Preparation method of photo-thermal anti-icing and deicing super-amphiphobic coating

Abstract

The invention discloses a preparation method of a photo-thermal anti-icing and deicing super-amphiphobic coating, which comprises the following steps: firstly, adding TiN nanoparticles into a dopamine solution, so that dopamine is subjected to an auto-polymerization grafting reaction on the surfaces of the TiN nanoparticles to obtain PDA-TiN nanoparticles; dispersing the PDA-TiN nanoparticles, the SiO2 nanoparticles, the epoxy resin and the epoxy resin curing agent into absolute ethyl alcohol, adding TEOS and FAS, and dispersing; stirring the dispersion liquid twice to obtain uniformly dispersed spraying liquid; meanwhile, dispersing epoxy resin and an epoxy resin curing agent into absolute ethyl alcohol, spraying dispersion liquid onto a substrate material, and depositing an epoxy resin layer on the surface of the substrate material; and finally, uniformly spraying the spraying liquid on the surface of the epoxy resin layer, and then sequentially carrying out two times of solvent volatilization to obtain the photo-thermal type anti-icing and deicing super-amphiphobic coating loaded substrate material. A re-entering micro-nano structure and low surface energy required by the photo-thermal super-amphiphobic surface are formed on the substrate material through a spraying method and are used for preventing and removing ice.

Description

Technical Field

[0001] The present invention relates to the field of multifunctional coatings, and specifically to a preparation method of a photothermal anti-icing superhydrophobic coating. Background Art

[0002] In a low-temperature environment, icing is an inevitable natural phenomenon. The accumulation and adhesion of ice on the surface of outdoor objects can cause many serious problems, such as traffic jams, equipment failures, power outages, etc. in the power, aviation, and transportation industries. Therefore, the research on anti-icing technology has received increasing attention in recent years. The traditional anti-icing methods are mainly active anti-icing technologies, including electric heating, chemical methods, hot air flow, etc., which have the disadvantages of high energy consumption, high cost, environmental pollution, etc., and are difficult to meet the development requirements of green and low-carbon.

[0003] As a representative of passive anti-icing technology, superhydrophobic coating technology has emerged in urgent demand. Thanks to the synergistic effect between the rough microtopography and the low surface energy, it can repel water droplets on the surface and delay interfacial heat transfer under most conditions, thus delaying icing, and has great application prospects in the field of anti-icing. However, the anti-icing performance of superhydrophobic surfaces is prone to failure under conditions of low temperature and high humidity as well as icing / de-icing cycles, and it is easy to form mechanical interlocks with the surface microstructures after icing, thus increasing the adhesion force during de-icing. At the same time, the inherent fragility of the material will lose its super-repellent property to water after simple wear. The superposition of these factors limits the development of the technology. In addition, there are a large number of low surface energy substances (such as oils and humic acids, etc.) in real outdoor conditions. Superhydrophobic surfaces cannot withstand the pollution of such substances. After being polluted, the superhydrophobicity will weaken or even be lost, causing water to freeze more easily on the surface. Therefore, there is an urgent need for an anti-icing coating technology that can meet real outdoor scenarios.

[0004] A superamphiphobic surface refers to a surface that has super-repellency to both water and oil-based liquids. Its contact angles with water and oil-based liquids are both greater than 150°, and the sliding angles are both lower than 10°. It has a more delicate micro-nano re-entrant structure and lower surface energy than a superhydrophobic surface. Compared with a superhydrophobic surface, a superamphiphobic surface has a stronger repellency to water and can effectively repel oily substances. It is worth noting that a superamphiphobic surface still maintains superhydrophobicity to water after undergoing a certain degree of wear. Therefore, when the superamphiphobic surface is applied to the field of outdoor anti-icing, it shows greater advantages. Under the conditions of low temperature and high humidity and ice formation / de-icing cycles, it can further extend the ice formation time compared with a superhydrophobic surface, maintain the self-cleaning property of the surface for a longer time under outdoor conditions, and still maintain good anti-icing performance after a certain degree of wear. The literature "Youfa Zhang, et al. Endowing durable icephobicity by combination of a rough powder coating and a superamphiphobic coating[J]. Chemical Engineering Journal, 2024, 482:149001" reported a preparation method of a superamphiphobic coating for anti-icing. By using polyethylene terephthalate and silica nanoparticles for powder spraying, the formed coating still has good anti-icing performance after wear. However, its preparation steps are complex, requiring special and expensive instruments and cannot actively de-ice, thus limiting its application scope.

[0005] Although the superamphiphobic surface has good performance in delaying ice formation, it will inevitably ice over over time in a low-temperature and high-humidity environment. After icing, a mechanical interlocking phenomenon similar to that of a superhydrophobic surface may also occur. At this time, directly de-icing may damage the surface of the superamphiphobic coating. Therefore, it is necessary to introduce an automatic de-icing technology. A photothermal material is a material that generates heat under light irradiation. Introducing a photothermal material into the construction of a superamphiphobic material can achieve automatic de-icing of the superamphiphobic surface only under the action of light after icing. Recently, some photothermal superhydrophobic coatings have been reported for anti-icing. For example, the literature with the application number 202411199184.9 discloses a preparation method of a photothermal anti-ice superhydrophobic coating, but its preparation process is complex, the reagents used are toxic, and the photothermal conversion efficiency is low. In addition, the currently prepared photothermal superhydrophobic coatings have a greatly shortened service life in practical applications due to the lack of oil repellency, and the anti-icing and de-icing effects are not excellent enough, and it is easy to lose the original performance in the anti-icing and de-icing cycles. Therefore, there is an urgent need to develop an anti-icing and de-icing superamphiphobic coating with a simple preparation method, low cost, environmental friendliness, wear resistance, high photothermal conversion efficiency, and good anti-icing and de-icing cycles. However, how to achieve these functions has become a huge challenge. Summary of the Invention

[0006] Aiming at the deficiencies of the prior art, the technical problem to be solved by the present invention is to provide a preparation method of a photothermal anti-icing superhydrophobic and superoleophobic coating.

