Spinel type high-entropy oxide photo-thermal super-hydrophobic anti-icing coating and preparation thereof

Abstract

The invention relates to a spinel type high-entropy oxide photo-thermal super-hydrophobic anti-icing coating. The anti-icing coating is prepared from the following raw materials in parts by weight: 10 to 20 parts of spinel type high-entropy oxide, 20 to 40 parts of epoxy resin, 1 to 5 parts of stearic acid solution, 1 to 5 parts of polymethyl methacrylate solution, 5 to 10 parts of polydimethylsiloxane, 0.1 to 1 part of flatting agent, 0.1 to 1 part of dispersing agent, 0.1 to 1 part of defoaming agent, 0.5 to 1 part of curing agent and 30 to 60 parts of solvent. The spinel type high-entropy oxide is a powder material with the particle size of 50-600 nm, and the molecular formula of the spinel type high-entropy oxide is (A) 3O4. Meanwhile, the invention further discloses a preparation method of the coating. A coating prepared from the coating disclosed by the invention realizes coupling characteristics of photothermal conversion and super-hydrophobicity, not only has excellent super-hydrophobicity and light absorption characteristics, but also has good performance stability and durability in corrosion and wear environments.

Description

Technical Field

[0001] The present invention relates to high entropy oxide ceramic materials, photothermal active deicing and super-hydrophobic passive anti-icing application fields, and in particular to a spinel high entropy oxide photothermal super-hydrophobic anti-icing coating and its preparation method. Background Art

[0002] Under low temperature conditions, with the gradual accumulation of ice nuclei and the interconnection of ice bridges, various ice crystal forms gradually form and accumulate on the surface. Surface ice formation can cause serious economic losses to mechanical equipment, power equipment, wind power generation, air transportation, and daily life, and can also endanger the lives of crew members. At present, the traditional surface anti-icing and deicing methods mainly include: thermal deicing (hot air method, heating resistor method), vibration deicing (electric pulse method, piezoelectric vibration deicing, ultrasonic vibration method, etc.), mechanical deicing, solution deicing, etc., but these traditional deicing methods are accompanied by cumbersome processes, difficult construction, high energy consumption, and various safety hazards, which limits their scope of application and usage scenarios.

[0003] As a new deicing strategy, the photothermal super-hydrophobic anti-icing surface uses the synergistic effect of hydrophobicity, microstructure and functional particles to increase the nucleation energy barrier of ice, thereby achieving effective deicing on the surface. CN 113897134A discloses an energy-absorbing super-oleophobic super-hydrophobic anti-icing coating for power transmission lines and a preparation method thereof. The coating is mainly composed of fluorine-modified silicone resin, micro-nano composite functional particles and additives. The coating has the characteristics of super-hydrophobic super-oleophobic and energy absorption, so that the conductors, towers and insulators on the transmission line have relatively excellent deicing performance. However, the preparation process of the coating is relatively complicated, the functional filler involved is relatively expensive, the energy absorption and photothermal performance of the coating are relatively weak under the irradiation of light, and the temperature rise of the surface is relatively low in outdoor environments, which is difficult to be applied to the surface of the highly efficient deicing under severe cold climate conditions. CN114231113A discloses a photothermal hydrophobic anti-icing and anti-shedding coating material, which has a bonding and anti-shedding performance on the surface of the metal substrate, and has certain photothermal conversion and deicing performance under light irradiation. However, during the preparation process of this coating material, a complex modification process is required to prepare a large number of modified nanoparticles and modified photothermal nanoparticles, and it also involves the participation of some toxic substances (such as tetrahydrofuran, pyridine, etc.), which increases the production cost while also increasing the risk of damaging the environment and biological health.

[0004] In addition, the currently commonly used anti-icing coatings are mainly based on carbon and its allotropes, plasma nanoparticles or supersurfaces, metal ceramics, black oxides, polymers, MXene, high-entropy alloys and other materials as traditional photothermal materials are widely used, while there are few studies on the application of high-entropy oxide ceramic materials in anti-icing coatings and coatings.

[0005] As a high entropy oxide ceramic material, spinel high entropy oxide has high entropy characteristics that increase the d-band distribution near the Fermi level, promote inter-band transitions, and further enhance the material's absorption and conversion of light. With high mixing entropy and severe lattice distortion, spinel high entropy oxide has better thermal stability, corrosion resistance, wear resistance, and oxidation resistance than traditional spinel oxides. Therefore, it has broad application potential in the fields of efficient solar energy absorption and surface ice prevention in severe cold environments. Summary of the invention

[0006] The technical problem to be solved by the present invention is to provide a spinel high entropy oxide photothermal super hydrophobic anti-icing coating with good performance.

[0007] Another technical problem to be solved by the present invention is to provide the preparation of the spinel-type high entropy oxide photothermal super-hydrophobic anti-icing coating.

[0008] To solve the above problems, the present invention discloses a spinel high entropy oxide photothermal super hydrophobic anti-icing coating, characterized in that the anti-icing coating is composed of the following raw materials in parts by weight: 10 to 20 parts of spinel high entropy oxide, 20 to 40 parts of epoxy resin, 1 to 5 parts of stearic acid solution, 1 to 5 parts of polymethyl methacrylate solution, 5 to 10 parts of polydimethylsiloxane, 0.1 to 1 part of leveling agent, 0.1 to 1 part of dispersant, 0.1 to 1 part of defoaming agent, 0.5 to 1 part of curing agent, and 30 to 60 parts of solvent; the spinel high entropy oxide refers to a powder material with a particle size of 50 to 600 nm, and its molecular formula is (A) 3O4, wherein A is six elements of Cu, Mn, Fe, Cr, Co, Ti, and Ni, and has a spinel face-centered cubic crystal structure and is Fd-3m space point group.

[0009] The spinel high entropy oxide is prepared by the following method: Step 1: Take six kinds of powders of CuO, MnO2, Fe2O3, Cr2O3, Co3O4, TiO2 and NiO2 as raw materials, and weigh them according to the metal atomic molar ratio of 1:1:1:1:1:1; Step 2: ball-milling the powders weighed in step 1, drying them at 80-100° C. for 12-24 hours, and grinding them to obtain a mixture powder; Step 3: The mixture powder obtained in step 2 is calcined at high temperature in an air atmosphere and then cooled to room temperature to obtain the product.

