Photo-thermal super-hydrophobic anti-icing coating and preparation method thereof

Abstract

The invention belongs to the technical field of super-hydrophobic materials, and particularly relates to a photo-thermal super-hydrophobic anti-icing coating and a preparation method thereof. The photo-thermal super-hydrophobic anti-icing coating comprises a heat absorption polymer substrate and a super-hydrophobic particle layer located on the surface of the heat absorption polymer substrate. The heat absorption polymer substrate is prepared from resin and filler, and the super-hydrophobic particle layer is composed of super-hydrophobic particles. The photo-thermal super-hydrophobic anti-icing coating has good hydrophobic, anti-icing and deicing capacities, meanwhile has excellent mechanical strength and elasticity, and can enhance the wear resistance and prolong the service life of a substrate. In addition, the preparation method of the coating is controllable in process, the prepared product is stable in quality, and the preparation method is suitable for large-scale industrial production.

Description

Technical Field

[0001] The present invention belongs to the technical field of superhydrophobic materials, and particularly relates to a photothermal superhydrophobic anti-icing coating and a preparation method thereof. Background Art

[0002] Natural phenomena such as freezing, frosting, and freezing rain cause many troubles to daily life and production activities. In existing de-icing technologies, in addition to the fact that traditional de-icing means often require a large amount of human and material resources, various functional coating materials have also emerged in new anti-icing technologies. Among these materials, superhydrophobic anti-icing coatings have attracted much attention due to their unique properties. However, relying solely on superhydrophobic surfaces for anti-icing still has limitations in practical applications. When mechanical methods such as scraping, wiping, or sanding are used to remove ice, this treatment method is likely to damage the microscopic structure of the coating surface, resulting in a decrease in superhydrophobic performance and thus affecting the anti-icing effect.

[0003] Therefore, providing a coating that simultaneously has hydrophobic and anti-icing capabilities has become a problem to be solved. Summary of the Invention

[0004] Based on the above technical background, the main object of the present invention is to provide a photothermal superhydrophobic anti-icing coating and a preparation method thereof to overcome the deficiencies in the prior art.

[0005] To achieve the foregoing invention object, the technical solutions adopted by the present invention include:

[0006] In a first aspect of the present invention, there is provided a photothermal superhydrophobic anti-icing coating, which includes an endothermic polymer substrate and a superhydrophobic particle layer located on the surface of the endothermic polymer substrate;

[0007] The endothermic polymer substrate is prepared from a resin and a filler, and the mass ratio of the resin to the filler is 13:(1 - 2.5);

[0008] The superhydrophobic particle layer is composed of superhydrophobic particles, and the superhydrophobic particles are modified silica.

[0009] Preferably, the resin includes a low surface energy resin and a viscosity regulating resin, and the mass ratio of the low surface energy resin to the viscosity regulating resin is (30 - 50):14.

[0010] More preferably, the low surface energy resin is selected from one or two of tetrafluoro resin and fluorosilicon resin;

[0011] More preferably, the viscosity regulating resin is selected from one or two of alkyd resin and RTV.

[0012] Preferably, the filler is an endothermic particle, and the particle size of the endothermic particle is 20μm - 50μm;

[0013] The heat-absorbing particles are selected from one or more of squid ink powder, carbon black, and iron oxide;

[0014] The thickness of the photothermal superhydrophobic anti-icing coating is 80 μm to 150 μm; the particle size of the superhydrophobic particles is 5 nm to 20 nm.

[0015] The second aspect of the present invention lies in providing a preparation method of the photothermal superhydrophobic anti-icing coating described in the first aspect of the present invention, and the preparation method includes the following steps:

[0016] Step 1: Dissolve the resin in a polymer solvent and react under a nitrogen atmosphere to obtain a mixed solution;

[0017] Step 2: Add a filler to the mixed solution, stir, and then add a curing agent and continue stirring to obtain a photothermal base polymer mixed solution;

[0018] Step 3: Disperse silica and a low surface energy modifier in a solvent, and then perform magnetic stirring to obtain a superhydrophobic particle dispersion;

[0019] Step 4: Spray the photothermal base polymer mixed solution onto the surface of the substrate, and then bake it to obtain a heat-absorbing polymer substrate;

[0020] Step 5: Spray the superhydrophobic particle dispersion onto the surface of the heat-absorbing polymer substrate, and after drying, obtain a photothermal superhydrophobic anti-icing coating.

[0021] In Step 1,

[0022] Preferably, polytetrafluoroethylene resin, fluorosilicone resin, alkyd resin, and RTV are dissolved in a polymer solvent and reacted at 50 to 70 °C for 0.5 to 2 h under a nitrogen atmosphere;

[0023] Preferably, the polymer solvent is selected from one or more of butyl acetate, ethyl acetate, and ethanol.

[0024] In Step 2,

[0025] Preferably, the curing agent is selected from one or more of N3390, KH550, and KH560;

[0026] Preferably, add a filler to the mixed solution, stir at room temperature for 0.5 to 2 h, and then add a curing agent and continue stirring for 0.5 to 2 h.

[0027] In Step 3,

[0028] Preferably, disperse silica and a low surface energy modifier in a solvent, and perform magnetic stirring at 40 to 60 °C and a rotation speed of 500 to 1500 rpm for 20 to 25 h;

[0029] Preferably, the low surface energy modifier is perfluorooctyltriethoxysilane or n-octyltriethoxysilane.

[0030] In step 4,

[0031] Preferably, the spraying conditions are as follows: spraying onto the substrate surface at a speed of 0.3 - 0.5 g / s under the conditions of 20 - 30°C and a spraying distance of 40 - 60 cm;

[0032] Preferably, the baking conditions are as follows: baking at 50 - 70°C for 0.5 - 2 h.

