A kind of offshore wind power steel structure mooring pile anticorrosive wear-resistant quick repair coating and method

Abstract

This invention provides a rapid repair coating and method for corrosion-resistant and wear-resistant offshore wind turbine steel structure mooring piles. This rapid repair coating introduces polyurethane elastic segments into the epoxy resin structure, achieving high strength and toughness while imparting excellent shape memory function and hydrogen bond microcrack repair properties to the coating. Fillers such as alumina and zirconium dioxide are added to the resin system to improve the coating's wear resistance and toughness. Rust-converting fillers such as aluminum tripolyphosphate and zinc phosphate are added to the coating system to form a dense shielding layer even on substrates with low surface treatment. The added slow-release boehmite accelerates the release of corrosion inhibitors when the pH value changes in the microenvironment caused by corrosion, chelating with metal ions in the early stages of corrosion and adsorbing onto the metal surface to form a protective film, effectively inhibiting metal corrosion. This invention shortens the local repair construction cycle from the traditional 3-5 days to 1-2 days, improving construction efficiency by more than 60%.

Description

Technical Field

[0001] This invention belongs to the field of corrosion protection technology, specifically relating to a rapid repair coating and method for corrosion-resistant and wear-resistant offshore wind power steel structure docking piles. Background Technology

[0002] With the global energy structure shifting towards clean energy, offshore wind power has experienced rapid development as an important form of renewable energy. However, offshore wind power facilities are exposed to harsh environments such as seawater erosion, high humidity, strong ultraviolet radiation, and mechanical impact. Their surface protective coatings are prone to aging, peeling, and damage. In particular, mooring piles not only have to withstand marine corrosion but also the pressure and friction generated by ships mooring, making them more susceptible to coating peeling. This exposes the internal steel structure directly to humid air, leading to faster and more severe corrosion. If not repaired promptly, steel structural components will be damaged by corrosion, significantly increasing maintenance costs, jeopardizing equipment safety, shortening its lifespan, and even threatening the personal safety of maintenance personnel.

[0003] The existing traditional repair solutions for corrosion of the metal structure of mooring piles have three major technical pain points: First, the curing rate is slow, which is difficult to meet the construction requirements of short offshore operation windows; second, the wear resistance is insufficient and cannot withstand the long-term erosion of sand and gravel carried by the waves; and third, the interface bonding is poor, and the repair layer is prone to peeling off from the substrate and failing. Summary of the Invention

[0004] To address the aforementioned technical problems, this invention provides a rapid repair coating for corrosion and wear resistance of offshore wind power steel structure mooring piles, comprising a resin matrix, resin reinforcing agent, curing agent, wear-resistant filler, nano filler, rust-converting filler, auxiliary additives, and solvent; The wear-resistant filler comprises polytetrafluoroethylene powder and alumina. The resin matrix is ​​obtained by crosslinking epoxy resin and polyurethane prepolymer, with a mass ratio of 100:10~50. The amount of alumina added is 1.2~2 times the mass of epoxy resin, and the amount of resin reinforcing agent added is 0.3%~0.6% of the mass of the resin system. Based on the mass of the repair coating as 100%, the mass percentage of the nanofiller is 13%~16%, the mass percentage of the tetrafluoroethylene powder is 4%~6%, the mass percentage of the rust conversion filler is 5%~6%, the mass percentage of the auxiliary additives is 16%~18%, the mass percentage of the solvent is 7%~8%, and the mass percentage of the curing agent is 2%~3%.

[0005] Wear-resistant fillers primarily improve the wear resistance of materials by increasing the hardness of the matrix and reducing the coefficient of friction. Alumina has a high Mohs hardness and a dense crystalline structure. When dispersed in the coating matrix as powder, it forms a "rigid support skeleton": when the coating is subjected to external friction or impact, the alumina particles can directly bear the load, preventing wear caused by deformation of the matrix resin under stress, thus increasing the surface hardness of the coating compared to a pure resin matrix. Polytetrafluoroethylene (PTFE) micropowder increases interfacial slippage, reduces the surface energy of the coating, increases the air fraction on the surface, and increases the water contact angle. Simultaneously, it reduces interfacial resistance, thus enhancing scratch resistance and wear resistance during surface hardness testing.

[0006] Furthermore, the nanofiller includes nano ZrO2, slow-release boehmite, and nano titanium dioxide, with a mass ratio of 1:5 to 6:10.

[0007] Nano-titanium dioxide, added as a second microphase to the resin system, can be relatively uniformly dispersed in the epoxy resin system. When the system is subjected to external forces, cracks generated inside the material can be initiated into microcracks or terminated upon encountering nanoparticles, thereby improving the toughness of the epoxy resin. Nano-ZrO2 possesses excellent chemical stability, thermal stability, and mechanical stability. These unique properties make it a good high-temperature resistant, wear-resistant, and corrosion-resistant material.