[0010] The ball milling mixing conditions in step 2 refer to ball milling using a planetary ball mill, a ball milling speed of 300-500 r / min, a ball milling time of 5-12 hours, a ball material-water mass ratio of 2-5:1:3, and a ball milling process of: first ball milling for 1 hour, then pausing for 10 minutes, then ball milling for 1 hour, pausing for 10 minutes, and repeating the ball milling cycle.

[0011] The high temperature calcination conditions in step 3 refer to a calcination temperature of 900-1300° C., a heating rate of 10-15° C. / min, and a calcination time of 5-10 hours; and a cooling method of one of furnace cooling, air quenching cooling, and liquid nitrogen quenching cooling.

[0012] The mass concentrations of the stearic acid solution and the polymethyl methacrylate solution are both 10-20 mmol / L.

[0013] The leveling agent is one or two of Digo Glide 450 polyether siloxane leveling agent, AFCONA-3085-polyether modified silicone, and AFCONA-3587-polyether modified silicone; the dispersant is one or two of Digo TEGO 662 C and EFKA 5065; the defoamer is one or two of Digo TEGO 901W polyether siloxane defoamer and EFKA 2720 unsaturated polyester defoamer; the curing agent is SYLGARD 184; the solvent is one or more of anhydrous ethanol, acetone, and ethyl acetate.

[0014] The preparation method of a spinel high entropy oxide photothermal super hydrophobic anti-icing coating as described above is characterized in that: first, weigh according to the ratio; then add epoxy resin, spinel high entropy oxide, stearic acid solution, and polymethyl methacrylate solution to the solvent, and stir at a speed of 800-1000 r / min for 60-100 min to obtain a mixed suspension; finally, add polydimethylsiloxane, leveling agent, dispersant, defoaming agent, and curing agent to the mixed suspension in sequence, and stir at a low speed of 200-400 r / min for 30-60 min to obtain the spinel high entropy oxide photothermal super hydrophobic anti-icing coating.

[0015] A coating formed by an anti-icing coating prepared by the method as described above is characterized in that: the light absorption rate of the coating in the 0.3~2.5μm solar light band is greater than 96%, and the photothermal conversion efficiency exceeds 70%; and the water contact angle on the coating surface is greater than 155°, and the water rolling angle is less than 5°.

[0016] A method for preparing a coating as described above comprises the following steps: Step 1: Use quartz sand with a particle size of 60-100 mesh to sandblast the substrate surface so that the surface roughness of the substrate meets the requirements of Ra 12.5-Ra 6.3; Step 2: subjecting the substrate surface after sandblasting to ultrasonic cleaning for 30 to 60 minutes, and drying the cleaned substrate to obtain a treated substrate surface; Step 3: Fill the anti-icing coating into the spray gun and spray it on the treated substrate surface by spraying. Use a 1.5mm caliber spray gun, the spraying environment temperature is 15~30℃, the relative air humidity is 35~85%, the spraying pressure is 0.3~0.4MPa, and the spraying speed is 2~2.5m / min, so as to obtain a wet film with a thickness of 60~80μm; Step 4: Cure the wet film at room temperature for 24 hours or in a muffle furnace at 80°C for 2.5 to 3 hours to obtain a dry film with a thickness of 30 to 40 μm.

[0017] Compared with the prior art, the present invention has the following advantages: 1. The present invention uses high entropy oxide as the main functional filler. Since high entropy oxide has a spinel structure, more than five transition metal elements can be randomly distributed at the A position. The disorder of the elements and the differences in radius and mass cause the crystal structure of the material to present severe lattice distortion and produce a large number of oxygen vacancies. At the same time, relying on the 3d orbital arrangement characteristics of transition metal elements, an intermediate band is formed near the Fermi level, thereby effectively reducing the intrinsic band gap of the high entropy oxide material. In addition, the change in the valence of multivalent elements can produce small polarons and promote electronic transitions. Therefore, high entropy oxide ceramics can significantly broaden the light absorption characteristics of the material in the visible light range by enhancing electronic transitions, free carrier absorption, impurity energy level absorption and lattice vibration absorption, so that the light absorption rate of the formed coating in the 0.3~2.5μm solar light band exceeds 96%.

[0018] 2. The spinel high entropy oxide used in the present invention has a high configurational entropy, which reduces the Gibbs free energy while exhibiting a single-phase solid solution structure. This characteristic makes the spinel high entropy oxide have better thermal stability, corrosion resistance, wear resistance, and oxidation resistance than non-high entropy spinel oxides.

[0019] 3. The super-hydrophobic coating prepared by the present invention reduces the actual contact area between the supercooled droplets and the surface, increases the free energy barrier for the heterogeneous nucleation of the supercooled droplets, delays the nucleation and condensation process of the droplets, and also hinders the bridging process between the droplets, so that the anti-condensation time of the droplets on the surface exceeds 250 seconds under the condition of relative humidity exceeding 85%, showing excellent passive anti-icing performance. In addition, the super-hydrophobic property of the coating gives the surface lower water adhesion and self-rebound properties at a lower Weber number. When the tiny droplets hit the surface, a bouncing effect occurs, which avoids the rapid accumulation and condensation of the droplets on the surface, and the frosting mass on the surface can be reduced by about 50%, thereby showing excellent passive anti-fog and anti-frost properties.

[0020] 4. The coating prepared by the present invention has the coupling characteristics of super-hydrophobic effect and photothermal effect, which overcomes the pinning effect of traditional super-hydrophobic anti-icing coatings under extremely cold conditions. Due to the wide spectral absorptivity and photothermal effect of spinel high entropy oxide, the coating has good adaptability under different lighting conditions, and can quickly accumulate heat and transfer heat to the surface and substrate, thereby achieving fast and active defrosting performance. The surface temperature of the coating under standard sunlight can exceed 80°C, which can meet the surface anti-icing requirements under most extremely cold conditions. In addition, the coupling characteristics of the coating make the solid-solid contact interface between the coating surface and the frost layer transform into a solid-liquid-solid interface during the gradual melting of the micro-ice nuclei, reducing the adhesion strength between the unmelted ice layer and the coating surface, and the melted liquid layer has a lubricating effect. At -10°C, the ice layer on the surface can be de-iced within 30 seconds. Therefore, the frost layer covering the surface does not need to be completely melted to achieve efficient and timely de-icing and defrosting functions through external forces such as gravity or wind.

