Photo-thermal super-hydrophobic coating as well as preparation method and application thereof

Abstract

The invention relates to the technical field of coatings, in particular to a photo-thermal super-hydrophobic coating as well as a preparation method and application thereof. The invention provides a photo-thermal super-hydrophobic coating. The photo-thermal super-hydrophobic coating is prepared from the following raw materials in parts by weight: 3 to 5 parts of organic silicon polysilazane, 5 to 7 parts of methyl phenyl polysiloxane, 3 to 5 parts of vinyl chloride and vinyl acetate copolymer, 4 to 6 parts of modified ferroferric oxide, 5 to 7 parts of fluorinated multi-walled carbon nanotube, 4 to 6 parts of fluorinated black titanium dioxide, 59 to 82 parts of organic solvent and 0.02 to 0.2 part of defoaming agent. Wherein the modified ferroferric oxide is ferroferric oxide coated with copper chloride. The photo-thermal super-hydrophobic coating provided by the invention has ultrahigh hydrophobic performance and good photo-thermal conversion performance, the water contact angle can reach 155 degrees or above, the rolling angle is less than 10 degrees, the surface hardness of the coating is 4H or above, the adhesive force is grade 0, and the comprehensive performance is excellent.

Description

Technical Field

[0001] The present invention relates to the technical field of coatings, and in particular to a photothermal super-hydrophobic coating and a preparation method and application thereof. Background Art

[0002] Transmission lines are exposed to complex atmospheric environments for a long time and are extremely susceptible to extreme weather such as rain, snow, and ice, which seriously threatens the safe and stable operation of the power grid. Especially in cold and humid areas, ice and snow easily accumulate on the surface of power insulators and cables, resulting in reduced insulation performance, which in turn causes electrical faults such as flashover and pollution flashover. In addition, ice will increase the mechanical load of the line, causing accidents such as line breakage and tower collapse, which will not only bring huge economic losses, but also may affect the normal power supply of society.

[0003] At present, in order to reduce the impact of ice and snow disasters on transmission lines, super-hydrophobic coatings are usually applied on the surface of insulators or cables to reduce the adhesion of ice and snow by using their low surface energy characteristics. However, existing super-hydrophobic coatings still have the following technical defects: (1) After long-term exposure to external environments such as ultraviolet rays, temperature changes and mechanical friction, the microscopic rough structure of the coating is easily destroyed, resulting in a significant decrease in hydrophobic properties (such as water contact angle and rolling angle); (2) Traditional super-hydrophobic coatings lack active deicing capabilities and only rely on passive anti-icing. Ice accumulation may still occur under continuous low temperature and high humidity conditions; (3) Some fluorine-containing low surface energy materials such as polytetrafluoroethylene are prone to degradation after long-term outdoor use, further reducing the durability of the coating.

[0004] Therefore, existing super-hydrophobic coatings are still difficult to effectively prevent flashover accidents in the long term, and there is an urgent need to develop a new type of protective material that has both high hydrophobic stability and active de-icing function. Summary of the invention

[0005] In view of this, the present invention provides a photothermal super-hydrophobic coating and a preparation method and application thereof. The photothermal super-hydrophobic coating has ultra-high hydrophobicity and good photothermal conversion performance, a water contact angle of more than 155°, and a rolling angle of less than 10°.

[0006] To solve the above technical problems, the present invention provides a photothermal super-hydrophobic coating, comprising the following raw materials in parts by weight: 3-5 parts of organosilicon polysilazane, 5-7 parts of methylphenyl polysiloxane, 3-5 parts of vinyl chloride and vinyl acetate copolymer, 4-6 parts of modified ferrosoferric oxide, 5-7 parts of fluorinated multi-walled carbon nanotubes, 4-6 parts of fluorinated black titanium dioxide, 59-82 parts of organic solvents, and 0.02-0.2 parts of defoaming agents; the modified ferrosoferric oxide is ferrosoferric oxide coated with cupric chloride.

