Solvent type aerogel anticorrosive wear-resistant coating, preparation method and application thereof

Abstract

The application provides a solvent type aerogel anti-corrosion wear-resistant coating and a preparation method and application thereof, and belongs to the technical field of coatings. Fluorinated modified zirconium oxide aerogel is introduced to endow the coating with excellent super-hydrophobicity, corrosion resistance and anti-pollution performance; a gradient slow-release type core-shell structure is designed to realize precise release and long-acting protection of the corrosion inhibitor by taking ZIF-8 as a carrier; three-dimensional interpenetrating network silicon carbide is prepared by using a graphene template to enhance the wear resistance, thermal conductivity and corrosion resistance of the coating; and a hybrid material with high strength, flexibility and high-temperature resistance is prepared by modifying polyimide with organic silicon. These technologies optimize the mechanical properties, chemical stability and service life of the coating from multiple aspects, and meet the demand for high-performance coatings in complex environments.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of coatings, and relates to a solvent type aerogel anti-corrosion and wear-resistant coating as well as a preparation method and application thereof. BACKGROUND

[0002] Anti-corrosion and wear-resistant coatings play a crucial role in industrial and construction fields, and are widely used in chemical industry, petroleum industry, transportation, shipbuilding, construction and other fields. These coatings can significantly improve the corrosion resistance and wear resistance of materials, thereby prolonging the service life of equipment, structures and pipelines. In harsh environmental conditions such as high temperature, high humidity and chemical corrosion, the performance of the coating is particularly important, so it is particularly urgent to develop high-performance anti-corrosion and wear-resistant coatings.

[0003] Traditional anti-corrosion coatings usually rely on polymer matrices such as epoxy resin and polyurethane. Although these polymers have certain anti-corrosion properties, their corrosion resistance is often limited by the chemical properties of the matrix material. For example, many polymers are easily chemically degraded under the action of strong acid, strong base or other corrosive chemical media, resulting in aging, cracking and peeling of the coating. These phenomena not only reduce the protective effect of the coating, but also may cause corrosion and damage to the underlying material, resulting in economic losses and safety hazards.

[0004] In addition, wear resistance is also a key performance of anti-corrosion coatings. Many existing polymer coatings have relatively insufficient wear resistance when facing high-strength wear conditions, and are prone to wear, scratch and even peeling, making it difficult to meet the high requirements of wear resistance in industrial applications. In some heavy-load or high-frequency friction situations, such as the surface coating of mechanical equipment and vehicles, the performance of traditional coatings often fails to meet the expected results. SUMMARY

[0005] To solve the above problems, the present application aims to provide a solvent type aerogel corrosion resistant and wear resistant coating and its preparation method and application. The present application introduces zirconium oxide aerogel and modifies it by fluorination with perfluorooctyltriethoxysilane, which gives it superhydrophobicity, anti-pollution and chemical inert barrier functions, while retaining its lightweight porous structure, corrosion resistance and chemical stability. Secondly, a gradient slow-release core-shell structure is designed, with ZIF-8 as the core to load the corrosion inhibitor benzotriazole, and the porous structure is used to achieve self-adaptive release. The release rate is controlled by a polydopamine coating, and a silica shell is used to provide a physical barrier, which greatly extends the release time of the corrosion inhibitor and improves the corrosion resistance and service life. In addition, three-dimensional interpenetrating network silicon carbide is introduced to give the coating high porosity, light weight, high strength and excellent wear resistance and thermal conductivity. After plasma fluorination modification, a chemical inert layer is formed on the surface of the silicon carbide, further enhancing its hydrophobicity, corrosion resistance and mechanical stability. By introducing organic silicon segments to modify polyimide, an organic silicon-polyimide hybrid material is prepared, which maintains high strength and high temperature resistance while significantly improving toughness and impact resistance, and enhances the interfacial bonding strength between the matrix and the filler.

[0006] To achieve this purpose, the present application adopts the following technical solutions:

[0007] In a first aspect, the present application provides a preparation method of a solvent type aerogel corrosion resistant and wear resistant coating, which comprises:

[0008] S1: Disperse zirconium oxynitrate in an ethanol / water solution, adjust the pH with hydrochloric acid, and then stir at a constant temperature to obtain a zirconium sol. Disperse perfluorooctyltriethoxysilane in isopropanol to obtain a fluorination solution. Mix the fluorination solution with the zirconium sol, stir, and then stand to obtain a wet gel. After post-treatment, a fluorination modified zirconium oxide aerogel is obtained. Disperse the fluorination modified zirconium oxide aerogel in isopropanol to obtain a fluorination modified zirconium oxide aerogel dispersion;

[0009] S2: Prepare a N-methylpyrrolidone solution of bis(4-aminophenyl) ether, add diphthalic anhydride, and react to obtain a polyimide precursor solution. Add 3-glycidyl ether oxypropyl methyl diethoxysilane, adjust the pH to obtain a reaction liquid F, and then stir and react, and stepwise heat treatment to obtain a reaction liquid H. After cooling and post-treatment, an organic silicon-polyimide hybrid resin is obtained. Mix the organic silicon-polyimide hybrid resin with isopropanol to obtain an organic silicon-polyimide hybrid resin dispersion;

[0010] S3: Mix the organic silicon-polyimide hybrid resin dispersion and a dispersant, stir uniformly, then add the fluorination modified zirconium oxide aerogel dispersion and the fluorination modified interpenetrating network silicon carbide, ultrasonically disperse uniformly, and then add the gradient slow-release core-shell capsule. Stir uniformly at low speed to obtain a solvent type aerogel corrosion resistant and wear resistant coating.

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

[0012] Z1: A methanol solution of 2-methylimidazole is prepared, and after adjusting the pH, a methanol solution of zinc nitrate is added to obtain a mixed solution A. After reaction and treatment, a metal organic framework is obtained. The metal organic framework is added to ethanol with benzotriazole to obtain a mixed solution B. After solvent thermal treatment and treatment, a slow-release inner core is obtained. The slow-release inner core is dispersed in a Tris buffer solution, and dopamine hydrochloride is added to obtain a reaction solution C. After reaction, a suspension D is obtained. Tetraethyl orthosilicate is pre-hydrolyzed in an ethanol / water solution after adjusting the pH to obtain a pre-hydrolysis solution. The pre-hydrolysis solution is added to the suspension D, and reaction and treatment are carried out at room temperature to obtain a gradient slow-release core-shell capsule.

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

[0014] Z2: After graphene is dispersed in ethanol, freeze-dried and foamed, a graphene deposition template is obtained by pre-sintering in an inert atmosphere. A three-dimensional interpenetrating network silicon carbide is prepared by a chemical vapor infiltration method. The three-dimensional interpenetrating network silicon carbide is placed in a plasma treatment device, and carbon tetrafluoride gas is introduced to obtain a fluorinated modified interpenetrating network silicon carbide.

[0015] Specifically, S1: Zirconium oxynitrate is dispersed in an ethanol / water mixed solution to obtain a first dispersion solution. Hydrochloric acid is used to adjust the pH of the first dispersion solution to obtain a second dispersion solution. The second dispersion solution is stirred at a constant temperature to obtain a zirconium sol. Perfluorooctyltriethoxysilane is dispersed in isopropanol to obtain a fluorinated solution. The fluorinated solution is added to the zirconium sol to obtain a mixed solution. After stirring, the mixed solution is placed in a sealed container and left to stand to obtain a wet gel. The wet gel is soaked in anhydrous ethanol for immersion and aging to obtain a preliminary aerogel. The preliminary aerogel is dried in a supercritical carbon dioxide drying oven to obtain a fluorinated modified zirconia aerogel. The fluorinated modified zirconia aerogel is added to isopropanol. After adding polyvinylpyrrolidone, shear dispersion is carried out to obtain a fluorinated modified zirconia aerogel dispersion solution.

