CN113185871A - Tungsten bronze-based super-hydrophobic transparent heat-insulating coating and preparation method thereof - Google Patents
Tungsten bronze-based super-hydrophobic transparent heat-insulating coating and preparation method thereof Download PDFInfo
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- CN113185871A CN113185871A CN202110402810.XA CN202110402810A CN113185871A CN 113185871 A CN113185871 A CN 113185871A CN 202110402810 A CN202110402810 A CN 202110402810A CN 113185871 A CN113185871 A CN 113185871A
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D127/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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Abstract
The invention discloses a tungsten bronze-based super-hydrophobic transparent heat-insulating coating and a preparation method thereof, wherein the preparation method comprises the following steps: the tungsten bronze-based super-hydrophobic transparent heat-insulating coating is prepared by adding hydrophobically modified nano tungsten bronze and hydrophobically modified powder into a resin solution for dissolving and forming a film by using an organic solvent; according to the invention, nano cesium tungsten bronze and sodium tungsten bronze are synthesized by a solvothermal method, the nano cesium tungsten bronze, the nano sodium tungsten bronze and nano silicon dioxide are respectively modified to serve as inorganic components, organic resin is combined to prepare a super-hydrophobic coating, and the tungsten bronze-based super-hydrophobic transparent heat-insulating super-hydrophobic coating is coated on the surface of a matrix by adopting a film forming process; the static contact angles of the obtained tungsten bronze-based super-hydrophobic transparent heat-insulating coating are both larger than 155 degrees, and the rolling angles are smaller than 10 degrees. The nano tungsten bronze-based super-hydrophobic transparent heat-insulating super-hydrophobic coating disclosed by the invention is good in dispersibility, the prepared coating is good in adhesion with a matrix, and the transparent heat-insulating effect is good.
Description
Technical Field
The invention relates to a transparent heat-insulating coating, in particular to a tungsten bronze-based super-hydrophobic transparent heat-insulating coating and a preparation method thereof.
Background
In recent years, with the rapid development of social economy, people have increasingly increased demand and consumption of energy, and meanwhile, the consumption of energy also brings about a plurality of serious environmental problems, so that the energy and environmental problems become two major factors restricting the development of human society. In order to solve the problem of energy crisis, on one hand, novel clean energy is continuously developed, and on the other hand, the utilization rate of the energy is improved, the waste of the energy is reduced, and the energy-saving device is also beneficial to environmental protection.
According to the statistics of housing and urban and rural construction departments, in the whole energy consumption, the building energy consumption accounts for 30% -40% of the energy consumption of China, more than half of the energy consumption is consumed by heating and refrigeration of the building, and about 30% of the energy consumption is dissipated through doors and windows. Modern architectural design is increasingly using glass doors and windows and curtain walls, and needs sufficient lighting, such as: in classrooms, offices, meeting rooms and the like, glass meets the requirements of lighting and beauty, and simultaneously, the temperature in the room is increased by the sunlight emitted into the room, and especially in the south area of China, the air conditioner is needed to cool the room for a long time in one year. Therefore, in order to meet the requirements of indoor lighting and energy conservation, sunlight entering the indoor is selectively transmitted, and the visible light part of the sunlight is transmitted to block the near infrared light of the sunlight, so that the method is an important method for reducing the energy consumption of the air conditioner in southern areas.
There are several new insulating glass materials, such as: the film-coated glass, vacuum glass, metal coated glass, Low-E glass and the like can not be widely used due to Low visible light transmittance, poor heat insulation performance, complex process and high production cost, so that the preparation of the material with good heat insulation performance and high transmittance by adopting new materials and new technologies is particularly important, for example, the transparent heat insulation coating adds the nano material with selective light transmittance into the coating, and then coats the coating on the surface of the glass to ensure that the coating is applied to the surface of the glassA coating with transparent heat insulation capability. The transparent heat-insulating material studied at present comprises the above coated glass and some novel nano transparent heat-insulating materials, such as ATO, ITO and LaB6Reduced tungsten oxide, and tungsten bronze. Wherein ATO and ITO can only shield infrared rays with wave bands larger than 1500nm although the visible light transmittance is high, and the price is high, and the preparation process is complex. Lanthanum hexaboride can only shield the wave band of 750-. The reduced tungsten oxide can only shield the infrared band of 1000-3000nm, and the reduction degree is difficult to control. The tungsten bronze material not only has high visible light transmittance, but also has wide near-infrared shielding range, and can shield 780-2500nm infrared light.
Tungsten bronzes having the formula WO3The near band gap width (2.5-2.8 eV) has high visible light transmittance, and can shield ultraviolet rays in an intrinsic absorption mode. Cation M inserted into the gap in the tungsten bronze injects S orbital electrons into a conduction band to form free electrons, so that tungsten ions in the material are converted into a mixed valence state, and the material has high conductivity. Free electrons in the nano tungsten bronze under illumination can generate electromagnetic field oscillation along with light radiation, and local surface plasma resonance effect appears on the surface of the material, so that infrared light is strongly shielded.
The Chinese patent application CN109517517A discloses a bio-based fluorine modified polyurethane waterborne transparent heat insulation coating, which comprises the following components: 40.0-75.0% of bio-based fluorine modified waterborne polyurethane resin, 15.0-40.0% of nano transparent heat insulating agent, 3.0-12.0% of nano photocatalyst, 0-10.0% of transparent nano color paste, 2.0-6.0% of cosolvent, 0.2-2.5% of base material adhesive, 2.0-10.0% of auxiliary agent and 100% of deionized water; however, the technology is a water-based coating, and compared with an oil-based coating, the technology has poor weather resistance, acid and alkali resistance and friction resistance.
Chinese invention patent CN108949021A discloses an easy-to-clean transparent heat insulation coating and a use method thereof, wherein the easy-to-clean transparent heat insulation coating comprises the following components in parts by weight: 5-20 parts of modified hydrophobic polysilazane, 2-10 parts of nano heat-insulating slurry, 20-80 parts of organic solvent and 0.3-3 parts of auxiliary agent. However, the nano material only provides a coating heat insulation effect, the hydrophobic effect of the coating is provided by polysilazane, and the appearance of the nano heat insulation material cannot provide a certain roughness for the coating to achieve the super-hydrophobic effect, so that the coating only has the hydrophobic effect and cannot achieve the super-hydrophobic effect.
