Self-repairing anti-icing and anti-corrosion integrated coating and preparation method thereof

Abstract

The present invention discloses a method for preparing a self-repairing anti-icing and anti-corrosion integrated coating, specifically comprising: preparing a phase change heat storage spinning solution, electrostatically spinning the spinning solution to obtain an anti-corrosion heat storage fiber, and then sequentially preparing a photothermal polymer anti-corrosion filler and a self-repairing anti-icing and anti-corrosion coating, spraying the coating on the surface of an aluminum alloy, and drying to obtain a self-repairing anti-icing and anti-corrosion integrated coating. The present invention also discloses a coating prepared by this method, wherein the photothermal polymer of the present invention can actively perform photothermal de-icing when exposed to sunlight; cooperates with a phase change material to store most of the absorbed heat inside the phase change material, and can actively release heat to melt ice even in an extreme environment without sunlight after exposure to light; after adding fluorine-containing silane, the surface produces super-hydrophobic properties, greatly reducing the probability of icing; PVDF fiber can provide the coating with strong corrosion resistance; and epoxy resin provides the coating with repair ability while preventing local corrosion.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional coating preparation methods, and specifically relates to a method for preparing a self-repairing anti-icing and anti-corrosion integrated coating, and also relates to a coating prepared by the preparation method. Background Art

[0002] Under extreme climatic conditions, especially in low-temperature and humid environments, ice coating on the surface of metal substrates and subsequent corrosion are major challenges facing the industrial field today. Although there has been some progress in the anti-icing and anti-corrosion coatings on the current market, there are still some significant shortcomings. On the one hand, although methods such as simple super-hydrophobic surfaces and photothermal deicing coatings can effectively reduce ice adhesion and enhance anti-icing performance, their long-term stability in complex lightless environments is insufficient and is greatly affected by weather factors. On the other hand, these coatings have weak corrosion resistance. Although they can protect the metal substrate to a certain extent, they lack self-repairing functions and are difficult to deal with local corrosion caused by small cracks or damage. These corrosion phenomena will also increase their use costs to a certain extent, limiting their widespread application.

[0003] Existing coatings are exposed to extreme lightless environments for a long time, and the coating's photothermal deicing performance cannot function. While reducing the surface's anti-icing performance, it is also unable to cope with the performance degradation problem after the coating is damaged. The anti-corrosion performance is poor, and there are also disadvantages of not having active photothermal deicing and the problem of being unable to self-repair after the surface is damaged. Summary of the Invention

[0004] The purpose of the present invention is to provide a method for preparing a self-repairing anti-icing and anti-corrosion integrated coating, which solves the problem that the deicing performance and anti-corrosion performance of existing anti-icing coatings decrease in long-term extreme dark environments.

[0005] Another object of the present invention is to provide a coating prepared by a method for preparing a self-repairing anti-icing and anti-corrosion integrated coating.

[0006] The technical solution adopted by the present invention is a method for preparing a self-repairing anti-icing and anti-corrosion integrated coating, specifically: preparing a phase change heat storage spinning solution, electrospinning the spinning solution to obtain an anti-corrosion heat storage fiber, and then sequentially preparing a photothermal polymer anti-corrosion filler and a self-repairing anti-icing and anti-corrosion coating, spraying the coating on the surface of an aluminum alloy, and obtaining a self-repairing anti-icing and anti-corrosion integrated coating after drying.

[0007] The present invention is also characterized in that:

[0008] Please follow the steps below to implement it:

[0009] Step 1: Prepare phase change heat storage spinning solution

[0010] Phase change material, emulsifier, deionized water and surfactant were mixed in proportion and stirred at 30°C, TEOS and catalyst were added dropwise and stirred for 2.5 hours, and then washed and dried to obtain a heat storage filler. DMF and acetone with a mass ratio of 1:1 were used as solvents, PVDF was added and stirred for 15 minutes. The heat storage filler was added to the PVDF solution, stirred at 25°C for 5 hours and allowed to stand for 0.5 hours to obtain a phase change heat storage spinning solution.

[0011] Step 2: Electrospinning to prepare anti-corrosion heat storage fibers

[0012] The spinning solution prepared in step 1 was placed in a syringe, and an aluminum plate was used as a receiving device. The spinning distance was adjusted, and the voltage, temperature, humidity, and injection rate were controlled for spinning. The spinning was then dried at 70° C. for 8 h to obtain an anti-corrosion heat storage fiber.

