Active self-repairing anticorrosive paint for vibration sensor in severe corrosion environment as well as preparation method and application of active self-repairing anticorrosive paint

Abstract

The invention relates to the technical field of metal corrosion protection. The invention provides a preparation method of an active self-repairing anticorrosive coating for a vibration sensor in a severe corrosion environment. The preparation method comprises the following steps: (1) preparing mesoporous silica nanoparticles; (2) preparing carboxyl cerium dioxide nanoparticles; (3) preparing an activated carboxyl cerium dioxide nanoparticle mixed solution; (4) preparing a triazindene-accelerant M solution; (5) preparing a mesoporous silica loaded carboxyl cerium dioxide nanoparticle coated indene and accelerant M filler; and (6) uniformly stirring the filler obtained in the step (5) with epoxy resin to obtain the active self-repairing anticorrosive paint. The invention further provides an active self-repairing anticorrosive coating for the vibration sensor in the severe corrosion environment and application of the active self-repairing anticorrosive coating. According to the anticorrosive paint prepared by the invention, the performances of high carrier loading capacity, strong corrosion inhibitor protection effect, high pH reaction rate and the like are improved, and the performance defects of a traditional self-repairing coating are made up.

Description

Technical Field

[0001] The present invention relates to the technical field of metal corrosion protection, and particularly relates to an active self-healing anti-corrosion coating for vibration sensors in a severe corrosion environment, a preparation method thereof, and an application thereof. Background Art

[0002] Equipment operating in severe corrosion environments such as the ocean and mines will inevitably generate various vibrations. These vibrations bring many unpredictable negative impacts to the normal operation of the equipment. The marine environment has characteristics such as high temperature, high humidity, high salinity, and strong sunlight; the mine environment, especially the mine shaft environment, has characteristics such as high humidity (high relative humidity), rich oxygen, abundant harmful gases (CO2, SO2, H2S, nitrogen oxides), and a large amount of suspended coal and rock dust. They are very harsh and severe corrosion environments. For example, in an offshore wind turbine, the vibration of the tower barrel may cause the tower to tilt, and the vibration imbalance between the blades and the nacelle may lead to an overall collapse. Mine conveyor equipment usually generates continuous vibrations under heavy loads, which may cause loose connecting parts, belt deviation, or material spillage, affecting the stability of the overall structure. At this time, it is of great significance to detect the vibration behavior of various equipment in a timely manner and propose corresponding protection countermeasures. However, once various vibration sensor systems or devices are placed in such a harsh environment, even a tiny adsorbed liquid film or corrosion product on the main body material of the components will cause faults such as short circuits, open circuits, and poor contact in integrated circuits and electronic components, resulting in a reduction in the core components and sensitivity reliability of the vibration sensor, a shortened service life, affecting the normal service of production equipment, and causing huge economic losses. The organic coating protection technology stands out among many protection technologies for electronic and electrical equipment due to its advantages such as good anti-corrosion, moisture-proof, mildew-proof, low cost, and easy operation. However, the complex service environment will accelerate the deterioration, delamination, blistering, and penetration of the service coating on the sensor surface. At the same time, due to the coupling of environmental factors and various loads, the structure of the coating or metal will be damaged, causing a corrosion reaction. As the corrosion continues, the load-bearing capacity of the material will drop significantly, and in severe cases, it will lead to structural deformation or even fracture, directly threatening the integrity and safety of the metal structure. Therefore, the anti-corrosion work of vibration sensors in a severe corrosion environment is very important.

[0003] The anti-corrosion methods of vibration sensors mainly include coating protection and electrochemical protection methods. Organic coatings are the most widely used. For example, epoxy coatings have good adhesion, chemical resistance and wear resistance. Epoxy coatings can form a continuous protective film on the metal surface of vibration sensors, preventing corrosive media from contacting the metal matrix. However, their protection effect is single. To overcome these limitations, active intelligent anti-corrosion coatings that can respond to external influences are introduced, which can fill the gaps in single protection and self-healing, and enhance their protection ability. Inhibitor microcapsules are a technology that encapsulates inhibitors in tiny capsules. In the anti-corrosion coating system, when the coating is affected by external environmental factors (such as mechanical damage, pH change, etc.), the wall of the microcapsule will rupture or diffuse, thus releasing the inhibitor. The released inhibitor can form a protective film on the metal surface and inhibit the progress of the corrosion reaction. By adjusting the loading method and content of the inhibitor in the coating, the release rate of the inhibitor can be controlled. This method can achieve the slow release of the inhibitor and extend the time of its corrosion inhibition effect. However, the existing nano-containers loaded with inhibitors have a low content of inhibitors, resulting in unstable inhibitor loading or uncontrollable release mechanism, and weak coating protection effect. Traditional intelligent anti-corrosion coatings need to be recoated regularly to maintain their protection effect, increasing the maintenance cost and labor cost.

[0004] Chinese patent document CN106433409A discloses a preparation method of a self-healing anti-corrosion coating using urea-formaldehyde resin to encapsulate Chinese tallow kernel oil to form microcapsules; in terms of structure, a composite coating is composed of microcapsules (with vegetable oil as the core and resin as the shell) and rutile titanium dioxide, etc.; the microcapsules are mixed in waterborne epoxy resin, and after the scratch triggers damage, the vegetable oil contacts the air and oxidizes and cures into a film to repair the damage; the coating is environmentally friendly, economical, and has good salt water resistance and corrosion resistance; but there are obvious shortcomings, such as easy oxidation and failure of the oil during acidic high-temperature preparation, the release of microcapsules depends on mechanical rupture, the loading rate is low, and the performance decreases under high humidity.

[0005] Although the existing traditional preparation methods have low cost and simple process, the active substances are easy to inactivate, the efficiency of nanomaterials is insufficient, and the content of inhibitors loaded by nano-carriers is low, which cannot improve the corrosion inhibition rate of self-healing coatings.

[0006] The present invention proposes a preparation method of a self-healing anti-corrosion coating for sensors for vibration detection of equipment serving in a harsh corrosion environment, aiming to solve the technical problems of low inhibitor loading capacity of micro / nano containers and insufficient active protection efficiency of inhibitors. Summary of the Invention

[0007] The object of the present invention is to provide an active self - repairing anti - corrosion coating for vibration sensors in a severe corrosion environment, its preparation method and application. The present invention solves the problems of low content of corrosion inhibitors loaded in existing self - repairing anti - corrosion coatings, slow release rate and low protection efficiency in a severe corrosion environment. The active self - repairing anti - corrosion coating prepared by the present invention uses triazaindene and accelerator M as corrosion inhibitors, rod - shaped mesoporous silica nanoparticles encapsulating triazaindene and accelerator M as carriers for loading corrosion inhibitors, and cerium dioxide particles coated with triazaindene and accelerator M as capping devices as intelligent control switches for corrosion inhibitor release, so as to achieve excellent active corrosion protection effects. Compared with traditional corrosion inhibitor anti - corrosion coatings, the active self - repairing anti - corrosion coating provided by the present invention can preferably encapsulate corrosion inhibitors in rod - shaped nano - carriers, avoid direct contact and achieve a controllable release behavior. At the same time, the corrosion inhibitor carrying rate is high, and it can be repeatedly repaired in different pH environments, which can further enhance the corrosion protection performance. In the present invention, triazaindene is abbreviated as "BTA" for short; the chemical name of accelerator M is 2 - mercaptobenzothiazole, abbreviated as "MBT" for short; mesoporous silica nanoparticles are abbreviated as "HMSN" for short; cerium dioxide is abbreviated as "CeO2" for short.