[0007] The technical solution of the present invention to solve the above technical problem is to provide a preparation method of a photothermal anti-icing superhydrophobic and superoleophobic coating, which is characterized in that the method comprises the following steps:

[0008] Step 1: Dissolve dopamine hydrochloride in an alkaline solution to obtain a dopamine solution; then add TiN nanoparticles to the dopamine solution to enable self-polymerization grafting reaction of dopamine on the surface of the TiN nanoparticles; after the reaction is completed, perform suction filtration, and then dry and grind the filter cake to obtain PDA-TiN nanoparticles;

[0009] Step 2: Disperse the PDA-TiN nanoparticles, SiO2 nanoparticles, epoxy resin and epoxy resin curing agent obtained in Step 1 in anhydrous ethanol to obtain a uniformly dispersed PDA-TiN / SiO2 dispersion; then add TEOS and FAS to the dispersion and disperse to obtain a uniformly dispersed PDA-TiN / SiO2 / TEOS / FAS dispersion; subsequently, perform the first stirring on the dispersion to form micro-nano composite particles by self-assembly; then add FAS and perform the second stirring to further crosslink and lower the surface energy of the system to obtain a uniformly dispersed spraying liquid;

[0010] Disperse the epoxy resin and epoxy resin curing agent in anhydrous ethanol to obtain a uniformly dispersed epoxy resin dispersion; then spray the dispersion on the substrate material and dry it to deposit an epoxy resin layer on the surface of the substrate material;

[0011] Step 3: Uniformly spray the spraying liquid obtained in Step 2 on the surface of the epoxy resin layer of the substrate material obtained in Step 2; then place it to perform preliminary volatilization of the solvent in the spraying liquid, so as to form a preliminary film on the surface of the epoxy resin layer; then place it again to perform volatilization of the remaining solvent in the spraying liquid, so as to complete the final film formation on the surface of the epoxy resin layer to obtain a substrate material loaded with a photothermal anti-icing superhydrophobic and superoleophobic coating.

[0012] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0013] (1) The present invention forms the micronano structure and low surface energy required for the photothermal superhydrophobic surface on the substrate material by spraying method for anti-icing, which is not limited by the substrate material and has strong universality and durability.

[0014] (2) The superhydrophobic and superoleophobic coating formed by the present invention has excellent super-repellent property, photothermal conversion property and cyclic anti-icing performance, and is a multifunctional coating.

[0015] (3) All raw materials used in the present invention are inexpensive and easily available materials, and no further purification and synthesis are required during the coating preparation process; moreover, the preparation process is simple, can be processed on a large scale, and is conducive to scaled-up application.

[0016] (4) The superhydrophobic and superoleophobic coating formed by the present invention has a surface tension as low as 27.5 mN / n for maintaining superhydrophobic and superoleophobic properties towards liquids, demonstrating excellent superhydrophobic and superoleophobic performance.

[0017] (5) The superhydrophobic and superoleophobic coating formed by the present invention has excellent photothermal performance. Under one sun illumination, the surface temperature of the coating can be increased by 43.4 °C at 25 °C.

[0018] (6) The superhydrophobic and superoleophobic coating formed by the present invention has excellent anti-icing performance under low-temperature and high-humidity conditions and has excellent photothermal de-icing performance.

[0019] (7) The superhydrophobic and superoleophobic coating formed by the present invention has excellent cyclic anti-icing and de-icing performance.

[0020] (8) The superhydrophobic and superoleophobic coating formed by the present invention has excellent durability, and the coating still maintains good anti-icing and de-icing performance after abrasion. Description of the Drawings

[0021] Figure 1 is the scanning electron microscope image of the aluminum sheet loaded with the superhydrophobic and superoleophobic coating prepared in Example 1 of the present invention;

[0022] Figure 2 is the optical image of droplets with different surface tensions on the surface of the aluminum sheet loaded with the superhydrophobic and superoleophobic coating in Example 1 of the present invention;

[0023] Figure 3 is the anti-wetting property diagram of droplets with different surface tensions on the surface of the aluminum sheet loaded with the superhydrophobic and superoleophobic coating in Example 1 of the present invention;

[0024] Figure 4 is the performance diagram of the aluminum sheet loaded with the superhydrophobic and superoleophobic coating prepared in Example 1 of the present invention under one sun illumination;

[0025] Figure 5 is the anti-icing performance diagram of the aluminum sheet loaded with the superhydrophobic and superoleophobic coating prepared in Example 1 of the present invention at a temperature of -20 °C and a humidity of 80%;

[0026] Figure 6 is the photothermal de-icing performance diagram of the aluminum sheet loaded with the superhydrophobic and superoleophobic coating prepared in Example 1 of the present invention at a temperature of -15 °C and a humidity of 80%;

[0027] Figure 7 is the cyclic photothermal de-icing performance diagram of the aluminum sheet loaded with the superhydrophobic and superoleophobic coating prepared in Example 1 of the present invention at a temperature of -15 °C, a humidity of 80%, and an inclination of 20°;

[0028] Figure 8 Photothermal de-icing performance diagram of the aluminum sheet loaded with the superhydrophobic and oleophobic coating prepared in Example 1 of the present invention after wear under the environment of temperature -15°C and humidity 80%;

[0029] Figure 9 Anti-wetting diagram of droplets with different surface tensions on the surface of the glass sheet loaded with the superhydrophobic and oleophobic coating in Example 3 of the present invention;

[0030] Figure 10 Anti-wetting diagram of droplets with different surface tensions on the surface of the magnesium sheet loaded with the superhydrophobic and oleophobic coating in Example 4 of the present invention;

[0031] Figure 11 Anti-wetting diagram of droplets with different surface tensions on the surface of the cotton fabric loaded with the superhydrophobic and oleophobic coating in Example 5 of the present invention. Detailed implementation manners

[0032] The following are specific examples of the present invention. The specific examples are only used to further illustrate the present invention in detail and do not limit the protection scope of the present invention.

