Halogen-free low-volatility anti-icing photo-thermal super-hydrophobic coating for wind power blade surface and preparation method thereof

Abstract

The invention discloses a halogen-free low-volatility anti-icing photo-thermal super-hydrophobic coating for the surface of a wind power blade and a preparation method thereof. The coating is prepared by compounding functionalized modified multi-walled carbon nanotubes, functionalized modified nano titanium nitride, polydimethylsiloxane / nano silicon dioxide modified epoxy resin and a curing agent. Wherein the multi-walled carbon nanotubes are subjected to amidation and dual functionalization of lauric acid and 3-aminopropyl triethoxy silane; the surface of the nano titanium nitride is uniformly modified through bionic polydopamine coating; hydroxyl-terminated polydimethylsiloxane and nano SiO are doped into an epoxy resin base material, so that the system is endowed with low surface energy and high weather-resistant binding force. After curing and film forming at room temperature for 24 hours or at 80 DEG C for 2 hours, the water contact angle is greater than or equal to 155 DEG C, the ice adhesion strength is less than or equal to 10 kPa, the photo-thermal temperature is greater than or equal to 40 DEG C, and the performance is not attenuated after 50 times of heating and cooling tests; and after 150-hour damp heat, 500-hour ultraviolet radiation, acid corrosion and abrasive paper friction, the coating does not blister or fall off. The coating disclosed by the invention is green and environment-friendly, low in curing energy consumption, high in photo-thermal temperature rise and strong in super-hydrophobic durability, and can be used for remarkably improving the long-term anti-icing capability of wind power blades in cold and high-humidity regions.

Description

Technical Field

[0001] The present invention belongs to the technical field of coatings and relates to an anti-icing photothermal super-hydrophobic coating for the surface of a wind turbine blade and a preparation method thereof. Background Art

[0002] Wind power generation is a clean, renewable form of energy. As a key component of wind turbine systems, wind turbine blades' operating efficiency and stability directly impact overall turbine performance. However, in cold or humid environments, ice easily forms on the blade surfaces, leading to reduced aerodynamic performance, unbalanced loads, increased vibration, and, in severe cases, even safety hazards such as equipment downtime and structural damage. Therefore, developing efficient and reliable anti-icing technologies has become a pressing technical challenge for the wind power industry.

[0003] Superhydrophobic coatings have been widely developed due to their excellent water droplet rolling-off ability, ice suppression and delaying ability, and surface self-cleaning properties. However, the adaptability of a single superhydrophobic property to extreme icing environments is limited, and its long-term durability, adhesion, and environmental stability are still difficult to meet the actual application requirements of wind farms. In order to further improve the anti-icing performance of wind turbine blades in severe cold environments, it is urgent to develop a composite functional coating that combines photothermal deicing capabilities with superhydrophobic anti-icing properties. Photothermal materials can effectively absorb sunlight and convert it into heat energy, which is used to heat the blade surface and promote the melting of ice. Combined with the drainage performance of the superhydrophobic interface, it is expected to achieve an active anti-icing effect of "anti-melting" synergy.

[0004] Patent CN 116970336 B discloses a photothermal super-hydrophobic coating for wind turbine blade surfaces and its preparation method. Although this coating exhibits ice adhesion of less than 20 kPa in static tests at room temperature, it still suffers from high material costs, halogenated solvent emissions, difficulty in implementing on-site UV / heat curing, and insufficient response to comprehensive service environments such as rain erosion and dust. These issues make it difficult to meet the demand for low-cost, long-term anti-icing for wind turbine blades in cold regions throughout their lifecycle. To address these shortcomings, there is an urgent need to develop a new photothermal super-hydrophobic coating for wind turbine blades that combines green preparation, low-energy curing, high weather resistance, and long-term anti-icing capabilities, as well as its preparation method. Summary of the Invention

[0005] In response to the problems existing in the prior art, the present invention proposes a new halogen-free, low-volatile anti-icing photothermal super-hydrophobic coating for the surface of wind turbine blades and a preparation method thereof.

