CN117164939A - Micro-nano porous-granular composite radiation refrigeration film coating and preparation method thereof - Google Patents
Micro-nano porous-granular composite radiation refrigeration film coating and preparation method thereof Download PDFInfo
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- CN117164939A CN117164939A CN202311151797.0A CN202311151797A CN117164939A CN 117164939 A CN117164939 A CN 117164939A CN 202311151797 A CN202311151797 A CN 202311151797A CN 117164939 A CN117164939 A CN 117164939A
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Paints Or Removers (AREA)
Abstract
The invention relates to a micro-nano porous-particle composite radiation refrigeration film coating and a preparation method thereof, wherein the preparation flow of phase separation-solution casting is designed, polymer and a first solvent are prepared into solution, dielectric particles are added to form a dielectric particle-polymer uniform suspension system, casting or coating is carried out to form a film, the film is placed in a high humidity environment, a second solvent and the first solvent are subjected to solvent replacement, micro-nano level microsphere is formed in the coating, a porous structure is formed after the second solvent is removed by drying, and the film coating is obtained after separation. The invention has low cost of the needed raw materials, simple and convenient preparation and large-scale production. The prepared film coating has excellent and adjustable optical properties, and can be cooled by more than 15 ℃ under direct sunlight in the daytime, and has hydrophobicity and mechanical ductility. The invention is used as a refrigeration technology without power consumption and emission, is expected to reduce the energy consumption and carbon emission of the traditional refrigeration, and can be widely applied to spontaneous cooling of the surface of device facilities.
Description
Technical Field
The invention belongs to the field of passive daytime radiation refrigeration, and particularly relates to a micro-nano porous-particle composite radiation refrigeration film coating and a preparation method thereof.
Background
The increasing temperature stability requirements drive the widespread use of refrigeration, which has resulted in significant power consumption and carbon emissions. In order to break the vicious circle of the growth of climate warming and refrigeration, a passive, non-power-consumption and emission-free technology such as a passive radiation cooling (PDRC) technology in daytime is attracting attention, and the principle is to reflect solar radiation wave bands with the wavelength range of about 0.3-2.5 mu m back, and meanwhile, to emit self heat to a universe background of 3K through an atmospheric transparent window with the wavelength of 8-13 mu m. The passive radiation cooling technology can not only reduce the cold load of the building, but also be beneficial to relieving the urban heat island effect and the climate warming problem, realize the spontaneous cooling of the surface of the building, and greatly influence the world energy pattern.
In recent years, some advanced PDRC techniques have attracted extensive attention, and researchers have been widely exploring nanostructure materials, photonic crystals, stacked structures, metal-dielectric (periodic photon) structures, both experimentally and in simulation, in order to adjust optical properties and obtain selectively controlled spectral emissions. The structure can reflect in a broadband in the solar radiation range and emit strongly in an atmospheric transparent window, so that a good refrigerating effect is obtained. But these film designs require expensive preparation and complex and harsh processes to achieve satisfactory optical performance. Thus, complexity and high cost limit the practical application on a large scale. Moreover, this expensive approach is not repairable within theoretical limits of cooling power and temperature difference. Polymer-based film materials are favored for lower cost and potential for mass production, but the cooling effect produced by simple structural design is limited and further performance improvement is still required. Thus, research and development of PDRC materials that are simple, inexpensive, efficient, environmentally friendly, and mass producible is currently a challenge.
The main points of the radiation refrigeration film for photonic crystal and lamination type are as follows: the structure and the process are complex, and the preparation cost is high; mechanical bonding is not firm, falling-off phenomenon easily occurs between layers, the texture is harder, and the application scene is limited; the reflection form is specular reflection, and light pollution is easy to form.
Aiming at a polymer-based multistage hole radiation refrigeration film, the main defects are that: the reflectivity is formed by means of the conventional scattering capability of a single kind of scatterer, and has strong thickness dependence. The size of the scatterers is difficult to control.
