Corrosion-resistant composite tempered glass and preparation method thereof

Abstract

The invention relates to corrosion-resistant composite tempered glass and a preparation method thereof, and belongs to the technical field of glass products, and the tempered glass comprises a corrosion-resistant surface layer, a functional core layer and a force-bearing base layer which are sequentially arranged from outside to inside. Wherein the outer layer is borosilicate glass subjected to low-temperature ion exchange treatment in a potassium-sodium mixed salt bath containing nano silicon nitride, and the middle layer is formed by compounding epoxy acrylate resin, self-repairing microcapsules and fluorosilane modified silicon dioxide and integrates damage self-repairing, super-hydrophobic anti-fog and self-cleaning functions; and the inner layer is high-strength glass doped with aluminum oxide whiskers and rare earth oxides. A'resisting-repairing-strengthening 'systematic protection system is constructed through a gradient structure, the preparation process is energy-saving and efficient, and the technical problem that a single corrosion-resistant layer of traditional tempered glass is prone to failure under mechanical damage, water vapor condensation and dirt attachment is solved.

Description

Technical Field

[0001] This invention belongs to the field of glass product technology and relates to a corrosion-resistant composite tempered glass and its preparation method. Background Technology

[0002] Tempered glass, as an important safety glass material, is widely used in construction, transportation, industrial equipment and other fields. With the expansion of application areas and the improvement of environmental requirements, higher requirements are placed on the corrosion resistance of tempered glass.

[0003] Existing technologies for improving the corrosion resistance of tempered glass include: using various additives and ion exchange processes to improve corrosion resistance and freeze resistance, but these methods have problems such as a wide variety of raw materials, complex processes, high energy consumption, and relatively limited functionality; another method is to use multi-layer composite structures and interlayer membranes to improve stability and sound insulation, but corrosion resistance mainly depends on the interlayer membrane material, and interface aging may occur after long-term use.

[0004] However, the protective function of a corrosion-resistant barrier built on or between glass layers is immediately lost once this barrier is damaged. Mechanical damage such as transportation collisions, impacts from flying stones, and scratches during installation can create microcracks and scratches, which become rapid channels for corrosive media to penetrate. Furthermore, in environments with significant temperature variations, condensation and fogging easily form on the glass surface and between layers, creating a continuous water film that becomes a physical corrosive medium. Simultaneously, pollutants such as salt, acid rain, and industrial dust in the atmosphere also adhere to the glass surface, accelerating the corrosion process. Therefore, traditional corrosion-resistant glass often experiences performance degradation in practical use, failing to meet the urgent need for long-term, reliable corrosion resistance. Summary of the Invention

[0005] The purpose of this invention is to provide a corrosion-resistant composite tempered glass and its preparation method. It constructs a systematic protection system that can dynamically respond to environmental changes and autonomously maintain its performance. The outer layer forms a high surface compressive stress layer through low-temperature ion exchange and is composited with nano-silicon nitride, serving as the first rigid barrier against the penetration of corrosive media and mechanical wear. The middle layer integrates self-healing, superhydrophobic, and anti-fogging functions, forming an intelligent hub for active response and repair. It can autonomously repair micro-damage, prevent fogging and self-clean, and reduce the adhesion of pollutants. The inner layer provides mechanical support for the entire structure. The three layers work together to solve the industry problem of the overall performance degradation of traditional tempered glass due to the failure of a single protective layer.

[0006] The objective of this invention can be achieved through the following technical solutions: In one aspect, a corrosion-resistant composite tempered glass is provided, which is provided with a corrosion-resistant surface layer, a functional core layer and a load-bearing base layer stacked from the outside to the inside. The corrosion-resistant surface layer is a borosilicate glass layer that has undergone ion exchange treatment; The functional core layer is formed by curing a slurry containing the following components in parts by weight: 40-60 parts epoxy acrylate resin, 5-15 parts self-healing microcapsules, and 5-12 parts fluorosilane-modified silica. The load-bearing base layer is made from raw materials containing the following parts by weight: 60-75 parts quartz sand, 10-20 parts potassium feldspar, 1-5 parts rare earth oxides, and 2-8 parts alumina whiskers.

