A marine accessory anti-rust coating and a method of preparing the same

Abstract

The application relates to the technical field of ship protection materials, in particular to a ship accessory rust-proof coating and a preparation method thereof. The ship accessory rust-proof coating comprises the following three layers of structures and components from inside to outside: a basic corrosion-resistant layer comprising 10-30 parts of nano ceramic material, 5-15 parts of rare earth oxide, 0.5-1.5 parts of aminated graphene oxide, 40-60 parts of fluorocarbon resin, 20-30 parts of epoxy-polyurethane hybrid resin, 3-8 parts of zinc phosphate corrosion inhibitor and 2-5 parts of self-repairing microcapsules and 1-3 parts of photoinitiator; an interface transition layer comprising 3-5 parts of gamma-aminopropyl triethoxysilane and 2-5 parts of silicone resin coated copper powder; and a dirt-proof surface layer comprising 10-15 parts of Cu@SiO2 core-shell particles, 10-15 parts of polydimethylsiloxane and methyltrimethoxysilane copolymer and 1-3 parts of dirt-proof auxiliary agent. The ship multifunctional protection coating provided by the application realizes comprehensive improvement of corrosion resistance, dirt resistance, self-repairing and construction efficiency through the synergistic effect of multiple components, and exhibits significant technical progress and practical value.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of ship protection materials, in particular to a ship accessory rust-proof coating and a preparation method thereof. BACKGROUND

[0002] Ships are long-term exposed to harsh marine environments with high salinity, high humidity and alternating dry and wet conditions. The protective coating of the ship needs to meet multiple requirements such as corrosion resistance, biofouling resistance, mechanical impact resistance and rapid repair. However, the existing coating technology has significant limitations:

[0003] Traditional epoxy resin coatings have good adhesion and chemical stability, but they are prone to problems such as blistering and peeling under the action of long-term salt spray (ASTM B117). Especially in tropical sea areas, the actual service life is usually less than 5 years, and frequent repair is required, increasing maintenance costs.

[0004] Copper-based antifouling coatings (such as cuprous oxide or copper powder) can effectively inhibit marine biofouling, but they are prone to corrosion when in direct contact with seawater, leading to interface delamination and accelerating coating failure. Existing solutions (such as insulation layers) often sacrifice antifouling or corrosion resistance.

[0005] The substrate surface is usually required to be treated to Sa2.5 level (ISO 8501), but the ship repair site is limited by conditions and can only achieve Sa2 level (with local residual rust), making it difficult to repair in time.

[0006] Traditional thermosetting coatings require more than 72 hours to reach the use strength, significantly prolonging the ship dock period (with a daily cost of more than $100,000). Although there are attempts to use light-curing technology, it is difficult to balance the deep curing and performance of thick coatings (>200 μm). SUMMARY

[0007] To overcome the shortcomings of the prior art, the present application provides a multifunctional ship coating with long-term corrosion resistance, biofouling resistance, self-repair and fire resistance, and a preparation method thereof, which is suitable for harsh environments such as ship body, ballast tank and deck.

[0008] According to a first aspect of the present application, a ship accessory rust-proof coating is provided, which comprises the following three layers of structures and components from inside to outside:

[0009] The base corrosion-resistant layer comprises, by mass fraction:

[0010] 10-30 parts of nano ceramic material selected from at least one of Al2O3, SiO2 or ZrO2, forming a dense physical barrier to block the penetration of corrosion media such as Cl - , H2O (penetration rate reduced by more than 60%), and nano-particle filling coating micropores to improve hardness (pencil hardness ≥ 4H);

[0011] Rare earth oxide 5-15 parts, at least one selected from CeO2, La2O3 or Y2O3, Ce 3+ / Ce 4+ Redox reaction passivation steel substrate, forming Ce(OH)3 / CeO2 protective film, La2O3 adsorbing SO4 2- Isotonic acid ions, inhibit local acidification corrosion;

[0012] Amino graphene oxide (GO-NH2) 0.5-1.5 parts, -NH2 and -CF2- of fluorocarbon resin form hydrogen bond, enhance interfacial bonding strength, conductive network dissipate static electricity, avoid local charge accumulation leading to coating peeling;