[0008] To solve the above problems, the present invention provides the following technical solutions: A preparation method of an active self - repairing anti - corrosion coating for vibration sensors in a severe corrosion environment, comprising the following steps: (1) Prepare mesoporous silica nanoparticles; (2) Prepare carboxyl cerium dioxide nanoparticles; (3) Disperse the carboxyl cerium dioxide nanoparticles obtained in step (2) into water, then add 1 - (3 - dimethylaminopropyl) - 3 - ethylcarbodiimide, and continuously stir at room temperature for 1 - 3 h to obtain an activated carboxyl cerium dioxide nanoparticle mixed solution; (4) Prepare an aqueous sodium hydroxide solution, sequentially add cetyltrimethylammonium bromide, triazaindene and accelerator M, and continuously stir for 20 - 40 min until completely dissolved to obtain a triazaindene - accelerator M solution; (5) Add the mesoporous silica nanoparticles obtained in step (1) and the activated carboxyl cerium dioxide nanoparticle mixed solution obtained in step (3) into the triazaindene - accelerator M solution obtained in step (4), and then vigorously stir for 2 - 3 h to obtain a suspension of mesoporous silica nanoparticles - cerium dioxide - triazaindene - accelerator M; subsequently, centrifuge, wash and dry the suspension of mesoporous silica nanoparticles - cerium dioxide - triazaindene - accelerator M to obtain a filler of mesoporous silica - loaded carboxyl cerium dioxide nanoparticles coated with triazaindene and accelerator M; (6) Stir the mesoporous silica-supported carboxy-cerium dioxide nanoparticles coated with triazene and accelerator M filler obtained in step (5) evenly with epoxy resin to obtain an active self-healing anti-corrosion coating.

[0009] A preparation method of an active self-healing anti-corrosion coating for a vibration sensor in a severe corrosion environment as described above. The specific steps for preparing mesoporous silica nanoparticles in step (1) are as follows: Mix water and N,N-dimethylformamide to form a mixed solution, then dissolve cetyltrimethylammonium bromide in the mixed solution, add an aqueous ammonia solution and stir for 20 - 40 min, and then add tetraethyl orthosilicate and stir for 2 - 4 h. Mesoporous silica nanoparticles are obtained through centrifugation, washing, and vacuum drying.

[0010] A preparation method of an active self-healing anti-corrosion coating for a vibration sensor in a severe corrosion environment as described above. The specific steps for preparing carboxy-cerium dioxide nanoparticles in step (2) are as follows: Dissolve cerium nitrate hexahydrate in an aqueous methanol solution, then quickly add an aqueous ammonia solution and stir vigorously for 2 - 4 h to obtain a cerium dioxide product; subsequently, centrifuge and wash the cerium dioxide product to obtain a wet cerium dioxide product; disperse the wet cerium dioxide product in an aqueous citric acid solution and ultrasonically treat for 30 - 50 min, then add absolute ethanol to assist precipitation, centrifuge, collect the product, wash, and dry to obtain carboxy-cerium dioxide nanoparticles.

[0011] A preparation method of an active self-healing anti-corrosion coating for a vibration sensor in a severe corrosion environment as described above. In step (1), the aqueous ammonia solution is an aqueous ammonia solution with a mass percentage concentration of 25%, and the volume ratio of the aqueous ammonia solution to tetraethyl orthosilicate is (10 - 13):(10 - 13). Preferably, in step (1), the volume ratio of the aqueous ammonia solution to tetraethyl orthosilicate is 13:(10 - 12). Under this condition, rod-shaped silica nanoparticles can be prepared, which show more excellent corrosion inhibition effects than spherical silica nanoparticles and can store more corrosion inhibitors. Most preferably, in step (1), the volume ratio of the aqueous ammonia solution to tetraethyl orthosilicate is 13:10.

[0012] A preparation method of an active self - healing anti - corrosion coating for a vibration sensor in a severe corrosion environment as described above. In step (2), the methanol aqueous solution is a methanol aqueous solution with a mass percentage concentration of 50%, the ammonia aqueous solution is an ammonia aqueous solution with a mass percentage concentration of 25%, and the mass - to - volume ratio of cerium nitrate hexahydrate, methanol aqueous solution, and ammonia aqueous solution is (2 - 3):(40 - 45):(15 - 17), unit: g / mL / mL. Preferably, the mass - to - volume ratio of cerium nitrate hexahydrate, methanol aqueous solution, and ammonia aqueous solution is 2.55:42.5:16, unit: g / mL / mL. Under this condition, carboxyl - cerium dioxide nanoparticles can be prepared. Compared with ordinary cerium dioxide nanoparticles, carboxyl functional groups are introduced through surface modification, which can better combine with mesoporous silica to form a dense coating structure and enhance stability.

[0013] A preparation method of an active self - healing anti - corrosion coating for a vibration sensor in a severe corrosion environment as described above. In step (4), the mass ratio of triazaindene and accelerator M is (3 - 5):1. Preferably, in step (4), the mass ratio of triazaindene and accelerator M is (4 - 5):1. Under this condition, the hydrogen - bond interaction between triazaindene and accelerator M can promote their adsorption on the metal matrix surface and form an intelligent and dense protective film. Most preferably, in step (4), the mass ratio of triazaindene and accelerator M is 5:1.

[0014] A preparation method of an active self - healing anti - corrosion coating for a vibration sensor in a severe corrosion environment as described above. In step (6), the mass ratio of the mesoporous silica - loaded carboxyl - cerium dioxide nanoparticles coated with triazaindene and accelerator M filler to epoxy resin is (1 - 4):25. Most preferably, in step (6), the mass ratio of the mesoporous silica - loaded carboxyl - cerium dioxide nanoparticles coated with triazaindene and accelerator M filler to epoxy resin is 4:25. Under this condition, the mesoporous silica and carboxyl - cerium dioxide nanoparticles in the filler not only act as carriers of the self - healing anti - corrosion coating but also can form a good interfacial bond with epoxy resin, enhancing the synergistic effect during the self - healing process.

[0015] A preparation method of an active self-healing anti-corrosion coating for a vibration sensor in a harsh corrosion environment as described above. In step (3), the mass ratio of the carboxy cerium dioxide nanoparticles to 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide is (350-400):3. Most preferably, the mass ratio of the carboxy cerium dioxide nanoparticles to 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide is 400:3. Under this condition, the carboxyl groups on the surface of the carboxy cerium dioxide nanoparticles become more active and are more likely to form stable covalent bonds with amino groups or other nucleophilic groups in the coating matrix, thereby improving the overall stability and mechanical properties of the coating.

[0016] A preparation method of an active self-healing anti-corrosion coating for a vibration sensor in a harsh corrosion environment as described above. In step (5), the mass-to-volume ratio of the mesoporous silica nanoparticles obtained in step (1), the mixed solution of the activated carboxy cerium dioxide nanoparticles obtained in step (3), and the triazaindene-promoter M solution obtained in step (4) is 1:(40-45):(40-45), unit: g / mL / mL. Most preferably, in step (5), the mass-to-volume ratio of the mesoporous silica nanoparticles obtained in step (1), the mixed solution of the activated carboxy cerium dioxide nanoparticles obtained in step (3), and the triazaindene-promoter M solution obtained in step (4) is 1:45:45. Under this condition, by optimizing the ratio, the synergistic effect between the components is ensured, making the coating have more excellent corrosion resistance and self-healing ability.

