphene to increase the penetration path of corrosive media and seal the pores formed during the curing process of the coating layer, playing a physical barrier role while also possessing excellent corrosion resistance, greatly improving the corrosion resistance of aluminosilicate glass. During the high-temperature curing process, linear polysiloxane and tetraethyl orthosilicate undergo dehydration condensation and network densification. The network structure formed by Si-O-Si bonds can improve the hydrophobicity of aluminosilicate glass, effectively preventing the intrusion of water and corrosive media. The addition of tetraethyl orthosilicate can improve the integrity and density of the polysiloxane coating, avoiding the occurrence of cracks during the formation of the polysiloxane coating.

[0028] To further enhance the corrosion resistance of aluminosilicate glass, thiol groups in the linear polysiloxane structure on the graphene surface were modified. 8-methacrylic acid (POSS) was then introduced into the modified graphene oxide structure via a UV-guided click chemistry reaction. This was followed by free radical polymerization with 2-(perfluorooctyl)ethyl methacrylate to obtain fluorinated POSS-modified graphene oxide. Due to the low surface energy of the long-chain fluoroalkane structure, the POSS structure preferentially migrates to the surface of the coating layer during curing, forming a rough structure with interconnected micropores and mesopores. This imparts superhydrophobicity to the aluminosilicate glass, achieving superhydrophobic and dihydrophobic properties in conjunction with the surface fluorinated layer. The introduction of the POSS structure, due to its unique cage-like structure, increases the interlayer spacing of the graphene oxide, making the penetration path of corrosive media more tortuous. Because of the alkaline corrosion mechanism of glass, the outermost fluorinated layer prevents the silica network structure of the film from frequently contacting alkaline solutions. The combined effect of these two factors further improves the corrosion resistance of the aluminosilicate glass. Detailed Implementation

[0029] The technical solutions in the embodiments of the present invention will be clearly and completely described below. 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.

[0030] In the following examples, the graphene oxide was purchased from Changzhou Sixth Element Materials Technology Co., Ltd.; all other raw materials were commercially available.

[0031] The LAS aluminosilicate glass composition, by mass percentage, includes 70.81% SiO2, 4.76% Al2O3, 0.80% P2O5, 1.62% ZrO2, 1.39% MgO, 0.32% ZnO, 0.36% Na2O, 0.66% K2O, and 19.08% Li2O.

[0032] 0.20% B2O3;

[0033] The preparation method includes adding glass raw materials to a mixing tank and mixing them evenly, then pouring the mixture into a platinum crucible and heating it to 1600℃ for 6 hours to melt it. The molten glass is then poured into a mold to obtain a glass brick. The glass brick is placed in an annealing furnace at 480℃ and kept at that temperature for 48 hours for annealing treatment. The annealed glass brick is then wire-cut to obtain a LAS aluminosilicate glass sheet with dimensions of 50mm × 50mm × 0.8mm.

[0034] The preparation method of the mercapto quaternary ammonium salt polysiloxane includes the following steps:

[0035] Step (1): 3.5 mol of octamethylcyclotetrasiloxane, 2 mol of γ-chloropropylmethyldiethoxysilane and 3 mol of γ-mercaptopropyltriethoxysilane were added to a reaction vessel and stirred until homogeneous. 3.5 mol of concentrated sulfuric acid was added and the mixture was heated to 60°C and reacted for 6 h. The mixture was then extracted with deionized water and dichloromethane. The reaction was repeated three times to remove the aqueous phase. The organic phase was heated to 40°C and the solvent was removed by rotary evaporation to obtain mercaptochloropropyl polysiloxane.

[0036] Step (2): Add 1g of sodium iodide to acetone and stir evenly. Add 4g of mercaptochloropropyl polysiloxane and heat to 70°C and reflux for 48h. Filter and heat the filtrate to 60°C to remove the solvent by rotary evaporation. Extract the residue with ether and heat to 35°C to remove the ether by rotary evaporation to obtain mercaptochloropropyl polysiloxane.