Patent publication No.: CN110216924 a discloses a composite radiation refrigeration film, the film has holes and additives in the emission layer, which can improve the emissivity of atmospheric window band, but not the spectral reflectivity of solar radiation, the patent sets a reflection layer under the emission layer to realize high reflection of solar band, and the reflection layer still uses metal material. Therefore, the structure of the patent is complicated, and ultraviolet absorption of the metal cannot be avoided.
Patent publication No.: CN 114714692A discloses a visible-near infrared frequency division type radiation refrigeration film based on bionic rose petal micro-nano structure, the film is provided with a transparent bionic micro-nano structure layer and a multi-layer film structure layer from top to bottom through the bionic rose petal micro-nano structure, the selective transmission of solar radiation energy by the radiation refrigeration film is realized, the visible-near infrared band frequency division function and the high emission performance of an atmospheric window are realized, lighting and refrigeration performances are considered, and the application range of the radiation refrigeration material is widened. Although the thin film uses low-cost polymer materials, the processing of the bionic micro-nano structure introduces a wet etching technology and a template hot stamping method, and meanwhile, the multi-layer film structure layer uses a vacuum magnetron sputtering method, an electron beam evaporation method and a chemical vapor deposition method, and the processing technology has high cost and limited size by equipment, so the thin film does not have the advantage of large-scale application.
Patent publication No.: CN 112375418A discloses a preparation method of a multistage porous radiation refrigeration film coating, and the invention enhances the reflectivity of solar radiation wave bands by generating a multistage pore structure through a simple low-cost preparation method, but the cooling effect is not obvious enough due to limited structure regulation and control effect.
Disclosure of Invention
The invention aims to provide a micro-nano porous-particle composite radiation refrigeration film coating which is high in efficiency, low in cost and capable of being produced in large scale and a preparation method thereof. As the film coating has a micro-nano pore structure and a nano particle structure, the solar reflectivity is up to 96.3%, the emissivity of an infrared atmospheric window band (8-13 μm) is up to 98.3%, the emissivity of a middle infrared band (5-25 μm) is up to 96.7%, and the temperature can be reduced by about 10 ℃ under the direct solar radiation at noon. In addition, the film coating has a series of advantages of simple preparation, good hydrophobicity, excellent mechanical ductility, low cost and the like, and can be applied to various complex surfaces in a large scale.
The invention is realized by adopting the following technical scheme:
the preparation method of the micro-nano porous-particle composite radiation refrigeration film coating comprises the following steps:
(1) Adding a high molecular polymer or silane and an additive into a first solvent, and uniformly mixing to obtain an organic solution or emulsion;
(2) Adding micro-nano-sized dielectric particles into the organic solution or emulsion obtained in the step (1), and obtaining a uniformly dispersed suspension through stirring and ultrasonic action;
(3) Pouring the suspension obtained in the step (2) into a mould with a required size or attaching the suspension to a substrate plane in a coating mode to obtain an initial coating;
(4) Carrying out solvent replacement on the initial coating obtained in the step (3) and a second solvent to obtain a multiphase mixed coating with water phase invasion replacement;
(5) And (3) placing the multiphase mixed coating obtained in the step (4) and a die or a substrate plane in a heating and drying device, drying at a set temperature to obtain a cured micro-nano porous-particle coating, and directly stripping the cured micro-nano porous-particle coating from the die or the substrate plane to obtain the micro-nano porous-particle composite radiation refrigeration film.
The invention is further improved in that in the step (1), the high molecular polymer is any one or more of ethylene polymer, fluoroethylene homopolymer, polyurethane, epoxy resin polymer, styrene polymer, polyethylene terephthalate, polyvinylidene fluoride-hexafluoropropylene, (methyl) acrylic ester polymer or organic siloxane polymer;
the silane is any one or more of dimethyl siloxane, methyltriethoxysilane, vinyl triethoxysilane, dimethyl diethoxysilane or tetraethoxysilane;
the additive is any one or more of curing agent, adhesive or initiator for maintaining or adjusting the state of the organic solution or emulsion, and the volume ratio of any additive to the high molecular polymer or silane is 1:8 to 1:10;
the first solvent is any one or more of toluene, xylene, octane, cyclohexane, cyclohexanone, chlorobenzene, dichloromethane, methanol, ethanol, isopropanol, epoxypropane, N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, methyl acetate, ethyl acetate, propyl acetate, acetone, methyl butanone, methyl isobutyl ketone, N-methylpyrrolidone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, trichloroethylene, tetrahydrofuran, acetonitrile or triethanolamine;
the proportion of the high molecular polymer or the silane to the organic solution or the emulsion is 10-60wt%.