[0016] S2: An N-methylpyrrolidone solution of bis(4-aminophenyl) ether is prepared. Biphenyltetracarboxylic dianhydride is added to obtain a reaction solution E. After stirring and reaction, a polyimide precursor solution is obtained. 3-Glycidyl ether oxypropyl methyl diethoxysilane is added to obtain an organosilicon-modified solution. Acetic acid is used to adjust the pH to obtain a reaction solution F. After stirring and reaction, a mixed solution G is obtained. After step-by-step heat treatment under nitrogen protection, a reaction solution H is obtained. After cooling and post-treatment, an organosilicon-polyimide hybrid resin is obtained. The organosilicon-polyimide hybrid resin is mixed with isopropanol to obtain an organosilicon-polyimide hybrid resin dispersion solution.

[0017] S3: The organosilicon-polyimide hybrid resin dispersion solution and a dispersant are mixed and stirred uniformly. The fluorinated modified zirconia aerogel dispersion solution, the fluorinated modified interpenetrating network silicon carbide, and the gradient slow-release core-shell capsule are sequentially added. After ultrasonic dispersion, a solvent-based aerogel anticorrosion and wear-resistant coating is obtained by low-speed stirring.

[0018] The preparation method of the gradient 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, then add the methanol solution of zinc nitrate at room temperature to obtain a mixed solution A, stir and react, centrifuge, wash and dry to obtain a metal organic framework; prepare an ethanol dispersion solution of benzotriazole, add the metal organic framework to obtain a mixed solution B, perform a solvothermal treatment, then centrifuge, wash and dry to obtain a slow-release inner core; disperse the slow-release inner core in a Tris buffer solution, add dopamine hydrochloride to obtain a reaction solution C, stir and react to obtain a suspension D; add tetraethyl orthosilicate to an ethanol / water mixed solution to obtain a silicon coating layer solution, adjust the pH by adding ammonia water to obtain a pre-hydrolysis solution, and then add the pre-hydrolysis solution to the suspension D to obtain a reaction solution E, react at room temperature, centrifuge, wash and dry to obtain a gradient release core-shell capsule;

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

[0021] Z2: add graphene powder to ethanol, ultrasonically disperse, freeze-dry and foam to obtain a pretreated template, pre-sinter in an inert atmosphere to obtain a graphene deposition template; place the graphene deposition template in a reaction zone, introduce a mixed gas to perform chemical vapor infiltration to obtain a three-dimensional interpenetrating network silicon carbide, and place the three-dimensional interpenetrating network silicon carbide in a plasma treatment device, introduce carbon tetrafluoride gas to perform treatment, to obtain a fluorinated modified interpenetrating network silicon carbide;

[0022] As a preferred technical solution of the present application, 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 values not listed in this range are also applicable.

[0023] In some optional embodiments, the concentration of the first dispersion solution 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 values not listed in this range are also applicable.

[0024] In some optional embodiments, the first dispersion solution is adjusted to a pH of 3-4 using hydrochloric acid, for example, it can be 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 values not listed in this range are also applicable.

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

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

[0028] In some optional embodiments, the amount of the perfluorooctyltriethoxysilane is 8-10% of the moles of zirconyl nitrate, 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 not only limited to the listed values, other values not listed in the range are also applicable.

[0029] In some optional embodiments, the mixed solution is stirred for 1-2h and then left to obtain a wet gel, 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 not only limited to the listed values, other values not listed in the range are also applicable.

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

[0031] In some alternative embodiments, the temperature at which the wet gel is aged after being soaked in anhydrous ethanol is 40-50°C, such as 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 recited values, as other, non-recited values within this range are equally serviceable.

[0032] In some alternative embodiments, the time at which the wet gel is aged after being soaked in anhydrous ethanol is 20-24h, such as can be 20h, 20.4h, 20.8h, 21.2h, 21.6h, 22h, 22.4h, 22.8h, 23.2h, 23.6h, or 24h, but is not limited to the recited values, as other, non-recited values within this range are equally serviceable.

[0033] In some alternative embodiments, the temperature at which the preliminary aerogel is supercritical carbon dioxide dried is 40-50°C, such as 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 recited values, as other, non-recited values within this range are equally serviceable.

[0034] In some alternative embodiments, the pressure at which the preliminary aerogel is supercritical carbon dioxide dried is 25-30MPa, such as can be 25MPa, 25.5MPa, 26MPa, 26.5MPa, 27MPa, 27.5MPa, 28MPa, 28.5MPa, 29MPa, 29.5MPa, or 30MPa, but is not limited to the recited values, as other, non-recited values within this range are equally serviceable.

[0035] In some alternative embodiments, the time at which the preliminary aerogel is supercritical carbon dioxide dried is 6-7h, such as 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 recited values, as other, non-recited values within this range are equally serviceable.

[0036] In some alternative embodiments, the solid-liquid mass ratio of the fluorinated modified zirconia aerogel to isopropyl alcohol is 1:20-30, such as 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 recited values, as other, non-recited values within this range are equally serviceable.

[0037] In some optional embodiments, the amount of polyvinylpyrrolidone is 0.1-0.2% of the mass of the fluorinated modified zirconium oxide 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 not limited to the listed values, and other values not listed in the 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 not limited to the listed values, and other values not listed in the 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 not limited to the listed values, and other values not listed in the range are also applicable.

[0040] The shear dispersion is paused for 1 min every 5 min;

[0041] In some optional embodiments, the particle size of the fluorinated modified zirconium oxide aerogel in the fluorinated modified zirconium oxide 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 not limited to the listed values, and other values not listed in the range are also applicable.

[0042] As a preferred technical solution of the present application, 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 not limited to the listed values, and other values not listed in the range are also applicable.

[0043] The molar ratio of the biphenyl tetracarboxylic dianhydride to bis(4-aminophenyl) ether is 1:1.

[0044] In some optional embodiments, the reaction liquid E is stirred for 3-4 h to obtain a polyimide precursor solution, for example, 3 h, 3.1 h, 3.2 h, 3.3 h, 3.4 h, 3.5 h, 3.6 h, 3.7 h, 3.8 h, 3.9 h or 4 h, but not only limited to the listed values, other values not listed in the 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, 15%, 15.5%, 16%, 16.5%, 17%, 17.5%, 18%, 18.5%, 19%, 19.5% or 20%, but not only limited to the listed values, other values not listed in the 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 not only limited to the listed values, other values not listed in the range are also applicable.

[0047] In some optional embodiments, the reaction liquid F is stirred at a temperature of 50-60°C, for example, 50°C, 51°C, 52°C, 53°C, 54°C, 55°C, 56°C, 57°C, 58°C, 59°C or 60°C, but not only limited to the listed values, other values not listed in the range are also applicable.

[0048] In some optional embodiments, the reaction liquid F is stirred for 1-2 h, for example, 1 h, 1.1 h, 1.2 h, 1.3 h, 1.4 h, 1.5 h, 1.6 h, 1.7 h, 1.8 h, 1.9 h or 2 h, but not only limited to the listed values, other values not listed in the range are also applicable.

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

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

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

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

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

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

[0055] In some optional embodiments, the mass ratio of the isopropyl alcohol to the silicone-polyimide hybrid resin is 2.5-3.5:1, which 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 values not listed in the range are also applicable.

[0056] As a preferred technical solution of the present application, in step S3, the dispersant is octylphenoxypolyethoxyethanol, 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 in this range are also applicable.

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

[0058] As a preferred technical solution of the present application, 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 values not listed in this range are also applicable.

[0059] In some optional embodiments, the concentration of the methanol solution of zinc nitrate 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 values not listed in this range are also applicable.

[0060] In some optional embodiments, the methanol solution of 2-methylimidazole is adjusted to a pH of 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 values not listed in this range are also applicable.

[0061] In some optional embodiments, the molar ratio of 2-methylimidazole to zinc nitrate 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 values not listed in this range are also applicable.

[0062] In some optional embodiments, the mixture A is stirred for 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 not only limited to the listed values, other values not listed in the range of values are also applicable.

[0063] In some optional embodiments, the concentration of the ethanol dispersion of benzotriazole is 8-10 mg / mL, for example, it can be 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 not only limited to the listed values, other values not listed in the range of values are also applicable.

[0064] In some optional embodiments, the solid-liquid mass ratio of the metal organic framework and 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 not only limited to the listed values, other values not listed in the range of values are also applicable.

[0065] In some optional embodiments, the temperature of the solvothermal treatment of the mixture 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 not only limited to the listed values, other values not listed in the range of values are also applicable.