[0037] Step (3): Add 9g of mercaptoiodopropyl polysiloxane to tetrahydrofuran, add 4g of triethylamine, heat to 40℃ and stir for 72h, heat to 60℃ to remove solvent by rotary evaporation, wash with ethanol, and dry at 60℃ to obtain mercapto quaternary ammonium salt polysiloxane.

[0038] Example 1: A method for preparing high-strength corrosion-resistant aluminosilicate glass: S1: 0.002g of graphene oxide is ultrasonically dispersed in deionized water, 0.1M sodium hydroxide is added to adjust the pH to 7.5, 0.15g of chloroform solution of mercaptoquaternary ammonium salt polysiloxane is added, and ultrasonic dispersion is carried out for 30-45min to obtain modified graphene oxide.

[0039] S2: 1g of modified graphene oxide was added to a dichloromethane solution of 4098-methacrylic acid POSS and 0.15wt% 2-hydroxy-2-methylacetophenone, irradiated with ultraviolet light for 40min, washed with ethanol, and dried at 60℃ to obtain POSS-modified graphene oxide; 0.15g of POSS-modified graphene oxide and azobisisobutyronitrile were added to HFO, heated to 85℃ under a nitrogen atmosphere, and a mixture of 692-(perfluorooctyl)ethyl methacrylate, azobisisobutyronitrile, and HFO was added. The mixture was kept at this temperature for 1h, washed with ethanol, and dried at 60℃ to obtain fluorinated POSS-modified graphene oxide;

[0040] S3: 0.03 g of fluorinated POSS-modified graphene oxide was ultrasonically dispersed in deionized water to obtain a graphene dispersion with a concentration of 0.003 g / mL; 3.5 mL of tetraethyl orthosilicate was added to 5 mL of ethanol and stirred evenly, then 1.5 mL of hydrochloric acid was added, and the mixture was heated to 30 °C and stirred for 24 h to obtain a tetraethyl orthosilicate hydrolysate; 0.05 g of fluorinated POSS-modified graphene oxide, 15 mL of graphene dispersion, and 10 mL of tetraethyl orthosilicate hydrolysate were placed at 30 °C and stirred for 7 h to obtain a coating solution;

[0041] S4: Sonicate the LAS glass sequentially in ethanol, acetone and deionized water for 15 minutes each, and set aside.

[0042] S5: Spin-coat the coating solution onto the LAS glass surface, heat to 100℃ for 1 hour at a heating rate of 2℃ / min under a nitrogen atmosphere, continue heating to 600℃ for 2 hours at a heating rate of 2℃ / min, and cool to room temperature to obtain high-strength corrosion-resistant aluminosilicate glass; the coating solution thickness is 5μm.

[0043] Example 2: A method for preparing high-strength corrosion-resistant aluminosilicate glass: S1: 0.002g of graphene oxide is ultrasonically dispersed in deionized water, 0.1M sodium hydroxide is added to adjust the pH to 7.5, 0.3g of chloroform solution of mercaptoquaternary ammonium salt polysiloxane is added, and ultrasonic dispersion is carried out for 30-45min to obtain modified graphene oxide.

[0044] S2: 1g of modified graphene oxide was added to a dichloromethane solution of 4098-methacrylic acid POSS and 0.15wt% 2-hydroxy-2-methylacetophenone, irradiated with ultraviolet light for 40min, washed with ethanol, and dried at 60℃ to obtain POSS-modified graphene oxide; 0.15g of POSS-modified graphene oxide and azobisisobutyronitrile were added to HFO, heated to 85℃ under a nitrogen atmosphere, and a mixture of 692-(perfluorooctyl)ethyl methacrylate, azobisisobutyronitrile, and HFO was added. The mixture was kept at this temperature for 1h, washed with ethanol, and dried at 60℃ to obtain fluorinated POSS-modified graphene oxide;

[0045] S3: 0.03 g of fluorinated POSS-modified graphene oxide was ultrasonically dispersed in deionized water to obtain a graphene dispersion with a concentration of 0.003 g / mL; 3.5 mL of tetraethyl orthosilicate was added to 5 mL of ethanol and stirred evenly, then 1.5 mL of hydrochloric acid was added, and the mixture was heated to 30 °C and stirred for 24 h to obtain a tetraethyl orthosilicate hydrolysate; 0.05 g of fluorinated POSS-modified graphene oxide, 15 mL of graphene dispersion, and 10 mL of tetraethyl orthosilicate hydrolysate were placed at 30 °C and stirred for 7 h to obtain a coating solution;

[0046] S4: Sonicate the LAS glass sequentially in ethanol, acetone and deionized water for 15 minutes each, and set aside.

