A nano-composite electro-optical-thermal super-hydrophobic de-icing coating and its preparation method and application

Abstract

The application discloses a kind of nano composite electro-optical thermal super-hydrophobic deicing coating and its preparation method and application, belong to wind power equipment anti-icing technical field.The method includes preparation super-hydrophobic nano SiO2 sol and photo-thermal MoS2 sol, after mixing, with epoxy resin and curing agent preparation composite surface layer coating, again with TiC-fluorocarbon resin bottom coating is successively sprayed on the surface of substrate solidification forming.The application is designed by double-layer structure, in combination with the micro-nano rough structure of SiO2 and the photo-thermal effect of MoS2, realizes excellent super-hydrophobicity, self-cleaning ability and efficient electro-optical thermal synergistic deicing performance, significantly improves the protection and durability of coating under complex environment.

Description

Technical Field

[0001] This invention belongs to the field of wind power equipment anti-icing technology, and particularly relates to a nanocomposite electro-photothermal superhydrophobic de-icing coating, its preparation method and application. Background Technology

[0002] Wind power, as a clean and renewable energy source, is widely used around the world. However, wind turbine blades operating in low-temperature and high-humidity environments are prone to icing, which severely affects the aerodynamic performance and power generation efficiency of the turbine, and may even lead to turbine shutdown or damage, thereby impacting the operation and safety of the power grid. Therefore, wind turbine blade de-icing technology has become crucial for improving the stability and operating efficiency of wind turbines.

[0003] Currently, common de-icing technologies include heating de-icing, mechanical de-icing, and surface coating anti-icing technology. While heating de-icing is effective, it is energy-intensive and the system is complex; mechanical de-icing, while direct, is inconvenient to operate and may damage the blades. Surface coating anti-icing technology, due to its lower cost, no additional energy consumption, and ease of operation, has become a more ideal solution.

[0004] While existing superhydrophobic coating technologies can effectively reduce ice adhesion, most coatings lack sufficient durability and have limited anti-icing effects in low-temperature environments. Furthermore, traditional coating technologies typically rely on single physical properties or chemical reactions, making them ill-suited for complex low-temperature and humid environments.

[0005] Existing technologies have included research on the preparation of SiO2-MoS2 photothermal superhydrophobic functional coatings, which can improve surface hydrophobicity and photothermal response to a certain extent. However, in the long-term service environment of wind turbine blades, relying solely on a single functional coating still suffers from problems such as insufficient bonding stability with the substrate, limited performance retention after mechanical wear, and insufficient active de-icing capability under low temperature and high humidity conditions. Furthermore, a single superhydrophobic or photothermal coating cannot simultaneously address droplet retention suppression, photothermal heating, coating durability, and ice removal efficiency. Therefore, there is an urgent need to develop a composite coating that combines superhydrophobic retention reduction, photothermal heating, and substrate reinforcement. Summary of the Invention

[0006] To address the shortcomings of existing SiO2-MoS2 photothermal superhydrophobic coatings under long-term service conditions in wind turbine blades, such as insufficient adhesion stability, limited mechanical durability, and room for improvement in de-icing efficiency of single-layer structures, this invention proposes a TiC-SiO2-MoS2 nanocomposite electro-photothermal superhydrophobic de-icing coating. This coating is not simply a repetition of the SiO2-MoS2 functional layer; instead, a TiC-fluorocarbon resin functional underlayer is introduced between the substrate and the SiO2-MoS2 functional layer, forming a functionally gradient bilayer structure from the inside out. This structure simultaneously enhances substrate adhesion, reduces surface hydrophobicity and retention, promotes photothermal heating and ice removal, thereby achieving a comprehensive anti-icing effect superior to single-functional coatings and single-layer composite coatings. To aid in analyzing the influence of coating surface wettability on de-icing performance, computational analysis methods can be used to illustrate the changing trends of relevant parameters.

[0007] To achieve the above objectives, the present invention provides the following technical solution: A method for preparing a nanocomposite electro-photothermal superhydrophobic de-icing coating includes the following steps: (1) Superhydrophobic nano-SiO2 sol and photothermal nano-MoS2 sol are mixed and dispersed, and epoxy resin and curing agent are added to prepare SiO2-MoS2 composite functional surface coating. (2) TiC nanoparticles were mixed with fluorocarbon resin and dispersant to prepare TiC-fluorocarbon resin functional undercoat coating; (3) After pretreatment of the substrate surface, the TiC-fluorocarbon resin functional bottom layer coating is first bonded to the substrate surface to form a bonding bottom layer, and then the SiO2-MoS2 composite functional top layer coating is sprayed. After curing, a double-layer composite coating is obtained, namely the nano-composite electro-photothermal superhydrophobic de-icing coating.