[0033] In step 5,

[0034] Preferably, the spraying conditions are as follows: spraying onto the surface of the endothermic polymer substrate at a speed of 0.3 - 0.5 g / s under the conditions of 20 - 30°C and a spraying distance of 40 - 60 cm;

[0035] Preferably, dry for 1 - 3 h after spraying.

[0036] The beneficial effects of the present invention:

[0037] (1) The photothermal superhydrophobic anti-icing coating of the present invention includes an endothermic polymer substrate and a superhydrophobic particle layer formed on its surface. The endothermic polymer substrate is composed of a low molecular weight copolymer (low surface energy resin) and a high molecular weight copolymer (viscosity regulating resin). The low molecular weight copolymer serves as the flexible copolymer of the substrate, and the added high molecular weight copolymer can significantly improve the mechanical strength of the substrate, enabling the endothermic polymer substrate to have excellent elastic and strength properties, thereby further enhancing the wear resistance of the substrate.

[0038] (2) Through the synergistic effect of the endothermic polymer substrate and the superhydrophobic particle layer formed on the surface of the endothermic polymer substrate, the hydrophobicity of the hydrophobic anti-icing coating is enhanced, which can effectively prevent water droplets from freezing on its surface, delay the icing process. At the same time, this hydrophobic anti-icing coating can also utilize the photothermal effect to rapidly heat up under light conditions and accelerate the melting of ice, thereby significantly enhancing the anti-icing and de-icing capabilities of the hydrophobic anti-icing coating.

[0039] (3) The preparation method of the photothermal superhydrophobic anti-icing coating of the present invention has a controllable process, and the obtained product has stable quality, which is suitable for large-scale industrial production. Description of the Drawings

[0040] Figure 1 Scanning electron micrograph showing the surface microstructure of the coating prepared in Example 1;

[0041] Figure 2 Schematic diagram of the wear resistance test instrument;

[0042] Figure 3Schematic diagram showing the results of 20 wear resistance tests on the coatings prepared in Examples 1-6 and Comparative Examples 1-3;

[0043] Figure 4 Schematic diagram showing the change in ice adhesion force of the coatings prepared in Examples 1-6 and Comparative Examples 1-3. Detailed implementation manners

[0044] The present invention will be described in detail below, and the features and advantages of the present invention will become clearer and more definite with these descriptions.

[0045] The first aspect of the present invention is to provide a photothermal superhydrophobic anti-icing coating, and the photothermal superhydrophobic anti-icing coating includes an endothermic polymer substrate and a superhydrophobic particle layer located on the surface of the endothermic polymer substrate.

[0046] The endothermic polymer substrate is prepared from a resin and a filler, and the mass ratio of the resin to the filler is 13:(1-2.5). Preferably, the mass ratio of the resin to the filler is 6.75:1.

[0047] The resin includes a low surface energy resin and a viscosity adjusting resin. The mass ratio of the low surface energy resin to the viscosity adjusting resin is (30-50):14. Preferably, the mass ratio of the low surface energy resin to the viscosity adjusting resin is 40:14.

[0048] The low surface energy resin is selected from one or two of tetrafluoro resin and fluorosilicon resin. Tetrafluoro resin and fluorosilicon resin have a low surface energy.

[0049] Preferably, the low surface energy resin is a mixture of tetrafluoro resin and fluorosilicon resin, and the mass ratio of tetrafluoro resin to fluorosilicon resin is (10-15):28.

[0050] More preferably, the mass ratio of tetrafluoro resin to fluorosilicon resin is 12:28.

[0051] The viscosity adjusting resin is selected from one or two of alkyd resin and RTV (room temperature vulcanized silicone rubber).

[0052] Preferably, the viscosity adjusting resin is a mixture of alkyd resin and RTV, and the mass ratio of alkyd resin to RTV is (3-5):10.

[0053] More preferably, the mass ratio of alkyd resin to RTV is 4:10.

[0054] The use of low surface energy resin enables the substrate itself to have a certain degree of hydrophobicity. Adding viscosity regulating resin can endow the coating with both high strength and flexibility, thus improving the wear resistance and durability of the coating. In addition, the addition of viscosity regulating resin can enhance the photothermal conversion efficiency of the copolymer, thereby further improving the anti-icing and de-icing effects of the coating. The structural design of the coating also ensures its superhydrophobicity under low temperature conditions, further extending the service life of the coating.

[0055] The filler is heat-absorbing particles, the heat-absorbing particles are micron-sized black particles, and the particle size of the heat-absorbing particles is 20μm - 50μm.

[0056] The heat-absorbing particles are selected from one or more of cuttlefish ink powder, carbon black, and iron oxide. Preferably, the carbon black is micron-sized and the iron oxide is nano-sized iron oxide.

[0057] The polymer substrate formed by tetrafluoro resin, fluorosilicon resin, alkyd resin, and RTV provides good mechanical strength and elasticity, ensuring the wear resistance and long-term stability of the coating. The heat-absorbing particles not only have a photothermal effect and achieve efficient de-icing under light irradiation, but the micron-sized convex structure formed by them on the polymer substrate can also provide protection for nano-sized hydrophobic particles, enhancing the long-term stability of the coating.

[0058] The superhydrophobic particle layer is composed of superhydrophobic particles, and the superhydrophobic particles are modified silica.

[0059] Preferably, the superhydrophobic particle layer is prepared from nano-sized silica modified by octyltriethoxysilane or nano-sized silica modified by perfluorooctyltriethoxysilane.

