An active self-repairing anti-corrosion coating for vibration sensors in harsh corrosive environments, and its preparation method and application

Abstract

The present invention relates to the technical field of metal corrosion protection. The present invention provides a method for preparing an active self-repairing anti-corrosion coating for a vibration sensor in a harsh corrosive environment, comprising the following steps: (1) preparing mesoporous silica nanoparticles; (2) preparing carboxyl cerium dioxide nanoparticles; (3) preparing a mixed solution of activated carboxyl cerium dioxide nanoparticles; (4) preparing a triazole-promoter M solution; (5) preparing a filler containing mesoporous silica-loaded carboxyl cerium dioxide nanoparticles coated with triazole and promoter M; and (6) uniformly stirring the filler obtained in step (5) with epoxy resin to obtain an active self-repairing anti-corrosion coating. The present invention also provides an active self-repairing anti-corrosion coating for a vibration sensor in a harsh corrosive environment and its application. The anti-corrosion coating prepared by the present invention has improved properties such as high carrier loading, strong corrosion inhibitor protection, and fast pH reaction rate, thereby making up for the performance defects of traditional self-repairing coatings.

Description

Technical Field

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

[0002] Equipment operating in harsh, corrosive environments, such as the ocean and mines, inevitably generates various types of vibration. These vibrations can have numerous unpredictable negative impacts on the equipment's normal operation. Marine environments are characterized by high temperatures, high humidity, high salinity, and strong sunlight. Mining environments, particularly those in underground pits, are characterized by high humidity (high relative humidity), rich oxygen, abundant harmful gases (CO2, SO2, H2S, and nitrogen oxides), and high levels of suspended coal and rock dust. These environments are extremely harsh and corrosive. For example, tower vibration in offshore wind turbines can cause the tower to tilt, and vibration imbalance between the blades and the nacelle can lead to collapse. Mining conveying equipment often experiences continuous vibration under heavy loads, which can cause loosening of connections, deviation of conveyor belts, or material spillage, compromising overall structural stability. Therefore, timely detection of vibration behavior in various types of equipment and the development of appropriate protective measures are crucial. However, once various vibration sensor systems or devices are exposed to such harsh environments, even trace amounts of adsorbed liquid films or corrosion products on the component body can cause short circuits, open circuits, and poor contact in integrated circuits and electronic components. This reduces the reliability of the vibration sensor's core components and sensitivity, shortens the service life, and impacts the normal operation of production equipment, resulting in significant economic losses. Organic coating protection technology, with its advantages of excellent corrosion resistance, moisture and mildew resistance, low cost, and ease of operation, has become a leading technology for protecting electronic and electrical equipment. However, complex service environments can accelerate the degradation, delamination, blistering, and penetration of the service coating on the sensor surface. Furthermore, the coupling of environmental factors with various loads can damage the coating or metal structure, causing corrosion reactions. As corrosion continues, the material's load-bearing capacity decreases significantly. In severe cases, the structure can deform or even fracture, directly threatening the integrity and safety of the metal structure. Therefore, corrosion protection for vibration sensors in harsh corrosive environments is crucial.

[0003] Corrosion protection for vibration sensors primarily involves coating and electrochemical methods. Organic coatings are the most widely used. Epoxy coatings, for example, offer excellent adhesion, chemical resistance, and wear resistance. Epoxy coatings form a continuous protective film on the metal surface of vibration sensors, preventing corrosive media from contacting the metal substrate. However, their protective effect is limited. To overcome these limitations, the introduction of intelligent anti-corrosion coatings that react to external influences and respond to external influences has addressed the gaps in single-layer protection and self-healing, enhancing their protective capabilities. Corrosion inhibitor microencapsulation is a technology that encapsulates corrosion inhibitors within tiny capsules. In an anti-corrosion coating system, when the coating is exposed to environmental factors (such as mechanical damage or pH changes), the microcapsule walls rupture or diffuse, releasing the corrosion inhibitor. The released inhibitor forms a protective film on the metal surface, inhibiting corrosion reactions. The release rate of the inhibitor can be controlled by adjusting the loading method and content of the inhibitor in the coating. This approach allows for a slow release of the inhibitor, extending its duration of action. However, existing nanocontainers loaded with corrosion inhibitors contain low levels of the agent, resulting in unstable loading or uncontrollable release mechanisms, and weak coating protection. Traditional intelligent anti-corrosion coatings require regular reapplication to maintain their effectiveness, increasing maintenance and labor costs.

[0004] Chinese patent document CN106433409A discloses a method for preparing a self-repairing anti-corrosion coating using microcapsules formed from Chinese tallow tree oil wrapped in urea-formaldehyde resin. Structurally, the coating comprises microcapsules (with a vegetable oil core and a resin shell) and rutile titanium dioxide, among other components. The microcapsules are mixed in a water-based epoxy resin. When scratches trigger damage, the vegetable oil oxidizes and solidifies in air to form a film, repairing the damage. The coating is environmentally friendly and economical, and is resistant to salt water and corrosion. However, it has significant shortcomings: the acidic, high-temperature preparation easily causes the oil to oxidize and become ineffective, the release of the microcapsules relies on mechanical rupture, the loading rate is low, and performance degrades under high humidity.

[0005] Although the existing traditional preparation methods are low-cost and simple in process, the active substances are easily deactivated, the nanomaterials are insufficiently effective, and the content of corrosion inhibitors loaded on the nanocarriers is low, which cannot increase the rate at which the self-healing coating inhibits corrosion.

[0006] The present invention proposes a method for preparing a self-repairing anti-corrosion coating for sensors used in vibration detection equipment serving in harsh corrosive environments, aiming to solve the technical problems of low corrosion inhibitor loading capacity in micro / nano containers and insufficient active protection efficiency of corrosion 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 harsh corrosive environments, and its preparation method and application. The present invention solves the problems of low corrosion inhibitor content, slow release rate and low protection efficiency of existing self-repairing anti-corrosion coatings in harsh corrosive environments. The active self-repairing anti-corrosion coating prepared by the present invention uses triazoline and promoter M as corrosion inhibitors, rod-shaped mesoporous silica nanoparticles encapsulating triazoline and promoter M as carriers for constructing loaded corrosion inhibitors, and cerium dioxide particles coating triazoline and promoter M as capping devices as intelligent control switches for corrosion inhibitor release, thereby achieving 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 enable the corrosion inhibitor to be preferably encapsulated in rod-shaped nanocarriers, avoid direct contact and achieve controlled release behavior, while the corrosion inhibitor carrying rate is high, and it can be repeatedly repaired under different pH environments, which can further enhance the corrosion protection performance. In the present invention, brinzyl triazole may be referred to as "BTA" for short; the chemical name of the promoter M is 2-mercaptobenzothiazole, or "MBT" for short; the mesoporous silica nanoparticles may be referred to as "HMSN" for short; and the cerium dioxide may be referred to as "CeO2" for short.

