Preparation method of photothermal energy storage super-hydrophobic all-weather anti-icing coating

Abstract

The present invention discloses a method for preparing a photothermal energy storage super-hydrophobic all-weather anti-icing coating, comprising: step 1, preparing long-afterglow nanoparticles, step 2, in-situ modifying a double-shell microcapsule phase change material with the long-afterglow nanoparticles, step 3, performing low-surface-energy modification treatment on the composite particles, and step 4, preparing a photothermal energy storage super-hydrophobic anti-icing coating; the anti-icing coating prepared by the present invention delays freezing by means of a super-hydrophobic surface formed by super-hydrophobic micro-nanostructured particles; photothermal materials are used to efficiently convert solar energy into thermal energy, thereby achieving instant anti-icing and storing the remaining heat in the phase change material; long-afterglow materials are used to store sunlight for nighttime photothermal conversion, and combined with the stored heat released by the phase change material, long-lasting nighttime anti-icing and de-icing are achieved; the present invention achieves effective all-weather anti-icing through a multi-level anti-icing mechanism, thereby solving the problem of poor all-weather anti-icing / de-icing effects of existing coatings under low-temperature and high-humidity conditions, and has important application prospects in anti-icing fields such as power transmission lines and aircraft wings.

Description

Technical Field

[0001] The present invention belongs to the field of anti-icing, and specifically relates to a method for preparing a photothermal energy storage super-hydrophobic all-weather anti-icing coating. Background Art

[0002] In winter, the southern coastal areas of my country, the Yangtze River Basin and areas south of it often experience low temperatures and high humidity, making icing a common occurrence. Icing can have a significant impact on the operational reliability of aircraft, power grids, outdoor equipment, and even cause economic losses and safety accidents. Traditional deicing technologies, including hot air, electric heating, anticoagulants, and mechanical vibration, have the disadvantages of high cost, high energy consumption, environmental pollution, and low efficiency. Against this background, anti-icing coating strategies have attracted widespread attention from researchers. Currently, the field of anti-icing coatings mostly adopts a combination of photothermal active deicing and superhydrophobic passive anti-icing, aiming to use superhydrophobic surfaces to reduce the adhesion of water droplets and use the photothermal effect to generate heat to achieve anti-icing / deicing effects. However, this method is limited by the low energy density of solar energy and the characteristics of day and night alternation, especially in low temperature and high humidity environments, making it difficult to achieve all-weather anti-icing / deicing effects. Organic phase change materials, due to their high latent heat and adjustable phase change temperature range, are considered to be a solution to prolong anti-icing performance. This type of material can store thermal energy when there is sufficient solar energy (such as during the day), and release the stored thermal energy through a phase change process when the ambient temperature drops or solar energy is insufficient (such as at night or on rainy days) to maintain or increase the temperature of the material surface, thereby preventing or removing ice. However, there is a serious problem with phase change materials, which is that the time for continuous heat release is relatively short, making it difficult to cover the entire night cycle. Long afterglow materials are functional materials that continue to emit light in the visible or near-infrared region for a long time after being excited by energy such as ultraviolet light and visible-near-infrared light. As a light storage material combined with photothermal materials, it has significant advantages and feasibility in extending the nighttime anti-icing and de-icing performance of coatings. Therefore, the combination of photothermal materials, phase change materials and long afterglow materials is of great significance for solving the problem of all-weather anti-icing / de-icing of coatings in low temperature and high humidity environments.

[0003] Wei et al. (Huan Wei, Haihang Luo, Weiwei Fan, et al. A passive-active anti / deicing coating integrating superhydrophobicity, thermal insulation, and photo / electrothermal conversion effects [J], ACS Applied Materials & Interfaces, 2024, 16, 27, 35613-35625.) Using copper sulfide loaded activated biochar as photoelectric material, polydimethylsiloxane as hydrophobic component, and thermal expansion microspheres as foaming agent, an anti-icing / deicing coating integrating thermal insulation, superhydrophobicity, and light / electrothermal effect was constructed, which showed excellent passive anti-icing and active deicing effects. However, the coating can only be deiced by the electrothermal effect at night, with high energy consumption and poor electrothermal deicing efficiency, which is not conducive to achieving all-weather anti-icing / deicing performance.

[0004] Hou et al. (Mingtai Hou, Zeyi Jiang, Wen Sun, et al. Efficient photothermalanti- / deicing enabled by 3D Cu 2-x S encapsulated phase change materials mixed superhydrophobic coatings[J], Advanced Materials, 2024, 36, 3, 2310312.) designed a three-dimensional Cu2O layer with Cu2O as the first layer. 2-x A multifunctional photothermal phase-change superhydrophobic composite coating, using double-shell octahedral microcapsules as the second layer and combining them with the hydrolysis and polycondensation product of octadecyltrichlorosilane, was fabricated. This coating combines photothermal effects, phase-change thermal storage, and superhydrophobicity, demonstrating excellent anti-icing properties under low-temperature and high-humidity conditions. However, the heat stored in the phase-change material in the coating is released too quickly, making it difficult to maintain its anti-icing properties for extended periods at night.

[0005] The Chinese patent "Photothermal phase change composite material, preparation method thereof and application in anti-icing and de-icing" (application number: 202110363707.9, application publication number: CN 115181548A, publication date: 2022.10.14) discloses a photothermal phase change composite material, preparation method thereof and application in anti-icing and de-icing. A phase change energy storage filler is introduced into the photothermal absorption and conversion carrier. The phase change energy storage filler is used to absorb, store and release a large amount of heat in the form of latent heat to maintain the constant surface temperature of the composite material itself and realize the function of de-icing at night. However, in a dark environment, the heat released by the phase change material can only keep the material temperature above the water supercooling point temperature for about 300 seconds, which cannot prevent / de-ice for a long time at night.