[0006] In order to achieve the above objectives, the present invention provides the following technical solutions: The present invention first discloses a halogen-free, low-volatile, anti-icing, photothermal, and super-hydrophobic coating for the surface of a wind turbine blade, which is composed of the following components in parts by weight: 1-3 parts of functionalized multi-walled carbon nanotubes; 9-12 parts of functionalized nano-titanium nitride; 4-6 parts of modified epoxy resin; 1~2 parts of curing agent.

[0007] The present invention also discloses a method for preparing an anti-icing photothermal super-hydrophobic coating for a wind turbine blade surface as described above, comprising the following steps: S1. Preparation of functionalized modified multi-walled carbon nanotubes 1-3 parts of hydroxylated multi-walled carbon nanotubes (MWCNTs) were placed in a reaction vessel. 60-80 parts of anhydrous ethanol was added as a solvent, along with a mixture of 1 part lauric acid and 0.2 parts 3-aminopropyltriethoxysilane (APTES) as a modifier. The mixture was stirred at 500-1500 r / min and gradually heated to 70-75°C for 4 hours to undergo an amidation reaction. During the reaction, lauric acid and APTES were chemically grafted onto the surface of the hydroxylated carbon nanotubes via amide bonds, while the ethoxy groups of the aminosilane formed a stable chemically bonded coating on the surface. The product was then cooled to room temperature, washed sequentially with deionized water and anhydrous ethanol, centrifuged, and dried in a vacuum oven at 55-65°C for 8 hours to obtain a multi-walled carbon nanotube powder with a dual functionalization of long-chain aliphatic structures and epoxyphilic amino groups on the surface.

[0008] S2. Preparation of functionalized modified nano-titanium nitride Take 9 parts of nano-titanium nitride with a particle size of 20 nm and place it in a nitrogen-protected reaction container, add 30 parts of anhydrous ethanol and 0.8 parts of dopamine hydrochloride, slowly heat to 50-60°C under stirring conditions and react for 3 hours to form a uniform polydopamine functional coating on the surface of the nano-titanium nitride. After natural cooling and centrifugal washing, it is dried in a vacuum drying oven at 60-70°C for 8 hours to obtain surface-modified polydopamine-functionalized nano-titanium nitride particles.

[0009] S3. Preparation of modified epoxy resin Four parts of bisphenol A epoxy resin were placed in a reactor and heated to a molten state at 80-90°C. An ethanol dispersion containing 0.4 parts of hydroxyl-terminated polydimethylsiloxane and 0.2 parts of nano-silica was slowly added dropwise. After stirring and mixing, the temperature was raised to 120-140°C, and the ethanol was removed in vacuo. After stirring and reacting for 2 hours, the temperature was cooled to room temperature to prepare a siloxane nano-modified epoxy resin base material with excellent weather resistance, low surface energy and high adhesion properties.

[0010] S4. Preparation of anti-icing photothermal superhydrophobic coating 1-3 parts of functionalized multi-walled carbon nanotubes obtained in step S1 and 9-12 parts of functionalized nano-titanium nitride prepared in step S2 are added to 80 parts of anhydrous ethanol, ultrasonically dispersed for 30 minutes, and then magnetically stirred to make them uniform. Then, 4-6 parts of modified epoxy resin prepared in step S3 are added, and stirring is continued to make them uniform. 1-2 parts of curing agent (polyamide curing agent 651 type) are added and stirred until a uniform and stable coating system is formed.

[0011] When in use, the prepared coating is loaded into a spray gun with a diameter of 1.5 mm, sprayed twice (with an interval of 10 minutes) at a pressure of 0.35 MPa and a spray distance of 12 cm, and then left to cure at room temperature for 24 hours or heated at 80°C for 2 hours to obtain a new type of wind turbine blade photothermal superhydrophobic coating with high weather resistance and long-term anti-icing ability.