The invention is further improved in that in the step (2), the dielectric particles are one or more of silicon dioxide, aerosol silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, barium sulfate, calcium carbonate, calcium sulfate, calcium oxide, magnesium carbonate, magnesium oxide, zinc oxide, yttrium oxide, silver chloride, lead sulfate or boron nitride; titanium dioxide includes P25, anatase and rutile;
preferably, the dielectric particles account for 5-75% of the volume of the suspension and have a particle size of 10nm-1000 μm.
The invention further improves that in the step (3), the coating mode comprises the following steps: any one or more of spin coating, knife coating, spray coating or roll coating;
the substrate plane comprises: any one or more of glass, polytetrafluoroethylene, stainless steel, wood or cloth fabrics.
The invention is further improved in that in the step (4), the second solvent is any one or more of water, methanol, ethanol, diethyl ether or propanol;
the method for solvent replacement of the coating with the second solvent comprises the following steps: placing the initial coating in a high-humidity environment with the relative humidity of a second solvent being more than 50%, immersing the initial coating in the second solvent, or spraying an atomized second solvent on the initial coating; wherein the second solvent is soluble with the first solvent and the second solvent is insoluble with the high molecular polymer or silane in step (1);
the duration of the solvent replacement process is 0.5-2h.
The invention is further improved in that the heating and drying device in the step (5) comprises a tube furnace, a drying oven, an oven or a heating table;
the temperature is set at 20-80 ℃ and the drying time is 5-20h in the heating process.
The micro-nano porous-granular composite radiation refrigeration film coating is prepared by adopting the preparation method, and the thickness of the micro-nano porous-granular composite radiation refrigeration film coating is 100-10000 mu m.
The invention is further improved in that the pore size distribution of the micro-nano porous-granular composite radiation refrigeration film coating is as follows: the nanometer level pores are distributed at 400+/-230 nm, and the micrometer level pores are distributed at 7.25+/-12.86 mu m.
The invention further improves that the porosity of the micro-nano porous-granular composite radiation refrigeration film coating is 20-70%.
The invention is further improved in that the solar radiation wave band reflectivity of the micro-nano porous-particle composite radiation refrigeration film coating is up to 96.2%, the emissivity of an infrared atmospheric window wave band, namely 8-13 mu m, is up to 98.3%, and the emissivity of a middle infrared wave band, namely 5-25 mu m, is up to 96.7%;
the average daytime temperature of the micro-nano porous-granular composite radiation refrigeration film coating is reduced by about 7-15 ℃, and the noon temperature is reduced by 10-27 ℃;
the water contact angle of the micro-nano porous-particle composite radiation refrigeration film coating is 90-150 degrees;
the breaking strain of the micro-nano porous-particle composite radiation refrigeration film coating is 15% -500%, and the breaking stress is 0.4-1.5MPa.
The invention has at least the following beneficial technical effects:
(1) In the invention, the film coating is internally distributed with abundant micro-nano pore structures, the porosity is up to more than 70%, a tiny scattering interface with different refractive indexes is constructed by the pore cavity and the nano particles, the reflectivity of solar radiation is improved by strengthening multiple scattering, and the micron-level air holes and the thermal emissivity can be increased. The dielectric particles are thermally excited through a local hybridization surface mode, namely, the surface phonon polaritons improve the emissivity of the middle infrared band; (2) In the invention, the film coating has obvious cooling effect, and realizes higher temperature difference in the same type of radiation refrigeration film; (3) In the invention, the material selection cost of the film is low, the preparation process is simple, the production does not need to depend on complex equipment technology, and the film can be produced in a large scale; (4) In the invention, the film coating has excellent hydrophobic property and mechanical ductility; (5) In the present invention, the multiphase mixture system can be formed into a film or can be used directly as a coating.
