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

Abstract

The invention discloses a preparation method of a photo-thermal energy storage super-hydrophobic all-weather anti-icing coating. The preparation method comprises the following steps: step 1, preparing long afterglow nanoparticles; step 2, performing in-situ modification on a double-shell microcapsule phase change material by using the long afterglow nanoparticles; step 3, performing low surface energy modification treatment on composite particles; according to the anti-icing coating prepared by the invention, icing is delayed by virtue of a super-hydrophobic surface formed by the super-hydrophobic micro-nano structure particles; solar energy is efficiently converted into heat energy through the photo-thermal material, ice is prevented instantly, and residual heat is stored in the phase-change material; the long-afterglow material is used for storing sunlight for night photo-thermal conversion, and the stored heat released by the phase-change material is combined to jointly realize night long-acting ice prevention and removal; all-weather effective anti-icing is achieved through a multi-layer anti-icing mechanism, the problem that an existing coating is poor in all-weather anti-icing / deicing effect under the low-temperature and high-humidity condition is solved, and the coating has important application prospects in the anti-icing field of power transmission lines, aircraft wings and the like.

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, low temperature and high humidity often occur in the coastal areas of southern my country, the Yangtze River Basin and its south, and other areas, which are prone to ice accumulation. Ice accumulation will have a significant impact on the operational reliability of aircraft, power grids, outdoor equipment, etc., and may even cause economic losses and safety accidents. Traditional deicing technologies, including hot air, electric heating, anticoagulants, mechanical vibration, etc., have the disadvantages of high cost, high energy consumption, environmental pollution, and low efficiency. In this context, the anti-icing coating strategy has attracted widespread attention from researchers. At present, 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 photothermal effects 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, and it is difficult to achieve all-weather anti-icing / deicing effects. Organic phase change materials are considered to be a solution to extend anti-icing performance due to their high latent heat and adjustable phase change temperature range. 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 the 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 continuous heat release time is relatively short and it is difficult to cover the entire night cycle. Long afterglow material is a functional material that continues to emit light for a long time in the visible or near-infrared region after being excited by energy such as ultraviolet light and visible-near-infrared light. As a light storage material combined with photothermal material, 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.) used copper sulfide loaded activated biochar as photoelectric material, polydimethylsiloxane as hydrophobic component, and thermal expansion microspheres as foaming agent to construct an anti-icing / deicing coating integrating thermal insulation, superhydrophobicity, and light / electrothermal effect, which showed excellent passive anti-icing and active deicing effects. However, the coating can only be deiced by 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 mixedsuperhydrophobic coatings[J], Advanced Materials, 2024, 36, 3, 2310312.) Designed with Cu 2 O is the first layer, three-dimensional Cu 2-x S is the second layer of double-shell octahedral microcapsule phase change material, and it is combined with the hydrolysis and polycondensation product of octadecyltrichlorosilane to prepare a multifunctional photothermal phase change super-hydrophobic composite coating, which integrates photothermal effect, phase change heat storage and super-hydrophobicity, and has excellent anti-icing performance under low temperature and high humidity conditions. However, the heat release time after the phase change material in the coating is too short, and the anti-icing performance at night is difficult to maintain for a long time.

[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 on the photothermal absorption and conversion carrier, and 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 keep the surface temperature of the composite material constant 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, and it cannot prevent / de-ice for a long time at night.

[0006] The Chinese patent "A self-regulating photothermal anti-icing and de-icing coating and coating" (application number: CN202310000344.1, authorization announcement number: CN115873490B, announcement date: 2024.03.12) discloses a self-regulating photothermal anti-icing and de-icing coating and coating, which is composed of a resin prepolymer and a thermochromic dye microcapsule, and can self-regulate the photothermal conversion performance according to the ambient temperature. It is dark at low temperatures, has high photothermal conversion performance, and can absorb heat and release heat through phase change energy to achieve anti-icing and de-icing functions. However, the aging time of the thermochromic dye microcapsules is relatively short, and the heat release time after heat storage is short, which cannot guarantee the 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 the solution was 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 Zn 2 Ga 2.98-x Y x Cr 0.02 Ge 0.75 O 8 Long-lasting nanoparticles;

