Super-hydrophobic coating with dual functions of refrigeration and heat release and preparation method of super-hydrophobic coating

Abstract

The invention discloses a super-hydrophobic coating with double functions of refrigeration and heat release and a preparation method of the super-hydrophobic coating. The dual functions of refrigeration and heat release are realized by preparing a reversible thermochromic microcapsule through an in-situ polymerization method. The preparation method specifically comprises the following steps: firstly, preparing a reversible thermochromic microcapsule through an in-situ polymerization method; secondly, reversible thermochromic microcapsules and a super-hydrophobic technology are combined, and the super-hydrophobic coating with the refrigeration and heat release dual functions is prepared through a phase separation method. And finally, coating the surface of a substrate with the coating through a spraying process, and curing to form the super-hydrophobic coating with dual functions of refrigeration and heat release. According to the preparation method of the super-hydrophobic coating with the refrigeration and heat release functions, the super-hydrophobic coating has the super-hydrophobic characteristic, and meanwhile, the super-hydrophobic coating has the annual photo-thermal deicing / radiation refrigeration effect.

Description

Technical Field

[0001] This invention belongs to the field of superhydrophobic materials technology, specifically relating to a superhydrophobic coating with both cooling and heat-releasing functions and its preparation method. Background Technology

[0002] In fields such as power transmission, aerospace, and building curtain walls, equipment surfaces are susceptible to environmental factors such as icing and high-temperature exposure, leading to safety hazards and performance degradation. For example, icing on power transmission lines can cause them to break due to overload, icing on aircraft wings can impair aerodynamic performance, and high-temperature exposure on building exterior walls can increase air conditioning energy consumption. Therefore, there is an urgent need for surface protective materials that combine anti-icing, cooling, and water-repellent functions. While traditional superhydrophobic coatings can achieve a "lotus effect" through low surface energy and micro / nano structures to reduce water adhesion and delay icing, their hydrophobic properties easily degrade at low temperatures and they cannot solve the problem of equipment overheating at high temperatures. Radiative cooling technology uses the high infrared emissivity of materials in the 8–13 μm atmospheric window to transfer heat to outer space in the form of radiation, achieving passive cooling. However, its surface is highly hydrophilic, making it prone to frost and ice formation, which limits its application in low-temperature environments. Photothermal anti-icing technology utilizes the high absorption characteristics of materials for sunlight to convert light energy into heat energy, melting surface ice or preventing icing. However, traditional photothermal materials are mostly dark-colored, easily absorbing excessive solar radiation in summer, leading to overheating of equipment and contradicting the cooling requirements. Currently, the main function of this coating can be achieved through thermochromic microcapsules: at low temperatures, the core material of the microcapsule is dark, enhancing the absorption efficiency of sunlight to achieve photothermal anti-icing; at high temperatures, the microcapsule undergoes a phase transition and turns into a light color, reducing solar radiation absorption while its shell structure can synergistically maintain a high infrared emissivity in the 8-13μm band, ensuring radiative cooling effect. Furthermore, the microcapsules can be combined with superhydrophobic substrates, further optimizing hydrophobic properties through the superposition of micro-nano structures. Summary of the Invention

[0003] The purpose of this invention is to provide a superhydrophobic coating with both cooling and heat release functions and its preparation method.

[0004] A superhydrophobic coating with both cooling and heat dissipation functions is prepared by superhydrophobic particles and resin coating; the mass ratio of the superhydrophobic particles to the resin coating is 1:(5-15).

[0005] The superhydrophobic particles are prepared from silica, diatomaceous earth and reversible thermochromic microcapsules, with the mass ratio of silica, diatomaceous earth and thermochromic microcapsules being 0.1:(1-3):1; the silica is prepared by hydrolysis of tetraethyl orthosilicate.

[0006] The reversible thermochromic microcapsule is made of styrene-maleic anhydride, core material, and shell material; the mass ratio of styrene-maleic anhydride, core material, and shell material is 5:(5-15):(5-15); the shell material is a mixture of melamine-formaldehyde polymer and gelatin; the core material is a mixture of 2-phenylamino-3-methyl-6-dibutylaminofluorane, bisphenol A, and dodecanol, with a mass ratio of 1:(2-4):100.

[0007] The resin coating is a mixture of resin and solvent, with a mass ratio of resin to solvent of 1:(1-3); the resin is vulcanized silicone rubber, epoxy resin, fluorocarbon resin or fluorosilicone resin; the solvent is butyl acetate, water or ethanol.

[0008] The method for preparing the superhydrophobic coating with both cooling and heat dissipation functions is carried out according to the following steps: (1) 2-phenylamino-3-methyl-6-dibutylaminofluorane, bisphenol A and dodecanol were heated to 70-90℃ and stirred for 20-40 minutes to prepare the core material; melamine-formaldehyde polymer and gelatin were mixed evenly to prepare the shell material; styrene-maleic anhydride was added to water and stirred to react, then NaOH was added to adjust the pH of the solution to 5.5, then the core material was added and stirred, then the shell material and HCl were added to adjust the pH to 3.5, stirred, filtered, washed, dried and ground to obtain reversible thermochromic microcapsules; (2) Mix diatomaceous earth and reversible thermochromic microcapsules, stir, and obtain mixed particles; (3) Disperse the mixed particles in an ethanol solution, add tetraethyl orthosilicate and n-octyltriethoxysilane, add ammonia water to adjust the pH to 8-9, heat and stir in a water bath, then vacuum filter, wash with anhydrous ethanol and deionized water 2-4 times, and dry to obtain superhydrophobic particles. (4) Stir and mix the resin coating, superhydrophobic particles and ethanol until uniform to obtain a superhydrophobic coating with both cooling and heat release functions. (5) The superhydrophobic coating with both cooling and heat release functions is sprayed onto the substrate surface and cured to form a superhydrophobic coating with both cooling and heat release functions.