[0007] The present invention uses organosilicon polysilazane, methylphenyl polysiloxane, and vinyl chloride and vinyl acetate copolymer as mixed film-forming materials to obtain a strong, wear-resistant, durable and weather-resistant coating film. Among them, organosilicon polysilazane and methylphenyl polysiloxane have good electrical properties, mechanical properties and weather resistance, ensuring that the coating has good comprehensive properties; vinyl chloride and vinyl acetate copolymer are used as bonding main forces to enhance the adhesion of the coating and the coagulation force of the coating on the powder filler. Copper chloride-coated ferroferric oxide, fluorinated black titanium dioxide and fluorinated multi-walled carbon nanotubes are used as metal-based, ceramic-based and carbon-based materials in the photothermal conversion unit, respectively. The three are used in combination to produce high conversion efficiency, long-lasting conversion time and other effects, so that the coating surface has a super-hydrophobic bionic micro-nano structure and extremely low surface tension, thereby taking into account super-hydrophobic and photothermal effects.

[0008] Moreover, the present invention utilizes the differences in density and particle size of copper chloride-coated ferroferric oxide, fluorinated black titanium dioxide and fluorinated multi-walled carbon nanotubes, and sprays them as fillers onto the surface of an object. The copper chloride-coated ferroferric oxide and fluorinated black titanium dioxide of the heating unit are interlaced with each other, and the fluorinated multi-walled carbon nanotubes are located in the outermost layer of the coating, so that a finer micro-nano structure is formed on the surface of the coating, ensuring that the photothermal unit can receive direct sunlight and increase the temperature of the coating surface.

[0009] In combination with the first aspect, the modified ferroferric oxide is prepared according to the following method: adding ferroferric oxide to a cupric chloride aqueous solution and stirring for 4-6 hours, then separating the solid and liquid, collecting the ferroferric oxide and drying the water, and continuing to sinter at 650-750° C. for 1-3 hours.

[0010] Exemplarily, the modified ferroferric oxide is prepared as follows: 180-220 g of cupric chloride powder is added to 1 L of water to obtain a cupric chloride aqueous solution, 100 g of ferroferric oxide powder is added, and stirred for 4-6 hours, followed by solid-liquid separation, collecting the solid ferroferric oxide powder and drying it in an oven to evaporate the water, and then transferring the dried ferroferric oxide powder into a crucible and sintering it at 700° C. for 2 hours to melt the cupric chloride on the surface of the ferroferric oxide, and then cooling and sieving to obtain copper chloride-coated ferroferric oxide powder.

[0011] Coating the ferroferric oxide powder with copper chloride can not only ensure a good light-to-heat conversion rate of the coating, but also reduce the surface tension of the ferroferric oxide powder, allowing it to be more evenly dispersed in the coating and avoid agglomeration.

[0012] In combination with the first aspect, the particle size of the modified ferrosoferric oxide is 2-6 μm, preferably 2.6-5.5 μm.

[0013] In combination with the first aspect, the fluorinated multi-walled carbon nanotubes and the fluorinated black titanium dioxide are both fluorinated using ammonium hexafluorotitanate and boric acid, and the steps include: Multi-walled carbon nanotubes and black titanium dioxide are added to water to obtain a suspension, and after heating to 55-75° C., ammonium hexafluorotitanate is added under stirring, and the pH value of the suspension is adjusted to 2.5-3 with boric acid, and stirring is continued for 3-4 hours. After solid-liquid separation, washing and drying, fluorinated multi-walled carbon nanotubes and fluorinated black titanium dioxide are obtained.

[0014] Exemplarily, the fluorinated multi-walled carbon nanotubes and fluorinated black titanium dioxide are both fluorinated using ammonium hexafluorotitanate and boric acid, and the steps include: adding 28-32g of multi-walled carbon nanotubes and 23-28g of black titanium dioxide to 1L of water and ultrasonically homogenizing to obtain a suspension, magnetically stirring and heating to 55-75°C, dropping 10g of ammonium hexafluorotitanate under stirring, adding boric acid to adjust the pH value to 2.5-3, continuing stirring for 3-4 hours, then separating the solid and the liquid, washing the solid with water to remove free ammonium hexafluorotitanate, and drying to obtain fluorinated multi-walled carbon nanotubes and fluorinated black titanium dioxide.

[0015] In combination with the first aspect, the fluorinated multi-walled carbon nanotubes have an outer diameter of 5-30 nm and a length of 2-10 μm.

[0016] Preferably, the fluorinated multi-walled carbon nanotubes have an outer diameter of 10-20 nm and a length of 2-8 μm.