[0007] Furthermore, the corrosion-resistant surface layer is composited with nano-silicon nitride, and the surface compressive stress is 650±50 MPa.

[0008] Furthermore, the wall material of the self-healing microcapsule is urea-formaldehyde resin, and the core material is a mixture of butyl acrylate and methyl methacrylate.

[0009] Furthermore, the preparation method of the self-healing microcapsule includes: mixing urea and formaldehyde solution at a weight ratio of 1:2.0-3.5, adjusting the pH to 8-9, reacting at 60-70℃ to form a prepolymer, mixing butyl acrylate and methyl methacrylate at a weight ratio of 2-3:1 as the core material, and using in-situ polymerization to polymerize the prepolymer on the surface of the core material to form the capsule wall, thereby obtaining the self-healing microcapsule.

[0010] Furthermore, the rare earth oxide is a mixture of cerium oxide and yttrium oxide in a weight ratio of 1:1-3.

[0011] Secondly, a method for preparing corrosion-resistant composite tempered glass is provided, comprising the following steps: (1) Immerse the borosilicate glass substrate in a mixed salt bath containing a nano-silicon nitrate dispersion phase of potassium nitrate and sodium nitrate, and perform ion exchange treatment at 380-420°C for 2-6 hours. Remove, clean and dry to obtain a substrate for forming a corrosion-resistant surface layer. (2) Epoxy acrylate resin, self-healing microcapsules and fluorosilane modified silica are mixed in proportion, and solvent is added to adjust the viscosity to 800-1000 mPa·s to obtain functional core layer slurry. (3) Mix quartz sand, feldspar, rare earth oxides, alumina whiskers, clarifying agent and flux according to the ratio, melt and clarify at 1480-1520℃ and then cast into shape, and then perform annealing treatment: heat up to 550-580℃ at a rate of 2-5℃ / min, hold for 1-3 hours, then cool down to 450-500℃ at a rate of 0.5-2℃ / min and cool to room temperature to obtain the annealed substrate used to form the load-bearing base layer; (4) Coat the substrate surface obtained in step (1) with a 1-5% silane coupling agent ethanol solution and dry it. Coat the slurry obtained in step (2) evenly on it and perform UV pre-curing for 90-120 seconds. Attach the substrate obtained in step (3) to the pre-cured film layer and perform hot pressing composite. Then, perform final curing at 120-130℃ for 1-3 hours to obtain the corrosion-resistant composite tempered glass.

[0012] Further, in step (1), the mixed salt bath is composed of the following components in parts by weight: 65-75 parts potassium nitrate, 25-35 parts sodium nitrate, and 0.1-0.5 parts nano silicon nitride.

[0013] Further, in step (2), the solvent is ethyl acetate, acetone or N,N-dimethylformamide, and the amount used is 30-70 parts.

[0014] Further, in step (3), the clarifying agent is antimony trioxide, sodium sulfate or cerium oxide, and its addition amount is 0.5-2.5 parts, and the fluxing agent is sodium carbonate, potassium carbonate or borax, and its addition amount is 3-8 parts.

[0015] Further, in step (4), the conditions for ultraviolet pre-curing are: using an ultraviolet light source with a wavelength of 365nm and an irradiation intensity of 80-100mW / cm². 2 The hot-pressing composite process involves a pressure of 0.5-2.0 MPa, a temperature of 80-120°C, and a time of 10-30 minutes.

[0016] The beneficial effects of this invention are: (1) In this invention, the outer borosilicate glass undergoes low-temperature ion exchange in a potassium nitrate-sodium nitrate mixed salt bath containing a nano-silicon nitrate dispersion phase. This process forms a reinforcing layer on its surface with a compressive stress as high as 650±50 MPa, effectively passivating the surface and preventing the inward diffusion of corrosive media. At the same time, the nano-silicon nitrate particles in the salt bath are effectively adsorbed and composited on the glass surface during the ion exchange process, significantly improving the wear resistance of the glass surface and further preventing the penetration of active ions, such as H+. + OH - Cl - This synergistically enhances the chemical stability of the surface layer.