[0008] Furthermore, the auxiliary additives include dispersants, defoamers, rheology modifiers, and pigments.

[0009] Furthermore, the resin reinforcing agent is a BIB compound or an HFTC compound; The BIB compound was prepared by a dehydration condensation reaction of 3,3-diaminobenzidine and 3,4,5-trihydroxybenzoic acid under acidic conditions; the HFTC compound was prepared by a benzimidazole reaction of ethyl 3,4-diaminobenzoate and 3,4,5-trihydroxybenzaldehyde to generate an intermediate, which was then reacted with 1,1,1,3,3,3-hexafluoro-2-propanol.

[0010] Both BIB and HFTC compounds are additives containing pyrogallol and benzimidazole rings. These additives can interact with the active sites of the metal substrate (Fe) through the benzimidazole ring. 2＋ Al 3＋ It forms coordination bonds, and at the same time, the pyrogallol groups enhance the compatibility with the resin matrix, which can significantly improve the bonding strength and solve the problems of "easy delamination at low temperature and loss of adhesion at high temperature" of traditional repair materials.

[0011] Furthermore, the rust conversion filler is composed of aluminum tripolyphosphate and zinc phosphate, with a mass ratio of 2~3:7~8.

[0012] Furthermore, the preparation process of the resin matrix is ​​as follows: The epoxy resin and polyurethane prepolymer were preheated at 40-50℃ for 4-6 hours and then vacuum treated at -0.1MPa until the bubbles were completely eliminated. The epoxy resin and polyurethane prepolymer were then mixed and homogeneously sheared and stirred at 40-50℃ for 1-1.5 hours. After cooling to room temperature, polyurethane-modified epoxy resin was obtained.

[0013] The resin matrix of this invention utilizes the high activity of the isocyanate-terminated polyurethane prepolymer to chemically bond with the hydroxyl groups of epoxy resin, successfully preparing hydroxyl-terminated polybutadiene-modified epoxy resin. Its high strength and toughness can effectively resist mechanical impact damage to offshore wind turbine berthing components, pile foundations, and other parts.

[0014] Furthermore, the preparation process of the sustained-release boehmite is as follows: Boehmite was ultrasonically dispersed in N,N-dimethylacetamide for 3-10 min, then 5-amino-1,3,4-thiadiazole-2-thioacetic acid was added, followed by 3-5 drops of concentrated sulfuric acid. The mixture was reacted at 70-80 °C for 2 h, and then slowly heated to 135-140 °C for 4-5 h. The mass ratio of boehmite to 5-amino-1,3,4-thiadiazole-2-thioacetic acid was 1:2.5-6. After cooling, the solid was deposited and filtered. The solid was repeatedly washed with water and ethanol until the filtered solution no longer contained organic matter. The corrosion-inhibiting boehmite was obtained by vacuum drying at 70-80℃ for 10-12 hours.

[0015] Boehmite, after being grafted with 5-amino-1,3,4-thiadiazole-2-thioacetic acid (ATM), forms a slow-release boehmite. During the electrochemical corrosion of metals, OH- ions are released, creating a localized alkaline environment. Under alkaline conditions, the corrosion-inhibiting boehmite hydrolyzes, breaking ester bonds and accelerating the forward shift of the hydrolysis equilibrium, releasing AMT, which has a corrosion-inhibiting effect. AMT coordinates with the metal and adsorbs onto the metal surface, forming a protective film that effectively inhibits metal corrosion.

[0016] Furthermore, the preparation process of this rapid repair coating is as follows: After mixing and stirring the resin matrix, solvent, dispersant, and defoamer, rheology modifier, and pigment in the formulation to a uniform consistency, add the resin reinforcing agent, wear-resistant filler, nano filler, and rust-converting filler in the formulation to a uniform consistency. While stirring, add glass beads and grind for 4.5 to 5 hours. Then add the rheology modifier in the auxiliary additives, stir to a uniform consistency, grind for another 1.5 to 2 hours, and filter to obtain the final product.

[0017] On the other hand, the present invention also provides a rapid repair method for corrosion-resistant and wear-resistant offshore wind power steel structure mooring piles, using the above-mentioned rapid repair coating for corrosion-resistant and wear-resistant offshore wind power steel structure mooring piles, including the following steps: Step 1) Surface preparation: Rust removal and sanding to Sa2.0 grade; Step 2) Primer application: Use a roller to apply 3 coats of the above-mentioned anti-corrosion and wear-resistant quick repair coating as primer along the texture of the substrate. The number of round trips should be ≤2. The thickness of each primer coat should be 100μm. Allow the primer to dry for 2 hours before applying the next coat. Step 3) Topcoat application: Apply two coats of topcoat using a roller, rolling along the texture of the substrate, with ≤2 back-and-forth passes. The thickness of each coat should be 150μm. Allow the surface to dry for 1 hour before applying the next coat.