[0033] The present invention provides a preparation method of a photothermal anti-icing superhydrophobic and oleophobic coating (abbreviated as method), which is characterized in that the method includes the following steps:

[0034] Step 1: Dissolve dopamine hydrochloride in an alkaline solution to obtain a dopamine solution; then add TiN (titanium nitride) nanoparticles to the dopamine solution so that dopamine undergoes self-polymerization grafting reaction on the surface of the TiN nanoparticles, and assemble and grow to form PDA-TiN (polydopamine-titanium nitride) nanoparticles; after the reaction is completed, perform suction filtration, and then dry and grind the filter cake to obtain PDA-TiN nanoparticles;

[0035] Preferably, in Step 1, in the dopamine solution, the concentration of dopamine hydrochloride is 15 - 30 g / L; the dissolution temperature is room temperature (i.e., 20 - 30°C); the alkaline solution is Tris-HCl solution (tris(hydroxymethyl)aminomethane-hydrochloric acid solution) or NaOH solution, and the pH is 8 - 9.

[0036] Preferably, in Step 1, the average particle size of the TiN nanoparticles is 10 - 100 nm.

[0037] Preferably, in Step 1, the mass ratio of the TiN nanoparticles to dopamine hydrochloride is (1 - 10):(1 - 20).

[0038] Preferably, in Step 1, the process of the self-polymerization grafting reaction is: adopt a stirring method, the stirring speed is 400 - 800 rpm, the stirring time is 8 - 24 h, and the stirring temperature is room temperature (i.e., 20 - 30°C).

[0039] Preferably, in step 1, the drying temperature is 60 - 100 °C and the time is 4 - 8 h.

[0040] Preferably, in step 1, grinding is carried out using an agate mortar or a ceramic mortar.

[0041] Step 2: Disperse the PDA-TiN nanoparticles, SiO2 nanoparticles, epoxy resin, and epoxy resin curing agent obtained in step 1 in absolute ethanol to obtain a uniformly dispersed PDA-TiN / SiO2 dispersion; then add TEOS (tetraethyl orthosilicate) and FAS (fluorosilane) to the dispersion and disperse to obtain a uniformly dispersed PDA-TiN / SiO2 / TEOS / FAS dispersion; subsequently, carry out the first stirring on the dispersion to form micro-nano composite particles by self-assembly; then add FAS and carry out the second stirring to further crosslink and lower the surface energy of the system to obtain a uniformly dispersed spraying liquid;

[0042] Disperse the epoxy resin and the epoxy resin curing agent in absolute ethanol to obtain a uniformly dispersed epoxy resin dispersion; then spray the dispersion on the substrate material and dry it to deposit an epoxy resin layer on the surface of the substrate material;

[0043] Preferably, step 2 is carried out at room temperature.

[0044] Preferably, in step 2, the average particle size of the SiO2 nanoparticles is 10 - 100 nm.

[0045] Preferably, in step 2, the epoxy equivalent of the epoxy resin is 200 - 2000.

[0046] Preferably, in step 2, the mass ratio of PDA-TiN nanoparticles, SiO2 nanoparticles, epoxy resin, epoxy resin curing agent, and the volume of absolute ethanol in the PDA-TiN / SiO2 dispersion is (1 - 10 g):(1 - 15 g):(1 - 20 g):(1 - 10 g):(0.5 - 200 mL).

[0047] Preferably, in step 2, the epoxy resin curing agent is a commercially available product to cure the epoxy resin.

[0048] Preferably, in step 2, ultrasonic dispersion is used for all dispersions; the power of ultrasonic dispersion is 400 - 800 W and the time is 5 - 20 min.

[0049] Preferably, in step 2, the volume ratio of TEOS, FAS, and absolute ethanol is (1 - 10):(1 - 15):(10 - 200).

[0050] Preferably, in step 2, the FAS is one of 1H,1H,2H,2H-perfluorooctyltrimethoxysilane, 1H,1H,2H,2H-perfluorooctyltriethoxysilane, 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, 1H,1H,2H,2H-perfluorodecyltriethoxysilane or 1H,1H,2H,2H-perfluorodecyltrichlorosilane.

[0051] Preferably, in step 2, the speed of the first stirring is 400 - 800 rpm and the time is 8 - 24 h.

[0052] Preferably, in step 2, the volume ratio of the added FAS to absolute ethanol is (1 - 10):(20 - 200).

[0053] Preferably, in step 2, the speed of the second stirring is 400 - 800 rpm and the time is 0.5 - 8 h.

[0054] Preferably, in step 2, in the epoxy resin dispersion, the mass ratio of the epoxy resin, the epoxy resin curing agent to the volume of absolute ethanol is (1 - 20 g):(1 - 10 g):(1 - 30 mL).

[0055] Preferably, in step 2, the spraying process is: the spraying pressure is 0.1 - 0.6 MPa, the spraying distance is 10 - 40 cm, the diameter of the nozzle used for spraying is 0.5 - 2.5 mm, and the spraying amount is 0.5 - 1 ml / cm 2 。

[0056] Preferably, in step 2, the substrate material is an aluminum sheet, a magnesium sheet, an iron sheet, a copper sheet, a filter paper, glass, a cotton fabric or a sponge, with a length and width of 2.5 cm × 5 cm or 5 cm × 5 cm.