[0066] In some optional embodiments, the time of the solvothermal treatment of the mixture 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 not only limited to the listed values, other values not listed in the range of values 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 not only limited to the listed values, other values not listed in the range of values are also applicable.

[0068] In some alternative embodiments, the concentration of the sustained-release core in the Tris buffer is 2-3 mg / mL, for example, it can be 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 not limited to the listed values, other values not listed in the range are also applicable.

[0069] In some alternative embodiments, the concentration of the dopamine hydrochloride in the reaction solution C is 2-3 mg / mL, for example, it can be 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 not limited to the listed values, other values not listed in the range are also applicable.

[0070] In some alternative embodiments, the volume ratio of the tetraethyl 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 not limited to the listed values, other values not listed in the range are also applicable.

[0071] In some alternative embodiments, the pH of the silicon coating layer solution is adjusted to 11-12 by adding ammonia water, 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 not limited to the listed values, other values not listed in the range are also applicable.

[0072] In some alternative embodiments, the silicon coating layer solution is pre-hydrolyzed at room temperature for 2-3 h after adjusting the pH, for example, it can be 2 h, 2.1 h, 2.2 h, 2.3 h, 2.4 h, 2.5 h, 2.6 h, 2.7 h, 2.8 h, 2.9 h or 3 h, but not limited to the listed values, other values not listed in the range are also applicable.

[0073] In some alternative embodiments, the mass ratio of the dopamine hydrochloride to the tetraethyl 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 not limited to the listed values, other values not listed in the range are also applicable.

[0074] In some optional embodiments, the reaction liquid E is reacted at room temperature for 8-9 h, for example, 8 h, 8.1 h, 8.2 h, 8.3 h, 8.4 h, 8.5 h, 8.6 h, 8.7 h, 8.8 h, 8.9 h or 9 h, but not only limited to the listed values, other values not listed in the range are also applicable.

[0075] As a preferred technical solution of the present application, in step Z2, the concentration of the graphene powder in ethanol is 3-5 mg / mL, for example, 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 not only limited to the listed values, other values not listed in the range are also applicable.

[0076] In some optional embodiments, the pre-sintering temperature of the pre-treatment template under inert atmosphere is 700-800°C, for example, 700°C, 710°C, 720°C, 730°C, 740°C, 750°C, 760°C, 770°C, 780°C, 790°C or 800°C, but not only limited to the listed values, other values not listed in the range are also applicable.

[0077] In some optional embodiments, the pre-sintering time of the pre-treatment template under inert atmosphere is 3-4 h, for example, 3 h, 3.1 h, 3.2 h, 3.3 h, 3.4 h, 3.5 h, 3.6 h, 3.7 h, 3.8 h, 3.9 h or 4 h, but not only limited to the listed values, other values not listed in the 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, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19 or 1:20, but not only limited to the listed values, other values not listed in the range are also applicable.

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

[0080] In some alternative embodiments, the pressure of the chemical vapor infiltration is 10-15 kPa, such as 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 recited values, as other, non-recited values within this range are equally serviceable.

[0081] In some alternative embodiments, the time of the chemical vapor infiltration is 2-4 h, such as can be 2 h, 2.2 h, 2.4 h, 2.6 h, 2.8 h, 3.0 h, 3.2 h, 3.4 h, 3.6 h, 3.8 h, or 4 h, but is not limited to the recited values, as other, non-recited values within this range are equally serviceable.

[0082] In some alternative embodiments, the gas flow rate of the chemical vapor infiltration is 50-100 seem, such as can be 50 seem, 55 seem, 60 seem, 65 seem, 70 seem, 75 seem, 80 seem, 85 seem, 90 seem, 95 seem, or 100 seem, but is not limited to the recited values, as other, non-recited values within this range are equally serviceable.

[0083] In some alternative embodiments, the power of the three-dimensional interpenetrating network silicon carbide plasma treatment is 50-100 W, such as can be 50 W, 55 W, 60 W, 65 W, 70 W, 75 W, 80 W, 85 W, 90 W, 95 W, or 100 W, but is not limited to the recited values, as other, non-recited values within this range are equally serviceable.

[0084] In some alternative embodiments, the temperature of the three-dimensional interpenetrating network silicon carbide plasma treatment is 90-100 °C, such as 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 recited values, as other, non-recited values within this range are equally serviceable.

[0085] In some alternative embodiments, the time of the three-dimensional interpenetrating network silicon carbide plasma treatment is 60-80 min, such as 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 recited values, as other, non-recited values within this range are equally serviceable.

[0086] In a second aspect, the present application provides a solvent-based aerogel anticorrosive and wear-resistant coating. The solvent-based aerogel anticorrosive and wear-resistant coating comprises a silicone-polyimide hybrid resin, a fluorinated modified zirconia aerogel, a fluorinated modified interpenetrating network silicon carbide, and a gradient release type core-shell capsule.

[0087] Traditional silica aerogels are widely used in functional coatings due to their high specific surface area and good thermal insulation performance, but they have great limitations in complex environments. First, the chemical stability of silica aerogels is poor, and they can easily dissolve in strong acid or strong base conditions, leading to rapid degradation of their structure and performance. Second, due to the high hydroxyl content on the surface of silica aerogels, they have strong hygroscopicity, which not only reduces their hydrophobicity, but also accelerates the decline of their protective performance in humid environments. At the same time, the hydrophobicity of silica aerogels is not stable in corrosive environments, further limiting their practical application in high-performance anticorrosive coatings. Based on this, the present application introduces zirconia aerogel as a filler substrate to replace traditional silica aerogels, thereby overcoming the above problems.

[0088] Zirconia aerogel is an ideal choice due to its excellent performance. As a ceramic material, zirconia has extremely high hardness and melting point, as well as excellent chemical stability and corrosion resistance. This material not only remains stable in complex chemical environments such as acid and base, but its porous aerogel structure also gives it light weight, high specific surface area, and extremely low thermal conductivity, making it suitable for high-performance coating design. In addition, the surface of zirconia is rich in hydroxyl groups, which can react with functional molecules through chemical modification, enhancing the bonding force with the coating matrix. This surface activity allows it not only to serve as a functional filler in coating design, but also to impart more performance to the coating through modification.

[0089] To further enhance the performance of zirconia aerogel, the present application uses perfluorooctyltriethoxysilane to modify it. The fluorocarbon segment in the perfluorooctyltriethoxysilane molecule has extremely low surface energy, and the modified zirconia aerogel surface 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 mist on the surface of the coating, allowing it to remain stable in harsh environments. In addition, fluorination treatment forms a chemically inert barrier on the surface of the aerogel, significantly preventing the penetration of moisture, oxygen, and corrosive media, thereby significantly improving the corrosion resistance of the coating. At the same time, fluorination modification reduces the polarity of the surface of the zirconia aerogel, improving its dispersibility in the organic matrix and avoiding the occurrence of particle agglomeration, thereby ensuring the uniformity and density of the coating.

[0090] Through fluorination modification, the performance of zirconium oxide aerogel in the coating system is comprehensively optimized. The modified aerogel not only maintains excellent characteristics such as light weight and high specific surface area, but also exhibits superhydrophobicity and enhanced chemical corrosion resistance, which can adapt to more complex and harsh service environments. At the same time, the modification significantly improves the adhesion and dispersibility of the aerogel with the coating matrix, so that the coating has significantly improved performance in corrosion protection, wear resistance, and anti-pollution.

[0091] In the present application, 2-methyl imidazole is used to assemble metal organic frameworks with zinc ions, which has significant advantages as a carrier for corrosion inhibitors. Metal organic frameworks (ZIF-8) have high specific surface area and stable porous structure, and exhibit excellent chemical stability in acidic and alkaline media, making them an ideal carrier for corrosion inhibitors. The channel structure of ZIF-8 not only effectively accommodates corrosion inhibitor molecules through physical adsorption and chemical bonding, but also realizes 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 corrosion microzones, avoiding waste of corrosion inhibitors and improving corrosion protection efficiency.

[0092] As a corrosion inhibitor, benzotriazole is used in the present application. Benzotriazole is a classic corrosion inhibitor molecule that can form a dense passivation film on the metal surface through chemical reaction. This passivation film can firmly adhere 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 enables the inner core inhibitor system to have good slow-release performance and adaptive release capability.