[0017] In combination with the first aspect, the organic solvent includes 50-68 parts of ethyl acetate and / or butyl acetate, and 9-14 parts of cyclohexanone and / or xylene.

[0018] Preferably, the organic solvent comprises 56 parts of ethyl acetate and / or butyl acetate and 11 parts of cyclohexanone and / or xylene.

[0019] In combination with the first aspect, the defoamer is an organosilicon defoamer. The organosilicon defoamer has extremely low surface tension and strong diffusivity, and can break, defoam and suppress bubbles in the coating, making the coating surface smooth and the internal structure compact.

[0020] In combination with the first aspect, the particle size of the fluorinated black titanium dioxide is 1-3 μm, preferably 1-2 μm.

[0021] A second aspect of the present invention provides a method for preparing the above-mentioned photothermal super-hydrophobic coating, comprising the steps of: adding the organosilicon polysilazane, methylphenyl polysiloxane and vinyl chloride and vinyl acetate copolymer to the organic solvent and mixing them evenly, adding the defoamer and mixing them evenly to obtain a dilution of a film-forming material; continuing to add the modified ferrosoferric oxide, fluorinated multi-walled carbon nanotubes and fluorinated black titanium dioxide while stirring, and ultrasonicating for 2 to 3 hours to evenly disperse the raw materials to obtain the photothermal super-hydrophobic coating.

[0022] In order to ensure the uniformity of the texture of the obtained coating, the coating can be filtered after 2 to 3 hours of ultrasound to better meet the applicable requirements.

[0023] Exemplarily, 80-mesh nylon filter cloth may be used for filtering, or other filtering methods may be used.

[0024] The third aspect of the present invention also provides an application of the above-mentioned photothermal super-hydrophobic coating or the photothermal super-hydrophobic coating prepared according to the above-mentioned preparation method in power cables, building materials, vehicles and industrial facilities.

[0025] Applying the photothermal super-hydrophobic coating provided by the present invention to power cables or insulators can effectively prevent the external environment from damaging the power lines. In particular, after the power lines are covered with ice, the coating formed by the coating can increase the surface temperature under sunlight and accelerate the melting of ice and snow, thereby reducing or even avoiding the occurrence of flashover, and effectively ensuring the safe operation of the power system.

[0026] The photothermal super-hydrophobic coating provided by the present invention has significant advantages in the field of power system protection. When the coating is applied to the surface of power cable or insulator, a functional coating with excellent protective performance can be formed. The coating effectively blocks the erosion of the external environment to the power line by super-hydrophobic characteristics on the one hand, and on the other hand, by virtue of its photothermal conversion performance, the surface temperature can be significantly improved under sunlight irradiation, and this characteristic enables the coating to accelerate the melting process of ice and snow in the case of winter ice coating, thereby greatly reducing the probability of occurrence of dirty flash accidents. Applying the coating to power equipment can significantly improve its operational reliability in harsh environments, and provides important guarantees for the safe and stable operation of power systems.

[0027] The present invention obtains a super-hydrophobic coating having a water contact angle greater than 150 ° and a water rolling angle less than 10 ° by making a specific selection of the formula composition; the surface temperature of the coating will be significantly higher than the ambient temperature after being irradiated by natural light, so that the melting of ice and snow on the coating surface can be promoted to avoid line failure. Moreover, the coating formed after the coating is cured also has a higher hardness, and the water contact angle is still above 150 ° after being polished 10 times with 80 mesh sandpaper with a weight of 500g. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 The hydrophobic effect diagram of the coating obtained in Example 1 corresponds to the coating; Figure 2 This is a test diagram of the water contact angle of the coating corresponding to the coating obtained in Example 1; Figure 3 This is a test diagram of the rolling angle of the coating corresponding to the coating obtained in Example 1; Figure 4 These are photos of on-site testing of the photothermal effect of the coating corresponding to the coating obtained in Example 1. DETAILED DESCRIPTION

[0029] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with specific embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0030] Those skilled in the art will appreciate that, unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as those generally understood by those skilled in the art in the art to which the present invention belongs. It should also be understood that terms such as those defined in general dictionaries should be understood to have meanings consistent with the meanings in the context of the prior art, and will not be interpreted with idealized or overly formal meanings unless specifically defined.