[0021] 5. The anti-icing coating prepared by the present invention maintains excellent stability in the photothermal properties and superhydrophobicity of the coating under multiple deicing and defogging cycles. This is attributed to the rapid melting of micro ice nuclei by spinel high entropy oxide particles during the deicing process, that is, the droplets after the melted ice nuclei can act as a lubricant to accelerate the detachment of the ice layer, and also avoid the rigid friction between the ice nuclei and the surface micro-nanostructure, so that the lateral shear force between the ice nuclei and the surface is weakened, thereby protecting the superhydrophobic micro-nanostructure composed of the micro-skeleton structure and the microporous structure. At the same time, the morphological integrity of the superhydrophobic micro-nanostructure also protects the distribution characteristics of the spinel high entropy oxide particles in the micro-nanostructure, ensuring the stability of the photothermal properties. Under 10 deicing and icing cycle tests, the average deicing time of the coating was less than 30s, indicating the stability of the superhydrophobic and photothermal properties of the coating. Figure 6 shown.

[0022] 6. The coating prepared by the present invention has strong adaptability in corrosive and abrasive environments. This adaptability comes from the excellent mechanical strength and tensile strength of polymethyl methacrylate, the good bonding strength and alkali resistance of epoxy resin, and the intrinsic corrosion resistance, wear resistance, and oxidation resistance of spinel high entropy oxide particles. Figure 7 As shown. For example, after the coating was immersed in 1 mol / L acid, alkali and salt solution for 72 hours, the super-hydrophobic and photothermal coupling properties of the coating surface were still maintained; after the coating was rubbed on 800 mesh gauze paper for 8 m under 9.8 kPa pressure, the contact angle of the surface was still >150°, which maintained the super-hydrophobic properties of the coating; in 20 bending tests, the coating had no cracking and maintained the super-hydrophobic properties; in 20 tape adhesion tests, the coating had no obvious peeling and the super-hydrophobic properties of the surface were still maintained. In addition, the super-hydrophobic properties of the surface endowed the coating with anti-fouling and self-cleaning properties, so that the coating can also be used to prevent ice coating under different climatic conditions.

[0023] 7. The present invention is simple to operate, has high production efficiency, does not require complicated processing procedures, can be matched with a variety of substrates, has a dense coating surface, and has no blistering, cracking, etc. It can be used in aviation and navigation, wind power generation, power transmission, chemical industry, seawater desalination, agricultural equipment and other fields in cold environments. Anti-icing and deicing needs. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] The specific implementation modes of the present invention are further described in detail below in conjunction with the accompanying drawings.

[0025] Figure 1 This is the XRD pattern of the spinel high entropy oxide (CoCrFeMnCuTi)3O4 powder material prepared in Example 1 of the present invention.

[0026] Figure 2 This is a SEM image of the spinel high entropy oxide (CoCrFeMnCuTi)3O4 powder material prepared in Example 2 of the present invention.

[0027] Figure 3 Surface morphology and contact angle diagram of the spinel high entropy oxide photothermal super hydrophobic anti-icing coating prepared in Example 2 of the present invention.

[0028] Figure 4 This is an infrared temperature diagram of the spinel high entropy oxide photothermal super hydrophobic anti-icing coating prepared in Example 3 of the present invention under standard sunlight irradiation.

[0029] Figure 5 This is a diagram of the defrosting process of the spinel high entropy oxide photothermal super hydrophobic anti-icing coating prepared in Example 4 of the present invention.

[0030] Figure 6 This is a deicing time diagram of the spinel high entropy oxide photothermal super hydrophobic anti-icing coating prepared in Example 4 of the present invention under multiple deicing-icing cycles.

[0031] Figure 7 This is a surface wettability diagram of the spinel high entropy oxide photothermal super hydrophobic anti-icing coating prepared in Example 5 of the present invention under different destructive tests. DETAILED DESCRIPTION

[0032] A spinel high entropy oxide photothermal super hydrophobic anti-icing coating, the anti-icing coating is composed of the following raw materials in parts by weight (g): 10-20 parts of spinel high entropy oxide, 20-40 parts of epoxy resin, 1-5 parts of stearic acid solution, 1-5 parts of polymethyl methacrylate solution, 5-10 parts of polydimethylsiloxane, 0.1-1 parts of leveling agent, 0.1-1 parts of dispersant, 0.1-1 parts of defoamer, 0.5-1 parts of curing agent, and 30-60 parts of solvent. The spinel high entropy oxide refers to a powder material with a particle size of 50-600 nm, and its molecular formula is (A)3O4, wherein A is six elements of Cu, Mn, Fe, Cr, Co, Ti, and Ni, and has a spinel face-centered cubic crystal structure and is Fd-3m space point group.

[0033] Wherein: the spinel high entropy oxide is prepared by the following method: Step 1: Use six kinds of CuO, MnO2, Fe2O3, Cr2O3, Co3O4, TiO2 and NiO2 powders as raw materials and weigh them according to the metal atomic molar ratio of 1:1:1:1:1:1.

[0034] Step 2: The powder weighed in step 1 is ball-milled and mixed using a planetary ball mill, the ball milling speed is 300-500 r / min, the ball milling time is 5-12 hours, the mass ratio of ball material to water (g / g) is 2-5:1:3, and the ball milling process is: first ball milling for 1 hour, then pausing for 10 minutes, then ball milling for 1 hour, pausing for 10 minutes, and this is a cycle of ball milling. After ball milling, it is dried at 80-100°C for 12-24 hours, and then ground to obtain a mixture powder.

[0035] Step 3: calcining the mixture powder obtained in step 2 at 900-1300°C for 5-10 hours in an air atmosphere at a heating rate of 10-15°C / min; then cooling to room temperature by one of furnace cooling, air quenching cooling and liquid nitrogen quenching cooling.

[0036] The mass concentrations of stearic acid solution and polymethyl methacrylate solution are both 10-20 mmol / L.

