CN113292874A - Passive radiation refrigeration coating, preparation method thereof and coating structure - Google Patents
Passive radiation refrigeration coating, preparation method thereof and coating structure Download PDFInfo
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- 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
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/22—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen
- C08G77/24—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen and oxygen halogen-containing groups
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- 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
- C09D127/18—Homopolymers or copolymers of tetrafluoroethene
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- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/04—Polysiloxanes
- C09D183/08—Polysiloxanes containing silicon bound to organic groups containing atoms other than carbon, hydrogen, and oxygen
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/004—Reflecting paints; Signal paints
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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/10—Transparent films; Clear coatings; Transparent materials
Abstract
The invention discloses a passive radiation refrigeration coating, a preparation method thereof and a coating structure. The paint comprises a passive radiation refrigeration primer and a transparent self-cleaning finish paint, wherein the transparent self-cleaning finish paint is a super-hydrophobic/super-oleophobic finish paint. The preparation method comprises the steps of preparing super-hydrophobic/super-oleophobic finish paint as transparent self-cleaning finish paint by using hydrophilic nano-silica, absolute ethyl alcohol, ammonia water, ethyl orthosilicate and perfluoro decyl triethoxysilane; the passive radiation refrigeration primer is prepared from pure acrylic emulsion, polytetrafluoroethylene powder, silicon dioxide, a dispersing agent, a wetting agent, a defoaming agent, a flatting agent, a film-forming assistant and water. The coating structure is a double-layer structure formed by passive radiation refrigeration priming paint and transparent self-cleaning finish paint. The invention has the beneficial effects that: by combining the most advanced day passive radiation refrigeration technology of surface science with the super-hydrophobic/super-oleophobic self-cleaning technology, the active effect of mutually promoting respective performances is achieved.
Description
Technical Field
The invention belongs to the technical field of passive radiation refrigeration, and particularly relates to a passive radiation refrigeration coating, a preparation method thereof and a coating structure.
Background
The refrigeration energy consumption of the building in summer accounts for about 15% of the total global energy consumption, and the peak of the refrigeration energy consumption usually occurs when sunlight is directly irradiated at noon in summer, and at the moment, the solar irradiation intensity is strongest. The traditional air-conditioning refrigeration belongs to active refrigeration, and only discharges heat in a building to the outdoor environment while consuming electric energy, thereby inevitably enhancing the urban heat island effect. The radiation refrigeration in the daytime belongs to passive refrigeration, does not need to consume electric energy, does not need refrigerant Freon, and can directly radiate the heat in the building to the atmosphere or a cold universe space (+3K or-270 ℃) outside the atmosphere through the building envelope structure, thereby being beneficial to relieving urban heat island effect and global warming tendency.
In order to realize the radiation refrigeration with the surface temperature lower than the ambient temperature in the direct incidence of sunlight in daytime, particularly at noon, the surface solar reflectivity of the radiation refrigeration body is strictly required to be not lower than 94%, and the selective infrared radiance of the surface in an atmospheric window or the whole infrared radiance in the whole infrared region is higher and better. Solar reflectance is a measure of the ability of a surface to reflect or suppress solar heat absorption, while infrared radiance is a measure of the ability of a surface to dissipate its own heat. Since no material with both high solar short-wave reflectivity and high infrared long-wave radiance (absorptivity) exists in nature, until 2014, scientists have not increased the solar reflectivity of the surface to 97% by plating rare metal silver with the highest natural solar reflectivity on a silicon crystal plate, and then alternately plating seven layers of atmospheric window selective radiation non-metallic materials, namely silicon dioxide and hafnium dioxide, on the silver to increase the selective infrared radiance of the surface at the atmospheric window to 67%, thereby realizing the daytime radiation refrigeration phenomenon that the surface temperature is lower than the ambient temperature when the sunlight directly irradiates for the first time in human history.
To date, the worldwide daytime radiation refrigeration technology is classified into silver-plated silicon crystal plates, silver-plated polymer films, vinylidene fluoride-hexafluoropropylene copolymer films, refrigerated woods, coating materials, and the like. Without exception, these refrigeration technology surfaces are all single white in color because white color has the highest solar reflectance, facilitating the absorption of solar heat by the pressing surface. But the white surface is easily stained with dust, mold and oily contaminants, causing a decrease in solar reflectance and loss of refrigeration performance.