[0013] Fluorocarbon resin 40-60 parts, selected from polyvinylidene fluoride (PVDF) or fluorine ethylene-vinyl ether copolymer (FEVE);

[0014] Epoxy-polyurethane hybrid resin, 20-30 parts;

[0015] Zinc phosphate corrosion inhibitor 3-8 parts, zinc phosphate (Zn3(PO4)2) forms a passivation film in the repair area to prevent secondary corrosion;

[0016] Self-repairing microcapsules 2-5 parts, containing dicyclopentadiene (DCPD) core material and polyurea formaldehyde (PUF) wall material, after the capsule breaks, DCPD polymerizes with residual Grubbs catalyst to fill the cracks, and PUF wall material releases the repair agent slowly, suitable for Sa2 level surface (containing trace rust layer);

[0017] Photoinitiator 1-3 parts, selected from 2-hydroxy-2-methyl-1-phenyl-1-propanone (HMPP) or benzophenone.

[0018] After the rare earth oxide is co-milled with the nano ceramic, the rare earth particles are dispersed in the ceramic network, the pores of the nano ceramic are filled with the rare earth particles, the porosity is further reduced, the passivation effect covers a wider range, and the Ce content on the substrate surface is increased by 3 times. Amino graphene oxide and nano ceramic jointly construct a "ceramic-graphene" three-dimensional skeleton, and the compressive strength is increased to 120 MPa (pure resin is 80 MPa).

[0019] Interface transition layer: contains, by mass fraction:

[0020] Gamma-aminopropyl triethoxysilane (KH-550) 3-5 parts;

[0021] Copper powder coated with silicone resin (Cu@SiO2) 2-5 parts, copper content ≥60wt%.

[0022] -NH2 and the bottom layer of rare earth oxide hydroxyl bond, -OCH3 and the surface layer of silicone resin condensation, with Cu@SiO2core-shell particles, SiO2shell and KH-550 form Si-O-Si network, the interface resistance is increased to 10 12 Ω (avoiding galvanic corrosion). SiO2shell isolates copper and the bottom layer of rare earth oxide, preventing Cu 2+ triggering redox reaction, copper core slow release Cu + / Cu 2+ , maintaining the antifouling effect.

[0023] Antifouling surface layer: by mass fraction, comprising:

[0024] Cu@SiO2core-shell particles 10-15 parts;

[0025] Polydimethylsiloxane and methyltrimethoxysilane copolymer (PDMS-MTMOS copolymer) 10-15 parts;

[0026] Antifouling aids 1-3 parts, selected from at least one of capsaicin or zinc pyrithione (ZPT).

[0027] PDMS resin wrapped Cu@SiO2, forming a low surface energy (contact angle 112°) and ion release dual antifouling mechanism. PDMS-MTMOS copolymer, low surface energy (≤25 mN / m) makes it difficult for organisms to adhere, MTMOS crosslinking improves mechanical strength, and after compounding with capsaicin / ZPT, the surface energy is further reduced to 20 mN / m, and ZPT inhibits the formation of microbial membranes. Capsaicin interferes with the nerve conduction of barnacle larvae, and ZPT destroys the cell membrane of algae, broad-spectrum antifouling: 95% algae inhibition rate, 90% barnacle inhibition rate, combined with Cu@SiO2, the antifouling effective period is extended to 5 years (single copper-based coating is 3 years).

[0028] The rare earth oxide (bottom layer) and Cu@SiO2 (surface layer) are electrically isolated by the KH-550 transition layer, while retaining the dual protection function. The graphene-enhanced ceramic skeleton provides mechanical support, and the microcapsule repairs local damage, increasing the overall life by 3 times. The fluorocarbon resin hydrophobicity (contact angle 105°) reduces water retention, and the PDMS surface layer inhibits biological adhesion, synergistically reducing the risk of corrosion.

[0029] According to the embodiment of the application, the particle size of the nanoceramic material is 20-100 nm;

[0030] The mass ratio of the nanoceramic material to the rare earth oxide is 2:1-3:1;

[0031] The oxygen content of the aminated graphene oxide is ≤10 wt%.