[0009] The stirring rate in step (2) is 200-400 r / min, and the time is 5-15 min.

[0010] In step (3), the mass ratio of tetraethyl orthosilicate to n-octyltriethoxysilane is (8-12):1; the water bath heating and stirring step is: stirring at a stirring speed of 500-700 r / min for 3-4 hours under water bath conditions of 50-60℃.

[0011] The mixing conditions in step (4) are as follows: after stirring the resin coating and superhydrophobic particles at a stirring speed of 500-700 r / min for 20-45 min, add ethanol and stir at a stirring speed of 800-1000 r / min for 20-45 min.

[0012] In step (5), the substrate is polished by grinding or belt grinding until the roughness Ra value is less than 0.64 μm. Then, it is ultrasonically cleaned in anhydrous ethanol and deionized water for 20-30 minutes each time. After natural drying, it is ready for use. The coating thickness is not less than 1 mm.

[0013] The substrate is made of copper alloy, aluminum alloy, or steel, and its thickness is not less than 5 mm.

[0014] The beneficial effects of this invention are as follows: The superhydrophobic coating with dual cooling and heat release functions described in this invention is prepared from a superhydrophobic coating and thermochromic microcapsules. The raw materials for preparing the superhydrophobic coating include superhydrophobic particles and a coating system. The superhydrophobic particles can significantly reduce the surface energy of the coating, while simultaneously constructing a micro / nano structure to enhance the hydrophobic properties of the coating, thereby reducing coating loss, improving coating durability, and extending the coating's service life. The thermochromic microcapsules, as the coating's regulating material, allow the core material inside the capsules to achieve a black color at low temperatures and a white color at high temperatures. By adjusting the color, the coating's reflection of sunlight is altered, achieving the effect of absorbing sunlight at low temperatures to aid in de-icing and reflecting sunlight at high temperatures to protect equipment from overheating. The preparation method of the superhydrophobic coating with dual cooling and heat release functions described in this invention is simple, can be completed at room temperature or low temperature, has low energy consumption, and can be mass-produced industrially. This invention employs a spraying process to uniformly spray a superhydrophobic coating with both cooling and heat-releasing functions onto the surface of a substrate. This ensures that the coating particles are tightly bonded to the substrate, resulting in a coating with excellent superhydrophobic properties. It also has the characteristics of limiting surface icing and delaying the icing process. Furthermore, it exhibits ultra-low ice adhesion strength during cyclic freezing / de-icing and provides a cooling effect in high-temperature environments. This superhydrophobic coating and coating system have promising application prospects in the field of superhydrophobic materials technology. Attached Figure Description

[0015] Figure 1 This is a scanning electron microscope image of the reversible thermochromic microcapsule of Example 1.

[0016] Figure 2 This is a scanning electron microscope image of the superhydrophobic coating with both cooling and heat dissipation functions in Example 1.

[0017] Figure 3 The ice adhesion strength of different resin substrates.

[0018] Figure 4 This refers to the adhesion strength of different resin substrates.

[0019] Figure 5 This is a delayed icing diagram of the superhydrophobic coating with dual cooling and heat release functions in Example 1.

[0020] Figure 6 The image shows the cooling data of the superhydrophobic coating with dual cooling and heat release functions in Example 1.

[0021] Figure 7 The diagram shows the superhydrophobic performance of the superhydrophobic coating with both cooling and heat dissipation functions in Example 1.

[0022] Figure 8 The diagram shows the superhydrophobic properties and anti-icing properties of the superhydrophobic coating with both cooling and heat release functions in the examples and comparative examples. Detailed Implementation

[0023] To facilitate understanding of the present invention, a more comprehensive description will be given below. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided to provide a thorough and complete understanding of the disclosure of the present invention. Example 1

[0024] A method for preparing a superhydrophobic coating with dual cooling and heat dissipation functions is carried out according to the following steps: (1) 2-phenylamino-3-methyl-6-dibutylaminofluorane (ODB-2), bisphenol A (BPA) and dodecanol were stirred at 80°C for 30 min in a mass ratio of 1:3:100 to prepare the core material; melamine-formaldehyde polymer and gelatin (mass ratio 1:1) were mixed evenly to prepare the shell material; styrene-maleic anhydride was added to water and stirred at 40°C for 2 h at a speed of 400 r / min. Then, alkali (NaOH) was added to adjust the pH of the solution to 5.5. The core material was then added and stirred at 1000 r / min for 20 min. The shell material was then added and acid (HCl) was added to adjust the pH to 3.5. The mixture was stirred for 2 h and then filtered, washed, dried and ground to obtain reversible thermochromic microcapsules. The mass ratio of styrene-maleic anhydride, core material and shell material was 1:5:4.

