Solvent type aerogel anti-corrosion and wear-resistant coating as well as preparation method and application thereof

Abstract

The invention provides a solvent type aerogel anti-corrosion and wear-resistant coating as well as a preparation method and application thereof, and belongs to the technical field of coatings. The fluorinated modified zirconium oxide aerogel is introduced, so that the coating is endowed with excellent super-hydrophobicity, corrosion resistance and pollution resistance; a gradient slow-release core-shell structure is designed, and precise release and long-acting protection of the corrosion inhibitor are realized by taking ZIF-8 as a carrier; the graphene template is used for preparing three-dimensional interpenetrating network silicon carbide, so that the wear resistance, the thermal conductivity and the corrosion resistance of the coating are enhanced; the hybrid material with high strength, flexibility and high temperature resistance is prepared through organic silicon modified polyimide. According to the technologies, the mechanical property, the chemical stability and the service life of the coating are optimized from multiple aspects, and the requirement for a high-performance coating in a complex environment is met.

Description

Technical Field

[0001] The invention belongs to the technical field of coatings and relates to a solvent-based aerogel anticorrosive and wear-resistant coating and a preparation method and application thereof. Background Art

[0002] Anti-corrosion and wear-resistant coatings play a vital role in industry and construction, with applications spanning a wide range of sectors, including chemical engineering, petroleum, transportation, shipbuilding, and construction. These coatings significantly improve the corrosion and wear resistance of materials, thereby extending the service life of equipment, structures, and pipelines. In harsh environmental conditions, such as high temperature, high humidity, and chemical corrosion, coating performance is particularly critical, making the development of high-performance anti-corrosion and wear-resistant coatings particularly urgent.

[0003] Traditional anti-corrosion coatings typically rely on polymer matrices, such as epoxy resins and polyurethanes. While these polymers offer some corrosion protection, their corrosion resistance is often limited by the chemical properties of the base material. For example, many polymers are susceptible to chemical degradation in the presence of strong acids, bases, or other corrosive chemical media, leading to coating degradation, cracking, and delamination. These phenomena not only reduce the coating's protective effectiveness but can also lead to corrosion and damage to the base material, resulting in economic losses and safety hazards.

[0004] Wear resistance is also a key performance characteristic of anti-corrosion coatings. Many existing polymer coatings lack sufficient wear resistance when subjected to high-intensity abrasion conditions, becoming susceptible to wear, scratching, and even flaking, making them difficult to meet the stringent wear resistance requirements of industrial applications. In applications subject to heavy loads or high-frequency friction, such as surface coatings on machinery and vehicles, traditional coatings often struggle to meet expected performance targets. Summary of the Invention

[0005] In response to the above problems, the purpose of the present invention is to provide a solvent-based aerogel anti-corrosion and wear-resistant coating, and its preparation method and application. The present invention introduces zirconium oxide aerogel and fluorinates it with perfluorooctyltriethoxysilane to give it super-hydrophobicity, anti-pollution and chemically inert barrier function, while retaining its lightweight porous structure, corrosion resistance and chemical stability; secondly, a gradient slow-release core-shell structure is designed, and the corrosion inhibitor benzotriazole is loaded with ZIF-8 as the core, and its porous structure is used to achieve adaptive release; the release rate is regulated by a polydopamine coating, and a physical barrier is provided by a silica shell layer, which greatly prolongs the release time of the corrosion inhibitor and improves the corrosion resistance. performance and service life; in addition, the introduction of three-dimensional interpenetrating silicon carbide network gives the coating high porosity, light weight, high strength and excellent wear resistance and thermal conductivity. After plasma fluorination modification, a chemically inert layer is formed on the surface of silicon carbide, which further enhances its hydrophobicity, corrosion resistance and mechanical stability; by introducing silicone chain segment to modify polyimide, a silicone-polyimide hybrid material is prepared, which significantly improves the toughness and impact resistance while maintaining high strength and high temperature resistance, and enhances the interfacial bonding strength between the matrix and the filler.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] In a first aspect, the present invention provides a method for preparing a solvent-based aerogel anticorrosion and wear-resistant coating, the method comprising:

[0008] S1: Dispersing zirconyl nitrate in an ethanol / water solution, adjusting the pH with hydrochloric acid, and stirring at a constant temperature to obtain a zirconium sol; dispersing perfluorooctyltriethoxysilane in isopropanol to obtain a fluorinated solution; mixing the fluorinated solution with the zirconium sol, stirring, and then allowing to stand to obtain a wet gel; and post-treating to obtain a fluorinated modified zirconia aerogel; and shear-dispersing the fluorinated modified zirconia aerogel in isopropanol to obtain a fluorinated modified zirconia aerogel dispersion;

[0009] S2: preparing a solution of bis(4-aminophenyl) ether in N-methylpyrrolidone, adding biphenyltetracarboxylic dianhydride, reacting to obtain a polyimide precursor solution, adding 3-glycidyloxypropylmethyldiethoxysilane, adjusting the pH to obtain a reaction solution F, stirring the reaction, and performing step-by-step heat treatment to obtain a reaction solution H, cooling and post-treating to obtain an organosilicon-polyimide hybrid resin; and mixing the reaction solution with isopropyl alcohol to obtain an organosilicon-polyimide hybrid resin dispersion.

[0010] S3: Mix the organosilicon-polyimide hybrid resin dispersion and the dispersant, stir evenly, then add the fluorinated modified zirconia aerogel dispersion and the fluorinated modified interpenetrating silicon carbide network in sequence, ultrasonically disperse evenly, add the gradient sustained-release core-shell capsule, and stir evenly at low speed to obtain a solvent-based aerogel anticorrosion and wear-resistant coating.

[0011] The preparation method of the gradient sustained-release core-shell capsule is as follows:

[0012] Z1: Prepare a methanol solution of 2-methylimidazole, adjust the pH, and then add it to a methanol solution of zinc nitrate to obtain a mixed solution A, which is reacted and treated to obtain a metal organic framework; add it and benzotriazole to ethanol to obtain a mixed solution B, and perform solvent thermal treatment to obtain a sustained-release core; disperse the sustained-release core in Tris buffer, add dopamine hydrochloride to obtain a reaction solution C, and react to obtain a suspension D; adjust the pH of ethyl orthosilicate in an ethanol / water solution to obtain a prehydrolyzed solution, add it to the suspension D, react and treat at room temperature to obtain a gradient sustained-release core-shell capsule;

[0013] The preparation method of fluorinated modified interpenetrating silicon carbide network is as follows:

[0014] Z2: After graphene is dispersed in ethanol, freeze-dried and foamed, it is pre-sintered in an inert atmosphere to obtain a graphene deposition template; a three-dimensional interpenetrating silicon carbide network is prepared by chemical vapor infiltration; the three-dimensional interpenetrating silicon carbide network is placed in a plasma treatment device and treated with carbon tetrafluoride gas to obtain a fluorinated interpenetrating silicon carbide network.

[0015] Specifically, S1: dispersing zirconyl nitrate in an ethanol / water mixed solution to obtain a first dispersion, adjusting the pH thereof with hydrochloric acid to obtain a second dispersion, and stirring at a constant temperature to obtain a zirconium sol; dispersing perfluorooctyltriethoxysilane in isopropanol to obtain a fluorination solution, adding the fluorination solution to the zirconium sol to obtain a mixed solution, stirring and placing the mixed solution in a sealed container to obtain a wet gel, soaking the mixed solution in anhydrous ethanol and aging the mixed solution to obtain a preliminary aerogel, and drying the mixed solution in a supercritical carbon dioxide drying kettle to obtain a fluorinated modified zirconia aerogel; adding the mixed solution to isopropanol, adding polyvinyl pyrrolidone, and then shearing and dispersing the mixed solution to obtain a fluorinated modified zirconia aerogel dispersion;

[0016] S2: preparing a solution of bis(4-aminophenyl) ether in N-methylpyrrolidone, adding biphenyltetracarboxylic dianhydride to obtain a reaction solution E, stirring and reacting to obtain a polyimide precursor solution; adding 3-glycidyloxypropylmethyldiethoxysilane to obtain an organosilicon-modified solution, adjusting the pH with acetic acid to obtain a reaction solution F, stirring and reacting to obtain a mixed solution G, performing step-by-step heat treatment under nitrogen protection to obtain a reaction solution H, cooling and post-treating to obtain an organosilicon-polyimide hybrid resin, and mixing the reaction solution with isopropyl alcohol to obtain an organosilicon-polyimide hybrid resin dispersion;

[0017] S3: Mix the organosilicon-polyimide hybrid resin dispersion and the dispersant, stir evenly, then add the fluorinated modified zirconia aerogel dispersion and the fluorinated modified interpenetrating silicon carbide network in sequence, ultrasonically disperse evenly, add the gradient sustained-release core-shell capsule, and stir evenly at low speed to obtain a solvent-based aerogel anticorrosion and wear-resistant coating.