[0008] In order to solve the above problems, the present invention provides the following technical solutions:

[0009] A method for preparing an active self-repairing anti-corrosion coating for a vibration sensor in a harsh corrosive environment comprises the following steps:

[0010] (1) Preparation of mesoporous silica nanoparticles;

[0011] (2) Preparation of carboxylated cerium dioxide nanoparticles;

[0012] (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;

[0013] (4) Prepare a sodium hydroxide aqueous solution, add hexadecyltrimethylammonium bromide, triazoline and accelerator M in sequence, and continue stirring for 20 to 40 minutes until they are completely dissolved to obtain a triazoline-accelerator M solution;

[0014] (5) adding the mixed solution of the mesoporous silica nanoparticles obtained in step (1) and the activated carboxyl ceria 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, centrifuging the mesoporous silica nanoparticles-cerium dioxide-triazole-promoter M suspension, washing, and drying to obtain a mesoporous silica-loaded carboxyl ceria nanoparticle-coated triazole and promoter M filler;

[0015] (6) The mesoporous silica-loaded carboxyl cerium dioxide nanoparticles coated with triazine and accelerator M filler obtained in step (5) are mixed evenly with epoxy resin to obtain an active self-repairing anti-corrosion coating.

[0016] In the method for preparing an active self-repairing anti-corrosion coating for a vibration sensor in a harsh corrosive environment as described above, 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 ammonia aqueous 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.

[0017] The method for preparing an active self-repairing anti-corrosion coating for a vibration sensor in a harsh corrosive environment as described above, wherein 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; dispersing the wet cerium dioxide product in a citric acid aqueous solution and ultrasonically treating it for 30 to 50 minutes, then adding anhydrous ethanol to assist precipitation, centrifuging, collecting the product, washing, and drying it to obtain carboxyl cerium dioxide nanoparticles.

[0018] As described above, in the method for preparing an active self-repairing anti-corrosion coating for a vibration sensor in a harsh corrosive environment, in step (1), the ammonia aqueous solution is an ammonia aqueous solution with a mass percentage concentration of 25%, and the volume ratio of the ammonia aqueous solution to tetraethyl orthosilicate is (10-13):(10-13). Preferably, in step (1), the volume ratio of the ammonia aqueous solution to tetraethyl orthosilicate is 13:(10-12). Under this condition, rod-shaped silica nanoparticles can be prepared, which exhibit a better corrosion inhibition effect than spherical silica nanoparticles and can store more corrosion inhibitors. Most preferably, in step (1), the volume ratio of the ammonia aqueous solution to tetraethyl orthosilicate is 13:10.

[0019] As described above, a method for preparing an active self-repairing anti-corrosion coating for a vibration sensor in a harsh corrosive environment, in step (2), 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 volume ratio of the hexahydrated cerium nitrate, the methanol aqueous solution, and the ammonia aqueous solution is (2-3): (40-45): (15-17), unit: g / mL / mL. Preferably, the mass volume ratio of the hexahydrated cerium nitrate, the methanol aqueous solution, and the ammonia aqueous solution is 2.55:42.5:16, unit: g / mL / mL. Under these conditions, carboxyl cerium dioxide nanoparticles can be prepared. Compared with ordinary cerium dioxide nanoparticles, the introduction of carboxyl functional groups through surface modification can better combine with mesoporous silica to form a dense coating structure and enhance stability.

[0020] In the above-mentioned method for preparing an active self-repairing anti-corrosion coating for a vibration sensor in a harsh corrosive environment, in step (4), the mass ratio of the triazoline to the promoter M is (3-5):1. Preferably, in step (4), the mass ratio of the triazoline to the promoter M is (4-5):1. Under this condition, the hydrogen bond interaction between the triazoline and the promoter M can promote its adsorption on the surface of the metal substrate to form an intelligent and dense protective film. Most preferably, in step (4), the mass ratio of the triazoline to the promoter M is 5:1.

[0021] In the above-mentioned method for preparing an active self-repairing anti-corrosion coating for a vibration sensor in a harsh corrosive environment, in step (6), the mass ratio of the mesoporous silica-loaded carboxyl cerium dioxide nanoparticles coated with triazole and accelerator M filler to the epoxy resin is (1 to 4):25. Most preferably, in step (6), the mass ratio of the mesoporous silica-loaded carboxyl cerium dioxide nanoparticles coated with triazole and accelerator M filler to the epoxy resin is 4:25. Under this condition, the mesoporous silica and carboxyl cerium dioxide nanoparticles in the filler not only serve as carriers of the self-repairing anti-corrosion coating, but also form a good interface bond with the epoxy resin, thereby enhancing the synergistic effect in the self-repair process.

[0022] In the above-mentioned method for preparing an active self-repairing anti-corrosion coating for a vibration sensor in a harsh corrosive environment, in step (3), the mass ratio of the carboxyl cerium dioxide nanoparticles to 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide is (350-400):3. Most preferably, the mass ratio of the carboxyl cerium dioxide nanoparticles to 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide is 400:3. Under these conditions, the carboxyl groups on the surface of the carboxyl 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.

[0023] As described above, in the preparation method of an active self-repairing anti-corrosion coating for a vibration sensor in a harsh corrosive environment, in step (5), the mass volume ratio of the mesoporous silica nanoparticles obtained in step (1), the mixed solution of the activated carboxyl cerium dioxide nanoparticles obtained in step (3), and the triazole-promoter M solution obtained in step (4) is 1: (40-45): (40-45), unit: g / mL / mL. Most preferably, in step (5), the mass volume ratio of the mesoporous silica nanoparticles obtained in step (1), the mixed solution of the activated carboxyl cerium dioxide nanoparticles obtained in step (3), and the triazole-promoter M solution obtained in step (4) is 1:45:45. Under this condition, by optimizing the ratio to ensure the synergistic effect between the components, the coating has both better corrosion resistance and self-repairing ability.