[0006] The Chinese patent "A Self-Regulating Photothermal Anti-Icing and De-icing Paint and Coating" (Application Number: CN202310000344.1, Authorization Announcement Number: CN115873490B, Announcement Date: March 12, 2024) discloses a self-regulating photothermal anti-icing and de-icing paint and coating. The paint is composed of a resin prepolymer and thermochromic dye microcapsules. It can self-regulate its photothermal conversion performance according to the ambient temperature, appears dark at low temperatures, has high photothermal conversion performance, and can absorb and release heat through phase change energy to achieve anti-icing and de-icing functions. However, the thermochromic dye microcapsules have a relatively short aging time and a short heat release time after heat storage, which cannot guarantee long-term anti-icing function at night. Summary of the Invention

[0007] The purpose of the present invention is to provide a method for preparing a photothermal energy storage super-hydrophobic all-weather anti-icing coating, which solves the problem of poor all-weather anti-icing / de-icing effect of the coating under low temperature and high humidity conditions.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is:

[0009] A method for preparing a photothermal energy storage super-hydrophobic all-weather anti-icing coating is specifically implemented according to the following steps:

[0010] Step 1, preparation of long afterglow nanoparticles:

[0011] Zinc acetate, gallium nitrate, germanium tetrachloride, chromium nitrate and yttrium nitrate were dissolved in deionized water, the pH value of the solution was adjusted with dilute hydrochloric acid and sodium hydroxide, and then fully stirred, followed by hydrothermal treatment. After the reaction was completed, the solution was washed with water and dried, and then vacuum heat treated to obtain Zn2Ga 2.98-x Y x Cr 0.02 Ge 0.75 O8 long afterglow nanoparticles;

[0012] Step 2: In-situ modification of double-shell microcapsule phase change material:

[0013] Step 2.1, adding hexadecyltrimethylammonium bromide and a phase change material to deionized water, mechanically emulsifying, adding a copper sulfate aqueous solution and stirring in a water bath for the first time, then dropping a glucose aqueous solution and a sodium hydroxide solution, stirring in a water bath for the second time and aging treatment to obtain a Cu2O microcapsule phase change material;

[0014] Step 2.2: Ultrasonic dispersion of Cu2O microcapsule phase change material and long afterglow nanoparticles obtained in step 1 in deionized water, adding thioacetamide aqueous solution and sodium hydroxide solution, stirring and etching for the third time, filtering, washing, and vacuum drying to obtain Zn2Ga 2.98-x Y x Cr 0.02 Ge 0.75 O8 / double-layer Cu2O@Cu 2y-1 S y Micro-nanostructured particles;

[0015] Step 3: Low surface energy modification of composite particles:

[0016] Immersing the micro-nanostructured particles obtained in step 2 in a mixed solution consisting of a low surface energy modifier and a solvent, stirring in a water bath, centrifuging, washing, and drying to obtain superhydrophobic micro-nanostructured particles;

[0017] Step 4: Prepare a photothermal energy storage super-hydrophobic anti-icing coating:

[0018] The super-hydrophobic micro-nanostructured particles obtained in step 3 are mixed with an adhesive and a solvent, and stirred evenly to obtain a photothermal energy storage super-hydrophobic all-weather anti-icing coating.

[0019] Furthermore, in step 1, the mass percentages of zinc acetate, gallium nitrate, germanium tetrachloride, chromium nitrate, yttrium nitrate and deionized water are 12.62% to 13.02%, 21.54% to 22.53%, 4.62% to 4.77%, 0.23% to 0.24%, 0.13% to 0.65%, and 58.79% to 60.86%, respectively, and the sum of the above components is 100%; the concentrations of dilute hydrochloric acid and sodium hydroxide solution are both 0.1 mol / L, the pH value of the solution is adjusted to 8 to 8.5, the stirring speed is 500 to 800 rpm, the stirring time is 0.5 to 1 h, the hydrothermal treatment temperature is 180 ° C, the hydrothermal time is 4 to 5 h, the drying temperature is 50 to 60 ° C, the drying time is 8 to 12 h, and the vacuum degree is 10 -1 ~10 -2 Pa, vacuum heat treatment temperature is 800℃, and heat treatment time is 1 to 2h.

[0020] Furthermore, in step 2.1, the mass percentages of the hexadecyltrimethylammonium bromide, phase change material, deionized water, copper sulfate aqueous solution, glucose aqueous solution and sodium hydroxide solution are 1.68% to 1.96%, 1.68% to 1.96%, 19.95% to 32.61%, 18.23% to 22.67%, 21.87% to 25.63%, and 23.93% to 27.83%, respectively, and the sum of the above components is 100%; the concentration of the copper sulfate aqueous solution is 0.08 to 0.12 g / mL, the concentration of the glucose aqueous solution is 0.05 to 0.06 g / mL, and the concentration of the sodium hydroxide solution is 0.14 to 0.165 g / mL; the phase change material is any one of n-eicosane, lauric acid and stearic acid.

[0021] Furthermore, in step 2.1, the mechanical emulsification temperature is 60-70°C, the mechanical emulsification stirring speed is 400-600rpm, the emulsification time is 0.5-1h, the first water bath stirring temperature is 60-70°C, the first water bath stirring speed is 400-600rpm, the first water bath stirring time is 2-3h, the second water bath stirring temperature is 60-70°C, the second water bath stirring speed is 400-600rpm, the second water bath stirring time is 6-8h, the aging treatment temperature is 60-70°C, and the aging treatment time is 8-12h.

[0022] Furthermore, in step 2.2, the mass percentages of the Cu2O microcapsule phase change material, long afterglow nanoparticles, deionized water, thioacetamide aqueous solution, and sodium hydroxide solution are 0.96% to 0.97%, 0.72% to 1.07%, 37.43% to 39.45%, 38.86% to 39.49%, and 20.01% to 21.04%, respectively, and the total of the above components is 100%; the concentration of the thioacetamide aqueous solution is 0.011 to 0.019 g / mL, and the concentration of the sodium hydroxide solution is 0.033 to 0.040 g / mL.