[0018] The preparation method of the gradient sustained-release core-shell capsule is as follows:

[0019] Z1: Prepare a methanol solution of 2-methylimidazole and a methanol solution of zinc nitrate, adjust the pH of the methanol solution of 2-methylimidazole, and add the methanol solution of zinc nitrate at room temperature to obtain a mixed solution A, stir to react, centrifuge, wash, and dry to obtain a metal-organic framework; prepare an ethanol dispersion of benzotriazole, add the metal-organic framework to obtain a mixed solution B, solvent-thermal treatment, centrifuge, wash, and dry to obtain a sustained-release core; disperse it in Tris buffer, add dopamine hydrochloride to obtain a reaction solution C, and stir to obtain a suspension D; add tetraethyl orthosilicate to an ethanol / water mixed solution to obtain a silicon coating layer solution, add ammonia water to adjust the pH, and pre-hydrolyze at room temperature to obtain a pre-hydrolyzed solution, which is added to the suspension D to obtain a reaction solution E, react at room temperature, centrifuge, wash, and dry to obtain a gradient sustained-release core-shell capsule;

[0020] The preparation method of fluorinated modified interpenetrating silicon carbide network is as follows:

[0021] Z2: adding graphene powder to ethanol, ultrasonically dispersing it, freeze-drying it, and foaming it to obtain a pre-treated template, which was then pre-sintered under an inert atmosphere to obtain a graphene deposition template; placing it in a reaction zone, introducing a mixed gas for chemical vapor infiltration to obtain a three-dimensional interpenetrating silicon carbide network; placing it in a plasma treatment device, introducing carbon tetrafluoride gas to obtain a fluorinated interpenetrating silicon carbide network;

[0022] As a preferred technical solution of the present invention, in step S1, the volume ratio of ethanol to deionized water in the ethanol / water mixed solution is 3-4:1, for example, it can be 3:1, 3.1:1, 3.2:1, 3.3:1, 3.4:1, 3.5:1, 3.6:1, 3.7:1, 3.8:1, 3.9:1 or 4:1, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0023] In some optional embodiments, the concentration of the first dispersion is 0.2-0.3M, for example, it can be 0.2M, 0.21M, 0.22M, 0.23M, 0.24M, 0.25M, 0.26M, 0.27M, 0.28M, 0.29M or 0.3M, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0024] In some optional embodiments, the pH of the first dispersion is adjusted to 3-4 using hydrochloric acid, for example, 3, 3.1, 3.2, 3.3, 3.4, 3.5, 3.6, 3.7, 3.8, 3.9 or 4, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0025] In some optional embodiments, the temperature of the constant temperature stirring of the second dispersion is 25-30°C, for example, it can be 25°C, 25.5°C, 26°C, 26.5°C, 27°C, 27.5°C, 28°C, 28.5°C, 29°C, 29.5°C or 30°C, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0026] In some optional embodiments, the constant temperature stirring time of the second dispersion is 30-40 min, for example, it can be 30 min, 31 min, 32 min, 33 min, 34 min, 35 min, 36 min, 37 min, 38 min, 39 min or 40 min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0027] In some optional embodiments, the mass fraction of the fluorinated solution is 0.5-1wt.%, for example, it can be 0.5wt.%, 0.55wt.%, 0.6wt.%, 0.65wt.%, 0.7wt.%, 0.75wt.%, 0.8wt.%, 0.85wt.%, 0.9wt.%, 0.95wt.% or 1wt.%, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0028] In some optional embodiments, the feeding amount of the perfluorooctyltriethoxysilane is 8-10% of the molar number of zirconium oxynitrate, for example, it can be 8%, 8.2%, 8.4%, 8.6%, 8.8%, 9%, 9.2%, 9.4%, 9.6%, 9.8% or 10%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0029] In some optional embodiments, the mixed solution is stirred for 1-2 hours and then allowed to stand to obtain a wet gel, for example, 1 hour, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours or 2 hours, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0030] In some optional embodiments, the wet gel is soaked in anhydrous ethanol for 24-48 hours, for example, 24 hours, 26 hours, 28 hours, 30 hours, 32 hours, 34 hours, 36 hours, 38 hours, 40 hours, 42 hours, 44 hours, 46 hours or 48 hours, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0031] In some optional embodiments, the aging temperature of the wet gel after immersion in anhydrous ethanol is 40-50°C, for example, it can be 40°C, 41°C, 42°C, 43°C, 44°C, 45°C, 46°C, 47°C, 48°C, 49°C or 50°C, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0032] In some optional embodiments, the aging time of the wet gel after immersion in anhydrous ethanol is 20-24 hours, for example, it can be 20 hours, 20.4 hours, 20.8 hours, 21.2 hours, 21.6 hours, 22 hours, 22.4 hours, 22.8 hours, 23.2 hours, 23.6 hours or 24 hours, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0033] In some optional embodiments, the temperature of the preliminary aerogel supercritical carbon dioxide drying is 40-50°C, for example, it can be 40°C, 41°C, 42°C, 43°C, 44°C, 45°C, 46°C, 47°C, 48°C, 49°C or 50°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0034] In some optional embodiments, the pressure of the initial aerogel supercritical carbon dioxide drying is 25-30 MPa, for example, it can be 25 MPa, 25.5 MPa, 26 MPa, 26.5 MPa, 27 MPa, 27.5 MPa, 28 MPa, 28.5 MPa, 29 MPa, 29.5 MPa or 30 MPa, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0035] In some optional embodiments, the time for the preliminary aerogel supercritical carbon dioxide drying is 6-7h, for example, it can be 6h, 6.1h, 6.2h, 6.3h, 6.4h, 6.5h, 6.6h, 6.7h or 7h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0036] In some optional embodiments, the solid-liquid mass ratio of the fluorinated modified zirconia aerogel to isopropyl alcohol is 1:20-30, for example, it can be 1:20, 1:21, 1:22, 1:23, 1:24, 1:25, 1:26, 1:27, 1:28, 1:29 or 1:30, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0037] In some optional embodiments, the feeding amount of the polyvinyl pyrrolidone is 0.1-0.2% of the mass of the fluorinated modified zirconia aerogel, for example, it can be 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19% or 0.2%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0038] In some optional embodiments, the first rotation speed of the shear dispersion is 2000 rpm, and the time is 10-15 min, for example, it can be 10 min, 10.5 min, 11 min, 11.5 min, 12 min, 12.5 min, 13 min, 13.5 min, 14 min, 14.5 min or 15 min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0039] In some optional embodiments, the second rotation speed of the shear dispersion is 5000 rpm, and the time is 15-20 min, for example, it can be 15 min, 15.5 min, 16 min, 16.5 min, 17 min, 17.5 min, 18 min, 18.5 min, 19 min, 19.5 min or 20 min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0040] During the shear dispersion, pause for 1 minute every 5 minutes;

[0041] In some optional embodiments, the particle size of the fluorinated modified zirconia aerogel in the fluorinated modified zirconia aerogel dispersion is 5-10 μm, for example, it can be 5 μm, 5.5 μm, 6 μm, 6.5 μm, 7 μm, 7.5 μm, 8 μm, 8.5 μm, 9 μm, 9.5 μm or 10 μm, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0042] As a preferred technical solution of the present invention, in step S2, the concentration of the N-methylpyrrolidone solution of bis(4-aminophenyl) ether is 0.1-0.2 g / mL, for example, it can be 0.1 g / mL, 0.11 g / mL, 0.12 g / mL, 0.13 g / mL, 0.14 g / mL, 0.15 g / mL, 0.16 g / mL, 0.17 g / mL, 0.18 g / mL, 0.19 g / mL or 0.2 g / mL, but is not limited to the listed values, and other values ​​not listed within this numerical range are also applicable.

[0043] The molar ratio of biphenyltetracarboxylic dianhydride to bis(4-aminophenyl)ether is 1:1;

[0044] In some optional embodiments, the reaction liquid E is stirred for 3-4 hours to obtain a polyimide precursor solution, for example, it can be 3 hours, 3.1 hours, 3.2 hours, 3.3 hours, 3.4 hours, 3.5 hours, 3.6 hours, 3.7 hours, 3.8 hours, 3.9 hours or 4 hours, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0045] In some optional embodiments, the feeding amount of the 3-glycidyloxypropylmethyldiethoxysilane is 15-20% of the mass of the polyimide precursor, for example, it can be 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5% or 20%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0046] In some optional embodiments, the pH of the organosilicon-modified solution is adjusted to 4.3-4.7 with acetic acid, for example, 4.3, 4.35, 4.4, 4.45, 4.5, 4.55, 4.6 or 4.7, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0047] In some optional embodiments, the temperature of the stirring reaction of the reaction liquid F is 50-60°C, for example, it can be 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C, 59°C or 60°C, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0048] In some optional embodiments, the stirring reaction time of the reaction liquid F is 1-2h, for example, it can be 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0049] In some optional embodiments, the first temperature of the mixed liquid G in the step-by-step heat treatment under nitrogen protection is 80-100°C, for example, it can be 80°C, 82°C, 84°C, 86°C, 88°C, 90°C, 92°C, 94°C, 96°C, 98°C or 100°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0050] In some optional embodiments, the first time of the step-by-step heat treatment of the mixed liquid G under nitrogen protection is 1-2h, for example, it can be 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0051] In some optional embodiments, the second temperature of the mixed liquid G in the step-by-step heat treatment under nitrogen protection is 150-200°C, for example, it can be 150°C, 155°C, 160°C, 165°C, 170°C, 175°C, 180°C, 185°C, 190°C, 195°C or 200°C, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0052] In some optional embodiments, the second time of the step-by-step heat treatment of the mixed liquid G under nitrogen protection is 1-2h, for example, it can be 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0053] In some optional embodiments, the third temperature of the mixed liquid G in the step-by-step heat treatment under nitrogen protection is 300-310°C, for example, it can be 300°C, 301°C, 302°C, 303°C, 304°C, 305°C, 306°C, 307°C, 308°C, 309°C or 310°C, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0054] In some optional embodiments, the third time of the step-by-step heat treatment of the mixed liquid G under nitrogen protection is 2-3h, for example, it can be 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h or 3h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0055] In some optional embodiments, the mass ratio of isopropyl alcohol to silicone-polyimide hybrid resin is 2.5-3.5:1, for example, it can be 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1, 3:1, 3.1:1, 3.2:1, 3.3:1, 3.4:1 or 3.5:1, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0056] As a preferred technical solution of the present invention, in step S3, the dispersant is octoxynol, and the feeding amount of the dispersant is 0.1-0.2% of the mass of the silicone-polyimide hybrid resin, for example, it can be 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15%, 0.16%, 0.17%, 0.18%, 0.19% or 0.2%, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0057] The mass ratio of the organic silicon-polyimide hybrid resin, the fluorinated modified zirconia aerogel, the fluorinated modified interpenetrating silicon carbide network, and the gradient sustained-release core-shell capsule in the solvent-based aerogel anticorrosion and wear-resistant coating is 100:(5-8):(3-5):(1-2).