[0018] Furthermore, the topcoat in step 3) is composed of PU45-04 polyurea and pyrogallol-modified polyurethane curing agent in a mass ratio of 1.5:1.

[0019] The beneficial effects of this invention are as follows: The corrosion-resistant and wear-resistant rapid repair coating provided by this invention introduces polyurethane elastic segments into the epoxy resin structure, achieving a high-strength and toughening effect of epoxy resin while endowing the coating with excellent shape memory function and hydrogen bond microcrack repair characteristics. Fillers such as alumina and zirconium dioxide are added to the resin system to improve the coating's wear resistance and toughness. Rust-converting fillers such as aluminum tripolyphosphate and zinc phosphate are added to the coating system to form a dense shielding layer even on substrates with low surface treatment. The added slow-release boehmite accelerates the release of corrosion inhibitors when the pH value changes in the microenvironment caused by corrosion. It chelates with metal ions in the early stages of corrosion, adsorbs onto the metal surface, and forms a protective film on the metal surface, effectively inhibiting metal corrosion.

[0020] The coating of this invention achieves a balance in mechanical strength, corrosion resistance, and workability. The coating has a salt spray resistance of up to 5000 hours without rust and an abrasion resistance of <5mg (750g / 1000r), which fully meets the requirements of the C5-M corrosion environment for offshore wind power. It can effectively resist mechanical impact damage to offshore wind power components, pile foundations, and other parts.

[0021] The corrosion-resistant and wear-resistant rapid repair method provided by this invention has a thorough substrate treatment, and the coating forms an effective bond with the substrate. The primer and topcoat are applied by roller, which shortens the local repair construction cycle from the traditional 3 to 5 days to 1 to 2 days, and improves the construction efficiency by more than 60%. Attached Figure Description

[0022] Figure 1 This is a schematic diagram of a steel structure docking pile; Figure 2 It is the infrared spectrum of the resin structure; Figure 3 These are the tensile properties test results of polyurethane-modified epoxy resin; Figure 4 These are the test results for the flexural properties of polyurethane-modified epoxy resin. Figure 5 This is the infrared absorption spectrum of BIB; Figure 6 It is the infrared absorption spectrum of the intermediate product; Figure 7 This is the infrared absorption spectrum of HFTC; Figure 8 This is a process flow diagram of the rapid repair method of the present invention.

[0023] 1. Tower; 2. Dock pile; 3. Steel; 4. Primer; 5. Topcoat. Detailed Implementation

[0024] The following specific embodiments illustrate the implementation of the invention. Those skilled in the art can easily understand other advantages and effects of the invention from the content disclosed in this specification.

[0025] Exemplary embodiments of the invention are now described with reference to the accompanying drawings. However, the invention may be embodied in many different forms and is not limited to the embodiments described herein. These embodiments are provided to fully and completely disclose the invention and to fully convey its scope to those skilled in the art. The terminology used in the exemplary embodiments illustrated in the drawings is not intended to limit the invention.

[0026] Unless otherwise stated, the terms used herein (including technical terms) have their common meaning as understood by one of ordinary skill in the art. Furthermore, it is understood that terms defined in commonly used dictionaries should be understood to have a meaning consistent with the context of their relevant field, and not to be interpreted as having an idealized or overly formal meaning.

[0027] Example 1 Preparation of resin matrix: The amount of polyurethane prepolymer is crucial to the flexibility and strength of polyurethane-modified epoxy (resin matrix). To investigate the effect of polyurethane content, formulations were prepared with epoxy resin:polyurethane prepolymer ratios of 100:10, 100:20, 100:30, and 100:50, and their tensile properties, flexural properties, adhesive properties, and curing time were tested. The curing agent was pyrogallol-modified polyamide.

[0028] In this embodiment, the epoxy resin is bisphenol A type epoxy resin E44; the polyurethane prepolymer is an isocyanate-terminated polyurethane prepolymer, and its properties are shown in Table 1.

[0029] Table 1 Properties of Polyurethane Prepolymers The terminal isocyanate groups and some unreacted -NCO groups in TDI react with the hydroxyl groups in epoxy resin, as shown in the following equation: 1. Infrared spectroscopy was performed on epoxy resin, polyurethane prepolymer, and modified epoxy resin (polyurethane prepolymer content was 20%). The results are as follows: Figure 2 As shown.