[0025] (2) The diatomaceous earth and reversible thermochromic microcapsules were mixed at a mass ratio of 2:1 and stirred at a speed of 300 r / min for 10 min to obtain mixed particles; (3) Disperse the mixed particles in ethanol, add tetraethyl orthosilicate and n-octyltriethoxysilane, add ammonia to adjust the pH to 8.5, stir at 600 r / min in a water bath at 55°C for 4 h, wash three times with anhydrous ethanol and deionized water, and dry to obtain superhydrophobic particles; the mass ratio of the mixed particles, ethanol, tetraethyl orthosilicate and n-octyltriethoxysilane is 20:150:10:1.

[0026] (4) After mixing the vulcanized silicone rubber and butyl acetate, stir the superhydrophobic particles at a stirring speed of 600 r / min for 30 min, then add ethanol and stir at a stirring speed of 1000 r / min for 30 min until uniform, and obtain a superhydrophobic coating with both cooling and heat release functions; the mass ratio of the vulcanized silicone rubber, butyl acetate, superhydrophobic particles and ethanol is 10:20:1:5.

[0027] (5) Select a spraying process to uniformly spray the superhydrophobic coating with both cooling and heat release functions onto the aluminum alloy surface. After curing, a superhydrophobic coating with both cooling and heat release functions is formed. Example 2

[0028] A method for preparing a superhydrophobic coating with dual cooling and heat dissipation functions is carried out according to the following steps: (1) 2-phenylamino-3-methyl-6-dibutylaminofluorane (ODB-2), bisphenol A (BPA) and dodecanol were stirred at 80°C for 30 min in a mass ratio of 1:3:100 to prepare the core material; melamine-formaldehyde polymer and gelatin (mass ratio 1:1) were mixed evenly to prepare the shell material; styrene-maleic anhydride was added to water and stirred at 40°C for 2 h at a speed of 400 r / min. Then NaOH was added to adjust the pH of the solution to 5.5. The core material was then added and stirred at 1000 r / min for 20 min. The shell material was then added and HCl was added to adjust the pH to 3.5. The mixture was stirred for 2 h. After filtration, washing, drying and grinding, reversible thermochromic microcapsules were obtained. The mass ratio of styrene-maleic anhydride, core material and shell material was 1:5:4.

[0029] (2) The diatomaceous earth and reversible thermochromic microcapsules were mixed at a mass ratio of 2:1 and stirred at a speed of 300 r / min for 10 min to obtain mixed particles; (3) Disperse the mixed particles in ethanol, add tetraethyl orthosilicate and n-octyltriethoxysilane, add ammonia to adjust the pH to 8.5, stir at 600 r / min in a water bath at 55°C for 4 h, wash three times with anhydrous ethanol and deionized water, and dry to obtain superhydrophobic particles; the mass ratio of the mixed particles, ethanol, tetraethyl orthosilicate and n-octyltriethoxysilane is 20:150:10:1.

[0030] (4) After mixing epoxy resin and butyl acetate, stir with superhydrophobic particles at a stirring speed of 600 r / min for 30 min, then add ethanol and stir at a stirring speed of 1000 r / min for 30 min until uniform, and obtain a superhydrophobic coating with both cooling and heat release functions; the mass ratio of epoxy resin, butyl acetate, superhydrophobic particles and ethanol is 10:20:1:5.

[0031] (5) Select a spraying process to uniformly spray the superhydrophobic coating with both cooling and heat release functions onto the aluminum alloy surface. After curing, a superhydrophobic coating with both cooling and heat release functions is formed. Example 3

[0032] A method for preparing a superhydrophobic coating with dual cooling and heat dissipation functions is carried out according to the following steps: (1) 2-phenylamino-3-methyl-6-dibutylaminofluorane (ODB-2), bisphenol A (BPA) and dodecanol were stirred at 80°C for 30 min in a mass ratio of 1:3:100 to prepare the core material; melamine-formaldehyde polymer and gelatin (mass ratio 1:1) were mixed evenly to prepare the shell material; styrene-maleic anhydride was added to water and stirred at 40°C for 2 h at a speed of 400 r / min. Then NaOH was added to adjust the pH of the solution to 5.5. The core material was then added and stirred at 1000 r / min for 20 min. The shell material was then added and HCl was added to adjust the pH to 3.5. The mixture was stirred for 2 h. After filtration, washing, drying and grinding, reversible thermochromic microcapsules were obtained. The mass ratio of styrene-maleic anhydride, core material and shell material was 1:5:4.

[0033] (2) The diatomaceous earth and reversible thermochromic microcapsules were mixed at a mass ratio of 2:1 and stirred at a speed of 300 r / min for 10 min to obtain mixed particles; (3) Disperse the mixed particles in ethanol, add tetraethyl orthosilicate and n-octyltriethoxysilane, add ammonia to adjust the pH to 8.5, stir at 600 r / min in a water bath at 55°C for 4 h, wash three times with anhydrous ethanol and deionized water, and dry to obtain superhydrophobic particles; the mass ratio of the mixed particles, ethanol, tetraethyl orthosilicate and n-octyltriethoxysilane is 20:150:10:1.

[0034] (4) After mixing fluorosilicone resin and butyl acetate, stir with superhydrophobic particles at a stirring speed of 600 r / min for 30 min, then add ethanol and stir at a stirring speed of 1000 r / min for 30 min until uniform, and obtain a superhydrophobic coating with both cooling and heat release functions; the mass ratio of fluorosilicone resin, butyl acetate, superhydrophobic particles and ethanol is 10:20:1:5.