[0047] S5: Spin-coat the coating solution onto the LAS glass surface, heat to 100℃ for 1 hour at a heating rate of 2℃ / min under a nitrogen atmosphere, continue heating to 600℃ for 2 hours at a heating rate of 2℃ / min, and cool to room temperature to obtain high-strength corrosion-resistant aluminosilicate glass; the coating solution thickness is 5μm.

[0048] Example 3: A method for preparing high-strength corrosion-resistant aluminosilicate glass: S1: 0.002g of graphene oxide is ultrasonically dispersed in deionized water, 0.1M sodium hydroxide is added to adjust the pH to 7.5, 0.3g of chloroform solution of mercaptoquaternary ammonium salt polysiloxane is added, and ultrasonic dispersion is carried out for 30-45min to obtain modified graphene oxide.

[0049] S2: 1g of modified graphene oxide was added to a dichloromethane solution of 4098-methacrylic acid POSS and 0.15wt% 2-hydroxy-2-methylacetophenone, irradiated with ultraviolet light for 40min, washed with ethanol, and dried at 60℃ to obtain POSS-modified graphene oxide; 0.2g of POSS-modified graphene oxide and azobisisobutyronitrile were added to HFO, heated to 85℃ under a nitrogen atmosphere, and a mixture of 892-(perfluorooctyl)ethyl methacrylate, azobisisobutyronitrile, and HFO was added. The mixture was kept at this temperature for 1h, washed with ethanol, and dried at 60℃ to obtain fluorinated POSS-modified graphene oxide;

[0050] S3: 0.03 g of fluorinated POSS-modified graphene oxide was ultrasonically dispersed in deionized water to obtain a graphene dispersion with a concentration of 0.003 g / mL; 3.5 mL of tetraethyl orthosilicate was added to 5 mL of ethanol and stirred evenly, then 1.5 mL of hydrochloric acid was added, and the mixture was heated to 30 °C and stirred for 24 h to obtain a tetraethyl orthosilicate hydrolysate; 0.05 g of fluorinated POSS-modified graphene oxide, 15 mL of graphene dispersion, and 10 mL of tetraethyl orthosilicate hydrolysate were placed at 30 °C and stirred for 7 h to obtain a coating solution;

[0051] S4: Sonicate the LAS glass sequentially in ethanol, acetone and deionized water for 15 minutes each, and set aside.

[0052] S5: Spin-coat the coating solution onto the LAS glass surface, heat to 100℃ for 1 hour at a heating rate of 2℃ / min under a nitrogen atmosphere, continue heating to 600℃ for 2 hours at a heating rate of 2℃ / min, and cool to room temperature to obtain high-strength corrosion-resistant aluminosilicate glass; the coating solution thickness is 5μm.

[0053] Example 4: A method for preparing high-strength corrosion-resistant aluminosilicate glass: S1: 0.002g of graphene oxide is ultrasonically dispersed in deionized water, 0.1M sodium hydroxide is added to adjust the pH to 7.5, 0.3g of chloroform solution of mercaptoquaternary ammonium salt polysiloxane is added, and ultrasonic dispersion is carried out for 30-45min to obtain modified graphene oxide.