[0030] from Figure 2 It can be seen that in the infrared spectrum of (a) pure epoxy resin, 3475 cm⁻¹ -1 and 916cm -1 The characteristic absorption peaks for hydroxyl and epoxy groups are located at 2970 cm⁻¹, respectively; in the infrared spectrum of the polyurethane prepolymer (b), the characteristic absorption peak for hydroxyl and epoxy groups is located at 2970 cm⁻¹. -1 and 2870cm -1 Characteristic absorption peaks for methyl and methylene groups appear at 2278 cm⁻¹, and at 2278 cm⁻¹... -1 The characteristic absorption peak of -NCO appears at 2278 cm⁻¹, indicating that this polyurethane is an isocyanate-terminated long-chain flexible polyurethane; in the infrared spectrum of the modified epoxy resin (c), the characteristic absorption peak of -NCO appears at 2278 cm⁻¹. -1 No obvious isocyanate group (-NCO) characteristic absorption peak was observed at 3475 cm⁻¹. -1 The characteristic absorption peak of the hydroxyl group (-OH) at 916 cm⁻¹ -1 The characteristic absorption peak of the epoxy group at 3297 cm⁻¹ was also significantly weakened, while the peak at 3297 cm⁻¹ was also significantly weakened. -1 and 1703cm -1 The presence of stretching vibration peaks of -NH and -C=O in urethane (-NHCOO-) suggests that the hydroxyl (-OH) and epoxy groups in the epoxy resin underwent a chemical grafting reaction with the isocyanate groups (-NCO) in the polyurethane prepolymer.

[0031] 2. The test results of the mechanical properties of modified epoxy resins with different polyurethane prepolymer dosages are shown in Table 2. Figure 3 and Figure 4 As shown.

[0032] Table 2 Depend on Figure 4It can be seen that with the increase of polyurethane prepolymer content, tensile strength and flexural strength show a trend of first increasing and then decreasing. When the polyurethane prepolymer content is less than 20%, the crosslinking points in the system increase, and the tensile strength and flexural strength increase. When the polyurethane content is greater than 20%, the side chain content in EP increases, the intermolecular distance increases, and the intermolecular force decreases, so the tensile strength and flexural strength decrease. With the increase of polyurethane content, the elongation at break and flexural deformation show a trend of first increasing and then slightly decreasing. When the polyurethane content is less than 20%, -NCO and -OH react, and polyurethane is grafted onto the EP molecular chain to form an interpenetrating network structure, which significantly improves toughness. When the polyurethane content is greater than 20%, -OH has fully reacted, and the excess -NCO either undergoes self-polymerization or reacts with -NHCOO, destroying the homogeneity of the system, and the elongation at break and flexural deformation decrease slightly. To maintain the material's strength and toughness, the mechanical properties are optimal when the polyurethane content is 20%. At this level, the tensile strength is 18.49 MPa, the flexural strength is 16.9 MPa, the elongation at break is 51.3%, and the bending deformation is 3.9 mm, all of which are significantly improved compared to epoxy resin.

[0033] 3. The effect of the amount of elastic polyurethane prepolymer added on the performance of epoxy resin was characterized by impact test and tensile strength test. The test results are shown in Table 3.

[0034] Table 3 Results of Low Temperature Impact Resistance Test The resin matrix still faces two major challenges: firstly, the interfacial adhesion with the metal substrate is easily weakened by environmental erosion; secondly, it lacks active corrosion inhibition function, failing to suppress localized corrosion of the substrate after coating damage. To improve the material's adhesion, based on the biomimetic concept of mussels, catechol from mussel foot proteins is introduced into the material to enhance adhesion. The heterocyclic structure of benzimidazole can hinder the penetration of corrosive media such as chloride ions and water molecules into the metal, thus achieving active corrosion inhibition protection. By adding BIB or HFTC compounds, which both contain catechol functional groups that enhance adhesion and benzimidazole rings that inhibit corrosion, the compounds are added to epoxy resin to form a biomimetic adhesive, eliminating the need for further metal surface treatment and increasing the adhesion strength of the epoxy resin.

[0035] The preparation of BIB compounds includes: First, add a 4 mol / L hydrochloric acid solution to a clean 250 ml three-necked flask, add a magnetic stirrer, and place the flask in a magnetically stirred oil bath. Attach a condenser to the flask, then set the oil bath temperature to 60°C and stir the hydrochloric acid solution. Weigh out 3,3-diaminobenzidine (DAB) and 3,4,5-trihydroxybenzoic acid (GA) in a 1:2 molar ratio. First, slowly add 3,3-diaminobenzidine to the flask to disperse it evenly, then slowly add 3,4,5-trihydroxybenzoic acid. Add an appropriate amount of DMAC, and purge with nitrogen to remove air. Set the oil bath temperature to 150°C and the reaction time to 8 hours. As the reaction temperature and time increase, the solution color changes from brown to brownish-green. After the reaction solution cools to room temperature, pour it into a Buchner funnel, filter the filtrate using a circulating water vacuum pump, wash the solid in the funnel with deionized water, and collect the brownish-red liquid in the flask. The filtrate was poured into a beaker, and its pH was tested with pH paper; it was strongly acidic. The pH of the filtrate was adjusted using a 2 mol / L sodium hydroxide solution. The alkali solution was slowly added dropwise to the beaker while stirring with a glass rod, and the pH value was recorded at intervals. When the pH of the filtrate reached approximately 6, it began to become cloudy, followed by the precipitation of a large amount of white solid. Alkali solution was continued to be added dropwise until the pH approached 7, at which point the addition was stopped. The filtrate was poured into a Buchner funnel and filtered under vacuum. It was washed several times with deionized water and anhydrous ethanol. Washing was stopped when the liquid seeping through the funnel was observed to be colorless and transparent. Finally, the white solid was freeze-dried to obtain compound BIB.