[0012] The innovation of the present invention is as follows: the present invention utilizes the amidation reaction of lauric acid and aminosilane (APTES) to perform non-fluorine, halogen-free and environmentally friendly functional modification on multi-walled carbon nanotubes, realizing the synergistic bifunctional modification of long-chain aliphatic structure and amino functional groups, thereby improving the superhydrophobicity, interfacial adhesion strength and environmental stability of the coating; the polydopamine bionic coating method is used to perform surface functionalization treatment on nano-titanium nitride, solving the problems of poor dispersion and easy agglomeration of traditional nanoparticles, significantly improving the uniformity of nanoparticles in the coating and the stable photothermal conversion performance; by introducing polydimethylsiloxane and nano-silica composite modified epoxy resin base material, the effective combination of low surface energy, high adhesion and long-term environmental durability of the epoxy resin coating system is achieved, significantly improving the comprehensive service capability of the coating in the application environment of wind turbine blades.

[0013] The present invention is beneficial in that: (1) Environmentally friendly and low volatility: The formula of the present invention completely avoids the use of halogen-containing and highly volatile harmful solvents and uses anhydrous ethanol as the only solvent, which significantly reduces VOC emissions, meets the requirements of green manufacturing and environmental friendliness, and ensures construction safety and environmental compliance; (2) All-weather high-efficiency anti-icing performance: Functionalized multi-walled carbon nanotubes and nano-titanium nitride work together to build a stable and efficient photothermal conversion network. During the day, the photothermal effect of solar radiation is used to actively heat the surface, quickly melting ice and preventing ice. At night or in a dark environment, due to the extremely low surface energy and excellent super-hydrophobic micro-nanostructure of the coating, it can significantly delay the formation of ice, reduce the adhesion of ice to the blade surface, and reduce the speed and degree of ice accumulation, thereby achieving all-weather high-efficiency anti-icing effect, effectively making up for the deficiency of existing single photothermal coatings in anti-icing at night; (3) Long-term stable superhydrophobicity and weather resistance: The innovative functionalization method gives the coating surface a stable superhydrophobic structure, which maintains excellent anti-icing and superhydrophobic properties under harsh conditions such as long-term wind and sand erosion, hot and cold cycles, ultraviolet radiation, high humidity and salt spray. At the same time, the modified epoxy resin gives the coating excellent substrate adhesion. After long-term service, the coating will not crack or fall off, and its durability is significantly better than existing technologies. BRIEF DESCRIPTION OF THE DRAWINGS

[0014] Figure 1 This is a scanning electron microscope (SEM) image of the anti-icing photothermal superhydrophobic coating prepared in Example 1 of the present invention.

[0015] Figure 2 This is a contact angle test diagram of the anti-icing photothermal superhydrophobic coating prepared in Example 1 of the present invention after film formation on the surface of a wind turbine blade.

[0016] Figure 3 This is a graph showing the test results of a cyclic heating and cooling test of an anti-icing photothermal super-hydrophobic coating prepared in Example 1 of the present invention at an ambient temperature of -10°C and 80 consecutive times of 1-sun light irradiation. Specific implementation methods

[0017] The present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments, but the protection scope of the present invention is not specifically limited by the embodiments. Embodiment 1:

[0018] S1. Preparation of functionalized modified multi-walled carbon nanotubes Weigh 2 parts of commercially available hydroxylated multi-walled carbon nanotubes (inner diameter 5-10 nm, outer diameter 10-20 nm, length 10-30 μm, purity >99.5%) and place them in a 250 mL three-necked reaction flask. Add 60 parts of analytical grade anhydrous ethanol (purity ≥99.7%) as the dispersion medium and ultrasonically disperse for 20 min to make it fully uniform. Add 1 part of lauric acid (analytical grade) and 0.2 parts of 3-aminopropyltriethoxysilane (APTES, analytical grade) that have been mixed uniformly in advance to the above flask. Turn on the mechanical stirrer and stir at a speed of 500 r / min to mix uniformly. Slowly raise the temperature to 70°C and keep stirring at constant temperature for 4 minutes. h, forming an amide bond graft functional modification; after the reaction is completed, the product is cooled to room temperature (about 25°C), and then repeatedly washed with deionized water and anhydrous ethanol (volume ratio of 1:1) four times to remove unreacted raw materials; the washed product is centrifuged (4000 rpm, 10 min), and then placed in a vacuum oven at 65°C for 8 h to obtain black powdered functionalized multi-walled carbon nanotubes.

