Wear-resistant intelligent temperature control material, film and preparation method thereof

Abstract

The invention belongs to the field of functional materials, and particularly relates to a wear-resistant intelligent temperature control material, a film and a preparation method thereof. The method comprises the following steps: mixing a vanadium salt solution with a precipitant, reacting, and separating precipitates to obtain a vanadium-based precursor; mechanically mixing titanium powder, a carbon material, chlorine salt and the vanadium-based precursor to obtain a vanadium-titanium-based precursor; and heating the vanadium-titanium-based precursor to a preset temperature, preserving heat, cooling, dissolving the obtained solid in water, filtering and drying to obtain the wear-resistant intelligent temperature control material. The invention also provides a method for preparing a film by using the wear-resistant intelligent temperature control material. The method comprises the following steps: dispersing the wear-resistant intelligent temperature control material in an organic solvent of an ethyl acetate system, grinding to a preset particle size range to obtain slurry, adding the slurry into varnish, uniformly stirring, and coating on a substrate to obtain the film. The intelligent temperature control film prepared by the method has the characteristics of high hardness, high melting point, high strength, friction resistance, high temperature resistance, oxidation resistance and better chemical stability.

Description

Technical Field

[0001] The present invention belongs to the technical field of functional materials, and particularly relates to a wear-resistant intelligent temperature control material, a film and a preparation method thereof. Background Art

[0002] Vanadium dioxide (VO2) is in a semiconductor state at low temperature, with a monoclinic phase (M phase), and in a metallic state at high temperature, with a rutile phase (R phase). VO2 undergoes a phase transition from a low-temperature monoclinic structure to a high-temperature rutile structure at about 68 °C, during which significant changes occur in electrical conductivity and optical properties. This reversible phase transition characteristic makes it have application potential in many fields.

[0003] VO2 has a relatively low phase transition temperature and exhibits special non-linear electrical and optical properties during the MIT phase transition. Before and after the phase transition, its transmittance to infrared light changes from high to high reflectivity. Due to this unique phase transition property and excellent performance of VO2, in recent years, VO2 has been widely used in smart glass, optical storage, laser radiation protection films, lithium battery electrodes, highly sensitive temperature sensors, tunable microwave switch devices, infrared light modulation materials, etc.

[0004] However, since the phase transition temperature of VO2 is about 68 °C, significantly higher than room temperature, it is difficult to play a role in reality and its application is limited. Currently, there are some methods for modulating the phase transition temperature of VO2, which mainly include element doping, external electric field regulation, light irradiation, strain regulation, etc. Among them, element doping is an effective means to adjust the phase and MIT temperature of VO2. For example, Patent CN101265374A discloses an intelligent heat insulation film and a preparation method thereof, which uses a phase change intelligent nano-powder with a rutile crystal structure to dope vanadium dioxide V 1-x M x O2 (0 < X < 0.06), uniformly dispersed in a film-forming material to prepare an intelligent heat insulation film with a phase change function. This intelligent heat insulation film is a new type of energy-saving material, with a phase transition temperature adjustable within -10 °C - 70 °C, having a high infrared transmittance and a low reflectivity at low temperatures, excellent heat preservation performance; having a low infrared transmittance and a high reflectivity at high temperatures, good heat insulation effect. Although the existing element doping process can solve some problems, it will affect the visible light transmittance and solar light regulation ability.

[0005] The water resistance of traditional VO2 films cannot meet the requirements of long-term outdoor use of the coating. Moreover, VO2 has poor stability in the air and is easy to react with oxygen and water molecules to generate high-valent V2O5. V2O5 has no thermochromic effect, and the infrared regulation ability of the oxidized area is reduced, which seriously reduces the functionality of the film. At the same time, the oxidation process is accompanied by lattice expansion and structural distortion, which leads to cracks, holes and even peeling in the film. Moreover, during long-term outdoor use, VO2 films will inevitably be washed away by rain and rubbed by rags during cleaning. The current VO2 film materials are not resistant to rain erosion, friction, and easy to fall off, which seriously reduces the service life of the film.

[0006] Therefore, there is an urgent need in the art to develop a wear-resistant intelligent temperature control material with high wear resistance and strong antioxidant ability, a film including the wear-resistant intelligent temperature control material, and a preparation method thereof. Summary of the invention

[0007] In view of this, in order to solve the problems existing in the prior art, the present invention provides a wear-resistant intelligent temperature control material, a film and a preparation method thereof, thereby solving the problems that the basic vanadium dioxide film is easily oxidized, has poor stability, can be corroded by acid rain, and is not resistant to friction.