[0060] The photothermal superhydrophobic anti-icing coating consists of a heat-absorbing polymer substrate and a superhydrophobic silica particle layer formed on its surface. The micron-sized convex formed by the heat-absorbing particles provides protection for the nano-sized hydrophobic particles, which can greatly extend its service life. The black heat-absorbing particles have the effect of quickly realizing photothermal conversion, enabling the ice layer on the coating surface to rapidly heat up when irradiated by light, accelerating the melting of the ice layer and thus achieving efficient de-icing. In addition, on the one hand, the superhydrophobic particles can reduce the residence time of water droplets on the coating surface, and on the other hand, due to the superhydrophobic property, the contact area between the water droplets and the coating is relatively small, thereby reducing the adhesion strength between the ice layer and the coating, thus achieving the effect of anti-icing and de-icing.

[0061] The mass ratio of the heat-absorbing polymer substrate to the superhydrophobic particle layer is 30:(1 - 3). Preferably, the mass ratio of the heat-absorbing polymer substrate to the superhydrophobic particle layer is 30:1.

[0062] By controlling the mixing ratio of the low surface energy resin, viscosity regulating resin, and endothermic particles, as well as the mass ratio with superhydrophobic silica particles, the present invention achieves further optimization of the coating performance, enabling the coating to have both excellent mechanical strength and good flexibility, thereby improving the wear resistance and durability of the coating. In addition, by adjusting the ratio of the polymer substrate and superhydrophobic particles, the photothermal conversion efficiency and superhydrophobicity of the coating are finely regulated, further enhancing the anti-icing and de-icing effects of the coating.

[0063] The thickness of the photothermal superhydrophobic anti-icing coating is 80 μm to 150 μm; the particle size of the endothermic particles is 20 μm to 50 μm; the particle size of the superhydrophobic particles is 5 nm to 20 nm.

[0064] The thickness of the photothermal superhydrophobic anti-icing coating is controlled between 80 μm and 150 μm, enabling the anti-icing coating to have effective anti-icing and de-icing functions while optimizing the material usage efficiency and avoiding cost increase or mechanical property decline caused by unnecessary thickness increase. Controlling the coating thickness within the range of 80 μm to 150 μm can provide sufficient coverage to ensure the stability of the silica particle layer and will not affect the flexibility and adhesion of the coating due to excessive thickness. This thickness range also ensures the full play of the photothermal effect, enabling the coating to rapidly heat up under light irradiation to achieve efficient de-icing.

[0065] Controlling the particle size of the endothermic particles between 20 μm and 50 μm enables the endothermic particles to be evenly distributed in the coating, forming a stable micron-scale protrusion structure. In addition, controlling the particle size of the endothermic particles between 20 μm and 50 μm can form an appropriate surface roughness to enhance hydrophobicity. At the same time, the endothermic particles within this particle size range are more evenly distributed in the coating, contributing to improving the photothermal conversion efficiency of the coating and ensuring excellent anti-icing and de-icing performance of the coating under low-temperature conditions.

[0066] The particle size of the superhydrophobic particles is 5 nm to 20 nm, which adheres to the surface of the micron-scale protrusion structure to form a stable micro-nano composite structure, further enhancing the superhydrophobicity of the coating. Precise size control improves the overall performance of the coating, ensuring long-lasting anti-icing and wear resistance in practical applications.

[0067] The second aspect of the present invention lies in providing a preparation method for the photothermal superhydrophobic anti-icing coating described in the first aspect of the present invention, and the preparation method includes the following steps:

[0068] Step 1: Dissolve the resin in a polymer solvent and react under a nitrogen atmosphere to obtain a mixed solution;

[0069] Step 2: Add fillers to the mixed solution, stir, and then add a curing agent and continue stirring to obtain a photothermal substrate polymer mixed solution;

[0070] Step 3: Disperse silica and a low surface energy modifier in a solvent, and then carry out magnetic stirring to obtain a superhydrophobic particle dispersion liquid;

[0071] Step 4: Spray the photothermal substrate polymer mixture onto the surface of the substrate, and then carry out baking to obtain an endothermic polymer substrate;

[0072] Step 5: Spray the superhydrophobic particle dispersion liquid onto the surface of the endothermic polymer substrate, and after drying, obtain a photothermal superhydrophobic anti-icing coating.

[0073] The above steps are specifically described below.

[0074] In Step 1, dissolve tetrafluoro resin, fluorosilicone resin, alkyd resin and RTV in a polymer solvent, and react at 50 - 70 °C for 0.5 - 2 h under a nitrogen atmosphere.

[0075] Preferably, dissolve tetrafluoro resin, fluorosilicone resin, alkyd resin and RTV in a polymer solvent, and react at 60 °C for 1 h under a nitrogen atmosphere.

[0076] The polymer solvent is selected from one or more of butyl acetate, ethyl acetate and ethanol. Preferably, the polymer solvent is butyl acetate.

[0077] In this mixture, the concentration of the tetrafluoro resin is 12 wt% - 16 wt%, the concentration of the fluorosilicone resin is 28 wt% - 35 wt%, the concentration of the alkyd resin is 3 wt% - 5 wt%, and the concentration of the RTV is 10 wt% - 15 wt%.

[0078] Preferably, in this mixture, the concentration of the tetrafluoro resin is 12 wt%, the concentration of the fluorosilicone resin is 28 wt%, the concentration of the alkyd resin is 4 wt%, and the concentration of the RTV is 10 wt%.

[0079] In Step 2, the curing agent is selected from one or more of N3390, KH550, KH560. Preferably, the curing agent is N3390, KH550 or KH560.

[0080] Add a filler to the mixture, stir at room temperature for 0.5 - 2 h, and then add the curing agent and continue stirring for 0.5 - 2 h.

[0081] Preferably, add a filler to the mixture, stir at room temperature for 1 h, and then add the curing agent and continue stirring for 1 h.

[0082] The addition amount of the filler is 8 wt% - 15 wt% of the mixture. Preferably, the addition amount of the filler is 8 wt% of the mixture.

[0083] The addition amount of the curing agent is 0.01 wt% - 0.015 wt% of the mixed solution. Preferably, the addition amount of the curing agent is 0.015 wt% of the mixed solution.