[0057] Preferably, in step 2, the substrate material is successively washed with water and absolute ethanol before use to remove surface impurities, and for metal substrates, sandpaper is required for polishing.

[0058] Preferably, in step 2, the mesh number of the sandpaper used for polishing is 200, 400, 800, 1000, 2000 or 3000 mesh.

[0059] Preferably, in step 2, the drying is carried out at room temperature for 4 - 36 h.

[0060] Step 3: Uniformly spray the spraying liquid obtained in Step 2 onto the surface of the epoxy resin layer of the substrate material obtained in Step 2; then let it stand to allow the preliminary volatilization of the solvent in the spraying liquid, thereby initially forming a film on the surface of the epoxy resin layer; then let it stand again to allow the volatilization of the remaining solvent in the spraying liquid, thereby completing the final film formation on the surface of the epoxy resin layer, and obtaining a substrate material loaded with a photothermal anti-icing superhydrophobic and oleophobic coating (abbreviated as superhydrophobic and oleophobic coating).

[0061] Preferably, in Step 3, the spraying is carried out at room temperature, the spraying pressure is 0.2 - 0.6 MPa, the spraying distance is 10 - 40 cm, the diameter of the nozzle used for spraying is 0.5 - 2.5 mm, and the spraying amount is 1 - 2 ml / cm 2 .

[0062] Preferably, in Step 3, the process for the preliminary volatilization of the solvent is: let it stand at room temperature for 5 - 300 min.

[0063] Preferably, in Step 3, the process for the volatilization of the remaining solvent is: the temperature is 80 - 140 °C, and the time is 0.5 - 12 h.

[0064] Example 1:

[0065] (1) At room temperature, dissolve 2.4 g of dopamine hydrochloride in 100 ml of Tris-HCl solution with a pH of 8.5 to obtain a dopamine solution; then add 1.5 g of TiN nanoparticles with a particle size of 20 nm to the dopamine solution and stir at a speed of 800 rpm for 12 h to enable the self-polymerization grafting reaction of dopamine on the surface of the TiN nanoparticles; after the stirring ends, perform suction filtration, dry the filter cake at 80 °C for 4 h and grind it using an agate mortar to obtain PDA-TiN nanoparticles;

[0066] (2) At room temperature, ultrasonically disperse 300 mg of PDA-TiN nanoparticles, 150 mg of SiO2 nanoparticles with a particle size of 20 nm, 450 mg of epoxy resin with an epoxy equivalent of 250, and 225 mg of epoxy resin curing agent in 15 ml of anhydrous ethanol for 10 min using a power of 600 W to obtain a uniformly dispersed PDA-TiN / SiO2 dispersion; then add 185 μL of TEOS and 500 μL of perfluorodecyltriethoxysilane to the dispersion and ultrasonically disperse it again for 10 min using a power of 600 W to obtain a uniformly dispersed PDA-TiN / SiO2 / TEOS / FAS dispersion; subsequently, stir the dispersion at a speed of 500 rpm for 12 h, then add 150 μL of perfluorodecyltriethoxysilane and continue to stir at a speed of 500 rpm for 2 h to obtain a uniformly dispersed spraying liquid;

[0067] 3 g of epoxy resin with an epoxy equivalent weight between 220 and 280 and 1.5 g of epoxy resin curing agent were dispersed in 10 ml of anhydrous ethanol using an ultrasonic dispersion with a power of 600 W for 20 min to obtain a uniformly dispersed epoxy resin dispersion; the dispersion was then sprayed on a 2.5 cm×5 cm aluminum sheet that had been polished and cleaned with 400-mesh sandpaper at a spray distance of 20 cm, a spray pressure of 0.4 MPa, and a 0.5 mm nozzle, and dried at room temperature for 14 h to deposit an epoxy resin layer on the surface of the aluminum sheet;

[0068] (3) The spraying liquid is evenly sprayed on the surface of the epoxy resin layer at a spraying distance of 20 cm, a spraying pressure of 0.2 MPa and a 0.5 mm nozzle. After the spraying is completed, it is placed at room temperature for 2 hours to allow the solvent to evaporate initially, thereby initially forming a film on the surface of the epoxy resin layer; then it is placed at 120°C for another 6 hours to allow the remaining solvent to evaporate, thereby completing the final film formation on the surface of the epoxy resin layer, and obtaining an aluminum sheet loaded with a photothermal anti-icing super-amphiphobic coating.

[0069] Depend on Figure 1 It can be seen that the coating surface has a rough reentrant micro-nanostructure.

[0070] Depend on Figure 2 It can be seen that all droplets are spherical on the coating surface, and the contact angles are all greater than 150°, showing excellent super-amphiphobic properties.

[0071] Depend on Figure 3 It can be seen that the droplets are all spherical and cannot wet the aluminum sheet.

[0072] Depend on Figure 4 It can be seen that after 9 minutes of exposure to sunlight, the surface temperature increased from 26.0°C to 69.4°C.

[0073] Depend on Figure 5 It can be seen that the freezing time of a 60μL water droplet on the surface of an aluminum sheet loaded with a super-amphiphobic coating can be extended to 106.8s, showing excellent anti-icing performance.

[0074] Depend on Figure 6 It can be seen that the 60 μL ice droplet melts into a water droplet in 202.1 s, thus demonstrating excellent photothermal deicing performance.