Disclosure of Invention
Aiming at the defects in the application field of the prior transparent heat-insulating coating, the durability and the weather resistance of the coating are poor, and the transparent heat-insulating effect is easily influenced by dust and pollutants, so that the service life of the coating is shortened.
The prior art cannot well utilize the morphology of tungsten bronze to construct a micro-nano composite structure of a super-hydrophobic coating, so that the coating has good self-cleaning performance. According to the invention, the tungsten bronze super-hydrophobic composite coating is prepared, the morphology of the synthesized tungsten bronze powder is controlled by oleic acid, a certain shape of a nano flower cluster is grown, pure tungsten bronze powder cannot be self-assembled into a super-hydrophobic micro-nano composite structure, but the nano powder can be self-assembled into the micro-nano composite structure by virtue of the interaction force between the nano powder with high visible light transmittance and the nano tungsten bronze powder, so that the super-hydrophobic effect is achieved, the coating is endowed with self-cleaning performance, the coating can keep high visible light transmittance and near-infrared barrier performance for a long time, and the use and cleaning cost of the coating is reduced. The invention adopts an organic-inorganic composite method to mix the modified tungsten bronze powder and the nano powder, thereby reducing the cost while ensuring the heat-insulating performance and preparing the super-hydrophobic transparent heat-insulating coating with good mechanical property and excellent self-cleaning performance.
The purpose of the invention is realized by the following technical scheme:
a tungsten bronze-based super-hydrophobic transparent heat-insulating coating is characterized in that: the hydrophobic modified nano tungsten bronze and the hydrophobic modified powder are added into an organic solvent to be dissolved into a resin solution for film forming to obtain the hydrophobic modified nano tungsten bronze; the hydrophobically modified nano tungsten bronze is prepared by adding nano tungsten bronze into a normal hexane solvent, uniformly stirring at room temperature to obtain a uniformly dispersed mixed solution, then adding a hydrophobic modifier, stirring for reaction, washing, centrifuging and drying; the hydrophobically modified powder is prepared by adding nano powder into an absolute ethyl alcohol solvent, uniformly stirring at room temperature to obtain a uniformly dispersed mixed solution, then adding a silane coupling agent hydrolysate and a hydrophobic modifier into the mixed solution, stirring and reacting at 60-90 ℃, washing, centrifuging and drying; the hydrophobic modifier in the preparation of the hydrophobic modified nano tungsten bronze and the hydrophobic modified powder is one or more of trimethylchlorosilane, perfluorodecyl triethoxysilane, hexamethyldisilazane and dodecyl trimethoxysilane.
The preparation method of the tungsten bronze-based super-hydrophobic transparent heat-insulating coating comprises the following steps:
1) and (3) synthesis of nano tungsten bronze: adding tungsten hexachloride into an organic solvent at room temperature, and ultrasonically stirring for dissolving to obtain a solution A; adding the hydroxide of the alkali metal into the solution A at room temperature, heating and stirring until the hydroxide is dissolved to obtain a suspension B; adding a morphology control agent oleic acid into the suspension B, uniformly stirring to obtain a solution C, and reacting at the temperature of 200-240 ℃ for 6-24 h; cooling, washing and drying the reactant to obtain the nano tungsten bronze;
2) hydrophobic modification of nano tungsten bronze: adding the nano tungsten bronze into a normal hexane solvent, uniformly stirring at room temperature to obtain a uniformly dispersed mixed solution, then adding a hydrophobic modifier, stirring for reacting for 1-3 hours, washing, centrifuging and drying to obtain the hydrophobically modified nano tungsten bronze; the hydrophobic modifier is one or more of trimethylchlorosilane, perfluorodecyl triethoxysilane, hexamethyl disilazane and dodecyl trimethoxysilane;
3) hydrophobic modification of the nano powder: adding the nano powder into an absolute ethyl alcohol solvent, uniformly stirring at room temperature to obtain a uniformly dispersed mixed solution, then adding a silane coupling agent hydrolysate and a hydrophobic modifier into the mixed solution, stirring and reacting for 1-3 hours at 60-90 ℃, washing, centrifuging and drying to obtain hydrophobically modified powder; the nano powder is silicon dioxide; the silane coupling agent is one or more of vinyl triethoxysilane, aminopropyl triethoxysilane and methacryloxypropyl trimethoxysilane; the hydrophobic modifier is one or more of trimethylchlorosilane, perfluorodecyl triethoxysilane, hexamethyl disilazane and dodecyl trimethoxysilane;
4) preparing a super-hydrophobic coating: dissolving resin for film formation by using an organic solvent to obtain a uniform and transparent resin solution, then adding the hydrophobically modified nano tungsten bronze and the hydrophobically modified powder, and uniformly stirring to obtain the tungsten bronze-based transparent heat-insulating super-hydrophobic coating.
To further achieve the object of the present invention, preferably, the organic solvent in step 1) is benzyl alcohol, and the concentration of tungsten hexachloride in the solution a is 22 mmol/L; wherein the hydroxide of the alkali metal is one or more of cesium hydroxide, sodium hydroxide, potassium hydroxide and rubidium hydroxide, wherein the molar ratio of cesium ions or sodium ions to tungsten hexachloride ions in the suspension B is 0.5; the heating and stirring are carried out in a constant-temperature water bath heating magnetic stirrer; the temperature of a water bath kettle of the thermostatic water bath is 50-60 ℃; the time for heating and stirring the suspension B is 10-15 min; the amount of oleic acid in the solution C is 10% of the total solution; the washing is 5-6 times of washing with ethanol.
Preferably, the low surface energy hydrophobic modifier in the step 2) accounts for 10-100% of the mass of the tungsten bronze; the washing in the step 2) is carried out for more than 3 times by using absolute ethyl alcohol.
Preferably, the silane coupling agent hydrolysate in the step 3) is prepared from the following components in parts by weight: water: absolute ethanol ═ 2: 1: 7, the silane coupling agent accounts for 10 to 50 percent of the nano powder; step 3), the hydrophobic modifier with low surface energy accounts for 10-100% of the weight of the nano powder; the nano powder in the step 3) is one or more of nano silicon dioxide, nano zinc oxide and nano titanium oxide with high transparency and nano particle size of 5-50 nm.
Preferably, the film-forming resin in the step 4) accounts for 5-40% of the organic solvent by mass; the film-forming resin is one or more of polyurethane resin, fluorocarbon resin, polyvinyl chloride resin, acrylic resin and epoxy resin; the organic solvent is one or more of ester solvents, alcohol solvents, ketone solvents and n-hexane.
