Polyurethane-ceramic composite coating, and coating method

Abstract

The present application discloses a polyurethane-ceramic composite coating and a coating method. The coating comprises two base materials: a bottom layer and a surface layer, wherein the bottom layer is provided on the surface of a fan blade and is a polyurethane base material, and the surface layer is provided on the bottom layer and is a ceramic base material. An intermediate layer, namely a polyurethane-ceramic composite coating layer, is formed between the surface layer and the bottom layer and serves as an adhesive between the bottom layer and the surface layer, combining the bottom layer and the surface layer more closely. The ceramic has water resistant properties, alcohol resistant properties, wear resistant properties, scratch resistant properties, and high temperature resistant properties, enhances the strength of the coating on the surface of the fan blade, protects the polyurethane base material of the bottom layer, and lengthens the service life of the polyurethane base material. The polyurethane-ceramic composite coating material is coated on the fan blade, lengthening the service life thereof.

Description

Polyurethane-ceramic composite coating and spraying method

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to the Chinese patent application filed with the China Patent Office on August 28, 2023, with application number 202311090244.9 and invention name “A polyurethane-ceramic composite coating and spraying method”, the entire contents of which are incorporated herein by reference. Technical Field

[0003] The present application belongs to the technical field of wind power generation and relates to a polyurethane-ceramic composite coating and a spraying method. Background Art

[0004] Wind turbines are typically installed in remote areas, operating in harsh environments. As the sole component capturing wind energy, the leading edge of the blade is subject to long-term friction from wind and the impact of sand, salt spray, and rain, making it the most susceptible to corrosion. The leading edge of the blade is particularly susceptible to corrosion, as it is relatively thin and experiences high linear speeds. Corrosion at this location is the most severe on the entire blade. Corrosion on the leading edge of a wind turbine blade affects its aerodynamic shape, resulting in reduced power generation. If leading edge corrosion is not promptly addressed, the blade will suffer more severe damage over time, posing a potential risk to the safe operation of the wind turbine. Therefore, leading edge protection is a key challenge in the development of large blades.

[0005] Currently, common anti-corrosion coatings for wind turbine surfaces include polyurethane, fluorocarbon, and polysiloxane coatings. Polyurethane, with its advantages of a long shelf life and rapid surface drying, represents the future of wind turbine coatings. However, polyurethane coatings have drawbacks such as low impact and compressive strength, poor resistance to rain erosion, and poor resistance to high and low temperatures and weathering. In harsh wind farms, blade leading edge protection materials can fail after three to five years, leading to leading edge corrosion. Therefore, developing highly protective, weather-resistant leading edge protection materials that can absorb the stress of rain impact is an urgent challenge that needs to be addressed.

[0006] Summary of the Invention

[0007] The purpose of this application is to overcome the shortcomings of the above-mentioned prior art and provide a polyurethane-ceramic composite coating and spraying method; to solve the problems in the prior art that the polyurethane coating is poorly resistant to rain erosion, high and low temperature resistance and weather resistance, and the leading edge of the blade is easily corroded.

[0008] To achieve the above objectives, this application adopts the following technical solutions:

[0009] A polyurethane-ceramic composite coating, comprising a bottom layer, an intermediate layer, and a surface layer, wherein the bottom layer is arranged on the outer surface of a wind turbine blade, the intermediate layer is arranged on the outer surface of the bottom layer, and the surface layer is arranged on the outer surface of the intermediate layer; the bottom layer is a polyurethane base material, the surface layer is a ceramic base material, and the intermediate layer is a polyurethane-ceramic coating;

[0010] The polyurethane base material is composed of 20-25% of diisocyanate, 15-20% of polyether diol, 2.5-7.5% of post-chain extender, 1-2% of hydrophilic chain extender, 1-3.5% of first catalyst, 0.5-2% of neutralizer and 50% of solvent by mass fraction;

[0011] The ceramic base material is composed of a multifunctional silane coupling agent, a multifunctional silicone resin, a functional filler and an additive in a mass ratio of 1:1:1.5, and a second catalyst with a mass ratio of 0.1 to 0.2% is also added;

[0012] The polyurethane-ceramic coating is prepared by mixing a polyurethane base material and a ceramic base material in a ratio of (1 to 1.5):1;

[0013] The surface layer is a three-dimensional network cross-linked structure, and functional fillers and additives are distributed inside the three-dimensional network cross-linked structure. A part of the three-dimensional network cross-linked structure is spontaneously generated by a multifunctional silane coupling agent, and the other part is generated by the reaction of a multifunctional silicone resin and a multifunctional silane coupling agent.

[0014] Further improvements of this application are:

[0015] Optionally, the diisocyanate is a mixture of one or more of isophorone diisocyanate, hexamethylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate;

[0016] The polyether glycol is a mixture of one or more of polytetramethylene glycol (PTMG), polyethylene glycol and polypropylene glycol.

[0017] Optionally, the post-chain extender is sodium N-[(2-amino)-amino]ethane sulfonate; and the hydrophilic chain extender is one or a mixture of 2,2-dihydroxymethylpropionic acid and dihydroxymethylbutanoic acid.