[0008] The technical solution adopted by the present invention is as follows: A first aspect of the present invention provides a method for preparing a wear-resistant intelligent temperature control material, the method comprising the following steps: Step S1: mixing a vanadium salt solution containing tetravalent vanadium with a precipitant containing hydroxide, and separating the precipitate after the reaction to obtain a vanadium-based precursor; Step S2: mechanically mixing titanium powder, carbon material, chloride salt and the vanadium-based precursor to obtain a vanadium-titanium-based precursor, wherein the carbon material comprises a combination of carbon nanotubes and at least one of the following: carbon black, graphite; Step S3: heating the vanadium-titanium-based precursor to a predetermined temperature and keeping the temperature, dissolving the obtained solid in water after cooling, filtering and drying to obtain the wear-resistant intelligent temperature control material.

[0009] According to one embodiment of the present invention, the vanadium salt is selected from at least one of vanadyl sulfate, vanadyl chloride and vanadyl nitrate, and the concentration of the vanadium salt in the vanadium salt solution is 0.8-2 mol / L.

[0010] According to one embodiment of the present invention, the chloride salt is selected from at least one of sodium chloride, potassium chloride and calcium chloride.

[0011] According to one embodiment of the present invention, the molar ratio of the titanium powder to the carbon material is 0.9-1.2:1, the mass percentage of the carbon nanotubes in the carbon material is 30%-60%, and the mass of the chloride salt is 8-20 times the total mass of the titanium powder, the carbon material and the vanadium-based precursor.

[0012] According to one embodiment of the present invention, the chloride salt includes two different components, and the molar ratio of the two components is 1:1.

[0013] According to one embodiment of the present invention, the method further comprises vacuum drying the precipitate separated in step S1 at 35-45°C.

[0014] According to one embodiment of the present invention, the predetermined temperature in step S3 is 850-1000° C., the holding time is 1-4 hours, heating is performed in a vacuum or inert protective atmosphere, and the solid obtained after cooling is dissolved in water at 80-100° C.

[0015] A second aspect of the present invention provides a wear-resistant intelligent temperature control material, which is prepared using a method according to any of the above embodiments.

[0016] A third aspect of the present invention provides a method for preparing a wear-resistant intelligent temperature control film, the method comprising the following steps: Dispersing the wear-resistant intelligent temperature control material prepared by the method described in any of the above embodiments in an organic solvent of an ethyl acetate system, grinding to a predetermined particle size range, and obtaining a slurry; The slurry is added into varnish, stirred evenly and then coated on a substrate to obtain the wear-resistant intelligent temperature control film.

[0017] According to one embodiment of the present invention, the mass ratio of the wear-resistant intelligent temperature control material to the organic solvent is 1:10-1:3, the organic solvent of the ethyl acetate system includes the following components in a mass ratio: ethyl acetate: compound alcohol solvent: coupling agent = 40:2:1-40:4:1, the compound alcohol solvent is composed of ethylene glycol and anhydrous ethanol in a mass ratio of 1:1, and the predetermined particle size range is 20-100nm.

[0018] A fourth aspect of the present invention provides a wear-resistant intelligent temperature control film, which is prepared by the method described in any of the above embodiments.

[0019] The beneficial effects of the present invention include at least one of the following: (1) The wear-resistant intelligent temperature control material and its film prepared by the present invention introduces titanium compounds including titanium carbide into the vanadium-based phase change material, so that the prepared material has both the intelligent temperature control characteristics of the vanadium-based phase change material and the advantages of wear resistance, acid resistance and oxidation resistance of the titanium-based material. The material has the characteristics of high hardness, high melting point, high strength, friction resistance, high temperature resistance, oxidation resistance and good chemical stability; (2) According to the method for preparing wear-resistant intelligent temperature control materials of the present invention, titanium-based materials are introduced into the synthesis stage of vanadium-based materials, and the titanium-based synthetic raw materials are calcined together with the vanadium-based precursors to synthesize vanadium-titanium-based wear-resistant powders in situ. There is no need to generate and then mix the vanadium-based and titanium-based materials in steps, and the mixing is more uniform, which reduces the production steps, improves efficiency and reduces costs. (3) The method for preparing the wear-resistant intelligent temperature control material according to the present invention has a lower temperature than the traditional synthetic titanium-based material. The temperature of the traditional synthetic titanium-based material is above 1300°C, while the calcination temperature of the present invention is only 850-1000°C, which reduces energy consumption and is more economical. (4) The method for preparing a wear-resistant intelligent temperature control film of the present invention comprehensively controls the composition and ratio of the organic solvent, the ratio of the solvent to the powder material, and the powder particle size, so that the powder can be evenly dispersed in the slurry, thereby improving the dispersion uniformity of the powder in the varnish and improving the film-forming property and uniformity of the film. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments or the description of the prior art will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present invention. For ordinary technicians in this field, other embodiments can be obtained based on these drawings without paying creative work.