Preferably, the nano-silica in the step 4) accounts for 2-12% of the mass of the coating, the tungsten bronze powder accounts for 2-12% of the mass of the coating, the film-forming resin accounts for 10-30% of the mass of the coating, and the organic solvent used for film forming accounts for 50-70% of the mass of the coating.
Preferably, in the step 2) and the step 3), the stirring time for stirring uniformly at room temperature is 20-40 minutes, and the stirring is magnetic stirring; in the step 3), stirring for the stirring reaction at the temperature of 60-90 ℃ is carried out in a water bath kettle; in the steps 1), 2) and 3), the drying temperature is 60-100 ℃, and the drying time is 8-24 hours.
Preferably, the obtained tungsten bronze-based super-hydrophobic transparent heat-insulating coating is coated on the surface of a matrix by adopting a film forming process to obtain a tungsten bronze-based transparent heat-insulating super-hydrophobic coating; the visible light transmittance of the obtained sodium tungsten bronze-based transparent heat-insulating super-hydrophobic coating is 52-60%, the near infrared blocking rate is 47-64%, the visible light transmittance of the obtained cesium tungsten bronze-based transparent heat-insulating super-hydrophobic coating is 46-60%, and the near infrared blocking rate is 65-83%;
coating the obtained tungsten bronze-based transparent heat-insulating coating on the surface of a matrix by adopting a film forming process to obtain a tungsten bronze-based transparent heat-insulating super-hydrophobic coating; the static contact angle of the obtained tungsten bronze-based transparent heat-insulating super-hydrophobic coating is larger than 150 degrees, the rolling angle is smaller than 10 degrees, the transparent heat-insulating super-hydrophobic coating is placed outdoors for a long time, the super-hydrophobic static contact angle is still larger than 150 degrees, the rolling angle is smaller than 10 degrees, the visible light transmittance is larger than 60 percent, and the near infrared blocking rate is still higher than 75 percent.
Preferably, the film forming process is one or more of spin coating, spray coating, blade coating and dip coating; the substrate is cleaned before coating and then dried for later use, and the substrate is a glass substrate, a metal substrate, a cement-based material or a concrete substrate; cleaning the substrate by ultrasonic cleaning with ethanol and deionized water for more than 30 minutes respectively; the drying is carried out in a blast drying oven with the temperature of above 60 ℃; for the substrate with a large area, the drying is carried out under the natural condition after the substrate is cleaned by a high-pressure water gun.
The film prepared by the product is subjected to transmittance test by adopting an ultraviolet visible near-infrared spectrophotometer, and the transmission spectrum test is performed by using the spectrophotometer to calculate the near-infrared light barrier rate and the visible light transmittance; the wavelength of near infrared light is 780-;
rejection rate R of near infrared lightNIRIs calculated by the formula
Transmittance of visible light TVisIs calculated by the formula
Wherein T (λ) is the transmittance measured by a spectrophotometer and has a unit of Wm-2And λ is wavelength in nm.
Compared with the prior art, the invention has the following advantages:
(1) the invention fully exerts the synergistic effect of the tungsten bronze powder and the nano powder; the tungsten bronze with transparent heat insulation and the transparent nano-silica are jointly used as the filler, the pure nano-tungsten bronze powder is difficult to achieve the super-hydrophobic effect, but the two nano-powders are mixed together, partial nano-powders can be self-assembled into a micro-nano composite structure due to the interaction force between the nano-powders, the coating can be endowed with the transparent heat insulation function and the super-hydrophobic property by means of a low surface energy substance, the hydrophobic property enables the coating to have the self-cleaning effect on hydrophilic pollutants such as dust, and the like, and the coating is particularly suitable for serving as building exterior wall coating.
(2) The modified tungsten bronze and the modified nano-silica have good dispersibility and compatibility in organic resin, the coating has good stability, and the prepared coating has good binding power and wear resistance.
(3) The tungsten bronze synthesized by the solvothermal method has the advantages of low synthesis cost, excellent performance of the synthesized tungsten bronze, greatly reduced cost due to the addition of a small amount of nano silicon dioxide powder, simple film forming process and obvious cost advantage compared with the prior art.
Drawings
FIG. 1 is an XRD pattern of cesium tungsten bronze and sodium tungsten bronze synthesized in examples 1 and 4.
FIG. 2 is a TEM spectrum of a cesium tungsten bronze powder in example 1.
FIG. 3 is a view showing the contact of the surface of the tungsten bronze based transparent thermal barrier coating prepared in example 1 with water droplets.
Fig. 4 is a view showing the contact of the surface of the coating layer prepared in comparative example 1 with water droplets.
FIG. 5 is a graph showing the transmittance spectra of the powder obtained in comparative example 1, example 1 and example 4 after spin-coating the glass.
FIG. 6 is a graph showing a comparison of the heat insulating effects of comparative example 1, example 1 and example 4.
Detailed description of the invention
For a better understanding of the present invention, the present invention will be further described below with reference to examples and the accompanying drawings, but the embodiments of the present invention are not limited thereto.
Description of the test methods:
(1) and (3) testing the transmittance: adopting an ultraviolet visible near-infrared spectrophotometer to carry out transmittance test on the film made of the product, and calculating the near-infrared light barrier rate and the visible light transmittance of the film; the wavelength of near infrared light is 780-;
rejection rate R of near infrared lightNIRIs calculated by the formula
Transmittance of visible light TVisIs calculated by the formula
Wherein T (λ) is the transmittance measured by a spectrophotometer and has a unit of Wm-2And λ is wavelength in nm.
(2) Super-hydrophobicity: the static Contact Angle (CA) and the rolling angle (SA) of water on the surface of the coating are used for characterization.
Example 1
A preparation method of a tungsten bronze-based transparent heat insulation coating comprises the following steps:
1) weighing 63ml of benzyl alcohol, pouring into a 100ml beaker, weighing 0.6000g of tungsten chloride, pouring into the benzyl alcohol, and performing ultrasonic dissolution to obtain an orange clear solution; and then 0.1270g of cesium hydroxide monohydrate is weighed and added into the solution, ultrasonic stirring is carried out for five minutes to obtain an orange transparent clear solution, 7ml of oleic acid is added into the orange transparent clear solution, the solution is stirred uniformly, the solution is transferred into a 100ml lining of a p-polyphenyl reaction kettle, the reaction kettle is placed into an oven, and the reaction is carried out for 8 hours at 220 ℃. After the reaction is finished, naturally cooling the reactant, washing the reactant for 6 times by using absolute ethyl alcohol, centrifuging the reactant, and drying the reactant for 8 hours at the temperature of 60 ℃ to obtain cesium tungsten bronze nano powder; FIG. 2 is a morphology diagram of the cesium tungsten bronze powder, and the synthesized nano powder is agglomerated into a powder with a size of 40-60nm and grows from the center to the periphery.