[0037] The leveling agent is one or two of Digo Glide 450 polyether siloxane leveling agent, AFCONA-3085-polyether modified silicone, and AFCONA-3587-polyether modified silicone; the dispersant is one or two of Digo TEGO 662 C and Efka EFKA5065; the defoamer is one or two of Digo TEGO 901W polyether siloxane defoamer and Efka EFKA 2720 unsaturated polyester defoamer; the curing agent is SYLGARD184; the solvent is one or more of anhydrous ethanol, acetone, and ethyl acetate.

[0038] A method for preparing a spinel-type high entropy oxide photothermal super-hydrophobic anti-icing coating: First, weigh according to the ratio; then add epoxy resin, spinel high entropy oxide, stearic acid solution, and polymethyl methacrylate solution into the solvent, and stir at a speed of 800-1000 r / min for 60-100 min to obtain a mixed suspension; finally, add polydimethylsiloxane, leveling agent, dispersant, defoaming agent, and curing agent into the mixed suspension in sequence, and stir at a low speed of 200-400 r / min for 30-60 min to obtain a spinel high entropy oxide photothermal superhydrophobic anti-icing coating.

[0039] The coating formed by the anti-icing coating prepared by the above method has a light absorption rate of >96% in the 0.3~2.5μm solar light band and a photothermal conversion efficiency of more than 70%; and the water contact angle on the coating surface is >155° and the water rolling angle is <5°.

[0040] The method for preparing the coating comprises the following steps: Step 1: Use quartz sand with a particle size of 60-100 mesh to sandblast the substrate surface so that the surface roughness of the substrate meets the requirements of Ra 12.5-Ra 6.3; Step 2: subjecting the substrate surface after sandblasting to ultrasonic cleaning for 30 to 60 minutes, and drying the cleaned substrate to obtain a treated substrate surface; Step 3: Fill the anti-icing coating into the spray gun and spray it on the treated substrate surface by spraying. Use a 1.5mm caliber spray gun, the spraying environment temperature is 15~30℃, the relative air humidity is 35~85%, the spraying pressure is 0.3~0.4MPa, and the spraying speed is 2~2.5m / min, so as to obtain a wet film with a thickness of 60~80μm; Step 4: Cure the wet film at room temperature for 24 hours or in a muffle furnace at 80°C for 2.5 to 3 hours to obtain a dry film with a thickness of 30 to 40 μm.

[0041] Example 1 A spinel high entropy oxide photothermal super hydrophobic anti-icing coating, the anti-icing coating is composed of the following raw materials: 10g of spinel high entropy oxide (CoCrFeMnCuTi)3O4, 20g of epoxy resin, 1g of stearic acid solution, 1g of polymethyl methacrylate solution, 5g of polydimethylsiloxane, 30g of solvent, 0.1g of Digo Glide 450 polyether siloxane leveling agent, 0.1g of Digo TEGO 662 C dispersant, 0.1g of Digo TEGO 901W polyether siloxane defoaming agent and 0.5g of SYLGARD 184 curing agent.

[0042] Its preparation method: First, weigh according to the ratio; then add epoxy resin, spinel high entropy oxide, stearic acid solution, and polymethyl methacrylate solution to the solvent, and stir at a speed of 800r / min for 60min to obtain a mixed suspension; finally, add polydimethylsiloxane, leveling agent, dispersant, defoaming agent, and curing agent to the mixed suspension in sequence, and stir at a low speed of 200r / min for 30min to obtain a spinel high entropy oxide photothermal superhydrophobic anti-icing coating.

[0043] Wherein: the mass concentrations of stearic acid solution and polymethyl methacrylate solution are both 10mmol / L.

[0044] Spinel high entropy oxide (CoCrFeMnCuTi)3O4 was prepared by the following method: Step 1: Weigh CuO (3 mol), MnO2 (3 mol), Fe2O3 (1.5 mol), Cr2O3 (1.5 mol), Co3O4 (1.0 mol), and TiO2 (3 mol) powders respectively.

[0045] Step 2: Pour zirconium oxide balls, raw materials and ultrapure water into the ball milling jar at a ball: material: water mass ratio (g / g) of 2:1:3; and place the ball milling jar on the ball milling station, first perform ball milling for 1 hour at a speed of 300r / min, then pause for 10 minutes, which is a ball milling cycle, and then perform ball milling for another hour after 10 minutes at a speed of 300r / min, for a total of 12 hours of ball milling. After ball milling, dry at 80~100℃ for 12~24 hours, and grind to obtain a mixed powder.

[0046] Step 3: The obtained mixture powder is placed in a muffle furnace, heated to 900°C in an air atmosphere (heating rate of 10°C / min), calcined for 5 hours, and then air-quenched and cooled to room temperature to obtain a single-phase (CoCrFeMnCuTi)3O4.

[0047] The obtained (CoCrFeMnCuTi)3O4 high entropy ceramic powder material was subjected to X-ray diffraction test, and the results are as follows Figure 1 As shown, the spectrum line is very consistent with the crystal form of the Fe3O4 spectrum line (PDF#19-0629) with a spinel structure in the ICDD database, indicating that the high entropy ceramic material prepared in this embodiment has a spinel structure.

[0048] The method for preparing the coating comprises the following steps: Step 1: Use quartz sand with a particle size of 60 mesh to sandblast the surface of the substrate so that the surface roughness of the substrate meets the requirements of Ra 12.5~Ra 6.3; Step 2: subjecting the substrate surface after sandblasting to ultrasonic cleaning for 30 minutes, and drying the cleaned substrate to obtain a treated substrate surface; Step 3: Fill the anti-icing coating into the spray gun and spray it on the treated substrate surface by spraying. Use a 1.5mm caliber spray gun, the spraying environment temperature is 15~30℃, the relative air humidity is 35~85%, the spraying pressure is 0.3~0.4MPa, and the spraying speed is 2~2.5m / min, so as to obtain a wet film with a thickness of 60μm; Step 4: Cure the wet film at room temperature for 24 hours or in a muffle furnace at 80°C for 2.5 to 3 hours to obtain a dry film with a thickness of 30 μm.