[0008] Optionally, in step (1), the preparation process of the superhydrophobic nano-SiO2 sol is as follows: The solvent containing tetraethyl orthosilicate was stirred to obtain an initial SiO2 nanoparticle sol. The sol was transferred to a reaction vessel, purged with nitrogen, and then activated with acetic acid. It was then fully fused with a fusion of FAS-17 and toluene to modify the SiO2 particles. The modified sol was fractionated and centrifuged. Finally, polyether-modified silicone oil and benzotriazole were added, and the particles were coated by high-pressure homogenization to obtain the superhydrophobic nano-SiO2 sol.

[0009] Beneficial effects: In the preparation of superhydrophobic nano-SiO2 sol, FAS-17 is used to reduce the surface energy of SiO2 particles, improving the hydrophobicity of the resulting coating; toluene, as a dispersion medium, facilitates sufficient contact and uniform modification between FAS-17 and the SiO2 particle surface; polyether-modified silicone oil improves the dispersion stability of particles in the system and reduces the tendency to agglomerate; benzotriazole forms a passivation film on the material surface through chemical adsorption, inhibiting electrochemical corrosion and improving system stability and environmental adaptability. Under the synergistic effect of the above components as defined in this invention, the surface energy of SiO2 is reduced, particle agglomeration is avoided, and dispersion stability and overall coating performance are improved.

[0010] Optionally, in step (1), the preparation process of the photothermal nano MoS2 sol is as follows: a molybdenum source and a sulfur source are mixed, a structure-directing agent is added for hydrothermal reaction, and after centrifugal purification, a surfactant is used for coating and dispersion to obtain a uniform photothermal nano MoS2 sol.

[0011] Furthermore, the molybdenum source is sodium molybdate; The sulfur source is thioacetamide; The structure-directing agent is cysteine; The surfactant is PEG-2000. Furthermore, the preparation process of the photothermal nano-MoS2 sol is as follows: Sodium molybdate and thioacetamide were dissolved in a solvent and magnetically stirred. Cysteine ​​was then added for hydrothermal pre-reaction for 1 h. PVP was then added and stirred thoroughly for 1 h to form a primary MoS2 crystal nucleus mixed solution. The primary MoS2 nucleus mixture was subjected to hydrothermal crystallization at 200 °C for 24 h, and then naturally cooled to room temperature to obtain MoS2 nanoparticles. After centrifugation and washing, the supernatant was removed, and the mixture was washed three times with alternating ethanol and water to remove impurities, resulting in purified MoS2 nanoparticle precipitate. The precipitate was resuspended and subjected to ultrasonic pulse treatment to form a homogeneous colloidal dispersion. PEG-2000 was mixed with a homogeneous colloidal dispersion and uniformly coated under magnetic stirring. After centrifugation and resuspension, MoS2 sol was finally prepared.

[0012] Optionally, in step (1), the mass ratio of the superhydrophobic nano-SiO2 sol to the photothermal nano-MoS2 sol is 0.25-2.5:0.1-0.5; The mass ratio of epoxy resin to curing agent is 1:0.05-0.35.

[0013] Furthermore, in step (1), the mass ratio of the superhydrophobic nano-SiO2 sol to the photothermal nano-MoS2 sol is 0.85:0.35; The mass ratio of epoxy resin to curing agent is 1:0.23.

[0014] Optionally, the specific preparation steps of step (1) are as follows: Anhydrous ethanol was thoroughly mixed with the superhydrophobic nano-SiO2 sol, and the SiO2 aggregates were ultrasonically dispersed. The water bath temperature was kept ≤30℃, and the mixture was stirred with a magnetic stirrer for 20 min. Then, photothermal nano-MoS2 sol was added and the mixture was further dispersed and stirred for 20 min. The SiO2-MoS2 dispersion was poured into epoxy resin and homogenized for 5 min until the target viscosity reached 300-500 mPa·s. Finally, a curing agent was added and the mixture was stirred for 30 min to obtain the SiO2-MoS2 composite functional surface coating.

[0015] Optionally, in step (2), the mass ratio of TiC nanoparticles to fluorocarbon resin is 3:5.

[0016] Optionally, in step (3), the spraying conditions are: the spraying distance is controlled at 15-20cm, the spraying pressure is 20-25 psi, and two sprayings are performed at 30min intervals.

[0017] Furthermore, the thickness of the spray coating is 90±5μm.

[0018] A nanocomposite electro-photothermal superhydrophobic de-icing coating is prepared by the above-described method.

[0019] The above-mentioned nanocomposite electro-photothermal superhydrophobic de-icing coating is applied in the field of anti-icing technology for wind power generation equipment.