Disclosure of Invention
The invention aims to: the passive radiation refrigeration coating is applied to the surfaces of buildings, oil and gas storage tanks, tank cars, Liquefied Natural Gas (LNG) ships, cold chain logistics, sunshade umbrellas, tents, grain bins and the like, and can ensure that the surface temperature of the objects is lower than the ambient temperature day and night while endowing the surfaces of the objects with super-hydrophobic/super-oleophobic self-cleaning performance, thereby achieving the aim of passive radiation refrigeration.
The super-hydrophobic/super-oleophobic double-hydrophobic coating is a self-cleaning coating which has double effects of resisting water-soluble pollution and resisting oily pollution, and overcomes the defect that the hydrophobic and oleophilic properties of the super-hydrophobic coating are easily stained by oily pollutants. The preparation method of the transparent super-hydrophobic/super-oleophobic coating is various, but the method which can be produced and applied in large scale belongs to the coating prepared by the sol-gel method. The raw materials prepared by the sol-gel method are usually nano-silica or nano-silica sol, tetraethoxysilane, perfluorosilane, solvent, catalyst and the like. Under the catalysis of acid or alkali, tetraethoxysilane and perfluorosilane are subjected to hydrolysis-copolycondensation reaction to form a-Si-O-network polymer on the surface of the nano silicon dioxide. The technical bottleneck restricting the large-scale application of the super-hydrophobic/super-oleophobic transparent coating is the binding force between the coating and the substrate, and a suitable adhesive is selected to prepare the durable super-amphiphobic coating.
It is well known that silica is transparent over a broad range of the sun, but has selective radiation over atmospheric windows. Therefore, a natural scientific assumption is that if the surface of the passive radiation refrigeration coating is covered with an ultra-thin super-hydrophobic/super-oleophobic coating as a finish during the daytime, the two leading edge technologies of surface science are compatible with each other and their respective performances are enhanced? The surface temperature of the coating system is far lower than the ambient temperature by the refrigeration primer, and the refrigeration primer has high ultraviolet reflectivity. Therefore, the daytime radiation refrigeration primer can enhance the thermal aging resistance and ultraviolet aging resistance of the super-hydrophobic/super-oleophobic refrigeration finish paint, and prolong the service life of the super-hydrophobic/super-oleophobic self-cleaning surface layer of the super-hydrophobic/super-oleophobic refrigeration finish paint. It is also self-cleaning superhydrophobic/superoleophobic top coats that enable the solar reflectance of passive radiation cooling during the day to be maintained for long periods of time without degradation due to contamination by aqueous and oily contaminants. The only problems that exist are: is the super hydrophobic/super oleophobic self-cleaning topcoat affecting the solar reflectance of the daytime radiant refrigeration primer? And if the selective radiation of the radiation refrigeration primer in the atmospheric window in the daytime is improved, so as to improve the overall infrared radiation rate and refrigeration performance of the primer?
The purpose of the invention is realized by the following technical scheme:
a passive radiation refrigeration coating comprises a passive radiation refrigeration primer and a transparent self-cleaning finish, wherein the transparent self-cleaning finish comprises hydrophilic nano silicon dioxide, absolute ethyl alcohol, ammonia water, ethyl orthosilicate and perfluorodecyl triethoxysilane, and the passive radiation refrigeration primer comprises pure acrylic emulsion, polytetrafluoroethylene powder, silicon dioxide, a dispersing agent, a wetting agent, a defoaming agent, a leveling agent, a film-forming assistant and water.