[0023] Furthermore, in the step 2.2, the ultrasonic dispersion power is 100 W, the ultrasonic dispersion time is 30 to 40 min, the third water bath stirring temperature is 40 to 50 ° C, the stirring speed is 400 to 600 rpm, the stirring time is 2 to 3 h, the washing solvents used for washing are petroleum ether, deionized water and anhydrous ethanol, each washed three times, the vacuum drying temperature is 35 to 50 ° C, the vacuum degree is ≤90 kPa, and the drying time is 48 to 60 h.

[0024] Furthermore, in step 3, the mass percentages of the micro-nanostructured particles, the low surface energy modifier, and the solvent are 0.18% to 1.20%, 1.06% to 9.60%, and 89.20% to 98.76%, respectively, and the total of the above components is 100%; the low surface energy modifier is any one of dodecanethiol, stearic acid, 1H,1H,2H,2H-perfluorodecyltrichlorosilane, and octadecyltrimethoxysilane, and the solvent is one or both of acetone and ethanol.

[0025] Furthermore, in step 3, the water bath temperature is 30-60°C, the stirring speed is 300-500 rpm, the stirring time is 1-9 hours, the centrifugal speed is 6000-8000 rpm, the centrifugal time is 3-5 minutes, and the drying temperature is 50-60°C, and the drying time is 8-12 hours.

[0026] Furthermore, in step 4, the mass percentages of the super-hydrophobic micro-nanostructure particles, the adhesive and the solvent are 13.27% to 13.83%, 4.30% to 8.20%, and 77.97% to 82.43%, respectively, and the sum of the above components is 100%; the adhesive is a coating varnish, which is composed of the following chemical components by mass fraction: acrylic resin 73% to 88.5%, ethylene glycol 10% to 20%, alcohol ester twelve 1% to 5% and defoamer BYK-0240.5% to 2%; the solvent is any one of ethanol and NN dimethylformamide, the stirring speed is 200 to 300 rpm, and the stirring time is 0.5 to 1 h.

[0027] Compared with the prior art, the present invention has the following beneficial effects:

[0028] A photothermal energy storage super-hydrophobic all-weather anti-icing coating can be directly applied to surfaces such as power lines, aircraft wings, transmission towers, and roads through spraying technology, forming a photothermal energy storage super-hydrophobic all-weather anti-icing coating with a rough coral structure. The super-hydrophobic surface formed by the super-hydrophobic micro-nanostructured particles in the coating under the action of the adhesive can reduce the adhesion of droplets, increase the energy barrier for ice nucleation, and prolong the freezing time of droplets, which is the first line of defense against icing. Double-shell porous Cu2O@Cu 2y-1 S yAs a second line of defense, photothermal materials efficiently convert daytime solar energy into thermal energy through light capture, broad-spectrum light absorption, and the photothermal effect. Some of this heat heats the coating surface, melting ice / frost and preventing new ice / frost formation, while the remaining heat is stored in the built-in phase-change material for later use. Meanwhile, long-afterglow materials absorb and store light energy under daylight conditions, continuing to emit light at night or in darkness. This not only improves nighttime visibility and reduces safety hazards, but also converts the released light into heat through the photothermal material. This, together with the heat released by the phase-change material, maintains the coating surface temperature above the supercooling point of water at night, forming a third line of defense against ice and de-icing. Furthermore, some of the heat generated by nighttime photothermal heat is also captured and stored by the phase-change material, effectively mitigating ineffective heat loss and increasing the duration of heat release, thereby extending the anti-icing period at night. The photothermal energy storage super-hydrophobic all-weather anti-icing coating of the present invention integrates the advantages of multiple materials such as super-hydrophobicity, photothermal conversion, phase change heat storage and long afterglow luminescence. It realizes long-term, all-weather anti-icing / de-icing functions through a multi-level anti-icing mechanism, solving the problem of all-weather anti-icing and has important application prospects in anti-icing fields such as power transmission lines, aircraft wings and roads. DETAILED DESCRIPTION

[0029] The present invention is described in detail below with reference to specific embodiments.

[0030] The technical solution adopted by the present invention is a method for preparing a photothermal energy storage super-hydrophobic all-weather anti-icing coating, which is specifically implemented according to the following steps:

[0031] Step 1, preparation of long afterglow nanoparticles:

[0032] Dissolve zinc acetate, gallium nitrate, germanium tetrachloride, chromium nitrate and yttrium nitrate in deionized water, adjust the pH value of the solution to 8-8.5 with 0.1 mol / L dilute hydrochloric acid and 0.1 mol / L sodium hydroxide, stir thoroughly at 500-800 rpm for 0.5-1 hour, then hydrothermally treat at 180°C for 4-5 hours, wash with water after the reaction is completed and dry at 50-60°C for 8-12 hours, then place at 10 -1 ~10 -2 Pa vacuum, 800 ℃ heat treatment for 1 to 2 hours, Zn2Ga 2.98-x Y x Cr 0.02 Ge 0.75 O8 long afterglow nanoparticles.

[0033] In step 1, the mass percentages of zinc acetate, gallium nitrate, germanium tetrachloride, chromium nitrate, yttrium nitrate and deionized water are 12.62% to 13.02%, 21.54% to 22.53%, 4.62% to 4.77%, 0.23% to 0.24%, 0.13% to 0.65% and 58.79% to 60.86%, respectively, and the sum of the above components is 100%.

[0034] Step 2: In-situ modification of double-shell microcapsule phase change material:

[0035] Step 2.1, cetyltrimethylammonium bromide and phase change material are added to deionized water, mechanically emulsified at 60-70°C at a stirring speed of 400-600 rpm for 0.5-1 hour, then copper sulfate aqueous solution is added and stirred for the first time at 60-70°C at a stirring speed of 400-600 rpm for 2-3 hours, then glucose aqueous solution and sodium hydroxide solution are added dropwise, and a second water bath stirring is performed at 60-70°C at a stirring speed of 400-600 rpm for 6-8 hours, followed by aging treatment at 60-70°C for 8-12 hours to obtain Cu2O microcapsule phase change material.