[0035] (5) Select a spraying process to uniformly spray the superhydrophobic coating with both cooling and heat release functions onto the aluminum alloy surface. After curing, a superhydrophobic coating with both cooling and heat release functions is formed. Example 4

[0036] A method for preparing a superhydrophobic coating with dual cooling and heat dissipation functions is carried out according to the following steps: (1) 2-phenylamino-3-methyl-6-dibutylaminofluorane (ODB-2), bisphenol A (BPA) and dodecanol were stirred at 80°C for 30 min in a mass ratio of 1:3:100 to prepare the core material; melamine-formaldehyde polymer and gelatin (mass ratio 1:1) were mixed evenly to prepare the shell material; styrene-maleic anhydride was added to water and stirred at 40°C for 2 h at a speed of 400 r / min. Then, alkali (NaOH) was added to adjust the pH of the solution to 5.5. The core material was then added and stirred at 1000 r / min for 20 min. The shell material was then added and acid (HCl) was added to adjust the pH to 3.5. The mixture was stirred for 2 h and then filtered, washed, dried and ground to obtain reversible thermochromic microcapsules. The mass ratio of styrene-maleic anhydride, core material and shell material was 1:5:4.

[0037] (2) The diatomaceous earth and reversible thermochromic microcapsules were mixed at a mass ratio of 2:1 and stirred at a speed of 300 r / min for 10 min to obtain mixed particles; (3) Disperse the mixed particles in ethanol, add tetraethyl orthosilicate and n-octyltriethoxysilane, add ammonia to adjust the pH to 8.5, stir at 600 r / min in a water bath at 55°C for 4 h, wash three times with anhydrous ethanol and deionized water, and dry to obtain superhydrophobic particles; the mass ratio of the mixed particles, ethanol, tetraethyl orthosilicate and n-octyltriethoxysilane is 20:150:10:1.

[0038] (4) After mixing the fluorocarbon resin and butyl acetate, stir the superhydrophobic particles at a stirring speed of 600 r / min for 30 min, then add ethanol and stir at a stirring speed of 1000 r / min for 30 min until uniform, and obtain a superhydrophobic coating with both cooling and heat release functions; the mass ratio of the fluorocarbon resin, butyl acetate, superhydrophobic particles and ethanol is 10:20:1:5.

[0039] (5) Select a spraying process to uniformly spray the superhydrophobic coating with both cooling and heat release functions onto the aluminum alloy surface. After curing, a superhydrophobic coating with both cooling and heat release functions is formed. Example 5

[0040] A method for preparing a superhydrophobic coating with dual cooling and heat dissipation functions is carried out according to the following steps: (1) 2-phenylamino-3-methyl-6-dibutylaminofluorane (ODB-2), bisphenol A (BPA) and dodecanol were stirred at 80°C for 30 min in a mass ratio of 1:3:100 to prepare the core material; melamine-formaldehyde polymer and gelatin (mass ratio 1:1) were mixed evenly to prepare the shell material; styrene-maleic anhydride was added to water and stirred at 40°C for 2 h at a speed of 400 r / min. Then NaOH was added to adjust the pH of the solution to 5.5. The core material was then added and stirred at 1000 r / min for 20 min. The shell material was then added and HCl was added to adjust the pH to 3.5. The mixture was stirred for 2 h. After filtration, washing, drying and grinding, reversible thermochromic microcapsules were obtained. The mass ratio of styrene-maleic anhydride, core material and shell material was 1:5:4.

[0041] (2) The diatomaceous earth and reversible thermochromic microcapsules were mixed at a mass ratio of 2:1 and stirred at a speed of 300 r / min for 10 min to obtain mixed particles; (3) Disperse the mixed particles in ethanol, add tetraethyl orthosilicate and n-octyltriethoxysilane, add ammonia to adjust the pH to 8.5, stir at 600 r / min in a water bath at 55°C for 4 h, wash three times with anhydrous ethanol and deionized water, and dry to obtain superhydrophobic particles; the mass ratio of the mixed particles, ethanol, tetraethyl orthosilicate and n-octyltriethoxysilane is 20:150:10:1.

[0042] (4) After mixing the vulcanized silicone rubber and the first ethanol, stir the superhydrophobic particles at a stirring speed of 600 r / min for 30 min, then add the second ethanol and stir at a stirring speed of 1000 r / min for 30 min. Stir until uniform to obtain a superhydrophobic coating with both cooling and heat release functions; the mass ratio of the vulcanized silicone rubber, the first ethanol, the superhydrophobic particles and the second ethanol is 10:20:1:5.

[0043] (5) Select a spraying process to uniformly spray the superhydrophobic coating with both cooling and heat release functions onto the aluminum alloy surface. After curing, a superhydrophobic coating with both cooling and heat release functions is formed. Example 6

[0044] A method for preparing a superhydrophobic coating with dual cooling and heat dissipation functions is carried out according to the following steps: (1) 2-phenylamino-3-methyl-6-dibutylaminofluorane (ODB-2), bisphenol A (BPA) and dodecanol were stirred at 80°C for 30 min in a mass ratio of 1:3:100 to prepare the core material; melamine-formaldehyde polymer and gelatin (mass ratio 1:1) were mixed evenly to prepare the shell material; styrene-maleic anhydride was added to water and stirred at 40°C for 2 h at a speed of 400 r / min. Then NaOH was added to adjust the pH of the solution to 5.5. The core material was then added and stirred at 1000 r / min for 20 min. The shell material was then added and HCl was added to adjust the pH to 3.5. The mixture was stirred for 2 h. After filtration, washing, drying and grinding, reversible thermochromic microcapsules were obtained. The mass ratio of styrene-maleic anhydride, core material and shell material was 1:5:4.