[0021] Figure 1 A schematic diagram of a film including the wear-resistant intelligent temperature control material according to the present invention; Figure 2 A flowchart of a method for preparing a wear-resistant intelligent temperature control material according to some embodiments of the present invention; Figure 3 The present invention is a flow chart of preparing a wear-resistant intelligent temperature control film according to some embodiments of the present invention. DETAILED DESCRIPTION

[0022] In order to make the purpose, technical solution and advantages of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention will be clearly and completely described below in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0023] Figure 1The figure is a schematic diagram of a film including a wear-resistant intelligent temperature control material according to the present invention, and the characteristics of the wear-resistant intelligent temperature control material are described in conjunction with the figure. The figure is only an example, and it does not limit the number, density, etc. of the vanadium-titanium-based powder contained. Among them, 1 represents a substrate for coating a film, 2 represents a spherical vanadium-based phase change material, 3 represents a fibrous titanium-based wear-resistant material, and 4 represents a spherical titanium-based wear-resistant material. The fibrous titanium-based wear-resistant material absorbs energy through crack deflection and fiber pull-out mechanisms, significantly improving the toughness of the film, and the spherical titanium-based wear-resistant material can be uniformly embedded in the VO2 matrix, and the hardness of the film can be improved through the dispersion strengthening mechanism. Therefore, the titanium-based hard phase in the matrix significantly improves the scratch resistance of the film, and the chemical inertness (acid and alkali resistance) of the titanium-based material can protect the VO2 matrix. The vanadium-based phase change material in the film matrix has the function of vanadium dioxide intelligent temperature control. When the temperature is low, the sun passes through the glass to heat and keep the room warm; when the temperature is high, this kind of glass transmits the visible band and reflects the near-infrared band, thereby achieving the purpose of indoor cooling.

[0024] An object of the present invention is to provide a method for preparing a wear-resistant intelligent temperature control material. Figure 2 A flow chart of a method for preparing a wear-resistant intelligent temperature control material according to some embodiments of the present invention is shown. The method mainly comprises the following steps: Step S1: mixing a vanadium salt solution containing tetravalent vanadium with a precipitant containing hydroxide, and separating the precipitate after the reaction to obtain a vanadium-based precursor; Step S2: mechanically mixing titanium powder, carbon material, chloride salt and vanadium-based precursor to obtain vanadium-titanium-based precursor, wherein the carbon material comprises a combination of carbon nanotubes and at least one of the following: carbon black, graphite; Step S3: heating the vanadium-titanium-based precursor to a predetermined temperature and keeping the temperature, dissolving the obtained solid in water after cooling, filtering and drying to obtain a wear-resistant intelligent temperature control material.

[0025] The following is an exemplary description of each step of the method.

[0026] In step S1, a vanadium salt solution containing tetravalent vanadium is mixed with a precipitant containing hydroxide, and the precipitate is separated after the reaction to obtain a vanadium-based precursor. In some embodiments, the vanadium salt is selected from at least one of vanadium sulfate, vanadium chloride, and vanadium nitrate, and the concentration of the vanadium salt in the vanadium salt solution is 0.8-2 mol / L. In some embodiments, the precipitant containing hydroxide can be one or more of sodium hydroxide, ammonia water, sodium bicarbonate, urea, etc. A precipitant containing hydroxide can be added to the vanadium salt solution containing tetravalent vanadium, heated and stirred (temperature controlled at 90-110°C, speed of 250-550r / min), and after constant temperature stirring for 2-5h, filtered, washed and precipitated, and the precipitated material is a vanadium-based precursor. Optionally, in some embodiments, the washed precursor is vacuum dried at a low temperature of about 35-45°C.

[0027] In step S2, titanium powder, carbon material, chloride salt and vanadium-based precursor are mechanically mixed to obtain vanadium-titanium-based precursor. The carbon material includes a combination of carbon nanotubes and at least one of the following: carbon black, graphite. Carbon nanotubes can react with titanium powder to generate fibrous titanium-based wear-resistant materials, which absorb energy through crack deflection and fiber pull-out mechanisms, significantly improving the toughness of the film. Carbon black and graphite can react with titanium powder to generate spherical titanium-based wear-resistant materials. The spherical titanium-based wear-resistant materials have high hardness and can be evenly embedded in the VO2 matrix. The hardness of the film is improved through a dispersion strengthening mechanism. The use of two forms of titanium-based carbides can achieve a hardness-toughness balance, and comprehensively improve the scratch resistance and wear resistance of the film.

[0028] In some embodiments, the molar ratio of titanium powder to carbon material is 0.9-1.2:1. The molar ratio of titanium powder to carbon material directly determines the generation rate of titanium carbide and the type of residue, which in turn affects the product performance. When the carbon material is seriously excessive, the excess free carbon may reduce the hardness of the film and increase the porosity. When the titanium powder is seriously excessive, the free titanium is easily oxidized to form TiO2 in subsequent use, weakening the oxidation resistance of the film.