[0017] (2) In this invention, the functional core layer contains self-healing microcapsules with urea-formaldehyde resin as the capsule wall and a mixture of butyl acrylate and methyl methacrylate as the core. When the microcracks on the glass surface extend to this layer, the stress at the crack tip causes the microcapsules to rupture. The core monomers undergo free radical polymerization under the capillary action of the crack and the catalysis of the peroxide initiator remaining in the resin system, such as benzoyl peroxide, to achieve autonomous filling and repair of the damage and actively maintain the integrity of the outer corrosion barrier. Secondly, the added fluorosilane-modified silica migrates directionally to the surface during the curing process. The long fluorocarbon chains on its surface endow the glass surface with extremely low surface energy, thereby forming a stable superhydrophobic surface with a water contact angle of 125° and a roll-off angle of 7°, making it difficult for droplets to spread and wet. This characteristic can be achieved. In humid environments, the superhydrophobic surface can greatly inhibit water vapor from condensing into a continuous fog film. Even if there is a small amount of condensation, it will quickly coalesce into water droplets that are easy to roll off, thus effectively preventing fogging on the glass surface and maintaining light transmittance and clear vision. When rainwater or other droplets roll on the superhydrophobic surface, they can easily carry away dust, salt particles and other pollutants, achieving self-cleaning of the surface. This reduces the adhesion and residence time of corrosive media on the glass surface and cuts off the local corrosion path caused by the accumulation of pollutants. At the same time, the self-healing microcapsules in the functional core layer ensure timely repair of surface micro-damage, thereby maintaining the integrity of the superhydrophobic function in the long term.

[0018] (3) In this invention, alumina whiskers and rare earth oxides are introduced into the inner high-strength matrix glass. Alumina whiskers, as nanoscale single crystal fibers, significantly toughen the glass matrix through crack deflection and whisker pull-out mechanisms. When cracks want to expand, they must bypass or break these hard whiskers, which improves the toughness and strength of the glass. Rare earth oxides can refine the glass network structure, making the glass structure denser and more stable, thereby improving the overall strength, heat resistance and anti-aging properties.

[0019] (4) The present invention optimizes the integration process based on the characteristics of each layer of materials. The outer layer adopts low-temperature ion exchange to avoid the thermal impact of high temperature on the intermediate layer material. The intermediate layer adopts ultraviolet light pre-curing to achieve rapid shaping. Combined with hot pressing composite, while ensuring the activity of heat-sensitive components such as microcapsules, strong interfacial bonding between layers is achieved. Finally, the internal stress of the composite is effectively eliminated through segmented annealing process. Through the synergistic effect of the process, efficient, energy-saving and reliable manufacturing is achieved while ensuring the high performance of the product. Detailed Implementation

[0020] To further illustrate the technical means and effects of the present invention in achieving its intended purpose, the following detailed description of the specific implementation methods, structures, features, and effects of the present invention, in conjunction with embodiments, is provided below.

[0021] Example 1

[0022] 1. Raw materials and formula

[0023] Outer substrate: Borosilicate glass, 0.3 parts nano-silicon nitride, 70 parts potassium nitrate, and 30 parts sodium nitrate.

[0024] Intermediate layer slurry formulation (by weight): 50 parts epoxy acrylate resin, 10 parts self-healing microcapsules (urea-formaldehyde capsule wall, core material is butyl acrylate: methyl methacrylate = 3:1), 8 parts fluorosilane modified silica, 2 parts silane coupling agent KH-570, and 50 parts ethyl acetate.

[0025] Inner layer substrate formulation (parts by weight): 68 parts of quartz sand, 15 parts of potassium feldspar, 3 parts of rare earth oxides (cerium oxide: yttrium oxide = 1:2), 5 parts of aluminum oxide whiskers, 1.5 parts of antimony trioxide, and 5 parts of sodium carbonate.