[0024] The present invention selects two corrosion inhibitors, triazoline and promoter M, with a preferred mass ratio of 5:1, to act together on the exposed metal substrate. The combination of triazoline and promoter M can promote its adsorption on the alloy surface through hydrogen bonding, forming a dense corrosion inhibitor film to slow down metal corrosion. The two corrosion inhibitors are encapsulated in mesoporous silica nanoparticles. The mesoporous silica nanoparticles are preferably rod-shaped, which has a higher loading capacity than traditional spherical structures and can further improve the protection efficiency. Cerium dioxide is used as the response shell of the corrosion inhibitor. Cerium dioxide has a faster response rate to acidic pH and increases the release rate of the corrosion inhibitor. Under acidic conditions, due to the exchange between cerium ions and hydrogen ions in ceria, the ceria encapsulating the corrosion inhibitor can dissolve rapidly, resulting in the accelerated release of the internal corrosion inhibitor triazoline and promoter M from the rod-shaped mesoporous silica. This structure forms a performance improvement with high carrier loading capacity, strong corrosion inhibitor protection effect, and fast reaction rate, which can largely make up for the performance defects of traditional self-healing coatings.

[0025] Based on the same inventive concept, the present invention provides an active self-repairing anti-corrosion coating prepared by the preparation method of the active self-repairing anti-corrosion coating suitable for vibration sensors in harsh corrosive environments as described above.

[0026] Based on the same inventive concept, the present invention provides an application of the active self-repairing anti-corrosion coating as described above in a harsh corrosive environment.

[0027] The application as described above has the following specific steps: applying the active self-repairing anti-corrosion coating to the surface of the vibration sensor, and forming an anti-seepage synergistic active repair coating with a thickness of 100 to 500 μm after the coating is dried and cured.

[0028] Compared with the existing technology, the present invention has the following beneficial effects and advantages:

[0029] This invention provides a method for preparing an active, self-healing anti-corrosion coating for vibration sensors in harsh corrosive environments. Cerium dioxide is synthesized to block the release of triazole and accelerator M corrosion inhibitors. This ceria is then encapsulated within rod-shaped mesoporous silica nanoparticles with a honeycomb structure, resulting in a highly active, self-healing anti-corrosion coating. This coating transcends the limitations of traditional anti-corrosion coatings, which rely on a single protective mechanism, and offers an innovative solution to the dynamic corrosion challenges faced by metal components in extreme environments, such as those found in oceans and mines.

[0030] 2. The present invention provides a method for preparing an active self-repairing anti-corrosion coating for a vibration sensor in a harsh corrosive environment. The prepared self-repairing anti-corrosion coating has the characteristic of repeated repair under different pH environments. When the coating is damaged, the corrosive medium passes through these defects to reach the metal surface, causing severe corrosion degradation. Due to the electrochemical action between ions, local cathodes and anodes are generated on the surface of the substrate. Oxidation and reduction occur at the local cathode and the local anode, resulting in changes in the local pH value of the substrate. The cerium dioxide particles will dissolve due to pH changes, releasing the internally enclosed corrosion inhibitor triazole and promoter M. The corrosion inhibitor diffuses to the defective area and adsorbs on the metal substrate to form a dense protective film, which can resist further corrosion from the corrosive medium.

[0031] 3. The active self-healing anti-corrosion coating provided by this invention significantly improves the self-healing protection rate, preventing corrosion caused by the initial intrusion of corrosive media into the substrate. The triazoline and accelerator M interact through hydrogen bonds, promoting their co-adsorption on the metal substrate surface, forming a dense protective film, increasing the protection rate and enhancing the protective effect.

[0032] 4. The active self-repairing anti-corrosion coating provided by the present invention is inexpensive, simple to make, and has high anti-corrosion efficiency. Its protective performance greatly improves the protective effect compared with traditional anti-corrosion coatings. It is suitable for the anti-corrosion of vibration sensors of service equipment in harsh corrosive environments such as oceans and mines. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1This is the TEM morphology of the rod-shaped mesoporous silica nanoparticles prepared in Example 1 of the present invention;

[0034] Figure 2 This is the TEM morphology of spherical mesoporous silica nanoparticles prepared in Example 3 of the present invention;

[0035] Figure 3 This is the SKP result of the active self-repairing coating prepared in Example 1 of the present invention after being scratched and immersed in a 3.5wt.% NaCl solution for 0 day;

[0036] Figure 4 This is the SKP result of the active self-repairing coating prepared in Example 1 of the present invention after being scratched and immersed in a 3.5 wt.% NaCl solution for 2 days;

[0037] Figure 5 This is the SKP result of the active self-repairing coating prepared in Example 1 of the present invention after being scratched and immersed in a 3.5 wt.% NaCl solution for 4 days;

[0038] Figure 6 This is the SKP result of the active self-repairing coating prepared in Example 1 of the present invention after being scratched and immersed in a 3.5 wt.% NaCl solution for 6 days;

[0039] Figure 7 These are the EIS test results of the active self-repairing anti-corrosion coatings prepared in Example 1 and Comparative Example 1 of the present invention and the self-repairing anti-corrosion coating using a single corrosion inhibitor prepared in Comparative Example 2;

[0040] Figure 8 The 0.01 Hz |Z| value observation test results 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;

[0041] Figure 9 The test results of the 0.01 Hz |Z| value of the scratched electrode of the single corrosion inhibitor self-repair coating prepared in Comparative Example 3 of the present invention and immersed in a 3.5 wt.% NaCl solution for 10 days are shown;

[0042] Figure 10 The |Z| value at 0.01 Hz was observed after the blank electrode prepared in the present invention was scratched and immersed in a 3.5 wt.% NaCl solution for 10 days.