[0054] S2: 1g of modified graphene oxide was added to a dichloromethane solution of 4098-methacrylic acid POSS and 0.15wt% 2-hydroxy-2-methylacetophenone, irradiated with ultraviolet light for 40min, washed with ethanol, and dried at 60℃ to obtain POSS-modified graphene oxide; 0.2g of POSS-modified graphene oxide and azobisisobutyronitrile were added to HFO, heated to 85℃ under a nitrogen atmosphere, and a mixture of 892-(perfluorooctyl)ethyl methacrylate, azobisisobutyronitrile, and HFO was added. The mixture was kept at this temperature for 1h, washed with ethanol, and dried at 60℃ to obtain fluorinated POSS-modified graphene oxide;

[0055] S3: 0.05 g of fluorinated POSS-modified graphene oxide was ultrasonically dispersed in deionized water to obtain a graphene dispersion with a concentration of 0.005 g / mL; 3.5 mL of tetraethyl orthosilicate was added to 5 mL of ethanol and stirred evenly, then 1.5 mL of hydrochloric acid was added, and the mixture was heated to 30 °C and stirred for 24 h to obtain a tetraethyl orthosilicate hydrolysate; 0.05 g of fluorinated POSS-modified graphene oxide, 15 mL of graphene dispersion, and 10 mL of tetraethyl orthosilicate hydrolysate were placed at 30 °C and stirred for 7 h to obtain a coating solution;

[0056] S4: Sonicate the LAS glass sequentially in ethanol, acetone and deionized water for 15 minutes each, and set aside.

[0057] S5: Spin-coat the coating solution onto the LAS glass surface, heat to 100℃ for 1 hour at a heating rate of 2℃ / min under a nitrogen atmosphere, continue heating to 600℃ for 2 hours at a heating rate of 2℃ / min, and cool to room temperature to obtain high-strength corrosion-resistant aluminosilicate glass; the coating solution thickness is 5μm.

[0058] Comparative Example 1: A method for preparing high-strength corrosion-resistant aluminosilicate glass: S1: 0.002g of graphene oxide was ultrasonically dispersed in deionized water, 0.1M sodium hydroxide was added to adjust the pH to 7.5, 0.15g of a chloroform solution of mercaptoquaternary ammonium salt polysiloxane was added, and ultrasonic dispersion was carried out for 30-45min to obtain modified graphene oxide.

[0059] S2: 1g of modified graphene oxide was added to a dichloromethane solution of 4098-methacrylic acid POSS and 0.15wt% 2-hydroxy-2-methylacetophenone, irradiated with ultraviolet light for 40min, washed with ethanol, and dried at 60℃ to obtain POSS-modified graphene oxide; 0.15g of POSS-modified graphene oxide and azobisisobutyronitrile were added to HFO, heated to 85℃ under a nitrogen atmosphere, and a mixture of 692-(perfluorooctyl)ethyl methacrylate, azobisisobutyronitrile, and HFO was added. The mixture was kept at this temperature for 1h, washed with ethanol, and dried at 60℃ to obtain fluorinated POSS-modified graphene oxide;

[0060] S3: 0.03 g of fluorinated POSS-modified graphene oxide was ultrasonically dispersed in deionized water to obtain a graphene dispersion with a concentration of 0.003 g / mL; 1 mL of tetraethyl orthosilicate was added to 5 mL of ethanol and stirred evenly, then 1.5 mL of hydrochloric acid was added, and the mixture was heated to 30 °C and stirred for 24 h to obtain a tetraethyl orthosilicate hydrolysate; 0.05 g of fluorinated POSS-modified graphene oxide, 15 mL of graphene dispersion, and 10 mL of tetraethyl orthosilicate hydrolysate were placed at 30 °C and stirred for 7 h to obtain a coating solution;

[0061] S4: Sonicate the LAS glass sequentially in ethanol, acetone and deionized water for 15 minutes each, and set aside.

[0062] S5: Spin-coat the coating solution onto the LAS glass surface, heat to 100℃ for 1 hour at a heating rate of 2℃ / min under a nitrogen atmosphere, continue heating to 600℃ for 2 hours at a heating rate of 2℃ / min, and cool to room temperature to obtain high-strength corrosion-resistant aluminosilicate glass; the coating solution thickness is 5μm.

[0063] Comparative Example 2: A method for preparing high-strength corrosion-resistant aluminosilicate glass: S1: 0.002g of graphene oxide was ultrasonically dispersed in deionized water, 0.1M sodium hydroxide was added to adjust the pH to 7.5, 0.15g of chloroform solution of mercaptoquaternary ammonium salt polysiloxane was added, and ultrasonic dispersion was carried out for 30-45min to obtain modified graphene oxide.