[0017] The present invention selects two corrosion inhibitors, triazaindene and promoter M, and their preferred mass ratio is 5:1 to act on the bare metal substrate together. The combination of triazaindene and promoter M can promote their adsorption on the alloy surface through hydrogen bonds, forming a dense corrosion inhibitor film and slowing down metal corrosion. Among them, the two corrosion inhibitors are encapsulated in the mesoporous silica nanoparticles. Preferably, the mesoporous silica nanoparticles are rod-shaped, which have a higher loading capacity compared to the traditional spherical structure and can further improve the protection efficiency. Cerium dioxide is used as the responsive shell of the corrosion inhibitor, and cerium dioxide has a relatively fast response rate to acidic pH, which can increase the release rate of the corrosion inhibitor. Under acidic conditions, due to the exchange between cerium ions and hydrogen ions in cerium dioxide, the cerium dioxide encapsulating the corrosion inhibitor can dissolve quickly, resulting in the accelerated release of the internal corrosion inhibitors, triazaindene and promoter M, from the rod-shaped mesoporous silica. This structure forms a performance improvement with a high carrier loading capacity, a strong corrosion protection effect of the corrosion inhibitor, and a fast reaction rate, which can largely make up for the performance defects of traditional self-healing coatings.

[0018] Based on the same inventive concept, the present invention provides an active self-healing anti-corrosion coating prepared by the preparation method of an active self-healing anti-corrosion coating for a vibration sensor in a harsh corrosion environment as described above.

[0019] Based on the same inventive concept, the present invention provides an application of the above-mentioned active self-healing anti-corrosion coating in a severe corrosion environment.

[0020] For the above-mentioned application, the specific steps of the application are as follows: Coating the active self-healing anti-corrosion coating on the surface of a vibration sensor, and after the coating is dried and cured, an anti-permeation synergistic active repair coating with a thickness of 100-500 μm is formed.

[0021] Compared with the existing technologies, the beneficial effects and advantages of the present invention are: 1. The preparation method of an active self-healing anti-corrosion coating for a vibration sensor in a severe corrosion environment provided by the present invention synthesizes cerium dioxide that blocks the release of triazaindene and promotes the release of inhibitor M, and encapsulates it in rod-shaped mesoporous silica nanoparticles with a honeycomb pore structure, and prepares a self-healing anti-corrosion coating with a high loading dose. This coating breaks through the limitations of the single protection mechanism of traditional anti-corrosion coatings, and provides an innovative solution for solving the dynamic corrosion problems of metal components in extreme environments such as the ocean or mines.

[0022] 2. The self-healing anti-corrosion coating prepared by the preparation method of an active self-healing anti-corrosion coating for a vibration sensor in a severe corrosion environment provided by the present invention has the characteristic of repeated repair in different pH environments. When the coating is damaged and the corrosive medium reaches the metal surface through these defects, causing serious corrosion deterioration, due to the electrochemical action between ions, local cathodes and anodes will be generated on the surface of the substrate. Redox occurs on the local cathode and the local anode, resulting in a change in the local pH value of the substrate. The cerium dioxide particles will dissolve due to the pH change, releasing the internally encapsulated inhibitor triazaindene and promoter M. The inhibitor diffuses to the defect site and adsorbs on the metal substrate to form a dense protective film, which can resist the further corrosion of the corrosive medium.

[0023] 3. The active self-healing anti-corrosion coating provided by the present invention can significantly improve the self-healing protection rate and avoid the initial intrusion of corrosive media into the matrix to cause corrosion. Triazaindene and promoter M interact through hydrogen bonds, promoting co-adsorption on the surface of the metal matrix, forming a dense protective film, improving the protection rate and enhancing the protection effect.

[0024] 4. The active self-healing anti-corrosion coating provided by the present invention is inexpensive, simple to manufacture, has a high anti-corrosion efficiency, and its protection performance greatly improves the protection effect compared with traditional anti-corrosion coatings. It is suitable for the anti-corrosion of vibration sensors of service equipment in severe corrosion environments such as the ocean and mines. Description of the Drawings

[0025] Figure 1 It is the TEM morphology of the rod-shaped mesoporous silica nanoparticles prepared in Example 1 of the present invention; Figure 2 TEM morphology of the spherical mesoporous silica nanoparticles prepared in Example 3 of the present invention; Figure 3 SKP results of the active self-healing coating prepared in Example 1 of the present invention after being scratched and immersed in 3.5 wt.% NaCl solution for 0 days; Figure 4 SKP results of the active self-healing coating prepared in Example 1 of the present invention after being scratched and immersed in 3.5 wt.% NaCl solution for 2 days; Figure 5 SKP results of the active self-healing coating prepared in Example 1 of the present invention after being scratched and immersed in 3.5 wt.% NaCl solution for 4 days; Figure 6 SKP results of the active self-healing coating prepared in Example 1 of the present invention after being scratched and immersed in 3.5 wt.% NaCl solution for 6 days; Figure 7 EIS test results of the active self-healing anti-corrosion coating prepared in Example 1 and Comparative Example 1 of the present invention and the single inhibitor self-healing anti-corrosion coating prepared in Comparative Example 2; Figure 8 Observation test results of the |Z| value at 0.01 Hz of the active self-healing coating electrode prepared in Example 1 of the present invention after being scratched and immersed in 3.5 wt.% NaCl solution for 10 days; Figure 9 Observation test results of the |Z| value at 0.01 Hz of the single inhibitor self-healing coating electrode prepared in Comparative Example 3 of the present invention after being scratched and immersed in 3.5 wt.% NaCl solution for 10 days; Figure 10 Observation test results of the |Z| value at 0.01 Hz of the blank electrode prepared in the present invention after being scratched and immersed in 3.5 wt.% NaCl solution for 10 days; Figure 11 Thermogravimetric analysis data graphs of the rod-shaped mesoporous silica nanoparticles, active self-healing anti-corrosion coating and original components prepared in Example 1 of the present invention; Figure 12 Thermogravimetric analysis data graphs of the spherical mesoporous silica nanoparticles, active self-healing anti-corrosion coating and original components prepared in Example 3 of the present invention. Detailed implementation manners

[0026] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the content in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0027] Unless otherwise defined, all technical and scientific terms used in this specification have the same meaning as commonly understood by those skilled in the technical field to which the present invention belongs. The terms used in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used in this specification includes any and all combinations of one or more of the related listed items.

[0028] The experimental methods used in the following examples are all conventional methods unless otherwise specified.

[0029] The materials, reagents, etc. used in the following examples can be obtained from commercial sources unless otherwise specified.

[0030] Example 1 (1) 65 mL of water and 4.5 mL of N,N-dimethylformamide were mixed at room temperature to form a mixed solution. Then, 0.55 g of cetyltrimethylammonium bromide was dissolved in the mixed solution, 7.8 mL of an aqueous ammonia solution with a mass percentage concentration of 25% was added, and the mixture was stirred for 30 min. Subsequently, 6 mL of tetraethyl orthosilicate was added and stirred at room temperature for 4 h. Rod-shaped mesoporous silica nanoparticles were obtained through centrifugation, washing, and vacuum drying. The TEM morphology of the rod-shaped mesoporous silica nanoparticles prepared in this example is as Figure 1 shown.

