CN112250973A - Porous radiation refrigeration film and preparation method thereof - Google Patents
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- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B23/00—Machines, plants or systems, with a single mode of operation not covered by groups F25B1/00 - F25B21/00, e.g. using selective radiation effect
- F25B23/003—Machines, plants or systems, with a single mode of operation not covered by groups F25B1/00 - F25B21/00, e.g. using selective radiation effect using selective radiation effect
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- C08J2327/00—Characterised by the use of 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; Derivatives of such polymers
- C08J2327/02—Characterised by the use of 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; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/12—Characterised by the use of 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; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
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- C08J2333/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
- C08J2333/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters
- C08J2333/06—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers esters of esters containing only carbon, hydrogen, and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C08J2333/10—Homopolymers or copolymers of methacrylic acid esters
- C08J2333/12—Homopolymers or copolymers of methyl methacrylate
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Abstract
The invention provides a porous radiation refrigeration film and a preparation method thereof, wherein the method comprises the following steps: (1) mutually dissolving a material with the infrared electromagnetic wave radiation capability corresponding to a radiation atmosphere window and a first solvent to form a uniform mixed solution; (2) forming the mixed solution on a substrate; (3) and forming a second solvent which does not dissolve the material on the substrate with the mixed solution, and obtaining the porous radiation cooling film, wherein the second solvent is mutually soluble with the first solvent. The porous passive radiation cooling film is prepared by a phase separation method, the preparation process is simple, the film forming speed is high, the micron pore diameter of the radiation cooling film can be accurately controlled, the radiation cooling intensity can be regulated and controlled, the reflectivity of the radiation cooling film to visible light can be effectively regulated and controlled, the film has the function of single-layer and all-day radiation cooling, and the functions of reducing indoor temperature, refrigerating, freezing, thermoelectric generation and the like can be achieved by the film prepared by the method, so that the purposes of energy conservation and emission reduction are achieved.
Description
Technical Field
The invention relates to the technical field of functional film materials, in particular to a preparation method of a radiation refrigeration film and the radiation refrigeration film prepared by the same.
Background
Today, the energy crisis is becoming more serious, people are very big to the demand of artificial refrigeration systems such as air conditioner, however most traditional refrigeration systems have power consumption greatly, release greenhouse gas, need switch on power supply scheduling problem at any time. Therefore, the research on the novel artificial refrigeration system has great significance.
The radiation cooling is a phenomenon that an object spontaneously radiates heat to the outer space through an atmospheric window, and the heat is exchanged with the outer space, so that the temperature is reduced. The film prepared by utilizing the radiation cooling principle has the advantages of no consumption of extra external energy, zero pollution, high efficiency and cleanness, and solves the problem of the traditional refrigeration system to a great extent.
The radiation refrigeration capacity is enhanced by enhancing the reflectivity of the film to sunlight (0.28-2.5 mu m) and simultaneously improving the infrared emissivity of the film at an atmospheric window waveband (8-13 mu m, 16-25 mu m).
In recent years, the proposed radiation refrigeration thin film is mainly divided into a multilayer metamaterial structure and a photonic system structure. The multilayer metamaterial structure is represented by Aaswave P.Raman and the like, and the proposed multilayer metamaterial structure takes Ag as a reflecting layer and seven SiO2The film structure composed of the HfO nano layer has an average emissivity of about 0.65 in an atmospheric window, the reflectivity can reach 0.97 in a visible light wave band, and the film structure can be cooled by 5 ℃ compared with the ambient temperature under direct solar radiation; the photonic system structure is represented by Yao ZHai and the like, and Ag is used as a reflecting layer, and polymethylpentene is used for wrapping SiO2The film structure of the microsphere has the infrared emissivity of 0.96, the visible light reflectivity of 0.96 and the refrigeration power of 96W/m under the direct sunlight2(ii) a However, theseThe structural thin film has the problems of complex structure, complex preparation process, high cost and the like, large-area production is difficult to realize, and the problems need to be solved urgently.