[0045] (2) The diatomaceous earth and reversible thermochromic microcapsules were mixed at a mass ratio of 2:1 and stirred at a speed of 300 r / min for 10 min to obtain mixed particles; (3) Disperse the mixed particles in ethanol, add tetraethyl orthosilicate and n-octyltriethoxysilane, add ammonia to adjust the pH to 8.5, stir at 600 r / min in a water bath at 55°C for 4 h, wash three times with anhydrous ethanol and deionized water, and dry to obtain superhydrophobic particles; the mass ratio of the mixed particles, ethanol, tetraethyl orthosilicate and n-octyltriethoxysilane is 20:150:10:1.

[0046] (4) After mixing epoxy resin and first ethanol, stir with superhydrophobic particles at a stirring speed of 600 r / min for 30 min, then add second ethanol and stir at a stirring speed of 1000 r / min for 30 min. Stir until uniform to obtain a superhydrophobic coating with both cooling and heat release functions; the mass ratio of epoxy resin, first ethanol, superhydrophobic particles and second ethanol is 10:20:1:5.

[0047] (5) Select a spraying process to uniformly spray the superhydrophobic coating with both cooling and heat release functions onto the aluminum alloy surface. After curing, a superhydrophobic coating with both cooling and heat release functions is formed. Example 7

[0048] A method for preparing a superhydrophobic coating with dual cooling and heat dissipation functions is carried out according to the following steps: (1) 2-phenylamino-3-methyl-6-dibutylaminofluorane (ODB-2), bisphenol A (BPA) and dodecanol were stirred at 80°C for 30 min in a mass ratio of 1:3:100 to prepare the core material; melamine-formaldehyde polymer and gelatin (mass ratio 1:1) were mixed evenly to prepare the shell material; styrene-maleic anhydride was added to water and stirred at 40°C for 2 h at a speed of 400 r / min. Then NaOH was added to adjust the pH of the solution to 5.5. The core material was then added and stirred at 1000 r / min for 20 min. The shell material was then added and HCl was added to adjust the pH to 3.5. The mixture was stirred for 2 h. After filtration, washing, drying and grinding, reversible thermochromic microcapsules were obtained. The mass ratio of styrene-maleic anhydride, core material and shell material was 1:5:4.

[0049] (2) The diatomaceous earth and reversible thermochromic microcapsules were mixed at a mass ratio of 2:1 and stirred at a speed of 300 r / min for 10 min to obtain mixed particles; (3) Disperse the mixed particles in ethanol, add tetraethyl orthosilicate and n-octyltriethoxysilane, add ammonia to adjust the pH to 8.5, stir at 600 r / min in a water bath at 55°C for 4 h, wash three times with anhydrous ethanol and deionized water, and dry to obtain superhydrophobic particles; the mass ratio of the mixed particles, ethanol, tetraethyl orthosilicate and n-octyltriethoxysilane is 20:150:10:1.

[0050] (4) After mixing the fluorosilicone resin and the first ethanol, stir the superhydrophobic particles at a stirring speed of 600 r / min for 30 min, then add the second ethanol and stir at a stirring speed of 1000 r / min for 30 min. Stir until uniform to obtain a superhydrophobic coating with both cooling and heat release functions; the mass ratio of the fluorosilicone resin, the first ethanol, the superhydrophobic particles and the second ethanol is 10:20:1:5.

[0051] (5) Select a spraying process to uniformly spray the superhydrophobic coating with both cooling and heat release functions onto the aluminum alloy surface. After curing, a superhydrophobic coating with both cooling and heat release functions is formed. Example 8

[0052] A method for preparing a superhydrophobic coating with dual cooling and heat dissipation functions is carried out according to the following steps: (1) 2-phenylamino-3-methyl-6-dibutylaminofluorane (ODB-2), bisphenol A (BPA) and dodecanol were stirred at 80°C for 30 min in a mass ratio of 1:3:100 to prepare the core material; melamine-formaldehyde polymer and gelatin (mass ratio 1:1) were mixed evenly to prepare the shell material; styrene-maleic anhydride was added to water and stirred at 40°C for 2 h at a speed of 400 r / min. Then NaOH was added to adjust the pH of the solution to 5.5. The core material was then added and stirred at 1000 r / min for 20 min. The shell material was then added and HCl was added to adjust the pH to 3.5. The mixture was stirred for 2 h. After filtration, washing, drying and grinding, reversible thermochromic microcapsules were obtained. The mass ratio of styrene-maleic anhydride, core material and shell material was 1:5:4.

[0053] (2) The diatomaceous earth and reversible thermochromic microcapsules were mixed at a mass ratio of 2:1 and stirred at a speed of 300 r / min for 10 min to obtain mixed particles; (3) Disperse the mixed particles in ethanol, add tetraethyl orthosilicate and n-octyltriethoxysilane, add ammonia to adjust the pH to 8.5, stir at 600 r / min in a water bath at 55°C for 4 h, wash three times with anhydrous ethanol and deionized water, and dry to obtain superhydrophobic particles; the mass ratio of the mixed particles, ethanol, tetraethyl orthosilicate and n-octyltriethoxysilane is 20:150:10:1.