[0013] Step 3: Preparation of photothermal polymer anticorrosive filler

[0014] Add 0.5 mol / L pyrrole monomer and 0.02 mol / L hybridizing agent to a phosphate buffer solution with a pH of 7 to prepare an electrolyte, electrodeposit polypyrrole fiber on the anti-corrosion heat storage fiber prepared in step 2, adjust the current density and reaction time, and wash and dry to obtain a photothermal polymer anti-corrosion filler;

[0015] Step 4: Prepare self-repairing anti-icing and anti-corrosion coating

[0016] The photothermal polymer anticorrosive filler, epoxy resin, solvent and fluorinated silane prepared in step 3 are mixed and stirred to uniformly disperse the filler, and then a curing agent and a defoaming agent are added and stirred to obtain a self-repairing anti-icing and anti-corrosion coating;

[0017] Step 5: Prepare a self-repairing, anti-icing, and anti-corrosion integrated coating

[0018] Add the coating in step 4 to the spray gun and slowly and evenly spray it at a 60° angle on the aluminum alloy surface that has been cleaned and dried with acetone. After drying after spraying, a self-repairing, anti-icing, and anti-corrosion integrated coating can be obtained.

[0019] The heat storage filler in step 1 is composed of the following substances in mass percentage: phase change material 10% to 20%, emulsifier 5% to 15%, surfactant 3% to 10%, TEOS 7% to 15%, catalyst 1% to 5%, deionized water 35% to 74%, the sum of the above components is 100%, the mass fraction of PVDF is 8% to 15%, and the mass ratio of the heat storage filler to the PVDF solution is 1:25 to 100.

[0020] In step 1, the phase change material is any one of n-tetradecane, dodecane, and decanol, the emulsifier is a complex of tween-80 and span-80 in a mass ratio of 1:1, the surfactant is any one of PVA and CTAB, and the catalyst is one of acetic acid or ammonia water.

[0021] The volume of the syringe in step 2 is 10 mL, the distance between the receiving device and the needle is 15 cm to 20 cm, the voltage is 10 kV to 20 kV, the rate at which the needle ejects the spinning solution is 0.1 mL / h to 1.0 mL / h, the temperature is 25 ° C, the humidity during the spinning process is controlled at 30% to 50%, and the diameter of the anti-corrosion heat storage fiber is 5 μm to 10 μm.

[0022] The hybridizing agent in step 3 is NSA, and the current density is 0.9 mA / cm 2 , the reaction time is 7 min, and the diameter of the deposited polypyrrole fibers is 100 nm to 300 nm.

[0023] The self-repairing anti-icing and anti-corrosion coating in step 4 is composed of the following substances in mass percentage: 1% to 10% of photothermal polymer anti-corrosion filler, 1% to 10% of fluorine-containing silane, 25% to 35% of epoxy resin, 0.5% to 1% of curing agent, 0.5% to 1% of defoaming agent, and 43% to 72% of solvent. The total of the above components is 100%.

[0024] In step 4, the solvent is any one of ethanol, dimethyl sulfoxide, dimethylformamide, and N-methylpyrrolidone, the fluorinated silane is any one of hexafluoro-1,1,2,2-tetrahydrodecyltrimethoxysilane, 1H,1H,2H,2H-perfluorodecyltriethoxysilane, and heptafluorodecyltrimethoxysilane, the curing agent is any one of N3390 curing agent and tertiary amine, and the defoaming agent is any one of fatty alcohol ethoxysiloxane and polyether siloxane.

[0025] Another technical solution adopted by the present invention is to prepare a coating using a method for preparing a self-repairing anti-icing and anti-corrosion integrated coating.

[0026] The beneficial effects of the present invention are:

[0027] The preparation method of the self-repairing anti-icing and anti-corrosion integrated coating of the present invention is that the photothermal polymer can perform active photothermal effect to remove ice when exposed to sunlight; it cooperates with the phase change material to store most of the absorbed heat inside the phase change material, and even in an extreme environment without sunlight after being exposed to light, the phase change material can actively release heat to melt ice; after adding fluorine-containing silane, the surface produces super-hydrophobic properties, which greatly reduces the probability of icing; PVDF fiber can provide the coating with strong corrosion resistance; epoxy resin provides the coating with a certain repair ability while preventing local corrosion, thereby further improving the corrosion resistance of the coating, and has important application prospects in the field of anti-icing. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 It is a schematic diagram of the morphology of the self-repairing anti-icing and anti-corrosion integrated coating prepared by the present invention. DETAILED DESCRIPTION

[0029] The present invention will be described in detail below with reference to specific embodiments and accompanying drawings.

[0030] The preparation method of the self-repairing anti-icing and anti-corrosion integrated coating of the present invention is specifically implemented according to the following steps:

[0031] Step 1: Prepare phase change heat storage spinning solution

[0032] Phase change material, emulsifier, deionized water and surfactant were mixed in proportion and stirred at 30°C, TEOS and catalyst were added dropwise and stirred for 2.5 hours, and then washed and dried to obtain a heat storage filler. DMF and acetone with a mass ratio of 1:1 were used as solvents, PVDF was added and stirred for 15 minutes. The heat storage filler was added to the PVDF solution, stirred at 25°C for 5 hours and allowed to stand for 0.5 hours to obtain a phase change heat storage spinning solution.