[0058] As a preferred technical solution of the present invention, in step Z1, the concentration of the methanol solution of 2-methylimidazole is 0.1-0.2M, for example, it can be 0.1M, 0.11M, 0.12M, 0.13M, 0.14M, 0.15M, 0.16M, 0.17M, 0.18M, ​​0.19M or 0.2M, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0059] In some optional embodiments, the concentration of the methanol solution of zinc nitrate is 0.1-0.2 M, for example, it can be 0.1 M, 0.11 M, 0.12 M, 0.13 M, 0.14 M, 0.15 M, 0.16 M, 0.17 M, 0.18 M, 0.19 M or 0.2 M, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0060] In some optional embodiments, the pH of the methanol solution of 2-methylimidazole is adjusted to 10-11, for example, it can be 10, 10.1, 10.2, 10.3, 10.4, 10.5, 10.6, 10.7, 10.8, 10.9 or 11, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0061] In some optional embodiments, the molar ratio of 2-methylimidazole to zinc nitrate is 3-4:1, for example, 3:1, 3.1:1, 3.2:1, 3.3:1, 3.4:1, 3.5:1, 3.6:1, 3.7:1, 3.8:1, 3.9:1 or 4:1, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0062] In some optional embodiments, the mixed liquid A is stirred for reaction for 30-40 minutes, for example, it can be 30 minutes, 31 minutes, 32 minutes, 33 minutes, 34 minutes, 35 minutes, 36 minutes, 37 minutes, 38 minutes, 39 minutes or 40 minutes, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0063] In some optional embodiments, the concentration of the ethanol dispersion of benzotriazole is 8-10 mg / mL, for example, 8 mg / mL, 8.2 mg / mL, 8.4 mg / mL, 8.6 mg / mL, 8.8 mg / mL, 9 mg / mL, 9.2 mg / mL, 9.4 mg / mL, 9.6 mg / mL, 9.8 mg / mL or 10 mg / mL, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0064] In some optional embodiments, the solid-liquid mass ratio of the metal organic framework to the ethanol solution of benzotriazole is 1:15-25, for example, it can be 1:15, 1:16, 1:17, 1:18, 1:19, 1:20, 1:21, 1:22, 1:23, 1:24 or 1:25, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0065] In some optional embodiments, the temperature of the solvent thermal treatment of the mixed liquid B is 110-120°C, for example, it can be 110°C, 111°C, 112°C, 113°C, 114°C, 115°C, 116°C, 117°C, 118°C, 119°C or 120°C, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0066] In some optional embodiments, the solvent thermal treatment time of the mixed liquid B is 30-60 min, for example, it can be 30 min, 33 min, 36 min, 39 min, 42 min, 45 min, 48 min, 51 min, 54 min, 57 min or 60 min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0067] In some optional embodiments, the pH of the Tris buffer is 8.5-9, for example, it can be 8.5, 8.55, 8.6, 8.65, 8.7, 8.75, 8.8, 8.85, 8.9, 8.95 or 9, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0068] In some optional embodiments, the concentration of the sustained-release core in Tris buffer is 2-3 mg / mL, for example, 2 mg / mL, 2.1 mg / mL, 2.2 mg / mL, 2.3 mg / mL, 2.4 mg / mL, 2.5 mg / mL, 2.6 mg / mL, 2.7 mg / mL, 2.8 mg / mL, 2.9 mg / mL or 3 mg / mL, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0069] In some optional embodiments, the concentration of dopamine hydrochloride in the reaction solution C is 2-3 mg / mL, for example, 2 mg / mL, 2.1 mg / mL, 2.2 mg / mL, 2.3 mg / mL, 2.4 mg / mL, 2.5 mg / mL, 2.6 mg / mL, 2.7 mg / mL, 2.8 mg / mL, 2.9 mg / mL or 3 mg / mL, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0070] In some optional embodiments, the volume ratio of the ethyl orthosilicate to ethanol is 1:4-5, for example, it can be 1:4, 1:4.1, 1:4.2, 1:4.3, 1:4.4, 1:4.5, 1:4.6, 1:4.7, 1:4.8, 1:4.9 or 1:5, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0071] In some optional embodiments, ammonia water is added to the silicon coating solution to adjust the pH to 11-12, for example, it can be 11, 11.1, 11.2, 11.3, 11.4, 11.5, 11.6, 11.7, 11.8, 11.9 or 12, but it is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0072] In some optional embodiments, the silicon coating solution is pre-hydrolyzed at room temperature for 2-3 hours after adjusting the pH, for example, 2 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours, 2.5 hours, 2.6 hours, 2.7 hours, 2.8 hours, 2.9 hours or 3 hours, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0073] In some optional embodiments, the mass ratio of dopamine hydrochloride to ethyl orthosilicate is 1:1.5-2, for example, it can be 1:1.5, 1:1.55, 1:1.6, 1:1.65, 1:1.7, 1:1.75, 1:1.8, 1:1.85, 1:1.9, 1:1.95 or 1:2, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0074] In some optional embodiments, the reaction solution E is reacted at room temperature for 8-9 hours, for example, 8 hours, 8.1 hours, 8.2 hours, 8.3 hours, 8.4 hours, 8.5 hours, 8.6 hours, 8.7 hours, 8.8 hours, 8.9 hours or 9 hours, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0075] As a preferred technical solution of the present invention, in step Z2, the concentration of the graphene powder in ethanol is 3-5 mg / mL, for example, it can be 3 mg / mL, 3.2 mg / mL, 3.4 mg / mL, 3.6 mg / mL, 3.8 mg / mL, 4 mg / mL, 4.2 mg / mL, 4.4 mg / mL, 4.6 mg / mL, 4.8 mg / mL or 5 mg / mL, but is not limited to the listed values, and other values ​​not listed within this numerical range are also applicable.

[0076] In some optional embodiments, the pre-sintering temperature of the pretreated template under an inert atmosphere is 700-800°C, for example, it can be 700°C, 710°C, 720°C, 730°C, 740°C, 750°C, 760°C, 770°C, 780°C, 790°C or 800°C, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0077] In some optional embodiments, the pre-sintering time of the pretreated template under an inert atmosphere is 3-4 hours, for example, it can be 3 hours, 3.1 hours, 3.2 hours, 3.3 hours, 3.4 hours, 3.5 hours, 3.6 hours, 3.7 hours, 3.8 hours, 3.9 hours or 4 hours, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0078] In some optional embodiments, the volume ratio of methyltrichlorosilane to hydrogen in the mixed gas is 1:10-20, for example, it can be 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19 or 1:20, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0079] In some optional embodiments, the temperature of the chemical vapor infiltration is 1200-1300°C, for example, it can be 1200°C, 1210°C, 1220°C, 1230°C, 1240°C, 1250°C, 1260°C, 1270°C, 1280°C, 1290°C or 1300°C, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0080] In some optional embodiments, the pressure of the chemical vapor infiltration is 10-15 kPa, for example, it can be 10 kPa, 10.5 kPa, 11 kPa, 11.5 kPa, 12 kPa, 12.5 kPa, 13 kPa, 13.5 kPa, 14 kPa, 14.5 kPa or 15 kPa, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0081] In some optional embodiments, the chemical vapor infiltration time is 2-4h, for example, it can be 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3.0h, 3.2h, 3.4h, 3.6h, 3.8h or 4h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0082] In some optional embodiments, the gas flow rate of the chemical vapor infiltration is 50-100 sccm, for example, it can be 50 sccm, 55 sccm, 60 sccm, 65 sccm, 70 sccm, 75 sccm, 80 sccm, 85 sccm, 90 sccm, 95 sccm or 100 sccm, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0083] In some optional embodiments, the power of the three-dimensional interpenetrating silicon carbide network plasma treatment is 50-100W, for example, it can be 50W, 55W, 60W, 65W, 70W, 75W, 80W, 85W, 90W, 95W or 100W, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0084] In some optional embodiments, the temperature of the three-dimensional interpenetrating silicon carbide network plasma treatment is 90-100°C, for example, it can be 90°C, 91°C, 92°C, 93°C, 94°C, 95°C, 96°C, 97°C, 98°C, 99°C or 100°C, but is not limited to the listed values, and other unlisted values ​​within this numerical range are also applicable.

[0085] In some optional embodiments, the time for the three-dimensional interpenetrating silicon carbide plasma treatment is 60-80 min, for example, it can be 60 min, 63 min, 66 min, 69 min, 72 min, 75 min, 78 min or 80 min, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0086] In a second aspect, the present invention provides a solvent-based aerogel anticorrosion and wear-resistant coating comprising an organosilicon-polyimide hybrid resin, fluorinated modified zirconia aerogel, fluorinated modified interpenetrating silicon carbide network, and a gradient sustained-release core-shell capsule.

[0087] Traditional silica aerogel is widely used in functional coatings due to its high specific surface area and good thermal insulation properties, but its performance in complex environments has great limitations. First, silica aerogel has poor chemical stability and is easily dissolved under strong acid or strong base conditions, resulting in rapid degradation of its structure and performance. Secondly, because the surface of silica aerogel is rich in hydroxyl groups and has strong hygroscopicity, this not only reduces its hydrophobicity, but also accelerates the decline of its protective performance in humid environments. At the same time, the hydrophobicity of silica aerogel in corrosive environments is not stable enough, further limiting its practical application in high-performance anti-corrosion coatings. Based on this, the present invention introduces zirconia aerogel as a filler substrate to replace traditional silica aerogel, thereby overcoming the above problems.

[0088] Zirconia aerogel is an ideal choice due to its excellent properties. As a ceramic material, zirconia possesses extremely high hardness and melting point, while exhibiting excellent chemical stability and corrosion resistance. This material not only remains stable in complex chemical environments such as acids and bases, but its porous aerogel structure also gives it a lightweight, high specific surface area, and extremely low thermal conductivity, making it suitable for the design of high-performance coatings. Furthermore, the zirconia surface is rich in hydroxyl groups, which can react with functional molecules through chemical modification, enhancing its bonding with the coating substrate. This surface activity not only allows it to serve as a functional filler in coating design, but can also be modified to impart additional properties to the coating.

[0089] In order to further improve the performance of zirconia aerogel, the present invention uses perfluorooctyltriethoxysilane to fluorinate it. The fluorocarbon segment in the perfluorooctyltriethoxysilane molecule has extremely low surface energy, and the surface of the modified zirconia aerogel exhibits superhydrophobicity. This superhydrophobicity not only significantly improves the anti-pollution performance of the aerogel, but also effectively reduces the adsorption of corrosive media such as moisture and salt spray on the coating surface, allowing it to remain stable in harsh environments. In addition, the fluorination treatment forms a chemically inert barrier on the surface of the aerogel, which greatly prevents the penetration of moisture, oxygen and corrosive media, thereby significantly improving the corrosion resistance of the coating. At the same time, the fluorination modification reduces the polarity of the zirconia aerogel surface, improves its dispersibility in the organic matrix, and avoids the occurrence of particle agglomeration, thereby ensuring the uniformity and density of the coating.