[0029] In some embodiments, the mass percentage of carbon nanotubes in the carbon material is 30%-60%.

[0030] In some embodiments, the chloride salt is selected from at least one of sodium chloride, potassium chloride, and calcium chloride. The chloride salt can be used as a flux and morphology regulator during subsequent calcination. The molten chloride salt provides an ionized environment (such as Cl⁻, Na⁺, K⁺) to accelerate the diffusion reaction between titanium powder, carbon material and vanadium-based precursor. Cl⁻ is adsorbed on the surface of new particles to reduce the interfacial energy and prevent particle agglomeration. Furthermore, the chloride salt uses two chloride salts with a molar ratio of 1:1. When two chloride salts are used (such as NaCl-KCl, molar ratio 1:1), the eutectic point can be reduced to about 650°C (pure NaCl melting point 801°C, KCl melting point 770°C), which can significantly reduce the calcination temperature and save energy.

[0031] In some embodiments, the mass of the chloride salt is 8-20 times the total mass of the titanium powder, the carbon material and the vanadium-based precursor. When the volume of the chloride salt is insufficient, the reactants are not in sufficient contact, resulting in a decrease in the hardness and wear resistance of the material after calcination. When the volume of the chloride salt is excessive, the concentration of the reactants is too low, the reaction rate decreases, and the calcination time needs to be extended.

[0032] In some embodiments, mechanical mixing is performed using a magnetic stirrer with a stirring speed of 150-450 r / min and a stirring time of 10-30 min.

[0033] In step S3, the vanadium-titanium-based precursor is heated to a predetermined temperature and kept warm. After cooling, the obtained solid is dissolved in water, filtered and dried to obtain a wear-resistant intelligent temperature control material.

[0034] In some embodiments, the vanadium-titanium-based precursor is heated in a vacuum or inert protective atmosphere (such as argon) to, for example, 850-1000°C for 1-4 hours, and after cooling with the furnace, the obtained solid is dissolved in hot water (80-100°C), washed, filtered, and dried (35-45°C) to obtain a wear-resistant intelligent temperature control material.

[0035] Another object of the present invention is to provide a wear-resistant intelligent temperature control material, which is prepared by the method described in any of the above embodiments.

[0036] Another object of the present invention is to provide a method for preparing a wear-resistant intelligent temperature control film. Figure 3 As shown, the method generally comprises the following steps: Step S1: mixing a vanadium salt solution containing tetravalent vanadium with a precipitant containing hydroxide, and separating the precipitate after the reaction to obtain a vanadium-based precursor; Step S2: mechanically mixing titanium powder, carbon material, chloride salt and vanadium-based precursor to obtain vanadium-titanium-based precursor, wherein the carbon material comprises a combination of carbon nanotubes and at least one of the following: carbon black, graphite; Step S3: heating the vanadium-titanium-based precursor to a predetermined temperature and keeping the temperature, dissolving the obtained solid in water after cooling, filtering and drying to obtain a wear-resistant intelligent temperature control material; Step S4: dispersing the prepared wear-resistant intelligent temperature control material in an organic solvent of an ethyl acetate system, grinding it to a predetermined particle size range, and obtaining a slurry; Step S5: adding the slurry into the varnish, stirring evenly and then coating the varnish on the substrate to obtain a wear-resistant intelligent temperature control film.

[0037] Among them, steps S1 to S3 are Figure 2 The corresponding steps described in the method for preparing the wear-resistant intelligent temperature control material are consistent and will not be repeated here for the sake of brevity.

[0038] In some embodiments, in step S4, the mass ratio of the wear-resistant intelligent temperature control material to the organic solvent is 1:10-1:3. The wear-resistant intelligent temperature control material is a powder, so the mass ratio of the wear-resistant intelligent temperature control material to the organic solvent has an important influence on the dispersibility of the powder in the slurry, and the powder ratio needs to be controlled within an appropriate range. The organic solvent is mainly a mixed reagent of ethyl acetate, ethylene glycol, anhydrous ethanol, and a coupling agent (BYK, KH-560, KH-570, etc.), and the organic solvent is obtained by mixing the mass ratio of ethyl acetate: ethylene glycol + anhydrous ethanol (1:1): coupling agent = 40:2:1 to 40:4:1. The solvent system can inhibit the sedimentation of the wear-resistant intelligent temperature control powder material, promote the deagglomeration of the powder, and make the powder evenly dispersed in the slurry. The slurry can be ground by a sand mill until the monitored particle size is 20-100nm. If the particle size is too large, the powder particles will settle at the bottom of the slurry and cannot be evenly dispersed in the slurry.