[0093] To better realize the gradient slow-release function, the present application designs a multifunctional core-shell structure by layering polydopamine coating and silica shell on the surface of the slow-release inner core. First, under alkaline conditions, the precursor dopamine hydrochloride is deposited on the surface of the slow-release inner core through self-oxidation polymerization to form a polydopamine coating. The polydopamine coating has significant pH responsiveness and partially hydrolyzes under acidic conditions, thereby promoting the release of benzotriazole. This responsive mechanism makes the release of corrosion inhibitors more targeted, enabling precise release of corrosion inhibitors in local corrosion microzones (such as acidic environments on the metal surface). In addition, the polydopamine coating also plays multiple functions: on the one hand, it encapsulates and protects the inner core structure, preventing premature leakage of corrosion inhibitors during storage or transportation; on the other hand, the chemical active functional groups on its surface provide binding sites for the subsequent deposition of silica shell, significantly enhancing the structural stability of the core-shell microcapsule.

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

[0095] Through the above multi-layer design, the gradient release type core-shell structure realizes the organic combination of multiple functions. The ZIF-8 in the inner core provides efficient drug loading capacity and ion response triggering mechanism for benzotriazole; 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 functional sites for the deposition of the outer shell layer; the outer silicon dioxide shell layer 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 prolongs the release time of the corrosion inhibitor and makes the release rate more controllable, but also significantly improves the corrosion resistance and service life of the coating, showing great application potential.

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

[0097] The design of the three-dimensional interpenetrating network structure endows the silicon carbide material with unique performance advantages. On the one hand, the interpenetrating network structure provides excellent mechanical support performance and crack resistance, which can maintain structural stability under high mechanical load; on the other hand, the pore structure enhances the mechanical interlocking effect between the resin matrix, making it exhibit excellent wear resistance in the composite coating. This network structure makes the material have high strength and high thermal conductivity while ensuring lightweight, which is more suitable for protective coating design requiring high wear resistance and toughness.

[0098] Silicon carbide itself is a hard, high-temperature-resistant, and chemical corrosion-resistant inorganic ceramic material, and its 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 the silicon carbide material is further optimized, not only improving its crack resistance and toughness, but also endowing the structure with excellent thermal conductivity and mechanical stability. This multifunctional property makes three-dimensional interpenetrating network silicon carbide an ideal reinforcing 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 modify the surface of silicon carbide. By treating the surface of silicon carbide with carbon tetrafluoride plasma, fluorine atoms are introduced onto the surface, forming a layer of 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 not only effectively resists the corrosion of corrosive media such as moisture, salt spray, and acid and alkali solutions, but also provides long-term chemical protection in harsh environments. In addition, 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 load and complex service conditions.

[0100] The three-dimensional interpenetrating network silicon carbide prepared by the guiding action of the graphene template and the chemical vapor infiltration technology, combined with the surface fluorination modification by plasma treatment, not only realizes the overall enhancement of the mechanical properties, wear resistance, and crack resistance of the silicon carbide material, but also endows it with superhydrophobicity and corrosion resistance. This multifunctional composite material has broad application prospects in high-performance protective coatings and can meet the multiple performance requirements of coatings in harsh environments.

[0101] In the present application, polyimide is selected as the base material because it is a high-performance polymer with excellent heat resistance, mechanical strength and chemical corrosion resistance, making it an ideal base material for high-performance coatings. The rigid aromatic ring and imine ring structure in the polyimide molecular backbone gives it excellent high-temperature resistance and excellent dimensional stability. In addition, the rigid molecular structure of polyimide also provides excellent wear resistance, enabling it to exhibit excellent mechanical stability under harsh conditions such as high temperature and high friction. However, the rigid molecular chain structure of polyimide also has a significant drawback, which is that the material has high brittleness, resulting in insufficient impact resistance and flexibility. This limitation restricts the performance of polyimide in applications that require high mechanical load and high impact toughness.

[0102] To overcome the above-mentioned defects of polyimide, the present application introduces 3-glycidyloxypropylmethyldiethoxysilane into the polyimide backbone by sol-gel method to prepare a silicone-polyimide hybrid matrix material. The introduction of silicone segments can significantly improve the mechanical properties and surface properties of polyimide. During the sol-gel reaction, the siloxane segments form a cross-linked network through hydrolysis and condensation reaction, and are combined with 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 backbone of polyimide still gives the material very high temperature resistance and mechanical strength; on the other hand, the flexible nature of the silicone segment significantly improves the toughness and impact resistance of the material, effectively avoiding the problem of brittle fracture of traditional polyimide materials under high mechanical stress. In addition, the introduction of silicone segments also enhances the interfacial bonding strength between the polyimide matrix and the functional fillers. The chemical active functional groups on the surface of the siloxane segment can form stronger interfacial bonding with the surface of the fillers, thereby improving the dispersion and stability of the fillers in the matrix and significantly improving the overall performance of the coating.

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

[0105] In a third aspect, the present application provides a solvent-based aerogel corrosion-resistant and wear-resistant coating for use in the preparation of a ship.

[0106] Compared with the prior art, the present application has the following advantages:

[0107] The present application introduces zirconia aerogel, which has excellent corrosion resistance, chemical stability and light porous structure; by fluorination modification with perfluorooctyltriethoxysilane, it is endowed with superhydrophobicity, anti-pollution and chemical inert barrier, which significantly improves the corrosion resistance and dispersibility. The modified zirconia aerogel overcomes the defects of traditional aerogel and exhibits excellent corrosion resistance, wear resistance and anti-pollution performance in coatings, which is suitable for high-performance coating design in complex environment;

[0108] The present application designs a gradient release type core-shell structure, taking metal organic framework ZIF-8 as the core, loading corrosion inhibitor benzotriazole, and triggering the release through the porous structure and ion response characteristics. The surface of the core is coated with a polydopamine coating with pH responsiveness, which is used to regulate the release of the corrosion inhibitor and enhance the structural stability. The outer layer provides a physical barrier through the silica shell, effectively prolonging the release time and improving the environmental performance. The 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] The present application constructs a template by graphene freeze-drying, and prepares a three-dimensional interpenetrating network silicon carbide by chemical vapor infiltration, which endows it with high porosity, light weight, high strength and excellent mechanical properties. The structure provides excellent mechanical support, crack resistance and mechanical interlocking effect with the matrix, significantly improving the wear resistance and thermal conductivity of the composite coating. In addition, through plasma fluorination modification, a chemical inert layer is formed on the surface of the silicon carbide, which enhances the hydrophobicity and corrosion resistance, while maintaining its high hardness and mechanical stability, making it an ideal reinforcing material for high-performance protective coatings;

[0110] The present application modifies polyimide by introducing organosilicon segments to prepare organosilicon-polyimide hybrid materials with high temperature resistance, high strength and flexibility. This design significantly improves the brittleness of polyimide while maintaining its excellent performance. In addition, the organosilicon segments form a cross-linked network through sol-gel reaction, enhancing the interfacial bonding strength between the matrix and the 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 application will be described in detail below in combination with specific embodiments. The embodiments described herein are specific specific embodiments of the present application, which are used to illustrate the concept of the present application; these descriptions are explanatory and exemplary, and should not be understood as limiting the embodiments of the present application and the protection scope of the present application. In addition to the embodiments described herein, those skilled in the art can also employ other technical solutions based on the disclosure of the present application claims and the specification, which include technical solutions employing any obvious substitutions and modifications to the embodiments described herein.

[0112] The chemical reagents used in the examples and comparative examples of the present application are commercially available and are not further purified or treated.