[0054] (4) After mixing the fluorocarbon resin and ethanol, stir the superhydrophobic particles at a stirring speed of 600 r / min for 30 min, then add ethanol and stir at a stirring speed of 1000 r / min for 30 min until uniform, and obtain a superhydrophobic coating with both cooling and heat release functions; the mass ratio of the fluorocarbon resin, ethanol, superhydrophobic particles and added ethanol is 10:20:1:5.

[0055] (5) Select a spraying process to uniformly spray the superhydrophobic coating with both cooling and heat release functions onto the aluminum alloy surface. After curing, a superhydrophobic coating with both cooling and heat release functions is formed.

[0056] Comparative Example 1 A method for preparing a superhydrophobic coating with dual cooling and heat dissipation functions is carried out according to the following steps: (1) 2-phenylamino-3-methyl-6-dibutylaminofluorane (ODB-2), bisphenol A (BPA) and dodecanol were stirred at 80°C for 30 min in a mass ratio of 1:3:100 to prepare the core material; melamine-formaldehyde polymer and gelatin (mass ratio 1:1) were mixed evenly to prepare the shell material; styrene-maleic anhydride was added to water and stirred at 40°C for 2 h at a speed of 400 r / min. Then NaOH was added to adjust the pH of the solution to 5.5. The core material was then added and stirred at 1000 r / min for 20 min. The shell material was then added and HCl was added to adjust the pH to 3.5. The mixture was stirred for 2 h. After filtration, washing, drying and grinding, reversible thermochromic microcapsules were obtained. The mass ratio of styrene-maleic anhydride, core material and shell material was 1:5:4.

[0057] (2) Mix diatomaceous earth and reversible thermochromic microcapsules at a mass ratio of 1:1 and stir at a speed of 300 r / min for 10 min to obtain mixed particles; (3) Disperse the mixed particles in ethanol, add tetraethyl orthosilicate and n-octyltriethoxysilane, add ammonia to adjust the pH to 8.5, stir at 600 r / min in a water bath at 55°C for 4 h, wash three times with anhydrous ethanol and deionized water, and dry to obtain superhydrophobic particles; the mass ratio of the mixed particles, ethanol, tetraethyl orthosilicate and n-octyltriethoxysilane is 20:150:10:1.

[0058] (4) After mixing the vulcanized silicone rubber and butyl acetate, stir the superhydrophobic particles at a stirring speed of 600 r / min for 30 min, then add ethanol and stir at a stirring speed of 1000 r / min for 30 min until uniform, and obtain a superhydrophobic coating with both cooling and heat release functions; the mass ratio of the vulcanized silicone rubber, butyl acetate, superhydrophobic particles and ethanol is 10:10:1:5.

[0059] (5) Select a spraying process to uniformly spray the superhydrophobic coating with both cooling and heat release functions onto the aluminum alloy surface. After curing, a superhydrophobic coating with both cooling and heat release functions is formed.

[0060] Comparative Example 2 A method for preparing a superhydrophobic coating with dual cooling and heat dissipation functions is carried out according to the following steps: (1) 2-phenylamino-3-methyl-6-dibutylaminofluorane (ODB-2), bisphenol A (BPA) and dodecanol were stirred at 80°C for 30 min in a mass ratio of 1:3:100 to prepare the core material; melamine-formaldehyde polymer and gelatin (mass ratio 1:1) were mixed evenly to prepare the shell material; styrene-maleic anhydride was added to water and stirred at 40°C for 2 h at a speed of 400 r / min. Then NaOH was added to adjust the pH of the solution to 5.5. The core material was then added and stirred at 1000 r / min for 20 min. The shell material was then added and HCl was added to adjust the pH to 3.5. The mixture was stirred for 2 h. After filtration, washing, drying and grinding, reversible thermochromic microcapsules were obtained. The mass ratio of styrene-maleic anhydride, core material and shell material was 1:5:4.

[0061] (2) The diatomaceous earth and reversible thermochromic microcapsules were mixed at a mass ratio of 2:1 and stirred at a speed of 300 r / min for 10 min to obtain mixed particles; (3) Disperse the mixed particles in ethanol, add tetraethyl orthosilicate and n-octyltriethoxysilane, add ammonia to adjust the pH to 8.5, stir at 600 r / min in a water bath at 55°C for 4 h, wash three times with anhydrous ethanol and deionized water, and dry to obtain superhydrophobic particles; the mass ratio of the mixed particles, ethanol, tetraethyl orthosilicate and n-octyltriethoxysilane is 20:150:10:1.

[0062] (4) After mixing the vulcanized silicone rubber and butyl acetate, stir the superhydrophobic particles at a stirring speed of 600 r / min for 30 min, then add ethanol and stir at a stirring speed of 1000 r / min for 30 min until uniform, and obtain a superhydrophobic coating with both cooling and heat release functions; the mass ratio of the vulcanized silicone rubber, butyl acetate, superhydrophobic particles and ethanol is 15:30:1:5.

[0063] (5) Select a spraying process to uniformly spray the superhydrophobic coating with both cooling and heat release functions onto the aluminum alloy surface. After curing, a superhydrophobic coating with both cooling and heat release functions is formed.