[0020] Compared with the prior art, the present invention has the following advantages and technical effects: (1) The composite electrothermal TiC-fluorocarbon resin bonding underlayer and the superhydrophobic photothermal nano SiO2-MoS2 composite coating disclosed in this invention achieve multifunctional synergy. Among them, TiC provides electrothermal conversion, MoS2 enhances photothermal efficiency, and SiO2 constructs a superhydrophobic micro-nano structure. The comprehensive performance is far superior to that of single material coatings, and the nano-level dispersion optimizes mechanical strength and durability. (2) The electrothermal TiC-fluorocarbon resin is used as the bonding substrate, and the upper layer is covered by a superhydrophobic photothermal nano SiO2-MoS2 composite coating. The upper composite coating has the function of protecting the bonding substrate and also has the effect of insulation. The bonding substrate, in turn, provides good adhesion and bonding conditions for the upper composite coating. (3) The coating disclosed in this invention passively delays icing through a superhydrophobic surface, and actively melts ice by combining electrothermal (Joule heating) and photothermal (sunlight / infrared) mechanisms. The dual mechanism significantly improves anti-icing efficiency, adapts to complex environments, reduces energy consumption, and solves the limitations of traditional single anti-icing technology. (4) The coating disclosed in this invention can utilize renewable energy (solar energy) through photothermal conversion, reducing dependence on electrothermal energy. In particular, the superhydrophobic structure reduces the use of de-icing agents, making it environmentally friendly. The coating of this invention has high long-term stability and is suitable for outdoor applications such as wind turbine blades, which is in line with the trend of green energy development. Attached Figure Description

[0021] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings: Figure 1 This is a flowchart of the coating preparation method of the present invention.

[0022] Figure 2 This is an experimental diagram showing the effect of the amount of SiO2 and MoS2 added on the contact angle of the coating in Example 3.

[0023] Figure 3 These are experimental graphs showing the effect of MoS2 addition on the temperature rise of the coating surface in Example 3, and the effect of the epoxy resin to curing agent ratio on the contact angle of the coating.

[0024] Figure 4 These are surface microstructure characterization images of the bilayer composite coating prepared under optimal conditions at different magnifications.

[0025] Figure 5 These are schematic diagrams of the adhesion performance test of the double-layer composite coating prepared under optimal conditions, where (a) is a schematic diagram of the cross-cut adhesion test, (b) is a schematic diagram of the pull-off test, and (c) is the result of the pull-off test.

[0026] Figure 6 These are test charts of the anti-icing and de-icing performance of different coatings. (a) is a schematic diagram of the experimental principle of dynamic icing weight gain and light-induced de-icing, and (b) is a comparison chart of dynamic icing weight gain of different coatings.

[0027] Figure 7 This is a schematic diagram illustrating the auxiliary analysis of the icing change trend under different contact angles in Example 8, where (a) is the icing thickness on the blade surface when the contact angle is 90°, (b) is the icing thickness on the blade surface when the contact angle is 130°, (c) is the icing thickness on the blade surface when the contact angle is 150°, and (d) is a curve of icing thickness data corresponding to different contact angles. Detailed Implementation

[0028] Various exemplary embodiments of the present invention will now be described in detail. This detailed description should not be considered as a limitation of the present invention, but rather as a more detailed description of certain aspects, features, and embodiments of the present invention.

[0029] It should be understood that the terminology used in this invention is merely for describing particular embodiments and is not intended to limit the invention. Furthermore, with respect to numerical ranges in this invention, it should be understood that each intermediate value between the upper and lower limits of the range is also specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range, and any other stated value or intermediate value within said range, is also included in this invention. The upper and lower limits of these smaller ranges may be independently included or excluded from the range.

[0030] Unless otherwise stated, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. While only preferred methods and materials have been described herein, any methods and materials similar or equivalent to those described herein may be used in the implementation or testing of this invention. All references to this specification are incorporated by way of citation to disclose and describe methods and / or materials associated with those references. In the event of any conflict with any incorporated reference, the content of this specification shall prevail.

[0031] Various modifications and variations can be made to the specific embodiments described in this specification without departing from the scope or spirit of the invention, as will be apparent to those skilled in the art. Other embodiments derived from this specification will also be apparent to those skilled in the art. This specification and embodiments are merely exemplary.

[0032] The terms “include,” “including,” “have,” “contain,” etc., used in this article are all open-ended terms, meaning that they include but are not limited to.

[0033] Unless otherwise specified, "room temperature" in this invention refers to 20-30℃.

[0034] All raw materials used in this invention were purchased from the market.

[0035] The technical solution of the present invention will be further illustrated by the following embodiments.

[0036] Example 1: Preparation of superhydrophobic nano-SiO2 sol: Add 500 mL of deionized water to the reaction flask, then add 182 mL of anhydrous ethanol. Inject 22.5 mL of ammonia solution using a micro-syringe at a rate of 0.5 mL / min. Turn on the magnetic stirrer and maintain the solution in the flask at a speed of 600 r / min to keep it in a dynamic state. Control the temperature of the reaction system at 35 ℃ ± 5 ℃. Add 40 mL of a mixture of tetraethyl orthosilicate (TEOS) and 60 mL of ethanol dropwise at a rate of 0.1 mL / s using a constant-pressure dropping funnel, monitoring the pH value in real time and maintaining it between 9.2 and 9.5 (using ammonia solution for pH adjustment).