According to the preparation method of the micro-nano porous-particle composite radiation refrigeration film coating, provided by the invention, the comprehensive radiation refrigeration performance is improved by improving the reflectivity of ultraviolet visible wave bands and enhancing the absorptivity of infrared wave bands including an atmospheric window. In the aspect of material selection, firstly, a high molecular polymer or silane with high absorptivity in an atmospheric window wave band is selected as a matrix material of the radiation refrigeration film, so that the whole film has better radiation performance; secondly, dielectric particles with smaller extinction coefficient of ultraviolet-visible wave band, larger band gap width and large refractive index difference with the matrix material and air are selected, so that high reflectivity is formed on the premise of not absorbing ultraviolet and visible light energy with high energy density, and the heat absorbed by the surface of the film coating is further controlled. In addition, the nano-sized dielectric particles can generate surface phonon polaritons under the excitation of an infrared band, and the effect can assist in enhancing the absorptivity of the infrared band; in the aspect of the preparation process, a porous structure is formed by dispersing a particle phase in a matrix material and using a phase separation mode, a plurality of solid-solid and solid-gas phase interfaces are introduced into the film coating, and the refractive index difference of the phase interfaces can cause light multiple scattering, so that the macroscopic reflectivity is enhanced.
Drawings
Fig. 1 is a photograph of (a) the appearance of the micro-nano porous-particulate composite radiation refrigeration film coating in example 1 and (b) the scanning electron microscope photograph of the micro-nano porous-particulate composite radiation refrigeration film coating in example 4.
FIG. 2 shows the reflectance spectrum and the emission spectrum of the micro-nano porous-particle composite radiation refrigeration film coating of examples 1-5 at a wavelength of 0.3-25 μm.
FIG. 3 shows the TiO of examples 1-5 2 -a TPU film coating with (a) a daytime temperature tracking curve and (b) a temperature difference curve from ambient air for each of them under insulated convection heat transfer.
Fig. 4 is an infrared image and temperature difference within 1 hour under direct solar noon under the condition that the micro-nano porous-particle composite radiation refrigeration film coating in example 4 does not isolate convection heat transfer.
Fig. 5 shows (a) a nano-scale pore size distribution and (b) a micro-scale pore size distribution of the micro-nano porous-particulate composite radiation refrigeration film coating of examples 1 to 5.
Fig. 6 is a water contact angle of micro-nano porous-particulate composite radiation refrigeration film coating in examples 1-5.
FIG. 7 is a compressive stress-strain curve of the micro-nano porous-particulate composite radiant refrigerant film coating of examples 1-5.
Detailed Description
For a clear and complete description of the technical solutions and advantages of the present invention, the present invention is further described below with reference to the specific embodiments and the accompanying drawings, which are a part of the illustration of the present invention, but the present invention is not limited to the following embodiments. The methods are conventional methods unless otherwise specified. The raw materials and the processing equipment are commercially available from public sources unless otherwise specified. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1: first, 2.2656g of thermoplastic polyurethane powder is added into 12mL of N, N-dimethylformamide, and the mixture is magnetically stirred for 20min at normal temperature to form a 20wt% solution; 0.46667g of TiO was added dropwise to the above solution 2 Stirring the nano particles (with the particle size of 200 nm) for 30min by a magnetic stirrer at normal temperature, performing ultrasonic dispersion for 30min to form a uniformly dispersed particle suspension mixed system, transferring the suspension into a polytetrafluoroethylene square mold with an opening at the top surface, standing for 5min at room temperature, performing surface solvent replacement with water vapor in air in advance to form an initial coating, then slowly immersing the mold and the initial coating in a deionized water tank for 30min, completely performing solvent replacement on the initial coating and water, and finishing water phase invasion to form a multiphase mixed coating. Taking out, drying in a drying oven at 40 ℃ for 10 hours, and evaporating the water phase in the drying oven to form a porous structure. Finally, stripping from the die to obtain 10% TiO 2 -TPU micro-nano porous-granular composite radiation refrigeration film coating.