[0113] Example 1

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

[0115] S1: dispersing zirconium oxynitrate in an ethanol / water mixed solution to obtain a first dispersion liquid with a concentration of 0.25M, wherein the volume ratio of ethanol to water in the ethanol / water mixed solution is 3.8:1, using hydrochloric acid to adjust the pH to 3 to obtain a second dispersion liquid, stirring at a constant temperature of 28℃ for 30min to obtain a zirconium sol; dispersing perfluorooctyltriethoxysilane in isopropanol to obtain a fluorinated solution with a mass fraction of 0.5wt.%, adding it to the zirconium sol to obtain a mixed solution, wherein the amount of perfluorooctyltriethoxysilane is 9% of the number of moles of zirconium oxynitrate, stirring for 1h and then placing it in a sealed container to obtain a wet gel, soaking it in anhydrous ethanol for 36h and aging at 40℃ for 24h to obtain a preliminary aerogel, placing it in a supercritical carbon dioxide drying oven to dry to obtain a fluorinated modified zirconia aerogel, wherein the drying temperature is 40℃, the pressure is 28MPa, and the time is 6h; adding it to isopropanol, wherein the solid-liquid mass ratio of the fluorinated modified zirconia aerogel to isopropanol is 1:25, adding 0.18% of the mass of the fluorinated modified zirconia aerogel of polyvinylpyrrolidone, and then performing shear dispersion, the first rotation speed of shear dispersion is 2000rpm, the time is 10min, the second rotation speed is 5000rpm, and the time is 15min, wherein it is paused for 1min every 5min to prevent the temperature from being too high, to obtain a fluorinated modified zirconia aerogel dispersion liquid, wherein the particle size of the fluorinated modified zirconia aerogel is 8μm;

[0116] S2: an N-methylpyrrolidone solution of bis(4-aminophenyl) ether with a concentration of 0.18 g / mL is prepared, and diphthalic anhydride is added to obtain a reaction liquid E, wherein the molar ratio of diphthalic anhydride to bis(4-aminophenyl) ether is 1:1, and the reaction is stirred for 3 h to obtain a polyimide precursor solution; 3-glycidyloxypropylmethyldiethoxysilane is added to obtain a silicone-modified solution, wherein the amount of 3-glycidyloxypropylmethyldiethoxysilane is 15% of the total mass of the polyimide precursor, and acetic acid is used to adjust the pH to 4.5 to obtain a reaction liquid F, which is stirred at 50°C for 1 h to obtain a mixed liquid G, which is stepwise heat-treated under nitrogen protection to obtain a reaction liquid H, wherein the first temperature of the stepwise heat treatment is 95°C, the first time is 1 h, the second temperature is 150°C, the second time is 1.8 h, the third temperature is 305°C, and the third time is 3 h, and the silicone-polyimide hybrid resin is obtained after cooling and post-processing, which is mixed with isopropyl alcohol at a mass ratio of 3:1 to obtain a silicone-polyimide hybrid resin dispersion;

[0117] S3: the silicone-polyimide hybrid resin dispersion and the dispersant octylphenoxyl alcohol are mixed, wherein the amount of the dispersant is 0.15% of the mass of the silicone-polyimide hybrid resin, and after being uniformly stirred, the fluorinated modified zirconium oxide aerogel dispersion, the fluorinated modified interpenetrating network silicon carbide, and the gradient sustained-release core-shell capsule are sequentially added, and after being uniformly dispersed by ultrasonic, the solvent-based aerogel corrosion-resistant and wear-resistant coating is obtained by uniformly stirring at a low speed, wherein the mass ratio of the silicone-polyimide hybrid resin, the fluorinated modified zirconium oxide aerogel, the fluorinated modified interpenetrating network silicon carbide, 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 methanol solution of 2-methylimidazole with a concentration of 0.18 M and a methanol solution of zinc nitrate with a concentration of 0.2 M, adjust the pH of the methanol solution of 2-methylimidazole to 10, 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 for 30 min, centrifuge, wash and dry to obtain a metal organic framework; prepare an ethanol dispersion of benzotriazole with a concentration of 9.5 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 1:20, after solvothermal treatment at 115℃ for 30 min, centrifuge, wash and dry to obtain a slow-release inner core; disperse it in a Tris buffer with a pH of 8.8, wherein the concentration of the slow-release inner 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, after stirring and reaction, a suspension D is obtained; add tetraethyl orthosilicate into an ethanol / water mixed solution to obtain a silicon coating layer solution, wherein the volume ratio of tetraethyl orthosilicate to ethanol is 1:4, after adjusting the pH to 11.5 by adding ammonia water, pre-hydrolysis is carried out at room temperature for 2 h to obtain a pre-hydrolysis solution, which is added to the suspension D to obtain a reaction solution E, wherein the mass ratio of dopamine hydrochloride to tetraethyl orthosilicate is 1:1.8, reaction is carried out at room temperature for 8 h, centrifugation, washing and drying are carried out to obtain a gradient slow-release core-shell capsule;

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

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

[0122] Example 2

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

[0124] S1: dispersing zirconyl nitrate in an ethanol / water mixed solution to obtain a first dispersion liquid with a concentration of 0.2 M, wherein the volume ratio of ethanol to water in the ethanol / water mixed solution is 3:1, and the pH of the solution is adjusted to 3.5 using hydrochloric acid to obtain a second dispersion liquid, and stirring at 27°C for 36 min to obtain a zirconium sol; dispersing perfluorooctyltriethoxysilane in isopropanol to obtain a fluorinated solution with a mass fraction of 0.8 wt.%, and adding the fluorinated solution to the zirconium sol to obtain a mixed solution, wherein the amount of perfluorooctyltriethoxysilane is 9.5% of the number of moles of zirconyl nitrate, and stirring for 2 h and then placing in a sealed container to obtain a wet gel, and soaking the wet gel in anhydrous ethanol for 42 h and aging at 45°C for 20 h to obtain a preliminary aerogel, and placing the preliminary aerogel in a supercritical carbon dioxide drying oven to obtain a fluorinated modified zirconia aerogel, wherein the drying temperature is 45°C, the pressure is 27 MPa, and the time is 7 h; adding the fluorinated modified zirconia aerogel to isopropanol, wherein the solid-liquid mass ratio of the fluorinated modified zirconia aerogel to isopropanol is 1:20, and adding 0.1% of the mass of the fluorinated modified zirconia aerogel of polyvinylpyrrolidone to perform shear dispersion, wherein the first rotation speed of shear dispersion is 2000 rpm, the time is 12 min, the second rotation speed is 5000 rpm, and the time is 20 min, with a pause of 1 min every 5 min to prevent the temperature from being too high, to obtain a fluorinated modified zirconia aerogel dispersion liquid, wherein the particle size of the fluorinated modified zirconia aerogel is 5 μm;

[0125] S2: preparing an N-methylpyrrolidone solution of bis(4-aminophenyl) ether with a concentration of 0.1 g / mL, and adding diphthalic anhydride to obtain a reaction liquid E, wherein the molar ratio of diphthalic anhydride to bis(4-aminophenyl) ether is 1:1, and stirring for 3.5 h to obtain a polyimide precursor solution; adding 3-glycidyloxypropylmethyldiethoxysilane to obtain a silicone-modified solution, wherein the amount of 3-glycidyloxypropylmethyldiethoxysilane is 18% of the total mass of the polyimide precursor, and adjusting the pH to 4.3 using acetic acid to obtain a reaction liquid F, and stirring at 55°C for 1.8 h to obtain a mixed liquid G, and stepwise heat treatment under nitrogen protection to obtain a reaction liquid H, wherein the first temperature of the stepwise heat treatment is 80°C, the first time is 1.5 h, the second temperature is 200°C, the second time is 1 h, the third temperature is 307°C, and the third time is 2 h, and cooling and post-treatment to obtain a silicone-polyimide hybrid resin, and mixing the silicone-polyimide hybrid resin with isopropanol at a mass ratio of 3.2:1 to obtain a silicone-polyimide hybrid resin dispersion liquid;

[0126] S3: mixing the silicone-polyimide hybrid resin dispersion liquid and the dispersant octylphenoxyl alcohol, wherein the feeding amount of the dispersant is 0.1% of the mass of the silicone-polyimide hybrid resin, after stirring uniformly, adding the fluorinated modified zirconium oxide aerogel dispersion liquid, the fluorinated modified interpenetrating network silicon carbide, and ultrasonic dispersion, adding the gradient sustained-release type core-shell capsule, and stirring uniformly at low speed to obtain a solvent type aerogel corrosion-resistant and wear-resistant coating, wherein the mass ratio of the silicone-polyimide hybrid resin, the fluorinated modified zirconium oxide aerogel, the fluorinated modified interpenetrating network silicon carbide, and the gradient sustained-release type core-shell capsule is 100:6:3:1.8;