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

[0013] Step 2.1, adding hexadecyltrimethylammonium bromide and phase change material into deionized water, after mechanical emulsification, adding copper sulfate aqueous solution and stirring in a water bath for the first time, then dropping glucose aqueous solution and sodium hydroxide solution, stirring in a water bath for the second time and aging treatment, to obtain Cu 2 O microencapsulated phase change materials;

[0014] Step 2.2, Cu 2 The O microcapsule phase change material and the long afterglow nanoparticles obtained in step 1 were ultrasonically dispersed in deionized water, and then stirred and etched for the third time after adding thioacetamide aqueous solution and sodium hydroxide solution, filtered, washed, and vacuum dried to obtain Zn 2 Ga 2.98-x Y x Cr 0.02 Ge 0.75 O 8 / Double-layer Cu 2 O@Cu 2y-1 S y Micro-nano structured particles;

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

[0016] The micro-nano structured 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, centrifuged, washed, and dried to obtain super-hydrophobic micro-nano structured particles;

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

[0018] The super-hydrophobic micro-nano structure 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] Further, in step 1, the mass percentages of the 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 the dilute hydrochloric acid and sodium hydroxide solutions 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, the vacuum heat treatment temperature is 800℃, and the 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, Cu 2 The mass percentages of the O 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%, 20.01% to 21.04%, respectively, and the sum 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 washing is performed 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 sum 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, 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-nano structure 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 in mass fractions: 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 the surfaces of power lines, aircraft wings, transmission towers, roads, etc. through spraying technology 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-nano structure particles in the coating under the action of the adhesive can reduce the adhesion of droplets, increase the energy barrier of ice nucleation, and prolong the freezing time of droplets. It is the first line of defense against icing. Double-shell porous Cu 2 O@Cu 2y-1 S yAs the second line of defense, photothermal materials efficiently convert daytime solar energy into thermal energy through light capture effect, wide-spectrum light absorption energy and photothermal effect. Part of the heat heats the coating surface to melt ice / frost and prevent new ice / frost from forming, and the other part of the heat is stored in the built-in phase change material for subsequent use. At the same time, long afterglow materials absorb and store light energy under light conditions, and continue to emit light at night or in dark conditions, which can not only improve nighttime visibility and reduce safety hazards, but also convert the released light into heat through photothermal materials, and together with the heat released by the phase change material, maintain the surface temperature of the coating at night above the supercooling point of water, forming the third line of defense against / de-icing. In addition, part of the heat generated by photothermal at night is also captured and stored by the phase change material, which effectively slows down the ineffective loss of heat and increases the continuous release time of heat, thereby extending the anti-icing time 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, and 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 transmission lines, aircraft wings, and roads. DETAILED DESCRIPTION

[0029] The present invention is described in detail below in conjunction with specific implementation modes.

[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 the solution at 500-800 rpm for 0.5-1 h, and then hydrothermally treat at 180 ° C for 4-5 h. After the reaction is completed, wash with water and dry at 50-60 ° C for 8-12 h, and then place at 10 -1 ~10 -2 Pa vacuum, 800℃ heat treatment for 1-2h, Zn 2 Ga 2.98-x Y x Cr 0.02 Ge 0.75 O 8 Long-lasting 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%, 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, adding hexadecyltrimethylammonium bromide and phase change material into deionized water, mechanically emulsifying at 60-70°C with a stirring speed of 400-600 rpm for 0.5-1h, adding copper sulfate aqueous solution and stirring at 60-70°C with a stirring speed of 400-600 rpm for a first stirring for 2-3h, then dropping glucose aqueous solution and sodium hydroxide solution, stirring at 60-70°C with a stirring speed of 400-600 rpm for a second water bath for 6-8h, and then aging treatment at 60-70°C for 8-12h to obtain Cu 2 O Microencapsulated phase change materials.

[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%, 23.93%-27.83%, respectively, and the sum of the above components is 100%; the concentration of copper sulfate aqueous solution is 0.08-0.12 g / mL, the concentration of glucose aqueous solution is 0.05-0.06 g / mL, and the concentration of 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, Cu 2 The O microcapsule phase change material and the long afterglow nanoparticles obtained in step 1 are dispersed in deionized water by ultrasonication at an ultrasonic power of 100 W for 30 to 40 min, and then thioacetamide aqueous solution and 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 h, 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 h to obtain Zn 2 Ga 2.98- x Y x Cr 0.02 Ge 0.75 O 8 / Double-layer Cu 2O@Cu 2y-1 S y Micro-nanostructured particles.