[0064] S2: 0.03 g of modified graphene oxide was ultrasonically dispersed in deionized water to obtain a graphene dispersion with a concentration of 0.003 g / mL; 3.5 mL of tetraethyl orthosilicate was added to 5 mL of ethanol and stirred evenly, then 1.5 mL of hydrochloric acid was added, and the mixture was heated to 30 °C and stirred for 24 h to obtain a tetraethyl orthosilicate hydrolysate; 0.05 g of modified graphene oxide, 15 mL of graphene dispersion, and 10 mL of tetraethyl orthosilicate hydrolysate were placed at 30 °C and stirred for 7 h to obtain a coating solution;

[0065] S3: Sonicate the LAS glass sequentially in ethanol, acetone and deionized water for 15 min each, and set aside.

[0066] S4: Spin-coat the coating solution onto the LAS glass surface, heat to 100℃ for 1 hour at a heating rate of 2℃ / min under a nitrogen atmosphere, continue heating to 600℃ for 2 hours at a heating rate of 2℃ / min, and cool to room temperature to obtain high-strength corrosion-resistant aluminosilicate glass; the coating solution thickness is 5μm.

[0067] Comparative Example 3: A method for preparing high-strength corrosion-resistant aluminosilicate glass: S1: 0.002g of graphene oxide was ultrasonically dispersed in deionized water, 0.1M sodium hydroxide was added to adjust the pH to 7.5, 0.15g of a chloroform solution of mercaptoquaternary ammonium salt polysiloxane was added, and ultrasonic dispersion was carried out for 30-45min to obtain modified graphene oxide.

[0068] S2: 1g of modified graphene oxide was added to a dichloromethane solution of 4098-methacrylic acid POSS and 0.15wt% 2-hydroxy-2-methylacetophenone, irradiated with ultraviolet light for 40min, washed with ethanol, and dried at 60℃ to obtain POSS-modified graphene oxide; 0.15g of POSS-modified graphene oxide and azobisisobutyronitrile were added to HFO, heated to 85℃ under a nitrogen atmosphere, and a mixture of 692-(perfluorooctyl)ethyl methacrylate, azobisisobutyronitrile, and HFO was added. The mixture was kept at this temperature for 1h, washed with ethanol, and dried at 60℃ to obtain fluorinated POSS-modified graphene oxide;

[0069] S3: 0.03 g of fluorinated POSS-modified graphene oxide was ultrasonically dispersed in deionized water to obtain a graphene dispersion with a concentration of 0.003 g / mL; 3.5 mL of tetraethyl orthosilicate was added to 5 mL of ethanol and stirred evenly, then 1.5 mL of hydrochloric acid was added, and the mixture was heated to 30 °C and stirred for 24 h to obtain a tetraethyl orthosilicate hydrolysate; 0.05 g of fluorinated POSS-modified graphene oxide, 15 mL of graphene dispersion, and 10 mL of tetraethyl orthosilicate hydrolysate were placed at 30 °C and stirred for 7 h to obtain a coating solution;

[0070] S4: Sonicate the LAS glass sequentially in ethanol, acetone and deionized water for 15 minutes each, and set aside.

[0071] S5: Spin-coat the coating solution onto the LAS glass surface, heat to 100℃ for 1 hour at a heating rate of 2℃ / min under a nitrogen atmosphere, continue heating to 800℃ for 2 hours at a heating rate of 2℃ / min, and cool to room temperature to obtain high-strength corrosion-resistant aluminosilicate glass; the coating solution thickness is 5μm.

[0072] Comparative Example 4: A method for preparing high-strength corrosion-resistant aluminosilicate glass: S1: 0.03 g of graphene oxide was ultrasonically dispersed in deionized water to obtain a graphene dispersion with a concentration of 0.003 g / mL; 3.5 mL of tetraethyl orthosilicate was added to 5 mL of ethanol and stirred evenly, then 1.5 mL of hydrochloric acid was added, and the mixture was heated to 30 °C and stirred for 24 h to obtain a tetraethyl orthosilicate hydrolysate; 0.05 g of graphene oxide, 15 mL of graphene dispersion, and 10 mL of tetraethyl orthosilicate hydrolysate were placed at 30 °C and stirred for 7 h to obtain a coating solution;

[0073] S2: Sonicate the LAS glass sequentially in ethanol, acetone and deionized water for 15 min each, and set aside.