[0036] The mass percentages of hexadecyltrimethylammonium bromide, phase change material, deionized water, copper sulfate aqueous solution, glucose aqueous solution and sodium hydroxide solution are 1.68%-1.96%, 1.68%-1.96%, 19.95%-32.61%, 18.23%-22.67%, 21.87%-25.63% and 23.93%-27.83%, respectively, and the total of the above components is 100%; the concentration of the copper sulfate aqueous solution is 0.08-0.12 g / mL, the concentration of the glucose aqueous solution is 0.05-0.06 g / mL, and the concentration of the sodium hydroxide solution is 0.14-0.165 g / mL; the phase change material is any one of n-eicosane, lauric acid and stearic acid.

[0037] Step 2.2, the Cu2O microcapsule phase change material and the long afterglow nanoparticles obtained in step 1 are dispersed in deionized water under an ultrasonic power of 100 W for 30 to 40 minutes, and then an aqueous solution of thioacetamide and a sodium hydroxide solution are added and stirred at 40 to 50 ° C at a stirring speed of 400 to 600 rpm for 2 to 3 hours, filtered, and washed three times with petroleum ether, deionized water and anhydrous ethanol respectively, and then dried in an oven at 35 to 50 ° C and a vacuum degree of ≤90 kPa for 48 to 60 hours to obtain Zn2Ga 2.98- x Y x Cr 0.02 Ge 0.75 O8 / double-layer Cu2O@Cu 2y-1 S y Micro-nanostructured particles.

[0038] The mass percentages of Cu2O microcapsule phase change material, long afterglow nanoparticles, deionized water, thioacetamide aqueous solution, and sodium hydroxide solution are 0.96% to 0.97%, 0.72% to 1.07%, 37.43% to 39.45%, 38.86% to 39.49%, and 20.01% to 21.04%, respectively, with the total of the above components being 100%. The concentration of the thioacetamide aqueous solution is 0.011 to 0.019 g / mL, and the concentration of the sodium hydroxide solution is 0.033 to 0.040 g / mL. Zn2Ga 2.98-x Y x Cr 0.02 Ge 0.75 O8 / double-layer Cu2O@Cu 2y-1 S y The micro-nanostructured particles include octahedral Cu2O microcapsule core, three-dimensional intersecting Cu 2y-1 S y Nanosheet shell and the gap between them, Zn2Ga 2.98-x Y x Cr 0.02 Ge 0.75 O8 is evenly distributed on the nanosheets of the shell. Zn2Ga 2.98- x Y x Cr 0.02 Ge 0.75 O8 / double-layer Cu2O@Cu 2y-1 S y In the micro-nanostructured particles, 0.01≤x≤0.05, y=1, 4, 5. Phase change materials are encapsulated in Cu2O@Cu 2y-1 S y Inside the microcapsule.

[0039] Step 3: Low surface energy modification of composite particles:

[0040] The micro-nanostructured particles obtained in step 2 are immersed in a mixed solution consisting of a low surface energy modifier and a solvent, stirred in a water bath at 30-60°C at a stirring speed of 300-500 rpm for 1-9 hours, then centrifuged at a speed of 6000-8000 rpm for 3-5 minutes, washed, and dried at 50-60°C for 8-12 hours to obtain superhydrophobic micro-nanostructured particles.

[0041] The mass percentages of the micro-nanostructured particles, the low surface energy modifier, and the solvent are 0.18% to 1.20%, 1.06% to 9.60%, and 89.20% to 98.76%, respectively, with the total of the above components being 100%. The low surface energy modifier is any one of dodecanethiol, stearic acid, 1H,1H,2H,2H-perfluorodecyltrichlorosilane, and octadecyltrimethoxysilane. The solvent is one or both of acetone and ethanol.

[0042] Step 4: Prepare a photothermal energy storage super-hydrophobic anti-icing coating:

[0043] The super-hydrophobic micro-nanostructured particles obtained in step 3 are mixed with an adhesive and a solvent, and stirred at a stirring speed of 200 to 300 rpm for 0.5 to 1 hour to obtain a photothermal energy storage super-hydrophobic all-weather anti-icing coating.

[0044] Among them, the mass percentages of superhydrophobic micro-nanostructured particles, adhesive and solvent are 13.27% to 13.83%, 4.30% to 8.20% and 77.97% to 82.43% respectively, and the sum of the above components is 100%; the adhesive is a coating varnish, which is composed of the following chemical components in mass fractions: acrylic resin 73% to 88.5%, ethylene glycol 10% to 20%, alcohol ester 1% to 5% and defoamer BYK-024 0.5% to 2%; the solvent is any one of ethanol and NN dimethylformamide.

[0045] The present invention provides a method for preparing a photothermal energy storage super-hydrophobic all-weather anti-icing coating. Long-afterglow nanoparticles are prepared by hydrothermal reaction and vacuum heat treatment, which serve the purpose of absorbing light and storing energy during the day and continuously emitting light at night. Through the water-in-oil micelle emulsion method, in-situ etching and electrostatic adsorption, and subsequent low-surface-energy modification, super-hydrophobic double-shell photothermal micro-nanostructure particles are obtained, which have an internal encapsulated phase change material, a surface-loaded long-afterglow nanoparticle, an octahedral microcapsule core, a three-dimensionally intersecting shell of nanosheets, and a nanoporous interlayer. The particles can efficiently convert sunlight into thermal energy. While photothermal anti-icing / de-icing during the day, the phase change material is used to stably store heat and the long-afterglow particles are used to stably store light. The stored energy is released at night to increase the coating temperature to ensure continuous anti-icing at night. At the same time, a super-hydrophobic rough surface is provided to delay droplet freezing and reduce ice adhesion, thereby achieving a long-lasting and durable all-weather anti-icing / de-icing function. By adjusting the ratio of superhydrophobic micro-nanostructured particles and adhesives, the micro-nanostructured particles are prevented from being embedded in the adhesive after spraying and curing, thereby obtaining a superhydrophobic anti-icing coating with a rough coral reef-like structure, which can not only achieve better anti-icing / de-icing effects, but also improve the mechanical stability and weather resistance of the coating.