[0038] Cu 2 The mass percentages of the O 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 sum 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. Zn 2 Ga 2.98-x Y x Cr 0.02 Ge 0.75 O 8 / Double-layer Cu 2 O@Cu 2y-1 S y Micro-nanostructured particles include octahedral Cu 2 O microcapsule core, three-dimensional intersecting Cu 2y-1 S y Nanosheet shell and the gap between them, Zn 2 Ga 2.98-x Y x Cr 0.02 Ge 0.75 O 8 Evenly distributed on the nanosheets of the shell. Zn 2 Ga 2.98- x Y x Cr 0.02 Ge 0.75 O 8 / Double-layer Cu 2 O@Cu 2y-1 S y In the micro-nano structure particles, 0.01≤x≤0.05, y=1, 4, 5. Phase change material is encapsulated in Cu 2 O@Cu 2y-1 S y Inside the microcapsule.

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

[0040] The micro-nano structured 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 to 60° C. at a stirring speed of 300 to 500 rpm for 1 to 9 hours, then centrifuged at a speed of 6000 to 8000 rpm for 3 to 5 minutes, washed, and dried at 50 to 60° C. for 8 to 12 hours to obtain superhydrophobic micro-nano structured particles.

[0041] The mass percentages of the micro-nano structure 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 sum 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. The solvent is one or two of acetone and ethanol.

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

[0043] The super-hydrophobic micro-nano structure 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-nanostructure particles, adhesives and solvents 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 dodecahydrate 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 discloses a method for preparing a photothermal energy storage super-hydrophobic all-weather anti-icing coating, wherein long afterglow nanoparticles are prepared by hydrothermal reaction and vacuum heat treatment, so as to achieve 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, a super-hydrophobic double-shell photothermal micro-nanostructure particle with internally encapsulated phase change material, surface-loaded long afterglow nanoparticles, and having an octahedral microcapsule inner core, a shell with three-dimensional intersection of nanosheets, and a nanoporous interlayer is obtained, which can efficiently convert sunlight into thermal energy, and while preventing / deicing during the day, phase change materials are used to stably store heat and long afterglow particles are used to stably store light, and the stored energy is released at night to increase the coating temperature to ensure continuous anti-icing at night, and a super-hydrophobic rough surface is provided to delay droplet freezing and reduce ice adhesion, so as to achieve a long-lasting and durable all-weather anti-icing / deicing function. By adjusting the ratio of superhydrophobic micro-nanostructure particles and adhesive, the micro-nanostructure particles can be prevented from embedding 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 effect, 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, which can be directly sprayed on the surfaces of transmission lines, aircraft wings, transmission towers, roads, etc., 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-nano structure particles in the coating under the action of the adhesive can reduce the adhesion of droplets, increase the energy barrier of ice nucleation, and prolong the freezing time of droplets, which is the first line of defense against icing. Double-shell porous Cu 2 O@Cu 2y-1 S y As the second line of defense, photothermal materials efficiently convert daytime solar energy into thermal energy through light capture effect, wide-spectrum light absorption energy and photothermal effect. Part of the heat heats the coating surface to melt ice / frost and prevent new ice / frost from forming, and the other part of the heat is stored in the built-in phase change material for subsequent use. At the same time, long afterglow materials absorb and store light energy under light conditions, and continue to emit light at night or in dark conditions, which can not only improve nighttime visibility and reduce safety hazards, but also convert the released light into heat through photothermal materials, and together with the heat released by the phase change material, maintain the surface temperature of the coating at night above the supercooling point of water, forming the third line of defense against / de-icing. In addition, part of the heat generated by photothermal at night is also captured and stored by the phase change material, which effectively slows down the ineffective loss of heat and increases the continuous release time of heat, thereby extending the anti-icing time 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, and 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 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 solution pH 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, followed by hydrothermal treatment at 180 ° C for 4 h. After the reaction was completed, the solution was washed with water and dried at 50 ° C for 12 h, and then placed at 10 -1 Pa vacuum, 800℃ heat treatment for 1h, Zn 2 Ga 2.98-x Y x Cr 0.02 Ge 0.75 O 8 Long-lasting 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 h. 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 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 stirred in a water bath for a second time at 60° C. at a stirring speed of 400 rpm for 8 h. Then, an aging treatment was performed at 60° C. for 12 h to obtain Cu 2 O microcapsule phase change material. 0.5g Cu 2 O and 0.55 g of long afterglow nanoparticles were dispersed in 20 mL of deionized water under an ultrasonic power of 100 W for 30 min, and then 20 mL of an aqueous solution containing 0.225 g of thioacetamide and 10 mL of an aqueous solution containing 0.35 g of sodium hydroxide were added, and the mixture was stirred and etched at 40 ° C at a stirring speed of 400 rpm for 3 h, 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 Zn 2 Ga 2.98- x Y x Cr 0.02 Ge 0.75 O 8 / Double-layer Cu 2 O@Cu 2y-1 S y Micro-nanostructured particles.