[0031] Existing super-hydrophobic coatings are exposed to ultraviolet rays or mechanical friction and other external environments for a long time, and the microstructure of the coating is easily destroyed, and the main material may also be degraded, so that the hydrophobic performance is significantly reduced; and traditional super-hydrophobic coatings have almost no photothermal effect, and ice accumulation may occur under continuous low temperature and high humidity conditions, increasing potential safety hazards. To this end, the present invention provides a kind of photothermal super-hydrophobic coating, which has excellent super-hydrophobic performance, good surface hardness and photothermal conversion ability, can not only reduce the attachment of ice, snow and rain on its surface, but also its surface temperature will increase under the irradiation of natural light, and then accelerate the melting of ice, avoid the occurrence of dirty flash accidents.

[0032] The preparation method provided by the present invention is described below through specific examples.

[0033] The raw materials, reagents and equipment used in the present invention are all conventional commercially available common reagents and common equipment.

[0034] The organosilicon polysilazane used is a main chain formed by silicon atoms and nitrogen atoms connected by covalent bonds, and contains organic groups as side groups. Its typical structural formula is shown in Formula I, wherein the methyl group in the side chain group can be partially or completely replaced by ethyl, vinyl, hydrogen or phenyl. Methylphenyl polysiloxane is a polymer with a silicon-oxygen bond as the main chain and containing methyl and phenyl organic groups, wherein part of the methyl and phenyl groups can be replaced by hydrogen, or the hydrogen in the methyl or phenyl groups can be replaced by halogen or methyl. Vinyl chloride and vinyl acetate copolymer is a polymer compound formed by the polymerization of two monomers, vinyl chloride and vinyl acetate, and its molecular formula is (C2H3Cl) x (C4H6O2) y The defoamer used is a commercially available silicone defoamer, for example, a defoamer of model BYK141 can be selected.

[0035]

[0036] Formula I Example 1 This embodiment provides a photothermal super-hydrophobic coating, comprising the following raw materials in parts by weight: 4 parts of organosilicon polysilazane, 6 parts of methylphenyl polysiloxane, 4 parts of vinyl chloride and vinyl acetate copolymer, 5 parts of ferrosoferric oxide powder coated with cupric chloride, 6 parts of fluorinated multi-walled carbon nanotubes, 5 parts of fluorinated black titanium dioxide, 56 parts of ethyl acetate, 11 parts of cyclohexanone, and 0.05 parts of organosilicon defoamer.

[0037] The photothermal super hydrophobic coating is prepared according to the following method: According to the above mass fractions, organosilicon polysilazane, methylphenyl polysiloxane and vinyl chloride and vinyl acetate copolymer are added to the mixed solution of ethyl acetate and cyclohexanone and stirred evenly, and then an organosilicon defoamer is added and mixed evenly to obtain a dilution of a film-forming material. Ferrous oxide powder, fluorinated multi-walled carbon nanotubes and fluorinated black titanium dioxide coated with cupric chloride are added while stirring, and each component is evenly dispersed by ultrasound for 2h to obtain a photothermal super-hydrophobic coating.

[0038] The copper chloride-coated ferroferric oxide powder is prepared as follows: Add 200g of copper chloride powder to 1L of water to obtain a copper chloride aqueous solution, add 100g of ferroferric oxide powder, stir for 5h, then separate the solid and liquid, collect the solid ferroferric oxide powder and dry it in an oven at 100℃ for 1h to evaporate the water, then transfer the dried ferroferric oxide powder into a crucible and sinter at 700℃ for 2h to melt the copper chloride on the surface of the ferroferric oxide, then cool and sieve to obtain copper chloride-coated ferroferric oxide powder.

[0039] The fluorinated multi-walled carbon nanotubes and fluorinated black titanium dioxide are prepared according to the following method: 30 g of multi-walled carbon nanotubes and 25 g of black titanium dioxide were added to 1 L of water and ultrasonically homogenized to obtain a suspension. The suspension was magnetically stirred and heated to 70°C. 10 g of ammonium hexafluorotitanate was added dropwise while stirring. Then, boric acid was added dropwise while stirring to adjust the pH value to 2.5-3. The stirring was continued for 4 hours (keeping the pH value at 2.5-3). After that, the solid-liquid separation was performed. The solid was washed with water to remove free ammonium hexafluorotitanate. The water was dried to obtain fluorinated multi-walled carbon nanotubes and fluorinated black titanium dioxide.