[0046] The present invention proposes a photothermal energy storage super-hydrophobic all-weather anti-icing coating that can be directly sprayed on surfaces such as power lines, aircraft wings, transmission towers, and roads to form a photothermal energy storage super-hydrophobic all-weather anti-icing coating with a rough coral structure. The super-hydrophobic surface formed by the super-hydrophobic micro-nanostructured particles in the coating under the action of the adhesive can reduce the adhesion of droplets, increase the energy barrier for ice nucleation, and prolong the freezing time of droplets, which is the first line of defense against icing. Double-shell porous Cu2O@Cu 2y-1 S yAs a second line of defense, photothermal materials efficiently convert daytime solar energy into thermal energy through light capture, broad-spectrum light absorption, and the photothermal effect. Some of this heat heats the coating surface, melting ice / frost and preventing new ice / frost formation, while the remaining heat is stored in the built-in phase-change material for later use. Meanwhile, long-afterglow materials absorb and store light energy under daylight conditions, continuing to emit light at night or in darkness. This not only improves nighttime visibility and reduces safety hazards, but also converts the released light into heat through the photothermal material. This, together with the heat released by the phase-change material, maintains the coating surface temperature above the supercooling point of water at night, forming a third line of defense against ice and de-icing. Furthermore, some of the heat generated by nighttime photothermal heat is also captured and stored by the phase-change material, effectively mitigating ineffective heat loss and increasing the duration of heat release, thereby extending the anti-icing period at night. The photothermal energy storage super-hydrophobic all-weather anti-icing coating of the present invention integrates the advantages of multiple materials such as super-hydrophobicity, photothermal conversion, phase change heat storage and long afterglow luminescence. It realizes long-term, all-weather anti-icing / de-icing functions through a multi-level anti-icing mechanism, solving the problem of all-weather anti-icing and has important application prospects in anti-icing fields such as power transmission lines, aircraft wings and roads.

[0047] Example 1

[0048] 4.39 g of zinc acetate, 7.60 g of gallium nitrate, 1.61 g of germanium tetrachloride, 0.08 g of chromium nitrate and 0.04 g of yttrium nitrate were dissolved in 20 mL of deionized water. The pH value of the solution was adjusted to 8.3 with 0.1 mol / L of dilute hydrochloric acid and 0.1 mol / L of sodium hydroxide, and then stirred at 500 rpm for 1 h. The mixture was then hydrothermally treated at 180 ° C for 4 h. After the reaction was completed, the mixture was washed with water and dried at 50 ° C for 12 h, and then placed in a 10 -1 Pa vacuum, 800 ℃ heat treatment for 1h, Zn2Ga 2.98-x Y x Cr 0.02 Ge 0.75 O8 long afterglow nanoparticles.

[0049] 2.4 g of hexadecyltrimethylammonium bromide and 2.4 g of n-eicosane were added to 40 mL of deionized water, and mechanically emulsified at 60°C at a stirring speed of 400 rpm for 1 hour. Then, 30 mL of an aqueous solution containing 2.4 g of copper sulfate was added and stirred for the first time at 60°C at a stirring speed of 400 rpm for 3 hours. Then, 30 mL of an aqueous solution containing 1.5 g of glucose and 30 mL of an aqueous solution containing 4.2 g of sodium hydroxide were added dropwise, and a second water bath stirring was carried out at 60°C at a stirring speed of 400 rpm for 8 hours. Then, the mixture was aged at 60°C for 12 hours to obtain a Cu2O microcapsule phase change material. 0.5 g Cu2O and 0.55 g long afterglow nanoparticles were dispersed in 20 mL deionized water under ultrasonic power of 100 W for 30 min, and then 20 mL of an aqueous solution containing 0.225 g thioacetamide and 10 mL of an aqueous solution containing 0.35 g sodium hydroxide were added and stirred at 40 ° C at a stirring speed of 400 rpm for 3 h. The mixture was filtered and washed three times with petroleum ether, deionized water and anhydrous ethanol respectively, and then dried in an oven at 35 ° C and a vacuum degree of ≤90 kPa for 60 h to obtain Zn2Ga 2.98- x Y x Cr 0.02 Ge 0.75 O8 / double-layer Cu2O@Cu 2y-1 S y Micro-nanostructured particles.

[0050] 0.141 g of micro-nanostructured particles were immersed in a mixed solution consisting of 0.845 g of dodecanethiol and 78.9 g of ethanol, stirred in a water bath at 30°C at a stirring speed of 300 rpm for 1 hour, then centrifuged at 6000 rpm for 5 minutes, washed, and dried at 50°C for 12 hours to obtain superhydrophobic micro-nanostructured particles.

[0051] 2g of superhydrophobic micro-nanostructured particles, 0.946g of coating varnish and 11.835g of ethanol were mixed and stirred at a stirring speed of 200 rpm for 1 hour to obtain a photothermal energy storage superhydrophobic all-weather anti-icing coating.

[0052] Example 2

[0053] 4.39 g of zinc acetate, 7.49 g of gallium nitrate, 1.61 g of germanium tetrachloride, 0.08 g of chromium nitrate and 0.22 g of yttrium nitrate were dissolved in 20 mL of deionized water. The pH value of the solution was adjusted to 8 with 0.1 mol / L of dilute hydrochloric acid and 0.1 mol / L of sodium hydroxide, and then the solution was stirred at 800 rpm for 0.5 h. The solution was then hydrothermally treated at 180 ° C for 5 h. After the reaction, the solution was washed with water and dried at 60 ° C for 8 h, and then placed in a 10 -2 Pa vacuum, 800 ℃ heat treatment for 2h, Zn2Ga 2.98-x Yx Cr 0.02 Ge 0.75 O8 long afterglow nanoparticles.