[0033] The heat storage filler in step 1 is composed of the following substances in percentage by mass: 10% to 20% phase change material, 5% to 15% emulsifier, 3% to 10% surfactant, 7% to 15% TEOS, 1% to 5% catalyst, 35% to 74% deionized water, the sum of the above components is 100%, the mass fraction of PVDF is 8% to 15%, and the mass ratio of the heat storage filler to the PVDF solution is 1:25 to 100;

[0034] In step 1, the phase change material is any one of n-tetradecane, dodecane, and decanol, the emulsifier is a complex of tween-80 and span-80 in a mass ratio of 1:1, the surfactant is any one of PVA and CTAB, and the catalyst is one of acetic acid or ammonia;

[0035] Step 2: Electrospinning to prepare anti-corrosion heat storage fibers

[0036] The spinning solution prepared in step 1 was placed in a syringe, and an aluminum plate was used as a receiving device. The spinning distance was adjusted, and the voltage, temperature, humidity, and injection rate were controlled for spinning. The spinning was then dried at 70° C. for 8 h to obtain an anti-corrosion heat storage fiber.

[0037] The syringe volume in step 2 is 10 mL, the distance between the receiving device and the needle is 15 cm to 20 cm, the voltage is 10 kV to 20 kV, the needle ejects the spinning solution at a rate of 0.1 mL / h to 1.0 mL / h, the temperature is 25 ° C, the humidity during the spinning process is controlled at 30% to 50%, and the diameter of the anti-corrosion heat storage fiber is 5 μm to 10 μm;

[0038] Step 3: Preparation of photothermal polymer anticorrosive filler

[0039] Add 0.5 mol / L pyrrole monomer and 0.02 mol / L hybridizing agent to a phosphate buffer solution with a pH of 7 to prepare an electrolyte, electrodeposit polypyrrole fiber on the anti-corrosion heat storage fiber prepared in step 2, adjust the current density and reaction time, and wash and dry to obtain a photothermal polymer anti-corrosion filler;

[0040] The hybridizing agent in step 3 is NSA (β-naphthalenesulfonic acid hybridizing agent), and the current density is 0.9 mA / cm 2 , the reaction time is 7 min, and the diameter of the deposited polypyrrole fibers is 100 nm to 300 nm;

[0041] Step 4: Prepare self-repairing anti-icing and anti-corrosion coating

[0042] The photothermal polymer anticorrosive filler, epoxy resin, solvent and fluorinated silane prepared in step 3 are mixed and stirred to uniformly disperse the filler, and then a curing agent and a defoaming agent are added and stirred to obtain a self-repairing anti-icing and anti-corrosion coating;

[0043] The self-repairing anti-icing and anti-corrosion coating in step 4 is composed of the following substances by mass percentage: 1% to 10% of a photothermal polymer anti-corrosion filler, 1% to 10% of a fluorine-containing silane, 25% to 35% of an epoxy resin, 0.5% to 1% of a curing agent, 0.5% to 1% of a defoaming agent, and 43% to 72% of a solvent, the total of which is 100%;

[0044] In step 4, the solvent is any one of ethanol, dimethyl sulfoxide, dimethylformamide, and N-methylpyrrolidone, the fluorinated silane is any one of hexafluoro-1,1,2,2-tetrahydrodecyltrimethoxysilane, 1H,1H,2H,2H-perfluorodecyltriethoxysilane, and heptafluorodecyltrimethoxysilane, the curing agent is any one of N3390 curing agent and tertiary amine, and the defoaming agent is any one of fatty alcohol ethoxysiloxane and polyether siloxane;

[0045] Step 5: Prepare a self-repairing, anti-icing, and anti-corrosion integrated coating

[0046] Add the coating in step 4 to the spray gun and slowly and evenly spray it at a 60° angle on the aluminum alloy surface that has been cleaned and dried with acetone. After drying after spraying, a self-repairing, anti-icing, and anti-corrosion integrated coating can be obtained.

[0047] The present invention enhances the ice-melting ability of the coating by adding a phase-change material to prepare a heat-storage filler. By selecting different phase-change materials and controlling their dosage, the amount of heat stored / released and the phase transition point of the coating can be regulated. The phase-change heat-storage filler is stored within the PVDF fiber structure through an electrospinning process, enhancing the coating's corrosion resistance under strong acid and alkali conditions. The incompatibility of PVDF with SiO2 ensures that the sol-gel reaction of fluorosilane and TEOS forms a stable super-hydrophobic surface on the fiber exterior, significantly reducing the likelihood of substrate ice accumulation and improving ice-melting efficiency. Furthermore, the self-healing properties of epoxy resin can also, to a certain extent, prevent localized corrosion caused by micro-cracks. By electroplating a polypyrrole fiber layer with a photothermal effect on the PVDF surface, while solving the heat source problem of the phase-change material, the addition of a sulfonic acid hybridizing agent can improve the orderliness of the polypyrrole fiber to block the corrosive medium. Furthermore, the F element in PVDF and the fluorosilane acts as a larger hydrophobic anion doped in the polypyrrole, significantly increasing the service life of the self-healing, anti-icing, and anti-corrosion integrated coating.