[0037] After TEOS was added, the mixture was treated at 600 r / min and 35 ℃±5 ℃ for 2.5 h, then adjusted to 400 r / min and 45 ℃±5 ℃ for 1.5 h, and finally treated at 300 r / min and 65 ℃±5 ℃ for 4 h to obtain an initial SiO2 nanoparticle sol of 80 nm.

[0038] The SiO2 nanoparticle sol was transferred to a reactor with a pressure of 0.3 MPa and purged with nitrogen three times to suppress solvent evaporation and maintain an inert environment. 0.7 wt% acetic acid was added as a proton activator, and the sol was activated at 55 °C for 1.5 h. Then, it was fully fused with 8.2 g FAS-17 (heptadecyltriethoxysilane) and 40 mL toluene at 80 °C for 35 min to fully modify the SiO2 particles and reduce their surface energy.

[0039] The modified sol was fractionated and centrifuged at 3200 rpm for 15 min to remove SiO2 agglomerates >300 nm. SiO2 nanoparticles of the desired particle size were then collected at 16000 rpm for 40 min. Finally, 0.2 wt% polyether-modified silicone oil (purchased from Huixin Chemical Co., Ltd., model H-350) and 0.2 wt% benzotriazole were added to the sol, and the particles were homogenized using a high-pressure homogenizer to complete the preparation of superhydrophobic nano-SiO2. The hydrophilic ends of the polyether-modified silicone oil combined with the hydroxyl groups on the SiO2 surface to form a stable hydrophobic layer, preventing SiO2 nanoparticle aggregation while ensuring uniform particle distribution. Benzotriazole formed a passivation film on the material surface through chemical adsorption, inhibiting electrochemical corrosion and contributing to improved system stability and environmental adaptability.

[0040] The SiO2 sol prepared using Example 1 can be used as a rough structure building component in the composite functional surface layer of the present invention, providing a basis for the coating to form a high contact angle and low droplet retention interface.

[0041] Example 2: Preparation of photothermal nano-MoS2 sol: 0.5 M sodium molybdate and 1 M thioacetamide were dissolved in 70 mL of deionized water at a molar ratio of 1:2. Sodium molybdate and thioacetamide provided the molybdenum and sulfur sources, respectively, for the synthesis materials. The solution was thoroughly dissolved using a magnetic stirrer (800 r / min, 25 ℃, 40 min). Subsequently, 100 mL of 0.5 M cysteine ​​was added, and the mixture was subjected to hydrothermal pre-reaction at 200 ℃ for 1 h. Cysteine ​​acted as a structure-directing agent to regulate the growth of the layered structure. 5 wt% PVP was then added, and the mixture was stirred thoroughly for another 1 h to form a primary MoS2 nucleus mixture solution.

[0042] The mixture was transferred to a polytetrafluoroethylene-lined reactor (70-80% filling) and subjected to hydrothermal crystallization at 200 °C for 24 h. The high temperature and high pressure environment promoted crystal growth and improved crystallinity. After natural cooling to room temperature, M was obtained. O MoS2 nanoparticles were centrifuged at 12000 r / min for 20 minutes, and the supernatant was removed. The nanoparticles were washed three times with alternating ethanol and water to remove impurities and obtain purified MoS2 nanoparticle precipitate. The precipitate was resuspended in 200 mL of deionized water containing 0.1% PVP and subjected to ultrasonic pulse treatment (100 W, 1 h) to form a homogeneous colloidal dispersion.

[0043] PEG-2000 was mixed with the homogeneous colloidal dispersion obtained in the previous step at a mass ratio of 1:10, and magnetically stirred at 500 r / min for 12 h to ensure uniform coating. The mixture was then centrifuged at 8000 r / min for 15 min to remove unbound PEG-2000, and the precipitate was resuspended in deionized water to obtain the final MoS2 sol, which was stored at 4℃.

[0044] The MoS2 sol prepared using Example 2 can be used as a photothermal response component in the composite functional surface layer of the present invention to improve the light absorption and photothermal conversion capabilities of the coating.

[0045] Example 3: Preparation of SiO2-MoS2 composite functional surface layer (This example uses a single variable for control, and all other parameters are optimal): It should be noted that the preparation of the SiO2-MoS2 composite functional surface layer in this embodiment can be carried out with reference to the existing public methods. This invention does not take the preparation process of this surface layer as the main innovation point, but uses it as the upper functional surface layer to jointly construct a double-layer composite coating system with the subsequent TiC-fluorocarbon resin functional bottom layer.