[0031] (2) 2.55 g of cerium nitrate hexahydrate was dissolved in 42.5 mL of an aqueous methanol solution with a mass percentage concentration of 50% at 60 °C. Then, 16 mL of an aqueous ammonia solution with a mass percentage concentration of 25% was quickly added, and the mixture was vigorously stirred for 3 h to obtain a yellow cerium dioxide product. Subsequently, the yellow cerium dioxide product was centrifuged and then washed three times with absolute ethanol to obtain a wet cerium dioxide product. The wet cerium dioxide product was dispersed in 100 mL of an aqueous citric acid solution with a mass percentage concentration of 30% and ultrasonicated for 40 min. Then, 300 mL of absolute ethanol was added to assist precipitation, followed by centrifugation. The product was collected, washed three times with ethanol, and vacuum dried to obtain carboxyl cerium dioxide nanoparticles; (3) Disperse 2 g of the carboxyl cerium dioxide nanoparticles obtained in step (2) into 45 mL of water, add 15 mg of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, and continuously stir at room temperature for 1 h to obtain an activated carboxyl cerium dioxide nanoparticle mixed solution; (4) Dissolve 10 mg of sodium hydroxide in 45 mL of deionized water, add 150 mg of cetyltrimethylammonium bromide, 100 mg of triazene, and 20 mg of accelerator M during stirring in an 80 °C water bath, and continuously stir for 30 min until completely dissolved to obtain a triazene-accelerator M solution; (5) Add 1 g of the mesoporous silica nanoparticles obtained in step (1) and 45 mL of the activated carboxyl cerium dioxide nanoparticle mixed solution obtained in step (3) to 45 mL of the triazene-accelerator M solution obtained in step (4), and then vigorously stir for 2 h to obtain a suspension of mesoporous silica nanoparticles-cerium dioxide-triazene-accelerator M. Subsequently, centrifuge the suspension of mesoporous silica nanoparticles-triazene-accelerator M at 8000 rpm for 5 min, wash twice with deionized water, and dry in an oven at 70 °C for 24 h to obtain a filler of mesoporous silica-supported carboxyl cerium dioxide nanoparticles coated with triazene and accelerator M; (6) Stir the filler of mesoporous silica-supported carboxyl cerium dioxide nanoparticles coated with triazene and accelerator M obtained in step (5) and epoxy resin evenly according to a mass ratio of 4:25 to obtain an active self-healing anti-corrosion coating.

[0032] Example 2 (1) Mix 65 mL of water and 4.5 mL of N,N-dimethylformamide at room temperature to form a mixed solution, then dissolve 0.55 g of cetyltrimethylammonium bromide in the mixed solution, add 7.8 mL of an aqueous ammonia solution with a mass percentage concentration of 25% and stir for 30 min. Subsequently, add 7.2 mL of tetraethyl orthosilicate and stir at room temperature for 4 h. Obtain rod-shaped mesoporous silica nanoparticles through centrifugation, washing, and vacuum drying.

[0033] (2) Dissolve 2.55 g of cerium nitrate hexahydrate in 42.5 mL of a 50% methanol aqueous solution at 60 °C, then quickly add 16 mL of a 25% ammonia aqueous solution, and stir vigorously for 3 h to obtain a yellow cerium dioxide product. Subsequently, centrifuge the yellow cerium dioxide product, and then wash it three times with absolute ethanol to obtain a wet cerium dioxide product. Disperse the wet cerium dioxide product in 100 mL of a 30% citric acid aqueous solution and sonicate for 40 min, then add 300 mL of absolute ethanol to assist precipitation, centrifuge, collect the product, wash it three times with ethanol, and dry it under vacuum to obtain carboxyl cerium dioxide nanoparticles.

[0034] (3) Disperse 2 g of the carboxyl cerium dioxide nanoparticles obtained in step (2) in 45 mL of water, add 15 mg of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, and continuously stir at room temperature for 1 h to obtain an activated carboxyl cerium dioxide nanoparticle mixed solution.

[0035] (4) Dissolve 10 mg of sodium hydroxide in 45 mL of deionized water, add 150 mg of cetyltrimethylammonium bromide, 100 mg of triazene, and 20 mg of accelerator M during stirring in an 80 °C water bath, and continuously stir for 30 min until completely dissolved to obtain a triazene-accelerator M solution.

[0036] (5) Add 1 g of the mesoporous silica nanoparticles obtained in step (1) and 45 mL of the activated carboxyl cerium dioxide nanoparticle mixed solution obtained in step (3) to 45 mL of the triazene-accelerator M solution obtained in step (4), and then stir vigorously for 2 h to obtain a suspension of mesoporous silica nanoparticles-cerium dioxide-triazene-accelerator M. Subsequently, centrifuge the suspension of mesoporous silica nanoparticles-triazene-accelerator M at 8000 rpm for 5 min, wash it twice with deionized water, and dry it in an oven at 70 °C for 24 h to obtain a filler of mesoporous silica-supported carboxyl cerium dioxide nanoparticles coated with triazene and accelerator M.

[0037] (6) Stir the filler of mesoporous silica-supported carboxyl cerium dioxide nanoparticles coated with triazene and accelerator M obtained in step (5) and epoxy resin evenly according to a mass ratio of 4:25 to obtain an active self-healing anti-corrosion coating.

[0038] Example 3 (1) Mix 73 mL of water and 5.2 mL of N,N-dimethylformamide at room temperature to form a mixed solution. Then dissolve 0.63 g of cetyltrimethylammonium bromide in the mixed solution, add 6 mL of an aqueous ammonia solution with a mass percentage concentration of 25%, and stir for 30 min. Subsequently, add 7.2 mL of tetraethyl orthosilicate and stir at room temperature for 4 h. Obtain spherical mesoporous silica nanoparticles through centrifugation, washing, and vacuum drying. The TEM morphology of the spherical mesoporous silica nanoparticles prepared in this example is as shown in Figure 2 shown.

[0039] (2) Dissolve 2.55 g of cerium(III) nitrate hexahydrate in 42.5 mL of an aqueous methanol solution with a mass percentage concentration of 50% at 60 °C. Then quickly add 16 mL of an aqueous ammonia solution with a mass percentage concentration of 25%, and stir vigorously for 3 h to obtain a yellow cerium dioxide product. Subsequently, centrifuge the yellow cerium dioxide product and then wash it three times with absolute ethanol to obtain a wet cerium dioxide product. Disperse the wet cerium dioxide product in 100 mL of an aqueous citric acid solution with a mass percentage concentration of 30% and sonicate for 40 min. Then add 300 mL of absolute ethanol to assist precipitation, centrifuge, collect the product, wash it three times with ethanol, and dry it under vacuum to obtain carboxylated cerium dioxide nanoparticles.

[0040] (3) Disperse 2 g of the carboxylated cerium dioxide nanoparticles obtained in step (2) in 45 mL of water, add 15 mg of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, and continuously stir at room temperature for 1 h to obtain an activated carboxylated cerium dioxide nanoparticle mixed solution.

[0041] (4) Dissolve 10 mg of sodium hydroxide in 45 mL of deionized water. During the stirring process of heating in an 80 °C water bath, add 150 mg of cetyltrimethylammonium bromide, 100 mg of 2,2':6',2''-terpyridine, and 20 mg of accelerator M, and continue stirring for 30 min until completely dissolved to obtain a 2,2':6',2''-terpyridine-accelerator M solution.