[0019] S2. Preparation of functionalized modified nano-titanium nitride 9 parts of 99.9% pure nano-titanium nitride powder with an average particle size of approximately 20 nm were weighed and placed in a 250 mL four-necked flask. The flask was pre-filled with high-purity nitrogen, and 30 parts of anhydrous ethanol and 0.8 parts of dopamine hydrochloride (purity ≥98%) were added. Under mechanical stirring (speed of 400 r / min), the temperature was slowly raised to 55°C and kept at this temperature for 3 h to allow oxidative polymerization of dopamine, forming a uniform and dense polydopamine coating on the surface of the titanium nitride particles. After the reaction, the flask was cooled to room temperature (25°C) and washed three times with deionized water and anhydrous ethanol (each time with ultrasonic-assisted washing for 15 min). The washed product was centrifuged (4000 rpm, 10 min) and then dried in vacuo at 70°C for 8 h to obtain functionalized nano-titanium nitride powder.

[0020] S3. Preparation of modified epoxy resin Weigh 4 parts of bisphenol A epoxy resin (E51 type, epoxy value 0.51 mol / 100 g), place them in a 100 mL three-necked flask, and place it on a magnetic stirrer; after raising the temperature to 85°C to fully melt the epoxy resin, slowly add a pre-mixed dispersion of 0.4 parts of hydroxyl-terminated polydimethylsiloxane (PDMS, average molecular weight of about 2000) and 0.2 parts of nano-silica (particle size 15 nm, surface unmodified) in anhydrous ethanol; after the addition is completed, continue to raise the temperature to 120°C, remove the ethanol in vacuo, and stir the reaction for 2 hours to fully blend and modify the PDMS and epoxy resin, and form a uniform and stable nano-composite structure with the cooperation of nano-silica; cool to room temperature to obtain a light yellow transparent modified epoxy resin base material.

[0021] S4. Preparation and spraying method of anti-icing photothermal super-hydrophobic coating Two parts of functionalized multi-walled carbon nanotubes prepared in step S1 and 11 parts of functionalized nano-titanium nitride prepared in step S2 were added to 80 parts of anhydrous ethanol and ultrasonically dispersed for 30 min using a 600 W ultrasonic disperser; after uniform dispersion, the mixture was transferred to a magnetic stirrer, and 5 parts of modified epoxy resin base prepared in step S3 were added at a stirring speed of 400 r / min. After stirring evenly, 2 parts of polyamide curing agent 651 were slowly added and continued to stir evenly to obtain a stable and uniform anti-icing photothermal superhydrophobic coating.

[0022] A 1.5 mm caliber high-pressure spray gun was used for coating. The air pressure was set to 0.35 MPa during spraying. The vertical distance between the spray gun and the surface of the pretreated wind turbine blade sample was about 12 cm. Two passes were sprayed at a uniform speed of 2 m / min, with an interval of 10 minutes between each pass. After spraying, the coated sample was placed in a room temperature environment (25℃±3℃, humidity 50%±5%) and allowed to cure for 24 hours to obtain a uniform and dense black coating.

[0023] Figure 1 This is a SEM image of the surface microstructure of the anti-icing photothermal superhydrophobic coating prepared in Example 1. It can be seen that the coating surface structure is dense and uniform, with uniform distribution of functionalized nanoparticles and a distinct nanoscale rough protrusion structure. This structure facilitates the capture of air to form a stable air cushion, significantly reducing the surface energy of the coating surface, and achieving a static water contact angle of approximately 162° ( Figure 2 ), the ice adhesion strength is only 9 kPa, showing excellent superhydrophobic and anti-icing effects.