[0018] Optionally, the catalyst is a mixture of one or more of dibutyltin dilaurate, stannous octoate, and dibutyltin oxide; the neutralizer is a mixture of one or more of triethylamine, tripropylamine, formic acid, acetic acid, and triethanolamine; and the solvent is N,N-dimethylformamide.

[0019] Optionally, the multifunctional silane coupling agent is triethoxysilane, and the multifunctional silicone resin is ethoxyphenyl silicone resin.

[0020] Optionally, it is characterized in that the functional filler and additives are composed of nano-titanium dioxide, acrylate and organic amine; the second catalyst is composed of octamethylcyclotetrasiloxane and potassium hydroxide in a volume ratio of 100: (0.2-0.3).

[0021] Optionally, the thickness of the bottom layer is 125-175 um, the thickness of the middle layer is 100-120 um, and the thickness of the surface layer is 120-135 um.

[0022] A spraying method for the above-mentioned polyurethane-ceramic composite coating is characterized in that the polyurethane base material is scraped onto the surface of the wind blade substrate, cured at 80°C for 18 hours, and cooled to obtain a base layer; the polyurethane-ceramic coating is scraped onto the base layer, cured at 80°C for 18 hours, and cooled to obtain an intermediate layer; the ceramic base material is scraped onto the intermediate layer, cured at 50°C for 10 hours, and cooled to obtain a surface layer.

[0023] Optionally, the preparation process of the polyurethane base material comprises the following steps:

[0024] (1) Weighing diisocyanate, polyether diol, post-chain extender, hydrophilic chain extender, catalyst, neutralizer and solvent;

[0025] (2) After drying the polyether diol, place it in a container, introduce nitrogen into the container and stir, then add a catalyst and diisocyanate, heat and stir; then add a hydrophilic chain extender and stir to react, cool the reaction system and add a neutralizer to carry out a neutralization reaction, cool the neutralization reaction product and add a post-chain extender and a solvent, stir to obtain a polyurethane base material.

[0026] Optionally, the preparation process of the ceramic base material includes the following steps:

[0027] 100 parts of octamethylcyclotetrasiloxane are placed in a container, 0.2 to 0.3 parts of potassium hydroxide are added to the container, and after heating and stirring, a transparent potassium hydroxide alkali glue is prepared to obtain a second catalyst;

[0028] After mixing and stirring a multifunctional silane coupling agent, N,N-dimethylformamide and a second catalyst, a multifunctional silicone resin is added, and after stirring, functional fillers and additives are added, and after stirring, a ceramic base material is obtained.

[0029] Compared with the prior art, this application has the following beneficial effects:

[0030] The present application discloses a polyurethane-ceramic composite coating, which includes three base materials: a bottom layer, an intermediate layer, and a surface layer. The bottom layer is arranged on the surface of the wind turbine blade and is a polyurethane base material; the intermediate layer is a polyurethane-ceramic composite coating, which is arranged on the bottom layer; and the surface layer is arranged on the intermediate layer and is a ceramic base material. An intermediate layer, namely a polyurethane-ceramic composite coating, is formed between the surface layer and the bottom layer, and serves as an adhesive between the bottom layer and the surface layer, which can more tightly bond the bottom layer and the surface layer. The polyurethane base material of the bottom layer includes: diisocyanate, polyether diol, a post-chain extender, a hydrophilic chain extender, a catalyst, a neutralizer, and a solvent. The hydrophilic chain extender gives the polyurethane base material a certain hydrophilicity, which plays a role in buffering and decomposing the impact of raindrops when they wash onto the surface of the wind turbine blade; the polyurethane prepared by adding the post-chain extender has high stability, uniform emulsion dispersion, and can quickly form a film, and can effectively reduce the damage of rain erosion on the wetted surface. The surface ceramic base material is composed of three components: (1) a multifunctional silane coupling agent (component A) to form a dense three-dimensional network cross-linked structure by a sol-gel reaction; (2) a multifunctional silicone resin (component B) that can participate in the sol-gel reaction of the silane coupling agent to increase the strength and toughness of the three-dimensional cross-linked structure; (3) functional fillers and additives (component C) including fillers (for reinforcement, toughening, thermal conductivity, wear resistance, and ablation resistance), leveling agents, dispersants, etc. (4) a second catalyst, namely potassium hydroxide alkali glue. Because ceramics are resistant to water, alcohol, wear, scratches, and high temperatures, they increase the strength of the wind turbine blade surface coating, protect the underlying polyurethane base material, and extend the service life of the polyurethane base material. When the polyurethane-ceramic composite coating is sprayed on the wind turbine blade, scanning electron microscopy can be used to observe that the number of bubbles on the leading edge of the blade is reduced and the hole size is significantly reduced. Due to the large specific surface area of ​​ceramics, they are very tightly bonded with polyurethane. With ceramics as the skeleton, polyurethane can completely cover the ceramic foam. The two are very tightly bonded and have good interfacial adhesion. This allows stress to be fully transmitted to the substrate along the ceramic skeleton, making the overall stress of the composite material uniform, thereby improving the rain erosion impact resistance of the leading edge of the wind turbine blade.