[0042] (5) Add 1 g of the mesoporous silica nanoparticles obtained in step (1) and 45 mL of the activated carboxylated cerium dioxide nanoparticle mixed solution obtained in step (3) to 45 mL of the 2,2':6',2''-terpyridine-accelerator M solution obtained in step (4), and then stir vigorously for 2 h to obtain a suspension of mesoporous silica nanoparticles-cerium dioxide-2,2':6',2''-terpyridine-accelerator M. Subsequently, centrifuge the suspension of mesoporous silica nanoparticles-2,2':6',2''-terpyridine-accelerator M at 8000 rpm for 5 min, wash it twice with deionized water, and dry it in an oven at 70 °C for 24 h to obtain a filler of mesoporous silica-supported carboxylated cerium dioxide nanoparticles coated with 2,2':6',2''-terpyridine and accelerator M.

[0043] (6) Stir the mesoporous silica-supported carboxy-cerium dioxide nanoparticles coated with azonaphthalene and accelerator M filler obtained in step (5) and epoxy resin evenly at a mass ratio of 4:25 to obtain an active self-healing anti-corrosion coating.

[0044] Example 4 (1) Mix 65 mL of water and 4.5 mL of N,N-dimethylformamide at room temperature to form a mixed solution. Then dissolve 0.55 g of cetyltrimethylammonium bromide in the mixed solution, add 7.8 mL of an aqueous ammonia solution with a mass percentage concentration of 25%, stir for 30 min, and then add 6 mL of tetraethyl orthosilicate and stir at room temperature for 4 h. Obtain rod-shaped mesoporous silica nanoparticles through centrifugation, washing, and vacuum drying.

[0045] (2) Dissolve 2.55 g of cerium nitrate hexahydrate in 42.5 mL of an aqueous methanol solution with a mass percentage concentration of 50% at 60 °C, then quickly add 16 mL of an aqueous ammonia solution with a mass percentage concentration of 25%, and stir vigorously for 3 h to obtain a yellow cerium dioxide product. Then centrifuge the yellow cerium dioxide product, and wash it 3 times with absolute ethanol to obtain a wet cerium dioxide product. Disperse the wet cerium dioxide product in 100 mL of an aqueous citric acid solution with a mass percentage concentration of 30% and ultrasonically treat it for 40 min, then add 300 mL of absolute ethanol to assist precipitation, centrifuge, collect the product, wash it 3 times with ethanol, and vacuum dry it to obtain carboxy-cerium dioxide nanoparticles; (3) Disperse 2 g of the carboxy-cerium dioxide nanoparticles obtained in step (2) into 45 mL of water, add 15 mg of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, and continuously stir at room temperature for 1 h to obtain an activated carboxy-cerium dioxide nanoparticle mixed solution; (4) Dissolve 10 mg of sodium hydroxide in 45 mL of deionized water, add 150 mg of cetyltrimethylammonium bromide, 80 mg of azonaphthalene, and 20 mg of accelerator M during the stirring process of heating in a water bath at 80 °C, and continuously stir for 30 min until completely dissolved to obtain an azonaphthalene-accelerator M solution; (5) Add 1 g of the mesoporous silica nanoparticles obtained in step (1) and 45 mL of the mixed solution of activated carboxyl cerium dioxide nanoparticles obtained in step (3) to 45 mL of the solution of triazene-promoter M obtained in step (4), and then stir vigorously for 2 h to obtain a suspension of mesoporous silica nanoparticles-cerium dioxide-triazene-promoter M. Subsequently, centrifuge the suspension of mesoporous silica nanoparticles-triazene-promoter M at 8000 rpm for 5 min, wash it twice with deionized water, and dry it in an oven at 70 °C for 24 h to obtain a filler of mesoporous silica-supported carboxyl cerium dioxide nanoparticles coated with triazene and promoter M; (6) Stir the filler of mesoporous silica-supported carboxyl cerium dioxide nanoparticles coated with triazene and promoter M obtained in step (5) and epoxy resin evenly according to a mass ratio of 4:25 to obtain an active self-healing anti-corrosion coating.

[0046] Comparative Example 1 (1) Mix 65 mL of water and 4.5 mL of N,N-dimethylformamide at room temperature to form a mixed solution, then dissolve 0.55 g of cetyltrimethylammonium bromide in the mixed solution, add 7.8 mL of an aqueous ammonia solution with a mass percentage concentration of 25%, stir for 30 min, and then add 6 mL of tetraethyl orthosilicate and stir at room temperature for 4 h. Obtain rod-shaped mesoporous silica nanoparticles through centrifugation, washing, and vacuum drying.

[0047] (2) Dissolve 2.55 g of cerium nitrate hexahydrate in 42.5 mL of an aqueous methanol solution with a mass percentage concentration of 50% at 60 °C, then quickly add 16 mL of an aqueous ammonia solution with a mass percentage concentration of 25%, and stir vigorously for 3 h to obtain a yellow cerium dioxide product. Subsequently, centrifuge the yellow cerium dioxide product, and then wash it 3 times with absolute ethanol to obtain a wet cerium dioxide product. Disperse the wet cerium dioxide product in 100 mL of an aqueous citric acid solution with a mass percentage concentration of 30% and ultrasonically treat it for 40 min, then add 300 mL of absolute ethanol to assist precipitation, centrifuge, collect the product, wash it 3 times with ethanol, and vacuum dry it to obtain carboxyl cerium dioxide nanoparticles.

[0048] (3) Disperse 2 g of the carboxyl cerium dioxide nanoparticles obtained in step (2) in 45 mL of water, add 15 mg of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, and continuously stir at room temperature for 1 h to obtain a mixed solution of activated carboxyl cerium dioxide nanoparticles.

[0049] (4) Dissolve 10 mg of sodium hydroxide in 45 mL of deionized water. During the stirring process of heating in a water bath at 80 °C, add 150 mg of cetyltrimethylammonium bromide and 100 mg of terpyridine, and continue stirring for 30 min until completely dissolved to obtain a terpyridine solution.

[0050] (5) Add 1 g of the mesoporous silica nanoparticles obtained in step (1) and 45 mL of the mixed solution of activated carboxyl cerium dioxide nanoparticles obtained in step (3) to 45 mL of the terpyridine solution obtained in step (4), and then stir vigorously for 2 h to obtain a suspension of mesoporous silica nanoparticles - cerium dioxide - terpyridine. Subsequently, centrifuge the suspension of mesoporous silica nanoparticles - cerium dioxide - terpyridine at 8000 rpm for 5 min, wash it twice with deionized water, and dry it in an oven at 70 °C for 24 h to obtain a filler of mesoporous silica supported carboxyl cerium dioxide nanoparticles coated with terpyridine.

[0051] (6) Stir the filler of mesoporous silica supported carboxyl cerium dioxide nanoparticles coated with terpyridine obtained in step (5) and epoxy resin evenly according to a mass ratio of 4:25 to obtain a single inhibitor self - repairing anti - corrosion coating.

[0052] Comparative Example 2 (1) Mix 65 mL of water and 4.5 mL of N,N - dimethylformamide at room temperature to form a mixed solution. Then dissolve 0.55 g of cetyltrimethylammonium bromide in the mixed solution, add 7.8 mL of an aqueous ammonia solution with a mass percentage concentration of 25%, stir for 30 min, and then add 6 mL of tetraethyl orthosilicate and stir at room temperature for 4 h. Obtain rod - shaped mesoporous silica nanoparticles through centrifugation, washing, and vacuum drying.