[0084] In the present invention, first, a low surface energy resin, a viscosity adjusting resin, and heat absorbing particles are uniformly mixed and cured, then sprayed on the surface of a substrate, and dried to form a photothermal heat absorbing polymer substrate; a superhydrophobic particle dispersion liquid is sprayed, and after curing, a stable and efficient superhydrophobic photothermal anti-icing coating is formed.

[0085] Mixing the low surface energy resin and the viscosity adjusting resin helps to form a polymer substrate with ideal mechanical properties, flexibility, and certain hydrophobicity. After coating this polymer substrate on the surface of the substrate and undergoing a drying treatment, it can firmly adhere and form a uniform polymer substrate.

[0086] Subsequently, a superhydrophobic silica particle layer is formed on the surface of the heat absorbing polymer substrate, enhancing the superhydrophobicity and photothermal conversion ability of the coating. This layer structure can not only effectively prevent the freezing of water droplets on the surface of the coating, but also rapidly heat up under light irradiation to achieve efficient de-icing. Each step in the entire preparation process cooperates with each other to ensure the overall performance of the coating.

[0087] In step 3, silica and a low surface energy modifier are dispersed in a solvent and magnetically stirred at a rotation speed of 40 - 60 °C and 500 - 1500 rpm for 20 - 25 h.

[0088] Preferably, silica and a low surface energy modifier are dispersed in a solvent and magnetically stirred at 50 °C and a rotation speed of 1000 rpm for 24 h.

[0089] The solvent is selected from one or more of ethanol, methanol, and glycerol. Preferably, the solvent is ethanol.

[0090] The low surface energy modifier is perfluorooctyltriethoxysilane or n-octyltriethoxysilane.

[0091] The mass ratio of the silica to the low surface energy modifier is 4 - 7:0.5. Preferably, the mass ratio of the silica to the low surface energy modifier is 5:0.5.

[0092] In the present invention, by preparing superhydrophobic particles to form a particle layer with superhydrophobicity, the anti-icing and de-icing properties of the coating can be significantly improved. By precisely controlling the dispersion of the particles and the addition of the low surface energy modifier to ensure uniform modification of the particles, superhydrophobicity can be achieved. The finally prepared superhydrophobic silica particles can stably adhere to the surface of the polymer substrate, forming a dense and uniform coating, improving the wear resistance and durability of the coating.

[0093] Through the precise selection of low surface energy modifiers and silica particles and the control of the addition ratio, the efficient preparation of superhydrophobic particles is ensured. The addition of low surface energy modifiers such as perfluorooctyltriethoxysilane effectively improves the hydrophobicity of silica particles through chemical bonding, endowing the coating with excellent superhydrophobic properties and long-lasting anti-icing effects. In addition, this material selection and ratio design make the preparation process more controllable and the product quality more stable, suitable for large-scale industrial production.

[0094] In step 4, the spraying conditions are as follows: spraying onto the substrate surface at a speed of 0.3 - 0.5 g / s under the conditions of 20 - 30 °C and a spraying distance of 40 - 60 cm.

[0095] Preferably, the spraying conditions are as follows: spraying onto the substrate surface at a speed of 0.4 g / s under the conditions of 25 °C and a spraying distance of 50 cm.

[0096] The baking conditions are as follows: baking at 50 - 70 °C for 0.5 - 2 h.

[0097] Preferably, the baking conditions are as follows: baking at 60 °C for 1 h.

[0098] In step 5, the spraying conditions are as follows: spraying onto the surface of the endothermic polymer substrate at a speed of 0.3 - 0.5 g / s under the conditions of 20 - 30 °C and a spraying distance of 40 - 60 cm.

[0099] Preferably, the spraying conditions are as follows: spraying onto the surface of the endothermic polymer substrate at a speed of 0.4 g / s under the conditions of 25 °C and a spraying distance of 50 cm.

[0100] After spraying, dry for 1 - 3 h, preferably dry for 2 h.

[0101] Examples

[0102] The present invention will be further elaborated through specific examples below. These examples are only for illustrating the present invention and not for limiting the scope of the present invention. The raw materials used in the examples of the present invention are all commercially available.

[0103] Example 1

[0104] Example 1 provides a photothermal superhydrophobic anti-icing coating, which includes an endothermic polymer substrate and a superhydrophobic particle layer formed on the surface of the endothermic polymer substrate;

[0105] The endothermic polymer substrate is prepared from a resin and a filler. The resin includes a tetrafluoro resin and a fluorosilicon resin with a relatively low surface energy, and also includes an alkyd resin and RTV for adjusting the viscosity of the primer to meet the requirements of different construction methods. The filler is made from endothermic particles, and the endothermic particles are composed of micron-sized black particles;

[0106] The superhydrophobic particle layer is mainly composed of the distribution of nanoscale silica particles modified with low surface energy.

[0107] The mass ratio of the endothermic polymer substrate to the superhydrophobic particle layer is 30:1;

[0108] Among them, the thickness of the photothermal superhydrophobic anti-icing coating is 150 μm; the particle size D50 of the superhydrophobic particles is 10 nm.

[0109] Example 1 provides a method for preparing a photothermal superhydrophobic anti-icing coating, which includes the following steps:

[0110] Step 1: Dissolve 12 g of tetrafluoro resin, 28 g of fluorosilicon resin, 4 g of alkyd resin and 10 g of RTV in 100 mL of butyl acetate, and react the mixture at 60 °C for 1 h under a nitrogen atmosphere to obtain a mixed solution;

[0111] Step 2: Add 8 g of nanoscale black iron oxide to the mixed solution obtained in Step 1, continue to stir at room temperature for 1 h, and then add 0.015 wt% of N3390 and continue to stir for 1 h to obtain a photothermal substrate polymer mixed solution.