Disclosure of Invention
In view of this, embodiments of the present invention provide a porous radiation refrigeration film and a preparation method thereof, so as to solve the above technical problems in the prior art.
According to a first aspect, an embodiment of the present invention provides a method for preparing a porous radiation refrigeration film, where the method includes the following steps:
(1) mutually dissolving a material with the infrared electromagnetic wave radiation capability corresponding to a radiation atmosphere window and a first solvent to form a uniform mixed solution;
(2) forming the mixed solution on a substrate;
(3) and forming a second solvent which does not dissolve the material with the radiation atmosphere window corresponding to the infrared electromagnetic wave radiation capacity on the substrate with the mixed solution to obtain the porous radiation cooling film, wherein the second solvent is mutually soluble with the first solvent.
Further, step (4) is also included during or after step (3): carrying out curing or natural air drying treatment on the film;
preferably, the curing comprises putting the film into a heating device at 50-80 ℃ for drying treatment for 1-10 hours;
preferably, the heating means comprises an oven, a hot plate or a tube furnace;
preferably, the method of forming the mixed solution on a substrate includes: at least one of spin coating, spray coating, blade coating and roll coating;
preferably, the method of forming the second solvent that does not dissolve the material having the ability to radiate the infrared electromagnetic wave radiation corresponding to the atmospheric window on the substrate on which the mixed solution is formed includes: placing the substrate into the second solvent, or spraying the second solvent on the substrate;
preferably, the weight percentage of the first solvent in the mixed solution is 70-90%.
Further, the material having the capability of radiating the atmosphere window corresponding to the infrared electromagnetic wave radiation comprises at least one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, polystyrene, ethyl cellulose, cellulose acetate and the like; the first solvent comprises at least one of acetone, dimethyl ammonium formate, dimethyl acetamide, dimethyl sulfoxide, N-methyl pyrrolidone, N, N-dimethyl formamide, triethyl phosphate, toluene, xylene and the like; the second solvent comprises at least one of water, alcohol, methanol, acetone, diethyl ether, etc.
Further, the material having the capability of radiating the atmospheric window corresponding to the infrared electromagnetic wave radiation includes powder, particles or liquid.
Further, defoaming treatment is performed after the mixed solution is formed.
Further, the substrate comprises glass, metal, wood or plastic.
Further, the film obtained in the step (3) is in an attached state or an independent state.
Further, the porous radiation refrigeration film is characterized in that the thickness of the porous radiation refrigeration film is not less than 50 mu m, and the pore diameter is 0.02-8 mu m.
The invention also provides a porous radiation refrigeration film, which is prepared by any one of the methods.
The porous passive radiation cooling film is prepared by a phase separation method, the preparation process is simple, the film forming speed is high, the micron pore diameter of the radiation cooling film can be accurately controlled, the radiation cooling intensity can be regulated and controlled, the reflectivity of the radiation cooling film to visible light can be effectively regulated and controlled, the film has the function of single-layer and all-day radiation cooling, and the functions of reducing indoor temperature, refrigerating, freezing, thermoelectric generation and the like can be achieved by the film prepared by the method, so that the purposes of energy conservation and emission reduction are achieved.
Compared with the prior art, the technical scheme of the application has the advantages that the preparation process is simple, and similar effects can be achieved without complex processes.
Drawings
The features and advantages of the present invention will be more clearly understood by reference to the accompanying drawings, which are illustrative and not to be construed as limiting the invention in any way, and in which:
FIG. 1 is a diagram showing the effect of the porous radiation refrigeration film in the present invention in the refrigeration test.
FIG. 2 is an SEM image of a porous radiation refrigeration film prepared by using DMAC as a solvent in the invention.
FIG. 3 is an SEM image of a porous radiation refrigerating film prepared by taking DMSO as a solvent in the invention.
FIG. 4 is an SEM image of a porous radiation refrigeration film prepared by using NMP as a solvent in the invention.
FIG. 5 is an SEM image of a porous radiation refrigerating film prepared by using acetone as a solvent in the invention.