[0075] Depend on Figure 7 It can be seen that the deicing time of the coating increases from 23.2 s at the beginning to 34.3 s after 20 anti-icing cycles, thus demonstrating excellent cyclic anti-icing and deicing performance.

[0076] Depend on Figure 8It can be seen that the 60 μL ice droplets melted into water droplets in 294.1 s, which is 92 s longer than that of the unworn sample, still showing excellent photothermal de-icing performance, thus demonstrating the excellent wear resistance of the coating.

[0077] Comparative Example 1:

[0078] This comparative example is exactly the same as Example 1, except that in step (2), TEOS was not added to the dispersion liquid, and an aluminum sheet loaded with a double-hydrophobic coating was obtained.

[0079] Compared with the aluminum sheet loaded with the super double-hydrophobic coating in Example 1, the performance of the aluminum sheet loaded with the double-hydrophobic coating obtained in Comparative Example 1 decreased significantly. It only showed super-repellency to water and ethylene glycol. The contact angle with soybean oil was 145.1°, and hexadecane could wet the aluminum sheet.

[0080] Example 2:

[0081] (1) At room temperature, 3 g of dopamine hydrochloride was dissolved in 100 ml of Tris-HCl solution with a pH of 8.5 to obtain a dopamine solution; then 1.8 g of TiN nanoparticles with a particle size of 20 nm were added to the dopamine solution and stirred at a rotation speed of 1000 rpm for 12 h to enable the self-polymerization grafting reaction of dopamine on the surface of the TiN nanoparticles; after the stirring was completed, suction filtration was carried out, and the filter cake was dried at 90 °C for 3 h and ground using an agate mortar to obtain PDA-TiN nanoparticles;

[0082] (2) At room temperature, 450 mg of PDA-TiN nanoparticles, 225 mg of SiO2 nanoparticles with a particle size of 20 nm, 675 mg of epoxy resin with an epoxy equivalent of 250, and 338 mg of epoxy resin curing agent were ultrasonically dispersed in 25 ml of absolute ethanol for 20 min using a power of 600 W to obtain a uniformly dispersed PDA-TiN / SiO2 dispersion liquid; then 250 μL of TEOS and 750 μL of perfluorodecyltriethoxysilane were added to the dispersion liquid and ultrasonically dispersed again for 10 min using a power of 600 W to obtain a uniformly dispersed PDA-TiN / SiO2 / TEOS / FAS dispersion liquid; then the dispersion liquid was stirred at a rotation speed of 500 rpm for 12 h, and then 150 μL of perfluorodecyltriethoxysilane was added and continued to be stirred at a rotation speed of 500 rpm for 2 h to obtain a uniformly dispersed spraying liquid;

[0083] 5.0 g of epoxy resin with an epoxy equivalent between 220 and 260 and 2.5 g of epoxy resin curing agent were ultrasonically dispersed in 15 ml of absolute ethanol for 20 min using a power of 600 W to obtain a uniformly dispersed epoxy resin dispersion; then the dispersion was sprayed onto a 5 cm × 5 cm aluminum sheet polished with 1000 - mesh sandpaper and cleaned at a spraying distance of 20 cm, a spraying pressure of 0.4 MPa, and using a 1.0 - mm nozzle, and dried at room temperature for 14 h to deposit an epoxy resin layer on the aluminum sheet surface;

[0084] (3) The spraying solution was uniformly sprayed onto the epoxy resin layer at a spraying distance of 20 cm, a spraying pressure of 0.3 MPa, and using a 1.0 - mm nozzle. After spraying, it was placed at room temperature for 3 h for the preliminary volatilization of the solvent, thereby initially forming a film on the surface of the epoxy resin layer; then it was placed at 110 °C for another 8 h for the volatilization of the remaining solvent, thereby completing the final film - forming on the surface of the epoxy resin layer to obtain an aluminum sheet loaded with a photothermal anti - icing super - hydrophobic and super - oleophobic coating.

[0085] The aluminum sheet loaded with the formed super - hydrophobic and super - oleophobic coating exhibited excellent super - hydrophobicity, super - oleophobicity, photothermal property, and anti - icing property. After being irradiated by one sunlight for 9 minutes, the surface temperature of the coating rose from 26.0 °C to 69.2 °C. In an environment with a temperature of - 20 °C and a humidity of 80%, the icing time of 60 μL of water droplets on the surface of the aluminum sheet loaded with the super - hydrophobic and super - oleophobic coating could be extended to 104.7 s. In an environment with a temperature of - 15 °C and a humidity of 80%, 60 μL of ice droplets melted into water droplets in 208.4 s. After 20 anti - icing cycles, it increased from 25.6 s to 38.7 s. After being worn with a 200 g weight and 2000 - mesh sandpaper for 1.5 m and in an environment with a temperature of - 15 °C and a humidity of 80%, 60 μL of ice droplets melted into water droplets in 302.4 s, an increase of 94.0 s compared with the unworn sample.