[0049] The solar absorptivity of the material was evaluated using a Lambda 950 UV / visible / near-infrared spectrophotometer (equipped with a 150 mm integrating sphere) manufactured by PerkinElmer, USA, and its absorptivity in the 0.3-2.5 μm band was measured. The solar absorptivity was then calculated according to the calculation formula in the international standard ISO 9845-1 (1992). The solar absorptivity of the coating prepared in Example 1 in the 0.3-2.5 μm band was measured to be 0.966.

[0050] The water contact angle and water sliding angle of the surface were characterized by an angular contact meter (JY-PHb). The volume of the test water droplet was 10 μL. The water contact angle of the coating prepared in Example 1 was measured to be 155°, and the water sliding angle was 4.2°.

[0051] Example 2 A spinel high entropy oxide photothermal super hydrophobic anti-icing coating, the anti-icing coating is composed of the following raw materials: 10g of spinel high entropy oxide (CoCrFeMnCuTi)3O4, 30g of epoxy resin, 1g of stearic acid solution, 1g of polymethyl methacrylate solution, 5g of polydimethylsiloxane, 40g of solvent, 0.1g of Digo Glide 450 polyether siloxane leveling agent, 0.1g of Digo TEGO 662 C dispersant, 0.1g of Digo TEGO 901W polyether siloxane defoaming agent and 0.5g of SYLGARD 184 curing agent.

[0052] Its preparation method: First, weigh according to the ratio; then add epoxy resin, spinel high entropy oxide, stearic acid solution, and polymethyl methacrylate solution into the solvent, and stir at 800r / min for 70min to obtain a mixed suspension; finally, add polydimethylsiloxane, leveling agent, dispersant, defoaming agent, and curing agent into the mixed suspension in sequence, and stir at a low speed of 200r / min for 30min to obtain a spinel high entropy oxide photothermal superhydrophobic anti-icing coating.

[0053] Wherein: the mass concentrations of stearic acid solution and polymethyl methacrylate solution are both 15mmol / L.

[0054] Spinel high entropy oxide (CoCrFeMnCuTi)3O4 was prepared by the following method: Step 1: Weigh CuO (3 mol), MnO2 (3 mol), Fe2O3 (1.5 mol), Cr2O3 (1.5 mol), Co3O4 (1.0 mol), and TiO2 (3 mol) powders respectively.

[0055] Step 2: Pour zirconium oxide balls, raw materials and ultrapure water into the ball milling jar at a ball: material: water mass ratio (g / g) of 2:1:3; and place the ball milling jar on the ball milling station, first perform ball milling for 1 hour at a speed of 300r / min, then pause for 10 minutes, which is a ball milling cycle, and then perform ball milling for another hour after 10 minutes at a speed of 300r / min, for a total of 12 hours of ball milling. After ball milling, dry at 80~100℃ for 12~24 hours, and grind to obtain a mixture powder.

[0056] Step 3: The obtained mixture powder is placed in a muffle furnace, heated to 1000°C in an air atmosphere (heating rate of 10°C / min), calcined for 8 hours, and then air-quenched and cooled to room temperature to obtain a single-phase (CoCrFeMnCuTi)3O4.

[0057] The obtained (CoCrFeMnCuTi)3O4 high entropy ceramic powder material was subjected to X-ray diffraction testing, and its spectrum was very consistent with the crystal form of Fe3O4 spectrum (PDF#19-0629) with spinel structure in the ICDD database, indicating that the high entropy ceramic material prepared in this example has a spinel structure.

[0058] Figure 2 This is the SEM image of (CoCrFeMnCuTi)3O4 high entropy ceramic powder material, which shows that the powder particle size is between 50~600 nm.

[0059] The method for preparing the coating comprises the following steps: Step 1: Use quartz sand with a particle size of 80 mesh to sandblast the surface of the substrate so that the surface roughness of the substrate meets the requirements of Ra 12.5~Ra 6.3; Step 2: subjecting the substrate surface after sandblasting to ultrasonic cleaning for 30 minutes, and drying the cleaned substrate to obtain a treated substrate surface; Step 3: Fill the anti-icing coating into the spray gun and spray it on the treated substrate surface by spraying. Use a 1.5mm caliber spray gun, the spraying environment temperature is 15~30℃, the relative air humidity is 35~85%, the spraying pressure is 0.3~0.4MPa, and the spraying speed is 2~2.5m / min, so as to obtain a wet film with a thickness of 64μm; Step 4: Cure the wet film at room temperature for 24 hours or in a muffle furnace at 80°C for 2.5 to 3 hours to obtain a dry film with a thickness of 31 μm.

[0060] The absorptivity, water contact angle and water sliding angle tests of the prepared coating in the 0.3~2.5 μm band were the same as those in Example 1. The solar absorptivity of the coating prepared in Example 2 in the 0.3~2.5 μm band was measured to be 0.971, the water contact angle was 156.8°, and the water sliding angle was 4.0°.

[0061] Figure 3 The surface morphology SEM image and contact angle image of the prepared coating show that the coating surface has micro-nano morphology and super-hydrophobic properties.

[0062] Example 3 A spinel high entropy oxide photothermal super hydrophobic anti-icing coating, the anti-icing coating is composed of the following raw materials: 15g spinel high entropy oxide (CoCrFeMnCuTi)3O4, 30g epoxy resin, 1g stearic acid solution, 1g polymethyl methacrylate solution, 8g polydimethylsiloxane, 70g solvent, 0.1g Digo Glide 450 polyether siloxane leveling agent, 0.1g Digo TEGO 662 C dispersant, 0.1g Digo TEGO 901W polyether siloxane defoaming agent and 1g SYLGARD 184 curing agent.

[0063] Its preparation method: First, weigh according to the ratio; then add epoxy resin, spinel high entropy oxide, stearic acid solution, and polymethyl methacrylate solution to the solvent, and stir at a speed of 800r / min for 80 minutes to obtain a mixed suspension; finally, add polydimethylsiloxane, leveling agent, dispersant, defoaming agent, and curing agent to the mixed suspension in sequence, and stir at a low speed of 400r / min for 45 minutes to obtain a spinel high entropy oxide photothermal superhydrophobic anti-icing coating.

[0064] Wherein: the mass concentration of the stearic acid solution is 15 mmol / L, and the mass concentration of the polymethyl methacrylate solution is 10 mmol / L.