[0050] 0.141 g of the 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] 2 g of super-hydrophobic micro-nanostructure particles were mixed with 0.946 g of coating varnish and 11.835 g of ethanol, and stirred at 200 rpm for 1 hour to obtain a photothermal energy storage super-hydrophobic 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 solution pH was adjusted to 8 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, followed by hydrothermal treatment 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 at 10 -2 Pa vacuum, 800℃ heat treatment for 2h, Zn 2 Ga 2.98-x Y x Cr 0.02 Ge 0.75 O 8 Long-lasting 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 at 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 at 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 stirred in a water bath for a second time at 70°C at a stirring speed of 600 rpm for 6 h, followed by aging treatment at 70°C for 8 h to obtain Cu 2 O microcapsule phase change material. 0.5g Cu 2 O and 0.55 g of long afterglow nanoparticles were dispersed in 20 mL of deionized water under an ultrasonic power of 100 W for 40 min, and then 20 mL of an aqueous solution containing 0.376 g of thioacetamide and 10 mL of an aqueous solution containing 0.4 g of sodium hydroxide were added, and the mixture was stirred and etched at 50 ° C at a stirring speed of 600 rpm for 2 h, 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 Zn 2 Ga 2.98-x Y x Cr 0.02 Ge 0.75 O 8 / Double-layer Cu 2 O@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] 2 g of super-hydrophobic micro-nanostructure particles were mixed with 0.622 g of coating varnish and 11.835 g of ethanol, and stirred at 300 rpm for 0.5 h to obtain a photothermal energy storage super-hydrophobic 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 solution pH was adjusted to 8.5 with 0.1 mol / L of dilute hydrochloric acid and 0.1 mol / L of sodium hydroxide, and then stirred at 600 rpm for 0.5 h, followed by hydrothermal treatment at 180 ° C for 4.5 h. After the reaction was completed, the solution was washed with water and dried at 55 ° C for 10 h, and then placed at 10 -2 Pa vacuum, 800℃ heat treatment for 1.5h, Zn 2 Ga 2.98-x Y x Cr 0.02 Ge 0.75 O 8 Long-lasting 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 at 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 at 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 stirred in a water bath for a second time at 65°C at a stirring speed of 500 rpm for 7 h. Then, an aging treatment was performed at 65°C for 10 h to obtain Cu 2 O microcapsule phase change material. 0.5g Cu 2O and 0.375 g of long afterglow nanoparticles were dispersed in 20 mL of deionized water under an ultrasonic power of 100 W for 35 min, and then 20 mL of an aqueous solution containing 0.229 g of thioacetamide and 10.6 mL of an aqueous solution containing 0.354 g of sodium hydroxide were added, and the mixture was stirred and etched at 45 ° C at a stirring speed of 500 rpm for 2.5 h, 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 Zn 2 Ga 2.98-x Y x Cr 0.02 Ge 0.75 O 8 / Double-layer Cu 2 O@Cu 2y-1 S y Micro-nanostructured particles.