[0031] This application also discloses a method for preparing a polyurethane-ceramic composite coating. Because polyaspartic acid polyurea reacts rapidly with water, deionized water cannot be used as a solvent for the ceramic base material. This application uses the polar organic solvent N,N-dimethylformamide as a solvent. The addition of a second catalyst promotes the sol-gel reaction in the ceramic base material, forming a dense three-dimensional cross-linked network structure, ensuring the stability of the composite coating. The ceramic, due to its unique network structure and large specific surface area, bonds tightly with the polyurethane. Furthermore, due to its light weight and excellent mechanical properties, it is an ideal material for enhancing the strength and other mechanical properties of polyurethane composites. This spray coating method is flexible and simple to operate, and is suitable for large-scale production. DETAILED DESCRIPTION

[0032] One embodiment of the present application discloses a polyurethane-ceramic composite coating, which includes two base materials: a bottom layer and a surface layer. The bottom layer is provided on the surface of a wind turbine blade and is a polyurethane base material; the surface layer is provided on the bottom layer and is a ceramic base material. The polyurethane base material of the bottom layer includes: diisocyanate, polyether diol, post-chain extender, hydrophilic chain extender, first catalyst, neutralizer, and solvent. The surface layer ceramic base material is composed of three components: (1) a multifunctional silane coupling agent (component A) to undergo a sol-gel reaction to form a dense three-dimensional network cross-linked structure; (2) a multifunctional silicone resin (component B) that can participate in the sol-gel reaction of the silane coupling agent to increase the strength and toughness of the three-dimensional network cross-linked structure; (3) functional fillers and additives (component C) including fillers (for reinforcement, toughening, thermal conductivity, wear resistance, ablation resistance, etc.), leveling agents, dispersants, catalysts, or curing agents; and (4) a second catalyst (component D).

[0033] Specifically, the diisocyanate is a mixture of any one or more of isophorone diisocyanate, hexamethylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate, and its mass content is 20-25% of the polyurethane base material;

[0034] Specifically, the polyether diol is a mixture of one or more of polytetramethylene glycol (PTMG), polyethylene glycol, and polypropylene glycol, and its mass content is 15-20% of the polyurethane base material;

[0035] Specifically, the post-chain extender is sodium N-[(2-amino)-amino]ethane sulfonate, and its mass content is 2.5-7.5% of the polyurethane base material;

[0036] Specifically, the hydrophilic chain extender is one or a mixture of 2,2-dimethylol propionic acid and dimethylol butyric acid, and its mass content is 1-2% of the polyurethane base material;

[0037] Specifically, the first catalyst is one or more of dibutyltin dilaurate, stannous octoate, and dibutyltin oxide, and its mass content is 1 to 3.5% of the polyurethane base material;

[0038] Specifically, the neutralizing agent is one or more of triethylamine, tripropylamine, formic acid, acetic acid, and triethanolamine, and its mass content is 0.5-2% of the polyurethane base material.

[0039] Specifically, the solvent is N,N-dimethylformamide, and its mass content is 50% of the polyurethane base material.

[0040] Specifically, the ceramic base material consists of four components: (Component A) triethoxysilane; (Component B) ethoxyphenyl silicone resin; and (Component C) nano-titanium dioxide, acrylate, and organic amine, with the nano-titanium dioxide serving as a reinforcing filler, the acrylate serving as a leveling agent, and the organic amine serving as a pH adjuster. The weight ratio of these three components in the ceramic is 1:1:1.5. Component D is a second catalyst, comprising octamethylcyclotetrasiloxane and potassium hydroxide, with a catalyst content of 0.1-0.2% by weight in the ceramic.

[0041] One embodiment of the present application discloses a method for preparing and spraying a polyurethane-ceramic composite coating, the steps of which are as follows:

[0042] (1) Weighing the diisocyanate, polyether diol, post-chain extender, hydrophilic chain extender, first catalyst, neutralizer, and solvent according to a set mass ratio;

[0043] (2) Dry the weighed polyether diol at 110°C for 5 h.

[0044] (3) The polyether diol dried in step (2) was taken out and added into a three-necked round-bottom flask. Nitrogen was introduced into the flask and stirring was started. The stirring conditions were: 350 r / min for 20 min.

[0045] (4) Add the weighed first catalyst and diisocyanate to the flask of step (3) and start stirring. The stirring conditions are: 350 r / min, 88°C, 30 to 60 min.

[0046] (5) Add the weighed hydrophilic chain extender to the flask of step (4) and start stirring. The stirring conditions are: 350 r / min, 80°C, 2-3 h;

[0047] (6) The reaction product of step (5) was cooled to 50° C., and a weighed neutralizing agent was added to carry out a neutralization reaction for 30 to 40 minutes.

[0048] (7) The reaction product of step (6) was cooled to 35° C., and the weighed post-chain extender and solvent were added, and stirring was started at 900 r / min for 30 to 40 minutes to finally obtain the bottom polyurethane base material.

[0049] (8) The bottom polyurethane base material is applied to the surface of the wind turbine blade substrate by knife coating and cured at 80° C. for 18 h. After cooling, the bottom polyurethane base material layer is obtained with a thickness of 125 to 175 μm.