[0053] (2) Dissolve 2.55 g of cerium(III) nitrate hexahydrate in 42.5 mL of an aqueous methanol solution with a mass percentage concentration of 50% at 60 °C, then quickly add 16 mL of an aqueous ammonia solution with a mass percentage concentration of 25%, and stir vigorously for 3 h to obtain a yellow cerium dioxide product. Subsequently, centrifuge the yellow cerium dioxide product, and then wash it 3 times with absolute ethanol to obtain a wet cerium dioxide product. Disperse the wet cerium dioxide product in 100 mL of an aqueous citric acid solution with a mass percentage concentration of 30% and ultrasonically treat it for 40 min, then add 300 mL of absolute ethanol to assist precipitation, centrifuge, collect the product, wash it 3 times with ethanol, and vacuum dry it to obtain carboxyl cerium dioxide nanoparticles.

[0054] (3) Disperse 2 g of the carboxyl cerium dioxide nanoparticles obtained in step (2) in 45 mL of water, then add 15 mg of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, and continuously stir at room temperature for 1 h to obtain an activated carboxyl cerium dioxide nanoparticle mixed solution.

[0055] (4) Dissolve 10 mg of sodium hydroxide in 45 mL of deionized water, add 150 mg of cetyltrimethylammonium bromide and 100 mg of accelerator M during stirring in a water bath at 80 °C, and continuously stir for 30 min until completely dissolved to obtain an accelerator M solution.

[0056] (5) Add 1 g of the mesoporous silica nanoparticles obtained in step (1) and 45 mL of the activated carboxyl cerium dioxide nanoparticle mixed solution obtained in step (3) to 45 mL of the accelerator M solution obtained in step (4), and then vigorously stir for 2 h to obtain a suspension of mesoporous silica nanoparticles-cerium dioxide-accelerator M. Subsequently, centrifuge the suspension of mesoporous silica nanoparticles-cerium dioxide-accelerator M at 8000 rpm for 5 min, wash twice with deionized water, and dry in an oven at 70 °C for 24 h to obtain a filler of mesoporous silica-supported carboxyl cerium dioxide nanoparticles coated with accelerator M.

[0057] (6) Stir the filler of mesoporous silica-supported carboxyl cerium dioxide nanoparticles coated with accelerator M obtained in step (5) and epoxy resin evenly according to a mass ratio of 4:25 to obtain a single inhibitor self-healing anti-corrosion coating.

[0058] Comparative Example 3 (1) Mix 65 mL of water and 4.5 mL of N,N-dimethylformamide at room temperature to form a mixed solution, then dissolve 0.55 g of cetyltrimethylammonium bromide in the mixed solution, add 7.8 mL of an aqueous ammonia solution with a mass percentage concentration of 25%, stir for 30 min, and then add 6 mL of tetraethyl orthosilicate and stir at room temperature for 4 h. Obtain rod-shaped mesoporous silica nanoparticles through centrifugation, washing, and vacuum drying.

[0059] (2) Dissolve 2.55 g of cerium nitrate hexahydrate in 42.5 mL of a 50% methanol aqueous solution at 60 °C, then quickly add 16 mL of a 25% ammonia aqueous solution, and stir vigorously for 3 h to obtain a yellow cerium dioxide product. Subsequently, centrifuge the yellow cerium dioxide product, and then wash it three times with absolute ethanol to obtain a wet cerium dioxide product. Disperse the wet cerium dioxide product in 100 mL of a 30% citric acid aqueous solution and sonicate for 40 min, then add 300 mL of absolute ethanol to assist precipitation, centrifuge, collect the product, wash it three times with ethanol, and dry it under vacuum to obtain carboxyl cerium dioxide nanoparticles.

[0060] (3) Disperse 2 g of the carboxyl cerium dioxide nanoparticles obtained in step (2) into 45 mL of water, add 15 mg of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, and continuously stir at room temperature for 1 h to obtain an activated carboxyl cerium dioxide nanoparticle mixed solution.

[0061] (4) Dissolve 10 mg of sodium hydroxide in 45 mL of deionized water and stir until completely dissolved to obtain a sodium hydroxide solution; add 0.25 mL of 1 M HCl to the sodium hydroxide solution to adjust the pH to 9 to obtain a weakly basic sodium hydroxide solution; add 150 mg of cetyltrimethylammonium bromide and 100 mg of sodium phytate to the weakly basic sodium hydroxide solution during stirring in a 60 °C water bath, and continuously stir for 30 min until completely dissolved, and cool to obtain a sodium phytate solution.

[0062] (5) Add 1 g of the mesoporous silica nanoparticles obtained in step (1) and 45 mL of the activated carboxyl cerium dioxide nanoparticle mixed solution obtained in step (3) to 45 mL of the sodium phytate solution obtained in step (4), and then stir vigorously for 2 h to obtain a suspension of mesoporous silica nanoparticles-cerium dioxide-sodium phytate. Subsequently, centrifuge the suspension of mesoporous silica nanoparticles-cerium dioxide-sodium phytate at 8000 rpm for 5 min, wash it twice with deionized water, and dry it in an oven at 70 °C for 24 h to obtain a filler of mesoporous silica-supported carboxyl cerium dioxide nanoparticles coated with sodium phytate.

[0063] (6) Stir the filler of mesoporous silica-supported carboxyl cerium dioxide nanoparticles coated with sodium phytate obtained in step (5) and epoxy resin evenly according to a mass ratio of 4:25 to obtain a single inhibitor self-healing anti-corrosion coating.

[0064] Test Example Test objects: Self-healing anti-corrosion coatings prepared in Example 1, Example 3, Comparative Example 1, Comparative Example 2, and Comparative Example 3.

[0065] Test items: (1) Electrochemical impedance (EIS): Refer to "ISO 16773 - Protective anticorrosive coatings using electrochemical impedance spectroscopy"; (2) Transmission electron microscopy (TEM): Refer to "ASTM E2859 - Standard guide for measuring the size of nanoparticles using transmission electron microscopy"; (3) Scanning Kelvin probe (SKP): Refer to "ASTM G3 - Standard practice for specification of practices applicable to electrochemical measurements in corrosion testing"; (4) Thermogravimetric analysis (TG): Refer to "ASTM E1131 - Standard test method for thermogravimetric compositional analysis";

[0066] The surface morphologies of the mesoporous silica nanoparticles prepared in Example 1 and Example 3 were observed by transmission electron microscopy (TEM), as Figure 1 and Figure 2 shown.

[0067] The surface potential difference of the active self - healing anticorrosive coating prepared in Example 1 was measured by moving a scanning Kelvin probe (SKP) on the coating surface, as Figures 3 - 6 shown.

[0068] The corrosion resistance and its protection mechanism of the self - healing anticorrosive coatings prepared in Example 1, Comparative Example 1 and Comparative Example 2 were evaluated by electrochemical impedance spectroscopy (EIS) non - destructive testing technology, as Figure 7 shown.

[0069] The corrosion resistance of the self - healing anticorrosive coating electrodes prepared in Example 1 and Comparative Example 3 and the blank electrode was measured by electrochemical impedance spectroscopy (EIS) to evaluate |Z| at 0.01 Hz, as Figures 8 - 10 shown.