2) Adding 1g of cesium tungsten bronze nano powder into 20ml of n-hexane, stirring for 30min, adding 1g of perfluorodecyl triethoxysilane, stirring for reaction for 3h at room temperature, then washing for more than 3 times by using absolute ethyl alcohol, and then drying in a vacuum drying oven at 60 ℃ for 8h to obtain hydrophobically modified cesium tungsten bronze powder;
3) respectively adding 4g of silicon dioxide and 120ml of absolute ethyl alcohol solvent into a beaker, stirring for 30min at room temperature to obtain a uniformly dispersed mixed solution, then adding 4gKH550 hydrolysate and 1g of perfluorodecyl triethoxysilane into the mixed solution, continuously heating and stirring for 3h in a 75 ℃ constant-temperature water bath kettle, then washing for more than 3 times by using absolute ethyl alcohol, and then placing the mixture in a 60 ℃ vacuum drying oven for drying for 24h to obtain the hydrophobically modified silicon dioxide;
4) dissolving 0.6g of fluorocarbon resin for film formation with 2.4g of butyl acetate solvent to obtain a uniform and transparent resin solution, then adding 0.24g of hydrophobically modified nano cesium tungsten bronze and 0.12g of hydrophobically modified silicon dioxide, and uniformly stirring to obtain a super-hydrophobic coating for coating;
taking 1.5ml of the super-hydrophobic coating by a dropper each time, coating the super-hydrophobic coating on the surface of a cleaned glass substrate by adopting a spin coating process, wherein the spin coating frequency is 2, drying at room temperature to obtain the cesium tungsten bronze-based transparent heat-insulation super-hydrophobic coating, and after drying, carrying out transmission spectrum test by using a spectrophotometer and calculating the near infrared light blocking rate and the visible light transmission rate of the coating, wherein the measured visible light transmission rate is 60% and the near infrared blocking rate is 83% as shown in figure 4. Fig. 3 is a graph of the contact condition between the superhydrophobic coating prepared in this example and a water drop obtained by photographing with a contact angle measuring instrument, and fig. 3 shows that the sphericity of the water drop on the surface of the superhydrophobic coating is good, and as shown in table 1, the static contact angle is 169.8 ° and the rolling angle is 4.4 °, further illustrating that the superhydrophobic performance of the coating is good.
Comparative example 1
The step (4) of the example 1 is changed into the step of dissolving 0.6g of fluorocarbon resin for film formation with 2.4g of butyl acetate solvent to obtain a uniform and transparent resin solution, then adding 0.36g of silicon dioxide after hydrophobic modification, and uniformly stirring to obtain the super-hydrophobic coating for coating, wherein the rest steps are the same. Fig. 3 shows the contact condition of the superhydrophobic coating prepared in this embodiment and a water drop photographed by a contact angle measuring apparatus, wherein the water drop and the surface are hemispherical, and the surface is difficult to reach a superhydrophobic state under the same amount of powder. After drying, a transmission spectrum test is performed by using a spectrophotometer, and the near infrared light blocking rate and the visible light transmittance of the sample are calculated, as shown in fig. 4, the measured visible light transmittance is 70%, and the near infrared blocking rate is 10%. The static contact angle is 144.3 degrees, the rolling angle is 16.5 degrees, and as shown in figure 4, the sphericity of the water drop on the surface of the coating is not complete, which indicates that the coating only has a hydrophobic effect.
Example 2
A preparation method of a tungsten bronze-based transparent heat insulation coating comprises the following steps:
(1) weighing 63ml of benzyl alcohol, pouring into a 100ml beaker, weighing 0.6000g of tungsten chloride, pouring into the benzyl alcohol, and performing ultrasonic dissolution to obtain an orange clear solution; and then 0.1270g of cesium hydroxide monohydrate is weighed and added into the solution, ultrasonic stirring is carried out for five minutes to obtain an orange transparent clear solution, 7ml of oleic acid is added into the orange transparent clear solution, the solution is stirred uniformly, the solution is transferred into a 100ml lining of a p-polyphenyl reaction kettle, the reaction kettle is placed into an oven, and the reaction is carried out for 8 hours at 220 ℃. After the reaction is finished, naturally cooling the reactant, washing the reactant for 6 times by using absolute ethyl alcohol, centrifuging the reactant, and drying the reactant for 10 hours at the temperature of 60 ℃ to obtain cesium tungsten bronze nano powder;
(2) adding 1g of cesium tungsten bronze nano powder into 20ml of n-hexane, stirring for 30min, adding 1g of dodecyl trimethoxy silane, stirring and reacting for 3h at room temperature, then cleaning for more than 3 times by using absolute ethyl alcohol, and then drying in a vacuum drying oven at 70 ℃ for 8h to obtain hydrophobically modified cesium tungsten bronze powder;
(3) respectively adding 4g of silicon dioxide and 120ml of absolute ethyl alcohol solvent into a beaker, stirring for 30min at room temperature to obtain a uniformly dispersed mixed solution, then adding 4gKH550 hydrolysate and 1g of dodecyl trimethoxy silane into the mixed solution, continuously heating and stirring for 3h in a 75 ℃ constant-temperature water bath kettle, then washing for more than 3 times by using absolute ethyl alcohol, and then placing the mixture in a 70 ℃ vacuum drying oven for drying for 12h to obtain the hydrophobically modified silicon dioxide;
(4) dissolving 0.6g of fluorocarbon resin for film formation with 2.4g of butyl acetate solvent to obtain a uniform and transparent resin solution, then adding 0.18g of hydrophobically modified nano cesium tungsten bronze and 0.18g of hydrophobically modified silicon dioxide, and uniformly stirring to obtain a super-hydrophobic coating for coating;
(5) and (3) taking 1.5ml of the super-hydrophobic coating by using a dropper each time, coating the super-hydrophobic coating on the surface of the cleaned glass substrate by adopting a spin coating process, wherein the spin coating times are 2, and drying at room temperature to obtain the cesium tungsten bronze-based transparent heat-insulation super-hydrophobic coating. After drying, a spectrophotometer is used for carrying out transmission spectrum test and calculating the near infrared light blocking rate and the visible light transmission rate of the product, the measured visible light transmission rate is 47%, and the near infrared blocking rate is 73%.