[0086] Example 3:

[0087] (1) At room temperature, 2.4 g of dopamine hydrochloride was dissolved in 100 ml of Tris - HCl solution with a pH of 8.5 to obtain a dopamine solution; then 1.5 g of TiN nanoparticles with a particle size of 20 nm were added to the dopamine solution and stirred at a rotation speed of 600 rpm for 20 h to enable the self - polymerization grafting reaction of dopamine on the surface of the TiN nanoparticles; after stirring, suction filtration was carried out, and the filter cake was dried at 100 °C for 2 h and ground using an agate mortar to obtain PDA - TiN nanoparticles;

[0088] (2) At room temperature, 350 mg of PDA-TiN nanoparticles, 175 mg of SiO2 nanoparticles with a particle size of 20 nm, 500 mg of epoxy resin with an epoxy equivalent of 250, and 250 mg of epoxy resin curing agent were ultrasonically dispersed in 18 ml of absolute ethanol for 15 min using a power of 600 W to obtain a uniformly dispersed PDA-TiN / SiO2 dispersion; then 200 μL of TEOS and 600 μL of perfluorodecyltriethoxysilane were added to the dispersion and ultrasonically dispersed again for 15 min using a power of 600 W to obtain a uniformly dispersed PDA-TiN / SiO2 / TEOS / FAS dispersion; subsequently, the dispersion was stirred at a speed of 550 rpm for 16 h, and then 200 μL of perfluorodecyltriethoxysilane was added and stirring was continued at a speed of 550 rpm for 2 h to obtain a uniformly dispersed spraying solution;

[0089] 3.0 g of epoxy resin with an epoxy equivalent between 220 and 260 and 1.5 g of epoxy resin curing agent were ultrasonically dispersed in 10 ml of absolute ethanol for 20 min using a power of 600 W to obtain a uniformly dispersed epoxy resin dispersion; then the dispersion was sprayed onto a 2.5 cm × 5 cm glass slide at a spraying distance of 20 cm, a spraying pressure of 0.4 MPa, and using a 1.0 mm nozzle, and dried at room temperature for 16 h to deposit an epoxy resin layer on the surface of the glass slide;

[0090] (3) The spraying solution was uniformly sprayed on the epoxy resin layer at a spraying distance of 20 cm, a spraying pressure of 0.4 MPa, and using a 1.0 mm nozzle. After spraying, it was placed at room temperature for 4 h for preliminary volatilization of the solvent, thereby forming a preliminary film on the surface of the epoxy resin layer; then it was placed at 120 °C for another 8 h for volatilization of the remaining solvent, thereby completing the final film formation on the surface of the epoxy resin layer to obtain a glass slide loaded with a photothermal anti-icing superhydrophobic and superoleophobic coating.

[0091] The glass slide loaded with the formed superhydrophobic and superoleophobic coating exhibits excellent superhydrophobicity, photothermal property, and anti-icing property. Figure 9It can be seen that the droplets are all spherical and cannot wet the glass sheet. Unlike Example 1, the super repellency to hexadecane is relatively reduced, and the contact angle is reduced to 150.8°. After 9 minutes of exposure to sunlight, the surface temperature of the coating rose from 26.0°C to 69.7°C. Under a temperature of -20°C and a humidity of 80%, the freezing time of a 60μL water droplet on the surface of a glass sheet loaded with a super-amphiphobic coating can be extended to 108.2s. Under a temperature of -15°C and a humidity of 80%, a 60μL ice droplet melts into a water droplet in 201.4s. After 20 anti-icing cycles, it increased from 28.7s to 41.5s. After abrasion for 1.5m with a 200g weight and 2000-grit sandpaper, a 60μL ice droplet melted into a water droplet in 312.4s at a temperature of -15°C and a humidity of 80%, an increase of 111.4s over the unworn sample.

[0092] Embodiment 4:

[0093] (1) At room temperature, 2 g of dopamine hydrochloride was dissolved in 100 ml of a Tris-HCl solution with a pH of 9 to obtain a dopamine solution; 1.5 g of TiN nanoparticles with a particle size of 20 nm were added to the dopamine solution and stirred at a speed of 1000 rpm for 12 h, so that dopamine was self-polymerized and grafted on the surface of the TiN nanoparticles; after the stirring was completed, the mixture was filtered, and the filter cake was dried at 90° C. for 4 h and ground using an agate mortar to obtain PDA-TiN nanoparticles;

[0094] (2) At room temperature, 325 mg of PDA-TiN nanoparticles, 165 mg of SiO2 nanoparticles with a particle size of 15 nm, 500 mg of epoxy resin with an epoxy equivalent of 250, and 250 mg of epoxy resin curing agent were dispersed in 15 ml of anhydrous ethanol using an ultrasonic dispersion of 600 W for 20 min to obtain a uniformly dispersed PDA-TiN / SiO2 dispersion; then, 200 μL of TEOS and 550 μL of perfluorodecyltriethoxysilane were added to the dispersion and the dispersion was again dispersed using an ultrasonic dispersion of 600 W for 15 min to obtain a uniformly dispersed PDA-TiN / SiO2 / TEOS / FAS dispersion; the dispersion was then stirred at 700 rpm for 12 h, and then 100 μL of perfluorodecyltriethoxysilane was added and the stirring was continued at 700 rpm for 1.5 h to obtain a uniformly dispersed spray solution;

[0095] 3.0 g of epoxy resin with an epoxy equivalent between about 280 and 340 and 1.5 g of an epoxy resin curing agent were ultrasonically dispersed in 15 ml of absolute ethanol for 20 min using a power of 600 W to obtain a uniformly dispersed epoxy resin dispersion; then the dispersion was sprayed onto a 2.5 cm × 5 cm magnesium sheet polished with 600 - mesh sandpaper and cleaned at a spraying distance of 15 cm, a spraying pressure of 0.6 MPa, and using a 0.5 - mm nozzle, and dried at room temperature for 12 h to deposit an epoxy resin layer on the surface of the magnesium sheet;

[0096] (3) The spraying liquid was uniformly sprayed onto the epoxy resin layer at a spraying distance of 15 cm, a spraying pressure of 0.25 MPa, and using a 1.0 - mm nozzle. After spraying, it was placed at room temperature for 4 h for preliminary volatilization of the solvent, thereby preliminarily forming a film on the surface of the epoxy resin layer; then it was placed at 120 °C for another 4 h for volatilization of the remaining solvent, thereby completing the final film formation on the surface of the epoxy resin layer to obtain a magnesium sheet loaded with a photothermal anti - icing super - dual - hydrophobic coating.