[0026] 2. Preparation process

[0027] (1) Fabrication of the outer substrate: Prepare a mixed salt bath: its composition is 70 parts potassium nitrate, 30 parts sodium nitrate, and 0.3 parts nano silicon nitride. Mix the components evenly, heat to 400℃ to melt and continuously stir to form a uniformly dispersed nano-composite molten salt bath. The borosilicate glass was immersed in the above salt bath and treated for 4 hours, during which the salt bath was slowly stirred at 90 rpm. Remove the glass, ultrasonically clean it with 80℃ deionized water for 10 minutes, and dry it to obtain a chemically tempered glass substrate with nano-silicon nitride composite on the surface.

[0028] (2) Preparation of intermediate layer slurry: Mix 50 parts epoxy acrylate resin, 10 parts self-healing microcapsules, 8 parts fluorosilane-modified silica and 2 parts KH-570, and stir in a planetary mixer at 500 rpm for 1 hour. Add 50 parts ethyl acetate and adjust the slurry viscosity to 900 mPa·s.

[0029] The preparation method of the self-healing microcapsule includes: mixing urea and formaldehyde solution at a weight ratio of 1:3, adjusting the pH to 8.5, reacting at 65°C to form a prepolymer, mixing butyl acrylate and methyl methacrylate at a weight ratio of 2.5:1 as the core material, and using in-situ polymerization to polymerize the prepolymer on the surface of the core material to form the capsule wall, thereby obtaining the self-healing microcapsule.

[0030] (3) Fabrication of the inner layer substrate: Mix all the raw materials in the inner layer evenly and place them in an alumina crucible; Melt at 1500℃ in an electric furnace and clarify and homogenize for 2 hours.

[0031] Molten glass is poured into a cast iron mold and pressed into a plate.

[0032] The substrate is transferred to an annealing furnace, heated to 565°C at 3°C / min, held for 2 hours, then cooled to 475°C at 1°C / min and cooled to room temperature to obtain an annealed substrate for use as a load-bearing base layer.

[0033] (4) Composite and curing: Spray a 2% KH-570 ethanol solution onto the surface of the outer substrate and dry at 100°C for 10 minutes.

[0034] An automatic coating machine is used to apply the intermediate layer slurry to the treated surface, and the wet film thickness is controlled to be 0.6 mm.

[0035] Immediately pass through a UV curing machine (365nm, intensity 90 mW / cm²). 2 Irradiate and cure for 105 seconds.

[0036] The inner substrate is attached to the pre-cured film and then fed into a hot press.

[0037] Set the hot pressing parameters: pressure 1.0 MPa, temperature 100℃, hot pressing time 20 minutes.

[0038] After hot pressing, the composite is placed in a 125℃ oven for final curing for 2 hours to obtain a corrosion-resistant tempered glass product.

[0039] Example 2

[0040] 1. Raw materials and formula

[0041] Outer substrate: Borosilicate glass, 0.1 parts of nano-silicon nitride, 65 parts of potassium nitrate, and 25 parts of sodium nitrate.

[0042] Intermediate layer slurry formulation (by weight): 40 parts epoxy acrylate resin, 5 parts self-healing microcapsules (urea-formaldehyde capsule wall, core material is butyl acrylate: methyl methacrylate = 2:1), 5 parts fluorosilane modified silica, 1 part silane coupling agent KH-570, and 30 parts ethyl acetate.

[0043] Inner layer substrate formulation (parts by weight): 60 parts of quartz sand, 10 parts of potassium feldspar, 1 part of rare earth oxides (cerium oxide: yttrium oxide = 1:2), 2 parts of aluminum oxide whiskers, 0.5 parts of antimony trioxide, and 3 parts of sodium carbonate.

[0044] 2. Preparation process

[0045] (1) Fabrication of the outer substrate: Prepare a mixed salt bath: its composition is 65 parts potassium nitrate, 25 parts sodium nitrate, and 0.1 parts nano silicon nitride. Mix the components evenly, heat to 380℃ to melt and continuously stir to form a uniformly dispersed nano-composite molten salt bath. The borosilicate glass was immersed in the above salt bath and treated for 6 hours, during which the salt bath was slowly stirred at 100 rpm. Remove the glass, ultrasonically clean it with 80℃ deionized water for 10 minutes, and dry it to obtain a chemically tempered glass substrate with nano-silicon nitride composite on the surface.