The prepared film coating had a bright white appearance under daytime illumination as shown in fig. 1 (a).
Example 2: experimental apparatus and procedure As in example 1, 0.46667g of TiO 2 Nanoparticle exchange for 1.05g TiO 2 A nanoparticle; the magnetic stirring in the dissolution step is changed into mechanical stirring, and the stirring time is 10min. The rest conditions are unchanged, thus obtaining 20 percent of TiO 2 -TPU micro-nano porous-granular composite radiation refrigeration film coating.
Example 3: experimental apparatus and procedure As in example 1, 0.46667g of TiO 2 Nanoparticle exchange for 1.8g TiO 2 A nanoparticle; immersing in deionized water, spraying water mist twice, and standing for 20min after each spraying. The rest conditions are unchanged, thus obtaining 30 percent of TiO 2 TPU micro-nano porous-granular compositeA radiation refrigeration film coating.
Example 4: experimental apparatus and procedure As in example 1, 0.46667g of TiO 2 Nanoparticle exchange for 2.8g TiO 2 A nanoparticle; the suspension was transferred to a top-side open polytetrafluoroethylene square mold and doctor-coated onto the polytetrafluoroethylene surface. The rest conditions are unchanged, thus obtaining 40 percent of TiO 2 -TPU micro-nano porous-granular composite radiation refrigeration film coating.
The cross-sectional scanning electron microscope picture of the prepared film coating is shown in fig. 1 (b), which shows that the interior contains micro-and nano-scale porous and nano-particle structures, so that the reflectivity can be enhanced.
Example 5: experimental apparatus and procedure As in example 1, 0.46667g of TiO 2 The nanoparticles (particle size 200 nm) were exchanged for 2.8g TiO 2 Nanoparticles (particle size 100 nm); the suspension was transferred to a top-side open polytetrafluoroethylene square mold and spin-coated onto the glass surface. The rest conditions are unchanged, thus obtaining 50 percent of TiO 2 -TPU micro-nano porous-granular composite radiation refrigeration film coating.
Example 6: experimental apparatus and procedure As in example 1, 0.46667g of TiO 2 The nanoparticles (particle size 200 nm) were exchanged for 4.6285g Al 2 O 3 Nanoparticles (particle size 500 nm), 2.2656g of thermoplastic polyurethane was replaced with 1.1865g of polyvinylidene fluoride-hexafluoropropylene, 12mL of n, n-dimethylformamide was replaced with 12mL of acetone; the suspension was transferred to a polytetrafluoroethylene square mold with an open top surface, spin-coated on a glass surface, and dried in a drying oven at 40℃for 10 hours, instead of a drying oven at 80℃for 5 hours. The rest conditions are unchanged, and 30 percent of Al can be obtained 2 O 3 -P (VDF-HFP) micro-nano porous-particulate composite radiant refrigerant film coating.
Example 7: experimental apparatus and procedure As in example 1, 0.46667g of TiO 2 The nanoparticles (particle size 200 nm) were exchanged for 1.5g CaCO 3 Nanoparticles (particle size 300 nm), transfer suspension to top-side open polytetrafluoroethylene square mold by changing the thermoplastic polyurethane N, N-dimethylformamide solution to 11mL Polydimethylsiloxane (PDMS) and 1.1mL Dow Corning DC184 curative mixtureThe glass is coated on the glass surface by a 500 μm scraper, immersed in deionized water is sprayed with water mist for three times, kept stand for 30min after each spraying, and dried in a drying oven at 40 ℃ for 20h after drying in a drying oven at 80 ℃. The rest conditions are unchanged, thus obtaining 20 percent CaCO 3 -PDMS micro-nano porous-particulate composite radiation refrigerating film coating.
Example 8: experimental facility and procedure As in example 6, 4.6285g of Al 2 O 3 The nanoparticle (particle size 500 nm) was exchanged for 1.3895g BaSO 4 The nano particles (with the particle size of 1000 nm) are immersed in the deionized water tank for 30min instead of 2h, and are dried in a drying oven at 40 ℃ for 12h instead of a drying oven at 25 ℃. The rest conditions are unchanged, and 5 percent of BaSO can be obtained 4 -PDMS micro-nano porous-particulate composite radiation refrigerating film coating.