[0054] 2.84 g of hexadecyltrimethylammonium bromide and 2.84 g of lauric acid were added to 40 mL of deionized water, and mechanically emulsified at 70°C with a stirring speed of 600 rpm for 0.5 h. Then, 30 mL of an aqueous solution containing 2.84 g of copper sulfate was added and stirred for the first time at 70°C with a stirring speed of 600 rpm for 2 h. Then, 30 mL of an aqueous solution containing 1.77 g of glucose and 30 mL of an aqueous solution containing 4.96 g of sodium hydroxide were added dropwise, and a second water bath stirring was carried out at 70°C with a stirring speed of 600 rpm for 6 h. Then, the product was aged at 70°C for 8 h to obtain a Cu2O microcapsule phase change material. 0.5 g Cu2O and 0.55 g long afterglow nanoparticles were dispersed in 20 mL deionized water under ultrasonic power of 100 W for 40 min, and then 20 mL of an aqueous solution containing 0.376 g thioacetamide and 10 mL of an aqueous solution containing 0.4 g sodium hydroxide were added and stirred at 50 ° C at a stirring speed of 600 rpm for 2 h. The mixture was filtered and washed three times with petroleum ether, deionized water and anhydrous ethanol respectively, and then dried in an oven at 50 ° C and a vacuum degree of ≤90 kPa for 48 h to obtain Zn2Ga 2.98-x Y x Cr 0.02 Ge 0.75 O8 / double-layer Cu2O@Cu 2y-1 S y Micro-nanostructured particles.

[0055] 0.425 g of micro-nanostructured particles were immersed in a mixed solution consisting of 3.4 g of 1H, 1H, 2H, 2H-perfluorodecyltrichlorosilane, 15.78 g of ethanol and 15.82 g of acetone, stirred in a water bath at 60°C at a stirring speed of 500 rpm for 3 h, then centrifuged at 8000 rpm for 3 min, washed, and dried at 60°C for 8 h to obtain superhydrophobic micro-nanostructured particles.

[0056] 2g of superhydrophobic micro-nanostructured particles, 0.622g of coating varnish and 11.835g of ethanol were mixed and stirred at a stirring speed of 300 rpm for 0.5h to obtain a photothermal energy storage superhydrophobic all-weather anti-icing coating.

[0057] Example 3

[0058] 4.39 g of zinc acetate, 7.49 g of gallium nitrate, 1.61 g of germanium tetrachloride, 0.08 g of chromium nitrate and 0.05 g of yttrium nitrate were dissolved in 21 mL of deionized water. The pH value of the solution was adjusted to 8.5 with 0.1 mol / L of dilute hydrochloric acid and 0.1 mol / L of sodium hydroxide, and then the solution was stirred at 600 rpm for 0.5 h. The solution was then hydrothermally treated at 180 ° C for 4.5 h. After the reaction, the solution was washed with water and dried at 55 ° C for 10 h, and then placed in a 10 -2 Pa vacuum, 800 ℃ heat treatment for 1.5h, Zn2Ga 2.98-x Y x Cr 0.02 Ge 0.75 O8 long afterglow nanoparticles.

[0059] 2.4 g of hexadecyltrimethylammonium bromide and 2.4 g of stearic acid were added to 30 mL of deionized water, and mechanically emulsified at 65°C with a stirring speed of 500 rpm for 0.5 h. Then, 20 mL of an aqueous solution containing 2.4 g of copper sulfate was added and stirred for the first time at 65°C with a stirring speed of 500 rpm for 2.5 h. Then, 30 mL of an aqueous solution containing 1.5 g of glucose and 30 mL of an aqueous solution containing 4.2 g of sodium hydroxide were added dropwise, and a second water bath stirring was carried out at 65°C with a stirring speed of 500 rpm for 7 h. Then, the mixture was aged at 65°C for 10 h to obtain a Cu2O microcapsule phase change material. 0.5 g Cu2O and 0.375 g long afterglow nanoparticles were dispersed in 20 mL deionized water under ultrasonic power of 100 W for 35 min, and then 20 mL of an aqueous solution containing 0.229 g thioacetamide and 10.6 mL of an aqueous solution containing 0.354 g sodium hydroxide were added and stirred at 45 ° C with a stirring speed of 500 rpm for 2.5 h. The mixture was filtered and washed three times with petroleum ether, deionized water and anhydrous ethanol respectively, and then dried in an oven at 40 ° C and a vacuum degree of ≤90 kPa for 55 h to obtain Zn2Ga 2.98-x Y x Cr 0.02 Ge 0.75 O8 / double-layer Cu2O@Cu 2y-1 S y Micro-nanostructured particles.

[0060] 0.5 g of micro-nanostructured particles were immersed in a mixed solution consisting of 2.94 g of octadecyltrimethoxysilane and 273 g of ethanol, stirred in a water bath at 50°C at a stirring speed of 400 rpm for 9 hours, then centrifuged at 7000 rpm for 4 minutes, washed, and dried at 55°C for 10 hours to obtain superhydrophobic micro-nanostructured particles.

[0061] 2g of superhydrophobic micro-nanostructured particles, 0.648g of coating varnish and 12.424g of NN dimethylformamide were mixed and stirred at a stirring speed of 300 rpm for 0.5h to obtain a photothermal energy storage superhydrophobic all-weather anti-icing coating.

[0062] Example 4

[0063] 4.39 g of zinc acetate, 7.60 g of gallium nitrate, 1.61 g of germanium tetrachloride, 0.08 g of chromium nitrate and 0.22 g of yttrium nitrate were dissolved in 19.8 mL of deionized water. The pH value of the solution was adjusted to 8.3 with 0.1 mol / L of dilute hydrochloric acid and 0.1 mol / L of sodium hydroxide, and then stirred at 800 rpm for 0.5 h. The solution was then hydrothermally treated at 180 ° C for 5 h. After the reaction was completed, the solution was washed with water and dried at 60 ° C for 8 h, and then placed in a 10 -2 Pa vacuum, 800 ℃ heat treatment for 2h, Zn2Ga 2.98-x Y x Cr 0.02 Ge 0.75 O8 long afterglow nanoparticles.