[0046] (2) Preparation of intermediate layer slurry: Mix 40 parts epoxy acrylate resin, 5 parts self-healing microcapsules, 5 parts fluorosilane-modified silica and 1 part KH-570, and stir in a planetary mixer at 500 rpm for 1 hour. Add 30 parts of ethyl acetate to adjust the slurry viscosity to 800 mPa·s.

[0047] The preparation method of the self-healing microcapsule includes: mixing urea and formaldehyde solution at a weight ratio of 1:2.0, adjusting the pH to 8, reacting at 60°C to form a prepolymer, mixing butyl acrylate and methyl methacrylate at a weight ratio of 2:1 as the core material, and using in-situ polymerization to polymerize the prepolymer on the surface of the core material to form the capsule wall, thereby obtaining the self-healing microcapsule.

[0048] (3) Fabrication of the inner layer substrate: Mix all the raw materials in the inner layer evenly and place them in an alumina crucible; Melt at 1480°C in an electric furnace and clarify and homogenize for 2 hours.

[0049] Molten glass is poured into a cast iron mold and pressed into a plate.

[0050] The substrate is transferred to an annealing furnace, heated to 550°C at a rate of 2°C / min, held for 3 hours, and then cooled to 450°C at a rate of 0.5°C / min. The substrate is then cooled to room temperature to obtain an annealed substrate that can be used to form a load-bearing base layer.

[0051] (4) Composite and curing: Spray a 2% KH-570 ethanol solution onto the surface of the outer substrate and dry at 100°C for 10 minutes.

[0052] An automatic coating machine is used to apply the intermediate layer slurry to the treated surface, and the wet film thickness is controlled to be 0.6 mm.

[0053] Immediately pass through a UV curing machine (365nm, intensity 80 mW / cm²). 2 Irradiate and cure for 120 seconds.

[0054] The inner substrate is attached to the pre-cured film and then fed into a hot press.

[0055] Set the hot pressing parameters: pressure 0.5 MPa, temperature 80℃, hot pressing time 30 minutes.

[0056] After hot pressing, the composite is placed in a 120℃ oven for final curing for 3 hours to obtain a corrosion-resistant tempered glass product.

[0057] Example 3

[0058] 1. Raw materials and formula

[0059] Outer substrate: Borosilicate glass, 0.5 parts nano silicon nitride, 75 parts potassium nitrate, and 35 parts sodium nitrate.

[0060] Intermediate layer slurry formulation (by weight): 60 parts epoxy acrylate resin, 15 parts self-healing microcapsules (urea-formaldehyde capsule wall, core material is butyl acrylate: methyl methacrylate = 3:1), 12 parts fluorosilane modified silica, 2 parts silane coupling agent KH-570, and 70 parts ethyl acetate.

[0061] Inner layer substrate formulation (parts by weight): 75 parts of quartz sand, 20 parts of potassium feldspar, 5 parts of rare earth oxides (cerium oxide: yttrium oxide = 1:3), 8 parts of aluminum oxide whiskers, 2.5 parts of antimony trioxide, and 8 parts of sodium carbonate.

[0062] 2. Preparation process

[0063] (1) Fabrication of the outer substrate: Prepare a mixed salt bath: its composition is 75 parts potassium nitrate, 35 parts sodium nitrate, and 0.5 parts nano silicon nitride. Mix the components evenly, heat to 420℃ to melt and continuously stir to form a uniformly dispersed nano-composite molten salt bath. The borosilicate glass was immersed in the above salt bath and treated for 2 hours, during which the salt bath was slowly stirred at 80 rpm. Remove the glass, ultrasonically clean it with 80℃ deionized water for 10 minutes, and dry it to obtain a chemically tempered glass substrate with nano-silicon nitride composite on the surface.