The hydrophilic nano silicon dioxide is transparent in the solar spectrum range (0.25-2.5 microns), but has selective radiation in the atmospheric window (8-13 microns), and the nano silicon dioxide is used for constructing the finish paint, so that the solar reflectivity of the refrigeration primer paint is not influenced, the selective radiation of the refrigeration primer paint in the atmospheric window is enhanced, and the total infrared radiation rate of the refrigeration primer paint is improved; on the other hand, the nano-silica is a carrier and a template of a micro-nano structure required by constructing super-hydrophobic/super-oleophobic self-cleaning. Under the catalysis of catalyst ammonia water, ethyl orthosilicate is subjected to alcoholysis to form silanol, perfluorodecyl triethoxy silanol is subjected to alcoholysis to form perfluorodecyl silanol, and the two types of silanol form a copolymer with a long fluorocarbon side chain with ultralow surface energy and a main chain of a-Si-O-Si-structure on the surface of the nano silicon dioxide through copolycondensation reaction, so that a coarse micro-nano structure is provided. The super-low surface energy and the rough micro-nano structure endow the finish with excellent super-hydrophobic/super-oleophobic self-cleaning performance.
As is well known, the material with the highest solar reflectance in nature is noble metal silver, and the solar reflectance is 97%; fluorocarbon polymers, including synthetic polymeric materials, have very high solar reflectance. The material with the highest solar reflectance among all the materials is a synthetic polymer polytetrafluoroethylene tablet, which is generally used as the inner wall of the integrating sphere and the standard plate (solar reflectance 100%) of the ultraviolet/visible/near infrared spectrophotometer. Therefore, the polytetrafluoroethylene powder is selected to solve the weak point of strong absorption of rutile titanium dioxide in the ultraviolet region, and obtain very high solar reflectance. Silica is used to enhance the selectivity of the coating to infrared radiation in the atmospheric window.
Further, the transparent self-cleaning finish paint comprises, by weight, 0.5-1 part of hydrophilic nano silicon dioxide, 75-85 parts of absolute ethyl alcohol, 13-23 parts of ammonia water, 0.05-0.2 part of ethyl orthosilicate and 0.9-2 parts of perfluorodecyl triethoxysilane.
Furthermore, the contact angles of the surface of the transparent self-cleaning finish paint with water and n-hexadecane are both larger than 150 degrees, and the rolling angles of the two liquids are both smaller than 10 degrees.
Further, the passive radiation refrigeration primer comprises, by weight, 20-30 parts of a pure acrylic emulsion, 30-40 parts of polytetrafluoroethylene powder, 10-20 parts of silicon dioxide, 1-2 parts of a dispersing agent, 1-2 parts of a wetting agent, 1-2 parts of a defoaming agent, 1-2 parts of a leveling agent, 1-2 parts of a film forming assistant and 10-28 parts of water.
Furthermore, the non-radiative heat transfer coefficient in conduction and convection is 4.55-5.15 Wm-2K-1In the daytime and at noon in sunny days in summer, the surface temperature of the coating of the aluminum plate coated with the passive radiation refrigeration coating is lower than the ambient temperature (9.13 +/-0.25) DEG C to (12.41 +/-0.54).
The preparation method of the passive radiation refrigeration coating comprises the steps of preparing a super-hydrophobic/super-oleophobic finish as a transparent self-cleaning finish by using hydrophilic nano-silica, absolute ethyl alcohol, ammonia water, ethyl orthosilicate and perfluorodecyl triethoxysilane; the passive radiation refrigeration primer is prepared from pure olefine acid emulsion, polytetrafluoroethylene powder, silicon dioxide, a dispersing agent, a wetting agent, a defoaming agent, a flatting agent, a film-forming assistant and water.
Further, anhydrous ethanol, ammonia water, hydrophilic nano-silica, ethyl orthosilicate and perfluorodecyl triethoxysilane are weighed according to the formula amount, added into a reaction container, subjected to ultrasonic dispersion, subjected to high-speed dispersion to prepare a super-hydrophobic/super-oleophobic suspension, mixed with a fluorocarbon surfactant, stirred and dispersed to prepare the super-hydrophobic/super-oleophobic coating.
Further, mixing pure acrylic emulsion, polytetrafluoroethylene powder, silicon dioxide, water, a dispersing agent, a wetting agent, a defoaming agent and a flatting agent according to the formula amount, stirring at a high speed for dispersing, then grinding the dispersed mixture, adding a film-forming assistant according to the formula amount under low-speed stirring, and dispersing to prepare the white passive radiation refrigeration primer.