[0024] Figure 3 The results of the cyclic photothermal temperature rise and fall stability test of the coating prepared in Example 1. Under an ambient temperature of -10°C, the coating surface was subjected to a continuous cyclic temperature rise and fall test using 1 sun irradiation (1 sun, about 1000 W / m²), for a total of 80 complete temperature rise-cooling cycles. It can be clearly seen from the figure that the surface temperature of the coating rose rapidly to about 45°C under each light irradiation, and after 80 repeated tests, the temperature rise performance of the coating did not show obvious attenuation or fluctuation, and the temperature rise amplitude and speed were always highly stable. This shows that the anti-icing photothermal super-hydrophobic coating of the present invention has excellent durability and stability, and can ensure the reliability of the anti-icing performance of the coating in long-term practical applications. Example 2:

[0025] S1. Preparation of functionalized multi-walled carbon nanotubes 1 part of commercially available hydroxylated multi-walled carbon nanotubes (inner diameter 5-10 nm, outer diameter 10-20 nm, length 10-30 μm, purity >99.5%) was weighed and placed in a 250 mL three-necked reaction flask; 60 parts of analytical grade anhydrous ethanol (purity ≥99.7%) was added as a dispersion medium and ultrasonically dispersed for 20 min to make it fully uniform; 1 part of lauric acid (analytical grade) and 0.2 parts of 3-aminopropyltriethoxysilane (APTES, analytical grade) that had been mixed uniformly in advance were added to the above flask; a mechanical stirrer was turned on and uniformly mixed at a stirring speed of 1500 r / min, and the temperature was slowly raised to 75°C. Stirring was maintained at this temperature and the reaction was carried out for 4 h to form an amide bond graft functional modification; after the reaction was completed, the product was cooled to room temperature (about 25°C) and then repeatedly washed four times with deionized water and anhydrous ethanol (volume ratio 1:1) to remove unreacted raw materials; the washed product was centrifuged (4000 rpm, 10 min), and then dried in a vacuum oven at 65 °C for 8 h to obtain black powdery functionalized multi-walled carbon nanotubes.

[0026] S2. Preparation of functionalized nano-titanium nitride 9 parts of 99.9% pure nano-titanium nitride powder with an average particle size of approximately 20 nm were weighed and placed in a 250 mL four-necked flask. The flask was pre-filled with high-purity nitrogen, and 30 parts of anhydrous ethanol and 0.8 parts of dopamine hydrochloride (purity ≥98%) were added. Under mechanical stirring (speed of 400 r / min), the temperature was slowly raised to 50°C and kept at this temperature for 3 h to allow oxidative polymerization of dopamine, forming a uniform and dense polydopamine coating on the surface of the titanium nitride particles. After the reaction, the flask was cooled to room temperature (25°C) and washed three times with deionized water and anhydrous ethanol (each time with ultrasonic-assisted washing for 15 min). The washed product was centrifuged (4000 rpm, 10 min) and then vacuum-dried at 60°C for 8 h to obtain functionalized nano-titanium nitride powder.

[0027] S3. Preparation of modified epoxy resin Four parts of bisphenol A epoxy resin (E51, epoxy value 0.51 mol / 100g) were weighed and placed in a 100 mL three-necked flask on a magnetic stirrer. The temperature was raised to 80°C to fully melt the epoxy resin, and then a pre-mixed dispersion of 0.4 parts of hydroxyl-terminated polydimethylsiloxane (PDMS, average molecular weight approximately 2000) and 0.2 parts of nano-silica (particle size 15 nm, unmodified) in anhydrous ethanol was slowly added dropwise. After the addition was complete, the temperature was further raised to 140°C, the ethanol was removed in vacuo, and the reaction was stirred for 2 h to fully blend and modify the PDMS and epoxy resin, and form a uniform and stable nanocomposite structure in collaboration with the nano-silica. The temperature was cooled to room temperature to obtain a light yellow, transparent modified epoxy resin base.