[0039] In some embodiments, in step S5, the varnish may be a transparent varnish such as polyurethane varnish, epoxy resin varnish, etc., which is commonly available in the market, so as to facilitate film coating. After being stirred evenly, a film with a thickness of 20-200 μm is formed on the substrate by means of coating, spin coating, magnetron sputtering, etc., and the film is a wear-resistant vanadium-titanium-based intelligent temperature control film. The substrate may be a transparent flat material such as PET film and glass.

[0040] Another object of the present invention is to provide a wear-resistant intelligent temperature control film, which is prepared by the method described in any of the above embodiments.

[0041] In order to further illustrate the technical solution and beneficial effects of the present invention, the present invention further provides specific embodiments: Example 1 Sodium hydroxide is added to a 1 mol / L vanadyl sulfate solution, heated to 95°C with stirring, at a speed of 300 r / min, and kept at this temperature for 2 hours, then filtered, washed, and precipitated. The precipitated material is vanadium-based precursor A, and precursor A is dried at a low temperature of about 40°C in a vacuum.

[0042] Titanium powder, carbon material (carbon nanotubes + carbon black, mass ratio of 3:7), chloride salt (potassium chloride: sodium chloride, molar ratio of 1:1) and vanadium-based precursor A were mixed evenly by magnetic stirring at a stirring speed of 200r / min for 20min to obtain vanadium-titanium-based precursor B. The molar ratio of titanium powder to carbon material is 1:1, and the mass of chloride salt is 10 times that of titanium powder + carbon material + vanadium-based precursor A.

[0043] The vanadium-titanium-based precursor B prepared in advance was heated to 900°C under vacuum and kept at this temperature for 2 hours. After cooling down with the furnace, the obtained solid was dissolved in 90°C hot water, washed, filtered, and dried at 40°C to obtain vanadium-titanium-based powder C.

[0044] The obtained powder C is dispersed in an organic solvent and ground by a sand mill until the monitored particle size is about 50 nm. The mass ratio of powder to slurry is 1:5. The organic solvent is mainly ethyl acetate, ethylene glycol, anhydrous ethanol, and coupling agent BYK mixed reagent, ethyl acetate: ethylene glycol + anhydrous ethanol (1:1): coupling agent = 40:2:1, and slurry D is obtained at this time.

[0045] Slurry D is added into polyurethane varnish, stirred evenly, and then a film with a thickness of 50 μm is formed on the substrate PET film by a coating method. This film is a wear-resistant vanadium-titanium-based intelligent temperature control film.

[0046] After the film is dried, relevant performance tests are carried out to detect the effect of this film. After testing, the static contact angle of the coated surface is 155°, it has super hydrophobic properties and certain self-cleaning functions, low-temperature visible light transmittance is 72%, high-temperature visible light transmittance is 68%, sunlight regulation efficiency is 15.2%, and wear resistance is 0.026mg / min. After aging at high temperature and high humidity for 240h, the static contact angle of the film surface is still 140°, the low-temperature visible light transmittance is 75%, the high-temperature visible light transmittance is 72%, the sunlight regulation efficiency is 14.9%, and the wear resistance is still maintained at 0.026mg / min.

[0047] Example 2 Urea is added to a 1.5 mol / L vanadyl sulfate solution, heated to 100°C with stirring, at a speed of 350 r / min, and kept at this temperature for 2.5 hours, then filtered, washed, and precipitated. The precipitated material is vanadium-based precursor A, and precursor A is dried at a low temperature of about 45°C in a vacuum.

[0048] Titanium powder, carbon material (carbon nanotubes + carbon black, mass ratio 1:1), chloride salt (calcium chloride: sodium chloride, molar ratio 1:1) and vanadium-based precursor A were mixed evenly by magnetic stirring at a stirring speed of 250r / min for 20min to obtain vanadium-titanium-based precursor B. The molar ratio of titanium powder to carbon material is 1:1, and the mass of chloride salt is 12 times that of titanium powder + carbon material + vanadium-based precursor A.

[0049] The vanadium-titanium-based precursor B prepared in advance was heated to 950°C under vacuum and kept at this temperature for 1.5 hours. After cooling down with the furnace, the obtained solid was dissolved in 95°C hot water, washed, filtered, and dried at 45°C to obtain vanadium-titanium-based powder C.

[0050] The obtained powder C is dispersed in an organic solvent and ground by a sand mill until the monitored particle size is about 100 nm. The mass ratio of powder to slurry is 1:8. The organic solvent is mainly a mixed reagent of ethyl acetate, ethylene glycol, anhydrous ethanol, and coupling agent KH560, ethyl acetate: ethylene glycol + anhydrous ethanol (1:1): coupling agent = 40:3:1, and slurry D is obtained at this time.

[0051] Slurry D is added into polyurethane varnish, stirred evenly, and then a film with a thickness of 100 μm is formed on the substrate PET film by a coating method. This film is a wear-resistant vanadium-titanium-based intelligent temperature control film.