[0112] Step 3: Disperse 5 g of silica particles and 0.5 g of n-octyltriethoxysilane into 50 mL of ethanol, and magnetically stir at a speed of 1000 rpm at 50 °C for 24 h to obtain a superhydrophobic particle dispersion;

[0113] Step 4: Pour the prepared photothermal substrate polymer mixed solution into an air spray gun, and spray it onto the surface of the substrate at a speed of 0.4 g / s at room temperature of 25 °C and a spray distance of 50 cm, and bake it in an oven at 60 °C for 1 h to obtain an endothermic polymer substrate for standby;

[0114] Step 5: Spray the superhydrophobic particle dispersion onto the surface of the endothermic polymer substrate at a speed of 0.4 g / s at room temperature of 25 °C and a spray distance of 50 cm, and continue to dry for 2 h to prepare a photothermal superhydrophobic anti-icing coating. The scanning electron microscope of its surface microstructure is as Figure 1 shown, Figure 1 in which, the superhydrophobic particles are of uniform size and evenly distributed, indicating that the superhydrophobic particle distribution on the surface of the photothermal superhydrophobic anti-icing coating described in the present invention is uniform.

[0115] Among them, the substrate is a 45# steel sheet, and the surface is polished by a grinding process until the roughness Ra value is less than 0.64 μm, and it is ultrasonically cleaned alternately with absolute ethanol and deionized water, each cleaning for 20 min, and then dried naturally for standby.

[0116] Example 2

[0117] Example 2 provides a photothermal superhydrophobic anti-icing coating, which includes an endothermic polymer substrate and a superhydrophobic particle layer formed on the surface of the endothermic polymer substrate;

[0118] The endothermic polymer substrate is prepared from a resin and a filler. The resin includes a tetrafluoro resin and a fluorosilicon resin with a low surface energy, and also includes an alkyd resin and RTV for adjusting the viscosity of the primer to meet the requirements of different construction methods. The filler is made of endothermic particles, and the endothermic particles are composed of micron-sized black particles;

[0119] The superhydrophobic particle layer is mainly composed of low surface energy-modified nano-sized silica particles distributed therein.

[0120] The mass ratio of the endothermic polymer substrate to the superhydrophobic particle layer is 30:1;

[0121] Among them, the thickness of the photothermal superhydrophobic anti-icing coating is 150 μm; the particle size D50 of the superhydrophobic particles is 10 nm.

[0122] Example 2 provides a method for preparing a photothermal superhydrophobic anti-icing coating, which includes the following steps:

[0123] Step 1: Dissolve 12 g of tetrafluoro resin, 28 g of fluorosilicon resin, 4 g of alkyd resin and 10 g of RTV in 100 mL of butyl acetate, and react the mixture at 60 °C for 1 h under a nitrogen atmosphere to obtain a mixed solution;

[0124] Step 2: Add 8 g of cuttlefish ink powder to the mixed solution obtained in Step 1, continue to stir at room temperature for 1 h, and then add 0.015 wt% KH550 and continue to stir for 1 h to obtain a photothermal base polymer mixed solution.

[0125] Steps 3, 4, and 5 have the same operating steps as those of the photothermal polymer substrate in Example 1.

[0126] Example 3

[0127] Example 3 provides a photothermal superhydrophobic anti-icing coating, which includes an endothermic polymer substrate and a superhydrophobic particle layer formed on the surface of the endothermic polymer substrate;

[0128] The endothermic polymer substrate is prepared from a resin and a filler. The resin includes a tetrafluoro resin and a fluorosilicon resin with a low surface energy, and also includes an alkyd resin and RTV for adjusting the viscosity of the primer to meet the requirements of different construction methods. The filler is made of endothermic particles, and the endothermic particles are composed of micron-sized black particles;

[0129] The superhydrophobic particle layer is mainly composed of low surface energy-modified nano-sized silica particles distributed therein.

[0130] The mass ratio of the heat-absorbing polymer substrate to the superhydrophobic particle layer is 30:1;

[0131] Among them, the thickness of the photothermal superhydrophobic anti-icing coating is 150 μm; the particle size D50 of the superhydrophobic particles is 10 nm.

[0132] Example 3 provides a method for preparing a photothermal superhydrophobic anti-icing coating, including the following steps:

[0133] Step 1: Dissolve 12 g of tetrafluoro resin, 28 g of fluorosilicon resin, 4 g of alkyd resin, and 10 g of RTV in 100 mL of butyl acetate, and react the mixture at 60 °C for 1 h under a nitrogen atmosphere to obtain a mixed solution;

[0134] Step 2: Add 8 g of carbon black to the mixed solution obtained in Step 1, continue stirring at room temperature for 1 h, and then add 0.015 wt% KH560 and continue stirring for 1 h to obtain a photothermal substrate polymer mixed solution.

[0135] The operating steps of Step 3, Step 4, and Step 5 are the same as those in Example 1 for the photothermal polymer substrate.

[0136] Example 4

[0137] Example 4 provides a photothermal superhydrophobic anti-icing coating, which includes a heat-absorbing polymer substrate and a superhydrophobic particle layer formed on the surface of the heat-absorbing polymer substrate;

[0138] The heat-absorbing polymer substrate is made of resin and filler. The resin includes tetrafluoro resin and fluorosilicon resin with low surface energy, and also includes alkyd resin and RTV for adjusting the viscosity of the primer to meet the requirements of different construction methods. The filler is made of heat-absorbing particles, and the heat-absorbing particles are composed of micron-sized black particles;

[0139] The superhydrophobic particle layer is mainly composed of the distribution of nano-sized silica particles modified with low surface energy.

[0140] The mass ratio of the heat-absorbing polymer substrate to the superhydrophobic particle layer is 30:1;

[0141] Among them, the thickness of the photothermal superhydrophobic anti-icing coating is 150 μm; the particle size D50 of the superhydrophobic particles is 10 nm.