FIG. 2 shows the TiO of examples 1-5 2 -the reflectivity and emissivity spectrum of the TPU film coating and TPU film at wavelengths of 0.3-25 μm, exhibiting a solar radiation band reflectivity of up to 96.2% and exhibiting broadband reflection characteristics; the emissivity of the infrared atmospheric window band (8-13 μm) is up to 98.3%, the emissivity of the mid-infrared band (5-25 μm) is up to 96.7%, and the broadband emission characteristic is presented, so that the self heat can be radiated into the universe background greatly. It can be seen that with the addition of nanoparticles, the solar radiation band reflectance increases significantly.
FIG. 3 compares the air temperature with the TPU and the TiO of examples 1 to 5 2 The daytime temperature tracking curve (11:30-16:00) of the TPU film coating under isolated convective heat transfer and the temperature difference curve between the TPU film coating and ambient air can be seen as TiO 2 The TPU itself is always at a temperature lower than the ambient air temperature, 50% TiO 2 The average temperature of the TPU is reduced by about 15.9℃and the temperature of the pure TPU film coating is reduced by only about 7.4℃but 30% TiO 2 The TPU is able to achieve an instantaneous maximum cooling of about 26.22 ℃.
FIG. 4 shows 40% TiO in example 4 2 Infrared image within 1 hour under direct solar noon conditions with actual measurement of the coating of TPU film (without isolation of convective heat transfer). It can be seen that the overall temperature of the film is lowThe temperature of the hot spot of the clothes is about 10 ℃, the temperature difference is not reduced with time, and the stability of the practical application is shown.
FIG. 5 (a) shows the TiO of examples 1-5 2 The nano-scale pore size distribution of the TPU film coating reveals the micro-scale pore size distribution of the film coating.
As shown in FIG. 6, tiO in examples 1-5 2 The TPU film coating has excellent hydrophobic properties, and the water contact angles of the TPU film coating are all larger than 120 degrees.
FIG. 7 shows the TiO of examples 1 to 5 2 The TPU film coating has mechanical superelasticity and ductility.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (10)
1. The preparation method of the micro-nano porous-particle composite radiation refrigeration film coating is characterized by comprising the following steps of:
(1) Adding a high molecular polymer or silane and an additive into a first solvent, and uniformly mixing to obtain an organic solution or emulsion;
(2) Adding micro-nano-sized dielectric particles into the organic solution or emulsion obtained in the step (1), and obtaining a uniformly dispersed suspension through stirring and ultrasonic action;
(3) Pouring the suspension obtained in the step (2) into a mould with a required size or attaching the suspension to a substrate plane in a coating mode to obtain an initial coating;
(4) Carrying out solvent replacement on the initial coating obtained in the step (3) and a second solvent to obtain a multiphase mixed coating with water phase invasion replacement;
(5) And (3) placing the multiphase mixed coating obtained in the step (4) and a die or a substrate plane in a heating and drying device, drying at a set temperature to obtain a cured micro-nano porous-particle coating, and directly stripping the cured micro-nano porous-particle coating from the die or the substrate plane to obtain the micro-nano porous-particle composite radiation refrigeration film.
2. The method for preparing the micro-nano porous-particle composite radiation refrigeration film coating according to claim 1, wherein in the step (1), the high molecular polymer is any one or more of ethylene polymer, fluoroethylene homopolymer, polyurethane, epoxy resin polymer, styrene polymer, polyethylene terephthalate, polyvinylidene fluoride-hexafluoropropylene, (methyl) acrylate polymer or organosiloxane polymer;
the silane is any one or more of dimethyl siloxane, methyltriethoxysilane, vinyl triethoxysilane, dimethyl diethoxysilane or tetraethoxysilane;
the additive is any one or more of curing agent, adhesive or initiator for maintaining or adjusting the state of the organic solution or emulsion, and the volume ratio of any additive to the high molecular polymer or silane is 1:8 to 1:10;
the first solvent is any one or more of toluene, xylene, octane, cyclohexane, cyclohexanone, chlorobenzene, dichloromethane, methanol, ethanol, isopropanol, epoxypropane, N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, methyl acetate, ethyl acetate, propyl acetate, acetone, methyl butanone, methyl isobutyl ketone, N-methylpyrrolidone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, trichloroethylene, tetrahydrofuran, acetonitrile or triethanolamine;
the proportion of the high molecular polymer or the silane to the organic solution or the emulsion is 10-60wt%.