[0052] After the film is dried, relevant performance tests are carried out to detect the effect of this film. After testing, the static contact angle of the coating surface is 150°, it has super hydrophobic properties and certain self-cleaning functions, low-temperature visible light transmittance is 73%, high-temperature visible light transmittance is 69%, sunlight regulation efficiency is 15%, and wear resistance is 0.03mg / min. After aging at high temperature and high humidity for 240h, the static contact angle of the film surface is still 140°, the low-temperature visible light transmittance is 76%, the high-temperature visible light transmittance is 70%, the sunlight regulation efficiency is 14.4%, and the wear resistance is still maintained at 0.03mg / min.

[0053] Example 3 Add ammonia water to a 1.2 mol / L vanadyl sulfate solution, heat to 105°C with stirring, rotate at 400 r / min, keep constant temperature for 2 hours, filter, wash and precipitate. The precipitate is vanadium-based precursor A. Precursor A is dried at about 45°C in a low-temperature vacuum.

[0054] Titanium powder, carbon material (carbon nanotubes + graphite, mass ratio 6:4), chloride salt (potassium chloride: sodium chloride, molar ratio 1:1) and vanadium-based precursor A were mixed evenly by magnetic stirring at a stirring speed of 300r / min for 30min to obtain vanadium-titanium-based precursor B. The molar ratio of titanium powder to carbon material is 1:1, and the mass of chloride salt is 16 times that of titanium powder + carbon material + vanadium-based precursor A.

[0055] The vanadium-titanium-based precursor B prepared in advance was heated to 1000°C under vacuum and kept warm for 1 hour. After cooling down with the furnace, the obtained solid was dissolved in 95°C hot water, washed, filtered, and dried at 45°C to obtain vanadium-titanium-based powder C.

[0056] The obtained powder C is dispersed in an organic solvent and ground by a sand mill until the monitored particle size is about 30 nm. The mass ratio of powder to slurry is 1:10. The organic solvent is mainly a mixed reagent of ethyl acetate, ethylene glycol, anhydrous ethanol, and coupling agent KH570, ethyl acetate: ethylene glycol + anhydrous ethanol (1:1): coupling agent = 40:4:1, and slurry D is obtained at this time.

[0057] Slurry D is added into polyurethane varnish, stirred evenly, and then a film with a thickness of 200 μm is formed on the substrate PET film by a coating method. This film is a wear-resistant vanadium-titanium-based intelligent temperature control film.

[0058] After the film is dried, relevant performance tests are carried out to detect the effect of this film. After testing, the static contact angle of the coated surface is 145°, it has super hydrophobic properties and certain self-cleaning functions, low-temperature visible light transmittance is 75%, high-temperature visible light transmittance is 71%, sunlight regulation efficiency is 14.8%, and wear resistance is 0.028mg / min. After aging at high temperature and high humidity for 240h, the static contact angle of the film surface is still 135°, the low-temperature visible light transmittance is 78%, the high-temperature visible light transmittance is 73%, the sunlight regulation efficiency is 14.1%, and the wear resistance is still maintained at 0.028mg / min.

[0059] Example 4 Sodium hydroxide is added to a 0.8 mol / L vanadium oxychloride solution, heated to 95°C with stirring, at a speed of 300 r / min, and kept at this temperature for 2 hours, then filtered, washed, and precipitated. The precipitated material is vanadium-based precursor A, and the precursor A is dried at a low temperature of about 35°C in a vacuum.

[0060] Titanium powder, carbon material (carbon nanotubes + graphite, mass ratio 1:1), chloride salt (potassium chloride: sodium chloride, molar ratio 1:1) and vanadium-based precursor A were mixed evenly by magnetic stirring at a stirring speed of 200r / min for 25min to obtain vanadium-titanium-based precursor B. The molar ratio of titanium powder to carbon material is 0.9:1, and the mass of chloride salt is 8 times that of titanium powder + carbon material + vanadium-based precursor A.

[0061] The vanadium-titanium-based precursor B prepared in advance was heated to 850°C under vacuum and kept at this temperature for 4 hours. After cooling down with the furnace, the obtained solid was dissolved in 80°C hot water, washed, filtered, and dried at 35°C to obtain vanadium-titanium-based powder C.

[0062] The obtained powder C is dispersed in an organic solvent and ground by a sand mill until the monitored particle size is about 20 nm. The mass ratio of powder to slurry is 1:3. The organic solvent is mainly ethyl acetate, ethylene glycol, anhydrous ethanol, and coupling agent BYK mixed reagent, ethyl acetate: ethylene glycol + anhydrous ethanol (1:1): coupling agent = 40:2:1, and slurry D is obtained at this time.