[0064] 2.4 g of hexadecyltrimethylammonium bromide and 2.4 g of n-eicosane were added to 40 mL of deionized water, and mechanically emulsified at 60°C at a stirring speed of 400 rpm for 1 hour. Then, 30 mL of an aqueous solution containing 2.4 g of copper sulfate was added and stirred for the first time at 60°C at a stirring speed of 400 rpm for 3 hours. Then, 30 mL of an aqueous solution containing 1.5 g of glucose and 30 mL of an aqueous solution containing 4.2 g of sodium hydroxide were added dropwise, and a second water bath stirring was carried out at 60°C at a stirring speed of 400 rpm for 8 hours. Then, the mixture was aged at 60°C for 12 hours to obtain a Cu2O microcapsule phase change material. 0.5 g Cu2O and 0.55 g long afterglow nanoparticles were dispersed in 20 mL deionized water under ultrasonic power of 100 W for 40 min, and then 20 mL of an aqueous solution containing 0.521 g thioacetamide and 10 mL of an aqueous solution containing 0.4 g sodium hydroxide were added and stirred at 40 ° C at a stirring speed of 600 rpm for 3 h. The mixture was filtered and washed three times with petroleum ether, deionized water and anhydrous ethanol respectively, and then dried in an oven at 35 ° C and a vacuum degree of ≤90 kPa for 60 h to obtain Zn2Ga 2.98- x Y x Cr 0.02 Ge 0.75 O8 / double-layer Cu2O@Cu 2y-1 S y Micro-nanostructured particles.

[0065] 0.71 g of micro-nanostructured particles were immersed in a mixed solution consisting of 5.68 g of stearic acid and 52.78 g of ethanol, stirred in a water bath at 50°C at a stirring speed of 400 rpm for 2 h, then centrifuged at 8000 rpm for 4 min, washed, and dried at 55°C for 10 h to obtain superhydrophobic micro-nanostructured particles.

[0066] 2g of superhydrophobic micro-nanostructured particles were mixed with 1.186g of coating varnish and 11.275g of ethanol, and stirred at a stirring speed of 300 rpm for 0.5h to obtain a photothermal energy storage superhydrophobic all-weather anti-icing coating.

[0067] Place the coating sample in a temperature-controlled container and control the temperature of the container to -10°C. Then, use an air humidifier (relative humidity 99%, water consumption 0.04L / h) to generate water spray in the temperature-controlled container. When the coating surface becomes opaque or frosted, record the frost delay time. After the coating is frozen, use a constant light intensity of 1000W / m 2 The xenon lamp simulates sunlight to illuminate the coating and test its surface temperature.

[0068] Table 1 compares the performance of polydimethylsiloxane coatings, activated carbon / copper sulfide-polydimethylsiloxane coatings, tetradecane@expanded graphite-polydimethylsiloxane coatings, and photothermal energy storage super-hydrophobic all-weather anti-icing coatings prepared in Examples 1 and 2. As can be seen from the table, the polydimethylsiloxane coating has poor hydrophobicity, a very short delay time for droplet freezing at low temperatures, and does not have a photothermal deicing function. After being placed in the dark under low temperature and high humidity conditions for 12 hours, the surface is completely covered with ice, and the anti-icing effect is poor. The activated carbon / copper sulfide-polydimethylsiloxane coating has super-hydrophobicity, can delay ice formation, and can also perform photothermal deicing, but the photothermal conversion efficiency is low and it cannot actively deicer in the dark. The tetradecane@expanded graphite-polydimethylsiloxane coating also has a super-hydrophobic surface and photothermal deicing effect, but the effect of delaying droplet freezing is poor. Although it can use phase change materials to store heat for nighttime anti-icing / deicing, the stored heat release time is too short, making it difficult to maintain anti-icing performance at night. Compared with the above-mentioned coatings, the coatings prepared in Examples 1 and 2 have superhydrophobicity and high light conversion efficiency, which can significantly delay ice formation. Thanks to the synergistic effect of heat storage of phase change materials and light storage of long afterglow materials, the coatings can maintain a temperature above freezing for a long time under dark conditions, and have an all-weather anti-icing effect.

[0069] Table 1

[0070]

[0071] The above description of the present invention is merely a partial embodiment, and the present invention is not limited to the above embodiments. The above embodiments are illustrative and not restrictive. All specific extensions of the materials and methods of the present invention that do not depart from the scope of the present invention and the scope of the claims are within the scope of protection of the present invention.

Claims

1. A method for preparing a photothermal energy storage super-hydrophobic all-weather anti-icing coating, characterized in that: Please follow the steps below to implement it: Step 1, preparation of long afterglow nanoparticles: Zinc acetate, gallium nitrate, germanium tetrachloride, chromium nitrate and yttrium nitrate were dissolved in deionized water, the pH value of the solution was adjusted with dilute hydrochloric acid and sodium hydroxide, and then fully stirred, followed by hydrothermal treatment. After the reaction was completed, the solution was washed with water and dried, and then vacuum heat treated to obtain Zn2Ga 2.98-x Y x Cr 0.02 Ge 0.75 O8 long afterglow nanoparticles; Step 2: In-situ modification of double-shell microcapsule phase change material: Step 2.1, adding hexadecyltrimethylammonium bromide and a phase change material to deionized water, mechanically emulsifying, adding a copper sulfate aqueous solution and stirring in a water bath for the first time, then dropping a glucose aqueous solution and a sodium hydroxide solution, stirring in a water bath for the second time and aging treatment to obtain a Cu2O microcapsule phase change material; Step 2.2: Ultrasonic dispersion of Cu2O microcapsule phase change material and long afterglow nanoparticles obtained in step 1 in deionized water, adding thioacetamide aqueous solution and sodium hydroxide solution, stirring and etching for the third time, filtering, washing, and vacuum drying to obtain Zn2Ga 2.98-x Y x Cr 0.02 Ge 0.75 O8 / double-layer Cu2O@Cu 2y-1 S y Micro-nanostructured particles; Step 3: Low surface energy modification of composite particles: Immersing the micro-nanostructured particles obtained in step 2 in a mixed solution consisting of a low surface energy modifier and a solvent, stirring in a water bath, centrifuging, washing, and drying to obtain superhydrophobic micro-nanostructured particles; Step 4: Prepare a photothermal energy storage super-hydrophobic anti-icing coating: The super-hydrophobic micro-nanostructured particles obtained in step 3 are mixed with an adhesive and a solvent, and stirred evenly to obtain a photothermal energy storage super-hydrophobic all-weather anti-icing coating.