[0043] Figure 11 This is a thermogravimetric analysis data chart of rod-shaped mesoporous silica nanoparticles, active self-repairing anti-corrosion coating, and original components prepared in Example 1 of the present invention;

[0044] Figure 12This is a thermogravimetric analysis data chart of the spherical mesoporous silica nanoparticles, active self-healing anti-corrosion coating, and original components prepared in Example 3 of the present invention. DETAILED DESCRIPTION

[0045] The following will be combined with the contents of the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0046] Unless otherwise defined, all technical and scientific terms used in this specification have the same meanings as those commonly understood by those skilled in the art to which this invention pertains. The terms used in this specification are intended solely for the purpose of describing specific embodiments and are not intended to limit the invention. The term "and / or" as used in this specification includes any and all combinations of one or more of the associated listed items.

[0047] Unless otherwise specified, the experimental methods used in the following examples are conventional methods.

[0048] Unless otherwise specified, the materials and reagents used in the following examples can be obtained from commercial sources.

[0049] Example 1

[0050] (1) 65 mL of water and 4.5 mL of N,N-dimethylformamide were mixed at room temperature to form a mixed solution. 0.55 g of hexadecyltrimethylammonium bromide was then dissolved in the mixed solution. 7.8 mL of a 25% ammonia aqueous solution was added and stirred for 30 min. 6 mL of tetraethyl orthosilicate was then added and stirred at room temperature for 4 h. Rod-shaped mesoporous silica nanoparticles were obtained by centrifugation, washing, and vacuum drying. The TEM morphology of the rod-shaped mesoporous silica nanoparticles prepared in this example is shown in FIG. Figure 1 shown.

[0051] (2) 2.55 g of cerium nitrate hexahydrate was dissolved in 42.5 mL of a 50% by mass methanol aqueous solution at 60 °C, and then 16 mL of a 25% by mass ammonia aqueous solution was quickly added and vigorously stirred for 3 h to obtain a yellow cerium dioxide product. The yellow cerium dioxide product was then centrifuged and washed three times with anhydrous ethanol to obtain a wet cerium dioxide product. The wet cerium dioxide product was dispersed in 100 mL of a 30% by mass citric acid aqueous solution and ultrasonically treated for 40 min, and then 300 mL of anhydrous ethanol was added to assist precipitation, centrifuged, and the product was collected, washed three times with ethanol, and vacuum dried to obtain carboxyl cerium dioxide nanoparticles;

[0052] (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 stir continuously at room temperature for 1 h to obtain a mixed solution of activated carboxyl cerium dioxide nanoparticles;

[0053] (4) Dissolve 10 mg of sodium hydroxide in 45 mL of deionized water. Add 150 mg of hexadecyltrimethylammonium bromide, 100 mg of indolizine, and 20 mg of promoter M while stirring in a water bath at 80°C. Continue stirring for 30 min until the solution is completely dissolved to obtain a indolizine-promoter M solution.

[0054] (5) 1 g of the mesoporous silica nanoparticles obtained in step (1) and 45 mL of the mixed solution of the activated carboxyl ceria nanoparticles obtained in step (3) were added to 45 mL of the triazole-promoter M solution obtained in step (4), and then vigorously stirred for 2 h to obtain a suspension of mesoporous silica nanoparticles-cerium dioxide-triazole-promoter M. Subsequently, the suspension of mesoporous silica nanoparticles-triazole-promoter M was centrifuged at 8000 rpm for 5 min, washed twice with deionized water, and dried in an oven at 70 °C for 24 h to obtain mesoporous silica-loaded carboxyl ceria nanoparticles coated with triazole and promoter M filler;

[0055] (6) The mesoporous silica-loaded carboxyl cerium dioxide nanoparticles obtained in step (5) are coated with triazole and accelerator M filler and epoxy resin in a mass ratio of 4:25 to obtain an active self-repairing anti-corrosion coating.

[0056] Example 2

[0057] (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 hexadecyltrimethylammonium bromide was dissolved in the mixed solution. 7.8 mL of 25% ammonia aqueous solution was added and stirred for 30 min. Subsequently, 7.2 mL of tetraethyl orthosilicate was added and stirred at room temperature for 4 h. Rod-shaped mesoporous silica nanoparticles were obtained by centrifugation, washing, and vacuum drying.

[0058] (2) 2.55 g of cerium nitrate hexahydrate was dissolved in 42.5 mL of a 50% by mass methanol aqueous solution at 60 °C, and then 16 mL of a 25% by mass ammonia aqueous solution was quickly added and vigorously stirred for 3 h to obtain a yellow cerium dioxide product. The yellow cerium dioxide product was then centrifuged and washed three times with anhydrous ethanol to obtain a wet cerium dioxide product. The wet cerium dioxide product was dispersed in 100 mL of a 30% by mass citric acid aqueous solution and ultrasonically treated for 40 min. Then, 300 mL of anhydrous ethanol was added to assist precipitation, centrifuged, and the product was collected, washed three times with ethanol, and vacuum dried to obtain carboxyl cerium dioxide nanoparticles.

[0059] (3) Disperse 2 g of the carboxylated cerium dioxide nanoparticles obtained in step (2) into 45 mL of water, add 15 mg of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, and stir continuously at room temperature for 1 h to obtain a mixed solution of activated carboxylated cerium dioxide nanoparticles.

[0060] (4) Dissolve 10 mg of sodium hydroxide in 45 mL of deionized water. Add 150 mg of hexadecyltrimethylammonium bromide, 100 mg of triazoline, and 20 mg of promoter M while stirring in a water bath at 80°C. Continue stirring for 30 min until the solution is completely dissolved to obtain a triazoline-promoter M solution.

[0061] (5) 1 g of the mesoporous silica nanoparticles obtained in step (1) and 45 mL of the mixed solution of activated carboxyl ceria nanoparticles obtained in step (3) were added to 45 mL of the triazole-promoter M solution obtained in step (4), and then vigorously stirred for 2 h to obtain a suspension of mesoporous silica nanoparticles-cerium dioxide-triazole-promoter M. Subsequently, the suspension of mesoporous silica nanoparticles-triazole-promoter M was centrifuged at 8000 rpm for 5 min, washed twice with deionized water, and dried in an oven at 70 °C for 24 h to obtain a mesoporous silica-supported carboxyl ceria nanoparticle-coated triazole and promoter M filler.

[0062] (6) The mesoporous silica-loaded carboxyl cerium dioxide nanoparticles obtained in step (5) are coated with triazole and accelerator M filler and epoxy resin in a mass ratio of 4:25 to obtain an active self-repairing anti-corrosion coating.