[0046] 20 mL of anhydrous ethanol was mixed with different masses of superhydrophobic nano-SiO2 sol (0.25-2.5 g, specifically as shown in Example 1 above) prepared in Example 1. Figure 2 (As shown) Mix thoroughly. Then, use a probe-type ultrasonic cleaner (20 kHz, 300 W) to disperse and break up the SiO2 agglomerates, maintaining the water bath temperature ≤30℃, and stir with a magnetic stirrer at 800 r / min for 20 min. Figure 2 As shown in the left figure, when 0.85 g of superhydrophobic nano-SiO2 sol was added to 20 mL of anhydrous ethanol, the contact angle was the largest at a friction distance of 100 cm, indicating optimal hydrophobicity. Therefore, this concentration of silica sol was chosen as the basis for subsequent experiments. 0.85 g of superhydrophobic nano-SiO2 sol was added to 20 mL of anhydrous ethanol, followed by the addition of 0.1–0.5 g (specifically as follows). Figure 2The MoS2 sol (prepared in Example 2) shown in the right figure was further dispersed and stirred for 20 min. Figure 2 As shown in the middle right figure, the contact angle is largest when the amount of photothermal MoS2 sol added is 0.35g; at the same time, Figure 3 The middle left figure shows that the temperature rise within 100 minutes at this addition amount is only slightly lower than 0.4g and 0.5g, but the difference is small. Therefore, 0.85g of superhydrophobic nano SiO2 sol + 0.35g of photothermal MoS2 sol was selected as the SiO2-MoS2 dispersion for subsequent experiments.

[0047] The SiO2-MoS2 dispersion prepared above was slowly poured into 1 g of epoxy resin solution (purchased from Huixin Chemical Co., Ltd., model E-51), and homogenized for 5 min using a high-speed shear emulsifier (10,000 rpm) until the target viscosity reached 300-500 mPa·s. Polyamide 650 (purchased from Huixin Chemical Co., Ltd., model T-31), a high-curing agent, was added, wherein the mass ratio of curing agent to epoxy resin was 0.05-0.35:1, as detailed below. Figure 3 (As shown in the right figure), increase the gel curing time and continue stirring for 30 min to obtain a SiO2-MoS2 composite functional topcoat for spraying. Figure 3 As shown in the middle right figure, the contact angle is the largest when the mass ratio of curing agent to epoxy resin is 0.23:1.

[0048] Therefore, the composite topcoat with the best performance is formed when 0.85g of superhydrophobic nano-SiO2 sol + 0.35g of photothermal MoS2 sol + 1g of epoxy resin solution, with a mass ratio of curing agent to epoxy resin of 0.23:1.

[0049] Example 4: Preparation of TiC-fluorocarbon resin functional substrate: 6 g of TiC nanoparticles (purchased from Huixin Chemical Co., Ltd., model TiC-30) were mixed with 15 ml of butyl acetate / acetone (volume ratio 3:1) solvent and 0.4 g of BYK-110 dispersant. The mixture was ultrasonically treated (30 min, 500 W) to form a stable suspension. 10 g of fluorocarbon resin (purchased from Wanbo New Materials Technology Co., Ltd., model WB-FEVE-500) was added and magnetically stirred (1000 rpm, 1 h) until homogeneous. 2.5 g of isocyanate curing agent (purchased from Huixin Chemical Co., Ltd., model N3390) was slowly added. The mixture was then filtered through a 200-mesh sieve to remove agglomerates, thus obtaining the final TiC-fluorocarbon resin functional undercoat.

[0050] TiC-fluorocarbon resin functional underlayer is not only used as a regular primer. On the one hand, it improves the bonding stability between the coating and the substrate through fluorocarbon resin. On the other hand, TiC nanoparticles endow the underlayer with a certain thermal response capability, enabling it to form a synergistic de-icing structure with the upper SiO2-MoS2 photothermal superhydrophobic functional layer.

[0051] Example 5: Preparation and spraying process of composite coating samples: Deionized water was used to rinse away dust from the surface of the material sample to be sprayed, and sodium dodecyl sulfate (SDS) solution was used for cleaning. TiC-fluorocarbon resin coating was used to apply a base coat to the surface of the sample to be sprayed, forming a continuous and uniform adhesive base coat. After the base coat was surface dry, a high-pressure airless sprayer was used to spray the air-dried sample with a SiO2-MoS2 composite coating. The spraying distance was controlled at 18 cm, the spraying pressure was 22 psi, and two sprayings were performed at 30 min intervals to complete the spraying experiment of the sample. The total thickness of the obtained composite coating was controlled at 90±5 μm, and the thickness uniformity CV<5% met the ISO 2178 standard.

[0052] This embodiment employs a spraying sequence of first applying a TiC-fluorocarbon resin functional underlayer, followed by a SiO2-MoS2 composite functional toplayer. This spraying sequence places the TiC functional underlayer between the substrate and the toplayer, which helps improve the bonding stability of the substrate while avoiding direct exposure of TiC particles, which could lead to a rough surface structure and damage to the low surface energy interface.

[0053] Example 6: Coating Formulation and Process Parameter Optimization Experiment: To obtain a composite coating with good hydrophobicity, wear resistance and photothermal properties, the amount of SiO2 added, the amount of MoS2 added and the ratio of resin to curing agent were used as the main variables. First, single-factor experiments were carried out for optimization, and then a central composite design was used for comprehensive optimization based on the single-factor experiments.