[0064] (2) Preparation of intermediate layer slurry: Mix 50 parts epoxy acrylate resin, 115 parts self-healing microcapsules, 12 parts fluorosilane-modified silica and 2 parts KH-570, and stir in a planetary mixer at 500 rpm for 1 hour. Add 70 parts of ethyl acetate to adjust the slurry viscosity to 1000 mPa·s.

[0065] The preparation method of the self-healing microcapsule includes: mixing urea and formaldehyde solution at a weight ratio of 1:3.5, adjusting the pH to 9, reacting at 70°C to form a prepolymer, mixing butyl acrylate and methyl methacrylate at a weight ratio of 3:1 as the core material, and using in-situ polymerization to polymerize the prepolymer on the surface of the core material to form the capsule wall, thereby obtaining the self-healing microcapsule.

[0066] (3) Fabrication of the inner layer substrate: Mix all the raw materials in the inner layer evenly and place them in an alumina crucible; Melt at 1520°C in an electric furnace and clarify and homogenize for 2 hours.

[0067] Molten glass is poured into a cast iron mold and pressed into a plate.

[0068] The substrate is transferred to an annealing furnace, heated to 580°C at 5°C / min, held for 1 hour, then cooled to 500°C at 2°C / min and cooled to room temperature to obtain an annealed substrate for use as a load-bearing base layer.

[0069] (4) Composite and curing: Spray a 2% KH-570 ethanol solution onto the surface of the outer substrate and dry at 100°C for 10 minutes.

[0070] An automatic coating machine is used to apply the intermediate layer slurry to the treated surface, and the wet film thickness is controlled to be 0.6 mm.

[0071] Immediately pass through a UV curing machine (365nm, intensity 100 mW / cm²). 2 Irradiate and cure for 90 seconds.

[0072] The inner substrate is attached to the pre-cured film and then fed into a hot press.

[0073] Set the hot pressing parameters: pressure 2.0 MPa, temperature 120℃, hot pressing time 10 minutes.

[0074] After hot pressing, the composite is placed in a 130℃ oven for final curing for 1 hour to obtain a corrosion-resistant tempered glass product.

[0075] Comparative Example 1

[0076] Based on Example 1, all functional materials of the outer, middle and inner layers are mixed in proportion, such as nano silicon nitride, epoxy acrylate resin, self-healing microcapsules, fluorosilane modified silicon dioxide, alumina whiskers, etc., and directly melted into a single-component tempered glass, with other conditions remaining the same as in Example 1.

[0077] Comparative Example 2

[0078] Based on Example 1, without adding self-healing microcapsules, all other conditions remain the same as in Example 1.

[0079] Comparative Example 3

[0080] Based on Example 1, fluorosilane-modified silica was not added, and other conditions were the same as those in Example 1.

[0081] Comparative Example 4

[0082] Based on Example 1, alumina whiskers and rare earth oxides were not added, and other conditions were the same as those in Example 1.

[0083] Comparative Example 5

[0084] Based on Example 1, nano-silicon nitride was not added, and other conditions were the same as those in Example 1.

[0085] Comparative Example 6

[0086] Based on Example 1, the ion exchange temperature in step (1) was changed to the traditional high temperature of 650 °C, and at the same time, the ultraviolet light pre-curing step was cancelled, and all relied on the thermal curing during the hot pressing process. Other conditions were the same as those in Example 1.

[0087] Effect Test

[0088] Systematic tests were carried out on the samples prepared in the above Examples 1-3 and Comparative Examples 1-6. The test items included impact resistance, alkali resistance, surface stress, self-repairability, and anti-fogging, hydrophobic and self-cleaning properties. The test methods for each performance index are as follows: [[ID=3o]] The test methods for impact resistance and surface stress refer to GB15763.2-2005 "Building Safety Glass - Part 2: Tempered Glass". For impact resistance: 6 pieces of tempered glass were taken for the test. If the number of damaged specimens did not exceed 1 piece, it was qualified; if it was more than or equal to 3 pieces, it was unqualified. When the number of damaged specimens was 2 pieces, another 6 pieces were taken for the test, and all specimens must not be damaged to be qualified. For surface stress: The surface stress of tempered glass should not be less than 90 Mpa. Taking the product as the specimen, 3 specimens were taken for the test. When all met the requirements, it was qualified; if 2 specimens did not meet the requirements, it was unqualified. When 2 specimens met the requirements, another 3 specimens were added. If all 3 specimens met the requirements, it was qualified.