Example 3
A preparation method of a tungsten bronze-based transparent heat insulation coating comprises the following steps:
(1) weighing 63ml of benzyl alcohol, pouring into a 100ml beaker, weighing 0.6000g of tungsten chloride, pouring into the benzyl alcohol, and performing ultrasonic dissolution to obtain an orange clear solution; and then 0.1270g of cesium hydroxide monohydrate is weighed and added into the solution, ultrasonic stirring is carried out for five minutes to obtain an orange transparent clear solution, 7ml of oleic acid is added into the orange transparent clear solution, the solution is stirred uniformly, the solution is transferred into a 100ml lining of a p-polyphenyl reaction kettle, the reaction kettle is placed into an oven, and the reaction is carried out for 8 hours at 220 ℃. After the reaction is finished, naturally cooling the reactant, washing the reactant for 6 times by using absolute ethyl alcohol, centrifuging the reactant, and drying the reactant for 8 hours at the temperature of 60 ℃ to obtain cesium tungsten bronze nano powder;
(2) adding 1g of cesium tungsten bronze nano powder into 20ml of n-hexane, stirring for 30min, adding 1g of trimethylchlorosilane, stirring for reaction for 3h at room temperature, then washing for more than 3 times by using absolute ethyl alcohol, and then drying in a vacuum drying oven at 60 ℃ for 10h to obtain hydrophobically modified cesium tungsten bronze powder;
(3) respectively adding 4g of zinc dioxide and 120ml of absolute ethyl alcohol solvent into a beaker, stirring for 30min at room temperature to obtain a uniformly dispersed mixed solution, then adding 4gKH550 hydrolysate and 1g of trimethylchlorosilane into the mixed solution, continuously heating and stirring for 3h in a 75 ℃ constant-temperature water bath kettle, then washing for more than 3 times by using absolute ethyl alcohol, and then placing the mixture in a 80 ℃ vacuum drying oven for drying for 24h to obtain the hydrophobically modified zinc dioxide;
(4) dissolving 0.6g of fluorocarbon resin for film formation with 2.4g of butyl acetate solvent to obtain a uniform and transparent resin solution, then adding 0.12g of hydrophobically modified nano cesium tungsten bronze and 0.24g of hydrophobically modified zinc dioxide, and uniformly stirring to obtain a super-hydrophobic coating for coating;
(5) and (3) taking 1.5ml of the super-hydrophobic coating by using a dropper each time, coating the super-hydrophobic coating on the surface of the cleaned glass substrate by adopting a spin coating process, wherein the spin coating times are 2, and drying at room temperature to obtain the cesium tungsten bronze-based transparent heat-insulation super-hydrophobic coating. And after drying, performing transmission spectrum test by using a spectrophotometer and calculating the near infrared light blocking rate and the visible light transmission rate of the product, wherein the measured visible light transmission rate is 46 percent and the near infrared blocking rate is 65 percent.
Example 4
A preparation method of a tungsten bronze-based transparent heat insulation coating comprises the following steps:
(1) weighing 63ml of benzyl alcohol, pouring into a 100ml beaker, weighing 0.0303g of sodium hydroxide, pouring into the benzyl alcohol, and heating and stirring in a constant-temperature water bath kettle at 60 ℃ for 15min to obtain a transparent clear solution; and then 0.6000g of the solution is weighed and added into the solution, ultrasonic stirring is carried out for five minutes to obtain light blue transparent clear solution, 7ml of oleic acid is added into the solution, the solution is stirred uniformly, the solution is transferred into a 100ml of lining of a p-polyphenyl reaction kettle, the reaction kettle is placed into an oven, and the reaction is carried out for 8 hours under the condition of keeping the temperature of 220 ℃. After the reaction is finished, naturally cooling the reactant, washing the reactant for 6 times by using absolute ethyl alcohol, centrifuging the reactant, and drying the reactant for 6 hours at the temperature of 80 ℃ to obtain sodium tungsten bronze nano powder;
(2) adding 1g of sodium tungsten bronze nano powder into 20ml of n-hexane, stirring for 30min, adding 1g of perfluorodecyl triethoxysilane, stirring for reaction for 3h at room temperature, then washing for more than 3 times by using absolute ethyl alcohol, and then drying in a vacuum drying oven at 60 ℃ for 8h to obtain hydrophobically modified sodium tungsten bronze powder;
(3) respectively adding 4g of silicon dioxide and 120ml of absolute ethyl alcohol solvent into a beaker, stirring for 30min at room temperature to obtain a uniformly dispersed mixed solution, then adding 4gKH550 hydrolysate and 1g of perfluorodecyl triethoxysilane into the mixed solution, continuously heating and stirring for 3h in a 75 ℃ constant-temperature water bath kettle, then washing for more than 3 times by using absolute ethyl alcohol, and then placing the mixture in a 60 ℃ vacuum drying oven for drying for 24h to obtain the hydrophobically modified silicon dioxide;
(4) dissolving 0.6g of fluorocarbon resin for film formation with 2.4g of butyl acetate solvent to obtain a uniform and transparent resin solution, then adding 0.24g of hydrophobically modified nano sodium tungsten bronze and 0.12g of hydrophobically modified silicon dioxide, and uniformly stirring to obtain the super-hydrophobic coating for coating;
(5) and (3) taking 1.5ml of the super-hydrophobic coating by using a dropper each time, coating the super-hydrophobic coating on the surface of the cleaned glass substrate by adopting a spin coating process, wherein the spin coating times are 2, and drying at room temperature to obtain the cesium tungsten bronze-based transparent heat-insulation super-hydrophobic coating. And after drying, performing transmission spectrum test by using a spectrophotometer and calculating the near infrared light blocking rate and the visible light transmission rate of the product, wherein the measured visible light transmission rate is 60 percent and the near infrared blocking rate is 64 percent.
Fig. 1 is an XRD spectrum of cesium tungsten bronze and sodium tungsten bronze synthesized in examples 1 and 4, and it can be seen that the target product is synthesized by the present invention.