[0065] Spinel high entropy oxide (CoCrFeMnCuTi)3O4 was prepared by the following method: Step 1: Weigh CuO (3 mol), MnO2 (3 mol), Fe2O3 (1.5 mol), Cr2O3 (1.5 mol), Co3O4 (1.0 mol), and TiO2 (3 mol) powders respectively.

[0066] Step 2: Pour zirconium oxide balls, raw materials and ultrapure water into the ball milling jar at a ball: material: water mass ratio (g / g) of 2:1:3; and place the ball milling jar on the ball milling station, first perform ball milling for 1 hour at a speed of 300r / min, then pause for 10 minutes, which is a ball milling cycle, and then perform ball milling for another hour after 10 minutes at a speed of 300r / min, for a total of 12 hours of ball milling. After ball milling, dry at 80~100℃ for 12~24 hours, and grind to obtain a mixture powder.

[0067] Step 3: The obtained mixture powder is placed in a muffle furnace, heated to 1100°C in an air atmosphere (heating rate of 10°C / min), calcined for 8 hours, and then air-quenched and cooled to room temperature to obtain a single-phase (CoCrFeMnCuTi)3O4.

[0068] The obtained (CoCrFeMnCuTi)3O4 high entropy ceramic powder material was subjected to X-ray diffraction testing, and its spectrum was very consistent with the crystal form of Fe3O4 spectrum (PDF#19-0629) with spinel structure in the ICDD database, indicating that the high entropy ceramic material prepared in this example has a spinel structure.

[0069] The method for preparing the coating comprises the following steps: Step 1: Use quartz sand with a particle size of 80 mesh to sandblast the surface of the substrate so that the surface roughness of the substrate meets the requirements of Ra 12.5~Ra 6.3; Step 2: subjecting the substrate surface after sandblasting to ultrasonic cleaning for 30 minutes, and drying the cleaned substrate to obtain a treated substrate surface; Step 3: Fill the anti-icing coating into the spray gun and spray it on the treated substrate surface by spraying. Use a 1.5mm caliber spray gun, the spraying environment temperature is 15~30℃, the relative air humidity is 35~85%, the spraying pressure is 0.3~0.4MPa, and the spraying speed is 2~2.5m / min, so as to obtain a wet film with a thickness of 67μm; Step 4: Cure the wet film at room temperature for 24 hours or in a muffle furnace at 80°C for 2.5 to 3 hours to obtain a dry film with a thickness of 35 μm.

[0070] The absorptivity, water contact angle and water sliding angle tests of the prepared coating in the 0.3~2.5 μm band were the same as those in Example 1. The solar absorptivity of the coating prepared in Example 3 in the 0.3~2.5 μm band was measured to be 0.974, the water contact angle was 161.2°, and the water sliding angle was 3.8°.

[0071] Figure 4 The prepared coating was subjected to a light intensity of 1 kW / m 2 Infrared temperature diagram of the coating surface under irradiation conditions. The diagram shows that after 120 seconds of irradiation, the temperature of the coating can reach 83.7°C, which can meet the surface anti-icing requirements under most extremely cold conditions.

[0072] Example 4 A spinel high entropy oxide photothermal super hydrophobic anti-icing coating, the anti-icing coating is composed of the following raw materials: 20g of spinel high entropy oxide (CoCrFeMnCuTi)3O4, 40g of epoxy resin, 3g of stearic acid solution, 3g of polymethyl methacrylate solution, 10g of polydimethylsiloxane, 50g of solvent, 0.5g of Digo Glide 450 polyether siloxane leveling agent, 0.5g of Digo TEGO 662 C dispersant, 0.5g of Digo TEGO 901W polyether siloxane defoaming agent and 0.9g of SYLGARD 184 curing agent.

[0073] Its preparation method: First, weigh according to the ratio; then add epoxy resin, spinel high entropy oxide, stearic acid solution, and polymethyl methacrylate solution to the solvent, and stir at a speed of 900r / min for 100min to obtain a mixed suspension; finally, add polydimethylsiloxane, leveling agent, dispersant, defoaming agent, and curing agent to the mixed suspension in sequence, and stir at a low speed of 400r / min for 60min to obtain the spinel high entropy oxide photothermal superhydrophobic anti-icing coating.

[0074] Wherein: the mass concentration of the stearic acid solution is 10 mmol / L, and the mass concentration of the polymethyl methacrylate solution is 15 mmol / L.

[0075] Spinel high entropy oxide (CoCrFeMnCuTi)3O4 was prepared by the following method: Step 1: Weigh CuO (3 mol), MnO2 (3 mol), Fe2O3 (1.5 mol), Cr2O3 (1.5 mol), Co3O4 (1.0 mol), and TiO2 (3 mol) powders respectively.

[0076] Step 2: Pour zirconium oxide balls, raw materials and ultrapure water into the ball milling jar at a ball: material: water mass ratio (g / g) of 2:1:3; and place the ball milling jar on the ball milling station, first perform ball milling for 1 hour at a speed of 300r / min, then pause for 10 minutes, which is a ball milling cycle, and then perform ball milling for another hour after 10 minutes at a speed of 300r / min, for a total of 12 hours of ball milling. After ball milling, dry at 80~100℃ for 12~24 hours, and grind to obtain a mixture powder.

[0077] Step 3: The obtained mixture powder is placed in a muffle furnace, heated to 1200°C in an air atmosphere (heating rate of 10°C / min), calcined for 10 hours, and then air-quenched and cooled to room temperature to obtain a single-phase (CoCrFeMnCuTi)3O4.

[0078] The obtained (CoCrFeMnCuTi)3O4 high entropy ceramic powder material was subjected to X-ray diffraction testing, and its spectrum was very consistent with the crystal form of Fe3O4 spectrum (PDF#19-0629) with spinel structure in the ICDD database, indicating that the high entropy ceramic material prepared in this example has a spinel structure.