[0050] (9) 100 parts of octamethylcyclotetrasiloxane are placed in a beaker, and the beaker is placed in an oil bath; 0.2-0.3 parts of potassium hydroxide are slowly added into the beaker through a funnel, and the mixture is heated to 115-120° C. with stirring. After the potassium hydroxide is completely dissolved, the mixture is cooled to room temperature to obtain a transparent potassium hydroxide alkali gel, i.e., catalyst component D.

[0051] (10) Weigh the ceramic components A, B, and C separately, with the mass ratio of the three in the ceramic being 1:1:1.5. Also weigh the catalyst component D from step (8), with its mass content being 0.1-0.2%.

[0052] (11) Component A, triethoxysilane, N,N-dimethylformamide, and catalyst component D were placed in a 50°C water bath and stirred for 0.5 to 1 hour at a stirring speed of 100 to 180 r / min.

[0053] (12) Adding the ethoxyphenyl silicone resin of component B to the reaction product of step (11), stirring at room temperature for 2 to 2.5 hours at a stirring speed of 400 to 560 r / min.

[0054] (13) Add the nano-titanium dioxide, acrylic acid and organic amine in component C to the reaction product of step (12), stir at room temperature for 1 to 1.5 hours at a stirring speed of 400 to 500 r / min to obtain a surface ceramic base material.

[0055] (14) The polyurethane base material in step (7) and the ceramic base material in step (13) are weighed in a mass ratio of (1 to 1.5):1 and then stirred at room temperature at a stirring speed of 100 to 180 r / min for 2 to 2.5 h to obtain a polyurethane-ceramic coating.

[0056] (15) The polyurethane-ceramic base material is coated on the surface of the polyurethane base layer by scraping and cured at 80°C for 18 hours. After cooling, a polyurethane-ceramic base material intermediate layer with a thickness of 100 to 120 μm is obtained.

[0057] (16) The ceramic base material is coated on the surface of the polyurethane-ceramic intermediate layer by scraping and cured at 50°C for 10 h. After cooling, a ceramic surface layer with a thickness of 120 to 135 μm is obtained.

[0058] The following is further described with reference to specific embodiments.

[0059] Example 1

[0060] (1) Isophorone diisocyanate (IPDI), polytetramethylene glycol (PTMG), 2,2-dihydroxymethylpropionic acid (DMPA), triethylamine (TEA), dibutyltin dilaurate (DBTDL), sodium N-[(2-amino)-amino]ethane sulfonate (AAS), and N,N-dimethylformamide were weighed in the above proportions; the mass contents of each substance were 22%, 20%, 1%, 0.5%, 2%, and 4.5%, respectively.

[0061] (2) Dry the weighed polytetrahydrofuran diol at 110° C. for 5 h.

[0062] (3) taking out dried polytetrahydrofuran diol in step (2) and adding in three mouthfuls of round-bottomed flasks, in flask, generally pass into nitrogen, and open and stir, stirring condition is: 350r / min, 20min.

[0063] (4) Add weighed dibutyltin dilaurate (DBTDL) and isophorone diisocyanate (IPDI) to the flask of step (3), start stirring, and the stirring conditions are: 350 r / min, 88°C, 30-60 min;

[0064] (5) Add the weighed 2,2-dihydroxymethylpropionic acid (DMPA) to the flask in step (4) and start stirring. The stirring conditions are: 350 r / min, 80°C, 2 to 3 h;

[0065] (6) The reaction product of step (5) was cooled to 50° C., and weighed triethylamine (TEA) was added to carry out a neutralization reaction for 30 to 40 minutes.

[0066] (7) The reaction product of step (6) was cooled to 35° C., and weighed sodium N-[(2-amino)-amino]ethane sulfonate (AAS) and N,N-dimethylformamide were added, and stirring was started at 900 r / min for 30 to 40 minutes to finally obtain a bottom polyurethane base material.

[0067] (8) The bottom polyurethane base material is applied to the surface of the wind turbine blade substrate by knife coating and cured at 80°C for 18 hours. After cooling, the bottom polyurethane base material layer is obtained with a thickness of 125 μm.

[0068] (9) According to the mass fraction, 100 parts of octamethylcyclotetrasiloxane were placed in a beaker, and the beaker was placed in an oil bath. 0.2 parts of potassium hydroxide were slowly added to the beaker through a funnel, and the mixture was stirred and heated to 115°C. After the potassium hydroxide was completely dissolved, it was cooled to room temperature to obtain a transparent potassium hydroxide gel, i.e., catalyst component D.

[0069] (10) Weigh the ceramic components A, B, and C respectively, with the mass ratio of the three in the ceramic being 1:1:1.5. Also weigh the catalyst component D from step (8), with a mass content of 0.1%.

[0070] (11) Component A, triethoxysilane, N,N-dimethylformamide, and catalyst component D were placed in a 50°C water bath and stirred for 0.5 h at a stirring speed of 100 r / min.

[0071] (12) Add component B ethoxyphenyl silicone resin to the reaction product in step (11), and stir at room temperature for 2 h at a stirring speed of 400 r / min.

[0072] (13) Add the nano-titanium dioxide, acrylic acid and organic amine in component C to the reaction product of step (12), stir at room temperature for 1 hour at a stirring speed of 400 r / min to obtain a surface ceramic base material.