[0048] Example 1

[0049] The preparation method of the self-repairing anti-icing and anti-corrosion integrated coating of the present invention is specifically as follows:

[0050] Step 1, according to the mass percentage: 10% dodecane, 5% tween-80 and span-80 complex with a mass ratio of 1:1, 3% PVA, 7% TEOS, 1% acetic acid, and 74% deionized water, dodecane, 10% tween-80 and span-80 complex with a mass ratio of 1:1, deionized water, and PVA are mixed and stirred at 30°C, TEOS and acetic acid are added dropwise and stirred for 2.5 hours, and the mixture is washed and dried to obtain a heat storage filler; DMF and acetone with a mass ratio of 1:1 are used as a solvent, 8% PVDF is added and stirred for 15 minutes; then, the heat storage filler is added to the PVDF solution at a mass ratio of 1:25 to the PVDF solution, stirred at 25°C for 5 hours, and allowed to stand for 0.5 hours to obtain a phase change heat storage spinning solution;

[0051] Step 2: Place the phase change heat storage spinning solution into a 10 mL syringe, use an aluminum plate as a receiving device, and place it 15 cm away from the syringe needle. Squirt the spinning solution at a rate of 0.2 mL / h at a voltage of 10 kV, and maintain the spinning at 25 ° C and 30% humidity. Then, dry it at 70 ° C for 8 hours to obtain an anti-corrosion heat storage fiber with a diameter of 5 μm.

[0052] Step 3: Add 0.5 mol / L pyrrole monomer and 0.02 mol / L β-naphthalenesulfonic acid to a phosphate buffer solution at pH = 7 to prepare an electrolyte, and electro-deposit polypyrrole fiber on the anti-corrosion heat storage fiber at 0.9 mA / cm 2 The reaction was carried out at a current density of 100 nm for 7 min, and after washing and drying, a photothermal polymer anticorrosive filler with a polypyrrole fiber diameter of 100 nm was obtained;

[0053] Step 4, mixing and stirring the following components by mass percentage: 1% photothermal polymer anticorrosive filler, 1% hexafluoro-1,1,2,2-tetrahydrodecyltrimethoxysilane, 25% epoxy resin, 0.5% N3390 curing agent, 0.5% fatty alcohol ethoxysiloxane, and 72% ethanol to uniformly disperse the filler, thereby obtaining a self-repairing anti-icing and anti-corrosion coating;

[0054] Step 5: Add the self-repairing anti-icing and anti-corrosion coating to the spray gun, and slowly and evenly spray it at a 60° angle on the aluminum alloy surface that has been cleaned and dried with acetone. After drying after spraying, a self-repairing anti-icing and anti-corrosion integrated coating can be obtained.

[0055] Example 2

[0056] The preparation method of the self-repairing anti-icing and anti-corrosion integrated coating of the present invention is specifically as follows:

[0057] Step 1, according to the mass percentage: 20% n-tetradecane, 15% tween-80 and span-80 complex with a mass ratio of 1:1, 10% CTAB, 15% TEOS, 5% ammonia water, 35% deionized water, mix n-tetradecane, 1:1 tween-80 and span-80 complex, deionized water and CTAB, stir evenly at 30°C, then add TEOS and ammonia water dropwise and stir for 2.5h, wash and dry to obtain a heat storage filler. Use DMF and acetone with a mass ratio of 1:1 as solvent, add PVDF with a mass fraction of 15% and stir for 15 minutes. Then add the heat storage filler to the PVDF solution at a mass ratio of 1:100, stir at 25°C for 5h and let it stand for 0.5h to obtain a phase change heat storage spinning solution;

[0058] Step 2: Place the phase change heat storage spinning solution into a 10mL syringe and place an aluminum plate as a receiver, 20cm away from the syringe needle. The spinning solution is ejected at a rate of 1.0mL / h at a voltage of 20kV. Spinning is performed at 25°C and 50% humidity, followed by drying at 70°C for 8h to obtain a 10μm diameter anti-corrosion heat storage fiber.

[0059] Step 3: Add 0.5 mol / L pyrrole monomer and 0.02 mol / L β-naphthalenesulfonic acid to a phosphate buffer solution at pH = 7 to prepare an electrolyte, and electro-deposit polypyrrole fiber on the anti-corrosion heat storage fiber at 0.9 mA / cm 2 The reaction was carried out at a current density of 7 min, and after washing and drying, a photothermal polymer anticorrosive filler with a polypyrrole fiber diameter of 300 nm was obtained.