Example 5
A preparation method of a tungsten bronze-based transparent heat insulation coating comprises the following steps:
(1) weighing 63ml of benzyl alcohol, pouring into a 100ml beaker, weighing 0.0303g of sodium hydroxide, pouring into the benzyl alcohol, and heating and stirring in a constant-temperature water bath kettle at 60 ℃ for 15min to obtain a transparent clear solution; and then 0.6000g of the solution is weighed and added into the solution, ultrasonic stirring is carried out for five minutes to obtain light blue transparent clear solution, 7ml of oleic acid is added into the solution, the solution is stirred uniformly, the solution is transferred into a 100ml of lining of a p-polyphenyl reaction kettle, the reaction kettle is placed into an oven, and the reaction is carried out for 8 hours under the condition of keeping the temperature of 220 ℃. After the reaction is finished, naturally cooling the reactant, washing the reactant for 6 times by using absolute ethyl alcohol, centrifuging the reactant, and drying the reactant for 8 hours at the temperature of 60 ℃ to obtain sodium tungsten bronze nano powder;
(2) adding 1g of sodium tungsten bronze nano powder into 20ml of n-hexane, stirring for 30min, adding 1g of dodecyl trimethoxy silane, stirring and reacting for 3h at room temperature, then cleaning for more than 3 times by using absolute ethyl alcohol, and then drying in a vacuum drying oven at 70 ℃ for 8h to obtain hydrophobically modified sodium tungsten bronze powder;
(3) respectively adding 4g of silicon dioxide and 120ml of absolute ethyl alcohol solvent into a beaker, stirring for 30min at room temperature to obtain a uniformly dispersed mixed solution, then adding 4gKH550 hydrolysate and 1g of dodecyl trimethoxy silane into the mixed solution, continuously heating and stirring for 3h in a 75 ℃ constant-temperature water bath kettle, then washing for more than 3 times by using absolute ethyl alcohol, and then placing the mixture in a 70 ℃ vacuum drying oven for drying for 12h to obtain the hydrophobically modified silicon dioxide;
(4) dissolving 0.6g of fluorocarbon resin for film formation with 2.4g of butyl acetate solvent to obtain a uniform and transparent resin solution, then adding 0.18g of hydrophobically modified nano sodium tungsten bronze and 0.18g of hydrophobically modified silicon dioxide, and uniformly stirring to obtain the super-hydrophobic coating for coating;
(5) and (3) taking 1.5ml of the super-hydrophobic coating by using a dropper each time, coating the super-hydrophobic coating on the surface of the cleaned glass substrate by adopting a spin coating process, wherein the spin coating times are 2, and drying at room temperature to obtain the cesium tungsten bronze-based transparent heat-insulation super-hydrophobic coating. And after drying, performing transmission spectrum test by using a spectrophotometer and calculating the near infrared light blocking rate and the visible light transmission rate of the product, wherein the measured visible light transmission rate is 55 percent and the near infrared blocking rate is 53 percent.
Example 6
A preparation method of a tungsten bronze-based transparent heat insulation coating comprises the following steps:
(1) weighing 63ml of benzyl alcohol, pouring into a 100ml beaker, weighing 0.0303g of sodium hydroxide, pouring into the benzyl alcohol, and heating and stirring in a constant-temperature water bath kettle at 60 ℃ for 15min to obtain a transparent clear solution; and then 0.6000g of the solution is weighed and added into the solution, ultrasonic stirring is carried out for five minutes to obtain light blue transparent clear solution, 7ml of oleic acid is added into the solution, the solution is stirred uniformly, the solution is transferred into a 100ml of lining of a p-polyphenyl reaction kettle, the reaction kettle is placed into an oven, and the reaction is carried out for 8 hours under the condition of keeping the temperature of 220 ℃. After the reaction is finished, naturally cooling the reactant, washing the reactant for 6 times by using absolute ethyl alcohol, centrifuging the reactant, and drying the reactant for 8 hours at the temperature of 60 ℃ to obtain sodium tungsten bronze nano powder;
(2) adding 1g of sodium tungsten bronze nano powder into 20ml of n-hexane, stirring for 30min, adding 1g of trimethylchlorosilane, stirring for reaction for 3h at room temperature, then washing for more than 3 times by using absolute ethyl alcohol, and then drying in a vacuum drying oven at 60 ℃ for 10h to obtain hydrophobically modified sodium tungsten bronze powder;
(3) respectively adding 4g of zinc dioxide and 120ml of absolute ethyl alcohol solvent into a beaker, stirring for 30min at room temperature to obtain a uniformly dispersed mixed solution, then adding 4gKH550 hydrolysate and 1g of trimethylchlorosilane into the mixed solution, continuously heating and stirring for 3h in a 75 ℃ constant-temperature water bath kettle, then washing for more than 3 times by using absolute ethyl alcohol, and then placing the mixture in a 80 ℃ vacuum drying oven for drying for 24h to obtain the hydrophobically modified zinc dioxide;
(4) dissolving 0.6g of fluorocarbon resin for film formation with 2.4g of butyl acetate solvent to obtain a uniform and transparent resin solution, then adding 0.12g of hydrophobically modified nano sodium tungsten bronze and 0.24g of hydrophobically modified zinc dioxide, and uniformly stirring to obtain the super-hydrophobic coating for coating;
(5) and (3) taking 1.5ml of the super-hydrophobic coating by using a dropper each time, coating the super-hydrophobic coating on the surface of the cleaned glass substrate by adopting a spin coating process, wherein the spin coating times are 2, and drying at room temperature to obtain the cesium tungsten bronze-based transparent heat-insulation super-hydrophobic coating. And after drying, performing transmission spectrum test by using a spectrophotometer and calculating the near infrared light blocking rate and the visible light transmission rate of the product, wherein the measured visible light transmission rate is 52 percent and the near infrared blocking rate is 47 percent.
TABLE 1
TABLE 2
Table 1 shows the static Contact Angles (CA) and the rolling angles (SA) of the matrix coatings of examples 1-6, and the coatings prepared by the method have high super-hydrophobic performance, wherein the static contact angles are both larger than 155 degrees, and the rolling angles are both smaller than 10 degrees, as can be seen from Table 1; FIG. 4 is a graph of transmittance of comparative example 1, example 1 and example 4, in which the near infrared blocking rates of example 1 and example 4 at 780-2500nm band are 83% and 64%, respectively, and the visible light transmittance at 400-780nm band is 60%, respectively, which shows that the prepared coating has good transparent and heat-insulating properties, good transmittance for visible light, and blocking effect for near infrared band.