[0073] (14) The polyurethane base material in step (7) and the ceramic base material in step (13) were weighed in a mass ratio of (1:1) and stirred at room temperature at a stirring speed of 100 r / min for 2 h to obtain a polyurethane-ceramic coating.

[0074] (15) The polyurethane-ceramic base material was coated on the surface of the polyurethane base layer by scraping and cured at 80°C for 18 h. After cooling, a polyurethane-ceramic base material intermediate layer with a thickness of 100 μm was obtained.

[0075] (16) The ceramic base material was coated on the surface of the polyurethane-ceramic intermediate layer by scraping and cured at 50 °C for 10 h. After cooling, a ceramic surface layer with a thickness of 120 μm was obtained.

[0076] Example 2

[0077] (1) Hexamethylene diisocyanate, polytetramethylene glycol (PTMG), 2,2-dihydroxymethylpropionic acid (DMPA), tripropylamine, dibutyltin dilaurate (DBTDL), sodium N-[(2-amino)-amino]ethane sulfonate (AAS), and N,N-dimethylformamide were weighed to a mass content of 20%, 15%, 2%, 2%, 3.5%, 7.5%, and 50%, respectively.

[0078] (2) Dry the weighed polytetrahydrofuran diol at 110° C. for 5 h.

[0079] (3) taking out dried polytetrahydrofuran diol in step (2) and adding in three mouthfuls of round-bottomed flasks, in flask, generally pass into nitrogen, and open and stir, stirring condition is: 350r / min, 20min.

[0080] (4) Add weighed dibutyltin dilaurate (DBTDL) and isophorone diisocyanate (IPDI) to the flask in step (3) and start stirring. The stirring conditions are: 350 r / min, 88°C, 60 min;

[0081] (5) Add the weighed 2,2-dihydroxymethylpropionic acid (DMPA) to the flask in step (4) and start stirring. The stirring conditions are: 350 r / min, 80°C, and 3 h;

[0082] (6) The reaction product of step (5) was cooled to 50° C., and weighed triethylamine (TEA) was added to carry out a neutralization reaction for 40 min.

[0083] (7) The reaction product of step (6) was cooled to 35° C., and weighed sodium N-[(2-amino)-amino]ethane sulfonate (AAS) and N,N-dimethylformamide were added, and stirring was started at 900 r / min for 40 min to finally obtain the bottom polyurethane base material.

[0084] (8) The bottom polyurethane base material is applied to the surface of the wind turbine blade substrate by knife coating and cured at 80°C for 18 hours. After cooling, the bottom polyurethane base material layer is obtained with a thickness of 175 μm.

[0085] (9) Place 100 parts of octamethylcyclotetrasiloxane in a beaker, and place the beaker in an oil bath; slowly add 0.3 parts of potassium hydroxide into the beaker through a funnel, start stirring and heat to 120°C. After the potassium hydroxide is completely dissolved, cool to room temperature to obtain a transparent potassium hydroxide gel, i.e., catalyst component D.

[0086] (10) Weigh the ceramic components A, B, and C separately. The mass ratio of the three components in the ceramic is 1:1:1.5. Weigh the catalyst component D in step (8). Its mass content is 0.2%.

[0087] (11) Component A, triethoxysilane, N,N-dimethylformamide, and catalyst component D were placed in a 50°C water bath and stirred for 1 h at a stirring speed of 180 r / min.

[0088] (12) Add the ethoxyphenyl silicone resin of component B to the reaction product in step (11), and stir at room temperature for 2.5 hours at a stirring speed of 560 r / min.

[0089] (13) Add the nano-titanium dioxide, acrylic acid and organic amine in component C to the reaction product of step (12), stir at room temperature for 1.5 hours at a stirring speed of 500 r / min to obtain a surface ceramic base material.

[0090] (14) The polyurethane base material in step (7) and the ceramic base material in step (13) were weighed in a mass ratio of (1.5:1) and stirred at room temperature at a stirring speed of 180 r / min for 2.5 h to obtain a polyurethane-ceramic coating.

[0091] (15) The polyurethane-ceramic base material was coated on the surface of the polyurethane base layer by scraping and cured at 80°C for 18 h. After cooling, a polyurethane-ceramic base material intermediate layer with a thickness of 120 μm was obtained.

[0092] (16) The ceramic base material was coated on the surface of the polyurethane-ceramic intermediate layer by scraping and cured at 50°C for 10 h. After cooling, a ceramic surface layer with a thickness of 135 μm was obtained.

[0093] Example 3

[0094] (1) 4,4'-Dicyclohexylmethane diisocyanate, polyethylene glycol, 2,2-dihydroxymethylpropionic acid (DMPA), formic acid, dibutyltin dilaurate (DBTDL), sodium N-[(2-amino)-amino]ethane sulfonate (AAS), and N,N-dimethylformamide were weighed to a mass content of 25%, 18%, 1.5%, 1%, 1%, 3.5%, and 50%, respectively.

[0095] (2) Dry the weighed polytetrahydrofuran diol at 110° C. for 5 h.

[0096] (3) taking out dried polytetrahydrofuran diol in step (2) and adding in three mouthfuls of round-bottomed flasks, in flask, generally pass into nitrogen, and open and stir, stirring condition is: 350r / min, 20min.