2. The method for preparing a photothermal energy storage super-hydrophobic all-weather anti-icing coating according to claim 1, characterized in that: In step 1, the mass percentages of zinc acetate, gallium nitrate, germanium tetrachloride, chromium nitrate, yttrium nitrate and deionized water are 12.62% to 13.02%, 21.54% to 22.53%, 4.62% to 4.77%, 0.23% to 0.24%, 0.13% to 0.65%, and 58.79% to 60.86%, respectively, and the sum of the above components is 100%; the concentrations of dilute hydrochloric acid and sodium hydroxide solution are both 0.1 mol / L, the pH value of the solution is adjusted to 8 to 8.5, the stirring speed is 500 to 800 rpm, the stirring time is 0.5 to 1 h, the hydrothermal treatment temperature is 180 ° C, the hydrothermal time is 4 to 5 h, the drying temperature is 50 to 60 ° C, the drying time is 8 to 12 h, and the vacuum degree is 10 -1 ~10 -2 Pa, vacuum heat treatment temperature is 800℃, and heat treatment time is 1 to 2h.

3. The method for preparing a photothermal energy storage super-hydrophobic all-weather anti-icing coating according to claim 1, characterized in that: In step 2.1, the mass percentages of the hexadecyltrimethylammonium bromide, phase change material, deionized water, copper sulfate aqueous solution, glucose aqueous solution and sodium hydroxide solution are 1.68% to 1.96%, 1.68% to 1.96%, 19.95% to 32.61%, 18.23% to 22.67%, 21.87% to 25.63%, and 23.93% to 27.83%, respectively, and the sum of the above components is 100%; the concentration of the copper sulfate aqueous solution is 0.08 to 0.12 g / mL, the concentration of the glucose aqueous solution is 0.05 to 0.06 g / mL, and the concentration of the sodium hydroxide solution is 0.14 to 0.165 g / mL; the phase change material is any one of n-eicosane, lauric acid and stearic acid.

4. The method for preparing a photothermal energy storage super-hydrophobic all-weather anti-icing coating according to claim 1, characterized in that: In step 2.1, the mechanical emulsification temperature is 60-70°C, the mechanical emulsification stirring speed is 400-600rpm, the emulsification time is 0.5-1h, the first water bath stirring temperature is 60-70°C, the first water bath stirring speed is 400-600rpm, the first water bath stirring time is 2-3h, the second water bath stirring temperature is 60-70°C, the second water bath stirring speed is 400-600rpm, the second water bath stirring time is 6-8h, the aging treatment temperature is 60-70°C, and the aging treatment time is 8-12h.

5. The method for preparing a photothermal energy storage super-hydrophobic all-weather anti-icing coating according to claim 1, characterized in that: In the step 2.2, the mass percentages of the Cu2O microcapsule phase change material, the long afterglow nanoparticles, the deionized water, the thioacetamide aqueous solution, and the sodium hydroxide solution are 0.96% to 0.97%, 0.72% to 1.07%, 37.43% to 39.45%, 38.86% to 39.49%, and 20.01% to 21.04%, respectively, and the total of the above components is 100%; the concentration of the thioacetamide aqueous solution is 0.011 to 0.019 g / mL, and the concentration of the sodium hydroxide solution is 0.033 to 0.040 g / mL.

6. The method for preparing a photothermal energy storage super-hydrophobic all-weather anti-icing coating according to claim 1, characterized in that: In the step 2.2, the ultrasonic dispersion power is 100 W, the ultrasonic dispersion time is 30 to 40 minutes, the third water bath stirring temperature is 40 to 50° C., the stirring speed is 400 to 600 rpm, the stirring time is 2 to 3 hours, the washing solvents used for washing are petroleum ether, deionized water and anhydrous ethanol, each washing is done three times, the vacuum drying temperature is 35 to 50° C., the vacuum degree is ≤90 kPa, and the drying time is 48 to 60 hours.

7. The method for preparing a photothermal energy storage super-hydrophobic all-weather anti-icing coating according to claim 1, characterized in that: In step 3, the mass percentages of the micro-nanostructured particles, the low surface energy modifier, and the solvent are 0.18% to 1.20%, 1.06% to 9.60%, and 89.20% to 98.76%, respectively, and the total of the above components is 100%; the low surface energy modifier is any one of dodecanethiol, stearic acid, 1H,1H,2H,2H-perfluorodecyltrichlorosilane, and octadecyltrimethoxysilane, and the solvent is one or both of acetone and ethanol.

8. The method for preparing a photothermal energy storage super-hydrophobic all-weather anti-icing coating according to claim 1, characterized in that: In step 3, the water bath temperature is 30-60° C., the stirring speed is 300-500 rpm, the stirring time is 1-9 h, the centrifugal speed is 6000-8000 rpm, and the centrifugal time is 3-5 min; the drying temperature is 50-60° C., and the drying time is 8-12 h.

9. The method for preparing a photothermal energy storage super-hydrophobic all-weather anti-icing coating according to claim 1, characterized in that: In step 4, the mass percentages of the superhydrophobic micro-nanostructured particles, the binder, and the solvent are 13.27% to 13.83%, 4.30% to 8.20%, and 77.97% to 82.43%, respectively, and the sum of the above components is 100%; The adhesive is a coating varnish, which is composed of the following chemical components in mass fraction: 73% to 88.5% of acrylic resin, 10% to 20% of ethylene glycol, 1% to 5% of alcohol ester and 0.5% to 2% of defoaming agent BYK-024; the solvent is any one of ethanol and NN dimethylformamide, the stirring speed is 200 to 300 rpm, and the stirring time is 0.5 to 1 hour.

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