The passive radiation refrigeration primer and the transparent self-cleaning finish paint form a double-layer structure.
Furthermore, the layer thickness of the refrigeration primer is not less than 300 mu m, and the layer thickness of the transparent self-cleaning finishing paint is not more than 50 mu m. The solar reflectivity of the coating is not less than 96%, and the infrared radiance is not less than 90%.
The invention has the beneficial effects that: by combining the most advanced day passive radiation refrigeration technology of surface science with the super-hydrophobic/super-oleophobic self-cleaning two top-end technologies, the following positive effects of mutually promoting respective performances are achieved: the radiation refrigeration priming paint enhances the heat aging resistance and ultraviolet aging resistance of the super-hydrophobic/super-oleophobic self-cleaning finish paint in the daytime, and prolongs the service life of the finish paint; the super-hydrophobic/super-oleophobic self-cleaning finish paint enhances the selective infrared radiance of the radiation refrigeration primer in the atmospheric window in the daytime under the condition of hardly influencing the solar reflectivity of the radiation refrigeration primer in the daytime, thereby enhancing the refrigeration performance of the radiation refrigeration primer in the daytime; the super-hydrophobic/super-oleophobic self-cleaning finish paint endows the whole coating system with super-hydrophobic/super-oleophobic self-cleaning performance, so that the solar reflectivity of the whole coating system is maintained to be more than 94% for a long time, and the coating system is endowed with long-term daytime passive radiation refrigeration performance.
The main scheme and the further selection schemes can be freely combined to form a plurality of schemes which are all adopted and claimed by the invention; in the invention, the selection (each non-conflict selection) and other selections can be freely combined. The skilled person in the art can understand that there are many combinations, which are all the technical solutions to be protected by the present invention, according to the prior art and the common general knowledge after understanding the scheme of the present invention, and the technical solutions are not exhaustive herein.
Drawings
FIG. 1 is a graphical representation of the reflectivity of the super-amphiphobic refrigeration coating and the refrigeration coating at different wavelengths of example 1 of the present invention.
FIG. 2 is a schematic representation of the contact angles of the surface of the super-amphiphobic refrigeration coating of example 1 of the present invention with water (left) and n-hexadecane (right).
FIG. 3 is a schematic diagram of the surface temperature, ambient air temperature and illumination intensity of the aluminum plate at different times for the super-amphiphobic refrigeration coating of example 1 of the present invention.
FIG. 4 is a graphical representation of the reflectivity of the super-amphiphobic refrigeration coating and the refrigeration coating at different wavelengths of example 2 of the present invention.
FIG. 5 is a schematic representation of the contact angles of the surface of the super-amphiphobic refrigeration coating of example 2 of the present invention with water (left) and n-hexadecane (right).
FIG. 6 is a schematic diagram of the surface temperature, ambient air temperature and illumination intensity of the aluminum plate at different times for the super-amphiphobic refrigeration coating of example 2 of the present invention.
FIG. 7 is a graphical representation of the reflectivity of the super-amphiphobic refrigeration coating and the refrigeration coating at different wavelengths of example 3 of the present invention.
FIG. 8 is a schematic representation of the contact angles of the surface of the super-amphiphobic refrigeration coating of example 3 of the present invention with water (left) and n-hexadecane (right).
FIG. 9 is a schematic diagram of the surface temperature, ambient air temperature and illumination intensity of the aluminum plate at different times for the super-amphiphobic refrigeration coating of example 3 of the present invention.
Detailed Description
The following non-limiting examples serve to illustrate the invention.
The attached drawings are obtained by adopting the following experimental conditions: the prepared passive radiation refrigeration coating was coated on a 4cm x 4cm aluminum plate and the spectral and total solar and infrared reflectance of the coating were measured using an ultraviolet, visible, near infrared spectrophotometer (Pekin-Elmer Lambda950) and a portable infrared radiometer (AE1, Devices & Services co., Dallas, TX), respectively.