[0097] (4) Add weighed dibutyltin dilaurate (DBTDL) and isophorone diisocyanate (IPDI) to the flask in step (3) and start stirring at 350 r / min, 88°C, and 60 min;

[0098] (5) Add the weighed 2,2-dihydroxymethylpropionic acid (DMPA) to the flask in step (4) and start stirring. The stirring conditions are: 350 r / min, 80°C, and 3 h;

[0099] (6) The reaction product of step (5) was cooled to 50° C., and weighed triethylamine (TEA) was added to carry out a neutralization reaction for 40 min.

[0100] (7) The reaction product of step (6) was cooled to 35° C., and weighed sodium N-[(2-amino)-amino]ethane sulfonate (AAS) and N,N-dimethylformamide were added, and stirring was started at 900 r / min for 40 min to finally obtain the bottom polyurethane base material.

[0101] (8) The bottom polyurethane base material is applied to the surface of the wind turbine blade substrate by knife coating and cured at 80°C for 18 hours. After cooling, the bottom polyurethane base material layer is obtained with a thickness of 155 μm.

[0102] (9) 100 parts of octamethylcyclotetrasiloxane were placed in a beaker, and the beaker was placed in an oil bath; 0.3 parts of potassium hydroxide were slowly added to the beaker through a funnel, and the mixture was heated to 120° C. with stirring. After the potassium hydroxide was completely dissolved, the mixture was cooled to room temperature to obtain a transparent potassium hydroxide alkali gel, i.e., catalyst component D.

[0103] (10) Weigh the ceramic components A, B, and C separately. The mass ratio of the three components in the ceramic is 1:1:1.5. Weigh the catalyst component D in step (8). Its mass content is 0.15%.

[0104] (11) Component A, triethoxysilane, N,N-dimethylformamide, and catalyst component D were placed in a 50°C water bath and stirred for 1 h at a stirring speed of 180 r / min.

[0105] (12) Add the ethoxyphenyl silicone resin of component B to the reaction product in step (11), and stir at room temperature for 2.5 hours at a stirring speed of 560 r / min.

[0106] (13) Add the nano-titanium dioxide, acrylic acid and organic amine in component C to the reaction product of step (12), stir at room temperature for 1.5 hours at a stirring speed of 500 r / min to obtain a surface ceramic base material.

[0107] (14) The polyurethane base material in step (7) and the ceramic base material in step (13) were weighed in a mass ratio of (1.5:1) and stirred at room temperature at a stirring speed of 180 r / min for 2.5 h to obtain a polyurethane-ceramic coating.

[0108] (15) The polyurethane-ceramic base material was coated on the surface of the polyurethane base layer by scraping and cured at 80°C for 18 h. After cooling, a polyurethane-ceramic base material intermediate layer with a thickness of 110 μm was obtained.

[0109] (16) The ceramic base material was coated on the surface of the polyurethane-ceramic intermediate layer by scraping and cured at 50 °C for 10 h. After cooling, a ceramic surface layer with a thickness of 125 μm was obtained.

[0110] Example 4

[0111] (1) Isophorone diisocyanate (IPDI), polypropylene glycol, dimethylolbutyric acid, acetic acid, dibutyltin dilaurate (DBTDL), sodium N-[(2-amino)-amino]ethane sulfonate (AAS), and N,N-dimethylformamide were weighed to give a mass content of 23%, 20%, 2%, 0.5%, 2%, 2.5%, and 50%, respectively.

[0112] (2) Dry the weighed polytetrahydrofuran diol at 110° C. for 5 h.

[0113] (3) taking out dried polytetrahydrofuran diol in step (2) and adding in three mouthfuls of round-bottomed flasks, in flask, generally pass into nitrogen, and open and stir, stirring condition is: 350r / min, 20min.

[0114] (4) Add weighed dibutyltin dilaurate (DBTDL) and isophorone diisocyanate (IPDI) to the flask in step (3) and start stirring. The stirring conditions are: 350 r / min, 88°C, 60 min;

[0115] (5) Add the weighed 2,2-dihydroxymethylpropionic acid (DMPA) to the flask in step (4) and start stirring. The stirring conditions are: 350 r / min, 80°C, and 3 h;

[0116] (6) The reaction product of step (5) was cooled to 50° C., and weighed triethylamine (TEA) was added to carry out a neutralization reaction for 40 min.

[0117] (7) The reaction product of step (6) was cooled to 35° C., and weighed sodium N-[(2-amino)-amino]ethane sulfonate (AAS) and N,N-dimethylformamide were added, and stirring was started at 900 r / min for 40 min to finally obtain the bottom polyurethane base material.

[0118] (8) The bottom polyurethane base material is applied to the surface of the wind turbine blade substrate by knife coating and cured at 80°C for 18 hours. After cooling, the bottom polyurethane base material layer is obtained with a thickness of 145 μm.

[0119] (9) Place 100 parts of octamethylcyclotetrasiloxane in a beaker, and place the beaker in an oil bath; slowly add 0.3 parts of potassium hydroxide into the beaker through a funnel, start stirring and heat to 120°C. After the potassium hydroxide is completely dissolved, cool to room temperature to obtain a transparent potassium hydroxide gel, i.e., catalyst component D.