[0060] Step 4, mixing and stirring the following components by mass percentage: 10% photothermal polymer anticorrosive filler, 10% heptadecafluorodecyltrimethoxysilane, 35% epoxy resin, 1% tertiary amine, 1% polyether siloxane, and 43% N-methylpyrrolidone to uniformly disperse the filler, thereby obtaining a self-repairing anti-icing and anti-corrosion coating;

[0061] Step 5: Add the self-repairing anti-icing and anti-corrosion coating to the spray gun, and slowly and evenly spray it at a 60° angle on the aluminum alloy surface that has been cleaned and dried with acetone. After drying after spraying, a self-repairing anti-icing and anti-corrosion integrated coating can be obtained.

[0062] Example 3

[0063] The preparation method of the self-repairing anti-icing and anti-corrosion integrated coating of the present invention is specifically as follows:

[0064] Step 1, according to the mass percentage: 15% of n-tetradecane, 10% of tween-80 and span-80 compound with a mass ratio of 1:1, 6% of PVA, 10% of TEOS, 4% of acetic acid, and 55% of deionized water, mix n-tetradecane, 1:1 of tween-80 and span-80 compound, deionized water and PVA, stir evenly at 30°C, then add TEOS and acetic acid dropwise and stir for 2.5 hours, wash and dry to obtain a heat storage filler. Use DMF and acetone with a mass ratio of 1:1 as solvent, add PVDF with a mass fraction of 13% and stir for 15 minutes. Then add the heat storage filler to the PVDF solution at a mass ratio of 1:50, stir at 25°C for 5 hours and let it stand for 0.5 hours to obtain a phase change heat storage spinning solution;

[0065] Step 2: Place the phase change heat storage spinning solution into a 10mL syringe, using an aluminum plate as a receiver, 17cm away from the syringe needle. The spinning solution is ejected at a rate of 0.5mL / h at a voltage of 15kV. Spinning is performed at 25°C and 45% humidity, followed by drying at 70°C for 8h to obtain a 6μm diameter anti-corrosion heat storage fiber.

[0066] Step 3: Add 0.5 mol / L pyrrole monomer and 0.02 mol / L β-naphthalenesulfonic acid to a phosphate buffer solution at pH = 7 to prepare an electrolyte, and electro-deposit polypyrrole fiber on the anti-corrosion heat storage fiber at 0.9 mA / cm 2 The reaction was carried out at a current density of 100 nm for 7 min, and after washing and drying, a photothermal polymer anticorrosive filler with a polypyrrole fiber diameter of 200 nm was obtained;

[0067] Step 4, mixing and stirring the following components by mass percentage: 8% photothermal polymer anticorrosive filler, 8% 1H,1H,2H,2H-perfluorodecyltriethoxysilane, 34% epoxy resin, 0.5% tertiary amine, 0.5% polyether siloxane, and 49% dimethylformamide to uniformly disperse the filler, thereby obtaining a self-repairing anti-icing and anti-corrosion coating;

[0068] Step 5: Add the self-repairing anti-icing and anti-corrosion coating to the spray gun, and slowly and evenly spray it at a 60° angle on the aluminum alloy surface that has been cleaned and dried with acetone. After drying after spraying, a self-repairing anti-icing and anti-corrosion integrated coating can be obtained.

[0069] Example 4

[0070] The preparation method of the self-repairing anti-icing and anti-corrosion integrated coating of the present invention is specifically as follows:

[0071] Step 1, according to the mass percentage: 12% decanol, 12% tween-80 and span-80 complex with a mass ratio of 1:1, 7% CTAB, 8% TEOS, 3% acetic acid, 58% deionized water, decanol, 1:1 tween-80 and span-80 complex, deionized water and CTAB are mixed and stirred at 30°C, TEOS and acetic acid are added dropwise and stirred for 2.5 hours, and the heat storage filler is obtained after washing and drying. DMF and acetone with a mass ratio of 1:1 are used as solvents, 11% PVDF is added and stirred for 15 minutes. Then, the heat storage filler is added to the PVDF solution at a mass ratio of 1:75 to the PVDF solution, stirred at 25°C for 5 hours and allowed to stand for 0.5 hours to obtain a phase change heat storage spinning solution;

[0072] Step 2: Transfer the spinning solution into a 10mL syringe and place an aluminum plate as a receiver, 15cm from the syringe needle. The spinning solution is ejected at a rate of 0.8mL / h at a voltage of 15kV. Spinning is performed at 25°C and 40% humidity, followed by drying at 70°C for 8h to obtain a 7μm diameter anti-corrosion heat-storage fiber.