[0097] The magnesium sheet loaded with the formed super - dual - hydrophobic coating exhibited excellent super - dual - hydrophobicity, photothermal property, and anti - icing property. From Figure 10 it can be seen that the droplets all showed a spherical shape and could not wet the glass sheet. Different from Example 1, after being irradiated by sunlight for 9 minutes, the surface temperature of the coating rose from 26.0 °C to 68.7 °C. In an environment with a temperature of - 20 °C and a humidity of 80%, the icing time of 60 μL of water droplets on the surface of the magnesium sheet loaded with the super - dual - hydrophobic coating could be extended to 104.2 s. In an environment with a temperature of - 15 °C and a humidity of 80%, 60 μL of ice droplets melted into water droplets in 210.1 s. After 20 anti - icing cycles, it increased from 28.9 s to 42.3 s. After being worn with a 200 - g weight and 2000 - mesh sandpaper for 1.5 m and in an environment with a temperature of - 15 °C and a humidity of 80%, 60 μL of ice droplets melted into water droplets in 314.2 s, an increase of 104.1 s compared to the unworn sample.

[0098] Example 5:

[0099] (1) At room temperature, 2.4 g of hydrochloric acid dopamine was dissolved in 100 ml of Tris - HCl solution with a pH of 8.5 to obtain a dopamine solution; then 1.5 g of TiN nanoparticles with a particle size of 20 nm were added to the dopamine solution and stirred at a rotation speed of 1000 rpm for 10 h to enable the self - polymerization grafting reaction of dopamine on the surface of the TiN nanoparticles; after stirring, suction filtration was carried out, and the filter cake was dried at 80 °C for 6 h and ground using an agate mortar to obtain PDA - TiN nanoparticles;

[0100] (2) At room temperature, 250 mg of PDA-TiN nanoparticles, 125 mg of SiO2 nanoparticles with a particle size of 20 nm, 450 mg of epoxy resin with an epoxy equivalent of 250, and 250 mg of epoxy resin curing agent were ultrasonically dispersed in 15 ml of absolute ethanol for 10 min using a power of 600 W to obtain a uniformly dispersed PDA-TiN / SiO2 dispersion; then 190 μL of TEOS and 500 μL of perfluorodecyltriethoxysilane were added to the dispersion and ultrasonically dispersed again for 10 min using a power of 600 W to obtain a uniformly dispersed PDA-TiN / SiO2 / TEOS / FAS dispersion; subsequently, the dispersion was stirred at a speed of 500 rpm for 10 h, and then 200 μL of perfluorodecyltriethoxysilane was added and stirring was continued at a speed of 500 rpm for 3 h to obtain a uniformly dispersed spraying solution;

[0101] 3.0 g of epoxy resin with an epoxy equivalent between 220 and 250 and 1.5 g of epoxy resin curing agent were ultrasonically dispersed in 15 ml of absolute ethanol for 20 min using a power of 600 W to obtain a uniformly dispersed epoxy resin dispersion; then the dispersion was sprayed onto a 5 cm × 5 cm cotton fabric at a spraying distance of 15 cm, a spraying pressure of 0.6 MPa, and using a 1.0 mm nozzle, and dried at room temperature for 10 h to deposit an epoxy resin layer on the surface of the cotton fabric;

[0102] (3) The spraying solution was uniformly sprayed onto the epoxy resin layer at a spraying distance of 15 cm, a spraying pressure of 0.25 MPa, and using a 1.0 mm nozzle. After spraying, it was placed at room temperature for 4 h for preliminary volatilization of the solvent, so as to form a preliminary film on the surface of the epoxy resin layer; then it was placed at 125 °C for another 5 h for volatilization of the remaining solvent, so as to complete the final film formation on the surface of the epoxy resin layer, and a cotton fabric loaded with a photothermal anti-icing superhydrophobic and oleophobic coating was obtained.

[0103] The cotton fabric loaded with the formed superhydrophobic and oleophobic coating exhibits excellent superhydrophobicity, superoleophobicity, photothermal property, and anti-icing property. Figure 11It can be seen that the droplets are all spherical and cannot wet the glass sheet. Unlike Example 1, due to the multiple structures of cotton fabric, the wettability to the liquid increases. After 9 minutes of exposure to sunlight, the surface temperature of the coating rises from 26.0°C to 69.8°C. Under a temperature of -20°C and a humidity of 80%, the freezing time of a 60μL water droplet on the surface of a cotton fabric loaded with a super-amphiphobic coating can be extended to 121.1s. Under a temperature of -15°C and a humidity of 80%, a 60μL ice droplet melts into a water droplet in 184.1s. After 20 anti-icing cycles, it increased from 17.9s to 31.1s. After abrasion for 1.5m with a 200g weight and 2000-grit sandpaper, a 60μL ice droplet melted into a water droplet in 226.6s at a temperature of -15°C and a humidity of 80%, an increase of 105.5s over the unworn sample.

[0104] Any matters not described in the present invention are applicable to the prior art.