[0074] S3: Spin-coating the coating solution onto the LAS glass surface, heating it to 100℃ for 1 hour at a heating rate of 2℃ / min under a nitrogen atmosphere, continuing to heat it to 600℃ for 2 hours at a heating rate of 2℃ / min, and cooling it to room temperature to obtain high-strength corrosion-resistant aluminosilicate glass; the coating solution thickness is 5μm.

[0075] Experiment: Corrosion resistance: High-strength corrosion-resistant aluminosilicate glass was placed in an alkaline sodium hydroxide environment and allowed to stand for 30 days. A portion of the solution was then analyzed using ICP-OES to determine the Li content. + A1 3+ Si 4+ Ion concentration was used to evaluate the corrosion resistance of high-strength corrosion-resistant aluminosilicate glass; experimental data are shown in Table 1 below.

[0076] Table 1. Test data on corrosion resistance of high-strength corrosion-resistant aluminosilicate glass.

[0077] Example 1 0.1048 7.1254 6.6445 Example 2 0.0996 6.8974 6.1438 Example 3 0.0954 6.8011 5.8876 Example 4 0.0897 6.6544 5.2547 Comparative Example 1 0.1158 7.6547 7.1898 Comparative Example 2 0.1447 8.9387 7.4487 Comparative Example 3 0.2148 12.4738 10.9644 Comparative Example 4 0.1968 10.2578 9.4587

[0078] Conclusion: The high-strength, corrosion-resistant aluminosilicate glass prepared by this invention exhibits excellent corrosion resistance.

[0079] In Comparative Example 1, the reduced proportion of tetraethyl orthosilicate in the tetraethyl orthosilicate hydrolysate led to a decrease in the density of the coating layer, the appearance of fine cracks, and a reduction in corrosion resistance.

[0080] In Comparative Example 2, the modified graphene oxide did not incorporate a POSS structure and a fluorinated layer, lacking a rough structure with interconnected micropores and mesopores. This resulted in reduced interlayer spacing of the graphene oxide and the absence of a fluorinated layer to isolate alkaline solutions, leading to decreased corrosion resistance.

[0081] In Comparative Example 3, the high temperature during the curing process was too high, which caused the Si-O-Si bonds formed during the curing process to break, resulting in the cracking of the coating layer and a reduction in corrosion resistance.

[0082] In Comparative Example 4, unmodified commercially available graphene oxide was used, resulting in reduced corrosion resistance.