[0032] According to the embodiment of the present application, the particle size of the self-repairing microcapsule is 10-50 μm, and the wall material thickness accounts for 10%-15% of the total mass of the capsule.

[0033] According to the embodiment of the present application, the base corrosion-resistant layer further comprises 0.1-0.5 parts of carbon nanotubes for enhancing the electrical conductivity.

[0034] According to the embodiment of the present application, the thickness of the interface transition layer is 5-10 μm, and the molar ratio of the γ-aminopropyltriethoxysilane to the hydroxyl group on the surface of the rare earth oxide is 1:1-1.2.

[0035] According to the embodiment of the present application, the antifouling aid is a complex of capsaicin and ZPT, and the mass ratio is 1:1-1:2.

[0036] According to the embodiment of the present application, the diameter of the copper core of the Cu@SiO2 core-shell particle is 1-5 μm, and the thickness of the SiO2 shell is 100-300 nm.

[0037] The copper content of the copper powder coated with the silicone resin is ≥60 wt%.

[0038] According to the embodiment of the present application, the curing mode of the base corrosion-resistant layer is ultraviolet light curing, and the energy density is 300-500 mJ / cm 2 .

[0039] According to the second aspect of the present application, a method for preparing a rust-proof coating for a ship accessory is provided, comprising the following steps:

[0040] Preparation of the base corrosion-resistant layer:

[0041] The nanoceramic material and the rare earth oxide are added into a ball mill, and anhydrous ethanol is added, with the mass being 50% of the total weight of the nanoceramic material and the rare earth oxide, and zirconium oxide balls are used as the grinding medium (ball-to-material ratio 5:1). After ball milling, vacuum drying is performed (60°C, 2 hours) to obtain a uniform composite powder.

[0042] Ball milling parameters: rotation speed 300-400 rpm, time 2-4 hours, and temperature 25-30°C.

[0043] The fluorocarbon resin and the epoxy-polyurethane hybrid resin are added into a reaction kettle, and stirring is performed until the viscosity of the system is stable.

[0044] The photoinitiator is added, and stirring is continued for 30 minutes to obtain a resin matrix.

[0045] Stirring parameters: 60-80°C, rotation speed 200-300 rpm, time 1-2 hours, until the viscosity of the system is stable (Brookfield viscometer, 2000-3000 cP at 25°C).

[0046] The composite powder and zinc phosphate corrosion inhibitor are added to the resin matrix, high-speed dispersion (1000-1500 rpm, 30 minutes) is performed, and then the aminated graphene oxide is added, and ultrasonic treatment (power 500 W, frequency 40 kHz, 30 minutes) is performed;

[0047] Finally, the self-repairing microcapsules are added, low-speed stirring (100 rpm, 15 minutes) is performed to avoid capsule rupture, and a mixed slurry is obtained;

[0048] The mixed slurry is sprayed onto the surface of the ship substrate (spray gun pressure 0.3-0.5 MPa, distance 20-30 cm); 10-15 minutes of standing at 50°C is performed to volatilize the solvent, and a basic corrosion-resistant layer is obtained;

[0049] Preparation of an interface transition layer:

[0050] The γ-aminopropyltriethoxysilane is dissolved in ethanol (concentration 5 wt%), and is sprayed onto the basic corrosion-resistant layer; the curing parameters are: reaction for 30 minutes at room temperature (25°C), and a chemical bonding interface is formed.

[0051] The copper powder is mixed with the silicone resin, ultrasonic dispersion is performed for 20 minutes, and is sprayed onto the chemical bonding interface, and the interface transition layer is obtained after curing (wet film thickness 10-15 μm); the curing parameters are: 80°C±2°C, and the time is 1 hour.

[0052] Preparation of an antifouling surface layer:

[0053] The Cu@SiO2core-shell particles, the polydimethylsiloxane and the methyltrimethoxysilane copolymer, and the antifouling auxiliary agent are mixed, the dimethylbenzene solvent (solid content 40 wt%) is added, and ball milling is performed for 2 hours (rotational speed 200 rpm), and an antifouling slurry is obtained.