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

[0128] Z1: preparing a 0.2M methanol solution of 2-methylimidazole and a 0.15M methanol solution of zinc nitrate, adjusting the pH of the methanol solution of 2-methylimidazole to 10.5, and then adding 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, stirring for 38min, centrifuging, washing, and drying to obtain a metal organic framework; preparing an 8mg / mL ethanol dispersion of benzotriazole, and adding 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℃ for 40min, centrifuging, washing, and drying to obtain a sustained-release type inner core; dispersing the sustained-release type inner core in a Tris buffer with a pH of 8.7, wherein the concentration of the sustained-release type inner core is 2.7mg / mL, adding dopamine hydrochloride to obtain a reaction solution C, wherein the concentration of dopamine hydrochloride in the reaction solution C is 3mg / mL, and after stirring and reaction, a suspension D is obtained; adding tetraethyl orthosilicate to an ethanol / water mixed solution to obtain a silicon coating solution, wherein the volume ratio of tetraethyl orthosilicate to ethanol is 1:4.5, adjusting the pH to 11.8 after adding ammonia water, and pre-hydrolyzing at room temperature for 2.5h to obtain a pre-hydrolysis solution, adding the pre-hydrolysis solution to the suspension D to obtain a reaction solution E, wherein the mass ratio of dopamine hydrochloride to tetraethyl orthosilicate is 1:1.7, reacting at room temperature for 8.8h, centrifuging and washing, and drying to obtain a gradient sustained-release type core-shell capsule;

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

[0130] Z2: graphene powder was added to ethanol with a concentration of 4.5 mg / mL, after ultrasonic dispersion, freeze-drying, foaming and molding to obtain a pretreatment template, and pre-sintering at 750℃ for 4h in an inert atmosphere to obtain a graphene deposition template; the graphene deposition template was placed in a reaction zone, and mixed gas was introduced to perform chemical vapor infiltration to obtain a three-dimensional interpenetrating network silicon carbide, wherein the volume ratio of methyltrichlorosilane to hydrogen in the mixed gas was 1:15, the temperature of the chemical vapor infiltration was 1240℃, the pressure was 12kPa, the time was 4h, and the gas flow rate was 80sccm; the three-dimensional interpenetrating network silicon carbide was placed in a plasma treatment device, and carbon tetrafluoride gas was introduced for treatment, wherein the power of the plasma treatment was 50W, the time was 70min, and the temperature was 90℃, to obtain a fluorinated modified interpenetrating network silicon carbide.

[0131] Example 3

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

[0133] S1: zirconium oxynitrate was dispersed in an ethanol / water mixed solution to obtain a first dispersion liquid with a concentration of 0.28M, wherein the volume ratio of ethanol to water in the ethanol / water mixed solution was 3.5:1, hydrochloric acid was used to adjust the pH to 3.7 to obtain a second dispersion liquid, and stirring was performed at a constant temperature of 25℃ for 38min to obtain a zirconium sol; perfluorooctyltriethoxysilane was dispersed in isopropanol to obtain a fluorinated solution with a mass fraction of 0.7wt.%, and the fluorinated solution was added to the zirconium sol to obtain a mixed solution, wherein the amount of perfluorooctyltriethoxysilane was 8% of the number of moles of zirconium oxynitrate, and after stirring for 1.8h, the wet gel was placed in a sealed container to stand still, soaked in anhydrous ethanol for 24h, and aged at 48℃ for 22h to obtain a preliminary aerogel, which was dried in a supercritical carbon dioxide drying oven to obtain a fluorinated modified zirconia aerogel, wherein the drying temperature was 48℃, the pressure was 25MPa, and the time was 6.5h; the fluorinated modified zirconia aerogel was added to isopropanol, the solid-liquid mass ratio of the fluorinated modified zirconia aerogel to isopropanol was 1:30, and after adding 0.2% of the mass of the fluorinated modified zirconia aerogel of polyvinylpyrrolidone, shearing dispersion was performed, the first rotation speed of shearing dispersion was 2000rpm, the time was 14min, the second rotation speed was 5000rpm, and the time was 18min, wherein every 5min was paused for 1min to prevent the temperature from being too high, to obtain a fluorinated modified zirconia aerogel dispersion liquid, wherein the particle size of the fluorinated modified zirconia aerogel was 7μm;

[0134] S2: preparing an N-methylpyrrolidone solution of bis(4-aminophenyl) ether with a concentration of 0.15 g / mL, adding diphthalic anhydride to obtain a reaction liquid E, wherein the molar ratio of diphthalic anhydride to bis(4-aminophenyl) ether is 1:1, stirring for 3.8 h to obtain a polyimide precursor solution; adding 3-glycidyloxypropylmethyldiethoxysilane to obtain a silicone-modified solution, wherein the amount of 3-glycidyloxypropylmethyldiethoxysilane is 17% of the total mass of the polyimide precursor, adjusting the pH to 4.6 with acetic acid to obtain a reaction liquid F, stirring at 58°C for 2 h to obtain a mixed liquid G, and obtaining a reaction liquid H through stepwise heat treatment under nitrogen protection, wherein the first temperature of the stepwise heat treatment is 90°C, the first time is 1.8 h, the second temperature is 180°C, the second time is 1.5 h, the third temperature is 300°C, and the third time is 2.5 h, cooling and post-processing to obtain a silicone-polyimide hybrid resin, mixing the silicone-polyimide hybrid resin with isopropanol at a mass ratio of 2.5:1 to obtain a silicone-polyimide hybrid resin dispersion;

[0135] S3: mixing the silicone-polyimide hybrid resin dispersion and the dispersant octylphenoxyl alcohol, wherein the amount of the dispersant is 0.2% of the mass of the silicone-polyimide hybrid resin, and then adding a fluorinated modified zirconia aerogel dispersion, a fluorinated modified interpenetrating network silicon carbide, and a gradient sustained-release core-shell capsule in sequence, and uniformly dispersing under ultrasonic treatment to obtain a solvent-based aerogel corrosion-resistant and wear-resistant coating, wherein the mass ratio of the silicone-polyimide hybrid resin, the fluorinated modified zirconia aerogel, the fluorinated modified interpenetrating network silicon carbide, 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: a methanol solution of 2-methylimidazole with a concentration of 0.1 M and a methanol solution of zinc nitrate with a concentration of 0.18 M are prepared, the pH of the methanol solution of 2-methylimidazole is adjusted to 10.8, and then the methanol solution of zinc nitrate is added at room temperature to obtain a mixed solution A, wherein the molar ratio of 2-methylimidazole to zinc nitrate is 3.8:1, the reaction is stirred for 40 min, centrifuged, washed, and dried to obtain a metal organic framework; an ethanol dispersion of benzotriazole with a concentration of 9 mg / mL is prepared, and the metal organic framework is added 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 solvothermal treatment at 110℃ for 50 min, centrifugation, washing, and drying, a slow-release inner core is obtained; the slow-release inner core is dispersed in a Tris buffer solution with a pH of 8.5, wherein the concentration of the slow-release inner core is 2 mg / mL, and dopamine hydrochloride is added to obtain a reaction solution C, wherein the concentration of dopamine hydrochloride in the reaction solution C is 2.5 mg / mL, and after stirring and reaction, a suspension D is obtained; tetraethyl orthosilicate is added to an ethanol / water mixed solution to obtain a silicon coating layer solution, wherein the volume ratio of tetraethyl orthosilicate to ethanol is 1:4.8, ammonia water is added to adjust the pH to 11, and pre-hydrolysis is carried out at room temperature for 2.6 h to obtain a pre-hydrolysis solution, which is added to the suspension D to obtain a reaction solution E, wherein the mass ratio of dopamine hydrochloride to tetraethyl orthosilicate is 1:1.5, the reaction is carried out at room temperature for 8.5 h, centrifugation, washing, and drying are carried out to obtain a gradient slow-release core-shell capsule;

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

[0139] Z2: graphene powder is added to ethanol at a concentration of 3 mg / mL, ultrasonic dispersion is carried out, and then freeze-drying and foaming molding are carried out to obtain a pretreated template, pre-sintering is carried out at 780℃ for 3.5 h in an inert atmosphere to obtain a graphene deposition template; the graphene deposition template is placed in a reaction zone, and mixed gas is introduced for chemical vapor infiltration to obtain a three-dimensional interpenetrating network silicon carbide, wherein the volume ratio of methyltrichlorosilane to hydrogen in the mixed gas is 1:20, the temperature of the chemical vapor infiltration is 1200℃, the pressure is 14 kPa, the time is 3 h, and the gas flow rate is 100 sccm; the three-dimensional interpenetrating network silicon carbide is placed in a plasma treatment device, and carbon tetrafluoride gas is introduced for treatment, wherein the power of the plasma treatment is 60 W, the time is 74 min, and the temperature is 95℃, to obtain a fluorinated modified interpenetrating network silicon carbide.