[0090] Through fluorination, the performance of zirconia aerogel in coating systems has been comprehensively optimized. The modified aerogel not only maintains its excellent properties, such as lightweight and high specific surface area, but also exhibits superhydrophobicity and enhanced chemical resistance, making it suitable for more complex and demanding service environments. Furthermore, the modification significantly improves the adhesion and dispersibility of the aerogel to the coating substrate, significantly enhancing the coating's performance in corrosion resistance, wear resistance, and anti-fouling properties.

[0091] In the present invention, 2-methylimidazole is assembled with zinc ions to form a metal organic framework, which has significant advantages as a carrier of corrosion inhibitors. The metal organic framework (ZIF-8) has a high specific surface area and a stable porous structure, and exhibits excellent chemical stability in both acidic and alkaline media, making it an ideal corrosion inhibitor carrier. The pore structure of ZIF-8 can not only effectively accommodate corrosion inhibitor molecules through physical adsorption and chemical bonding, but also achieve a slow-release function. In addition, the selective response characteristics of ZIF-8 to chloride ions enable it to trigger the release of corrosion inhibitors in corrosive environments, thereby achieving adaptive protection. This ion response mechanism ensures that the release of corrosion inhibitors is limited to the corrosion micro-area, avoids the waste of corrosion inhibitors, and improves the anti-corrosion efficiency.

[0092] The present invention uses benzotriazole as a corrosion inhibitor. Benzotriazole is a classic corrosion inhibitor molecule that chemically reacts with metal surfaces to form a dense passivation film. This passivation film firmly adheres to the metal surface, effectively preventing the diffusion of oxygen, moisture, and other corrosive media, thereby inhibiting further oxidation of the metal surface. The combination of benzotriazole and ZIF-8 imparts excellent slow-release properties and adaptive release capabilities to the core corrosion inhibitor system.

[0093] In order to better realize the gradient sustained release function, the present invention constructs a multifunctional core-shell structure by designing a polydopamine coating and a silica shell layer layer by layer on the surface of the sustained-release core. First, under alkaline conditions, the precursor dopamine hydrochloride is deposited on the surface of the sustained-release core to form a polydopamine coating through self-oxidation polymerization. The polydopamine coating has significant pH responsiveness and is partially hydrolyzed under acidic conditions, thereby promoting the release of benzotriazole. This responsive mechanism makes the release of the corrosion inhibitor more targeted and can accurately release the corrosion inhibitor under local corrosion micro-area conditions (such as the acidic environment of the metal surface). In addition, the polydopamine coating further plays multiple functions: on the one hand, it encapsulates and protects the core structure to prevent the corrosion inhibitor from leaking prematurely during storage or transportation; on the other hand, the chemically active functional groups on its surface provide binding sites for the subsequent uniform deposition of the silica shell layer, significantly enhancing the structural stability of the core-shell microcapsules.

[0094] On the basis of the polydopamine coating, a silica shell is further coated. Through the hydrolysis and polycondensation reaction of ethyl orthosilicate under alkaline conditions, a silicon-oxygen-silicon network structure is formed, and the silica shell is gradually deposited on the surface of the core coated with polydopamine. The active functional groups on the surface of the polydopamine coating can react chemically with the silane precursor, further enhancing the binding force between silica and polydopamine, and ensuring the uniformity and stability of the silica shell. The outer silica shell not only provides a dense physical barrier, effectively delaying the release of benzotriazole and realizing the gradient release function of the corrosion inhibitor, but also significantly improves the mechanical strength and chemical stability of the core-shell microcapsules. The introduction of the silica shell enhances the environmental resistance of the microcapsules, enabling them to maintain integrity under harsh acid and alkali conditions and mechanical friction environments, thereby effectively protecting the core structure from damage by the external environment.

[0095] Through the above-mentioned multi-layer design, the gradient slow-release core-shell structure achieves an organic combination of multiple functions. The ZIF-8 core provides benzotriazole with efficient drug loading capacity and ion response triggering mechanism; the polydopamine coating in the middle layer regulates the initial release rate of the corrosion inhibitor through its pH responsiveness and chemical activity, and provides functionalized sites for the deposition of the outer shell layer; the outer silica shell further delays the release of the corrosion inhibitor through its high strength and chemical inertness, while providing long-term physical protection. This core-shell structure design not only effectively extends the release time of the corrosion inhibitor and makes the slow-release rate more controllable, but also significantly improves the corrosion resistance and service life of the coating, showing great application potential.

[0096] The present invention constructs a three-dimensional porous skeleton through graphene freeze-drying technology, providing an ideal template for the subsequent preparation of three-dimensional interpenetrating silicon carbide network. As a two-dimensional material with high conductivity and high specific surface area, the three-dimensional skeleton structure formed by freeze-drying of graphene has good uniform distribution during the chemical vapor infiltration process. This distribution significantly improves the penetration efficiency of the gaseous precursor during the reaction process, ensuring the uniform generation of silicon carbide material. Under high temperature conditions, methyltrichlorosilane undergoes a pyrolysis reaction to generate silicon carbide, and hydrogen as a carrier gas can effectively inhibit the formation of free carbon during the reaction process, thereby improving the purity of the generated silicon carbide. The final three-dimensional interpenetrating silicon carbide structure has high porosity and uniform pore size distribution. This structure significantly improves the specific surface area and mechanical properties while reducing the material density.

[0097] The design of the three-dimensional interpenetrating network structure endows silicon carbide with unique performance advantages. On the one hand, the interpenetrating network structure provides excellent mechanical support and crack propagation resistance, maintaining structural stability under high mechanical loads. On the other hand, the pore structure enhances the mechanical interlocking effect with the resin matrix, resulting in excellent wear resistance in the composite coating. This network structure enables the material to maintain lightweight properties while combining high strength and high thermal conductivity, making it ideal for protective coating designs requiring high wear resistance and high toughness.

[0098] As an inorganic ceramic material with high hardness, high temperature resistance, and chemical corrosion resistance, silicon carbide's mechanical strength and chemical stability provide a solid foundation for wear-resistant coatings. Through the design of a three-dimensional interpenetrating network, the overall performance of silicon carbide is further optimized, not only improving its crack resistance and toughness, but also imparting excellent thermal conductivity and mechanical stability to the structure. This multifunctional property makes 3D interpenetrating network silicon carbide an ideal reinforcement material for high-performance coatings.

[0099] In order to further enhance the functionality of silicon carbide in the coating system, the present invention uses plasma treatment technology to fluorinate its surface. Through carbon tetrafluoride plasma treatment, fluorine atoms are introduced on the surface of silicon carbide to form a chemically inert fluorinated surface layer. This modification significantly reduces the surface energy of silicon carbide, thereby enhancing its hydrophobicity and corrosion resistance. The presence of the fluorinated carbon layer can not only effectively resist the erosion of corrosive media (such as moisture, salt spray, acid and alkali solutions), but also provide long-term and stable chemical protection in harsh environments. In addition, the fluorination modification does not affect the high hardness and excellent mechanical properties of silicon carbide itself, and the material can still maintain its wear resistance and impact resistance under high loads and complex service conditions.

[0100] This invention utilizes a graphene-based template and chemical vapor infiltration to create a three-dimensional interpenetrating silicon carbide network. Combined with surface fluorination via plasma treatment, this method not only enhances the mechanical, wear, and crack resistance of the silicon carbide material, but also imparts superhydrophobicity and corrosion resistance. This multifunctional composite material has broad application prospects in high-performance protective coatings, capable of meeting the diverse performance requirements of coatings in harsh environments.

[0101] In the present invention, polyimide is selected as the matrix material because it is a high-performance polymer with excellent heat resistance, mechanical strength and chemical corrosion resistance, and is an ideal matrix choice for high-performance coatings. The polyimide molecular skeleton contains rigid aromatic rings and imide ring structures, and this characteristic gives it excellent high-temperature resistance and excellent dimensional stability. In addition, the rigid molecular structure of polyimide also provides excellent wear resistance, so that it exhibits excellent mechanical stability under harsh conditions such as high temperature and high friction. However, the rigid molecular chain structure of polyimide also brings obvious defects, namely, the material is more brittle, resulting in its insufficient impact resistance and flexibility. This defect limits the performance of polyimide in application scenarios that require high mechanical loads and high impact toughness.

[0102] To overcome the aforementioned drawbacks of polyimides, the present invention introduces 3-glycidyloxypropylmethyldiethoxysilane into the polyimide backbone via a sol-gel method to create an organosilicon-polyimide hybrid matrix material. The organosilicon segments possess excellent flexibility and low surface energy, significantly improving the mechanical and surface properties of the polyimide. During the sol-gel reaction, the siloxane segments form a crosslinked network through hydrolysis and polycondensation, and bond to the polyimide backbone through bonding, forming a uniform hybrid structure.

[0103] The design of this silicone-polyimide hybrid structure takes into account the advantages of both materials. On the one hand, the rigid molecular skeleton of polyimide still gives the material extremely high temperature resistance and mechanical strength; on the other hand, the flexible properties of the silicone segment significantly improve the material's toughness and impact resistance, thereby effectively avoiding the brittle fracture problem of traditional polyimide materials under high mechanical stress conditions. In addition, the introduction of the silicone segment also enhances the interfacial bonding strength between the polyimide matrix and the functional filler. The chemically active functional groups on the surface of the siloxane segment can form a stronger interfacial bond with the filler surface, thereby improving the dispersion and stability of the filler in the matrix and significantly improving the overall performance of the coating.

[0104] By introducing organosilicon segments, this invention successfully optimizes the flexibility of the polyimide matrix while maintaining its high-temperature resistance and mechanical strength. The hybrid structure design not only improves the mechanical properties of the matrix but also enhances the interfacial bonding between the matrix and the filler, further enhancing the overall mechanical properties and durability of the coating, providing important technical support for the design of high-performance coatings.

[0105] In a third aspect, the present invention provides an application of a solvent-based aerogel anti-corrosion and wear-resistant coating in the manufacture of ships.

[0106] Compared with the prior art, the present invention has the following beneficial effects:

[0107] This invention introduces zirconia aerogel, which possesses excellent corrosion resistance, chemical stability, and a lightweight porous structure. Fluorination modification with perfluorooctyltriethoxysilane imparts superhydrophobicity, anti-fouling properties, and a chemically inert barrier, significantly improving its corrosion resistance and dispersibility. The modified zirconia aerogel overcomes the shortcomings of traditional aerogels and exhibits exceptional corrosion resistance, wear resistance, and anti-fouling properties in coatings, making it suitable for the design of high-performance coatings in complex environments.