[0073] Step 3: Add 0.5 mol / L pyrrole monomer and 0.02 mol / L β-naphthalenesulfonic acid to a phosphate buffer solution at pH = 7 to prepare an electrolyte, and electro-deposit polypyrrole fiber on the anti-corrosion heat storage fiber at 0.9 mA / cm 2 The reaction was carried out at a current density of 100 nm for 7 min, and after washing and drying, a photothermal polymer anticorrosive filler with a polypyrrole fiber diameter of 300 nm was obtained;

[0074] Step 4, mixing and stirring the following components by mass percentage: 7% photothermal polymer anticorrosive filler, 6% heptadecafluorodecyltrimethoxysilane, 30% epoxy resin, 1% N3390 curing agent, 1% fatty alcohol ethoxysiloxane, and 55% dimethyl sulfoxide to uniformly disperse the filler, thereby obtaining a self-repairing anti-icing and anti-corrosion coating;

[0075] Step 5: Add the self-repairing anti-icing and anti-corrosion coating to the spray gun, and slowly and evenly spray it at a 60° angle on the aluminum alloy surface that has been cleaned and dried with acetone. After drying after spraying, a self-repairing anti-icing and anti-corrosion integrated coating can be obtained.

[0076] Example 5

[0077] The preparation method of the self-repairing anti-icing and anti-corrosion integrated coating of the present invention is specifically as follows:

[0078] Step 1, according to the mass percentage: 12% of n-tetradecane, 12% of tween-80 and span-80 complex with a mass ratio of 1:1, 7% of CTAB, 8% of TEOS, 3% of acetic acid, and 58% of deionized water, mix n-tetradecane, 1:1 tween-80 and span-80 complex, deionized water and CTAB, stir evenly at 30°C, then add TEOS and acetic acid dropwise and stir for 2.5 hours, wash and dry to obtain a heat storage filler. Use DMF and acetone with a mass ratio of 1:1 as solvent, add PVDF with a mass fraction of 11% and stir for 15 minutes. Then add the heat storage filler to the PVDF solution at a mass ratio of 1:75 to the PVDF solution, stir at 25°C for 5 hours and let it stand for 0.5 hours to obtain a phase change heat storage spinning solution;

[0079] Step 2: Transfer the spinning solution into a 10mL syringe and place an aluminum plate as a receiver, 15cm from the syringe needle. The spinning solution is ejected at a rate of 0.8mL / h at a voltage of 15kV. Spinning is performed at 25°C and 40% humidity, followed by drying at 70°C for 8h to obtain a 7μm diameter anti-corrosion heat-storage fiber.

[0080] Step 3: Add 0.5 mol / L pyrrole monomer and 0.02 mol / L β-naphthalenesulfonic acid to a phosphate buffer solution at pH = 7 to prepare an electrolyte, and electro-deposit polypyrrole fiber on the anti-corrosion heat storage fiber at 0.9 mA / cm 2 The reaction was carried out at a current density of 100 nm for 7 min, and after washing and drying, a photothermal polymer anticorrosive filler with a polypyrrole fiber diameter of 300 nm was obtained;

[0081] Step 4, mixing and stirring the following components by mass percentage: 7% photothermal polymer anticorrosive filler, 6% heptadecafluorodecyltrimethoxysilane, 30% epoxy resin, 1% N3390 curing agent, 1% fatty alcohol ethoxysiloxane, and 55% dimethyl sulfoxide to uniformly disperse the filler, thereby obtaining a self-repairing anti-icing and anti-corrosion coating;

[0082] Step 5: Add the self-repairing anti-icing and anti-corrosion coating to the spray gun, and slowly and evenly spray it at a 60° angle on the aluminum alloy surface that has been cleaned and dried with acetone. After drying after spraying, a self-repairing anti-icing and anti-corrosion integrated coating can be obtained.

[0083] Example 6

[0084] The preparation method of the self-repairing anti-icing and anti-corrosion integrated coating of the present invention is specifically as follows:

[0085] Step 1, according to the mass percentage: 12% decanol, 12% tween-80 and span-80 complex with a mass ratio of 1:1, 7% CTAB, 8% TEOS, 3% acetic acid, 58% deionized water, decanol, 1:1 tween-80 and span-80 complex, deionized water and CTAB are mixed and stirred at 30°C, TEOS and acetic acid are added dropwise and stirred for 2.5 hours, and the heat storage filler is obtained after washing and drying. DMF and acetone with a mass ratio of 1:1 are used as solvents, 11% PVDF is added and stirred for 15 minutes. Then, the heat storage filler is added to the PVDF solution at a mass ratio of 1:75 to the PVDF solution, stirred at 25°C for 5 hours and allowed to stand for 0.5 hours to obtain a phase change heat storage spinning solution;

[0086] Step 2: Place the phase change heat storage spinning solution into a 10mL syringe and place an aluminum plate as a receiver, 20cm away from the syringe needle. The spinning solution is ejected at a rate of 1.0mL / h at a voltage of 20kV. Spinning is performed at 25°C and 50% humidity, followed by drying at 70°C for 8h to obtain a 10μm diameter anti-corrosion heat storage fiber.