[0040] In addition, the particle size of the copper chloride-coated ferrosoferric oxide powder used in this embodiment is 2-4 μm, the outer diameter of the fluorinated multi-walled carbon nanotube is 20-30 nm, the tube length is 2-10 μm, and the particle size of the fluorinated black titanium dioxide is 1-2 μm.

[0041] Example 2 This embodiment provides a photothermal super-hydrophobic coating, comprising the following raw materials in parts by weight: 5 parts of organosilicon polysilazane, 7 parts of methylphenyl polysiloxane, 3 parts of vinyl chloride and vinyl acetate copolymer, 5 parts of ferrosoferric oxide powder coated with cupric chloride, 5 parts of fluorinated multi-walled carbon nanotubes, 6 parts of fluorinated black titanium dioxide, 52 parts of ethyl acetate, 14 parts of xylene, and 0.02 parts of organosilicon defoamer.

[0042] The photothermal super hydrophobic coating is prepared according to the following method: According to the above mass fractions, organosilicon polysilazane, methylphenyl polysiloxane and vinyl chloride and vinyl acetate copolymer are added to the mixed solution of ethyl acetate and cyclohexanone and stirred evenly, and then an organosilicon defoamer is added and mixed evenly to obtain a dilution of a film-forming material. Ferrous oxide powder, fluorinated multi-walled carbon nanotubes and fluorinated black titanium dioxide coated with cupric chloride are added while stirring, and each component is evenly dispersed by ultrasound for 3h to obtain a photothermal super-hydrophobic coating.

[0043] The copper chloride-coated ferroferric oxide powder is prepared as follows: 180g of copper chloride powder was added to 1L of water to obtain a copper chloride aqueous solution, and 100g of ferroferric oxide powder was added and stirred for 4h. Then, the solid-liquid separation was performed, and the solid ferroferric oxide powder was collected and dried in an oven at 100°C for 1h to evaporate the water. The dried ferroferric oxide powder was then transferred to a crucible and sintered at 650°C for 3h to melt the copper chloride on the surface of the ferroferric oxide. The solution was then cooled and sieved to obtain ferroferric oxide powder coated with copper chloride.

[0044] The fluorinated multi-walled carbon nanotubes and fluorinated black titanium dioxide are prepared according to the following method: 28 g of multi-walled carbon nanotubes and 28 g of black titanium dioxide were added to 1 L of water and ultrasonically homogenized to obtain a suspension. The suspension was magnetically stirred and heated to 60°C. 10 g of ammonium hexafluorotitanate was added dropwise while stirring. Then, boric acid was added dropwise while stirring to adjust the pH value to 2.5-3. The stirring was continued for 3.5 hours (keeping the pH value at 2.5-3). After that, the solid-liquid separation was performed. The solid was washed with water to remove free ammonium hexafluorotitanate. The water was dried to obtain fluorinated multi-walled carbon nanotubes and fluorinated black titanium dioxide.

[0045] In addition, the particle size of the copper chloride-coated ferrosoferric oxide powder used in this embodiment is 3-6 μm, the outer diameter of the fluorinated multi-walled carbon nanotube is 5-15 nm, the tube length is 2-6 μm, and the particle size of the fluorinated black titanium dioxide is 1-3 μm.

[0046] Example 3 This embodiment provides a photothermal super-hydrophobic coating, comprising the following raw materials in parts by weight: 3 parts of organosilicon polysilazane, 5 parts of methylphenyl polysiloxane, 5 parts of vinyl chloride and vinyl acetate copolymer, 6 parts of ferrosoferric oxide powder coated with cupric chloride, 7 parts of fluorinated multi-walled carbon nanotubes, 4 parts of fluorinated black titanium dioxide, 68 parts of butyl acetate, 9 parts of cyclohexanone, and 0.18 parts of organosilicon defoamer.

[0047] The photothermal super hydrophobic coating is prepared according to the following method: According to the above mass fractions, organosilicon polysilazane, methylphenyl polysiloxane and vinyl chloride and vinyl acetate copolymer are added to the mixed solution of ethyl acetate and cyclohexanone and stirred evenly, and then an organosilicon defoamer is added and mixed evenly to obtain a dilution of a film-forming material. Ferrous oxide powder, fluorinated multi-walled carbon nanotubes and fluorinated black titanium dioxide coated with cupric chloride are added while stirring, and each component is evenly dispersed by ultrasound for 2.5 hours to obtain a photothermal super-hydrophobic coating.