[0070] The loading amounts of corrosion inhibitors loaded on mesoporous silica with different morphologies were analyzed by thermogravimetric analysis (TG) for the mesoporous silica nanoparticles, active self - healing anticorrosive coatings and original components prepared in Example 1 and Example 3, as Figures 11 - 12 shown.

[0071] Figure 1 This is the TEM morphology of the rod - shaped silica prepared in Example 1 of the present invention.

[0072] Figure 2 This is the TEM morphology of the traditional spherical mesoporous silica microspheres prepared in Example 2 of the present invention.

[0073] Above Figures 1 - 2 It can be seen that mesoporous silica has advantages such as surface modifiability and good biocompatibility. Among them, Figure 1 is the rod - shaped mesoporous silica nanoparticles prepared in Example 1. By comparison,Figure 2 It can be seen from the spherical mesoporous silica nanoparticles prepared in Example 2 that the rod-shaped mesoporous silica has a larger pore volume and a highly ordered mesoporous structure, significantly improving the loading amount of the corrosion inhibitor and enhancing the corrosion inhibition rate of the corrosion inhibitor. Figure 1 The rod-shaped structure in Figure 2 shows a more excellent corrosion inhibition effect compared to the spherical structure in

[0074] Figure 3 This is the SKP result of the active self-healing coating prepared in Example 1 of the present invention after being scratched and immersed in a 3.5 wt.% NaCl solution for 0 days.

[0075] Figure 4 This is the SKP result of the active self-healing coating prepared in Example 1 of the present invention after being scratched and immersed in a 3.5 wt.% NaCl solution for 2 days; Figure 5 This is the SKP result of the active self-healing coating prepared in Example 1 of the present invention after being scratched and immersed in a 3.5 wt.% NaCl solution for 4 days; Figure 6 This is the SKP result of the active self-healing coating prepared in Example 1 of the present invention after being scratched and immersed in a 3.5 wt.% NaCl solution for 6 days.

[0076] The above Figures 3 to 6 are the SKP results of the self-healing coating prepared by the present invention after being scratched and immersed in a 3.5 wt.% NaCl solution for 0, 2, 4, and 6 days. The scratch repair process of the self-healing coating in a simulated seawater environment can be clearly presented through the dynamic change of the surface potential distribution. From Figure 3 it can be seen that at 0 day, the potential in the scratched center area is significantly lower than that of the surrounding intact coating, forming a highly active anode area, with a risk of local corrosion, and the self-healing process has not started yet. From Figure 4 it can be seen that after soaking for 2 days, the potential in the scratched area gradually rises, the potential difference between some areas and the coating potential decreases, and a "ring-shaped high-potential band" appears outside the scratch, indicating a rapid response of the self-healing mechanism. From Figure 5 it can be seen that when soaked to the 4th day, the potential in the scratched center area further approaches the coating value, the color transition is relatively gentle, the proportion of the red area increases, and the potential non-uniformity is improved, indicating that the corrosion inhibitor has completed the initial coverage of the exposed metal and the repair layer gradually forms a protective barrier. From Figure 6It can be seen that after 6 days of immersion, the potential difference between the scratched area and the surrounding coating decreases significantly, and the spatial potential distribution shows a homogenized characteristic. This indicates that the repair layer has constructed a continuous and dense protective layer, and the potential of the undamaged area remains stable within 6 days, proving that the coating matrix is structurally intact under long-term immersion and is not significantly affected. From Figures 3 to 6 The SKP results analysis of Figures 3 to 6 shows that the self-healing coating has an obvious repair effect on the scratched area. As the immersion time increases, the surface potential tends to be uniform, the self-healing process is ongoing, and the potential non-uniformity of the scratched area gradually decreases, achieving the self-healing effect.

[0077] Figure 7 This is the EIS test result of the active self-healing anti-corrosion coating prepared in Example 1 and Comparative Example 1 of the present invention and the single inhibitor self-healing anti-corrosion coating prepared in Comparative Example 2. Figure 7 In Example 1, Comparative Example 1, and Comparative Example 2, the inhibitors are triazaindene and accelerator M, triazaindene, and accelerator M, respectively. The coated electrodes of Example 1, Comparative Example 1, and Comparative Example 2 are immersed in a NaCl solution with pH = 7 for a 7-day immersion experiment, and the change trend of impedance is observed. From Figure 7 It can be seen that the change trend of the |Z| value of the coating prepared in Example 1 is greater than that of the coatings prepared in Comparative Example 1 and Comparative Example 2, indicating that the two inhibitors have a synergistic effect and have a stronger corrosion inhibition ability compared to a single inhibitor.

[0078] Figure 8 This is the test result of observing the |Z| value at 0.01 Hz of the active self-healing coating electrode prepared in Example 1 of the present invention after being scratched and immersed in a 3.5 wt.% NaCl solution for 10 days.

[0079] Figure 9 This is the test result of observing the |Z| value at 0.01 Hz of the single inhibitor self-healing coating electrode prepared in Comparative Example 3 of the present invention after being scratched and immersed in a 3.5 wt.% NaCl solution for 10 days.

[0080] Figure 10 This is the test result of observing the |Z| value at 0.01 Hz of the blank electrode prepared in the present invention after being scratched and immersed in a 3.5 wt.% NaCl solution for 10 days.

[0081] Figures 8 - 10 It can be seen that through the electrochemical impedance test of the three groups of electrodes in a 3.5% NaCl solution, the self-healing characteristics of the coating and the corrosion protection difference from the blank substrate can be visually compared. Figure 8 The component of the electrode self-healing coating is mesoporous silica loaded with carboxy cerium dioxide nanoparticles coated with triazaindene and accelerator M, Figure 9The component of the electrode self-repairing coating is phytic acid-coated cerium dioxide nanoparticles loaded on mesoporous silica and coated with carboxyl cerium dioxide nanoparticles. Figure 10 is a blank electrode. From Figure 8 it can be seen that |Z| 0.01Hz has an obvious rising and falling trend, rising rapidly at 0 d and reaching the maximum at 3 d, indicating that mechanical damage causes the rapid penetration of corrosive media; it starts to decline at 4 d and stabilizes until 7 d, which indicates that the release of triazene-promoter M in Example 1 effectively inhibits the corrosion expansion to a certain extent. From Figure 9 it can be seen that |Z| 0.01Hz shows a downward trend at 0-2 d, indicating that the corrosion process starts, and rises at 25 d, indicating the release of the corrosion inhibitor and the inhibition of the corrosion process. From Figure 10 it can be seen that the blank group only shows a simple monotonic decrease, corresponding to the overall corrosion characteristics of the metal substrate, reflecting that the unprotected metal substrate rapidly undergoes a corrosion reaction in the electrolyte. When the coating in Example 1 encounters a corrosive medium, it can rapidly release the corrosion inhibitor to interrupt the corrosion process. On the contrary, in Comparative Example 3, a corrosion reaction occurs when the corrosive medium reaches the substrate, and the corrosion inhibitor is released at 2 d to inhibit the corrosion process. This shows that the self-repairing coating in Example 1 can improve the protection rate against corrosion reactions, and the release of triazene-promoter M can timely inhibit the corrosion process.