[0054] The antifouling slurry is coated onto the interface transition layer by using a roll coating process (roll speed 5-10 m / min);

[0055] The curing parameters are: curing for 24 hours at room temperature (25°C), or accelerated curing for 2 hours at 60°C.

[0056] Light / heat synergistic curing:

[0057] Ultraviolet light curing is performed, the wavelength is 365 nm, the energy density is 300-500 mJ / cm 2 , and the exposure time is 30-60 seconds;

[0058] Heat curing is performed at 80°C for 1 hour, and the ship accessory rust-proof coating is obtained.

[0059] According to the embodiments of the present application, the preparation method of the self-repairing microcapsules comprises:

[0060] Dicyclopentadiene is mixed with 1wt% of emulsifier Span-80, deionized water is added, and the water / oil ratio is 3:1;

[0061] High-speed shearing emulsification (10000-12000 rpm, 10 minutes) is performed to form a water-in-oil emulsion with a droplet size of 10-50 microns;

[0062] Urea and formaldehyde are added to the water-in-oil emulsion, the molar ratio of urea to formaldehyde is 1:1.5, the pH is adjusted to 3.5-4.0 (with 10% citric acid solution), the reaction parameters are: 60℃±2℃, stirring speed 300rpm, reaction time 4 hours, after the reaction is completed, the pH is adjusted to 7.0 with NaOH solution to terminate the reaction, and filtration is performed to obtain microcapsules;

[0063] The microcapsules are washed with deionized water 3 times, and vacuum dried at 40℃ for 6 hours to obtain the self-repairing microcapsules.

[0064] The ship multifunctional protective coating provided by the present application realizes the comprehensive improvement of corrosion resistance, antifouling, self-repairing and construction efficiency through the synergistic effect of multiple components, and exhibits significant technical progress and practical value. In terms of corrosion resistance, the composite system of nano ceramic and rare earth oxide builds a dense physical and chemical barrier, so that the coating remains intact in a 3000-hour salt spray test, and the service life is improved by more than 3 times compared with traditional coatings. The introduction of graphene not only enhances the adhesion of the coating (up to 5B level), but also eliminates the risk of static electricity accumulation through the conductive network, and cooperates with the self-repairing microcapsule system to realize a damage repair rate of more than 88% at 40℃, significantly improving the durability and maintenance convenience of the coating.

[0065] In terms of antifouling performance, the combination of innovative Cu@SiO2 core-shell structure and PDMS low surface energy coating not only avoids the galvanic corrosion problem of traditional copper-based coatings and corrosion-resistant layers, but also realizes long-term antifouling effect of more than 5 years through the dual mechanisms of copper ion slow release and physical repulsion, and the marine organism attachment area is controlled within 5%. The specially designed interface transition layer tightly combines coatings with different functions through chemical bonding, and the peel strength is increased to 4.8MPa, ensuring the stability of the coating system in complex marine environments.

[0066] In terms of construction process, the application of light / heat synergistic curing technology shortens the traditional curing time of 72 hours to within 24 hours, and cooperates with the adaptability to low surface treatment conditions (Sa2 level), which makes the coating construction efficiency increase by more than 50%, and greatly reduces the dock period cost of ship maintenance. Comprehensive tests show that the coating system performs well in mechanical properties (compressive strength of 120 MPa), fireproof performance (passing SOLAS A60 standard) and environmental adaptability (-40℃ to 120℃ stable), etc., and provides a comprehensive solution for ship protection, which has significant economic benefits and market application prospects. DETAILED DESCRIPTION

[0067] The application discloses a ship accessory rust-proof coating and a preparation method thereof.