[0054] In the specific optimization process, the static water contact angle, post-wear contact angle, and photothermal response capability of the coating were used as comprehensive evaluation indicators. According to the statistical analysis results of the quadratic model in Design-Expert 13 software, when the mass ratio of hydrophobic silica sol, molybdenum disulfide sol, E-51 and T-31 is 3.70∶1.52∶4.35∶1.00, the obtained SiO2-MoS2 photothermal de-icing coating achieves superior comprehensive performance in terms of hydrophobicity, wear resistance and photothermal properties.

[0055] Therefore, in this embodiment, the SiO2-MoS2 composite surface layer is preferably prepared using the following parameters: the mass ratio of hydrophobic silica sol, molybdenum disulfide sol, epoxy resin E-51 and curing agent T-31 is 3.70:1.52:4.35:1.00. In this invention, this preferred surface layer can be further combined with the TiC functional underlayer described in Example 4.

[0056] Example 7: Coating performance test and de-icing effect verification: The composite coating sample prepared in Example 5 (optimal conditions) was placed on a contact angle testing device, and an equal volume of liquid droplets was dropped onto the sample surface to measure its static water contact angle. Multiple tests were conducted at different locations for each group of samples, and the average value was taken as the final result. To evaluate the hydrophobic retention capability after wear resistance, the sample was subjected to five rounds of abrasion treatment using sandpaper, and the contact angle was measured again. The results show that the static water contact angle and the contact angle after five rounds of abrasion are important indicators for evaluating the optimization effect and overall performance of the coating process. Under the optimized process conditions, the average contact angle after wear can reach 150.80°.

[0057] Specifically, under the aforementioned optimized formulation conditions, the model predicted that the contact angle of the double-layer composite coating after five rounds of sandpaper friction would be 150.25°. After actually preparing samples according to this predicted parameter, the average contact angle of the coating after five rounds of sandpaper friction was measured to be 150.80°. The predicted result is basically consistent with the measured result, indicating that the established process optimization model has good predictive reliability. Further test results show that the initial static water contact angle of the obtained coating can reach 155.60°, and the sliding angle is approximately 6.8°. The static water contact angle characterizes the degree of water droplet spread on the coating surface, while the sliding angle characterizes the ease with which water droplets roll off the coating surface. After five rounds of sandpaper friction, the coating contact angle still remains above 150°, and the sliding angle is approximately 10.50°, indicating that the coating can effectively inhibit water droplet spread and retention even after a certain degree of mechanical wear, exhibiting good superhydrophobic retention capability.

[0058] The microstructure morphology of the sample surface was observed using scanning electron microscopy (SEM). The observation revealed that the SiO2-MoS2 coating surface possessed abundant nanoscale rough structures, and these uniformly dispersed rough morphologies remained visible even under high magnification; simultaneously, its average roughness Ra was 0.46 μm. These results demonstrate that the described coating preparation method can form a micro-nano composite interface that is conducive to high contact angles and low droplet adhesion.

[0059] The composition of the bilayer composite coating was analyzed using infrared spectroscopy and X-ray photoelectron spectroscopy to confirm the successful introduction of functional components such as SiO2 and MoS2 into the composite surface layer. Simultaneously, ultraviolet-visible-near-infrared absorption spectroscopy was used to test the coating's light absorption capacity. The results showed that the optimized SiO2-MoS2 composite functional surface layer achieved an average light absorption rate of 86.8%. To further test its photothermal performance, the coated sample was placed in an environment of -8 °C and irradiated with a 200 W xenon lamp at a distance of 70 cm from the light source, with an average illuminance of 11000 lx on the sample surface. Under these conditions, the coating surface temperature rose by approximately 24.6 °C within 100 min; after 5 light / cooling cycles, the temperature rise retention rate was approximately 94.7%. These results indicate that the composite surface layer can effectively absorb light energy and convert it into heat, exhibiting good photothermal response and cycling stability.

[0060] The adhesion performance between the composite coating and the substrate was tested using the cross-cut adhesion test and the pull-off test to evaluate the adhesion stability of the composite coating under service conditions. The cross-cut adhesion rating was 0; the pull-off test showed a bond strength of 8.16 MPa, indicating that the prepared photothermal de-icing coating has good substrate adhesion performance. This result supports the claim that the composite coating in this invention possesses good mechanical bonding stability.