[0036] The infrared absorption spectrum of BIB is as follows: Figure 5 As shown in the figure. It can be seen from the graph that the spectral depth is 3343.6 cm⁻¹. -1 With 3125.6cm -1 The absorption peaks at 1640 and 1601.6 cm⁻¹ are absorption peaks generated by the stretching vibration of NH. -1 The absorption peak at 2968 cm⁻¹ belongs to the absorption peaks generated by the ordinary resonance vibration of C=N and the polarization vibration of NH. -1 The absorption peak at 1253 cm⁻¹ belongs to the stretching vibration of the phenolic hydroxyl group. -1 and 1040cm -1 The absorption peaks at 1340 cm⁻¹ belong to the bending vibrations of OH and the asymmetric stretching vibrations of CO, respectively. -1 The strong absorption peaks at 1499 and 1450 cm⁻¹ are attributed to the absorption peaks produced by CN stretching. -1 The absorption peak at 750 cm⁻¹ is an absorption peak generated by the skeletal vibration of the substituted benzene ring. -1 The absorption peak at this point is generated by the out-of-plane bending vibration of CH on the benzene ring.

[0037] Preparation of HFTC compounds: Preparation of intermediate products: First, a magnetic stirrer was added to a clean 100ml single-necked flask, followed by a 4mol / L hydrochloric acid solution. The flask was then placed in a magnetically stirred oil bath with a condenser attached. The oil bath temperature was set to 60℃, and the hydrochloric acid solution was stirred. Equimolar amounts of ethyl 3,4-diaminobenzoate and 3,4,5-trihydroxybenzaldehyde (THB) were weighed. Ethyl 3,4-diaminobenzoate was first added to the hydrochloric acid solution, and after it was evenly dispersed, 3,4,5-trihydroxybenzaldehyde was added, followed by an appropriate amount of DMF. The oil bath temperature was set to 120℃, and the reaction time was 10 hours. As time progressed, the color of the reaction solution changed from reddish-brown to pale green. The reaction was stopped, and the reaction solution in the flask was allowed to cool to room temperature. The solution was then poured into a Buchner funnel and filtered using a vacuum pump. The solid in the funnel was washed with deionized water, and the filtrate was collected. The filtrate was poured into a clean beaker; the filtrate was red. The filtrate was treated according to the pH adjustment method for compound BIB. When the pH approached 6, a black solid precipitated in the solution, suspended in the filtrate. The pH was further adjusted to near neutral. The filtrate was poured into a Buchner funnel and filtered under vacuum. It was washed three times with anhydrous ethanol, and finally washed with deionized water. Washing was stopped when the liquid seeping through the funnel changed from red to colorless and transparent. A black solid was obtained and freeze-dried. The intermediate product was obtained and named 2-(3,4,5-trihydroxyphenyl)-1H-benzo[d]imidazole-6-carboxylic acid.

[0038] Preparation of the target product: Cyclohexane was added to a single-necked flask, and a magnetic rotor was added. Intermediate product 2 was weighed and added to the flask. 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) was weighed in an equimolar ratio with intermediate product 2 according to calculations. Hexane was added as solvent, followed by a certain mass of N,N'-diisopropylcarbodiimide (DIC). A condenser was inserted, and air was evacuated from the flask and condenser using a vacuum pump. Nitrogen gas was introduced. The oil bath temperature was set to 50°C, and the reaction time was 4 hours. When the oil bath temperature reached 50°C, liquid reflux occurred inside the flask. After the reaction solution cooled to room temperature, it was poured into a Buchner funnel and filtered using a vacuum pump to remove the filtrate. The solution was washed three times with cyclohexane, then several times with anhydrous ethanol, and finally with deionized water. The solid was collected and freeze-dried in a freeze dryer to obtain a black solid, HFTC.