[0079] The method for preparing the coating comprises the following steps: Step 1: Use quartz sand with a particle size of 80 mesh to sandblast the surface of the substrate so that the surface roughness of the substrate meets the requirements of Ra 12.5~Ra 6.3; Step 2: subjecting the substrate surface after sandblasting to ultrasonic cleaning for 45 minutes, and drying the cleaned substrate to obtain a treated substrate surface; Step 3: Fill the anti-icing coating into the spray gun and spray it on the treated substrate surface by spraying. Use a 1.5mm caliber spray gun, the spraying environment temperature is 15~30℃, the relative air humidity is 35~85%, the spraying pressure is 0.3~0.4MPa, and the spraying speed is 2~2.5m / min, so as to obtain a wet film with a thickness of 75μm; Step 4: Cure the wet film at room temperature for 24 hours or in a muffle furnace at 80°C for 2.5 to 3 hours to obtain a dry film with a thickness of 36 μm.

[0080] The absorptivity, water contact angle and water sliding angle tests of the prepared coating in the 0.3~2.5 μm band were the same as those in Example 1. The solar absorptivity of the coating prepared in Example 4 in the 0.3~2.5 μm band was measured to be 0.972, the water contact angle was 159.3°, and the water sliding angle was 4.1°.

[0081] Figure 5 For a light intensity of 1kW / m 2 The defrosting process diagram of the prepared coating (SHSAC) and the surface without coating after sandblasting (Untreated) under irradiation conditions in an environment with a temperature of -10°C and an air relative humidity of 87%. The figure shows that the coating (SHSAC) prepared in Example 4 can achieve rapid surface defrosting, and the defrosting time and process are greatly shortened.

[0082] Figure 6 The figure is a graph of deicing time of different coating surfaces under multiple deicing cycles at -10°C. The figure shows that the coating (SHSAC) prepared in Example 4 can be deiced within 30 seconds on average after 10 deicing cycle tests, indicating that the superhydrophobic and photothermal properties of the coating have excellent stability and durability (the green curve represents the defrosting time of the coating surface prepared in Example 4).

[0083] Example 5 A spinel high entropy oxide photothermal super hydrophobic anti-icing coating, the anti-icing coating is composed of the following raw materials: 20g of spinel high entropy oxide (CoCrFeMnCuTi)3O4, 40g of epoxy resin, 5g of stearic acid solution, 5g of polymethyl methacrylate solution, 10g of polydimethylsiloxane, 60g of solvent, 1g of Digo Glide 450 polyether siloxane leveling agent, 1g of Digo TEGO 662 C dispersant, 1g of Digo TEGO 901W polyether siloxane defoaming agent and 1g of SYLGARD 184 curing agent.

[0084] Its preparation method: First, weigh according to the ratio; then add epoxy resin, spinel high entropy oxide, stearic acid solution, and polymethyl methacrylate solution into the solvent, and stir at a speed of 1000r / min for 100min to obtain a mixed suspension; finally, add polydimethylsiloxane, leveling agent, dispersant, defoaming agent, and curing agent into the mixed suspension in sequence, and stir at a low speed of 400r / min for 60min to obtain the spinel high entropy oxide photothermal superhydrophobic anti-icing coating.

[0085] Wherein: the mass concentrations of stearic acid solution and polymethyl methacrylate solution are both 20mmol / L.

[0086] Spinel high entropy oxide (CoCrFeMnCuTi)3O4 was prepared by the following method: Step 1: Weigh CuO (3 mol), MnO2 (3 mol), Fe2O3 (1.5 mol), Cr2O3 (1.5 mol), Co3O4 (1.0 mol), and TiO2 (3 mol) powders respectively.

[0087] Step 2: Pour zirconium oxide balls, raw materials and ultrapure water into the ball milling jar at a ball: material: water mass ratio (g / g) of 2:1:3; and place the ball milling jar on the ball milling station, first perform ball milling for 1 hour at a speed of 300r / min, then pause for 10 minutes, which is a ball milling cycle, and then perform ball milling for another hour after 10 minutes at a speed of 300r / min, for a total of 12 hours of ball milling. After ball milling, dry at 80~100℃ for 12~24 hours, and grind to obtain a mixture powder.

[0088] Step 3: The obtained mixture powder is placed in a muffle furnace, heated to 1300°C in an air atmosphere (heating rate of 15°C / min), calcined for 10 hours, and then air-quenched and cooled to room temperature to obtain a single-phase (CoCrFeMnCuTi)3O4.

[0089] The obtained (CoCrFeMnCuTi)3O4 high entropy ceramic powder material was subjected to X-ray diffraction testing, and its spectrum was very consistent with the crystal form of Fe3O4 spectrum (PDF#19-0629) with spinel structure in the ICDD database, indicating that the high entropy ceramic material prepared in this example has a spinel structure.

[0090] The method for preparing the coating comprises the following steps: Step 1: Use quartz sand with a particle size of 100 mesh to sandblast the surface of the substrate so that the surface roughness of the substrate meets the requirements of Ra 12.5~Ra 6.3; Step 2: subjecting the substrate surface after sandblasting to ultrasonic cleaning for 60 minutes, and drying the cleaned substrate to obtain a treated substrate surface; Step 3: Fill the anti-icing coating into the spray gun and spray it on the treated substrate surface by spraying. Use a 1.5mm caliber spray gun, the spraying environment temperature is 15~30℃, the relative air humidity is 35~85%, the spraying pressure is 0.3~0.4MPa, and the spraying speed is 2~2.5m / min, so as to obtain a wet film with a thickness of 80μm; Step 4: Cure the wet film at room temperature for 24 hours or in a muffle furnace at 80°C for 2.5 to 3 hours to obtain a dry film with a thickness of 40 μm.

[0091] The absorptivity, water contact angle and water sliding angle tests of the prepared coating in the 0.3~2.5 μm band were the same as those in Example 1. The solar absorptivity of the coating prepared in Example 4 in the 0.3~2.5 μm band was measured to be 0.968, the water contact angle was 158.1°, and the water sliding angle was 4.2°.

[0092] Figure 7 The surface wettability change diagram of the prepared coating under different destructive tests. The figure shows that after the prepared coating was immersed in 1mol / L acid, alkali and salt solutions for 72 hours, the micro-nano structure and superwettability of the coating surface were maintained; after the prepared coating was rubbed on 800 mesh gauze paper for 8m under 9.8kPa pressure, the water contact angle of the surface was still >150°, maintaining the superhydrophobic properties of the surface; in 20 bending tests, the surface coating of the prepared coating had no cracking phenomenon and maintained superhydrophobic properties; in 20 tape adhesion tests, the surface coating of the prepared coating had no obvious peeling phenomenon and the surface superhydrophobic properties were still maintained. The figure also shows that the superhydrophobic stability of the coating under different destructive tests maintains the photothermal properties of the coating.