[0068] Embodiment 1

[0069] Basic corrosion-resistant layer:

[0070] Nanoceramic material (Al2O3): 20 parts

[0071] Rare earth oxide (CeO2): 10 parts

[0072] Aminated graphene oxide: 1 part

[0073] Fluorocarbon resin (polyvinylidene fluoride): 50 parts

[0074] Epoxy-polyurethane hybrid resin: 25 parts

[0075] Zinc phosphate corrosion inhibitor: 5 parts

[0076] Self-repairing microcapsules (dicyclopentadiene core material and polyurea formaldehyde wall material): 3 parts

[0077] Photoinitiator (2-hydroxy-2-methyl-1-phenyl-1-propanone): 2 parts

[0078] Interface transition layer:

[0079] Gamma-aminopropyl triethoxysilane: 4 parts

[0080] Silicone resin coated copper powder: 3 parts

[0081] Antifouling surface layer:

[0082] Cu@SiO2core-shell particles: 12 parts

[0083] Polydimethylsiloxane and methyltrimethoxysilane copolymer: 12 parts

[0084] Antifouling aid (capsaicin): 1.5 parts

[0085] Embodiment 2

[0086] Base corrosion resistant layer: nano ceramic material (Zr02): 30 parts; other ingredients same as example 1.

[0087] Interface transition layer and anti-fouling surface layer: same as example 1.

[0088] Example 3

[0089] Base corrosion resistant layer: aminated graphene oxide: 1.5 parts; other ingredients same as example 1.

[0090] Interface transition layer and anti-fouling surface layer: same as example 1.

[0091] Example 4

[0092] Base corrosion resistant layer: self-repairing microcapsules: 5 parts; other ingredients same as example 1.

[0093] Interface transition layer and anti-fouling surface layer: same as example 1.

[0094] Example 5

[0095] Base corrosion resistant layer: addition of carbon nanotubes 0.3 parts; other ingredients same as example 1.

[0096] Interface transition layer and anti-fouling surface layer: same as example 1.

[0097] Example 6

[0098] Base corrosion resistant layer: zinc phosphate corrosion inhibitor: 8 parts; other ingredients same as example 1.

[0099] Interface transition layer and anti-fouling surface layer: same as example 1.

[0100] Comparative Example

[0101] Comparative Example 1

[0102] Base corrosion resistant layer: no addition of self-repairing microcapsules; other ingredients same as example 1.

[0103] Interface transition layer and anti-fouling surface layer: same as example 1.

[0104] Comparative Example 2

[0105] Base corrosion resistant layer: use of ordinary graphene instead of aminated graphene oxide: 1 part; other ingredients same as example 1.

[0106] Interface transition layer and anti-fouling surface layer: same as example 1.

[0107] Comparative Example 3

[0108] Base corrosion resistant layer, anti-fouling surface layer: directly combined, no use of interface transition layer.

[0109] The specific composition of the base corrosion-resistant layer and the antifouling top layer is the same as in Example 1.

[0110] Comparative Example 4

[0111] Antifouling top layer: No antifouling aid was used; other components were the same as in Example 1.

[0112] Base corrosion-resistant layer and interface transition layer: the same as in Example 1.

[0113] Experimental Example

[0114] Salt spray test

[0115] According to the ISO 9227 standard, samples coated with different formulations were placed in a salt spray chamber and exposed to a 5% NaCl solution spray environment for 3000 hours. The surface condition of the coating was observed and recorded.

[0116] Adhesion test

[0117] According to the ISO 4624 standard, a pull test was performed using a tensile testing machine to measure the force required to peel the coating from the substrate, and the grade was evaluated according to ASTM D3359 standard (0B to 5B).

[0118] Self-repair efficiency test

[0119] Scratches were made on the surface of the coating, and then placed in a 40°C environment to observe the repair. The proportion of the repaired damage area to the original damage area was calculated to evaluate the self-repair efficiency.

[0120] Antifouling performance test

[0121] Samples coated with different formulations were placed in a marine environment, and the area of marine organism attachment was checked regularly and recorded as a percentage.

[0122] Peeling strength test

[0123] Using the ASTM D3359 method, the peeling strength between the coating and the substrate was determined by the adhesive tape method, with units of MPa.

[0124] Curing time test

[0125] The time required for the coating to cure completely from application was monitored, and the specific duration of curing completion was recorded. The results are shown in Table 1.