[0039] The infrared absorption spectrum of the intermediate product is shown in Figure 6. As can be seen from the figure, at 3500 cm⁻¹... -1 Up to 2960cm -1 There is a broad absorption peak, which may be formed by the interaction between carboxyl and hydroxyl groups. (3216 and 3072 cm⁻¹) -1 The absorption peaks at 1629 and 1590 cm⁻¹ are absorption peaks generated by the stretching vibration of NH. -1The absorption peaks at 1507 and 774 cm⁻¹ belong to the absorption peaks generated by the ordinary resonance vibration of C=N and the polarization vibration of NH. -1 The absorption peaks at 1700 cm⁻¹ belong to the absorption peaks generated by the skeletal vibration of the benzene ring and the out-of-plane bending vibration of CH on the benzene ring, respectively. -1 The absorption peak at 1218 cm⁻¹ is due to the C=O stretching vibration. -1 and 1039cm -1 The absorption peaks at 1340 cm⁻¹ belong to the bending vibrations of OH and the asymmetric stretching vibrations of CO, respectively. -1 The strong absorption peak is attributed to the absorption peak generated by CN stretching.

[0040] The infrared absorption spectrum of HFTC is as follows: Figure 7 As shown in the diagram. The absorption spectra show that 3438 and 3223 cm⁻¹... -1 The absorption peak at 3050 cm⁻¹ is an absorption peak generated by the stretching vibration of NH. -1 The absorption peak at 2943 cm⁻¹ is caused by the stretching vibration of OH. -1 The absorption peak at 1703 cm⁻¹ is due to the stretching vibration of the methylene group (CH). -1 The absorption peaks at 1608 and 1572 cm⁻¹ are absorption peaks generated by the C=O stretching vibration. -1 The absorption peaks at 1525 and 773 cm⁻¹ belong to the absorption peaks generated by the ordinary resonance vibration of C=N and the polarization vibration of NH. -1 The absorption peaks at 1346 cm⁻¹ belong to the absorption peaks generated by the skeletal vibration of the benzene ring and the out-of-plane bending vibration of CH on the benzene ring, respectively. -1 The absorption peak at 1149 cm⁻¹ is due to CN stretching. -1 and 1006cm -1 The absorption peaks at 1113 cm⁻¹ belong to the bending vibrations of OH and the asymmetric stretching vibrations of CO, respectively. -1 The absorption peak at that point is due to the stretching vibration of CF, because HFTC contains carbon-fluorine bonds.

[0041] Example 2 The effect of different amounts of alumina added on the abrasion resistance of the coating was investigated when the mass ratio of epoxy resin to polyurethane prepolymer was 100:20. The formulation is shown in Table 4.

[0042] Table 4 Alumina has a Mohs hardness of 9 (second only to diamond) and a dense crystalline structure. When dispersed in powder form in coating matrices (such as epoxy resin, polyurethane, ceramic matrix, etc.), it can form a "rigid support skeleton." When the coating is subjected to external friction or impact, the alumina particles can directly bear the load, preventing wear caused by deformation of the matrix resin under stress, thus increasing the surface hardness of the coating compared to a pure resin matrix. The abrasion resistance test results of coatings with different alumina addition amounts are shown in Table 5.

[0043] Table 5 As shown in Table 5, the coating wear amount initially decreases and then increases with increasing alumina content. Particularly when the alumina content is 1.2 times that of epoxy resin, the coating wear amount decreases significantly. This is because the alumina is arranged in a close-packed manner within the coating, reducing the wear of other fillers and thus resulting in a substantial decrease in wear amount. The coating exhibits optimal wear resistance when the alumina-to-epoxy resin ratio reaches 2. However, as the alumina content continues to increase, the alumina is not completely coated by the resin, leading to increased coating wear.

[0044] Example 3 This embodiment provides a rapid repair coating for corrosion and wear resistance of offshore wind power steel structure docking piles, including a resin matrix, resin reinforcing agent, curing agent, wear-resistant filler, nano filler, rust-converting filler, auxiliary additives and solvent; The wear-resistant filler comprises polytetrafluoroethylene powder and alumina. The resin matrix is ​​obtained by crosslinking epoxy resin and polyurethane prepolymer in a mass ratio of 100:20. The amount of alumina added is twice the mass of epoxy resin, and the amount of resin reinforcing agent added is 0.3% to 0.6% of the mass of the resin system. Based on the mass of the repair coating as 100%, the mass percentage of the nanofiller is 13%~16%, the mass percentage of the tetrafluoroethylene powder is 4%~6%, the mass percentage of the rust conversion filler is 5%~6%, the mass percentage of the auxiliary additives is 16%~18%, the mass percentage of the solvent is 7%~8%, and the mass percentage of the curing agent is 2%~3%.