[0061] Samples with different coatings and an uncoated control sample were placed in the same dynamic icing environment. The mass changes before and after icing were recorded, and the weight gain per unit area due to icing was calculated to evaluate the inhibitory effect of different coating systems on icing formation. The results showed that the weight gain due to icing on the uncoated sample was 0.220 g / cm², the hydrophobic SiO2 coated sample decreased to 0.128 g / cm², the MoS2 photothermal coated sample was 0.198 g / cm², and the SiO2-MoS2 composite functional surface layer sample further decreased to 0.092 g / cm², a reduction of approximately 58.2% compared to the uncoated sample. When a double-layer composite coating was constructed using a TiC-fluorocarbon resin functional underlayer and a SiO2-MoS2 composite functional surface layer, the weight gain due to icing on the sample further decreased to 0.084 g / cm², a reduction of approximately 61.8% compared to the uncoated sample. The above results show that the superhydrophobic micro / nano structure constructed by SiO2 can effectively reduce the spread and retention of droplets on the surface, the introduction of MoS2 helps to enhance the photothermal response of the coating, and the bilayer synergistic structure of TiC functional bottom layer and SiO2-MoS2 composite surface layer can further improve the anti-icing effect of the coating.

[0062] To evaluate the de-icing effect of different coatings under light, an ice layer of approximately 1.12 mm thickness was pre-formed on the surface of the sample, and then a de-icing experiment was conducted under light in an environment of -8 ℃. A 200 W xenon lamp was used as the light source, the distance between the light source and the coating surface was 60 cm, the average illuminance on the sample surface was 11000 lx, and the time required for the ice layer to completely melt or detach was recorded. The results show that, under the same test conditions, the complete de-icing time for the uncoated sample was 54 min, with a de-icing rate of approximately 0.021 mm / min; the complete de-icing time for the hydrophobic SiO2-coated sample was 39 min, with a de-icing rate of approximately 0.029 mm / min; the complete de-icing time for the MoS2 photothermal-coated sample was 34 min, with a de-icing rate of approximately 0.033 mm / min; the complete de-icing time for the SiO2-MoS2 composite functional surface layer sample was shortened to 23 min, with a de-icing rate of approximately 0.049 mm / min; and the complete de-icing time for the double-layer composite coating sample was further shortened to 18 min, with a de-icing rate of approximately 0.062 mm / min. These results indicate that the SiO2-MoS2 composite surface layer can improve the photo-induced de-icing effect, and the addition of the TiC functional underlayer can further promote ice melting and detachment, thereby improving the overall de-icing efficiency. Specific performance data are shown in Tables 1 and 2.

[0063] Table 1. Comparison of dynamic icing weight gain of samples with different coatings Table 2 Comparison of light-induced de-icing performance of different coated samples The above tests show that the SiO2-MoS2 functional surface layer in the composite coating system of the present invention has high surface hydrophobicity, good hydrophobicity retention after wear resistance, high light absorption capacity, good substrate adhesion performance, and significant de-icing effect. After the functional surface layer is combined with the TiC functional bottom layer, a TiC-SiO2-MoS2 nanocomposite electro-photothermal superhydrophobic coating system suitable for wind turbine blade de-icing scenarios can be further formed.

[0064] Example 8: Auxiliary Analysis and Explanation Based on the surface wetting characteristics of the composite coating, this study uses analytical methods to illustrate the relationship between the apparent contact angle and droplet spreading, retention, and subsequent icing development, with the apparent contact angle as the primary analytical parameter. By setting different apparent contact angle conditions, the spread range of droplets on the coating surface, the liquid-solid contact area, the retention state, and the icing trend are compared and analyzed. Figure 7 As shown.

[0065] The apparent contact angle has a significant impact on the icing process. When the apparent contact angle is small, droplets are more likely to spread over a larger area after impacting or adhering to the blade surface, increasing the liquid-solid contact area, enhancing the droplet's tendency to remain on the surface, and making it easier for local water to accumulate and form a continuous liquid film. Under low-temperature conditions, such liquid accumulation areas are more conducive to freezing and ice growth, thus enhancing the tendency for icing to develop on the blade surface. When the apparent contact angle increases, the spread of droplets on the surface weakens, droplets tend to remain in a contracted state, the liquid-solid contact area decreases, the surface residence time is shortened, and the tendency for continuous liquid film formation decreases. Since the adhesion and diffusion of droplets on the surface are inhibited, the amount of liquid water that can participate in freezing per unit area on the blade surface is correspondingly reduced, which helps to weaken local icing formation and subsequent ice layer expansion. Therefore, a larger apparent contact angle helps to reduce the tendency for icing to develop on the blade surface.

[0066] Furthermore, a larger apparent contact angle can also reduce the stable adhesion of droplets to the surface after capture, making the droplets more prone to shrinkage, slippage, or detachment, thereby weakening the initial conditions for ice formation. Thus, increasing the contact angle not only improves surface hydrophobicity, but more importantly, indirectly affects the formation process and extent of icing by altering the spread and retention behavior of droplets on the blade surface. Therefore, the surface contact angle is one of the important parameters for evaluating the de-icing performance of the composite coating of this invention, and also one of the important bases for the formulation design and surface structure construction of this invention.

[0067] In addition, the surface temperature rise characteristics and overall heat transfer characteristics of the composite coating prepared by the present invention can also have a certain auxiliary effect on the icing process, but this part is only used as a supplementary explanation of the technical effect of the present invention and will not be elaborated here.