[0140] Example 4

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

[0142] S1: dispersing zirconyl nitrate in an ethanol / water mixed solution to obtain a first dispersion liquid with a concentration of 0.3 M, wherein the volume ratio of ethanol to water in the ethanol / water mixed solution is 4:1, and the pH of the solution is adjusted to 4 using hydrochloric acid to obtain a second dispersion liquid, and stirring at 30℃ for 40 min to obtain a zirconium sol; dispersing perfluorooctyltriethoxysilane in isopropanol to obtain a fluorinated solution with a mass fraction of 1wt.%, and adding the fluorinated solution to the zirconium sol to obtain a mixed solution, wherein the amount of perfluorooctyltriethoxysilane is 10% of the number of moles of zirconyl nitrate, and after stirring for 1.5 h, the wet gel is placed in a sealed container to obtain a wet gel, which is soaked in anhydrous ethanol for 48 h and aged at 50℃ for 21 h to obtain a preliminary aerogel, which is placed in a supercritical carbon dioxide drying oven to obtain a fluorinated modified zirconia aerogel, wherein the drying temperature is 50℃, the pressure is 30 MPa, and the time is 6.8 h; adding the fluorinated modified zirconia aerogel to isopropanol, wherein the solid-liquid mass ratio of the fluorinated modified zirconia aerogel to isopropanol is 1:28, and adding 0.15% of the mass of the fluorinated modified zirconia aerogel of polyvinylpyrrolidone to perform shearing dispersion, wherein the first rotation speed of shearing dispersion is 2000 rpm, the time is 15 min, the second rotation speed is 5000 rpm, and the time is 16 min, wherein each 5 min is paused for 1 min to prevent the temperature from being too high, to obtain a fluorinated modified zirconia aerogel dispersion liquid, wherein the particle size of the fluorinated modified zirconia aerogel is 10 μm;

[0143] S2: preparing an N-methylpyrrolidone solution of bis(4-aminophenyl) ether with a concentration of 0.2 g / mL, and adding diphthalic anhydride to obtain a reaction liquid E, wherein the molar ratio of diphthalic anhydride to bis(4-aminophenyl) ether is 1:1, and stirring for 4 h to obtain a polyimide precursor solution; adding 3-glycidyloxypropylmethyldiethoxysilane to obtain a silicone-modified solution, wherein the amount of 3-glycidyloxypropylmethyldiethoxysilane is 20% of the total mass of the polyimide precursor, and adjusting the pH to 4.7 using acetic acid to obtain a reaction liquid F, and stirring at 60℃ for 1.5 h to obtain a mixed liquid G, and stepwise heat treatment under nitrogen protection to obtain a reaction liquid H, wherein the first temperature of the stepwise heat treatment is 100℃, the first time is 2 h, the second temperature is 190℃, the second time is 2 h, the third temperature is 310℃, and the third time is 2.3 h, and cooling and post-treatment to obtain a silicone-polyimide hybrid resin, and mixing the silicone-polyimide hybrid resin with isopropanol at a mass ratio of 3.5:1 to obtain a silicone-polyimide hybrid resin dispersion liquid;

[0144] S3: mixing the silicone-polyimide hybrid resin dispersion liquid and the dispersant octylphenoxyl alcohol, wherein the feeding amount of the dispersant is 0.18% of the mass of the silicone-polyimide hybrid resin, after stirring uniformly, adding the fluorinated modified zirconium oxide aerogel dispersion liquid, the fluorinated modified interpenetrating network silicon carbide, and the gradient sustained-release type core-shell capsule after ultrasonic dispersion, stirring uniformly at low speed to obtain a solvent type aerogel corrosion-resistant and wear-resistant coating, wherein the mass ratio of the silicone-polyimide hybrid resin, the fluorinated modified zirconium oxide aerogel, the fluorinated modified interpenetrating network silicon carbide, and the gradient sustained-release type core-shell capsule is 100:8:5:2;

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

[0146] Z1: preparing a 0.12M methanol solution of 2-methylimidazole and a 0.1M methanol solution of zinc nitrate, adjusting the pH of the methanol solution of 2-methylimidazole to 11, and then adding 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, stirring for 35min, centrifuging, washing, and drying to obtain a metal organic framework; preparing a 10mg / mL ethanol dispersion of benzotriazole, and adding 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 thermal treatment at 120℃ for 60min, centrifuging, washing, and drying to obtain a sustained-release type inner core; dispersing the sustained-release type inner core in a Tris buffer with a pH of 9, wherein the concentration of the sustained-release type inner core is 3mg / mL, adding dopamine hydrochloride to obtain a reaction solution C, wherein the concentration of dopamine hydrochloride in the reaction solution C is 2.7mg / mL, and after stirring reaction, a suspension D is obtained; adding tetraethyl orthosilicate to an ethanol / water mixed solution to obtain a silicon coating solution, wherein the volume ratio of tetraethyl orthosilicate to ethanol is 1:5, adjusting the pH to 12 after adding ammonia water, and pre-hydrolyzing at room temperature for 3h to obtain a pre-hydrolysis liquid, adding the pre-hydrolysis liquid to the suspension D to obtain a reaction liquid E, wherein the mass ratio of dopamine hydrochloride to tetraethyl orthosilicate is 1:2, reacting at room temperature for 9h, centrifuging and washing, and drying to obtain a gradient sustained-release type core-shell capsule;

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

[0148] Z2: graphene powder was added to ethanol with a concentration of 5 mg / mL, and after ultrasonic dispersion, freeze-drying and foaming molding, a pretreatment template was obtained. The graphene deposition template was obtained by pre-sintering at 800℃ for 3.8h in an inert atmosphere. The three-dimensional interpenetrating network silicon carbide was obtained by chemical vapor infiltration by introducing a mixed gas into the reaction zone, wherein the volume ratio of methyltrichlorosilane to hydrogen in the mixed gas was 1:18, the chemical vapor infiltration temperature was 1300℃, the pressure was 15kPa, the time was 3.5h, and the gas flow rate was 70sccm; the fluorinated modified interpenetrating network silicon carbide was obtained by introducing carbon tetrafluoride gas into the plasma treatment device, wherein the power of the plasma treatment was 100W, the time was 80min, and the temperature was 100℃.

[0149] Comparative Example 1

[0150] The present comparative example provides a solvent type aerogel anti-corrosion and wear-resistant coating, which is different from Example 1 in that in Z1, the step of coating the slow-release core with polydopamine is omitted, and the other operation steps and process parameters are exactly the same as those of Example 1.

[0151] Comparative Example 2

[0152] The present comparative example provides a solvent type aerogel anti-corrosion and wear-resistant coating, which is different from Example 1 in that in Z1, the step of coating the slow-release core with silicon dioxide is omitted, and the other operation steps and process parameters are exactly the same as those of Example 1.

[0153] Comparative Example 3

[0154] The present comparative example provides a solvent type aerogel anti-corrosion and wear-resistant coating, which is different from Example 1 in that in S1, silicon dioxide aerogel is selected instead of zirconium oxide aerogel, and the other operation steps and process parameters are exactly the same as those of Example 1.

[0155] Comparative Example 4

[0156] The present comparative example provides a solvent type aerogel anti-corrosion and wear-resistant coating, which is different from Example 1 in that in S2, 3-glycidyloxypropylmethyldiethoxysilane is not added for silicone modification, and the other operation steps and process parameters are exactly the same as those of Example 1.