[0045] To improve corrosion and wear resistance, the following components were used in fixed quantities: epoxy resin 30g, polyurethane prepolymer 6g, pyrogallol-modified polyurethane curing agent 4.6g, auxiliary additives 32.5g (dispersant 0.5g, isooctanol defoamer 0.5g, rheology modifier silica 1.5g, iron oxide red 30g), alumina 60g and titanium dioxide 16g, compound HFTC reinforcing agent 0.9g, rust conversion filler 10g (aluminum tripolyphosphate 3g + zinc phosphate 7g), and solvent toluene 15g. The main factors investigated were polytetrafluoroethylene powder, zirconium dioxide, and boehmite. Each factor had four levels. The orthogonal experimental factor level table is shown in Table 6. Orthogonal experimental table L16(4) was selected. 3 The experiments were conducted, as shown in Table 7. To ensure consistent coating viscosity, hydroxyethyl cellulose ether was used as a thickener to adjust the coating viscosity. Four samples were prepared for each experiment for later testing. The neutral salt spray test time was used as the main evaluation index. The results of the coating appearance and abrasion resistance tests were also considered. Through intuitive analysis, the optimized coating formulation was finally obtained.

[0046] Table 6. Factor Level Table for Orthogonal Experiments Preparation process: The resin matrix, solvent, dispersant, defoamer, rheology modifier, and pigment of the formula are dispersed at 2000 rpm using a high-speed disperser for 20 minutes until the resin slurry is uniformly dispersed. Then, the resin reinforcing agent, wear-resistant filler, nano filler, and rust-converting filler of the formula are added and dispersed at 2000 rpm for 20 minutes. The high-speed dispersion disc is removed and replaced with a sand mill dispersion disc at 1500 rpm. While dispersing, glass beads of 30% to 70% of the coating weight are added to the dispersion tank. After grinding for 4.5 hours, the rheology modifier is added and stirred evenly. After grinding for another 1.5 to 2 hours, the machine is turned off, filtered, and the material is discharged.

[0047] Table 7 Orthogonal Test Table for Coatings L16 (4) 3 ) Analysis of orthogonal experiment results: The appearance evaluation is divided into two aspects: gloss and roughness. Gloss evaluation: Based on visual inspection, coatings with a bright silver color and gloss are rated 2 points, while coatings with a dark gray surface are rated 0 points. Coatings in between are appropriately divided into various evaluation levels. Abrasion resistance evaluation: Abrasion-resistant coating test conditions: drying time 7 days, film thickness 246 micrometers, 3 parallel plates; sample preparation method: air spraying test conditions: 500g, 500 rpm; film loss 30-40 micrometers; abrasion resistance test results are shown in Table 8 below. The final appearance evaluation score is the sum of the coating gloss and abrasion resistance evaluations; the higher the score, the better the surface coating quality.

[0048] Table 8 Test results of coatings with different wear-resistant fillers Therefore, factor A is optimally at level A1, factor B is optimally at level B1 or B2, and factor C is optimally at level C1. Thus, the most ideal combination is determined to be A1B2C1. The ideal formulation is shown in Table 9.

[0049] Table 9. Components and Optimal Proportions of Anti-corrosion and Wear-resistant Coatings The coating was tested in terms of its overall appearance, abrasion resistance, and corrosion resistance. The results are shown in Table 10.

[0050] Table 10 Example 4 This embodiment provides a rapid repair method for corrosion and wear resistance of offshore wind turbine steel structure berthing piles, using the aforementioned repair coating, such as... Figure 8 As shown, it includes the following steps: Step 1) Surface preparation: Rust removal and sanding to Sa2.0 grade; Step 2) Primer application: Use a roller to apply 3 coats of the above-mentioned anti-corrosion and wear-resistant quick repair coating as primer along the texture of the substrate. The number of round trips should be ≤2. The thickness of each primer coat should be 100μm. Allow the primer to dry for 2 hours before applying the next coat. Step 3) Topcoat application: Apply two coats of topcoat using a roller, rolling along the texture of the substrate, with ≤2 back-and-forth passes. The thickness of each coat should be 150μm. Allow the surface to dry for 1 hour before applying the next coat.

[0051] The bollard 2 is located directly below tower 1 and is completely outside tower 1, such as... Figure 1 As shown, the bollard 2 is made of steel. First, a primer 4 is rolled onto the surface of the steel 3, and then a topcoat 5 is rolled onto it.

[0052] The examples above are merely illustrative of the invention and do not constitute a limitation on the scope of protection of the invention. Any design that is the same as or similar to the invention falls within the scope of protection of the invention.

Claims

1. A rapid repair coating for corrosion and wear resistance of offshore wind turbine steel structure mooring piles, characterized in that, It includes resin matrix, resin reinforcing agent, curing agent, wear-resistant filler, nano filler, rust-converting filler, auxiliary additives and solvent; The wear-resistant filler comprises polytetrafluoroethylene powder and alumina. The resin matrix is ​​obtained by crosslinking epoxy resin and polyurethane prepolymer, with a mass ratio of 100:10~50. The amount of alumina added is 1.2~2 times the mass of epoxy resin, and the amount of resin reinforcing agent added is 0.3%~0.6% of the mass of the resin system. Based on the mass of the repair coating as 100%, the mass percentage of the nanofiller is 13%~16%, the mass percentage of the tetrafluoroethylene powder is 4%~6%, the mass percentage of the rust conversion filler is 5%~6%, the mass percentage of the auxiliary additives is 16%~18%, the mass percentage of the solvent is 7%~8%, and the mass percentage of the curing agent is 2%~3%.