[0063] Example 3

[0064] (1) 73 mL of water and 5.2 mL of N,N-dimethylformamide were mixed at room temperature to form a mixed solution. 0.63 g of hexadecyltrimethylammonium bromide was then dissolved in the mixed solution. 6 mL of a 25% by mass aqueous ammonia solution was added and stirred for 30 min. 7.2 mL of tetraethyl orthosilicate was then added and stirred at room temperature for 4 h. Spherical mesoporous silica nanoparticles were obtained by centrifugation, washing, and vacuum drying. The TEM morphology of the spherical mesoporous silica nanoparticles prepared in this example is shown in FIG. Figure 2 shown.

[0065] (2) 2.55 g of cerium nitrate hexahydrate was dissolved in 42.5 mL of a 50% by mass methanol aqueous solution at 60 °C, and then 16 mL of a 25% by mass ammonia aqueous solution was quickly added and vigorously stirred for 3 h to obtain a yellow cerium dioxide product. The yellow cerium dioxide product was then centrifuged and washed three times with anhydrous ethanol to obtain a wet cerium dioxide product. The wet cerium dioxide product was dispersed in 100 mL of a 30% by mass citric acid aqueous solution and ultrasonically treated for 40 min. Then, 300 mL of anhydrous ethanol was added to assist precipitation, centrifuged, and the product was collected, washed three times with ethanol, and vacuum dried to obtain carboxyl cerium dioxide nanoparticles.

[0066] (3) Disperse 2 g of the carboxylated cerium dioxide nanoparticles obtained in step (2) into 45 mL of water, add 15 mg of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, and stir continuously at room temperature for 1 h to obtain a mixed solution of activated carboxylated cerium dioxide nanoparticles.

[0067] (4) Dissolve 10 mg of sodium hydroxide in 45 mL of deionized water. Add 150 mg of hexadecyltrimethylammonium bromide, 100 mg of triazoline, and 20 mg of promoter M while stirring in a water bath at 80°C. Continue stirring for 30 min until the solution is completely dissolved to obtain a triazoline-promoter M solution.

[0068] (5) 1 g of the mesoporous silica nanoparticles obtained in step (1) and 45 mL of the mixed solution of activated carboxyl ceria nanoparticles obtained in step (3) were added to 45 mL of the triazole-promoter M solution obtained in step (4), and then vigorously stirred for 2 h to obtain a suspension of mesoporous silica nanoparticles-cerium dioxide-triazole-promoter M. Subsequently, the suspension of mesoporous silica nanoparticles-triazole-promoter M was centrifuged at 8000 rpm for 5 min, washed twice with deionized water, and dried in an oven at 70 °C for 24 h to obtain a mesoporous silica-supported carboxyl ceria nanoparticle-coated triazole and promoter M filler.

[0069] (6) The mesoporous silica-loaded carboxyl cerium dioxide nanoparticles obtained in step (5) are coated with triazole and accelerator M filler and epoxy resin in a mass ratio of 4:25 to obtain an active self-repairing anti-corrosion coating.

[0070] Example 4

[0071] (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 hexadecyltrimethylammonium bromide was dissolved in the mixed solution. 7.8 mL of 25% ammonia aqueous solution was added and 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 by centrifugation, washing, and vacuum drying.

[0072] (2) 2.55 g of cerium nitrate hexahydrate was dissolved in 42.5 mL of a 50% by mass methanol aqueous solution at 60 °C, and then 16 mL of a 25% by mass ammonia aqueous solution was quickly added and vigorously stirred for 3 h to obtain a yellow cerium dioxide product. The yellow cerium dioxide product was then centrifuged and washed three times with anhydrous ethanol to obtain a wet cerium dioxide product. The wet cerium dioxide product was dispersed in 100 mL of a 30% by mass citric acid aqueous solution and ultrasonically treated for 40 min, and then 300 mL of anhydrous ethanol was added to assist precipitation, centrifuged, and the product was collected, washed three times with ethanol, and vacuum dried to obtain carboxyl cerium dioxide nanoparticles;

[0073] (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 stir continuously at room temperature for 1 h to obtain a mixed solution of activated carboxyl cerium dioxide nanoparticles;

[0074] (4) Dissolve 10 mg of sodium hydroxide in 45 mL of deionized water. Add 150 mg of hexadecyltrimethylammonium bromide, 80 mg of indolizine, and 20 mg of promoter M while stirring in a water bath at 80°C. Continue stirring for 30 min until the solution is completely dissolved to obtain a indolizine-promoter M solution.

[0075] (5) 1 g of the mesoporous silica nanoparticles obtained in step (1) and 45 mL of the mixed solution of the activated carboxyl ceria nanoparticles obtained in step (3) were added to 45 mL of the triazole-promoter M solution obtained in step (4), and then vigorously stirred for 2 h to obtain a suspension of mesoporous silica nanoparticles-cerium dioxide-triazole-promoter M. Subsequently, the suspension of mesoporous silica nanoparticles-triazole-promoter M was centrifuged at 8000 rpm for 5 min, washed twice with deionized water, and dried in an oven at 70 °C for 24 h to obtain mesoporous silica-loaded carboxyl ceria nanoparticles coated with triazole and promoter M filler;

[0076] (6) The mesoporous silica-loaded carboxyl cerium dioxide nanoparticles obtained in step (5) are coated with triazole and accelerator M filler and epoxy resin in a mass ratio of 4:25 to obtain an active self-repairing anti-corrosion coating.

[0077] Comparative Example 1

[0078] (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 hexadecyltrimethylammonium bromide was dissolved in the mixed solution. 7.8 mL of 25% ammonia aqueous solution was added and 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 by centrifugation, washing, and vacuum drying.

[0079] (2) 2.55 g of cerium nitrate hexahydrate was dissolved in 42.5 mL of a 50% by mass methanol aqueous solution at 60 °C, and then 16 mL of a 25% by mass ammonia aqueous solution was quickly added and vigorously stirred for 3 h to obtain a yellow cerium dioxide product. The yellow cerium dioxide product was then centrifuged and washed three times with anhydrous ethanol to obtain a wet cerium dioxide product. The wet cerium dioxide product was dispersed in 100 mL of a 30% by mass citric acid aqueous solution and ultrasonically treated for 40 min. Then, 300 mL of anhydrous ethanol was added to assist precipitation, centrifuged, and the product was collected, washed three times with ethanol, and vacuum dried to obtain carboxyl cerium dioxide nanoparticles.