[0048] The copper chloride-coated ferroferric oxide powder is prepared as follows: Add 220g of copper chloride powder to 1L of water to obtain a copper chloride aqueous solution, add 100g of ferroferric oxide powder, stir for 6h, then separate the solid and liquid, collect the solid ferroferric oxide powder and dry it in an oven at 100℃ for 1h to evaporate the water, then transfer the dried ferroferric oxide powder into a crucible and sinter at 750℃ for 1h to melt the copper chloride on the surface of the ferroferric oxide, then cool and sieve to obtain copper chloride-coated ferroferric oxide powder.

[0049] The fluorinated multi-walled carbon nanotubes and fluorinated black titanium dioxide are prepared according to the following method: 32 g of multi-walled carbon nanotubes and 23 g of black titanium dioxide were added to 1 L of water and ultrasonically homogenized to obtain a suspension. The suspension was magnetically stirred and heated to 75°C. 10 g of ammonium hexafluorotitanate was added dropwise while stirring. Then, boric acid was added dropwise while stirring to adjust the pH value to 2.5-3. The stirring was continued for 4 hours (keeping the pH value at 2.5-3). After that, the solid-liquid separation was performed. The solid was washed with water to remove free ammonium hexafluorotitanate. The water was dried to obtain fluorinated multi-walled carbon nanotubes and fluorinated black titanium dioxide.

[0050] In addition, the particle size of the copper chloride-coated ferrosoferric oxide powder used in this embodiment is 2-6 μm, the outer diameter of the fluorinated multi-walled carbon nanotube is 10-30 nm, the tube length is 3-6 μm, and the particle size of the fluorinated black titanium dioxide is 1.5-3 μm.

[0051] Comparative Example 1 This comparative example provides a coating, comprising the following raw materials in parts by weight: 4 parts of organosilicon polysilazane, 6 parts of methylphenyl polysiloxane, 4 parts of vinyl chloride and vinyl acetate copolymer, 5 parts of ferrosoferric oxide powder, 6 parts of fluorinated multi-walled carbon nanotubes, 5 parts of fluorinated black titanium dioxide, 56 parts of ethyl acetate, 11 parts of cyclohexanone, and 0.05 parts of organosilicon defoamer.

[0052] The difference between the coating composition of this comparative example and that of Example 1 is that the ferroferric oxide powder used is not coated with cupric chloride, and the other raw materials and preparation methods are the same as those of Example 1, which will not be described in detail.

[0053] Comparative Example 2 This comparative example provides a coating, comprising the following raw materials in parts by weight: 4 parts of organosilicon polysilazane, 6 parts of methylphenyl polysiloxane, 4 parts of vinyl chloride and vinyl acetate copolymer, 5 parts of ferrosoferric oxide powder coated with cupric chloride, 6 parts of multi-walled carbon nanotubes, 5 parts of black titanium dioxide, 56 parts of ethyl acetate, 11 parts of cyclohexanone, and 0.05 parts of organosilicon defoamer.

[0054] The difference between the coating composition of this comparative example and that of Example 1 is that non-fluorinated multi-walled carbon nanotubes and black titanium dioxide are used, and the remaining raw materials and preparation methods are the same as those of Example 1, which will not be described in detail.

[0055] Comparative Example 3 This comparative example provides a coating, comprising the following raw materials in parts by weight: 8 parts of methylphenyl polysiloxane, 6 parts of vinyl chloride and vinyl acetate copolymer, 5 parts of ferrosoferric oxide powder coated with cupric chloride, 6 parts of fluorinated multi-walled carbon nanotubes, 5 parts of fluorinated black titanium dioxide, 56 parts of ethyl acetate, 11 parts of cyclohexanone, and 0.05 parts of silicone defoamer.

[0056] The difference between the coating composition of this comparative example and that of Example 1 is that no organosilicon polysilazane is added, and the remaining raw materials and preparation methods are the same as those of Example 1, which will not be described in detail.