[0028] S4. Preparation and spraying method of anti-icing photothermal super-hydrophobic coating 1 part of functionalized multi-walled carbon nanotubes prepared in step S1 and 9 parts of functionalized nano-titanium nitride prepared in step S2 were added to 80 parts of anhydrous ethanol and ultrasonically dispersed for 30 min using a 600 W ultrasonic disperser; after uniform dispersion, the mixture was transferred to a magnetic stirrer, and 4 parts of modified epoxy resin base prepared in step S3 were added at a stirring speed of 400 r / min. After stirring, 2 parts of polyamide curing agent 651 were slowly added and continued to stir evenly to obtain a stable and uniform anti-icing photothermal super-hydrophobic coating; A 1.5 mm caliber high-pressure spray gun was used for coating. The air pressure was set to 0.35 MPa during spraying. The vertical distance between the spray gun and the surface of the pretreated wind turbine blade sample was about 12 cm. Two passes were sprayed at a uniform speed of 2 m / min, with an interval of 10 minutes between each pass. After spraying, the coated sample was placed in a room temperature environment (25℃±3℃, humidity 50%±5%) and allowed to cure for 24 hours to obtain a uniform and dense black coating. Example 3:

[0029] S1. Preparation of functionalized multi-walled carbon nanotubes The preparation was carried out in full accordance with the method and proportions of step S1 in Example 1.

[0030] S2. Preparation of functionalized nano-titanium nitride The preparation was carried out in full accordance with the method and proportions of step S2 in Example 1.

[0031] S3. Preparation of modified epoxy resin Prepare completely according to the method and proportion of step S3 in Example 1.

[0032] S4. Preparation and spraying method of anti-icing photothermal super-hydrophobic coating The preparation and spraying were carried out completely according to the method of step S4 in Example 1. After the spraying was completed, the coated sample was placed in a preheated 80° C. oven for curing for 2 h to obtain a uniform and dense black coating. Comparative Example 1:

[0033] Compared with Example 1, in Comparative Example 1, multi-walled carbon nanotubes without functional modification were directly used, and other steps and raw materials were the same as those in Example 1. Comparative Example 2:

[0034] Compared with Example 1, in Comparative Example 2, nano-titanium nitride without functional modification was directly used, and other steps and raw materials were the same as in Example 1. Comparative Example 3:

[0035] Compared with Example 1, in Comparative Example 3, unmodified bisphenol A epoxy resin was directly used, and other steps and raw materials were the same as in Example 1. Comparative Example 4:

[0036] The fluorine-containing photothermal conversion super-hydrophobic wind turbine blade surface protective coating disclosed in patent CN 116970336 B was selected, and its preparation method is as follows: S1. Preparation of photothermal conversion modified nano-slurry In a four-necked flask equipped with a stirrer, thermometer, and condenser, 5 parts by weight of photothermal conversion two-dimensional nanographene particles, a mixed solution of 20 parts by weight of tetrachloroethylene, 1 part by weight of hexadecyltrimethylammonium bromide, and 0.5 parts by weight of isophorone diisocyanate were added. The mixture was heated to 60°C and allowed to react for 4 hours. After cooling to room temperature, the product was transferred to a rotary evaporator and the tetrachloroethylene was removed by vacuum distillation. 10 parts by weight of fluorinated silicone polyether polyol was then added and ultrasonically dispersed for 1 hour to produce a photothermal conversion modified nanoslurry.

[0037] S2. preparing a photothermal conversion modified nano-slurry modified fluorinated silicone waterborne polyurethane-fluorinated acrylate dispersion; First, 90 parts by mass of fluorinated silicone polyether polyol and 10 parts by mass of the photothermal conversion modified nano-slurry prepared in step S1 were added to a container, and the mixture was vacuum dehydrated at 105° C. for 2 h, cooled to room temperature, and 25 parts by mass of isophorone diisocyanate and 16 parts by mass of hexamethylene diisocyanate were added, and the mixture was reacted at 75° C. for 3 h, and then 5 parts by mass of 2,2-dihydroxymethylpropionic acid and 4 parts by mass of ethylene glycol were added, and the reaction temperature was 85° C. for 2 h, and 17 parts by mass of hydroxyethyl acrylate were added, and the reaction was continued for 1 h to prepare a polyurethane prepolymer; the polyurethane prepolymer prepared above was cooled to room temperature, 23 parts by mass of perfluoroacrylate monomer was added to reduce the viscosity, and then 3 parts by mass of triethylamine was added to neutralize and form a salt; the prepolymer was discharged into a disperser, 190 parts by mass of deionized water was added under stirring for dispersion, 1 part by mass of potassium persulfate was added, and the temperature was raised to 70° C. for reaction for 4 h. h, and cooled to room temperature to obtain a photothermal conversion modified nano slurry modified fluorinated silicone waterborne polyurethane-fluorinated acrylate dispersion.