[0157] The solvent type aerogel anti-corrosion and wear-resistant coatings of Examples 1-4 and Comparative Examples 1-4 were tested for performance, and the specific process was as follows:

[0158] The wear resistance of the sample was tested according to GB / T 1768-2006;

[0159] The salt spray corrosion resistance of the sample was tested according to GB / T 1771-2007.

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

[0161] Table 1: Test results of the solvent type aerogel corrosion-resistant wear-resistant coating performance of Examples 1-4 and Comparative Examples 1-4

[0162] Wear resistance (1000 g / 1000 r) / mg Salt spray test (1000 h) 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] From the test results of Example 1 and Comparative Example 1, when the polydopamine coating of the slow-release type core is omitted, the release of the slow-release agent cannot be effectively regulated, the slow-release behavior becomes uncontrollable, and the situation of over-fast release or instantaneous release occurs. This will cause the corrosion inhibitor to dissipate too quickly in the corrosive environment, thereby reducing the long-acting corrosion protection effect provided by the coating, and the corrosion resistance of the coating is reduced; when the polydopamine coating of the slow-release type core is omitted, the mechanical stability of the core decreases, and the corrosion inhibitor may be released too early during the coating processing, leading to an increase in local non-uniformity of the coating, thereby indirectly reducing the wear resistance.

[0164] From the test results of Example 1 and Comparative Example 2, the silica shell layer acts as a physical barrier, significantly slowing down the release rate of the corrosion inhibitor, and at the same time 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 significantly accelerated, thereby reducing the long-acting corrosion protection effect provided by the coating, and the corrosion resistance of the coating is reduced; after omitting the silica coating, the core-shell structure loses the mechanical protection of the outer layer, and the corrosion inhibitor capsules are easily broken during processing and use, leading to 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 the problem.

[0165] From the test results of Example 1 and Comparative Example 3, when the silica aerogel is used to replace the zirconia aerogel, the chemical stability and corrosion resistance of the silica aerogel are far inferior to those of the zirconia aerogel, especially in acidic or alkaline environments, its chemical corrosion resistance is weak, leading to a significant decrease in the corrosion resistance of the coating; when the silica aerogel is used to replace the zirconia aerogel, the mechanical strength, particle size uniformity and interfacial bonding strength of the silica aerogel are significantly lower than those of the zirconia aerogel, and its shear resistance is poor, leading to easier wear of the coating under friction conditions; in addition, the fluorination modification effect of the silica aerogel is weak, further reducing its contribution to the overall performance of the coating.

[0166] From the test results of Example 1 and Comparative Example 4, it can be seen that the introduction of the silicone segment can form a low-surface-energy chemical inert barrier on the surface of the coating, enhance the hydrophobicity and anti-fouling performance of the coating, and thus indirectly improve the corrosion resistance. When the polyimide is not modified with 3-glycidyloxypropylmethyldiethoxysilane, the hydrophobicity of the coating decreases, the penetration of corrosive media such as water and ions into the coating is accelerated, and the corrosion resistance is slightly reduced. When the polyimide is not modified with 3-glycidyloxypropylmethyldiethoxysilane, the flexibility of the substrate and the interfacial bonding strength of the filler are both weakened, the filler is more likely to fall off during friction, and the wear resistance of the coating is reduced.

[0167] The above merely provides a specific implementation of the present application, but the protection scope of the present application is not limited thereto. It should be understood by those skilled in the art that any changes or replacements within the technical scope disclosed by the present application can be easily conceived by those skilled in the art, and all such changes and replacements fall within the protection scope and disclosure scope of the present application.

Claims

1. A method for preparing a solvent-based aerogel anticorrosive wear-resistant coating, characterized in that, The preparation method comprises: S1: dispersing zirconium oxynitrate in an ethanol / water solution to obtain a first dispersion liquid, adjusting the pH with hydrochloric acid, and then stirring at a constant temperature to obtain a zirconia sol, dispersing perfluorooctyltriethoxysilane in isopropanol to obtain a fluorinated solution, mixing the fluorinated solution with the zirconia sol, stirring, and then standing to obtain a wet gel, and post-treating to obtain fluorinated modified zirconia aerogel; shearing and dispersing the fluorinated modified zirconia aerogel in isopropanol to obtain a fluorinated modified zirconia aerogel dispersion liquid; S2: preparing an N-methylpyrrolidone solution of bis(4-aminophenyl) ether, adding diphthalic anhydride to obtain a polyimide precursor solution, adding 3-glycidyl ether oxypropyl methyl diethoxysilane, adjusting the pH to obtain a reaction liquid F, stirring and reacting, stepwise heat treatment to obtain a reaction liquid H, cooling and post-treating to obtain a silicone-polyimide hybrid resin; mixing the silicone-polyimide hybrid resin with isopropanol to obtain a silicone-polyimide hybrid resin dispersion liquid; S3: mixing the silicone-polyimide hybrid resin dispersion liquid and a dispersant, stirring uniformly, then adding the fluorinated modified zirconia aerogel dispersion liquid and fluorinated modified interpenetrating network silicon carbide, ultrasonic dispersing uniformly, then adding gradient sustained-release core-shell capsules, and stirring uniformly at a low speed to obtain a solvent-based aerogel corrosion-resistant and wear-resistant coating; The preparation method of the gradient sustained-release core-shell capsules is as follows: Z1: preparing a methanol solution of 2-methylimidazole, adjusting the pH, and then adding a methanol solution of zinc nitrate to obtain a mixed liquid A, reacting and treating to obtain a metal organic framework; adding benzotriazole to ethanol to obtain a mixed liquid B, solvent thermal treatment, and then treating to obtain a sustained-release inner core; dispersing the sustained-release inner core in a Tris buffer solution, adding dopamine hydrochloride to obtain a reaction liquid C, and reacting to obtain a suspension D; pre-hydrolyzing tetraethyl orthosilicate in an ethanol / water solution after adjusting the pH to obtain a pre-hydrolysis liquid, adding the pre-hydrolysis liquid to the suspension D, and reacting and treating at room temperature to obtain gradient sustained-release core-shell capsules; The preparation method of the fluorinated modified interpenetrating network silicon carbide is as follows: Z2: dispersing graphene in ethanol, freeze-drying and foaming to obtain a graphene deposition template, pre-sintering the graphene deposition template in an inert atmosphere to obtain a graphene deposition template, introducing a mixed gas to prepare three-dimensional interpenetrating network silicon carbide by chemical vapor infiltration, and introducing carbon tetrafluoride gas into a plasma treatment device to obtain fluorinated modified interpenetrating network silicon carbide.

2. The method for preparing a solvent-based aerogel anti-corrosion 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 liquid is adjusted to 3-4 with hydrochloric acid; The amount of perfluorooctyltriethoxysilane is 8-10% of the number of moles of zirconium oxynitrate; The solid-liquid mass ratio of the fluorinated modified zirconia aerogel to isopropanol is 1:20-30.

3. The method for preparing a solvent-based aerogel anti-corrosion and wear-resistant coating according to claim 1, characterized in that, In S2: The concentration of the N-methylpyrrolidone solution of bis(4-aminophenyl) ether is 0.1-0.2 g / mL; The molar ratio of diphthalic anhydride to bis(4-aminophenyl) ether is 1:1; The amount of 3-glycidyl ether oxypropyl methyl diethoxysilane is 15-20% of the mass of the polyimide precursor; The mass ratio of isopropanol to silicone-polyimide hybrid resin is 2.5-3.5:

1.

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

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

6. The method for preparing a solvent-based aerogel anti-corrosion and wear-resistant coating according to claim 1, 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 network silicon carbide plasma treatment is 50-100 W; The temperature of the three-dimensional interpenetrating network silicon carbide plasma treatment is 90-100℃; The time of the three-dimensional interpenetrating network silicon carbide plasma treatment is 60-80 min.

7. A solvent type aerogel corrosion-resistant and wear-resistant coating prepared by the preparation method of any one of claims 1-6.

8. The application of a solvent type aerogel corrosion-resistant and wear-resistant coating prepared by the preparation method of any one of claims 1-6 in ship manufacturing.