[0064] Experimental Example 1: Matrix Material Performance Testing Electron microscopy was performed on the reversible thermochromic microcapsules prepared in Example 1, and the results are as follows: Figure 1 As shown. Electron microscopy was performed on the dual-functional superhydrophobic coating prepared in Example 1, and the results are as follows. Figure 2 As shown.

[0065] Ice adhesion strength tests were conducted on different substrate materials in Examples 1-4. The testing apparatus consisted of a climate chamber (QL-HWHS-100), a digital force gauge (DS2-500N), and a self-made precision displacement platform. The specific testing method was as follows: a substrate material sample was placed inside the climate chamber, and a polytetrafluoroethylene mold (10 mm × 10 mm × 1 mm) was gently placed on the center of the sample surface. The temperature of the climate chamber was set to -5°C, the relative humidity to 95%, and the chamber door was closed for pre-cooling for 30 minutes. 10 mL of deionized water was injected into the mold, allowing the water to freeze naturally on the sample surface for 2 hours to form a standard ice column. The displacement platform was controlled to push the ice column vertically at a rate of 0.5 mm / s, and the peel force curve was continuously recorded using the force gauge. The peak force value was used to calculate the ice adhesion strength. Specific results are shown in […]. Figure 3 The adhesion to the substrate material was tested according to the GB / T 5210-2006 standard. See the detailed results below. Figure 4 .

[0066] Figure 3 and Figure 4 The adhesion between RTV and the aluminum substrate reached 4.1 MPa, and the ice adhesion strength was 62 kPa. Epoxy resin showed adhesion of 11.6 MPa to the aluminum plate, but its ice adhesion strength was also high at 124 kPa, which is detrimental to the overall anti-icing performance of the coating. While fluorocarbon and fluorosilicone resins showed significantly lower ice adhesion strengths (24.8 kPa and 25.1 kPa respectively), their interfacial bonding strength with the aluminum plate was too weak (only 0.5 MPa). This weak interfacial bonding strength is easily affected by various external factors in practical applications, potentially leading to overall coating detachment. Therefore, to ensure sufficient adhesion and durable anti-icing capability of the prepared low-adhesion coating, RTV was the optimal choice as the coating substrate material.

[0067] Experiment Example 2: Anti-icing Performance Test The superhydrophobic coatings with dual cooling and heat release functions prepared in Example 1 and Comparative Examples 1 and 2 were used as the experimental group to test the change relationship of ice adhesion strength during cyclic freezing / de-icing. The tests were conducted in an environment with 40% humidity and -10°C. The test results are as follows: Figure 5 As shown.

[0068] like Figure 5The freezing process of water droplets was studied. The bare aluminum plate had a small contact angle (CA≈70°), a large solid-liquid contact area, and rapid heat conduction, resulting in complete freezing of the water droplets within 400 s. The RTV coating, due to its hydrophobicity (CA≈110°), reduced the contact area, extending the freezing time to 700 s. The surface of Example 1 slowly cooled to -10°C at 1000 s, and the water droplets on Example 1 completely froze at 1800 s. Example 1 exhibited the strongest delayed freezing capability because the water droplets contacted the coating in a near-spherical shape, with a contact angle greater than 150°, resulting in the smallest macroscopic contact area with Example 1. Furthermore, the surface of Example 1 had a micro-nano hierarchical structure, creating an air layer between the water droplets and the surface. This air layer further reduced the actual contact area between the water droplets and the coating, slowing down the heat transfer rate. Additionally, the heat stored in the phase change material within the capsule's core material further delayed the cooling rate of the coating surface.

[0069] Experiment Example 3: Cooling Performance Test Temperature tests were conducted in hot environments and under direct sunlight for Example 1. See the results below. Figure 6 .

[0070] The results showed that, when operating in a light-cooling mode above its phase transition temperature, Example 1 consistently maintained a temperature significantly lower than ambient air and the control sample, achieving an average cooling rate 2.1°C lower than the ambient temperature. Tests conducted during peak solar radiation periods further confirmed that the temperature of Example 1 was consistently lower than that of the control sample. This effect is attributed to the excellent infrared emissivity and porous structure of Example 1, which, with its denser structure, more effectively enhances radiative heat dissipation than the control material.

[0071] Experiment Example 4: Superhydrophobicity Test For Example 1, ISO 15989-2018 "Contact Angle Measurement of Plastics and Elastomers" and ASTM D7334-2013 "Standard Test Method for Determining the Wettability of Substrate Surfaces Using a Contact Angle Meter" were adopted, following the logical framework of "multi-point measurement - room temperature cycling comparison," focusing on the stability of superhydrophobic properties under room temperature conditions. A sample of the coating to be tested was selected (if a coating discoloration test is required, a sample of the same specification can be used). The surface was wiped with anhydrous ethanol to remove oil and impurities, and placed in an environment at room temperature (23±2℃) and relative humidity (50±5%) for 24 hours to equilibrate, ensuring that the sample temperature was consistent with the ambient temperature. The equilibrated sample was then stably fixed on the stage of the contact angle meter, ensuring that the sample surface was free of wrinkles and tilting.

[0072] The "seat drop method" was used for testing: 5 μL of deionized water was drawn with a microsyringe and slowly dripped onto the sample surface (avoiding the generation of air bubbles). After standing for 10 seconds to allow the water droplet shape to stabilize, the static contact angle (CA) value was read. Then, the stage was slowly tilted until the water droplet began to roll, and the tilt angle at this time was recorded as the roll-off angle (SA) value.