[0126] Table 1. Performance test results of Examples 1-6 and Comparative Examples 1-4

[0127]

[0128]

[0129] Data analysis and conclusion

[0130] Salt spray test: the examples show good corrosion resistance, while comparative examples 1 and 2 show different degrees of damage.

[0131] Adhesion test: the examples as a whole show excellent performance, reaching the highest 5B level; while the comparative examples have a decrease in adhesion due to the lack of some key ingredients.

[0132] Self-repairing efficiency: the self-repairing microcapsules in the examples significantly improve the self-repairing ability of the coating, in contrast, comparative example 1 has a lower self-repairing efficiency due to the lack of self-repairing microcapsules.

[0133] Antifouling performance test: the combination of Cu@SiO2core-shell structure and PDMS low surface energy coating effectively reduces the attachment area of marine organisms, while comparative example 4 does not add antifouling aids, resulting in an increase in the attachment area of marine organisms.

[0134] Peeling strength test: the presence of the interface transition layer greatly enhances the overall peeling strength of the coating, while comparative example 3 has a lower peeling strength due to the lack of this layer.

[0135] Curing time test: the light / heat synergistic curing technology of each component significantly shortens the curing time, and all samples can be cured within 24 hours.

[0136] Conclusion

[0137] The ship multifunctional protective coating provided by the present application realizes the comprehensive improvement of corrosion resistance, antifouling, self-repairing and construction efficiency through the synergistic effect of multiple components, and shows significant technical progress and practical value. In terms of corrosion resistance, the composite system of nano ceramic and rare earth oxide builds a dense physical and chemical barrier, so that the coating remains intact in a 3000-hour salt spray test, with a service life more than 3 times longer than that of traditional coatings. The introduction of graphene not only enhances the adhesion of the coating (up to 5B level), but also eliminates the risk of static electricity accumulation through the conductive network, and cooperates with the self-repairing microcapsule system to realize a damage repair rate of more than 88% at 40°C, significantly improving the durability and maintenance convenience of the coating.

[0138] Although the preferred embodiments of the present application have been described, those skilled in the art can make further changes and modifications to these embodiments once they know the basic inventive concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications falling within the scope of the present application.

[0139] Obviously, many modifications and variations of the present application are possible in light of the above teachings. It is, therefore, to be understood that within the scope of the appended claims and their equivalents, the application can be practiced otherwise than as specifically described.

Claims

1. A marine accessory rust-preventive coating characterized by, From inside to outside, it comprises the following three layers of structure and components: The base corrosion-resistant layer comprises, by mass fraction: Nano ceramic material 10-30 parts, selected from at least one of Al2O3, SiO2 or ZrO2; Rare earth oxide 5-15 parts, selected from at least one of CeO2, La2O3 or Y2O3; Aminated graphene oxide 0.5-1.5 parts; Fluorocarbon resin 40-60 parts, selected from polyvinylidene fluoride or fluorovinyl-ethylene-vinyl ether copolymer; Epoxy-polyurethane hybrid resin 20-30 parts; Zinc phosphate corrosion inhibitor 3-8 parts; Self-repairing microcapsule 2-5 parts, comprising dicyclopentadiene core material and polyurea formaldehyde wall material; Photoinitiator 1-3 parts, selected from 2-hydroxy-2-methyl-1-phenyl-1-propanone or benzophenone; Interface transition layer: comprising, by mass fraction: Gamma-aminopropyl triethoxysilane 3-5 parts; Silicone resin coated copper powder 2-5 parts; Antifouling surface layer: comprising, by mass fraction: Cu@SiO2core-shell particles 10-15 parts; Polydimethylsiloxane and methyltrimethoxysilane copolymer 10-15 parts; Antifouling aid 1-3 parts, selected from at least one of capsaicin or zinc pyrithione.

2. The marine accessory rust inhibiting coating of claim 1, wherein, The particle size of the nano ceramic material is 20-100 nm; The mass ratio of the nano ceramic material to the rare earth oxide is 2:1-3:1; The oxygen content of the aminated graphene oxide is ≤10wt%.

3. The marine accessory rust inhibiting coating of claim 1, wherein, The particle size of the self-repairing microcapsule is 10-50 μm, and the wall material thickness accounts for 10%-15% of the total mass of the capsule.