[0087] Step 3: Add 0.5 mol / L pyrrole monomer and 0.02 mol / L β-naphthalenesulfonic acid to a phosphate buffer solution at pH = 7 to prepare an electrolyte, and electro-deposit polypyrrole fiber on the anti-corrosion heat storage fiber at 0.9 mA / cm 2 The reaction was carried out at a current density of 100 nm for 7 min, and after washing and drying, a photothermal polymer anticorrosive filler with a polypyrrole fiber diameter of 300 nm was obtained;

[0088] Step 4, mixing and stirring the following components by mass percentage: 7% photothermal polymer anticorrosive filler, 6% heptadecafluorodecyltrimethoxysilane, 30% epoxy resin, 1% N3390 curing agent, 1% fatty alcohol ethoxysiloxane, and 55% dimethyl sulfoxide to uniformly disperse the filler, thereby obtaining a self-repairing anti-icing and anti-corrosion coating;

[0089] Step 5: Add the self-repairing anti-icing and anti-corrosion coating to the spray gun, and slowly and evenly spray it at a 60° angle on the aluminum alloy surface that has been cleaned and dried with acetone. After drying after spraying, a self-repairing anti-icing and anti-corrosion integrated coating can be obtained.

[0090] Table 1 compares the contact angle, ice adhesion, photothermal ice melting time, light-freeze ice melting time after one photothermal ice melting, surface contact resistance, and ice adhesion after 30 freeze / thaw cycles of the coatings prepared in Examples 1-4.

[0091] Table 1

[0092]

[0093]

[0094] Table 1 shows that the coating photothermally modified using only polypyrrole exhibits the smallest water contact angle and the greatest ice adhesion. Because all the heat from the photothermal conversion is used for deicing, the initial photothermal ice-melting period is the shortest. However, the subsequent dark-light melting period, due to minimal heat storage, results in the longest ice-melting period. The ice adhesion after cyclic freeze / thaw cycles is also the highest and increases significantly. The coating in Example 3 exhibits the highest contact angle, and its ice adhesion is significantly reduced due to hydrophobic modification. The phase change material increases the initial photothermal ice-melting period and stores a significant amount of heat, allowing for a shorter ice-melting period during subsequent dark-light melting periods. Furthermore, the ice adhesion after repeated freeze / thaw cycles shows little change, remaining at a low level.

[0095] Table 2 is a comparison of the surface contact resistance and mass loss rate of the coatings prepared in Examples 1-4.

[0096] Table 2

[0097]

[0098]

[0099] Table 2 shows that the photothermal coating modified solely with polypyrrole exhibits the highest surface contact resistance and the highest mass loss rate. However, the coating in Example 3 minimizes both surface contact resistance and mass loss rate due to the combined anti-corrosion effects of PVDF, polypyrrole, and epoxy resin. PVDF, while inherently strong in corrosion resistance, also enhances the stability of polypyrrole, and the self-healing properties of epoxy resin reduce surface damage while enhancing corrosion resistance.

[0100] Figure 1 Schematic diagram of the self-repairing anti-icing and anti-corrosion integrated coating prepared by the present invention. Figure 1 As can be seen, SiO2 accumulates on the outer surface of the corrosion-resistant heat storage fiber, forming a superhydrophobic interface that weakens ice adhesion. The photothermal layer, composed of polypyrrole fibers, adheres to the PVDF and grows on the coating surface, ensuring sufficient sunlight exposure. A cross-sectional view of the corrosion-resistant heat storage fiber shows that the phase change material is encapsulated within the PVDF fibers, ensuring both heat storage and the coating's corrosion resistance.

[0101] The present invention uses photothermal polymers to actively remove ice through photothermal effects when exposed to sunlight; it cooperates with phase change materials to store most of the absorbed heat inside the phase change materials, and even in extreme environments without sunlight after being exposed to light, the phase change materials can actively release heat to melt ice; after adding fluorinated silane, the surface produces super-hydrophobic properties, which greatly reduces the probability of icing; PVDF fibers can provide the coating with strong corrosion resistance; epoxy resin provides the coating with a certain repair ability while preventing local corrosion, thereby further improving the corrosion resistance of the coating, and has important application prospects in the field of anti-icing.