[0057] Comparative Example 4 This comparative example provides a coating, comprising the following raw materials in parts by weight: 7 parts of organosilicon polysilazane, 7 parts of vinyl chloride and vinyl acetate copolymer, 5 parts of ferrosoferric oxide powder coated with cupric chloride, 6 parts of fluorinated multi-walled carbon nanotubes, 5 parts of fluorinated black titanium dioxide, 56 parts of ethyl acetate, 11 parts of cyclohexanone, and 0.05 parts of organosilicon defoamer.

[0058] The difference between the coating composition of this comparative example and that of Example 1 is that methylphenyl polysiloxane is not added, and the remaining raw materials and preparation methods are the same as those of Example 1, which will not be described in detail.

[0059] Comparative Example 5 This comparative example provides a coating, comprising the following raw materials in parts by weight: 6 parts of organosilicon polysilazane, 8 parts of methylphenyl polysiloxane, 5 parts of ferrosoferric oxide powder coated with cupric chloride, 6 parts of fluorinated multi-walled carbon nanotubes, 5 parts of fluorinated black titanium dioxide, 56 parts of ethyl acetate, 11 parts of cyclohexanone, and 0.05 parts of organosilicon defoamer.

[0060] The difference between the coating composition of this comparative example and that of Example 1 is that no vinyl chloride and vinyl acetate copolymer is added, and the remaining raw materials and preparation methods are the same as those of Example 1, which will not be described in detail.

[0061] Comparative Example 6 This comparative example provides a coating, comprising the following raw materials in parts by weight: 4 parts of organosilicon polysilazane, 6 parts of methylphenyl polysiloxane, 4 parts of vinyl chloride and vinyl acetate copolymer, 9 parts of fluorinated multi-walled carbon nanotubes, 7 parts of fluorinated black titanium dioxide, 56 parts of ethyl acetate, 11 parts of cyclohexanone, and 0.05 parts of organosilicon defoamer.

[0062] The difference between the coating composition of this comparative example and that of Example 1 is that the ferroferric oxide powder coated with cupric chloride is not added, and the remaining raw materials and preparation methods are the same as those of Example 1, which will not be described in detail.

[0063] Comparative Example 7 This comparative example provides a coating, comprising the following raw materials in parts by weight: 4 parts of organosilicon polysilazane, 6 parts of methylphenyl polysiloxane, 4 parts of vinyl chloride and vinyl acetate copolymer, 9 parts of ferrosoferric oxide powder coated with cupric chloride, 10 parts of fluorinated black titanium dioxide, 56 parts of ethyl acetate, 11 parts of cyclohexanone, and 0.05 parts of organosilicon defoamer.

[0064] The difference between the coating composition of this comparative example and that of Example 1 is that no fluorinated multi-walled carbon nanotubes are added, and the remaining raw materials and preparation methods are the same as those of Example 1, which will not be described in detail.

[0065] Comparative Example 8 This comparative example provides a coating, comprising the following raw materials in parts by weight: 4 parts of organosilicon polysilazane, 6 parts of methylphenyl polysiloxane, 4 parts of vinyl chloride and vinyl acetate copolymer, 8 parts of ferrosoferric oxide powder coated with cupric chloride, 8 parts of fluorinated multi-walled carbon nanotubes, 56 parts of ethyl acetate, 11 parts of cyclohexanone, and 0.05 parts of organosilicon defoamer.

[0066] The difference between the coating composition of this comparative example and that of Example 1 is that no fluorinated black titanium dioxide is added, and the remaining raw materials and preparation methods are the same as those of Example 1, which will not be described in detail.

[0067] Test example The coatings obtained in Examples 1 to 3 and Comparative Examples 1 to 8 were respectively applied to the surface of the substrate with a film thickness of 15±2 μm and dried at room temperature of 25°C for 24 hours. The obtained coatings were tested for water contact angle and rolling angle (reference standard GB / T 45017-2024 "Mechanical stability test method for super-hydrophobic surface"), adhesion (reference standard GB / T1720-2020 "Paint film scratching test"), photothermal effect (natural light irradiation with a light power of 500 W / m² for 30 minutes) and hardness (reference standard GB / T 6739-2006 "Determination of paint film hardness by pencil method for paints and varnishes"), and the test results are shown in Table 1.