[0142] Example 3 provides a method for preparing a photothermal superhydrophobic anti-icing coating, including the following steps:

[0143] The operating steps of Step 1 and Step 2 are the same as those in Example 1.

[0144] Step 3: Disperse 5 g of silicon dioxide particles and 0.5 g of perfluorooctyltriethoxysilane into 50 mL of ethanol, and magnetically stir at a speed of 1000 rpm at 50 °C for 24 h to obtain a superhydrophobic particle dispersion;

[0145] Step 4: The operating steps of Step 5 and the photothermal polymer substrate are the same as those in Example 1.

[0146] Example 5

[0147] Example 5 provides a photothermal superhydrophobic anti-icing coating, which includes an endothermic polymer substrate and a superhydrophobic particle layer formed on the surface of the endothermic polymer substrate;

[0148] The endothermic polymer substrate is prepared from a resin and a filler. The resin includes a tetrafluoro resin and a fluorosilicon resin with a low surface energy, and also includes an alkyd resin and RTV for adjusting the viscosity of the primer to meet the requirements of different construction methods. The filler is made of endothermic particles, and the endothermic particles are composed of micron-sized black particles;

[0149] The superhydrophobic particle layer is mainly composed of the distribution of nano-sized silicon dioxide particles modified with a low surface energy.

[0150] The mass ratio of the endothermic polymer substrate to the superhydrophobic particle layer is 30:1;

[0151] Among them, the thickness of the photothermal superhydrophobic anti-icing coating is 150 μm; the particle size D50 of the superhydrophobic particles is 10 nm.

[0152] Example 5 provides a preparation method of a photothermal superhydrophobic anti-icing coating, which includes the following steps:

[0153] The operating steps of Step 1 and Step 2 are the same as those in Example 2.

[0154] The operating steps of Step 3 are the same as those in Example 4.

[0155] Step 4: The operating steps of Step 5 and the photothermal polymer substrate are the same as those in Example 1.

[0156] Example 6

[0157] Example 6 provides a photothermal superhydrophobic anti-icing coating, which includes an endothermic polymer substrate and a superhydrophobic particle layer formed on the surface of the endothermic polymer substrate;

[0158] The endothermic polymer substrate is prepared from a resin and a filler. The resin includes a tetrafluoro resin and a fluorosilicon resin with a low surface energy, and also includes an alkyd resin and RTV for adjusting the viscosity of the primer to meet the requirements of different construction methods. The filler is made of endothermic particles, and the endothermic particles are composed of micron-sized black particles;

[0159] The superhydrophobic particle layer is mainly composed of a distribution of nanoscale silica particles modified with low surface energy.

[0160] The mass ratio of the endothermic polymer substrate to the superhydrophobic particle layer is 30:1;

[0161] Among them, the thickness of the photothermal superhydrophobic anti-icing coating is 150 μm; the particle size D50 of the superhydrophobic particles is 10 nm.

[0162] Example 6 provides a method for preparing a photothermal superhydrophobic anti-icing coating, including the following steps:

[0163] The operating steps of Step 1 and Step 2 are the same as those in Example 3.

[0164] The operating steps of Step 3 are the same as those in Example 4.

[0165] The operating steps of Step 4 and Step 5 and the photothermal polymer substrate are the same as those in Example 1.

[0166] Comparative Example

[0167] Comparative Example 1

[0168] The difference between the photothermal superhydrophobic anti-icing coating provided by Comparative Example 1 and the coating provided by Example 1 is that: the endothermic polymer substrate is made of tetrafluoro resin and alkyd resin. Specifically as follows:

[0169] The endothermic polymer substrate is made of resin and filler. The resin includes tetrafluoro resin and alkyd resin. The filler is made of endothermic particles, and the endothermic particles are composed of micron-sized black particles;

[0170] The superhydrophobic particle layer is mainly composed of a distribution of nanoscale silica particles modified with low surface energy.

[0171] The mass ratio of the endothermic polymer substrate to the superhydrophobic particle layer is 30:1;

[0172] Among them, the thickness of the photothermal superhydrophobic anti-icing coating is 150 μm; the particle size D50 of the superhydrophobic particles is 10 nm.

[0173] Comparative Example 1 provides a method for preparing a photothermal superhydrophobic anti-icing coating, including the following steps:

[0174] Step 1: Dissolve 44 g of tetrafluoro resin and 10 g of alkyd resin in 100 mL of butyl acetate, and react the mixture at 60 °C for 1 h under a nitrogen atmosphere to obtain a mixed solution;

[0175] Step 2: Add 8 g of nanoscale black iron oxide to the mixed solution obtained in Step 1, continue to stir at room temperature for 1 h, and then add 0.015 wt% of N3390 and continue to stir for 1 h to obtain a photothermal substrate polymer mixed solution.

[0176] Step 3: Disperse 5 g of silica particles and 0.5 g of n-octyltriethoxysilane into 50 mL of ethanol, and magnetically stir at a speed of 1000 rpm at 50 °C for 24 h to obtain a superhydrophobic particle dispersion;

[0177] Step 4: Pour the prepared photothermal substrate polymer mixture into an airbrush, and spray it onto the surface of the substrate at a speed of 0.4 g / s at room temperature of 25 °C and a spraying distance of 50 cm, and bake it in an oven at 60 °C for 1 h to obtain a heat-absorbing polymer substrate for standby;

[0178] Step 5: Spray the superhydrophobic particle dispersion onto the surface of the photothermal polymer substrate at a speed of 0.4 g / s at room temperature of 25 °C and a spraying distance of 50 cm, and continue to dry for 2 h to prepare a photothermal superhydrophobic anti-icing coating.