Claims

1. A preparation method of a photothermal anti-icing superhydrophobic and oleophobic coating, characterized in that The method comprises the following steps: Step 1: Dissolve dopamine hydrochloride in an alkaline solution to obtain a dopamine solution; then add TiN nanoparticles to the dopamine solution to enable self-polymerization grafting reaction of dopamine on the surface of the TiN nanoparticles; after the reaction is completed, perform suction filtration, and then dry and grind the filter cake to obtain PDA-TiN nanoparticles; Step 2: Disperse the PDA-TiN nanoparticles, SiO2 nanoparticles, epoxy resin, and epoxy resin curing agent obtained in Step 1 in absolute ethanol to obtain a uniformly dispersed PDA-TiN / SiO2 dispersion; then add TEOS and FAS to the dispersion and disperse to obtain a uniformly dispersed PDA-TiN / SiO2 / TEOS / FAS dispersion; subsequently, perform the first stirring on the dispersion to self-assemble into micro-nano composite particles; then add FAS and perform the second stirring to further crosslink and lower the surface energy of the system to obtain a uniformly dispersed spraying liquid; Disperse the epoxy resin and the epoxy resin curing agent in absolute ethanol to obtain a uniformly dispersed epoxy resin dispersion; then spray the dispersion on a substrate material and dry it to deposit an epoxy resin layer on the surface of the substrate material; Step 3: Uniformly spray the spraying liquid obtained in Step 2 on the surface of the epoxy resin layer of the substrate material obtained in Step 2; then place it to perform preliminary volatilization of the solvent in the spraying liquid, thereby initially forming a film on the surface of the epoxy resin layer; then place it again to perform volatilization of the remaining solvent in the spraying liquid, thereby completing the final film formation on the surface of the epoxy resin layer to obtain a substrate material loaded with a photothermal anti-icing super-hydrophobic and super-oleophobic coating.

2. The preparation method of the photothermal anti-icing superamphiphobic coating according to claim 1, characterized in that, In Step 1, in the dopamine solution, the concentration of dopamine hydrochloride is 15-30 g / L; the dissolution temperature is room temperature; the alkaline solution is Tris-HCl solution or NaOH solution, and the pH is 8-9.

3. The preparation method of the photothermal anti-icing superhydrophobic and oleophobic coating according to claim 1, characterized in that, In Step 1, the average particle size of the TiN nanoparticles is 10-100 nm; In Step 1, the mass ratio of the TiN nanoparticles to dopamine hydrochloride is (1-10):(1-20).

4. The preparation method of the photothermal anti-icing superhydrophobic and oleophobic coating according to claim 1, characterized in that, In Step 1, the process of the self-polymerization grafting reaction is: in a stirred manner, the stirring speed is 400-800 rpm, the stirring time is 8-24 h, and the stirring temperature is room temperature; In Step 1, the drying temperature is 60-100 °C, and the time is 4-8 h; In Step 1, the grinding is carried out using an agate mortar or a ceramic mortar.

5. The preparation method of the photothermal anti-icing superhydrophobic and oleophobic coating according to claim 1, characterized in that, Step 2 is carried out at room temperature; In Step 2, the average particle size of the SiO2 nanoparticles is 10-100 nm; In Step 2, the epoxy equivalent of the epoxy resin is 200-2000; In Step 2, the mass ratio of the PDA-TiN nanoparticles, SiO2 nanoparticles, epoxy resin, epoxy resin curing agent, and the volume of absolute ethanol in the PDA-TiN / SiO2 dispersion is (1-10 g):(1-15 g):(1-20 g):(1-10 g):(0.5-200 mL); In Step 2, the dispersion is all carried out by ultrasonic dispersion; the power of the ultrasonic dispersion is 400-800 W, and the time is 5-20 min.

6. The preparation method of the photothermal anti-icing superhydrophobic and oleophobic coating according to claim 1, characterized in that, In Step 2, the volume ratio of TEOS, FAS to absolute ethanol is (1-10):(1-15):(10-200); In Step 2, FAS is one of 1H,1H,2H,2H-perfluorooctyltrimethoxysilane, 1H,1H,2H,2H-perfluorooctyltriethoxysilane, 1H,1H,2H,2H-perfluorodecyltrimethoxysilane, 1H,1H,2H,2H-perfluorodecyltriethoxysilane or 1H,1H,2H,2H-perfluorodecyltrichlorosilane.

7. The preparation method of the photothermal anti-icing superhydrophobic and oleophobic coating according to claim 1, wherein In Step 2, the speed of the first stirring is 400-800 rpm and the time is 8-24 h; In Step 2, the volume ratio of the added FAS to absolute ethanol is (1-10):(20-200); In Step 2, the speed of the second stirring is 400-800 rpm and the time is 0.5-8 h.

8. The preparation method of the photothermal anti-icing superhydrophobic and oleophobic coating according to claim 1, characterized in that, In Step 2, in the epoxy resin dispersion, the mass ratio of epoxy resin, epoxy resin curing agent to the volume of absolute ethanol is (1-20 g):(1-10 g):(1-30 mL); In Step 2, the spraying process is as follows: the spraying pressure is 0.1 - 0.6 MPa, the spraying distance is 10 - 40 cm, the nozzle diameter used for spraying is 0.5 - 2.5 mm, and the spraying amount is 0.5 - 1 ml / cm 2 .

9. The preparation method of the photothermal anti-icing superhydrophobic and oleophobic coating according to claim 1, wherein, In Step 2, the substrate material is aluminum sheet, magnesium sheet, iron sheet, copper sheet, filter paper, glass, cotton fabric or sponge; In Step 2, drying is carried out at room temperature for 4-36 h.

10. The preparation method of the photothermal anti-icing superhydrophobic and oleophobic coating according to claim 1, characterized in that, In Step 3, the spraying is carried out at room temperature, the spraying pressure is 0.2 to 0.6 MPa, the spraying distance is 10 to 40 cm, the nozzle diameter used for spraying is 0.5 to 2.5 mm, and the spraying amount is 1 to 2 ml / cm 2 ; In Step 3, the process of preliminary volatilization of the solvent is: placing at room temperature for 5-300 min; In Step 3, the process of volatilization of the remaining solvent is: the temperature is 80-140 °C and the time is 0.5-12 h.

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