[0089] The test method for alkali resistance performance refers to GB / T 6580-2021 "Test Method and Classification for Resistance of Glass to Attack by Boiling Mixed Alkali Aqueous Solutions". After 3 h of testing, according to the mass loss per unit surface area, the glass was classified as shown in Table 1: Table 1 Alkali Resistance Test Classification Table

[0090] The self-healing performance test method refers to the general test method for self-healing materials. A micro-scratcher is used to create a scratch 80 μm wide and 30 μm deep on the surface. After being placed at room temperature for 24 hours, the volume change of the scratch before and after repair is measured using a laser confocal microscope. The self-healing efficiency (%) is calculated as (initial volume - repaired volume) / initial volume × 100%.

[0091] Hydrophobicity, anti-fogging and self-cleaning performance tests were conducted. The basic hydrophobicity was determined by referring to GB / T 24368-2009 "Detection of Hydrophobic Contaminants on Glass Surface - Contact Angle Measurement Method", and the water contact angle and roll-off angle of the sample were measured. Anti-fogging performance: After the sample is placed in a high temperature and high humidity environment for equilibrium, such as 50℃ and relative humidity greater than 90%, its surface temperature is rapidly reduced to 5℃. The condensation morphology is observed. If the condensed water on the surface forms a continuous fog-like water film, that is, a hydrophilic surface, the performance is poor; if the surface forms discontinuous and discrete transparent water droplets, that is, a hydrophobic surface, the performance is good, showing excellent anti-condensation and anti-fogging ability.

[0092] Self-cleaning efficiency: 0.1g of standard dust pollutant was evenly coated on the sample surface, tilted at 30°, and simulated rainfall to wash the surface for 60 seconds. The self-cleaning efficiency was calculated as (initial pollutant amount - residual amount) / initial pollutant amount × 100%).

[0093] The test results are shown in Tables 2 and 3: Table 2 Results of Impact Resistance and Alkali Resistance Tests

[0094] Table 3. Test results of self-healing and anti-fog self-cleaning performance.

[0095] The results show that Examples 1-3 exhibited better overall performance, with Example 1 showing the best performance. The surface compressive stress of Example 1 reached 650±50 MPa, as measured by a surface stress meter. Compared to the Examples, Comparative Example 1 failed due to the high-temperature melting of all materials. Specifically, epoxy acrylate and microcapsules decompose and carbonize at high temperatures, making them unsuitable for use in glass. Nano-silicon nitride requires low-temperature treatment, and alumina whiskers require high-temperature melting. This demonstrates that gradient composite structures are an important pathway for integrating multifunctional heterogeneous materials and form the structural basis of this invention. Comparative Examples 2-5 showed a decrease in performance across all components. This indicates that self-healing microcapsules are crucial for maintaining the integrity of the post-damage protection system and preventing localized corrosion, significantly improving self-healing efficiency. Fluorosilane-modified silica provides excellent superhydrophobic, defogging, and self-cleaning properties, indirectly enhancing corrosion resistance. Alumina whiskers, rare earth oxides, and nano-silicon nitride improve mechanical properties. Comparative Example 6 also showed a decrease in overall performance, falling short of the Examples, indicating that the optimized preparation process itself contributes positively to improving overall performance.

[0096] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A corrosion-resistant composite tempered glass, characterized in that, From the outside to the inside, a corrosion-resistant surface layer, a functional core layer, and a load-bearing base layer are stacked in sequence. The corrosion-resistant surface layer is a borosilicate glass layer that has undergone ion exchange treatment; The functional core layer is formed by curing a slurry containing the following components in parts by weight: 40-60 parts epoxy acrylate resin, 5-15 parts self-healing microcapsules, and 5-12 parts fluorosilane-modified silica. The load-bearing base layer is made from raw materials containing the following parts by weight: 60-75 parts quartz sand, 10-20 parts feldspar, 1-5 parts rare earth oxides, and 2-8 parts alumina whiskers.