[0108] The present invention designs a gradient sustained-release core-shell structure with a metal-organic framework ZIF-8 as the core, loaded with the corrosion inhibitor benzotriazole, and triggered by its porous structure and ion-responsive properties. The core surface is coated with a pH-responsive polydopamine coating to regulate the release of the corrosion inhibitor while enhancing structural stability. The outer layer provides a physical barrier through the silica shell, effectively extending the sustained-release time and improving environmental resistance. This core-shell structure combines efficient drug loading, adaptive release, and long-term protection functions, significantly improving the corrosion resistance and service life of the coating;

[0109] This invention uses freeze-drying graphene to construct a template, combined with chemical vapor infiltration to produce a three-dimensional interpenetrating silicon carbide network, endowing it with high porosity, light weight, high strength, and excellent mechanical properties. This structure provides excellent mechanical support, crack resistance, and mechanical interlocking with the substrate, significantly improving the wear resistance and thermal conductivity of the composite coating. Furthermore, through plasma fluorination modification, a chemically inert layer is formed on the silicon carbide surface, enhancing its hydrophobicity and corrosion resistance while maintaining its high hardness and mechanical stability, making it an ideal reinforcement material for high-performance protective coatings.

[0110] This invention introduces organosilicon segments into polyimide to modify it, creating an organosilicon-polyimide hybrid material that combines high-temperature resistance, high strength, and flexibility. This design significantly improves the brittleness of polyimide while maintaining its excellent properties. Furthermore, the organosilicon segments form a cross-linked network through a sol-gel reaction, enhancing the interfacial bonding strength between the matrix and filler, improving the mechanical properties and durability of the coating, and providing an ideal matrix material for high-performance coatings. DETAILED DESCRIPTION

[0111] The technical solutions of the present invention are described in detail below with reference to specific embodiments. The embodiments described herein are specific embodiments of the present invention and are used to illustrate the concept of the present invention; these descriptions are explanatory and exemplary and should not be understood as limiting the embodiments of the present invention and the scope of protection of the present invention. In addition to the embodiments described herein, those skilled in the art can also adopt other obvious technical solutions based on the contents disclosed in the claims of this application and its specification, including technical solutions that adopt any obvious replacements and modifications made to the embodiments described herein.

[0112] The chemical reagents used in the examples and comparative examples of the present invention are all commercially available products without further purification or treatment.

[0113] Example 1

[0114] This embodiment provides a solvent-based aerogel anti-corrosion and wear-resistant coating and a preparation method thereof. The preparation method of the solvent-based aerogel anti-corrosion and wear-resistant coating specifically comprises the following steps:

[0115] S1: Disperse zirconyl nitrate in an ethanol / water mixed solution to obtain a first dispersion with a concentration of 0.25M, wherein the volume ratio of ethanol to water in the ethanol / water mixed solution is 3.8:1, use hydrochloric acid to adjust its pH to 3 to obtain a second dispersion, and stir at a constant temperature of 28°C for 30 minutes to obtain a zirconium sol; disperse perfluorooctyltriethoxysilane in isopropanol to obtain a fluorinated solution with a mass fraction of 0.5wt.%, and add the solution to the zirconium sol to obtain a mixed solution, wherein the amount of perfluorooctyltriethoxysilane added is 9% of the molar number of zirconyl nitrate, and after stirring for 1 hour, place the solution in a sealed container and let it stand to obtain a wet gel, which is then soaked in anhydrous ethanol for 36 hours and aged at 40°C for 24 hours to obtain a preliminary aerogel. The aerogel is placed in a supercritical carbon dioxide drying kettle and dried at a temperature of 40° C., a pressure of 28 MPa, and a drying time of 6 hours to obtain a fluorinated modified zirconia aerogel; the aerogel is added to isopropanol, wherein the solid-liquid mass ratio of the fluorinated modified zirconia aerogel to the isopropanol is 1:25; polyvinyl pyrrolidone is added in an amount of 0.18% of the mass of the fluorinated modified zirconia aerogel, and then shear dispersion is performed, wherein the first speed of the shear dispersion is 2000 rpm and the time is 10 minutes, and the second speed is 5000 rpm and the time is 15 minutes, wherein the shear dispersion is paused for 1 minute every 5 minutes to prevent the temperature from being too high, to obtain a fluorinated modified zirconia aerogel dispersion, wherein the particle size of the fluorinated modified zirconia aerogel is 8 μm;

[0116] S2: Prepare a 0.18 g / mL N-methylpyrrolidone solution of bis(4-aminophenyl) ether, add biphenyltetracarboxylic dianhydride to obtain a reaction solution E, wherein the molar ratio of biphenyltetracarboxylic dianhydride to bis(4-aminophenyl) ether is 1:1, and stir the reaction for 3 hours to obtain a polyimide precursor solution; add 3-glycidyloxypropylmethyldiethoxysilane to obtain an organosilicon modified solution, wherein the amount of 3-glycidyloxypropylmethyldiethoxysilane is 1:1 of the total mass of the polyimide precursor. 5%, adjusting the pH to 4.5 with acetic acid to obtain a reaction solution F, stirring and reacting at 50°C for 1 hour to obtain a mixed solution G, and performing step-by-step heat treatment under nitrogen protection to obtain a reaction solution H, wherein the step-by-step heat treatment has a first temperature of 95°C and a first time of 1 hour, a second temperature of 150°C and a second time of 1.8 hours, and a third temperature of 305°C and a third time of 3 hours, cooling and post-treating to obtain an organosilicon-polyimide hybrid resin, and mixing the organosilicon-polyimide hybrid resin with isopropyl alcohol at a mass ratio of 3:1 to obtain an organosilicon-polyimide hybrid resin dispersion;

[0117] S3: mixing an organosilicon-polyimide hybrid resin dispersion and a dispersant octoxynol, wherein the amount of the dispersant is 0.15% of the mass of the organosilicon-polyimide hybrid resin, stirring evenly, sequentially adding a fluorinated modified zirconia aerogel dispersion and a fluorinated modified interpenetrating silicon carbide network, ultrasonically dispersing evenly, adding a gradient sustained-release core-shell capsule, and stirring evenly at a low speed to obtain a solvent-based aerogel anticorrosion and wear-resistant coating, wherein the mass ratio of the organosilicon-polyimide hybrid resin, the fluorinated modified zirconia aerogel, the fluorinated modified interpenetrating silicon carbide network, and the gradient sustained-release core-shell capsule is 100:7:4:1.5;

[0118] The preparation method of the gradient sustained-release core-shell capsule is as follows:

[0119] Z1: Prepare a 0.18M methanol solution of 2-methylimidazole and a 0.2M methanol solution of zinc nitrate, adjust the pH of the methanol solution of 2-methylimidazole to 10, and then add the methanol solution of zinc nitrate at room temperature to obtain a mixed solution A, wherein the molar ratio of 2-methylimidazole to zinc nitrate is 3:1, stir and react for 30 minutes, centrifuge, wash, and dry to obtain a metal-organic framework; prepare a 9.5mg / mL ethanol dispersion of benzotriazole, add the metal-organic framework to obtain a mixed solution B, wherein the solid-liquid mass ratio of the metal-organic framework to the ethanol dispersion of benzotriazole is 1:20, and after solvent heat treatment at 115°C for 30 minutes, centrifuge, wash, and dry to obtain a sustained-release internal core; disperse it in a Tris buffer with a pH of 8.8, wherein the concentration of the sustained-release core is 2.5 mg / mL, add dopamine hydrochloride to obtain a reaction solution C, wherein the concentration of dopamine hydrochloride in the reaction solution C is 2 mg / mL, and stir to obtain a suspension D; add ethyl orthosilicate to an ethanol / water mixed solution to obtain a silicon coating layer solution, wherein the volume ratio of ethyl orthosilicate to ethanol is 1:4, add ammonia water to adjust the pH to 11.5, and then pre-hydrolyze at room temperature for 2 hours to obtain a pre-hydrolyzed solution, which is added to the suspension D to obtain a reaction solution E, wherein the mass ratio of dopamine hydrochloride to ethyl orthosilicate is 1:1.8, react at room temperature for 8 hours, centrifuge and wash, and dry to obtain a gradient sustained-release core-shell capsule;

[0120] The preparation method of fluorinated modified interpenetrating silicon carbide network is as follows:

[0121] Z2: Graphene powder was added to ethanol at a concentration of 4 mg / mL, and after ultrasonic dispersion, freeze-dried and foamed to obtain a pretreated template, which was pre-sintered at 700°C for 3 h under an inert atmosphere to obtain a graphene deposition template; it was placed in a reaction zone, and a mixed gas was introduced for chemical vapor infiltration to obtain a three-dimensional interpenetrating silicon carbide network, wherein the volume ratio of methyltrichlorosilane and hydrogen in the mixed gas was 1:10, the temperature of the chemical vapor infiltration was 1280°C, the pressure was 10 kPa, the time was 2 h, and the gas flow rate was 50 sccm; it was placed in a plasma treatment device, and carbon tetrafluoride gas was introduced for treatment, wherein the plasma treatment power was 80 W, the time was 60 min, and the temperature was 94°C to obtain a fluorinated interpenetrating silicon carbide network.