[0063] Slurry D is added into polyurethane varnish, stirred evenly, and then a film with a thickness of 30 μm is formed on the substrate PET film by a coating method. This film is a wear-resistant vanadium-titanium-based intelligent temperature control film.

[0064] After the film is dried, relevant performance tests are carried out to detect the effect of this film. After testing, the static contact angle of the coating surface is 148°, with super hydrophobic properties and certain self-cleaning functions, low-temperature visible light transmittance is 76%, high-temperature visible light transmittance is 72%, sunlight regulation efficiency is 16.3%, and wear resistance is 0.029mg / min. After aging at high temperature and high humidity for 240h, the static contact angle of the film surface is still 141°, the low-temperature visible light transmittance is 78%, the high-temperature visible light transmittance is 73%, the sunlight regulation efficiency is 15.7%, and the wear resistance is still maintained at 0.029mg / min.

[0065] Example 5 Sodium hydroxide is added to a 1.8 mol / L vanadyl sulfate solution, heated to 95°C with stirring, at a speed of 300 r / min, and kept at this temperature for 2 hours, then filtered, washed, and precipitated. The precipitated material is vanadium-based precursor A, and precursor A is dried at a low temperature of about 40°C in a vacuum.

[0066] Titanium powder, carbon material (carbon nanotubes + graphite + carbon black, mass ratio 1:1:1), chloride salt (potassium chloride: sodium chloride, molar ratio 1:1) and vanadium-based precursor A were mixed evenly by magnetic stirring at a stirring speed of 150r / min for 30min to obtain vanadium-titanium-based precursor B. The molar ratio of titanium powder to carbon material is 1.1:1, and the mass of chloride salt is 18 times that of titanium powder + carbon material + vanadium-based precursor A.

[0067] The vanadium-titanium-based precursor B prepared in advance was heated to 880°C under vacuum and kept warm for 3 hours. After cooling down with the furnace, the obtained solid was dissolved in 100°C hot water, washed, filtered, and dried at 40°C to obtain vanadium-titanium-based powder C.

[0068] The obtained powder C is dispersed in an organic solvent and ground by a sand mill until the monitored particle size is about 80 nm. The mass ratio of powder to slurry is 1:4. The organic solvent is mainly ethyl acetate, ethylene glycol, anhydrous ethanol, and coupling agent BYK mixed reagent, ethyl acetate: ethylene glycol + anhydrous ethanol (1:1): coupling agent = 40:2:1, and slurry D is obtained at this time.

[0069] Slurry D is added into polyurethane varnish, stirred evenly, and then a film with a thickness of 150 μm is formed on the substrate PET film by a coating method. This film is a wear-resistant vanadium-titanium-based intelligent temperature control film.

[0070] After the film is dried, relevant performance tests are carried out to detect the effect of this film. After testing, the static contact angle of the coating surface is 152°, it has super hydrophobic properties and certain self-cleaning functions, low-temperature visible light transmittance is 71%, high-temperature visible light transmittance is 69%, sunlight regulation efficiency is 17.2%, and wear resistance is 0.027mg / min. After aging at high temperature and high humidity for 240h, the static contact angle of the film surface is still 145°, the low-temperature visible light transmittance is 75%, the high-temperature visible light transmittance is 71%, the sunlight regulation efficiency is 16.2%, and the wear resistance is still maintained at 0.027mg / min.

[0071] Example 6 Sodium hydroxide is added to a 2 mol / L vanadium oxynitrate solution, heated to 95°C with stirring, at a speed of 300 r / min, and kept at a constant temperature for 2 hours, then filtered, washed, and precipitated. The precipitated material is vanadium-based precursor A, and precursor A is dried at a low temperature of about 40°C in a vacuum.

[0072] Titanium powder, carbon material (carbon nanotubes + graphite + carbon black, mass ratio 2:1:1), chloride salt (potassium chloride: sodium chloride, molar ratio 1:1) and vanadium-based precursor A were mixed evenly by magnetic stirring at a stirring speed of 200r / min for 20min to obtain vanadium-titanium-based precursor B. The molar ratio of titanium powder to carbon material is 1.2:1, and the mass of chloride salt is 10 times that of titanium powder + carbon material + vanadium-based precursor A.

[0073] The vanadium-titanium-based precursor B prepared in advance was heated to 950°C under vacuum and kept at this temperature for 2 hours. After cooling down with the furnace, the obtained solid was dissolved in 90°C hot water, washed, filtered, and dried at 40°C to obtain vanadium-titanium-based powder C.

[0074] The obtained powder C is dispersed in an organic solvent and ground by a sand mill until the monitored particle size is about 50 nm. The mass ratio of powder to slurry is 1:5. The organic solvent is mainly ethyl acetate, ethylene glycol, anhydrous ethanol, and coupling agent BYK mixed reagent, ethyl acetate: ethylene glycol + anhydrous ethanol (1:1): coupling agent = 40:2:1, and slurry D is obtained at this time.