[0082] Figure 11 This is the thermogravimetric analysis data graph of the rod-shaped mesoporous silica nanoparticles, the active self-repairing anti-corrosion coating, and the original components prepared in Example 1 of the present invention. The figure shows the rod-shaped mesoporous silica nanoparticles prepared in step (1) of Example 1 (a1), the cerium dioxide prepared in step (2) of Example 1 (b), the rod-shaped mesoporous silica loaded with carboxyl cerium dioxide nanoparticles coated with triazene and promoter M, that is, the active self-repairing anti-corrosion coating prepared in Example 1 (c1), promoter M (d), and triazene (e). From Figure 11 it can be seen that the rod-shaped mesoporous silica has a weight loss of about 5% from 0 °C to 800 °C, showing high thermal stability. The weight loss of cerium dioxide is less than 2%, and the thermal stability is extremely high. The curve (c1) starts from 100% at 0 °C and drops to about 95% at 200 °C. The weight drops significantly between 200 °C and 400 °C and is about 80% at 400 °C. Then it continues to drop slowly and stabilizes at 69% at 800 °C, with a total weight loss of 31%. From Figure 11 it can be obtained that the loading rate of the rod-shaped mesoporous silica loaded with the corrosion inhibitor in Example 1 is about 31%.

[0083] Figure 12TG analysis data graphs of the spherical mesoporous silica nanoparticles, active self-healing anticorrosive coatings, and original components prepared in Example 3 of the present invention. The figure shows the spherical mesoporous silica nanoparticles (a2) prepared in step (1) of Example 3, cerium dioxide (b) prepared in step (2) of Example 3, spherical mesoporous silica-supported carboxy cerium dioxide nanoparticles coated with triazene and accelerator M, i.e., the active self-healing anticorrosive coating (c2) prepared in Example 3, accelerator M (d), and triazene (e). From Figure 12 It can be seen that the weight loss part of the curve (c2) of spherical mesoporous silica-supported triazene-accelerator M corresponds to the decomposition of triazene-accelerator M. Therefore, the loading amount of the corrosion inhibitor in Example 3 is about 21-22%. By comparison, it can be known that under similar synthesis conditions, the corrosion inhibitor loading rate of rod-shaped mesoporous silica is 31%, which is higher than 21-22% of spherical mesoporous silica. This further shows that rod-shaped mesoporous silica has better performance in loading corrosion inhibitors.

[0084] It should be noted that the specific embodiments are only relatively representative examples of the present invention. Obviously, the technical solutions of the present invention are not limited to the above embodiments and there can be many variations. Those of ordinary skill in the art who obtain the present invention clearly disclosed or without any doubt according to the written description of the document shall be considered as the scope protected by this patent.

Claims

1. A method for preparing an active self-repairing anti-corrosion coating for a vibration sensor in a severe corrosive environment, characterized in that: The following steps are involved: (1) Preparation of mesoporous silica nanoparticles; (2) Preparation of carboxylated cerium dioxide nanoparticles; (3) dispersing the carboxyl cerium dioxide nanoparticles obtained in step (2) into water, adding 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, and continuously stirring at room temperature for 1 to 3 hours to obtain a mixed solution of activated carboxyl cerium dioxide nanoparticles; (4) Prepare a sodium hydroxide aqueous solution, add hexadecyltrimethylammonium bromide, triazoline and promoter M in sequence, and continue stirring for 20 to 40 minutes until they are completely dissolved to obtain a triazoline-promoter M solution; (5) adding the mixed solution of the mesoporous silica nanoparticles obtained in step (1) and the activated carboxyl cerium dioxide nanoparticles obtained in step (3) to the triazole-promoter M solution obtained in step (4), and then vigorously stirring for 2 to 3 hours to obtain a suspension of mesoporous silica nanoparticles-cerium dioxide-triazole-promoter M; Subsequently, the mesoporous silica nanoparticle-cerium dioxide-indolizine-promoter M suspension is centrifuged, washed, and dried to obtain mesoporous silica-supported carboxyl cerium dioxide nanoparticles coated with indolizine and promoter M filler; (6) The mesoporous silica-loaded carboxyl cerium dioxide nanoparticles obtained in step (5) are coated with triazole and accelerator M filler and epoxy resin and mixed evenly to obtain an active self-healing anti-corrosion coating.

2. The method for preparing an active self-repairing anti-corrosion coating for a vibration sensor in a severe corrosive environment according to claim 1, characterized in that: The specific steps of preparing mesoporous silica nanoparticles in step (1) are as follows: water and N,N-dimethylformamide are mixed to form a mixed solution, and then hexadecyltrimethylammonium bromide is dissolved in the mixed solution, an aqueous ammonia solution is added and stirred for 20 to 40 minutes, and then tetraethyl orthosilicate is added and stirred for 2 to 4 hours, and mesoporous silica nanoparticles are obtained by centrifugation, washing and vacuum drying.

3. The method for preparing an active self-repairing anti-corrosion coating for a vibration sensor in a severe corrosive environment according to claim 1, characterized in that: The specific steps of preparing carboxyl cerium dioxide nanoparticles in step (2) are as follows: dissolving cerium nitrate hexahydrate in a methanol aqueous solution, then quickly adding an ammonia aqueous solution, and vigorously stirring for 2 to 4 hours to obtain a cerium dioxide product; then centrifuging the cerium dioxide product and washing it to obtain a wet cerium dioxide product; The wet cerium dioxide product is dispersed in a citric acid aqueous solution and ultrasonically treated for 30 to 50 minutes, and then anhydrous ethanol is added to assist precipitation, centrifuged, and the product is collected, washed, and dried to obtain carboxyl cerium dioxide nanoparticles.

4. The method for preparing an active self-repairing anti-corrosion coating for a vibration sensor in a severe corrosive environment according to claim 2, characterized in that: In the step (1), the aqueous ammonia solution is an aqueous ammonia solution with a mass percentage concentration of 25%, and the volume ratio of the aqueous ammonia solution to tetraethyl orthosilicate is (10-13):(10-13).

5. The method for preparing an active self-repairing anti-corrosion coating for a vibration sensor in a severe corrosive environment according to claim 3, characterized in that: In the step (2), the methanol aqueous solution is a methanol aqueous solution with a mass percentage concentration of 50%, the ammonia aqueous solution is an ammonia aqueous solution with a mass percentage concentration of 25%, and the mass volume ratio of the cerium nitrate hexahydrate, the methanol aqueous solution, and the ammonia aqueous solution is (2-3): (40-45): (15-17), unit: g / mL / mL.

6. The method for preparing an active self-repairing anti-corrosion coating for a vibration sensor in a severe corrosive environment according to claim 1, characterized in that: In the step (4), the mass ratio of the triazoline to the promoter M is (3-5):

1.

7. The method for preparing an active self-repairing anti-corrosion coating for a vibration sensor in a severe corrosive environment according to claim 1, characterized in that: In the step (6), the mass ratio of the mesoporous silica-supported carboxyl cerium dioxide nanoparticles coated with triazole and the accelerator M filler to the epoxy resin is (1-4):

25.

8. An active self-repairing anti-corrosion coating prepared by the method for preparing an active self-repairing anti-corrosion coating for a vibration sensor in a severe corrosive environment as described in any one of claims 1 to 7.

9. Use of the active self-repairing anti-corrosion coating as claimed in claim 8 in a vibration sensor.

10. The use according to claim 9, characterized in that: The specific application steps are as follows: applying the active self-repairing anti-corrosion coating to the surface of the sensor, and after the coating is dried and cured, forming an anti-seepage synergistic active repair coating with a thickness of 100 to 500 μm.

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