[0122] Example 2

[0123] This embodiment provides a solvent-based aerogel anti-corrosion and wear-resistant coating and a preparation method thereof. The preparation method of the solvent-based aerogel anti-corrosion and wear-resistant coating specifically comprises the following steps:

[0124] S1: Dispersing zirconium oxynitrate in an ethanol / water mixed solution to obtain a first dispersion with a concentration of 0.2M, wherein the volume ratio of ethanol to water in the ethanol / water mixed solution is 3:1, using hydrochloric acid to adjust its pH to 3.5 to obtain a second dispersion, and stirring at a constant temperature of 27°C for 36 minutes to obtain a zirconium sol; dispersing perfluorooctyltriethoxysilane in isopropanol to obtain a fluorinated solution with a mass fraction of 0.8wt.%, adding the solution to the zirconium sol to obtain a mixed solution, wherein the amount of perfluorooctyltriethoxysilane added is 9.5% of the molar number of zirconium oxynitrate, stirring for 2 hours, and then placing in a sealed container to stand to obtain a wet gel, which is soaked in anhydrous ethanol for 42 hours and aged at 45°C for 20 hours to obtain a preliminary aerogel. The obtained product was placed in a supercritical carbon dioxide drying kettle and dried at a temperature of 45° C., a pressure of 27 MPa, and a drying time of 7 h to obtain a fluorinated modified zirconia aerogel; the obtained product was added to isopropanol, wherein the solid-liquid mass ratio of the fluorinated modified zirconia aerogel to the isopropanol was 1:20, and polyvinyl pyrrolidone was added in an amount of 0.1% of the mass of the fluorinated modified zirconia aerogel, followed by shear dispersion, wherein the first speed of the shear dispersion was 2000 rpm, the time was 12 min, and the second speed was 5000 rpm, the time was 20 min, wherein the drying was paused for 1 min every 5 min to prevent the temperature from being too high, to obtain a fluorinated modified zirconia aerogel dispersion, wherein the particle size of the fluorinated modified zirconia aerogel was 5 μm;

[0125] S2: Prepare a 0.1 g / mL solution of bis(4-aminophenyl)ether in N-methylpyrrolidone, add biphenyltetracarboxylic dianhydride to obtain reaction solution E, wherein the molar ratio of biphenyltetracarboxylic dianhydride to bis(4-aminophenyl)ether is 1:1, and stir for 3.5 hours to obtain a polyimide precursor solution; add 3-glycidyloxypropylmethyldiethoxysilane to obtain an organosilicon modified solution, wherein the amount of 3-glycidyloxypropylmethyldiethoxysilane is 18% of the total mass of the polyimide precursor. , adjusting the pH to 4.3 with acetic acid to obtain a reaction solution F, stirring and reacting at 55° C. for 1.8 hours to obtain a mixed solution G, and performing step-by-step heat treatment under nitrogen protection to obtain a reaction solution H, wherein the first temperature of the step-by-step heat treatment is 80° C., the first time is 1.5 hours, the second temperature is 200° C., the second time is 1 hour, and the third temperature is 307° C., and the third time is 2 hours. Cooling and post-treatment obtain an organosilicon-polyimide hybrid resin, which is mixed with isopropyl alcohol at a mass ratio of 3.2:1 to obtain an organosilicon-polyimide hybrid resin dispersion;

[0126] S3: mixing an organosilicon-polyimide hybrid resin dispersion and a dispersant octoxynol, wherein the amount of the dispersant is 0.1% of the mass of the organosilicon-polyimide hybrid resin, stirring evenly, sequentially adding a fluorinated modified zirconia aerogel dispersion and a fluorinated modified interpenetrating silicon carbide network, ultrasonically dispersing evenly, adding a gradient sustained-release core-shell capsule, and stirring evenly at a low speed to obtain a solvent-based aerogel anticorrosion and wear-resistant coating, wherein the mass ratio of the organosilicon-polyimide hybrid resin, the fluorinated modified zirconia aerogel, the fluorinated modified interpenetrating silicon carbide network, and the gradient sustained-release core-shell capsule is 100:6:3:1.8;

[0127] The preparation method of the gradient sustained-release core-shell capsule is as follows:

[0128] Z1: Prepare a 0.2M methanol solution of 2-methylimidazole and a 0.15M methanol solution of zinc nitrate, adjust the pH of the methanol solution of 2-methylimidazole to 10.5, and then add the methanol solution of zinc nitrate at room temperature to obtain a mixed solution A, wherein the molar ratio of 2-methylimidazole to zinc nitrate is 3.5:1, stir and react for 38 minutes, centrifuge, wash, and dry to obtain a metal-organic framework; prepare an ethanol dispersion of benzotriazole at a concentration of 8 mg / mL, add the metal-organic framework to obtain a mixed solution B, wherein the solid-liquid mass ratio of the metal-organic framework to the ethanol dispersion of benzotriazole is 1:22, and after solvent thermal treatment at 118°C for 40 minutes, centrifuge, wash, and dry to obtain a sustained-release core; The obtained solution was dispersed in a Tris buffer solution with a pH of 8.7, wherein the concentration of the sustained-release core was 2.7 mg / mL, and dopamine hydrochloride was added to obtain a reaction solution C, wherein the concentration of dopamine hydrochloride in the reaction solution C was 3 mg / mL, and the suspension D was obtained after stirring and reacting; ethyl orthosilicate was added to an ethanol / water mixed solution to obtain a silicon coating layer solution, wherein the volume ratio of ethyl orthosilicate to ethanol was 1:4.5, and ammonia was added to adjust the pH to 11.8, and then pre-hydrolyzed at room temperature for 2.5 hours to obtain a pre-hydrolyzed solution, which was added to the suspension D to obtain a reaction solution E, wherein the mass ratio of dopamine hydrochloride to ethyl orthosilicate was 1:1.7, and the reaction was carried out at room temperature for 8.8 hours. The solution was washed by centrifugation and dried to obtain a gradient sustained-release core-shell capsule;

[0129] The preparation method of fluorinated modified interpenetrating silicon carbide network is as follows:

[0130] Z2: Graphene powder was added to ethanol at a concentration of 4.5 mg / mL, and after ultrasonic dispersion, freeze-dried and foamed to obtain a pretreated template, which was pre-sintered at 750°C for 4 hours under an inert atmosphere to obtain a graphene deposition template; the template was placed in a reaction zone, and a mixed gas was introduced for chemical vapor infiltration to obtain a three-dimensional interpenetrating silicon carbide network, wherein the volume ratio of methyltrichlorosilane and hydrogen in the mixed gas was 1:15, the temperature of the chemical vapor infiltration was 1240°C, the pressure was 12 kPa, the time was 4 hours, and the gas flow rate was 80 sccm; the template was placed in a plasma treatment device, and carbon tetrafluoride gas was introduced for treatment, wherein the plasma treatment power was 50 W, the time was 70 minutes, and the temperature was 90°C to obtain a fluorinated interpenetrating silicon carbide network.

[0131] Example 3

[0132] This embodiment provides a solvent-based aerogel anti-corrosion and wear-resistant coating and a preparation method thereof. The preparation method of the solvent-based aerogel anti-corrosion and wear-resistant coating specifically comprises the following steps:

[0133] S1: Disperse zirconyl nitrate in an ethanol / water mixed solution to obtain a first dispersion with a concentration of 0.28M, wherein the volume ratio of ethanol to water in the ethanol / water mixed solution is 3.5:1, and use hydrochloric acid to adjust its pH to 3.7 to obtain a second dispersion, and stir at a constant temperature of 25°C for 38 minutes to obtain a zirconium sol; disperse perfluorooctyltriethoxysilane in isopropanol to obtain a fluorinated solution with a mass fraction of 0.7wt.%, and add the solution to the zirconium sol to obtain a mixed solution, wherein the amount of perfluorooctyltriethoxysilane added is 8% of the molar number of zirconyl nitrate, and after stirring for 1.8 hours, place it in a sealed container and let it stand to obtain a wet gel, which is soaked in anhydrous ethanol for 24 hours and aged at 48°C for 22 hours to obtain a preliminary aerogel. , placing it in a supercritical carbon dioxide drying kettle and drying it to obtain fluorinated modified zirconia aerogel, wherein the drying temperature is 48°C, the pressure is 25 MPa, and the time is 6.5 hours; adding it to isopropanol, wherein the solid-liquid mass ratio of the fluorinated modified zirconia aerogel to the isopropanol is 1:30, adding polyvinyl pyrrolidone in an amount of 0.2% of the mass of the fluorinated modified zirconia aerogel, and then shearing and dispersing it, the first speed of the shear dispersion is 2000 rpm, the time is 14 minutes, and the second speed is 5000 rpm, the time is 18 minutes, wherein the 1 minute pause every 5 minutes to prevent the temperature from being too high, to obtain a fluorinated modified zirconia aerogel dispersion, wherein the particle size of the fluorinated modified zirconia aerogel is 7 μm;

[0134] S2: Prepare a 0.15 g / mL solution of bis(4-aminophenyl)ether in N-methylpyrrolidone, add biphenyltetracarboxylic dianhydride to obtain reaction solution E, wherein the molar ratio of biphenyltetracarboxylic dianhydride to bis(4-aminophenyl)ether is 1:1, and stir the reaction for 3.8 hours to obtain a polyimide precursor solution; add 3-glycidyloxypropylmethyldiethoxysilane to obtain an organosilicon-modified solution, wherein the amount of 3-glycidyloxypropylmethyldiethoxysilane added is 17% of the total mass of the polyimide precursor. , adjusting the pH to 4.6 with acetic acid to obtain a reaction solution F, stirring and reacting at 58° C. for 2 hours to obtain a mixed solution G, and performing step-by-step heat treatment under nitrogen protection to obtain a reaction solution H, wherein the first temperature of the step-by-step heat treatment is 90° C. and the first time is 1.8 hours, the second temperature is 180° C. and the second time is 1.5 hours, and the third temperature is 300° C. and the third time is 2.5 hours. Cooling and post-treatment obtain an organosilicon-polyimide hybrid resin, which is mixed with isopropyl alcohol at a mass ratio of 2.5:1 to obtain an organosilicon-polyimide hybrid resin dispersion;

[0135] S3: mixing an organosilicon-polyimide hybrid resin dispersion and a dispersant octoxynol, wherein the amount of the dispersant is 0.2% of the mass of the organosilicon-polyimide hybrid resin, stirring evenly, sequentially adding a fluorinated modified zirconia aerogel dispersion and a fluorinated modified interpenetrating silicon carbide network, ultrasonically dispersing evenly, adding a gradient sustained-release core-shell capsule, and stirring evenly at a low speed to obtain a solvent-based aerogel anticorrosion and wear-resistant coating, wherein the mass ratio of the organosilicon-polyimide hybrid resin, the fluorinated modified zirconia aerogel, the fluorinated modified interpenetrating silicon carbide network, and the gradient sustained-release core-shell capsule is 100:5:4.5:1;

[0136] The preparation method of the gradient sustained-release core-shell capsule is as follows:

[0137] Z1: Prepare a 0.1M methanol solution of 2-methylimidazole and a 0.18M methanol solution of zinc nitrate, adjust the pH of the methanol solution of 2-methylimidazole to 10.8, and then add the methanol solution of zinc nitrate at room temperature to obtain a mixed solution A, wherein the molar ratio of 2-methylimidazole to zinc nitrate is 3.8:1, stir and react for 40 minutes, centrifuge, wash, and dry to obtain a metal-organic framework; prepare a 9mg / mL ethanol dispersion of benzotriazole, add the metal-organic framework to obtain a mixed solution B, wherein the solid-liquid mass ratio of the metal-organic framework to the ethanol dispersion of benzotriazole is 1:15, and after solvent thermal treatment at 110°C for 50 minutes, centrifuge, wash, and dry to obtain a sustained-release core. ; It was dispersed in a Tris buffer with a pH of 8.5, wherein the concentration of the sustained-release core was 2 mg / mL, and dopamine hydrochloride was added to obtain a reaction solution C, wherein the concentration of dopamine hydrochloride in the reaction solution C was 2.5 mg / mL, and the suspension D was obtained after stirring and reacting; Tetraethyl orthosilicate was added to an ethanol / water mixed solution to obtain a silicon coating layer solution, wherein the volume ratio of tetraethyl orthosilicate to ethanol was 1:4.8, and after adjusting the pH to 11 by adding ammonia water, the solution was pre-hydrolyzed at room temperature for 2.6 h to obtain a pre-hydrolyzed solution, which was added to the suspension D to obtain a reaction solution E, wherein the mass ratio of dopamine hydrochloride to tetraethyl orthosilicate was 1:1.5, and the reaction was carried out at room temperature for 8.5 h, centrifuged and washed, and dried to obtain a gradient sustained-release core-shell capsule;

[0138] The preparation method of fluorinated modified interpenetrating silicon carbide network is as follows:

[0139] Z2: Graphene powder was added to ethanol at a concentration of 3 mg / mL, and after ultrasonic dispersion, freeze-dried and foamed to obtain a pretreated template, which was pre-sintered at 780°C for 3.5 hours under an inert atmosphere to obtain a graphene deposition template; it was placed in a reaction zone, and a mixed gas was introduced for chemical vapor infiltration to obtain a three-dimensional interpenetrating silicon carbide network, wherein the volume ratio of methyltrichlorosilane and hydrogen in the mixed gas was 1:20, the temperature of the chemical vapor infiltration was 1200°C, the pressure was 14 kPa, the time was 3 hours, and the gas flow rate was 100 sccm; it was placed in a plasma treatment device, and carbon tetrafluoride gas was introduced for treatment, wherein the plasma treatment power was 60 W, the time was 74 minutes, and the temperature was 95°C to obtain a fluorinated interpenetrating silicon carbide network.

[0140] Example 4

[0141] This embodiment provides a solvent-based aerogel anti-corrosion and wear-resistant coating and a preparation method thereof. The preparation method of the solvent-based aerogel anti-corrosion and wear-resistant coating specifically comprises the following steps:

[0142] S1: Disperse zirconyl nitrate in an ethanol / water mixed solution to obtain a first dispersion with a concentration of 0.3M, wherein the volume ratio of ethanol to water in the ethanol / water mixed solution is 4:1, use hydrochloric acid to adjust its pH to 4 to obtain a second dispersion, and stir at a constant temperature of 30°C for 40 minutes to obtain a zirconium sol; disperse perfluorooctyltriethoxysilane in isopropanol to obtain a fluorinated solution with a mass fraction of 1wt.%, add the solution to the zirconium sol to obtain a mixed solution, wherein the amount of perfluorooctyltriethoxysilane added is 10% of the molar number of zirconyl nitrate, stir for 1.5 hours, and then place in a sealed container to stand to obtain a wet gel, which is soaked in anhydrous ethanol for 48 hours and aged at 50°C for 21 hours to obtain a preliminary aerogel, and place it The fluorinated zirconia aerogel was dried in a supercritical carbon dioxide drying kettle at a temperature of 50° C., a pressure of 30 MPa, and a drying time of 6.8 h. The aerogel was added to isopropanol at a solid-liquid mass ratio of the fluorinated zirconia aerogel to the isopropanol of 1:28, and polyvinyl pyrrolidone was added in an amount of 0.15% of the mass of the fluorinated zirconia aerogel, followed by shear dispersion. The first speed of the shear dispersion was 2000 rpm for 15 min, and the second speed was 5000 rpm for 16 min, with a pause of 1 min every 5 min to prevent the temperature from being too high, to obtain a fluorinated zirconia aerogel dispersion, wherein the particle size of the fluorinated zirconia aerogel was 10 μm.

[0143] S2: A 0.2 g / mL solution of bis(4-aminophenyl)ether in N-methylpyrrolidone was prepared, and biphenyltetracarboxylic dianhydride was added to obtain a reaction solution E, wherein the molar ratio of biphenyltetracarboxylic dianhydride to bis(4-aminophenyl)ether was 1:1, and the mixture was stirred for 4 hours to obtain a polyimide precursor solution; 3-glycidyloxypropylmethyldiethoxysilane was added to obtain an organosilicon-modified solution, wherein the amount of 3-glycidyloxypropylmethyldiethoxysilane added was 20% of the total mass of the polyimide precursor. Adjusting the pH to 4.7 with acetic acid to obtain a reaction solution F, stirring and reacting at 60° C. for 1.5 hours to obtain a mixed solution G, and subjecting the reaction solution to a stepwise heat treatment under nitrogen protection to obtain a reaction solution H, wherein the stepwise heat treatment has a first temperature of 100° C. and a first time of 2 hours, a second temperature of 190° C. and a second time of 2 hours, and a third temperature of 310° C. and a third time of 2.3 hours. Cooling and post-treatment to obtain an organosilicon-polyimide hybrid resin, which is mixed with isopropyl alcohol at a mass ratio of 3.5:1 to obtain an organosilicon-polyimide hybrid resin dispersion;

[0144] S3: mixing an organosilicon-polyimide hybrid resin dispersion and a dispersant octoxynol, wherein the amount of the dispersant is 0.18% of the mass of the organosilicon-polyimide hybrid resin, stirring evenly, sequentially adding a fluorinated modified zirconia aerogel dispersion and a fluorinated modified interpenetrating silicon carbide network, ultrasonically dispersing evenly, adding a gradient sustained-release core-shell capsule, and stirring evenly at a low speed to obtain a solvent-based aerogel anticorrosion and wear-resistant coating, wherein the mass ratio of the organosilicon-polyimide hybrid resin, the fluorinated modified zirconia aerogel, the fluorinated modified interpenetrating silicon carbide network, and the gradient sustained-release core-shell capsule is 100:8:5:2;

[0145] The preparation method of the gradient sustained-release core-shell capsule is as follows:

[0146] Z1: Prepare a 0.12M methanol solution of 2-methylimidazole and a 0.1M methanol solution of zinc nitrate, adjust the pH of the methanol solution of 2-methylimidazole to 11, and then add the methanol solution of zinc nitrate at room temperature to obtain a mixed solution A, wherein the molar ratio of 2-methylimidazole to zinc nitrate is 4:1, stir and react for 35 minutes, centrifuge, wash, and dry to obtain a metal organic framework; prepare a 10mg / mL ethanol dispersion of benzotriazole, add the metal organic framework to obtain a mixed solution B, wherein the solid-liquid mass ratio of the metal organic framework to the ethanol dispersion of benzotriazole is 1:25, and after solvent heat treatment at 120°C for 60 minutes, centrifuge, wash, and dry to obtain a slow a sustained-release core; dispersing it in a Tris buffer solution at a pH of 9, wherein the concentration of the sustained-release core is 3 mg / mL, adding dopamine hydrochloride to obtain a reaction solution C, wherein the concentration of dopamine hydrochloride in the reaction solution C is 2.7 mg / mL, and stirring to obtain a suspension D; adding ethyl orthosilicate to an ethanol / water mixed solution to obtain a silicon coating layer solution, wherein the volume ratio of ethyl orthosilicate to ethanol is 1:5, adding ammonia water to adjust the pH to 12, and pre-hydrolyzing at room temperature for 3 hours to obtain a pre-hydrolyzed solution, which is added to the suspension D to obtain a reaction solution E, wherein the mass ratio of dopamine hydrochloride to ethyl orthosilicate is 1:2, reacting at room temperature for 9 hours, centrifuging and washing, and drying to obtain a gradient sustained-release core-shell capsule;

[0147] The preparation method of fluorinated modified interpenetrating silicon carbide network is as follows:

[0148] Z2: Graphene powder was added to ethanol at a concentration of 5 mg / mL, and after ultrasonic dispersion, freeze-dried and foamed to obtain a pretreated template, which was pre-sintered at 800°C for 3.8 h under an inert atmosphere to obtain a graphene deposition template; it was placed in a reaction zone, and a mixed gas was introduced for chemical vapor infiltration to obtain a three-dimensional interpenetrating silicon carbide network, wherein the volume ratio of methyltrichlorosilane and hydrogen in the mixed gas was 1:18, the temperature of the chemical vapor infiltration was 1300°C, the pressure was 15 kPa, the time was 3.5 h, and the gas flow rate was 70 sccm; it was placed in a plasma treatment device, and carbon tetrafluoride gas was introduced for treatment, wherein the plasma treatment power was 100 W, the time was 80 min, and the temperature was 100°C to obtain a fluorinated interpenetrating silicon carbide network.

[0149] Comparative Example 1

[0150] This comparative example provides a solvent-based aerogel anticorrosive and wear-resistant coating. The difference from Example 1 is that in Z1, the step of polydopamine coating the sustained-release core is omitted, and the other operating steps and process parameters are exactly the same as those in Example 1.

[0151] Comparative Example 2

[0152] This comparative example provides a solvent-based aerogel anticorrosive and wear-resistant coating. The difference from Example 1 is that in Z1, the step of coating the sustained-release core with silica is omitted, and the other operating steps and process parameters are exactly the same as those in Example 1.

[0153] Comparative Example 3

[0154] This comparative example provides a solvent-based aerogel anticorrosion and wear-resistant coating, which differs from Example 1 in that, in S1, silica aerogel is used instead of zirconia aerogel, and the other operating steps and process parameters are exactly the same as those in Example 1.