[0179] Among them, the substrate is a 45# steel sheet, and the surface is polished by a grinding process until the Ra value of the roughness is less than 0.64 μm. Ultrasonic cleaning is alternately used with anhydrous ethanol and deionized water, and each cleaning is 20 min. After natural drying, it is ready for use.

[0180] Comparative Example 2

[0181] The difference between the photothermal superhydrophobic anti-icing coating provided by Comparative Example 2 and the coating provided by Example 1 is as follows:

[0182] Comparative Example 2 provides a photothermal superhydrophobic anti-icing coating, which includes a heat-absorbing polymer substrate and a superhydrophobic particle layer formed on the surface of the heat-absorbing polymer substrate;

[0183] The heat-absorbing polymer substrate is prepared from a resin and a filler. The resin includes a fluorosilicone resin and an alkyd resin. The filler is prepared from heat-absorbing particles, and the heat-absorbing particles are composed of micron-sized black particles;

[0184] The superhydrophobic particle layer is mainly composed of the distribution of nano-sized silica particles modified with low surface energy.

[0185] The mass ratio of the heat-absorbing polymer substrate to the superhydrophobic particle layer is 30:1;

[0186] Among them, the thickness of the photothermal superhydrophobic anti-icing coating is 150 μm; the particle size D50 of the superhydrophobic particles is 10 nm.

[0187] Comparative Example 2 provides a preparation method for a photothermal superhydrophobic anti-icing coating, which includes the following steps:

[0188] Step 1: Dissolve 44 g of fluorosilicone resin and 10 g of alkyd resin in 100 mL of butyl acetate, and react the mixture at 60 °C for 1 h under a nitrogen atmosphere to obtain a mixed solution;

[0189] Step 2: Add 8 g of nano-scale black iron oxide to the mixed solution obtained in Step 1, continue stirring at room temperature for 1 h, and then add 0.015 wt% of N3390 and continue stirring for 1 h to obtain a photo-thermal substrate polymer mixed solution.

[0190] The operating steps of Step 3 are the same as those in Comparative Example 1.

[0191] Steps 4 and 5: The operating steps and the photo-thermal polymer substrate are the same as those in Comparative Example 1.

[0192] Comparative Example 3

[0193] The difference between the photo-thermal superhydrophobic anti-icing coating provided by Comparative Example 3 and the coating provided by Example 1 lies in:

[0194] Comparative Example 3 provides a photo-thermal superhydrophobic anti-icing coating, which includes an endothermic polymer substrate and a superhydrophobic particle layer formed on the surface of the endothermic polymer substrate;

[0195] The endothermic polymer substrate is prepared from a resin and a filler. The resin includes RTV and alkyd resin, and the filler is prepared from endothermic particles, and the endothermic particles are composed of micron-scale black particles;

[0196] The superhydrophobic particle layer is mainly composed of the distribution of nano-scale silica particles modified with low surface energy.

[0197] The mass ratio of the endothermic polymer substrate to the superhydrophobic particle layer is 30:1;

[0198] Among them, the thickness of the photo-thermal superhydrophobic anti-icing coating is 150 μm; the particle size D50 of the superhydrophobic particles is 10 nm.

[0199] Comparative Example 3 provides a preparation method of a photo-thermal superhydrophobic anti-icing coating, including the following steps:

[0200] Step 1: Dissolve 44 g of RTV and 10 g of alkyd resin in 100 mL of butyl acetate, react the mixture at 60 °C under a nitrogen atmosphere for 1 h to obtain a mixed solution;

[0201] Step 2: Add 8 g of nano-scale black iron oxide to the mixed solution obtained in Step 1, continue stirring at room temperature for 1 h, and then add 0.015 wt% of N3390 and continue stirring for 1 h to obtain a photo-thermal substrate polymer mixed solution.

[0202] The operating steps of Step 3 are the same as those in Comparative Example 1.

[0203] Steps 4 and 5: The operating steps and the photo-thermal polymer substrate are the same as those in Comparative Example 1.

[0204] Experimental Example

[0205] Experimental Example 1 Wear Resistance Test of Coating

[0206] Adopt Figure 2 The described device was used to conduct a quantitative wear resistance test on the coatings prepared in Examples 1 - 6 and Comparative Examples 1 - 3 of the present invention. The specific steps were as follows: A 1000 - mesh sandpaper was fixed on a flat tabletop, the prepared super - slippery coating was attached to the sandpaper, and a 200 - g weight (pressure was 2.5 kPa) was placed on the coating. The linear motion device was used to make the coating move back and forth uniformly on the sandpaper. With 20 cm as a movement length, a round - trip movement of 40 cm was taken as a movement cycle. Record the relationship between the contact angle WCA and the rolling angle WRA of the coating changing with the wear distance during the whole process, as Figure 3 shown.

[0207] From Figure 3 it can be seen that after 20 times of friction, the contact angles of the coatings prepared in Examples 1 - 6 and Comparative Examples 1 - 3 became smaller, and the rolling angles became larger. Moreover, the increase amplitude of the rolling angles of the coatings in Comparative Examples 1 - 3 was higher than that of the coatings in Examples 1 - 6. In the initial state, the rolling angles of Examples 1 - 6 were all less than 10°, while those of the comparative examples were all greater than 10°. After 20 times of friction, the contact angles of the coatings in Examples 1 - 6 were all above 150°, while those of the comparative - example coatings were all below 150°. (The determination standard for super - hydrophobicity is that the contact angle is greater than 150° and the rolling angle is less than 10°). Thus, it can be seen that the super - hydrophobic effects of Examples 1 - 6 are better than those of the comparative examples, and they also perform excellently in terms of wear resistance. It shows that after 20 times of friction, there are no obvious damages on the surfaces of the coatings prepared in Examples 1 - 6 of the present invention, and they still possess excellent super - hydrophobic properties and wear resistance.