[0068] It should be noted that the auxiliary analysis described in this embodiment is only used to illustrate the influence of the contact angle parameter on icing behavior in the composite coating of the present invention, as well as the rationality of the technical solution design of the present invention, and does not constitute a separate protection subject of the present invention independent of the coating preparation method.

[0069] Summarize: (1) The TiC-SiO2-MoS2 nanocomposite coating used in this invention has good de-icing ability and combines superhydrophobicity and photothermal response characteristics. It can reduce the retention of droplets on the surface of wind turbine blades and promote de-icing, thereby reducing the amount of ice on the blades. Existing experimental results show that after spraying this type of photothermal de-icing coating, the dynamic amount of ice can be reduced by 61.8% compared with the uncoated sample; (2) The TiC-SiO2-MoS2 nanocomposite coating used in this invention has high light absorption capacity and surface temperature rise capacity, which can promote the melting of ice or delay freezing under light conditions. Tests show that its average light absorption rate can reach 86.8%, and the light-induced de-icing rate of the TiC-SiO2-MoS2 double-layer composite coating is about 200% higher than that of the uncoated sample; (3) The composite coating obtained by this invention has good bonding performance with the substrate, and has good resistance to mechanical damage and hydrophobic retention after wear. Tests show that the adhesion grade is 0, the pull-out bonding strength is 8.16 MPa, and the contact angle remains at a high level after wear; (4) This invention demonstrates the relationship between coating composition, surface wetting characteristics and de-icing effect through experimental testing and parameter analysis, thereby demonstrating the rationality of the preparation method and material combination. (5) This invention is applicable to various wind turbine generator sets, especially in low temperature and high humidity environments, and can improve the operational stability and economy of wind turbines.

[0070] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a nanocomposite electro-photothermal superhydrophobic de-icing coating, characterized in that, Includes the following steps: (1) Superhydrophobic nano-SiO2 sol and photothermal nano-MoS2 sol are mixed and dispersed, and epoxy resin and curing agent are added to prepare SiO2-MoS2 composite functional surface coating. (2) TiC nanoparticles were mixed with fluorocarbon resin and dispersant to prepare TiC-fluorocarbon resin functional undercoat coating; (3) After pretreatment of the substrate surface, the TiC-fluorocarbon resin functional bottom layer coating is first bonded to the substrate surface to form a bonding bottom layer, and then the SiO2-MoS2 composite functional top layer coating is sprayed. After curing, a double-layer composite coating is obtained, namely the nano-composite electro-photothermal superhydrophobic de-icing coating. The preparation process of the superhydrophobic nano-SiO2 sol is as follows: The solvent containing tetraethyl orthosilicate was stirred to obtain an initial SiO2 nanoparticle sol; the sol was transferred to a reaction vessel, purged with nitrogen, and then activated with acetic acid, which was then fused with a fusion of FAS-17 and toluene to modify the SiO2 particles; the modified sol was fractionated and centrifuged, and finally polyether-modified silicone oil and benzotriazole were added, and the particle surface was covered by a high-pressure homogenizer to prepare the superhydrophobic nano-SiO2 sol; In step (1), the preparation process of the photothermal nano MoS2 sol is as follows: a molybdenum source and a sulfur source are mixed, a structure-directing agent is added to carry out a hydrothermal reaction, and after centrifugal purification, a surfactant is used to coat and disperse the mixture to obtain a uniform photothermal nano MoS2 sol. The molybdenum source is sodium molybdate; The sulfur source is thioacetamide; The structure-directing agent is cysteine; The surfactant is PEG-2000; In step (1), the mass ratio of the superhydrophobic nano-SiO2 sol to the photothermal nano-MoS2 sol is 0.25-2.5:0.1-0.5; The mass ratio of epoxy resin to curing agent is 1:0.05-0.35; The specific preparation steps for step (1) are as follows: Anhydrous ethanol was thoroughly mixed with the superhydrophobic nano-SiO2 sol, ultrasonically dispersed, and magnetically stirred in a water bath; then photothermal nano-MoS2 sol was added and the dispersion and stirring continued; the SiO2-MoS2 dispersion was poured into epoxy resin and homogenized; finally, a curing agent was added and stirring continued to obtain the SiO2-MoS2 composite functional surface coating. In step (3), the spraying conditions are: spraying distance of 15-20 cm and spraying pressure of 20-25 psi.

2. The method for preparing a nanocomposite electro-photothermal superhydrophobic de-icing coating according to claim 1, characterized in that, The mass ratio of the superhydrophobic nano-SiO2 sol to the photothermal nano-MoS2 sol is 0.85:0.35; The mass ratio of epoxy resin to curing agent is 1:0.

23.

3. A nanocomposite electro-photothermal superhydrophobic de-icing coating, characterized in that, It is prepared by the preparation method according to any one of claims 1-2.

4. The application of the nanocomposite electro-photothermal superhydrophobic de-icing coating as described in claim 3 in the field of wind power equipment anti-icing technology.

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