[0060] 0.5 g of the 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] 2 g of super-hydrophobic micro-nanostructure particles, 0.648 g of coating varnish and 12.424 g of NN dimethylformamide were mixed, and stirred at a stirring speed of 300 rpm for 0.5 h to obtain a photothermal energy storage super-hydrophobic 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 solution pH 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, followed by hydrothermal treatment at 180 ° C for 5 h, after which the reaction was completed, the solution was washed with water and dried at 60 ° C for 8 h, and then placed at 10 -2 Pa vacuum, 800℃ heat treatment for 2h, Zn 2 Ga 2.98-x Y x Cr 0.02 Ge 0.75 O 8 Long-lasting 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 h. 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 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 stirred in a water bath for a second time at 60° C. at a stirring speed of 400 rpm for 8 h. Then, an aging treatment was performed at 60° C. for 12 h to obtain Cu 2 O microcapsule phase change material. 0.5g Cu 2 O and 0.55 g of long afterglow nanoparticles were dispersed in 20 mL of deionized water under an ultrasonic power of 100 W for 40 min, and then 20 mL of an aqueous solution containing 0.521 g of thioacetamide and 10 mL of an aqueous solution containing 0.4 g of sodium hydroxide were added, and the mixture was stirred and etched at 40 ° C at a stirring speed of 600 rpm for 3 h, 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 Zn 2 Ga 2.98- x Y x Cr 0.02 Ge 0.75 O 8 / Double-layer Cu 2 O@Cu 2y-1 S y Micro-nanostructured particles.

[0065] 0.71 g of the 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] 2 g of super-hydrophobic micro-nanostructure particles were mixed with 1.186 g of coating varnish and 11.275 g of ethanol, and stirred at 300 rpm for 0.5 h to obtain a photothermal energy storage super-hydrophobic 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 is a performance comparison of the photothermal energy storage super-hydrophobic all-weather anti-icing coating prepared by polydimethylsiloxane coating, activated carbon / copper sulfide-polydimethylsiloxane coating, tetradecane@expanded graphite-polydimethylsiloxane coating and Examples 1 and 2. As can be seen from the table, the polydimethylsiloxane coating has poor hydrophobicity, the droplet freezing delay time is very short at low temperature, and it does not have a photothermal deicing function. The surface is completely covered by ice layer after being placed under dark low temperature and high humidity conditions for 12h, and the anti-icing effect is not good; activated carbon / copper sulfide-polydimethylsiloxane coating has super-hydrophobicity, can delay ice formation, and can also photothermal deicing, but the photothermal conversion efficiency is low, and it cannot actively deicer in the dark; 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 phase change materials can be used to store heat for night anti-icing / deicing, the stored heat release time is too short, and the anti-icing performance at night is difficult to maintain. Compared with the above-mentioned coatings, the coatings prepared in Examples 1 and 2 have super-hydrophobicity and high light conversion efficiency, and 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 the freezing point 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 only a partial embodiment, but the present invention is not limited to the above embodiment. The above embodiment is illustrative and not restrictive. All specific extensions of the materials and methods of the present invention, without departing from the scope of protection of the present invention and 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: 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 the solution was 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 phase change material into deionized water, after mechanical emulsification, adding copper sulfate aqueous solution and stirring in a water bath for the first time, then dropping glucose aqueous solution and sodium hydroxide solution, stirring in a water bath for the second time and aging treatment, to obtain Cu2O microcapsule phase change material; Step 2.2, the Cu2O microcapsule phase change material and the long afterglow nanoparticles obtained in step 1 are ultrasonically dispersed in deionized water, and after adding thioacetamide aqueous solution and sodium hydroxide solution, a third stirring etching is performed, and then filtered, washed, and vacuum dried to obtain Zn2Ga 2.98-x Y x Cr 0.02 Ge 0.75 O8 / double-layer Cu2O@Cu 2y-1 S y Micro-nano structured particles; Step 3: Low surface energy modification of composite particles: The micro-nano structured 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, centrifuged, washed, and dried to obtain super-hydrophobic micro-nano structured particles; Step 4, preparing a photothermal energy storage super-hydrophobic anti-icing coating: The super-hydrophobic micro-nano structure 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%-13.02%, 21.54%-22.53%, 4.62%-4.77%, 0.23%-0.24%, 0.13%-0.65%, 58.79%-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 8-8.5, the stirring speed is 500-800 rpm, the stirring time is 0.5-1h, the hydrothermal treatment temperature is 180°C, the hydrothermal time is 4-5h, the drying temperature is 50-60°C, the drying time is 8-12h, and the vacuum degree is 10 -1 ~10 -2 Pa, the vacuum heat treatment temperature is 800℃, and the 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 sum 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 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 washing is 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.

7. 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 3, the mass percentages of the micro-nano structure 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 sum 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 hours, the centrifugal speed is 6000-8000 rpm, the centrifugal time is 3-5 minutes, the drying temperature is 50-60°C, and the drying time is 8-12 hours.

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 super-hydrophobic micro-nano structure 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 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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