Table 2 shows the measured light transmittance (T) for a period of time in examples 1 and 4VIS) Near infrared blocking ratio (R)NIR)、The change of the static Contact Angle (CA) and the rolling angle (SA) can be obviously seen, and after the coating is placed for 7 days, the coating still has good visible light transmittance and near infrared barrier property, and the super-hydrophobic contact angle is kept well.
The self-made device is adopted for the heat insulation test, and the specific method comprises the following steps: and (3) placing the glass sheet to be measured at the central opening at the top end of the heat insulation box, enabling the surface coated with the sample to face upwards, and placing a probe of the digital display thermometer in the heat insulation box. A100 w infrared lamp is used as a light source, and the distance from the lower surface of the infrared lamp to the center of the upper surface of the heat preservation box is 40 cm. The room temperature is kept constant, a stopwatch is used for timing while the infrared lamp is turned on, the temperature in the incubator is recorded every 5min, and the experiment time is 85 min.
FIG. 5 is a transmission spectrum of the powder obtained by spin-coating glass in comparative example 1, example 1 and example 4, wherein the visible light band of sunlight is 400-780nm, and the near-infrared band is 780-2500nm, so that the calculation results show that the near-infrared blocking rates of the powder obtained in comparative example 1, example 1 and example 4 at 780-2500nm are 10.19%, 82.83% and 64.24% in sequence, and the visible light transmission rates at 400-780nm are 70.37%, 59.74% and 60.02% in sequence, which indicates that the prepared examples 1 and example 4 have good visible light transmission rates and strong near-infrared blocking performance in the solar light band, and can ensure high visible light transmission rates and near-infrared blocking rates when applied outdoors, so that the powder obtained by spin-coating glass has a good application prospect.
FIG. 6 is a graph showing a comparison of the heat insulating effects of comparative example 1, example 1 and example 4, and it can be seen from FIG. 6 that the cesium tungsten bronze based transparent heat insulating superhydrophobic coating of example 1 lowers the temperature in the incubator by 6.9 ℃ and the sodium tungsten bronze based transparent heat insulating superhydrophobic coating of example 4 lowers the temperature in the incubator by 4.8 ℃ as compared with comparative example 1, and the heat insulating effect is remarkable.
According to the invention, by means of the interaction force between the nano powder with high visible light transmittance and the nano tungsten bronze powder, the nano powder can be self-assembled into a micro-nano composite structure, so that the super-hydrophobic effect is achieved, the coating is endowed with self-cleaning performance, the coating can maintain high visible light transmittance and near-infrared barrier performance for a long time outdoors, and the use and cleaning cost of the coating is reduced.
In the existing transparent heat-insulating super-hydrophobic coating, a more material is ATO, but due to the concentration of carriers of ATO, the resonance wavelength of plasma is above 1500nm, which can only shield near infrared light with wavelength more than 1500nm, while tungsten bronze has appropriate band gap (2.4eV-2.8eV) and high concentration free electrons, is cheap, nontoxic, strong in light transmission, wider in near infrared shielding range, better in transparent heat-insulating effect, short in synthesis time, and lower in cost compared with other methods. And the existing transparent heat insulation coating only achieves the hydrophobic effect and does not achieve super-hydrophobicity. According to the invention, the tungsten bronze synthesized by adopting a solvothermal method is uniform in appearance like a nano flower cluster by adding oleic acid, nano silicon dioxide or zinc oxide is spherical particles with small particle size, and a micro-nano composite structure is constructed by means of a part of silicon dioxide or zinc oxide and nano tungsten bronze powder, so that super-hydrophobicity is achieved, the visible light transmittance is good, the heat insulation effect is good, and the cost can be reduced. Meanwhile, the modified nano tungsten bronze powder can be well dispersed in an organic solvent, the coating has high hardness, scratch resistance and strong adhesive force, and organic matter dust on the surface can be taken away by utilizing the scouring action of rainwater, so that the erosion action of the external environment on the coating can be reduced, and a good transparent heat insulation effect can be still maintained.
The embodiments of the present invention are not limited to the above-mentioned embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and they are included in the scope of the present invention.
Claims (10)
1. A tungsten bronze-based super-hydrophobic transparent heat-insulating coating is characterized in that: the hydrophobic modified nano tungsten bronze and the hydrophobic modified powder are added into an organic solvent to be dissolved into a resin solution for film forming to obtain the hydrophobic modified nano tungsten bronze; the hydrophobically modified nano tungsten bronze is prepared by adding nano tungsten bronze into a normal hexane solvent, uniformly stirring at room temperature to obtain a uniformly dispersed mixed solution, then adding a hydrophobic modifier, stirring for reaction, washing, centrifuging and drying; the hydrophobically modified powder is prepared by adding nano powder into an absolute ethyl alcohol solvent, uniformly stirring at room temperature to obtain a uniformly dispersed mixed solution, then adding a silane coupling agent hydrolysate and a hydrophobic modifier into the mixed solution, stirring and reacting at 60-90 ℃, washing, centrifuging and drying; the hydrophobic modifier in the preparation of the hydrophobic modified nano tungsten bronze and the hydrophobic modified powder is one or more of trimethylchlorosilane, perfluorodecyl triethoxysilane, hexamethyldisilazane and dodecyl trimethoxysilane.