[0155] Comparative Example 4

[0156] This comparative example provides a solvent-based aerogel anticorrosion and wear-resistant coating, which differs from Example 1 in that, in S2, 3-glycidyloxypropylmethyldiethoxysilane is not added for organosilicon modification, and the other operating steps and process parameters are exactly the same as those in Example 1.

[0157] The performance test of the solvent-based aerogel anticorrosive and wear-resistant coatings of Examples 1-4 and Comparative Examples 1-4 was conducted, and the specific process is as follows:

[0158] The wear resistance of the samples was tested according to GB / T1768-2006;

[0159] The salt spray corrosion resistance of the samples was tested according to GB / T1771-2007.

[0160] The test results are shown in Table 1.

[0161] Table 1: Performance test results of solvent-based aerogel anticorrosive and wear-resistant coatings of Examples 1-4 and Comparative Examples 1-4

[0162] Abrasion resistance (1000g / 1000r) / mg Salt spray test (1000h) Example 1 70 No rust, no blistering Example 2 72 No rust, no blistering Example 3 71 No rust, no blistering Example 4 73 No rust, no blistering Comparative Example 1 74 Rust, blistering Comparative Example 2 78 Rust, blistering Comparative Example 3 85 Rust, blistering Comparative Example 4 76 Rust, blistering

[0163] The test results of Example 1 and Comparative Example 1 show that when polydopamine coating of the sustained-release core is omitted, the release of the sustained-release agent cannot be effectively regulated, and the sustained-release behavior becomes uncontrollable, resulting in excessive or instantaneous release. This can cause the corrosion inhibitor to dissipate too quickly in a corrosive environment, thereby reducing the long-term corrosion protection provided by the coating and degrading the corrosion resistance of the coating. When polydopamine coating of the sustained-release core is omitted, the mechanical stability of the core decreases, and the corrosion inhibitor may be released prematurely during the coating process, resulting in increased localized unevenness in the coating and indirectly reducing wear resistance.

[0164] From the test results of Example 1 and Comparative Example 2, it can be seen that the silica shell layer acts as a physical barrier, significantly slowing the release rate of the corrosion inhibitor and enhancing the environmental stability of the core-shell structure. After omitting the silica coating, the core is directly exposed to the environment, and the release rate of the corrosion inhibitor is greatly accelerated, thereby reducing the long-term anti-corrosion protection effect provided by the coating and reducing the anti-corrosion performance of the coating; after omitting the silica coating, the core-shell structure loses the mechanical protection of the outer layer, and the corrosion inhibitor capsule is easily broken during processing and use, resulting in a decrease in the wear resistance of the coating. In addition, the premature release of the corrosion inhibitor further destroys the uniformity of the coating, exacerbating this problem.

[0165] From the test results of Example 1 and Comparative Example 3, it can be seen that when silica aerogel is used to replace zirconia aerogel, the chemical stability and corrosion resistance of silica aerogel are far inferior to zirconia aerogel, especially in acidic or alkaline environments, its chemical corrosion resistance is weak, resulting in a significant decrease in the corrosion resistance of the coating; when silica aerogel is used to replace zirconia aerogel, the mechanical strength, particle size uniformity and interface bonding strength of silica aerogel with the substrate are significantly lower than those of zirconia aerogel, and its shear resistance is poor, resulting in the coating being more easily worn under friction conditions; in addition, the fluorination modification effect of silica aerogel is weak, further reducing its contribution to the overall performance of the coating.

[0166] The test results of Example 1 and Comparative Example 4 indicate that the introduction of organosilicon segments can form a low-surface-energy, chemically inert barrier on the coating surface, enhancing the coating's hydrophobicity and anti-fouling properties, thereby indirectly improving its corrosion resistance. Without the addition of 3-glycidyloxypropylmethyldiethoxysilane for organosilicon modification of polyimide, the coating's hydrophobicity decreases, potentially accelerating the penetration of corrosive media (such as water and ions) and slightly reducing its corrosion resistance. Without the addition of 3-glycidyloxypropylmethyldiethoxysilane for organosilicon modification, the substrate's flexibility and filler interfacial bonding strength are weakened, making the filler more likely to fall off during friction, resulting in a decrease in the coating's wear resistance.

[0167] The above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing a solvent-based aerogel anticorrosive and wear-resistant coating, characterized in that: The preparation method comprises: S1: Dispersing zirconyl nitrate in an ethanol / water solution to obtain a first dispersion, adjusting the pH with hydrochloric acid and stirring at a constant temperature to obtain a zirconium sol, dispersing perfluorooctyltriethoxysilane in isopropanol to obtain a fluorination solution, mixing the fluorination solution with the zirconium sol, stirring, and then allowing to stand to obtain a wet gel, and post-treating to obtain a fluorinated modified zirconia aerogel; placing the fluorinated modified zirconia aerogel in isopropanol for shear dispersion to obtain a fluorinated modified zirconia aerogel dispersion; S2: preparing a solution of bis(4-aminophenyl) ether in N-methylpyrrolidone, adding biphenyltetracarboxylic dianhydride, reacting to obtain a polyimide precursor solution, adding 3-glycidyloxypropylmethyldiethoxysilane, adjusting the pH to obtain a reaction solution F, stirring the reaction, and performing step-by-step heat treatment to obtain a reaction solution H, cooling and post-treating to obtain an organosilicon-polyimide hybrid resin; and mixing the reaction solution with isopropyl alcohol to obtain an organosilicon-polyimide hybrid resin dispersion. S3: Mix the organosilicon-polyimide hybrid resin dispersion and the dispersant, stir evenly, then add the fluorinated modified zirconia aerogel dispersion and the fluorinated modified interpenetrating silicon carbide network in sequence, ultrasonically disperse evenly, add the gradient sustained-release core-shell capsule, and stir evenly at low speed to obtain a solvent-based aerogel anticorrosion and wear-resistant coating.

2. The method for preparing a solvent-based aerogel anticorrosive and wear-resistant coating according to claim 1, characterized in that: In S1: The volume ratio of ethanol to water in the ethanol / water mixed solution is 3-4:1; The pH of the first dispersion is adjusted to 3-4 using hydrochloric acid; The feeding amount of the perfluorooctyltriethoxysilane is 8-10% of the molar number of zirconyl nitrate; The solid-liquid mass ratio of the fluorinated modified zirconia aerogel to isopropyl alcohol is 1:20-30.

3. The method for preparing a solvent-based aerogel anticorrosive and wear-resistant coating according to claim 1, characterized in that: In S2: The concentration of the bis(4-aminophenyl) ether N-methylpyrrolidone solution is 0.1-0.2 g / mL; The molar ratio of biphenyltetracarboxylic dianhydride to bis(4-aminophenyl)ether is 1:1; The feeding amount of the 3-glycidyloxypropylmethyldiethoxysilane is 15-20% of the mass of the polyimide precursor; The mass ratio of the isopropyl alcohol to the organosilicon-polyimide hybrid resin is 2.5-3.5:

1.

4. The method for preparing a solvent-based aerogel anticorrosive and wear-resistant coating according to claim 1, characterized in that: In S3: The dispersant is octoxynol, and the amount of the dispersant is 0.1-0.2% of the mass of the organosilicon-polyimide hybrid resin; The mass ratio of the organic silicon-polyimide hybrid resin, the fluorinated modified zirconia aerogel, the fluorinated modified interpenetrating silicon carbide network, and the gradient sustained-release core-shell capsule in the solvent-based aerogel anticorrosion and wear-resistant coating is 100:(5-8):(3-5):(1-2).

5. The method for preparing a solvent-based aerogel anticorrosive and wear-resistant coating according to claim 1, characterized in that: The preparation method of the gradient sustained-release core-shell capsule is as follows: Z1: Prepare a methanol solution of 2-methylimidazole, adjust the pH, and add it to a methanol solution of zinc nitrate to obtain a mixed solution A, which is reacted and treated to obtain a metal-organic framework; The mixture and benzotriazole are added to ethanol to obtain a mixed solution B, which is subjected to solvent thermal treatment to obtain a sustained-release core; the sustained-release core is dispersed in Tris buffer, dopamine hydrochloride is added to obtain a reaction solution C, and the reaction obtains a suspension D; ethyl orthosilicate is pre-hydrolyzed in an ethanol / water solution after adjusting the pH to obtain a pre-hydrolyzed solution, which is added to the suspension D, reacted and treated at room temperature to obtain a gradient sustained-release core-shell capsule.

6. The method for preparing a solvent-based aerogel anticorrosive and wear-resistant coating according to claim 5, characterized in that: In Z1: The molar ratio of 2-methylimidazole to zinc nitrate is 3-4:1; The solid-liquid mass ratio of the metal organic framework to the ethanol solution of benzotriazole is 1:15-25; The concentration of dopamine hydrochloride in reaction solution C is 2-3 mg / mL; The volume ratio of the ethyl orthosilicate to ethanol is 1:4-5; The mass ratio of the dopamine hydrochloride to the ethyl orthosilicate is 1:1.5-2.

7. The method for preparing a solvent-based aerogel anticorrosive and wear-resistant coating according to claim 1, characterized in that: The preparation method of the fluorinated modified interpenetrating silicon carbide network is: Z2: After graphene is dispersed in ethanol, freeze-dried and foamed, it is pre-sintered in an inert atmosphere to obtain a graphene deposition template; a mixed gas is introduced to perform chemical vapor infiltration to prepare a three-dimensional interpenetrating silicon carbide network; the three-dimensional interpenetrating silicon carbide network is placed in a plasma treatment device and treated with carbon tetrafluoride gas to obtain a fluorinated interpenetrating silicon carbide network.

8. The method for preparing a solvent-based aerogel anticorrosive and wear-resistant coating according to claim 7, characterized in that: In Z2: The volume ratio of methyltrichlorosilane to hydrogen in the mixed gas is 1:10-20; The gas flow rate of the chemical vapor infiltration is 50-100 sccm; The power of the three-dimensional interpenetrating silicon carbide network plasma treatment is 50-100W; The temperature of the three-dimensional interpenetrating silicon carbide network plasma treatment is 90-100° C.; The three-dimensional interpenetrating silicon carbide network plasma treatment time is 60-80 minutes.

9. A solvent-based aerogel anticorrosive and wear-resistant coating prepared by the preparation method according to any one of claims 1 to 8.

10. Use of a solvent-based aerogel anticorrosive and wear-resistant coating prepared by the preparation method according to any one of claims 1 to 8 in ship preparation.