[0120] (10) Weigh the ceramic components A, B, and C separately. The mass ratio of the three components in the ceramic is 1:1:1.5. Weigh the catalyst component D in step (8). Its mass content is 0.2%.

[0121] (11) Component A, triethoxysilane, N,N-dimethylformamide, and catalyst component D were placed in a 50°C water bath and stirred for 1 h at a stirring speed of 180 r / min.

[0122] (12) Add the ethoxyphenyl silicone resin of component B to the reaction product in step (11), and stir at room temperature for 2.5 hours at a stirring speed of 560 r / min.

[0123] (13) Add the nano-titanium dioxide, acrylic acid and organic amine in component C to the reaction product of step (12), stir at room temperature for 1.5 hours at a stirring speed of 500 r / min to obtain a surface ceramic base material.

[0124] (14) The polyurethane base material in step (7) and the ceramic base material in step (13) were weighed in a mass ratio of (1.5:1) and stirred at room temperature at a stirring speed of 180 r / min for 2.5 h to obtain a polyurethane-ceramic coating.

[0125] (15) The polyurethane-ceramic base material was coated on the surface of the polyurethane base layer by scraping and cured at 80°C for 18 h. After cooling, a polyurethane-ceramic base material intermediate layer with a thickness of 105 μm was obtained.

[0126] (16) The ceramic base material was coated on the surface of the polyurethane-ceramic intermediate layer by scraping and cured at 50 °C for 10 h. After cooling, a ceramic surface layer with a thickness of 125 μm was obtained.

[0127] Example 5

[0128] (1) Isophorone diisocyanate (IPDI), polytetramethylene glycol (PTMG), 2,2-dihydroxymethylpropionic acid (DMPA), triethanol, dibutyltin dilaurate (DBTDL), sodium N-[(2-amino)-amino]ethane sulfonate (AAS), and N,N-dimethylformamide were weighed to give a mass content of 21%, 17%, 1.5%, 1.5%, 3.5%, 5.5%, and 50%, respectively.

[0129] (2) Dry the weighed polytetrahydrofuran diol at 110° C. for 5 h.

[0130] (3) taking out dried polytetrahydrofuran diol in step (2) and adding in three mouthfuls of round-bottomed flasks, in flask, generally pass into nitrogen, and open and stir, stirring condition is: 350r / min, 20min.

[0131] (4) Add weighed dibutyltin dilaurate (DBTDL) and isophorone diisocyanate (IPDI) to the flask in step (3) and start stirring at 350 r / min, 88°C, and 60 min;

[0132] (5) Add the weighed 2,2-dihydroxymethylpropionic acid (DMPA) to the flask in step (4) and start stirring. The stirring conditions are: 350 r / min, 80°C, and 3 h;

[0133] (6) The reaction product of step (5) was cooled to 50° C., and weighed triethylamine (TEA) was added to carry out a neutralization reaction for 40 min.

[0134] (7) The reaction product of step (6) was cooled to 35° C., and weighed sodium N-[(2-amino)-amino]ethane sulfonate (AAS) and N,N-dimethylformamide were added, and stirring was started at 900 r / min for 40 min to finally obtain the bottom polyurethane base material.

[0135] (8) The bottom polyurethane base material is applied to the surface of the wind turbine blade substrate by knife coating and cured at 80°C for 18 hours. After cooling, the bottom polyurethane base material layer is obtained with a thickness of 175 μm.

[0136] (9) 100 parts of octamethylcyclotetrasiloxane were placed in a beaker, and the beaker was placed in an oil bath; 0.3 parts of potassium hydroxide were slowly added to the beaker through a funnel, and the mixture was heated to 120° C. with stirring. After the potassium hydroxide was completely dissolved, the mixture was cooled to room temperature to obtain a transparent potassium hydroxide alkali gel, i.e., catalyst component D.

[0137] (10) Weigh the ceramic components A, B, and C separately. The mass ratio of the three components in the ceramic is 1:1:1.5. Weigh the catalyst component D in step (8). Its mass content is 0.2%.

[0138] (11) Component A, triethoxysilane, N,N-dimethylformamide, and catalyst component D were placed in a 50°C water bath and stirred for 1 h at a stirring speed of 180 r / min.

[0139] (12) Add the ethoxyphenyl silicone resin of component B to the reaction product in step (11), and stir at room temperature for 2.5 hours at a stirring speed of 560 r / min.

[0140] (13) The nano-titanium dioxide, acrylic acid, and organic amine in component C were added to the reaction product of step (12), and stirred at room temperature for 1.5 hours at a stirring speed of 500 r / min to obtain a surface ceramic base material. The polyurethane base material in step (7) and the ceramic base material in step (13) were weighed in a mass ratio of (1.5:1) and thoroughly stirred at room temperature at a stirring speed of 180 r / min for 2.5 hours to obtain a polyurethane-ceramic coating.

[0141] (14) The polyurethane-ceramic base material was coated on the surface of the polyurethane base layer by scraping and cured at 80°C for 18 h. After cooling, a polyurethane-ceramic base material intermediate layer with a thickness of 120 μm was obtained.