[0080] (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 stir continuously at room temperature for 1 h to obtain a mixed solution of activated carboxyl cerium dioxide nanoparticles.

[0081] (4) Dissolve 10 mg of sodium hydroxide in 45 mL of deionized water. Add 150 mg of hexadecyltrimethylammonium bromide and 100 mg of triazoline while stirring in a water bath at 80°C. Continue stirring for 30 min until the solution is completely dissolved to obtain a triazoline solution.

[0082] (5) 1 g of the mesoporous silica nanoparticles obtained in step (1) and 45 mL of the mixed solution of activated carboxyl ceria nanoparticles obtained in step (3) were added to 45 mL of the triazole solution obtained in step (4), and the mixture was vigorously stirred for 2 h to obtain a suspension of mesoporous silica nanoparticles-ceria-triazole. Subsequently, the suspension of mesoporous silica nanoparticles-ceria-triazole was centrifuged at 8000 rpm for 5 min, washed twice with deionized water, and dried in an oven at 70 °C for 24 h to obtain a mesoporous silica-loaded carboxyl ceria nanoparticle-coated triazole filler.

[0083] (6) The mesoporous silica-loaded carboxyl cerium dioxide nanoparticles coated triazine filler obtained in step (5) and epoxy resin were mixed evenly in a mass ratio of 4:25 to obtain a single corrosion inhibitor self-repairing anti-corrosion coating.

[0084] Comparative Example 2

[0085] (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 hexadecyltrimethylammonium bromide was dissolved in the mixed solution. 7.8 mL of 25% ammonia aqueous solution was added and 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 by centrifugation, washing, and vacuum drying.

[0086] (2) 2.55 g of cerium nitrate hexahydrate was dissolved in 42.5 mL of a 50% by mass methanol aqueous solution at 60 °C, and then 16 mL of a 25% by mass ammonia aqueous solution was quickly added and vigorously stirred for 3 h to obtain a yellow cerium dioxide product. The yellow cerium dioxide product was then centrifuged and washed three times with anhydrous ethanol to obtain a wet cerium dioxide product. The wet cerium dioxide product was dispersed in 100 mL of a 30% by mass citric acid aqueous solution and ultrasonically treated for 40 min. Then, 300 mL of anhydrous ethanol was added to assist precipitation, centrifuged, and the product was collected, washed three times with ethanol, and vacuum dried to obtain carboxyl cerium dioxide nanoparticles.

[0087] (3) Disperse 2 g of the carboxylated cerium dioxide nanoparticles obtained in step (2) into 45 mL of water, add 15 mg of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide, and stir continuously at room temperature for 1 h to obtain a mixed solution of activated carboxylated cerium dioxide nanoparticles.

[0088] (4) Dissolve 10 mg of sodium hydroxide in 45 mL of deionized water. Add 150 mg of hexadecyltrimethylammonium bromide and 100 mg of accelerator M while stirring in a water bath at 80 °C. Continue stirring for 30 min until completely dissolved to obtain accelerator M solution.

[0089] (5) 1 g of the mesoporous silica nanoparticles obtained in step (1) and 45 mL of the mixed solution of activated carboxyl ceria nanoparticles obtained in step (3) were added to 45 mL of the promoter M solution obtained in step (4), and the mixture was vigorously stirred for 2 h to obtain a suspension of mesoporous silica nanoparticles-ceria-promoter M. Subsequently, the suspension of mesoporous silica nanoparticles-ceria-promoter M was centrifuged at 8000 rpm for 5 min, washed twice with deionized water, and dried in an oven at 70 °C for 24 h to obtain a mesoporous silica-loaded carboxyl ceria nanoparticle-coated promoter M filler.

[0090] (6) The mesoporous silica-loaded carboxyl cerium dioxide nanoparticles coated promoter M filler obtained in step (5) and the epoxy resin are mixed evenly in a mass ratio of 4:25 to obtain a single corrosion inhibitor self-repairing anti-corrosion coating.

[0091] Comparative Example 3

[0092] (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 hexadecyltrimethylammonium bromide was dissolved in the mixed solution. 7.8 mL of 25% ammonia aqueous solution was added and 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 by centrifugation, washing, and vacuum drying.

[0093] (2) 2.55 g of cerium nitrate hexahydrate was dissolved in 42.5 mL of a 50% by mass methanol aqueous solution at 60 °C, and then 16 mL of a 25% by mass ammonia aqueous solution was quickly added and vigorously stirred for 3 h to obtain a yellow cerium dioxide product. The yellow cerium dioxide product was then centrifuged and washed three times with anhydrous ethanol to obtain a wet cerium dioxide product. The wet cerium dioxide product was dispersed in 100 mL of a 30% by mass citric acid aqueous solution and ultrasonically treated for 40 min. Then, 300 mL of anhydrous ethanol was added to assist precipitation, centrifuged, and the product was collected, washed three times with ethanol, and vacuum dried to obtain carboxyl cerium dioxide nanoparticles.

[0094] (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 stir continuously at room temperature for 1 h to obtain a mixed solution of activated carboxyl cerium dioxide nanoparticles.

[0095] (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 weak alkaline sodium hydroxide solution; add 150 mg of hexadecyltrimethylammonium bromide and 100 mg of sodium phytate to the weak alkaline sodium hydroxide solution while stirring in a 60°C water bath, continue stirring for 30 min until completely dissolved, and cool to obtain a sodium phytate solution.

[0096] (5) 1 g of the mesoporous silica nanoparticles obtained in step (1) and 45 mL of the mixed solution of activated carboxyl ceria nanoparticles obtained in step (3) were added to 45 mL of the sodium phytate solution obtained in step (4), and the mixture was vigorously stirred for 2 h to obtain a suspension of mesoporous silica nanoparticles-ceria-sodium phytate. Subsequently, the suspension of mesoporous silica nanoparticles-ceria-sodium phytate was centrifuged at 8000 rpm for 5 min, washed twice with deionized water, and dried in an oven at 70 °C for 24 h to obtain a mesoporous silica-loaded carboxyl ceria nanoparticle-coated sodium phytate filler.