[0093] In summary, the powder materials obtained in Examples 1 to 5 are high entropy oxide ceramic particles with a spinel structure, and the anti-icing coating formed by the coating prepared using the particles has a solar absorptivity of more than 0.96 in the 0.3-2.5 μm band and has good superhydrophobic properties. Due to the photothermal conversion and superhydrophobic coupling characteristics of the coating, the coating has rapid anti-icing and defrosting properties. The coating also has excellent performance stability and durability, which provides conditions for the anti-icing application of the coating in extreme and complex environments.

[0094] The above is only an explanation of the best embodiment of the present invention, which should not be construed as a limitation on the claims. The present invention is not limited to the above embodiments. All changes made within the scope of protection of the independent claims of the present invention are within the scope of protection of the present invention.

Claims

1. A spinel-type high entropy oxide photothermal super-hydrophobic anti-icing coating, Features: The anti-icing coating is composed of the following raw materials in parts by weight: 10-20 parts of spinel high entropy oxide, 20-40 parts of epoxy resin, 1-5 parts of stearic acid solution, 1-5 parts of polymethyl methacrylate solution, 5-10 parts of polydimethylsiloxane, 0.1-1 parts of leveling agent, 0.1-1 parts of dispersant, 0.1-1 parts of defoamer, 0.5-1 parts of curing agent, and 30-60 parts of solvent; the spinel high entropy oxide refers to a powder material with a particle size of 50-600 nm, and its molecular formula is (A) 3 O 4 , where A is six elements from Cu, Mn, Fe, Cr, Co, Ti, and Ni, and has a spinel face-centered cubic crystal structure and is the Fd-3m space point group.

2. A spinel-type high entropy oxide photothermal super-hydrophobic anti-icing coating as claimed in claim 1, Features: The spinel high entropy oxide is prepared by the following method: Step 1: CuO, MnO 2 , Fe 2 O 3 Cr 2 O 3 、Co 3 O 4 、TiO 2 、NiO 2 Six of the powders were used as raw materials and were weighed according to a metal atom molar ratio of 1:1:1:1:1:1; Step 2: ball-milling the powders weighed in step 1, drying them at 80-100° C. for 12-24 hours, and grinding them to obtain a mixture powder; Step 3: The mixture powder obtained in step 2 is calcined at high temperature in an air atmosphere and then cooled to room temperature to obtain the product.

3. A spinel-type high entropy oxide photothermal super-hydrophobic anti-icing coating as claimed in claim 2, Features: The ball milling mixing conditions in step 2 refer to ball milling using a planetary ball mill, a ball milling speed of 300-500 r / min, a ball milling time of 5-12 hours, a ball material-water mass ratio of 2-5:1:3, and a ball milling process of: first ball milling for 1 hour, then pausing for 10 minutes, then ball milling for 1 hour, pausing for 10 minutes, and repeating the ball milling cycle.

4. A spinel-type high entropy oxide photothermal super-hydrophobic anti-icing coating as claimed in claim 2, Features: The high temperature calcination conditions in step 3 refer to a calcination temperature of 900-1300° C., a heating rate of 10-15° C. / min, and a calcination time of 5-10 hours; and a cooling method of one of furnace cooling, air quenching cooling, and liquid nitrogen quenching cooling.

5. A spinel-type high entropy oxide photothermal super-hydrophobic anti-icing coating as claimed in claim 1, Features: The mass concentrations of the stearic acid solution and the polymethyl methacrylate solution are both 10-20 mmol / L.

6. A spinel-type high entropy oxide photothermal super-hydrophobic anti-icing coating as claimed in claim 1, Features: The leveling agent is one or two of Digo Glide 450 polyether siloxane leveling agent, AFCONA-3085-polyether modified silicone, and AFCONA-3587-polyether modified silicone; the dispersant is one or two of Digo TEGO 662 C and EFKA 5065; the defoamer is one or two of Digo TEGO 901W polyether siloxane defoamer and EFKA 2720 unsaturated polyester defoamer; the curing agent is SYLGARD 184; the solvent is one or more of anhydrous ethanol, acetone, and ethyl acetate.

7. A method for preparing a spinel high entropy oxide photothermal super hydrophobic anti-icing coating according to any one of claims 1 to 6, Features: First, weigh according to the ratio; then add epoxy resin, spinel high entropy oxide, stearic acid solution, and polymethyl methacrylate solution into the solvent, and stir at a speed of 800-1000 r / min for 60-100 min to obtain a mixed suspension; finally, add polydimethylsiloxane, a leveling agent, a dispersant, a defoaming agent, and a curing agent into the mixed suspension in sequence, and stir at a low speed of 200-400 r / min for 30-60 min to obtain a spinel high entropy oxide photothermal superhydrophobic anti-icing coating.

8. A coating formed by the anti-icing coating prepared by the method according to claim 7, Features: The coating has a light absorption rate of >96% in the 0.3~2.5μm solar light band and a photothermal conversion efficiency of over 70%; the water contact angle on the coating surface is >155° and the water rolling angle is <5°.

9. A method for preparing a coating as claimed in claim 8, The following steps are involved: Step 1: Use quartz sand with a particle size of 60-100 mesh to sandblast the substrate surface so that the surface roughness of the substrate meets the requirements of Ra 12.5-Ra 6.3; Step 2: subjecting the substrate surface after sandblasting to ultrasonic cleaning for 30 to 60 minutes, and drying the cleaned substrate to obtain a treated substrate surface; Step 3: Fill the anti-icing coating into the spray gun and spray it on the treated substrate surface by spraying. Use a 1.5mm caliber spray gun, the spraying environment temperature is 15~30℃, the relative air humidity is 35~85%, the spraying pressure is 0.3~0.4MPa, and the spraying speed is 2~2.5m / min, so as to obtain a wet film with a thickness of 60~80μm; Step 4: Cure the wet film at room temperature for 24 hours or in a muffle furnace at 80°C for 2.5 to 3 hours to obtain a dry film with a thickness of 30 to 40 μm.

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