The prepared passive radiation refrigeration coating is coated on an aluminum alloy plate (31cm long, 31cm wide and 1.0cm thick) of a self-built refrigerator in an airless spraying mode, and the ambient temperature is measured by using a thermal resistor placed in a louver box near the refrigerator, because the aluminum alloy is a good heat conductor, the surface temperature of the coating is equal to the temperature of the aluminum alloy, and the surface temperature of the coating can be measured by using the thermal resistor inserted into a middle round hole of the aluminum alloy plate. The wind speed and the conduction and convection non-radiative heat transfer coefficients are measured by an anemometer, and the solar irradiation intensity is measured by an irradiator. The measured data are transmitted to the computer terminal through wireless.
Example 1
A passive radiation refrigeration coating. The paint comprises a passive radiation refrigeration primer and a transparent self-cleaning finish paint, wherein the transparent self-cleaning finish paint is a super-hydrophobic/super-oleophobic finish paint.
The transparent self-cleaning finish paint comprises the following components in parts by weight: 1 part of hydrophilic nano silicon dioxide, 83 parts of absolute ethyl alcohol, 15 parts of ammonia water, 0.1 part of ethyl orthosilicate and 0.9 part of perfluorodecyl triethoxysilane. The passive radiation refrigeration primer comprises the following components in parts by weight: 30 parts of pure acrylic emulsion, 40 parts of polytetrafluoroethylene, 15 parts of silicon dioxide, 10 parts of water, 1 part of dispersing agent, 1 part of wetting agent, 1 part of defoaming agent, 1 part of flatting agent and 1 part of film-forming assistant.
A preparation method of the passive radiation refrigeration coating.
The preparation method comprises the following steps of weighing absolute ethyl alcohol, ammonia water, hydrophilic nano silicon dioxide, ethyl orthosilicate and perfluoro decyl triethoxysilane according to the formula ratio, adding the materials into a reaction container, performing ultrasonic dispersion, and performing high-speed dispersion to prepare the super-hydrophobic/super-oleophobic suspension. And mixing the prepared super-hydrophobic/super-oleophobic suspension with a fluorocarbon surfactant, stirring and dispersing to prepare the super-hydrophobic/super-oleophobic coating.
And then weighing the pure acrylic emulsion, the polytetrafluoroethylene powder, the silicon dioxide, the water and the auxiliaries except the film-forming auxiliary according to the formula, mixing, stirring at a high speed for dispersing, then grinding the dispersed mixture, adding the film-forming auxiliary under low-speed stirring, and dispersing to prepare the white passive radiation refrigeration primer.
Coating the passive radiation refrigeration coating on an aluminum alloy plate of a self-built refrigerator in the daytime, and controlling the thickness of a dry film of the coating to be 300 mu m; after the surface of the primer is dried, spraying the super-hydrophobic/super-oleophobic finishing coat on the passive radiation refrigeration primer in the daytime, and controlling the thickness of the dry film of the coating to be 50 mu m. Thereby forming the coating structure of the passive radiation refrigeration coating.
FIG. 1 is a graph showing the reflectivity of the super-amphiphobic refrigeration coating and the refrigeration coating of this embodiment of the present invention at different wavelengths. The refrigeration coating is formed by the passive radiation refrigeration primer of the embodiment, the total infrared radiance of the passive radiation refrigeration primer is 90%, the total solar reflectance is 96%, and the ultraviolet spectrum reflectance, the visible light spectrum reflectance and the near infrared spectrum reflectance are 93.3%, 98.3% and 92.8% respectively.
The super-amphiphobic refrigeration coating is formed by compounding super-hydrophobic/super-oleophobic finish paint on the passive radiation refrigeration primer, the infrared radiance of the whole coating system is 91%, the total solar reflectance is 96%, and the ultraviolet spectral reflectance, the visible light spectral reflectance and the near infrared spectral reflectance are 93.9%, 98.2% and 93.1% respectively.
Therefore, the addition of the super-hydrophobic/super-oleophobic finishing coat enhances the selective infrared radiance of the coating system in an atmospheric window, and further improves the total infrared radiance of the coating system. The overall solar reflectance is essentially unchanged as expected, with only a slight decrease in the visible spectrum reflectance, but a slight increase in the ultraviolet and near infrared spectrum reflectances.