[0142] (15) The ceramic base material was coated on the surface of the polyurethane-ceramic intermediate layer by scraping and cured at 50°C for 10 h. After cooling, a ceramic surface layer with a thickness of 135 μm was obtained.

[0143] The above description is only a preferred embodiment of the present application and is not intended to limit the present application. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principles of the present application shall be included in the scope of protection of the present application.

Claims

1. A polyurethane-ceramic composite coating, characterized in that: It comprises a bottom layer, an intermediate layer and a surface layer, wherein the bottom layer is arranged on the outer surface of the wind turbine blade, the intermediate layer is arranged on the outer surface of the bottom layer, and the surface layer is arranged on the outer surface of the intermediate layer; the bottom layer is a polyurethane base material, the surface layer is a ceramic base material, and the intermediate layer is a polyurethane-ceramic coating; The polyurethane base material is composed of 20-25% of diisocyanate, 15-20% of polyether diol, 2.5-7.5% of post-chain extender, 1-2% of hydrophilic chain extender, 1-3.5% of first catalyst, 0.5-2% of neutralizer and 50% of solvent by mass fraction; The ceramic base material is composed of a multifunctional silane coupling agent, a multifunctional silicone resin, a functional filler and an additive in a mass ratio of 1:1:1.5, and a second catalyst is added in an amount of 0.1 to 0.2% by mass; The polyurethane-ceramic coating is prepared by mixing a polyurethane base material and a ceramic base material in a ratio of (1 to 1.5):1; The surface layer is a three-dimensional network cross-linked structure, and functional fillers and additives are distributed inside the three-dimensional network cross-linked structure. A part of the three-dimensional network cross-linked structure is spontaneously generated by a multifunctional silane coupling agent, and the other part is generated by the reaction of a multifunctional silicone resin and a multifunctional silane coupling agent.

2. The polyurethane-ceramic composite coating according to claim 1, characterized in that: The diisocyanate is a mixture of one or more of isophorone diisocyanate, hexamethylene diisocyanate, and 4,4'-dicyclohexylmethane diisocyanate; The polyether glycol is a mixture of one or more of polytetramethylene glycol (PTMG), polyethylene glycol and polypropylene glycol.

3. The polyurethane-ceramic composite coating according to claim 1, characterized in that: The post-chain extender is sodium N-[(2-amino)-amino]ethane sulfonate; the hydrophilic chain extender is one of 2,2-dihydroxymethylpropionic acid and dihydroxymethylbutyric acid or a mixture of the two.

4. The polyurethane-ceramic composite coating according to claim 1, characterized in that: The catalyst is one or a mixture of dibutyltin dilaurate, stannous octoate, and dibutyltin oxide; the neutralizer is one or a mixture of triethylamine, tripropylamine, formic acid, acetic acid, and triethanolamine; and the solvent is N,N-dimethylformamide.

5. The polyurethane-ceramic composite coating according to claim 1, characterized in that: The multifunctional silane coupling agent is triethoxysilane, and the multifunctional organic silicone resin is ethoxyphenyl silicone resin.

6. The polyurethane-ceramic composite coating according to claim 1, characterized in that: The functional filler and additives are composed of nano titanium dioxide, acrylate and organic amine; the second catalyst is composed of octamethylcyclotetrasiloxane and potassium hydroxide in a volume ratio of 100:(0.2-0.3).

7. The polyurethane-ceramic composite coating according to any one of claims 1 to 6, characterized in that: The thickness of the bottom layer is 125-175um, the thickness of the middle layer is 100-120um, and the thickness of the surface layer is 120-135um.

8. A method for spraying a polyurethane-ceramic composite coating according to claim 1, characterized in that: The polyurethane base material is scraped on the surface of the wind blade substrate, cured at 80°C for 18 hours, and cooled to obtain a base layer; the polyurethane-ceramic coating is scraped on the base layer, cured at 80°C for 18 hours, and cooled to obtain an intermediate layer; the ceramic base material is scraped on the intermediate layer, cured at 50°C for 10 hours, and cooled to obtain a surface layer.

9. The spraying method of the polyurethane-ceramic composite coating according to claim 8, characterized in that: The preparation process of the polyurethane base material comprises the following steps: (1) Weighing diisocyanate, polyether diol, post-chain extender, hydrophilic chain extender, catalyst, neutralizer and solvent; (2) After drying the polyether diol, place it in a container, introduce nitrogen into the container and stir, then add a catalyst and a diisocyanate, heat and stir; then add a hydrophilic chain extender and stir to react, cool the reaction system and add a neutralizer to carry out a neutralization reaction, cool the neutralization reaction product and add a post-chain extender and a solvent, stir to obtain a polyurethane base material.

10. The spraying method of the polyurethane-ceramic composite coating according to claim 8, characterized in that: The preparation process of the ceramic base material comprises the following steps: 100 parts of octamethylcyclotetrasiloxane are placed in a container, 0.2-0.3 parts of potassium hydroxide are added into the container, and a transparent potassium hydroxide alkali gel is obtained after heating and stirring to obtain a second catalyst; After mixing and stirring a multifunctional silane coupling agent, N,N-dimethylformamide and a second catalyst, a multifunctional silicone resin is added, and after stirring, functional fillers and additives are added, and after stirring, a ceramic base material is obtained.