[0097] (6) The mesoporous silica-loaded carboxyl cerium dioxide nanoparticles coated with sodium phytate filler obtained in step (5) and epoxy resin are mixed evenly in a mass ratio of 4:25 to obtain a single corrosion inhibitor self-repairing anti-corrosion coating.

[0098] Test Case

[0099] Test objects: self-repairing anti-corrosion coatings prepared in Example 1, Example 3, Comparative Example 1, Comparative Example 2, and Comparative Example 3.

[0100] Test items:

[0101] (1) Electrochemical impedance spectroscopy (EIS): refer to ISO 16773-Determination of protective anti-corrosion coatings using electrochemical impedance spectroscopy;

[0102] (2) Transmission electron microscopy (TEM): refer to ASTM E2859-Standard Guide for Nanoparticle Size Measurement Using Transmission Electron Microscopy;

[0103] (3) Scanning Kelvin probe (SKP): refer to ASTM G3-Standard Practice for Specification of Electrochemical Measurements in Corrosion Testing;

[0104] (4) Thermogravimetric analysis (TG): Refer to ASTM E1131-Standard Test Method for Composition Analysis by Thermogravimetric Method.

[0105] The surface morphology of the mesoporous silica nanoparticles prepared in Example 1 and Example 3 was observed by transmission electron microscopy (TEM). Figure 1 and Figure 2 shown.

[0106] The active self-repairing anti-corrosion coating prepared in Example 1 was moved on the coating surface by a scanning Kelvin probe (SKP) to measure the surface potential difference, as shown in FIG. Figure 3-Figure 6 shown.

[0107] The self-repairing anti-corrosion coatings prepared in Example 1, Comparative Example 1 and Comparative Example 2 were used to evaluate the corrosion resistance and protection mechanism of the protection system using electrochemical impedance spectroscopy (EIS) non-destructive testing technology. Figure 7 shown.

[0108] The corrosion resistance of the self-repairing anti-corrosion coating electrode prepared in Example 1 and Comparative Example 3 and the blank electrode was evaluated by electrochemical impedance spectroscopy (EIS) to measure the |Z| at 0.01 Hz. Figures 8-10 shown.

[0109] The mesoporous silica nanoparticles, active self-repairing anti-corrosion coatings and original components prepared in Example 1 and Example 3 were analyzed by thermogravimetric analysis (TG) to determine the loading amount of corrosion inhibitors loaded on mesoporous silica with different morphologies. Figure 11-12shown.

[0110] Figure 1 This is the TEM morphology of the rod-shaped silica prepared in Example 1 of the present invention.

[0111] Figure 2 This is the TEM morphology of traditional spherical mesoporous silica microspheres prepared in Example 2 of the present invention.

[0112] above Figure 1-Figure 2 It can be seen that mesoporous silica has the advantages of surface modifiability and good biocompatibility. Figure 1 The rod-shaped mesoporous silica nanoparticles prepared in Example 1 are compared Figure 2 From the spherical mesoporous silica nanoparticles prepared in Example 2, it can be seen that the rod-shaped mesoporous silica has a larger pore volume and a highly ordered mesoporous structure, which significantly increases the loading amount of the corrosion inhibitor and improves the corrosion rate suppressed by the corrosion inhibitor. Figure 1 The rod-like structure in Figure 2 The spherical structure in the rod exhibits superior corrosion inhibition and can store more corrosion inhibitors. Therefore, rod-shaped mesoporous silica has obvious advantages as a corrosion inhibitor carrier in applications requiring efficient loading and long-term protection.

[0113] 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 day.

[0114] Figure 4 This is the SKP result of the active self-repairing coating prepared in Example 1 of the present invention after being scratched and immersed in a 3.5 wt.% NaCl solution for 2 days;

[0115] Figure 5 This is the SKP result of the active self-repairing coating prepared in Example 1 of the present invention after being scratched and immersed in a 3.5 wt.% NaCl solution for 4 days;

[0116] Figure 6 SKP results 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.

[0117] above Figures 3 to 6 The SKP results of the self-repairing coating prepared by the present invention after being soaked in 3.5 wt.% NaCl solution for 0, 2, 4, and 6 days. The scratch repair process of the self-repairing coating in a simulated seawater environment can be clearly demonstrated by the dynamic changes in the surface potential distribution. Figure 3 It can be seen that the potential in the center of the scratch is significantly lower than that of the surrounding intact coating at 0 days, forming a highly active anodic area, which poses a risk of local corrosion and the self-repair process has not yet begun. Figure 4 It can be seen that after 2 days of immersion, the potential of the scratch area gradually recovered, the potential difference between some areas and the coating decreased, and a "ring-shaped high potential zone" appeared around the scratch, indicating the rapid response of the self-repair mechanism. Figure 5 It can be seen that on the fourth day of immersion, the potential of the scratch center area is closer to the coating value, the color transition is relatively smooth, the proportion of the red area increases, and the potential unevenness is improved, indicating that the corrosion inhibitor has completed the initial coverage of the exposed metal and the repair layer has gradually formed a protective barrier. Figure 6 It can be seen that after 6 days of immersion, the difference between the potential of the scratched area and the surrounding coating is significantly reduced, and the spatial potential distribution shows a uniform characteristic. This shows that the repair layer has built a continuous and dense protective layer, and the potential of the undamaged area has remained stable within 6 days, proving that the coating matrix is ​​structurally intact and has not been significantly affected by long-term immersion. Figures 3 to 6 The SKP result analysis shows that the self-healing coating has a significant effect on repairing the scratched area. As the immersion time increases, the surface potential tends to be uniform, the self-healing process continues, and the potential unevenness in the scratched area gradually decreases, achieving the self-healing effect.

[0118] Figure 7 These are the EIS test results of the active self-repairing anti-corrosion coatings prepared in Example 1 and Comparative Example 1 of the present invention and the single corrosion inhibitor self-repairing anti-corrosion coating prepared in Comparative Example 2. Figure 7 The corrosion inhibitors in Example 1, Comparative Example 1 and Comparative Example 2 are triazoline and accelerator M, triazoline and accelerator M, respectively. The electrodes coated with the coatings of Example 1, Comparative Example 1 and Comparative Example 2 were immersed in a NaCl solution with a pH of 7 for 7 days, and the impedance change trend was observed. Figure 7 It can be seen that the coating prepared in Example 1 has a greater trend in the change of the |Z| value than the coatings prepared in Comparative Examples 1 and 2, indicating that the two corrosion inhibitors have a synergistic effect and a stronger ability to inhibit corrosion than a single corrosion inhibitor.