2. The corrosion-resistant composite tempered glass according to claim 1, characterized in that, The corrosion-resistant surface layer is composited with nano-silicon nitride, and the surface compressive stress is 650±50 MPa.

3. The corrosion-resistant composite tempered glass according to claim 1, characterized in that, The self-healing microcapsule has a wall material of urea-formaldehyde resin and a core material of a mixture of butyl acrylate and methyl methacrylate.

4. The corrosion-resistant composite tempered glass according to claim 3, characterized in that, The method for preparing the self-healing microcapsules includes: mixing urea and formaldehyde solution at a weight ratio of 1:2.0-3.5, adjusting the pH to 8-9, reacting at 60-70℃ to form a prepolymer, mixing butyl acrylate and methyl methacrylate at a weight ratio of 2-3:1 as the core material, and using in-situ polymerization to polymerize the prepolymer on the surface of the core material to form the capsule wall, thereby obtaining the self-healing microcapsules.

5. The corrosion-resistant composite tempered glass according to claim 1, characterized in that, The rare earth oxide is a mixture of cerium oxide and yttrium oxide in a weight ratio of 1:1-3.

6. A method for preparing corrosion-resistant composite tempered glass as described in any one of claims 1-5, characterized in that, Includes the following steps: (1) Immerse the borosilicate glass substrate in a mixed salt bath containing a nano-silicon nitrate dispersion phase of potassium nitrate and sodium nitrate, and perform ion exchange treatment at 380-420°C for 2-6 hours. Remove, clean and dry to obtain a substrate for forming a corrosion-resistant surface layer. (2) Epoxy acrylate resin, self-healing microcapsules and fluorosilane modified silica are mixed in proportion, and solvent is added to adjust the viscosity to 800-1000 mPa·s to obtain functional core layer slurry. (3) Mix quartz sand, feldspar, rare earth oxides, alumina whiskers, clarifying agent and flux according to the ratio, melt and clarify at 1480-1520℃ and then cast into shape, and then perform annealing treatment: heat up to 550-580℃ at a rate of 2-5℃ / min, hold for 1-3 hours, then cool down to 450-500℃ at a rate of 0.5-2℃ / min and cool to room temperature to obtain the annealed substrate used to form the load-bearing base layer; (4) Coat the substrate surface obtained in step (1) with a 1-5% silane coupling agent ethanol solution and dry it. Coat the slurry obtained in step (2) evenly on it and perform UV pre-curing for 90-120 seconds. Attach the substrate obtained in step (3) to the pre-cured film layer and perform hot pressing composite. Then, perform final curing at 120-130℃ for 1-3 hours to obtain the corrosion-resistant composite tempered glass.

7. The method for preparing corrosion-resistant composite tempered glass according to claim 6, characterized in that, In step (1), the mixed salt bath is composed of the following components in parts by weight: 65-75 parts potassium nitrate, 25-35 parts sodium nitrate, and 0.1-0.5 parts nano silicon nitride.

8. The method for preparing corrosion-resistant composite tempered glass according to claim 6, characterized in that, In step (2), the solvent is ethyl acetate, acetone or N,N-dimethylformamide, and the amount used is 30-70 parts.

9. The method for preparing corrosion-resistant composite tempered glass according to claim 6, characterized in that, In step (3), the clarifying agent is antimony trioxide, sodium sulfate or cerium oxide, and its addition amount is 0.5-2.5 parts; the fluxing agent is sodium carbonate, potassium carbonate or borax, and its addition amount is 3-8 parts.

10. The method for preparing corrosion-resistant composite tempered glass according to claim 6, characterized in that, In step (4), the conditions for UV pre-curing are: using a UV light source with a wavelength of 365nm and an irradiance of 80-100mW / cm². 2 The hot-pressing composite process involves a pressure of 0.5-2.0 MPa, a temperature of 80-120°C, and a time of 10-30 minutes.

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