Fig. 2 is a schematic view of contact angles between the surface of the super-amphiphobic refrigeration coating of the embodiment of the invention and water (left) and n-hexadecane (right), which are 158.3 degrees and 150.7 degrees respectively, and rolling angles are both less than 10 degrees, so that the super-amphiphobic refrigeration coating has an obvious self-cleaning function.
FIG. 3 is a schematic diagram of the surface temperature, ambient air temperature and illumination intensity of the aluminum plate at different times of the super-amphiphobic refrigeration coating of the embodiment of the invention. As can be seen from FIG. 3, in the rainy cloudy day with the solar radiation intensity floating between 400-1000W/sq.m, the non-radiative heat transfer coefficient of conduction and convection is 4.55W/(m) in the midday period with poor radiation2K), the surface temperature of the coating is constantly below ambient temperature, the average value of the below-ambient temperature being 10.49. + -. 0.65 ℃.
Example 2
A passive radiation refrigeration coating. The paint comprises a passive radiation refrigeration primer and a transparent self-cleaning finish paint, wherein the transparent self-cleaning finish paint is a super-hydrophobic/super-oleophobic finish paint.
The transparent self-cleaning finish paint comprises the following components in parts by weight: 0.5 part of hydrophilic nano silicon dioxide, 85 parts of absolute ethyl alcohol, 13 parts of ammonia water, 0.2 part of ethyl orthosilicate and 2 parts of perfluorodecyl triethoxysilane. The passive radiation refrigeration primer comprises the following components in parts by weight: 20 parts of pure acrylic emulsion, 35 parts of polytetrafluoroethylene, 20 parts of silicon dioxide, 15 parts of water, 2 parts of dispersing agent, 2 parts of wetting agent, 2 parts of defoaming agent, 2 parts of flatting agent and 2 parts of film-forming assistant.
A preparation method and a coating structure of the passive radiation refrigeration coating are the same as those of the embodiment 1.
FIG. 4 is a graph showing the reflectivity of the super-amphiphobic refrigeration coating and the refrigeration coating of this embodiment of the present invention at different wavelengths. The refrigeration coating is formed by the passive radiation refrigeration primer of the embodiment, the total infrared radiance of the passive radiation refrigeration primer is 91%, the total solar reflectance is 96.82%, and the ultraviolet spectrum reflectance, the visible light spectrum reflectance and the near infrared spectrum reflectance are 95.12%, 98.81% and 94.31%, respectively.
The super-amphiphobic refrigeration coating is formed by compounding super-hydrophobic/super-oleophobic finish paint on the passive radiation refrigeration primer, the infrared radiance of the whole coating system is 91.6%, the total solar reflectance is 96.2%, and the ultraviolet spectral reflectance, the visible spectral reflectance and the near infrared spectral reflectance are 95.04%, 98.37% and 93.28% respectively.
The addition of the super-hydrophobic/super-oleophobic finishing coat enhances the selective infrared radiance of the coating system in an atmospheric window, thereby improving the total infrared radiance of the coating system. Unexpectedly, the overall solar reflectance, ultraviolet spectral reflectance, visible spectral reflectance and near infrared spectral reflectance were all slightly reduced, most likely due to the excessively thick thickness of the superhydrophobic/superoleophobic self-cleaning coating.
Fig. 5 is a schematic view of contact angles of the surface of the super-amphiphobic refrigeration coating with water (left) and n-hexadecane (right) of 155.9 degrees and 152.5 degrees respectively, rolling angles are both smaller than 6 degrees, and the super-amphiphobic refrigeration coating has an obvious self-cleaning function.
FIG. 6 is a schematic diagram of the surface temperature, ambient air temperature and illumination intensity of the aluminum plate at different times of the super-amphiphobic refrigeration coating of the embodiment of the invention. As can be seen from FIG. 3, in the noon period of a sunny summer day with the solar radiation intensity of 900-1000W/square meter, when the conduction and convection non-radiative heat transfer coefficients are 5.15W/(m)2K) the surface temperature of the coating is constantly below the ambient temperature, below the average value of the ambient temperatureThe temperature was 9.13. + -. 0.25 ℃. The reason why the lower sub-ambient temperature radiant cooling effect relative to example 1 was observed with higher solar reflectance, more sunny weather and radiation is due to the higher conductive and convective non-radiative heat transfer coefficients.