Claims

1. A method for preparing a self-repairing anti-icing and anti-corrosion integrated coating, characterized in that: Please follow the steps below to implement it: Step 1: Prepare phase change heat storage spinning solution Phase change material, emulsifier, deionized water and surfactant were mixed in proportion and stirred at 30°C, TEOS and catalyst were added dropwise and stirred for 2.5 hours, and then washed and dried to obtain a heat storage filler. DMF and acetone with a mass ratio of 1:1 were used as solvents, PVDF was added and stirred for 15 minutes. The heat storage filler was added to the PVDF solution, stirred at 25°C for 5 hours and allowed to stand for 0.5 hours to obtain a phase change heat storage spinning solution. Step 2: Electrospinning to prepare anti-corrosion heat storage fibers The spinning solution prepared in step 1 was placed in a syringe, and an aluminum plate was used as a receiving device. The spinning distance was adjusted, and the voltage, temperature, humidity, and injection rate were controlled for spinning. The spinning was then dried at 70° C. for 8 h to obtain an anti-corrosion heat storage fiber. Step 3: Preparation of photothermal polymer anticorrosive filler An electrolyte was prepared by adding 0.5 mol / L pyrrole monomer and 0.02 mol / L hybridizing agent to a phosphate buffer solution at pH=7, and polypyrrole fiber was electrodeposited on the anti-corrosion heat storage fiber prepared in step 2. The current density and reaction time were adjusted, and the photothermal polymer anti-corrosion filler was obtained after washing and drying. Step 4: Prepare self-repairing anti-icing and anti-corrosion coating The photothermal polymer anticorrosive filler, epoxy resin, solvent and fluorinated silane prepared in step 3 are mixed and stirred to uniformly disperse the filler, and then a curing agent and a defoaming agent are added and stirred to obtain a self-repairing anti-icing and anti-corrosion coating; Step 5: Prepare a self-repairing, anti-icing, and anti-corrosion integrated coating Add the coating in step 4 to the spray gun and slowly and evenly spray it at a 60° angle on the aluminum alloy surface that has been cleaned and dried with acetone. After drying after spraying, a self-repairing, anti-icing, and anti-corrosion integrated coating can be obtained.

2. The method for preparing the self-repairing anti-icing and anti-corrosion integrated coating according to claim 1, characterized in that: The heat storage filler in step 1 is composed of the following substances in percentage by mass: 10% to 20% phase change material, 5% to 15% emulsifier, 3% to 10% surfactant, 7% to 15% TEOS, 1% to 5% catalyst, and 35% to 74% deionized water. The total of the above components is 100%, the mass fraction of PVDF is 8% to 15%, and the mass ratio of the heat storage filler to the PVDF solution is 1:25 to 100.

3. The method for preparing the self-repairing anti-icing and anti-corrosion integrated coating according to claim 1, characterized in that: In step 1, the phase change material is any one of n-tetradecane, dodecane, and decanol, the emulsifier is a complex of tween-80 and span-80 in a mass ratio of 1:1, the surfactant is any one of PVA and CTAB, and the catalyst is one of acetic acid or ammonia.

4. The method for preparing the self-repairing anti-icing and anti-corrosion integrated coating according to claim 1, characterized in that: The syringe volume in step 2 is 10 mL, the distance between the receiving device and the needle is 15 cm to 20 cm, the voltage is 10 kV to 20 kV, the needle ejects the spinning solution at a rate of 0.1 mL / h to 1.0 mL / h, the temperature is 25°C, the humidity during the spinning process is controlled at 30% to 50%, and the diameter of the anti-corrosion heat storage fiber is 5 μm to 10 μm.

5. The method for preparing the self-repairing anti-icing and anti-corrosion integrated coating according to claim 1, characterized in that: The hybridizing agent in step 3 is NSA, and the current density is 0.9 mA / cm 2 , the reaction time is 7 min, and the diameter of the deposited polypyrrole fibers is 100 nm ~ 300 nm.

6. The method for preparing the self-repairing anti-icing and anti-corrosion integrated coating according to claim 1, characterized in that: The self-repairing anti-icing and anti-corrosion coating in step 4 is composed of the following substances in percentage by mass: 1% to 10% of photothermal polymer anti-corrosion filler, 1% to 10% of fluorine-containing silane, 25% to 35% of epoxy resin, 0.5% to 1% of curing agent, 0.5% to 1% of defoaming agent, and 43% to 72% of solvent, and the sum of the above components is 100%.

7. The method for preparing the self-repairing anti-icing and anti-corrosion integrated coating according to claim 1, characterized in that: In step 4, the solvent is any one of ethanol, dimethyl sulfoxide, dimethylformamide, and N-methylpyrrolidone, the fluorinated silane is any one of hexafluoro-1,1,2,2-tetrahydrodecyltrimethoxysilane, 1H, 1H, 2H, 2H-perfluorodecyltriethoxysilane, and heptafluorodecyltrimethoxysilane, the curing agent is any one of N3390 curing agent and tertiary amine, and the defoaming agent is any one of fatty alcohol ethoxysiloxane and polyether siloxane.

8. A coating prepared according to the method for preparing a self-repairing anti-icing and anti-corrosion integrated coating according to any one of claims 1 to 7.

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