[0075] Slurry D is added into polyurethane varnish, stirred evenly, and then a film with a thickness of 50 μm is formed on the substrate PET film by a coating method. This film is a wear-resistant vanadium-titanium-based intelligent temperature control film.

[0076] After the film is dried, relevant performance tests are carried out to detect the effect of this film. After testing, the static contact angle of the coating surface is 154°, with super hydrophobic properties and certain self-cleaning functions, low-temperature visible light transmittance of 73%, high-temperature visible light transmittance of 70%, sunlight regulation efficiency of 15.4%, and wear resistance of 0.025mg / min. After aging at high temperature and high humidity for 240h, the static contact angle of the film surface is still 145°, the low-temperature visible light transmittance is 76%, the high-temperature visible light transmittance is 73%, the sunlight regulation efficiency is 14.8%, and the wear resistance is still maintained at 0.025mg / min.

[0077] The technical features of the above embodiments may be combined arbitrarily. To make the description concise, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, they should be considered to be within the scope of this specification.

[0078] The above-mentioned embodiments only express several implementation methods of the present application, and the descriptions thereof are relatively specific and detailed, but they cannot be understood as limiting the scope of the invention patent. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present application, and these all belong to the protection scope of the present application.

Claims

1. A method for preparing a wear-resistant intelligent temperature control material, characterized in that: The following steps are involved: Step S1: mixing a vanadium salt solution containing tetravalent vanadium with a precipitant containing hydroxide, and separating the precipitate after the reaction to obtain a vanadium-based precursor; Step S2: mechanically mixing titanium powder, carbon material, chloride salt and the vanadium-based precursor to obtain a vanadium-titanium-based precursor, wherein the carbon material comprises a combination of carbon nanotubes and at least one of the following: carbon black, graphite; Step S3: heating the vanadium-titanium-based precursor to a predetermined temperature and keeping the temperature, dissolving the obtained solid in water after cooling, filtering and drying to obtain the wear-resistant intelligent temperature control material.

2. The method for preparing a wear-resistant intelligent temperature control material according to claim 1, characterized in that: The vanadium salt is selected from at least one of vanadyl sulfate, vanadyl chloride and vanadyl nitrate, and the concentration of the vanadium salt in the vanadium salt solution is 0.8-2 mol / L.

3. The method for preparing a wear-resistant intelligent temperature control material according to claim 1, characterized in that: The molar ratio of the titanium powder to the carbon material is 0.9-1.2:1, the mass percentage of the carbon nanotubes in the carbon material is 30%-60%, and the mass of the chloride salt is 8-20 times the total mass of the titanium powder, the carbon material and the vanadium-based precursor.

4. The method for preparing a wear-resistant intelligent temperature control material according to claim 1, characterized in that: The chloride salt is selected from at least one of sodium chloride, potassium chloride and calcium chloride.

5. The method for preparing a wear-resistant intelligent temperature control material according to claim 4, characterized in that: The chloride salt comprises two different components, and the molar ratio of the two components is 1:

1.

6. The method for preparing a wear-resistant intelligent temperature control material according to claim 1, characterized in that: The method further comprises drying the precipitate separated in step S1 at 35-45° C. under vacuum; and / or The predetermined temperature in step S3 is 850-1000° C., the holding time is 1-4 hours, heating is performed in a vacuum or inert protective atmosphere, and the obtained solid is dissolved in water at 80-100° C. after cooling.

7. A wear-resistant intelligent temperature control material, characterized in that: The wear-resistant intelligent temperature control material is prepared by the method according to any one of claims 1-6.

8. A method for preparing a wear-resistant intelligent temperature control film, characterized in that: The following steps are involved: Dispersing the wear-resistant intelligent temperature control material prepared by the method according to any one of claims 1 to 6 in an organic solvent of an ethyl acetate system, grinding to a predetermined particle size range, and obtaining a slurry; The slurry is added into varnish, stirred evenly and then coated on a substrate to obtain the wear-resistant intelligent temperature control film.

9. The method for preparing a wear-resistant intelligent temperature control film according to claim 8, characterized in that: The mass ratio of the wear-resistant intelligent temperature control material to the organic solvent is 1:10-1:3, the organic solvent of the ethyl acetate system includes the following components in a mass ratio: ethyl acetate: compound alcohol solvent: coupling agent = 40:2:1-40:4:1, the compound alcohol solvent is composed of ethylene glycol and anhydrous ethanol in a mass ratio of 1:1, and the predetermined particle size range is 20-100nm.

10. A wear-resistant intelligent temperature control film, characterized in that: The wear-resistant intelligent temperature control film is prepared by the method according to claim 8 or 9.

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