3. The method for preparing the micro-nano porous-particle composite radiation refrigeration film coating according to claim 1, wherein in the step (2), the dielectric particles are one or more of silicon dioxide, aerosol silicon dioxide, titanium dioxide, aluminum oxide, zirconium oxide, barium sulfate, calcium carbonate, calcium sulfate, calcium oxide, magnesium carbonate, magnesium oxide, zinc oxide, yttrium oxide, silver chloride, lead sulfate or boron nitride; titanium dioxide includes P25, anatase and rutile;
preferably, the dielectric particles account for 5-75% of the volume of the suspension and have a particle size of 10nm-1000 μm.
4. The method for preparing the micro-nano porous-particle composite radiation refrigeration film coating according to claim 1, wherein in the step (3), the coating mode comprises the following steps: any one or more of spin coating, knife coating, spray coating or roll coating;
the substrate plane comprises: any one or more of glass, polytetrafluoroethylene, stainless steel, wood or cloth fabrics.
5. The method for preparing the micro-nano porous-particle composite radiation refrigeration film coating according to claim 1, wherein in the step (4), the second solvent is any one or more of water, methanol, ethanol, diethyl ether and propanol;
the method for solvent replacement of the coating with the second solvent comprises the following steps: placing the initial coating in a high-humidity environment with the relative humidity of a second solvent being more than 50%, immersing the initial coating in the second solvent, or spraying an atomized second solvent on the initial coating; wherein the second solvent is soluble with the first solvent and the second solvent is insoluble with the high molecular polymer or silane in step (1);
the duration of the solvent replacement process is 0.5-2h.
6. The method for preparing the micro-nano porous-particle composite radiation refrigeration film coating according to claim 1, wherein the heating and drying device in the step (5) comprises a tube furnace, a drying oven, an oven or a heating table;
the temperature is set at 20-80 ℃ and the drying time is 5-20h in the heating process.
7. The micro-nano porous-granular composite radiation refrigeration film coating is characterized in that the micro-nano porous-granular composite radiation refrigeration film coating is prepared by adopting the preparation method described in claims 1 to 6, and the thickness of the micro-nano porous-granular composite radiation refrigeration film coating is 100-10000 mu m.
8. The micro-nano porous-particulate composite radiation refrigeration film coating according to claim 7, wherein the micro-nano porous-particulate composite radiation refrigeration film coating has a pore size distribution of: the nanometer level pores are distributed at 400+/-230 nm, and the micrometer level pores are distributed at 7.25+/-12.86 mu m.
9. The micro-nano porous-particle composite radiation refrigeration film coating according to claim 7, wherein the porosity of the micro-nano porous-particle composite radiation refrigeration film coating is 20-70%.
10. The micro-nano porous-granular composite radiation refrigeration film coating according to claim 7, wherein the solar radiation wave band reflectivity of the micro-nano porous-granular composite radiation refrigeration film coating is up to 96.2%, the infrared atmospheric window wave band emissivity of 8-13 μm is up to 98.3%, and the mid-infrared wave band emissivity of 5-25 μm is up to 96.7%;
the average daytime temperature of the micro-nano porous-granular composite radiation refrigeration film coating is reduced by about 7-15 ℃, and the noon temperature is reduced by 10-27 ℃;
the water contact angle of the micro-nano porous-particle composite radiation refrigeration film coating is 90-150 degrees;
the breaking strain of the micro-nano porous-particle composite radiation refrigeration film coating is 15% -500%, and the breaking stress is 0.4-1.5MPa.
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