[0208] Experimental Example 2 Anti - icing Test of Coating

[0209] The coatings prepared in Examples 1 - 6 and Comparative Examples 1 - 3 of the present invention were subjected to an anti - icing test. The test process was as follows: The coatings prepared in Examples 1 - 6 and Comparative Examples 1 - 3 were placed at a temperature of - 5°C, and a polytetrafluoroethylene template (the size of the template groove was 10 cm in length and 1 cm in width) was covered on the coating surface. An appropriate amount of supercooled water was placed in the template, and the supercooled water froze in the natural environment. A push - pull force gauge was used to calculate the de - icing adhesion force. The results of the 20 - cycle ice - pushing test for the examples and comparative examples are as Figure 4 shown.

[0210] From Figure 4As can be seen from the data shown, through the comparative analysis of the data in Examples 1-6 and Comparative Examples 1-3, during the process of increasing the ice-pushing times, the ice adhesion force shows an upward trend. The initial minimum ice adhesion force of Examples 1-6 can reach 11 Kpa, while the initial minimum ice adhesion force of the comparative examples is 20 Kpa. After completing 20 ice-pushing cycle tests, the maximum ice adhesion force of Examples 1-6 is 29 Kpa, and the maximum ice adhesion force of the comparative examples is 51 Kpa. The ice adhesion force values of the comparative examples are larger both at the initial ice-pushing and after 20 ice-pushings, indicating that the ice prevention effect of the comparative examples is poor. The above data fully demonstrate that the coatings in Examples 1-6 always maintain excellent ice prevention performance, thereby strongly proving that the photothermal superhydrophobic ice prevention coating described in the present invention has excellent ice prevention characteristics, can effectively resist the change of ice adhesion force caused by the increase of ice-pushing times, and continuously maintain a good ice prevention effect.

[0211] The present invention has been described in detail above in combination with specific embodiments and exemplary examples, but these descriptions should not be construed as limiting the present invention. Those skilled in the art understand that without departing from the spirit and scope of the present invention, various equivalent substitutions, modifications or improvements can be made to the technical solutions of the present invention and their implementation manners, and all of these fall within the scope of the present invention. The protection scope of the present invention is subject to the appended claims.

Claims

1. A photothermal superhydrophobic anti-icing coating, characterized in that, The photothermal superhydrophobic anti-icing coating includes an endothermic polymer substrate and a superhydrophobic particle layer on the surface of the endothermic polymer substrate; The endothermic polymer substrate is prepared from a resin and a filler, and the mass ratio of the resin to the filler is 13:(1-2.5); The superhydrophobic particle layer is composed of superhydrophobic particles, and the superhydrophobic particles are modified silica.

2. The photothermal superhydrophobic anti-icing coating according to claim 1, wherein The resin includes a low surface energy resin and a viscosity regulating resin, and the mass ratio of the low surface energy resin to the viscosity regulating resin is (30-50):

14.

3. The photothermal superhydrophobic anti-icing coating according to claim 2, wherein The low surface energy resin is selected from one or two of tetrafluoro resin and fluorosilicon resin; The viscosity regulating resin is selected from one or two of alkyd resin and RTV.

4. The photothermal superhydrophobic anti-icing coating according to claim 1, wherein The filler is an endothermic particle, and the particle size of the endothermic particle is 20μm-50μm; The endothermic particle is selected from one or several of cuttlefish ink powder, carbon black and iron oxide; The thickness of the photothermal superhydrophobic anti-icing coating is 80μm-150μm; the particle size of the superhydrophobic particles is 5nm-20nm.

5. A method for preparing the photo-thermal superhydrophobic anti-icing coating according to any one of claims 1 to 4, characterized in that, The preparation method includes the following steps: Step 1, dissolve the resin in a polymer solvent, and react under a nitrogen atmosphere to obtain a mixed solution; Step 2, add the filler to the mixed solution, stir, and then add a curing agent and continue to stir to obtain a photothermal base polymer mixed solution; Step 3, disperse silica and a low surface energy modifier in a solvent, and then perform magnetic stirring to obtain a superhydrophobic particle dispersion; Step 4, spray the photothermal base polymer mixed solution onto the surface of the substrate, and then bake to obtain an endothermic polymer substrate; Step 5, spray the superhydrophobic particle dispersion onto the surface of the endothermic polymer substrate, and after drying, obtain the photothermal superhydrophobic anti-icing coating.

6. The preparation method according to claim 5, characterized in that, In step 1, Dissolve tetrafluoro resin, fluorosilicon resin, alkyd resin and RTV in a polymer solvent, and react at 50-70°C for 0.5-2h under a nitrogen atmosphere; The polymer solvent is selected from one or several of butyl acetate, ethyl acetate and ethanol.

7. The preparation method according to claim 5, wherein In step 2, The curing agent is selected from one or several of N3390, KH550, KH560; Add the filler to the mixed solution, stir at room temperature for 0.5-2h, and then add the curing agent and continue to stir for 0.5-2h.

8. The preparation method according to claim 5, characterized in that, In step 3, Disperse silica and a low surface energy modifier in a solvent, and perform magnetic stirring at 40-60°C and a rotation speed of 500-1500rpm for 20-25h; The low surface energy modifier is perfluorooctyltriethoxysilane or n-octyltriethoxysilane.

9. The preparation method according to claim 5, characterized in that, In step 4, The spraying conditions are: spraying onto the surface of the substrate at a speed of 0.3-0.5g / s under the conditions of 20-30°C and a spraying distance of 40-60cm; The baking conditions are: baking at 50-70°C for 0.5-2h.

10. The preparation method according to claim 5, characterized in that, In step 5, The spraying conditions are as follows: spraying onto the surface of the endothermic polymer substrate at a speed of 0.3 - 0.5 g / s under the conditions of 20 - 30 °C and a spraying distance of 40 - 60 cm; After spraying, dry for 1 - 3 h.

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