[0038] S3. Preparation of micro-nano particle / fluorinated silane coupling agent modified slurry A four-necked flask equipped with a stirrer, thermometer, and condenser was charged with a mixed solution of 5 parts by mass of micro-nano titanium dioxide particles, 50 parts by mass of methanol, and 0.5 parts by mass of heptadecafluorodecyltrimethoxysilane. The mixture was heated to 70°C and refluxed for 12 hours. After cooling to room temperature, the product was transferred to a rotary evaporator and the methanol was removed by vacuum distillation. 31 parts by mass of ethanol was added, and ultrasonic dispersion was performed for 1 hour to prepare a micro-nano particle / fluorinated silane coupling agent modified slurry.

[0039] S4. Preparation of photothermal conversion super-hydrophobic wind turbine blade surface protective coating and preparation method thereof The photothermal conversion modified nano-slurry prepared in step S2 is modified with 100 parts by mass of the fluorinated silicone waterborne polyurethane-fluorinated acrylate dispersion, and 35 parts by mass of the micro-nanoparticle / fluorinated silane coupling agent modified slurry prepared in step S3, 2.0 parts by mass of a polyorganosiloxane leveling agent, and 0.5 parts by mass of an aqueous organosilicon defoamer are added. The various additives are mixed evenly for standby use, and 2.0 parts by mass of a commercial waterborne polyurethane curing agent is added before use to obtain a photothermal conversion super-hydrophobic wind turbine blade surface protective coating. The coating spraying method is the same as in Example 1 and is cured under ultraviolet light.

[0040] Performance Testing (1) Hygrothermal aging: Place the sample in a constant temperature and humidity chamber, set the temperature to 60°C and the relative humidity to 95%, and observe whether the coating bubbles or falls off; (2) UV aging: Use an accelerated aging test chamber, use a UVA-340 lamp, set the UV radiation intensity to 0.68W / m², and the cycle is 8 hours of light / 4 hours of condensation. Observe whether the coating bubbles or falls off; (3) Acid corrosion resistance: The coating sample was immersed in 8 wt% sulfuric acid solution for 24 h, taken out and naturally dried, and the surface integrity was observed; (4) Ice adhesion: Freeze water (5 mm thick) on the sample surface and test the maximum ice-detachment force using the pull-off method at –10°C. (5) Photothermal heating: In a constant temperature environment of -10°C, use an AM1.5 (1 sun, 1000W / m²) simulated light source to irradiate the sample vertically, and record the surface temperature after 20 minutes; (6) Wear resistance: Use 1000-grit sandpaper and slide the sample back and forth along the sandpaper surface 50 times under a load of 500 g, each time 10 cm. The contact angle and morphology changes before and after the test are tested.