2. The rapid repair coating for corrosion and wear resistance of offshore wind power steel structure mooring piles according to claim 1, characterized in that, The nanofiller includes nano ZrO2, slow-release boehmite, and nano titanium dioxide, with a mass ratio of 1:5 to 6:

10.

3. The rapid repair coating for corrosion and wear resistance of offshore wind power steel structure mooring piles according to claim 1, characterized in that, The auxiliary additives include dispersants, defoamers, rheology modifiers, and pigments.

4. The rapid repair coating for corrosion and wear resistance of offshore wind power steel structure mooring piles according to claim 1, characterized in that, The resin reinforcing agent is a BIB compound or an HFTC compound; The BIB compound was prepared by a dehydration condensation reaction of 3,3-diaminobenzidine and 3,4,5-trihydroxybenzoic acid under acidic conditions; the HFTC compound was prepared by a benzimidazole reaction of ethyl 3,4-diaminobenzoate and 3,4,5-trihydroxybenzaldehyde to generate an intermediate, which was then reacted with 1,1,1,3,3,3-hexafluoro-2-propanol.

5. The rapid repair coating for corrosion and wear resistance of offshore wind power steel structure mooring piles according to claim 1, characterized in that, The rust conversion filler is composed of aluminum tripolyphosphate and zinc phosphate, with a mass ratio of 2~3:7~8.

6. The rapid repair coating for corrosion and wear resistance of offshore wind power steel structure mooring piles according to claim 1, characterized in that, The preparation process of the resin matrix is ​​as follows: The epoxy resin and polyurethane prepolymer were preheated at 40-50℃ for 4-6 hours and then vacuum treated at -0.1MPa until the bubbles were completely eliminated. The epoxy resin and polyurethane prepolymer were then mixed and homogeneously sheared and stirred at 40-50℃ for 1-1.5 hours. After cooling to room temperature, polyurethane-modified epoxy resin was obtained.

7. The rapid repair coating for corrosion and wear resistance of offshore wind power steel structure mooring piles according to claim 2, characterized in that, The preparation process of the sustained-release boehmite is as follows: Boehmite was ultrasonically dispersed in N,N-dimethylacetamide for 3-10 min, then 5-amino-1,3,4-thiadiazole-2-thioacetic acid was added, followed by 3-5 drops of concentrated sulfuric acid. The mixture was reacted at 70-80 °C for 2 h, and then slowly heated to 135-140 °C for 4-5 h. The mass ratio of boehmite to 5-amino-1,3,4-thiadiazole-2-thioacetic acid was 1:2.5-6. After cooling, the solid was deposited and filtered. The solid was repeatedly washed with water and ethanol until the filtered solution no longer contained organic matter. The corrosion-inhibiting boehmite was obtained by vacuum drying at 70-80℃ for 10-12 hours.

8. A rapid repair coating for corrosion and wear resistance of offshore wind power steel structure mooring piles according to any one of claims 1 to 7, characterized in that, The preparation process is as follows: After mixing and stirring the resin matrix, solvent, dispersant, and defoamer, rheology modifier, and pigment in the formulation to a uniform consistency, add the resin reinforcing agent, wear-resistant filler, nano filler, and rust-converting filler in the formulation to a uniform consistency. While stirring, add glass beads and grind for 4.5 to 5 hours. Then add the rheology modifier in the auxiliary additives, stir to a uniform consistency, grind for another 1.5 to 2 hours, and filter to obtain the final product.

9. A rapid repair method for corrosion-resistant and wear-resistant offshore wind turbine steel structure mooring piles, using the rapid repair coating for corrosion-resistant and wear-resistant offshore wind turbine steel structure mooring piles as described in any one of claims 1 to 8, characterized in that, Includes the following steps: Step 1) Surface preparation: Remove rust and grind to Sa2.0 grade; Step 2) Primer application: Use a roller to apply 3 coats of the above-mentioned anti-corrosion and wear-resistant quick repair coating as primer along the texture of the substrate. The number of round trips should be ≤2. The thickness of each primer coat should be 100μm. Allow the primer to dry for 2 hours before applying the next coat. Step 3) Topcoat application: Apply two coats of topcoat using a roller, rolling along the texture of the substrate, with ≤2 back-and-forth passes. The thickness of each coat should be 150μm. Allow the surface to dry for 1 hour before applying the next coat.

10. A rapid repair method for corrosion and wear resistance of offshore wind power steel structure mooring piles according to claim 8, characterized in that, The topcoat in step 3) is composed of PU45-04 polyurea and pyrogallol-modified polyurethane curing agent in a mass ratio of 1.5:1.

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