[0119] 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 a 3.5 wt.% NaCl solution for 10 days.

[0120] Figure 9 This is the test result of observing the |Z| value at 0.01 Hz of the scratched electrode of the single corrosion inhibitor self-repairing coating prepared in Comparative Example 3 of the present invention after being immersed in a 3.5 wt.% NaCl solution for 10 days.

[0121] Figure 10 The blank electrode prepared in the present invention was scratched and immersed in a 3.5 wt.% NaCl solution for 10 days to observe the |Z| value at 0.01 Hz.

[0122] Figures 8-10 It can be seen that through the electrochemical impedance spectroscopy test of the three groups of electrodes in 3.5% NaCl solution, the corrosion protection differences between the coating self-healing properties and the blank substrate can be intuitively compared. Figure 8 The electrode self-repair coating component is mesoporous silica loaded carboxyl cerium dioxide nanoparticles coated with triazole and promoter M. Figure 9 The electrode self-repair coating component is mesoporous silica loaded with carboxyl ceria nanoparticles coated with sodium phytate. Figure 10 is a blank electrode. Figure 8 It can be seen that |Z| 0.01Hz There is an obvious rising and falling trend. It rises rapidly at 0 days and reaches the maximum value at 3 days, indicating that mechanical damage causes rapid penetration of the corrosive medium. It begins to decline at 4 days and becomes stable at 7 days. This shows that the release of triazole-accelerator M in Example 1 effectively inhibits the corrosion expansion to a certain extent. Figure 9 It can be seen that at 0-2 d |Z| 0.01Hz It shows a downward trend, indicating that the corrosion process has begun, and it rises at 25 days, indicating that the corrosion inhibitor is released and the corrosion process is suppressed. Figure 10 It can be seen that the blank group only shows a simple monotonic decrease, and the corresponding metal substrate shows comprehensive corrosion characteristics, reflecting that the unprotected metal substrate undergoes a rapid corrosion reaction in the electrolyte. When the coating in Example 1 encounters a corrosive medium, it can quickly release the corrosion inhibitor to interrupt the corrosion process. In contrast, in Comparative Example 3, a corrosion reaction occurs when the corrosive medium reaches the substrate, and the corrosion inhibitor is released after 2 days to inhibit the corrosion process. This shows that the self-healing coating in Example 1 can improve the protection rate against corrosion reactions, and the release of triazole-promoter M can timely inhibit the corrosion process.

[0123] Figure 11 The thermogravimetric analysis data of the rod-shaped mesoporous silica nanoparticles, active self-healing anti-corrosion coating and original components prepared in Example 1 of the present invention are shown. The figure shows the rod-shaped mesoporous silica nanoparticles (a1) prepared in step (1) of Example 1, cerium dioxide (b) prepared in step (2) of Example 1, rod-shaped mesoporous silica loaded with carboxyl cerium dioxide nanoparticles coated with triazole and promoter M, i.e., the active self-healing anti-corrosion coating (c1) prepared in Example 1, promoter M (d), and triazole (e). Figure 11It can be seen that rod-shaped mesoporous silica loses about 5% weight from 0°C to 800°C, showing high thermal stability. Ceria loses less than 2% weight, showing extremely high thermal stability. Curve (c1) starts at 100% at 0°C and drops to about 95% at 200°C. The weight loss is more significant between 200°C and 400°C, reaching about 80% at 400°C. It then continues to slowly decrease, stabilizing at 69% at 800°C, for a total weight loss of 31%. Figure 11 It can be seen that the loading rate of the rod-shaped mesoporous silica loaded with the corrosion inhibitor in Example 1 is about 31%.

[0124] Figure 12 The thermogravimetric analysis data of spherical mesoporous silica nanoparticles, active self-healing anti-corrosion coating and original components prepared in Example 3 of the present invention. The figure shows 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-loaded carboxyl cerium dioxide nanoparticles coated with triazole and promoter M, i.e. active self-healing anti-corrosion coating (c2) prepared in Example 3, promoter M (d), and triazole (e). Figure 12 It can be seen that the weight loss portion of curve (c2) of the spherical mesoporous silica loaded with triazoline-accelerator M corresponds to the decomposition of triazoline-accelerator M. Therefore, the loading amount of the corrosion inhibitor in Example 3 is approximately 21-22%. By comparison, under similar synthesis conditions, the corrosion inhibitor loading rate of rod-shaped mesoporous silica is 31%, which is higher than the 21-22% of spherical mesoporous silica, further demonstrating that rod-shaped mesoporous silica has better performance in loading corrosion inhibitors.

[0125] It should be noted that the specific embodiments are only representative examples of the present invention. Obviously, the technical solutions of the present invention are not limited to the above embodiments and may be subject to many variations. Those skilled in the art who are clear about the disclosure of the present invention or who can unambiguously derive the invention from the written description of the document should be considered to be within the scope of protection of this patent.

Claims

1. A method for preparing an active self-repairing anti-corrosion coating for a vibration sensor in a harsh corrosive environment, characterized in that: The following steps are involved: (1) preparing mesoporous silica nanoparticles; the mesoporous silica nanoparticles are rod-shaped; (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 an activated carboxyl cerium dioxide nanoparticle mixed solution; (4) Prepare a sodium hydroxide aqueous solution, add hexadecyltrimethylammonium bromide, triazoline and accelerator M in sequence, and continue stirring for 20 to 40 minutes until they are completely dissolved to obtain a triazoline-accelerator 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-triazole-promoter M suspension is centrifuged, washed, and dried to obtain a mesoporous silica-loaded carboxylcerium dioxide nanoparticle-coated triazole and promoter M filler; (6) The mesoporous silica-loaded carboxyl cerium dioxide nanoparticles coated with triazine and accelerator M filler obtained in step (5) are mixed evenly with epoxy resin to obtain an active self-repairing 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 ammonia aqueous solution is added and stirred for 20 to 40 minutes, and then tetraethyl orthosilicate is added and stirred for 2 to 4 hours. The 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. The product is centrifuged, 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 carboxylcerium 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 preparation method of an active self-repairing anti-corrosion coating for a vibration sensor in a harsh corrosive environment as claimed 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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