[0041] The performance tests of Examples 1 to 3 and Comparative Examples 1 to 4 were carried out, and the results were as follows: Table 1 Test results of Examples 1 to 3 and Comparative Examples 1 to 4 Test items 150 h damp heat aging 500 h UV aging Resistant to 8% sulfuric acid 1500 grit sandpaper rubbing 5 m Coating surface contact angle (°) Contact angle of coating surface after 480 h UV aging (°) Ice adhesion (kPa) Temperature under 1 sun intensity (℃) Example 1 No blistering, no shedding No blistering, no shedding No blistering, no shedding No blistering, no shedding 162 155 9 43 Example 2 No blistering, no shedding No blistering, no shedding No blistering, no shedding No blistering, no shedding 161 153 7 44 Example 3 No blistering, no shedding No blistering, no shedding No blistering, no shedding No blistering, no shedding 160 152 8 42 Comparative Example 1 No blistering, no shedding Falling off No blistering, no shedding No blistering, no shedding 130 100 110 23 Comparative Example 2 Falling off No blistering, no shedding Falling off Falling off 125 99 120 20 Comparative Example 3 No blistering, no shedding Falling off Falling off Falling off 133 80 130 19 Comparative Example 4 Falling off Falling off Falling off 161 153 18 30 The above-described embodiments merely express the implementation methods of the present invention, but should not be understood as limiting the scope of the patent of the present invention. It should be pointed out that for those skilled in the art, several variations and improvements can be made without departing from the concept of the present invention, and these all fall within the scope of protection of the present invention.

Claims

1. A halogen-free, low-volatility, anti-icing, photothermal, and super-hydrophobic coating for the surface of wind turbine blades, characterized in that: The components are as follows: 1-3 parts of functionalized modified multi-walled carbon nanotubes; 9-12 parts of functionalized modified nano-titanium nitride; 4-6 parts of modified epoxy resin; 1~2 parts of polyamide curing agent.

2. The method for preparing the coating according to claim 1, wherein: The steps include: S1. Preparation of Functionalized Modified Multi-walled Carbon Nanotubes Hydroxylated multi-walled carbon nanotubes, anhydrous ethanol, lauric acid and 3-aminopropyltriethoxysilane were mixed and reacted at 70-75°C for 4 h, washed and vacuum-dried at 55-65°C to obtain functionalized multi-walled carbon nanotubes. S2. Preparation of Functionalized Modified Nano-Titanium Nitride Nano-titanium nitride, anhydrous ethanol and dopamine hydrochloride were reacted at 50-60°C for 3 h, washed and dried in a vacuum at 60-70°C to obtain polydopamine-functionalized nano-titanium nitride. S3. Preparation of Modified Epoxy Resin Bisphenol A epoxy resin was mixed with hydroxyl-terminated polydimethylsiloxane and nano-silica at 80-140℃ and dealcoholized in vacuum for 2 h to obtain modified epoxy resin. S4. Preparation of Anti-icing Photothermal Superhydrophobic Coating According to the proportions of the components of claim 1, the components are mixed under ultrasonic dispersion and magnetic stirring, and a polyamide curing agent is added to prepare a coating; a 0.3-0.4 MPa spray gun is used to spray the coating on the substrate twice, with an interval of 10 minutes, and the coating is cured at room temperature for 24 hours or at 80°C for 2 hours to prepare a photothermal superhydrophobic coating.

3. The method of claim 2, wherein the molar ratio of lauric acid to 3-aminopropyltriethoxysilane in S1 is 1:(0.15-0.30).

4. The method according to claim 2, wherein the amount of dopamine hydrochloride in S2 is (6-10) wt% of the mass of the nano-titanium nitride.

5. The coating according to any one of claims 1 to 4, wherein the functionalized multi-walled carbon nanotubes have an outer diameter of 10-20 nm and an aspect ratio of 500-3000.

6. The coating according to any one of claims 1 to 4, wherein the hydroxyl-terminated polydimethylsiloxane in the modified epoxy resin accounts for 8 to 12 wt% of the epoxy resin, and the nano-silicon dioxide accounts for 2 to 6 wt%.

7. The method according to claim 2, wherein the wet film thickness after spraying is 120-160 μm, and the dry film thickness after curing is 50-80 μm.

8. The coating according to claim 1, wherein the static water contact angle is ≥155° and the ice adhesion strength is ≤10 kPa.

9. The coating according to any one of claims 1 to 4, wherein the coating uses only anhydrous ethanol as a solvent and does not contain halogen elements such as chlorine, bromine, and fluorine, and halogenated organic solvents.

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