[0083] Finally, it should be noted that the above descriptions are merely preferred embodiments of the present invention and are not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing high-strength, corrosion-resistant aluminosilicate glass, characterized in that: The process includes the following steps: S1: Fluorinated POSS-modified graphene oxide is ultrasonically dispersed in deionized water to obtain a graphene dispersion; tetraethyl orthosilicate is added to ethanol and stirred until homogeneous, hydrochloric acid is added, and the mixture is heated to 30-31℃ and stirred for 24 hours to obtain a tetraethyl orthosilicate hydrolysate; the fluorinated POSS-modified graphene oxide, graphene dispersion, and tetraethyl orthosilicate hydrolysate are placed at 30-31℃ and stirred for 7-8 hours to obtain a coating solution; S2: Sonicate the LAS glass sequentially in ethanol, acetone and deionized water for 15-30 minutes, and set aside. S3: Spin-coat the coating solution onto the LAS glass surface, heat to 100-101℃ and hold for 1-1.5h in a nitrogen atmosphere, continue heating to 550-650℃ and hold for 2-2.5h, then cool to room temperature to obtain high-strength corrosion-resistant aluminosilicate glass; The preparation method of the fluorinated POSS-modified graphene oxide includes the following steps: Graphene oxide was ultrasonically dispersed in deionized water, and 0.1M sodium hydroxide was added to adjust the pH to 7.5-8. A chloroform solution of mercaptoquaternary ammonium salt polysiloxane was added, and the mixture was ultrasonically dispersed for 30-45 minutes to obtain modified graphene oxide. Modified graphene oxide was added to a dichloromethane solution of 8-methacrylic acid (POSS) and 0.15-0.2 wt% 2-hydroxy-2-methylacetophenone, irradiated with ultraviolet light for 40-45 min, washed with ethanol, and dried at 60-65℃ to obtain POSS-modified graphene oxide. POSS-modified graphene oxide and azobisisobutyronitrile were added to 1H,1H,5H-octafluoropentyl-1,1,2,2-tetrafluoroethyl ether, heated to 85-87℃ under a nitrogen atmosphere, and 2-(perfluorooctyl)ethyl methacrylate, azobisisobutyronitrile, and HFO were added. The reaction was maintained at this temperature for 1-2 h, washed with ethanol, and dried at 60-65℃ to obtain fluorinated POSS-modified graphene oxide. In the modified graphene oxide, the mass ratio of graphene oxide to mercaptoquaternary ammonium polysiloxane is 0.002:(0.15-0.3). In the POSS-modified graphene oxide, the mass ratio of modified graphene oxide to 8-methacrylic acid POSS is 1:(40-50); in the fluorinated POSS-modified graphene oxide, the mass ratio of POSS-modified graphene oxide to 2-(perfluorooctyl)ethyl methacrylate is (0.15-0.2):(6-8). The preparation method of the mercapto quaternary ammonium salt polysiloxane includes the following steps: Step (1): Octamethylcyclotetrasiloxane, γ-chloropropylmethyldiethoxysilane and γ-mercaptopropyltriethoxysilane were added to a reaction vessel and stirred evenly. Concentrated sulfuric acid was added and heated to 60-65℃ for 6-8 hours. Extraction was performed to remove the aqueous phase and rotary evaporation was carried out to obtain mercaptochloropropyl polysiloxane. Step (2): Add sodium iodide to acetone and stir evenly. Add mercaptochloropropyl polysiloxane and heat to 70-75℃ and reflux for 48-50h. Filter, rotary evaporate, extract with ether, and rotary evaporate again to obtain mercaptoiodopropyl polysiloxane. Step (3): Add mercaptoiodopropyl polysiloxane to tetrahydrofuran, add triethylamine, heat to 40-45℃ and stir for 72-74h, rotary evaporate, wash, and dry at 60-65℃ to obtain mercapto quaternary ammonium salt polysiloxane.

2. The method for preparing high-strength corrosion-resistant aluminosilicate glass according to claim 1, characterized in that: In the mercaptochloropropyl polysiloxane, the molar ratio of octamethylcyclotetrasiloxane: γ-chloropropylmethyldiethoxysilane: γ-mercaptopropyltriethoxysilane: concentrated sulfuric acid is 3.5:(2-4):(1-3):3.

5.

3. The method for preparing high-strength corrosion-resistant aluminosilicate glass according to claim 1, characterized in that: In the mercaptoiodopropyl polysiloxane, the mass ratio of mercaptochloropropyl polysiloxane to sodium iodide is 4:(0.8-1).

4. The method for preparing high-strength corrosion-resistant aluminosilicate glass according to claim 1, characterized in that: In the mercaptoquaternary ammonium salt polysiloxane, the mass ratio of mercaptoiodopropyl polysiloxane to triethylamine is 9:(4-5).

5. The method for preparing a high-strength, corrosion-resistant aluminosilicate glass according to claim 1, characterized in that: The concentration of the graphene dispersion is 0.003-0.005 g / mL; in the tetraethyl orthosilicate hydrolysate, the volume ratio of tetraethyl orthosilicate: ethanol: hydrochloric acid is (3.5-3.75): 5: (1.25-1.5).

6. The high-strength corrosion-resistant aluminosilicate glass prepared by the method for preparing high-strength corrosion-resistant aluminosilicate glass according to any one of claims 1-5.