2. The method for preparing the tungsten bronze-based super-hydrophobic transparent heat-insulating coating according to claim 1, which is characterized by comprising the following steps:
1) and (3) synthesis of nano tungsten bronze: adding tungsten hexachloride into an organic solvent at room temperature, and ultrasonically stirring for dissolving to obtain a solution A; adding the hydroxide of the alkali metal into the solution A at room temperature, heating and stirring until the hydroxide is dissolved to obtain a suspension B; adding a morphology control agent oleic acid into the suspension B, uniformly stirring to obtain a solution C, and reacting at the temperature of 200-240 ℃ for 6-24 h; cooling, washing and drying the reactant to obtain the nano tungsten bronze;
2) hydrophobic modification of nano tungsten bronze: adding the nano tungsten bronze into a normal hexane solvent, uniformly stirring at room temperature to obtain a uniformly dispersed mixed solution, then adding a hydrophobic modifier, stirring for reacting for 1-3 hours, washing, centrifuging and drying to obtain the hydrophobically modified nano tungsten bronze; the hydrophobic modifier is one or more of trimethylchlorosilane, perfluorodecyl triethoxysilane, hexamethyl disilazane and dodecyl trimethoxysilane;
3) hydrophobic modification of the nano powder: adding the nano powder into an absolute ethyl alcohol solvent, uniformly stirring at room temperature to obtain a uniformly dispersed mixed solution, then adding a silane coupling agent hydrolysate and a hydrophobic modifier into the mixed solution, stirring and reacting for 1-3 hours at 60-90 ℃, washing, centrifuging and drying to obtain hydrophobically modified powder; the nano powder is silicon dioxide; the silane coupling agent is one or more of vinyl triethoxysilane, aminopropyl triethoxysilane and methacryloxypropyl trimethoxysilane; the hydrophobic modifier is one or more of trimethylchlorosilane, perfluorodecyl triethoxysilane, hexamethyl disilazane and dodecyl trimethoxysilane;
4) preparing a super-hydrophobic coating: dissolving resin for film formation by using an organic solvent to obtain a uniform and transparent resin solution, then adding the hydrophobically modified nano tungsten bronze and the hydrophobically modified powder, and uniformly stirring to obtain the tungsten bronze-based transparent heat-insulating super-hydrophobic coating.
3. The preparation method of the tungsten bronze-based super-hydrophobic transparent heat-insulating coating according to claim 2, characterized in that: the organic solvent in the step 1) is benzyl alcohol, and the concentration of tungsten hexachloride in the solution A is 22 mmol/L; wherein the hydroxide of the alkali metal is one or more of cesium hydroxide, sodium hydroxide, potassium hydroxide and rubidium hydroxide, wherein the molar ratio of cesium ions or sodium ions to tungsten hexachloride ions in the suspension B is 0.5; the heating and stirring are carried out in a constant-temperature water bath heating magnetic stirrer; the temperature of a water bath kettle of the thermostatic water bath is 50-60 ℃; the time for heating and stirring the suspension B is 10-15 min; the amount of oleic acid in the solution C is 10% of the total solution; the washing is 5-6 times of washing with ethanol.
4. The preparation method of the tungsten bronze-based super-hydrophobic transparent heat-insulating coating according to claim 2, characterized in that: step 2), the low surface energy hydrophobic modifier accounts for 10-100% of the mass of the tungsten bronze; the washing in the step 2) is carried out for more than 3 times by using absolute ethyl alcohol.
5. The preparation method of the tungsten bronze-based super-hydrophobic transparent heat-insulating coating according to claim 2, characterized in that: the silane coupling agent hydrolysate in the step 3) is prepared from the following components in parts by weight: water: absolute ethanol ═ 2: 1: 7, the silane coupling agent accounts for 10 to 50 percent of the nano powder; step 3), the hydrophobic modifier with low surface energy accounts for 10-100% of the weight of the nano powder; the nano powder in the step 3) is one or more of nano silicon dioxide, nano zinc oxide and nano titanium oxide with high transparency and nano particle size of 5-50 nm.
6. The preparation method of the tungsten bronze-based super-hydrophobic transparent heat-insulating coating according to claim 2, characterized in that: the film-forming resin in the step 4) accounts for 5-40% of the organic solvent by mass; the film-forming resin is one or more of polyurethane resin, fluorocarbon resin, polyvinyl chloride resin, acrylic resin and epoxy resin; the organic solvent is one or more of ester solvents, alcohol solvents, ketone solvents and n-hexane.
7. The preparation method of the tungsten bronze-based super-hydrophobic transparent heat-insulating coating according to claim 2, characterized in that: the nano silicon dioxide in the step 4) accounts for 2-12% of the mass of the coating, the tungsten bronze powder accounts for 2-12% of the mass of the coating, the film forming resin accounts for 10-30% of the mass of the coating, and the organic solvent used for film forming accounts for 50-70% of the mass of the coating.
8. The preparation method of the tungsten bronze-based super-hydrophobic transparent heat-insulating coating according to claim 2, characterized in that: in the step 2) and the step 3), the stirring time for stirring uniformly at room temperature is 20-40 minutes, and the stirring is magnetic stirring; in the step 3), stirring for the stirring reaction at the temperature of 60-90 ℃ is carried out in a water bath kettle; in the steps 1), 2) and 3), the drying temperature is 60-100 ℃, and the drying time is 8-24 hours.
9. The preparation method of the tungsten bronze-based super-hydrophobic transparent heat-insulating coating according to claim 2, characterized in that the obtained tungsten bronze-based super-hydrophobic transparent heat-insulating coating is coated on the surface of a matrix by adopting a film forming process to obtain a tungsten bronze-based transparent heat-insulating super-hydrophobic coating; the visible light transmittance of the obtained sodium tungsten bronze-based transparent heat-insulating super-hydrophobic coating is 52-60%, the near infrared blocking rate is 47-64%, the visible light transmittance of the obtained cesium tungsten bronze-based transparent heat-insulating super-hydrophobic coating is 46-60%, and the near infrared blocking rate is 65-83%;
coating the obtained tungsten bronze-based transparent heat-insulating coating on the surface of a matrix by adopting a film forming process to obtain a tungsten bronze-based transparent heat-insulating super-hydrophobic coating; the static contact angle of the obtained tungsten bronze-based transparent heat-insulating super-hydrophobic coating is larger than 150 degrees, the rolling angle is smaller than 10 degrees, the transparent heat-insulating super-hydrophobic coating is placed outdoors for a long time, the super-hydrophobic static contact angle is still larger than 150 degrees, the rolling angle is smaller than 10 degrees, the visible light transmittance is larger than 60 percent, and the near infrared blocking rate is still higher than 75 percent.
10. The preparation method of the tungsten bronze-based super-hydrophobic transparent heat-insulating coating according to claim 9, characterized in that: the film forming process is one or more of spin coating, spray coating, blade coating and dip coating; the substrate is cleaned before coating and then dried for later use, and the substrate is a glass substrate, a metal substrate, a cement-based material or a concrete substrate; cleaning the substrate by ultrasonic cleaning with ethanol and deionized water for more than 30 minutes respectively; the drying is carried out in a blast drying oven with the temperature of above 60 ℃; for the substrate with a large area, the drying is carried out under the natural condition after the substrate is cleaned by a high-pressure water gun.
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Application publication date: 20210730 |