[0068] Table 1

[0069] It can be seen from the data in Table 1 that the water contact angle of the photothermal super-hydrophobic coating provided by the present invention is more than 155°, the rolling angle is less than 10°, and it has good adhesion and photothermal conversion performance, the adhesion to the glass substrate and the stainless steel substrate is 0 level, the coating surface hardness is 4H, and after polishing, it can still maintain a water contact angle of more than 150°, indicating that the photothermal super-hydrophobic coating provided by the present invention has excellent comprehensive performance.

[0070] The hydrophobic effect diagram of the coating obtained in Example 1 is as follows: Figure 1 As shown, the water contact angle and rolling angle test diagrams of the corresponding coatings are Figure 2~3 As shown in the on-site test photos of the surface temperature and the surrounding environment temperature after irradiation with natural light of 500W / m² for 30 minutes. Figure 4 As shown, it can be seen that after exposure to light, the temperature of the coating surface is much higher than the temperature of the surrounding environment, indicating that the coating has good light-to-heat conversion performance.

[0071] What is described above is only a preferred specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Any technician familiar with the technical field can make equivalent replacements or changes according to the technical scheme and inventive concept of the present invention within the technical scope disclosed by the present invention, which should be covered by the protection scope of the present invention.

Claims

1. A photothermal super-hydrophobic coating, characterized in that: The invention comprises the following raw materials in parts by weight: 3-5 parts of organosilicon polysilazane, 5-7 parts of methylphenyl polysiloxane, 3-5 parts of vinyl chloride and vinyl acetate copolymer, 4-6 parts of modified ferrosoferric oxide, 5-7 parts of fluorinated multi-walled carbon nanotubes, 4-6 parts of fluorinated black titanium dioxide, 59-82 parts of organic solvent and 0.02-0.2 parts of defoaming agent; the modified ferrosoferric oxide is ferrosoferric oxide coated with cupric chloride.

2. The photothermal super-hydrophobic coating according to claim 1, wherein The modified ferroferric oxide is prepared according to the following method: adding ferroferric oxide to a cupric chloride aqueous solution and stirring for 4-6 hours, then separating the solid and liquid, collecting the ferroferric oxide and drying the water, and continuing to sinter at 650-750° C. for 1-3 hours.

3. The photothermal super-hydrophobic coating according to claim 2, wherein The particle size of the modified ferrosoferric oxide is 2-6 μm.

4. The photothermal super-hydrophobic coating according to claim 1, wherein The fluorinated multi-walled carbon nanotubes and the fluorinated black titanium dioxide are both fluorinated using ammonium hexafluorotitanate and boric acid, and the steps include: Multi-walled carbon nanotubes and black titanium dioxide are added to water to obtain a suspension, and after heating to 55-75° C., ammonium hexafluorotitanate is added under stirring, and the pH value of the suspension is adjusted to 2.5-3 with boric acid, and stirring is continued for 3-4 hours. After solid-liquid separation, washing and drying, fluorinated multi-walled carbon nanotubes and fluorinated black titanium dioxide are obtained.

5. The photothermal super-hydrophobic coating according to claim 4, wherein The fluorinated multi-walled carbon nanotubes have a diameter of 5-30 nm and a length of 2-10 μm.

6. The photothermal super-hydrophobic coating according to claim 4, wherein The particle size of the fluorinated black titanium dioxide is 1-3 μm.

7. The photothermal super-hydrophobic coating according to claim 1, wherein The organic solvent comprises 50-68 parts of ethyl acetate and / or butyl acetate and 9-14 parts of cyclohexanone and / or xylene.

8. The photothermal super-hydrophobic coating according to claim 1, wherein The defoamer is an organosilicon defoamer.

9. The preparation method of the photothermal super-hydrophobic coating according to any one of claims 1 to 8, characterized in that the steps include: According to the mass fraction, the organosilicon polysilazane, methylphenyl polysiloxane and vinyl chloride and vinyl acetate copolymer are added to the organic solvent and mixed evenly, the defoamer is added and mixed evenly to obtain a dilution of the film-forming material; the modified ferrosoferric oxide, fluorinated multi-walled carbon nanotubes and fluorinated black titanium dioxide are added while continuing to stir, and the raw materials are evenly dispersed by ultrasound for 2 to 3 hours to obtain the photothermal superhydrophobic coating.

10. the photothermal super-hydrophobic coating described in any one of claims 1 to 8 or the application of the photothermal super-hydrophobic coating prepared according to the preparation method described in claim 9 in power cables, building materials, vehicles and industrial facilities.

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