Example 3
A passive radiation refrigeration coating. The paint comprises a passive radiation refrigeration primer and a transparent self-cleaning finish paint, wherein the transparent self-cleaning finish paint is a super-hydrophobic/super-oleophobic finish paint.
The transparent self-cleaning finish paint comprises the following components in parts by weight: 0.8 part of hydrophilic nano silicon dioxide, 75 parts of absolute ethyl alcohol, 23 parts of ammonia water, 0.05 part of ethyl orthosilicate and 1.5 parts of perfluorodecyl triethoxysilane. The passive radiation refrigeration primer comprises the following components in parts by weight: 25 parts of pure acrylic emulsion, 30 parts of polytetrafluoroethylene, 10 parts of silicon dioxide, 28 parts of water, 1.4 parts of dispersing agent, 1.4 parts of wetting agent, 1.4 parts of defoaming agent, 1.4 parts of flatting agent and 1.4 parts of film-forming assistant.
A preparation method and a coating structure of the passive radiation refrigeration coating are the same as those of the embodiment 1.
FIG. 7 is a graph showing the reflectivity of the super-amphiphobic refrigeration coating and the refrigeration coating of this embodiment of the present invention at different wavelengths. The refrigeration coating is formed by the passive radiation refrigeration primer of the embodiment, the total infrared radiance of the passive radiation refrigeration primer is 91.2%, the total solar reflectance is 96.86%, and the ultraviolet spectrum reflectance, the visible spectrum reflectance and the near infrared spectrum reflectance are 95.12%, 98.81% and 94.31%, respectively.
The super-amphiphobic refrigeration coating is formed by compounding a super-hydrophobic/super-oleophobic finish paint on the passive radiation refrigeration primer, the infrared radiance of the whole coating system is 92%, the total solar reflectance is 96.67%, and the ultraviolet spectral reflectance, the visible spectral reflectance and the near infrared spectral reflectance are 94.51%, 98.6% and 94.18% respectively.
Similarly, the addition of the super-hydrophobic/super-oleophobic finish enhances the selective infrared radiance of the coating system in an atmospheric window, thereby improving the overall infrared radiance of the coating system. Unexpectedly, the overall solar reflectance, ultraviolet spectral reflectance, visible spectral reflectance and near infrared spectral reflectance were all slightly reduced, most likely due to the excessively thick thickness of the superhydrophobic/superoleophobic self-cleaning coating.
Fig. 8 is a schematic view of contact angles of the surface of the super-amphiphobic refrigeration coating with water (left) and n-hexadecane (right), which are 156.7 degrees and 151.0 degrees respectively, rolling angles are both smaller than 2 degrees, and the super-amphiphobic refrigeration coating has an obvious self-cleaning function.
FIG. 9 is a schematic diagram of the surface temperature, ambient air temperature and illumination intensity of the aluminum plate at different times for the super-amphiphobic refrigeration coating of the embodiment of the invention. As can be seen from FIG. 3, the heat transfer coefficient when conduction and convection are non-radiative is 4.10W/(m) during the noon in the relatively clear summer2K), the surface temperature of the coating is constantly below ambient temperature, the average value of the below-ambient temperature being 12.41. + -. 0.54 ℃.
The foregoing basic embodiments of the invention and their various further alternatives can be freely combined to form multiple embodiments, all of which are contemplated and claimed herein. In the scheme of the invention, each selection example can be combined with any other basic example and selection example at will. For example, fig. 1 can also be regarded as a combination of the basic example and the option 2, fig. 2 can also be regarded as a combination of the basic example and the option 3, and so on, which are not exhaustive, and those skilled in the art can know that there are many combinations.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A passive radiation refrigeration coating is characterized in that: the transparent self-cleaning finish paint comprises hydrophilic nano silicon dioxide, absolute ethyl alcohol, ammonia water, ethyl orthosilicate and perfluorodecyl triethoxysilane, and the passive radiation refrigeration primer paint comprises pure acrylic emulsion, polytetrafluoroethylene powder, silicon dioxide, a dispersing agent, a wetting agent, a defoaming agent, a leveling agent, a film-forming assistant and water.