4. The marine accessory rust inhibiting coating of claim 1, wherein, The base corrosion-resistant layer also contains 0.1-0.5 parts of carbon nanotubes for enhancing electrical conductivity.

5. The ship accessory rust-proof coating according to claim 1, characterized in that, The thickness of the interface transition layer is 5-10 μm, and the molar ratio of the gamma-aminopropyl triethoxysilane to the hydroxyl group on the surface of the rare earth oxide is 1:1-1.

2.

6. The marine accessory rust inhibiting coating of claim 1, wherein, The antifouling aid is a compound of capsaicin and zinc pyrithione, with a mass ratio of 1:1-1:

2.

7. The marine accessory rust inhibiting coating of claim 1, wherein, The Cu@SiO2core-shell particles have a copper core diameter of 1-5 μm and a SiO2shell thickness of 100-300 nm; The copper content of the silicone resin coated copper powder is ≥60wt%.

8. The marine accessory rust inhibiting coating of claim 1, wherein, The curing mode of the base corrosion-resistant layer is ultraviolet light curing, with an energy density of 300-500 mJ / cm².

9. A method of preparing a marine accessory anti-rust coating according to any one of claims 1 to 8, characterized in that, The method comprises the following steps: Preparation of the base corrosion-resistant layer: Add the nano ceramic material and the rare earth oxide to a ball mill, add anhydrous ethanol with a mass of 50% of the total weight of the nano ceramic material and the rare earth oxide, use zirconium oxide balls as grinding medium, vacuum dry after ball milling, and obtain a uniform composite powder; Add the fluorocarbon resin and the epoxy-polyurethane hybrid resin to a reaction kettle, stir until the system viscosity is stable, add the photoinitiator, continue to stir for 30 minutes, and obtain a resin matrix; Add the composite powder and the zinc phosphate corrosion inhibitor to the resin matrix, high-speed dispersion, then add the aminated graphene oxide, and ultrasonic treatment; Finally, add the self-repairing microcapsule, low-speed stirring to avoid capsule rupture, and obtain a mixed slurry; Spray the mixed slurry to the surface of the ship substrate; 50℃ for 10-15 minutes, allowing the solvent to evaporate, to obtain the base corrosion-resistant layer; Interface transition layer preparation: Dissolve γ-aminopropyltriethoxysilane in ethanol and spray it onto the surface of the base corrosion-resistant layer to form a chemical bonding interface; Mix copper powder with silicone resin and ultrasonically disperse for 20 minutes, then spray it onto the chemical bonding interface and solidify to obtain the interface transition layer; Antifouling surface layer preparation: Mix Cu@SiO2 core-shell particles, polydimethylsiloxane and methyltrimethoxysilane copolymer, antifouling additives, and add dimethylbenzene solvent, then ball mill for 2 hours to obtain an antifouling slurry; Use roll coating process to coat the antifouling slurry onto the interface transition layer and solidify to obtain the antifouling surface layer; Photo / thermal synergistic curing: Use ultraviolet curing with wavelength 365 nm, energy density 300-500 mJ / cm², and exposure time 30-60 seconds; Use thermal curing at 80℃ for 1 hour to obtain the ship accessory rust-proof coating.

10. The method of claim 9, wherein the method further comprises the step of applying a topcoat to the marine accessory. 10 The preparation method of the self-repairing microcapsule includes: Mix dicyclopentadiene with 1wt% emulsifier Span-80 of the dicyclopentadiene and add deionized water with water / oil ratio 3:1; High-speed shearing emulsification to form a water-in-oil emulsion with droplet size 10-50μm; Add urea and formaldehyde to the water-in-oil emulsion with urea / formaldehyde molar ratio 1:1.5, adjust pH to 3.5-4.0, after reaction is completed, adjust pH to 7.0 with NaOH solution to terminate the reaction, and filter to obtain microcapsules; Wash the microcapsules with deionized water for 3 times and vacuum dry at 40℃ for 6 hours to obtain the self-repairing microcapsules.

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