[0073] Multi-point measurement: Referring to the "five-point method," measure the center and four corners of the sample (≥5mm from the edge of the sample to avoid edge effects). Repeat the measurement three times at each point. Take the average CA and SA values ​​from the five points as the "initial standard values ​​at room temperature" (denoted as CA0 and SA0). Simultaneously record the test environment (temperature 23±2℃, relative humidity 50±5%). See details below. Figure 7 and Figure 8 .

[0074] The results show that Example 1 also exhibits superhydrophobicity to other droplets because the surface of Example 1, constructed by spraying, has a "micro-nano-scale rough structure" and "low surface energy chemical modification," thereby trapping a large amount of air within the rough structure. This allows the droplets to contact only a very small amount of solid surface, ultimately resulting in a superhydrophobic state. Furthermore, the superior properties of the matrix resin in Example 1 make its superhydrophobic and anti-icing properties superior to the comparative example.

[0075] The embodiments described above are merely illustrative of several implementations of the present invention, and while the descriptions are relatively specific and detailed, they should not be construed as limiting the scope of the invention patent. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the present invention, and these all fall within the protection scope of the present invention. Therefore, the protection scope of this invention patent should be determined by the appended claims.

Claims

1. A superhydrophobic coating with dual functions of refrigeration and heat release, characterized in that, The super-hydrophobic particles and the resin coating are prepared by mixing the super-hydrophobic particles and the resin coating in a mass ratio of 1: (5-15).

2. The superhydrophobic coating with both refrigeration and heat release functions according to claim 1, characterized in that, The super-hydrophobic particles are prepared by mixing silica, diatomite and reversible thermochromic microcapsules in a mass ratio of 0.1: (1-3): 1, wherein the silica is prepared by hydrolysis of tetraethyl orthosilicate.

3. The superhydrophobic coating with both refrigeration and heat release functions according to claim 2, characterized in that, The reversible thermochromic microcapsules are prepared by mixing styrene-maleic anhydride, core material and shell material in a mass ratio of 5: (5-15): (5-15), wherein the shell material is a mixture of melamine formaldehyde polymer and gelatin, and the core material is a mixture of 2-anilino-3-methyl-6-dibutylaminofluoran, bisphenol A and dodecanol in a mass ratio of 1: (2-4):

100.

4. The superhydrophobic coating with both refrigeration and heat release functions according to claim 1, characterized in that, The resin coating is prepared by mixing resin and solvent in a mass ratio of 1: (1-3), wherein the resin is vulcanized silicone rubber, epoxy resin, fluorocarbon resin or fluorosilicon resin, and the solvent is butyl acetate, water or ethanol.

5. The method of claim 1, wherein the method of preparing the superhydrophobic coating having a dual function of refrigeration and heat release is characterized by, The method comprises the following steps: (1) preparing core material by mixing 2-anilino-3-methyl-6-dibutylaminofluoran, bisphenol A and dodecanol and stirring at 70-90°C for 20-40 min, and preparing shell material by mixing melamine formaldehyde polymer and gelatin uniformly, and preparing reversible thermochromic microcapsules by adding styrene-maleic anhydride into water and stirring, then adding NaOH to adjust the pH of the solution to 5.5, then adding the core material and stirring, then adding the shell material and HCl to adjust the pH to 3.5, and then stirring, filtering, washing, drying and grinding; (2) mixing diatomite and reversible thermochromic microcapsules and stirring to obtain mixed particles; (3) dispersing the mixed particles in an ethanol solution, adding tetraethyl orthosilicate and n-octyl triethoxysilane, adding ammonia water to adjust the pH to 8-9, and then stirring in a water bath and vacuum filtering, and then washing with anhydrous ethanol and deionized water for 2-4 times, and then drying to obtain super-hydrophobic particles; (4) mixing resin coating, super-hydrophobic particles and ethanol by stirring to obtain super-hydrophobic coating with refrigeration and heat release functions; (5) spraying the super-hydrophobic coating with refrigeration and heat release functions on the surface of a substrate, and then solidifying to form a super-hydrophobic coating with refrigeration and heat release functions.

6. The method of claim 5, wherein the method is characterized by the steps of: The stirring rate in step (2) is 200-400 r / min, and the stirring time is 5-15 min.

7. The method of claim 5, wherein the method is characterized by the steps of: In step (3), the mass ratio of tetraethyl orthosilicate to n-octyl triethoxysilane is (8-12): 1, and the water bath stirring is performed at 50-60°C and at a stirring rate of 500-700 r / min for 3-4 h.

8. The method of claim 5, wherein the method is characterized by the steps of: In step (4), the stirring conditions are as follows: stirring the resin coating and the super-hydrophobic particles at a stirring rate of 500-700 r / min for 20-45 min, then adding ethanol and stirring at a stirring rate of 800-1000 r / min for 20-45 min.

9. The method of claim 5, wherein the method is characterized by the steps of: The base material is polished or sanded until the roughness Ra value is less than 0.64 μm, and then ultrasonic cleaned in anhydrous ethanol and deionized water, each for 20-30 min, and naturally dried for standby use; the coating thickness is not less than 1 mm. The base material is polished or sanded until the roughness Ra value is less than 0.64 μm, and then ultrasonic cleaned in anhydrous ethanol and deionized water, each for 20-30 min, and naturally dried for standby use; the coating thickness is not less than 1 mm.

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