2. The passive radiation refrigeration coating of claim 1, wherein: the transparent self-cleaning finish paint comprises, by weight, 0.5-1 part of hydrophilic nano silicon dioxide, 75-85 parts of absolute ethyl alcohol, 13-23 parts of ammonia water, 0.05-0.2 part of ethyl orthosilicate and 0.9-2 parts of perfluorodecyl triethoxysilane.
3. Passive radiation refrigeration coating according to claim 1 or 2, characterized in that: the contact angles of the surface of the transparent self-cleaning finish paint with water and n-hexadecane are both larger than 150 degrees, and the rolling angles of the two liquids are both smaller than 10 degrees.
4. The passive radiation refrigeration coating of claim 1, wherein: the passive radiation refrigeration primer comprises, by weight, 20-30 parts of pure acrylic emulsion, 30-40 parts of polytetrafluoroethylene powder, 10-20 parts of silicon dioxide, 1-2 parts of a dispersing agent, 1-2 parts of a wetting agent, 1-2 parts of a defoaming agent, 1-2 parts of a leveling agent, 1-2 parts of a film-forming assistant and 10-28 parts of water.
5. The passive radiation refrigeration coating of claim 1 or 4, wherein: the non-radiative heat transfer coefficient in conduction and convection is 4.55-5.15 Wm-2K-1In the daytime and at noon in sunny days in summer, the surface temperature of the coating of the aluminum plate coated with the passive radiation refrigeration coating is lower than the ambient temperature (9.13 +/-0.25) DEG C to (12.41 +/-0.54).
6. A preparation method of the passive radiation refrigeration coating as claimed in any one of claims 1 to 5, characterized in that: preparing super-hydrophobic/super-oleophobic finish paint serving as transparent self-cleaning finish paint by using hydrophilic nano silicon dioxide, absolute ethyl alcohol, ammonia water, ethyl orthosilicate and perfluoro decyl triethoxysilane; the passive radiation refrigeration primer is prepared from pure olefine acid emulsion, polytetrafluoroethylene powder, silicon dioxide, a dispersing agent, a wetting agent, a defoaming agent, a flatting agent, a film-forming assistant and water.
7. The method of claim 6, wherein: the preparation method comprises the following steps of weighing absolute ethyl alcohol, ammonia water, hydrophilic nano silicon dioxide, ethyl orthosilicate and perfluoro-decyl triethoxysilane according to the formula ratio, adding the weighed absolute ethyl alcohol, ammonia water, hydrophilic nano silicon dioxide, ethyl orthosilicate and perfluoro-decyl triethoxysilane into a reaction container, carrying out ultrasonic dispersion, then carrying out high-speed dispersion to prepare a super-hydrophobic/super-oleophobic suspension, mixing the super-hydrophobic/super-oleophobic suspension with a fluorocarbon surfactant, and carrying out stirring dispersion to prepare the super-hydrophobic/super-oleophobic coating.
8. The production method according to claim 6 or 7, characterized in that: mixing pure acrylic emulsion, polytetrafluoroethylene powder, silicon dioxide, water, a dispersing agent, a wetting agent, a defoaming agent and a flatting agent according to the formula amount, stirring at a high speed for dispersing, then grinding the dispersed mixture, adding a film-forming assistant according to the formula amount under low-speed stirring, and dispersing to prepare the white passive radiation refrigeration primer.
9. A coating structure of the passive radiation refrigeration coating of any one of claims 1 to 5, characterized in that: the passive radiation refrigeration primer and the transparent self-cleaning finish paint form a double-layer structure.
10. The coating architecture according to claim 9, wherein: the thickness of the refrigeration primer is not less than 300 mu m, the thickness of the transparent self-cleaning finish paint is not more than 50 mu m, the solar reflectivity of the coating is not less than 96%, and the infrared radiance is not less than 90%.
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