FIG. 6 is the UV-VIS reflectance spectrum of the porous radiation refrigeration film of the present invention.
FIG. 7 is a near infrared reflectance spectrum of the porous radiation refrigeration film of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of a porous radiation refrigeration film, which comprises the following steps:
(1) mutually dissolving a material with the infrared electromagnetic wave radiation capability corresponding to a radiation atmosphere window and a first solvent to form a uniform mixed solution;
(2) forming the mixed solution on a substrate;
(3) and forming a second solvent which does not dissolve the material with the radiation atmosphere window corresponding to the infrared electromagnetic wave radiation capacity on the substrate with the mixed solution to obtain the porous radiation cooling film, wherein the second solvent is mutually soluble with the first solvent.
In a specific embodiment, step (4) is further included during or after step (3): carrying out curing or natural air drying treatment on the film; the curing comprises the step of putting the film into a heating device at the temperature of 50-80 ℃ for drying treatment for 1-10 hours; the heating device comprises an oven, a hot plate or a tube furnace.
The method for forming the mixed solution on the substrate in the step (2) includes: at least one of spin coating, spray coating and blade coating;
the method for forming the second solvent which does not dissolve the material having the capability of radiating infrared electromagnetic wave radiation corresponding to the atmospheric window on the substrate formed with the mixed solution in the step (3) comprises the following steps: placing the substrate into the second solvent, or spraying the second solvent on the substrate; the weight percentage of the first solvent in the mixed solution is 70-90%.
The material with the capacity of radiating the atmosphere window corresponding to the infrared electromagnetic wave radiation comprises at least one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, polystyrene, ethyl cellulose, cellulose acetate and the like; the first solvent comprises at least one of acetone, dimethyl ammonium formate, dimethyl acetamide, dimethyl sulfoxide, N-methyl pyrrolidone, N, N-dimethyl formamide, triethyl phosphate, toluene, xylene and the like; the second solvent comprises at least one of water, alcohol, methanol, acetone, diethyl ether, etc.
In a specific embodiment, the material having the ability to radiate atmospheric radiation corresponding to infrared electromagnetic radiation comprises a powder, a granule, or a liquid.
In order to obtain a more flat film, the mixed solution is formed and then subjected to defoaming treatment.
The substrate comprises glass, metal, wood or plastic.
The film finally obtained in the step (3) is in an attached state or an independent state.
The thickness of the porous radiation refrigeration film prepared by the preparation method is not less than 50 mu m, and the pore diameter is 0.02-8 mu m.
In a specific embodiment, the porous radiation refrigerating film can be prepared by only the steps (1) to (3) without other steps.
Fig. 1 is a diagram showing the refrigeration test effect of the porous radiation refrigeration film of the present invention, and it can be seen from fig. 1 that, when the ambient temperature is 55 ℃, the temperature of the radiation refrigeration film is about 36-37 ℃, and the cooling effect is very obvious. According to the reflection spectrums of the porous radiation refrigeration film shown in fig. 6 and 7, the reflectivity of the porous radiation refrigeration film can reach more than 90% in the wavelength ranges of 0.4-0.9 μm and 0.9-1.6 μm, and can be maintained at more than 70% even in the wavelength range of 1.7-2.2 μm with longer wavelength.
Example 1:
the preparation of the porous radiation refrigeration film needs the following raw materials: the polymer is polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) (weight percentage is calculated) 15 wt%, the solvent is N, N-Dimethylformamide (DMF)85 wt%, and the non-solvent is water.
The preparation process of the porous radiation refrigeration film is as follows: fully mixing PVDF-HFP and DMF according to the mass percentage, and standing for defoaming treatment; after defoaming treatment, the mixed solution is spin-coated on a smooth glass substrate, and then the glass substrate coated with the mixed solution is quickly placed in normal-temperature water. And taking out the mixed solution after the mixed solution is formed into a film and falls off. And finally, putting the taken-out film into an oven at 60 ℃ for drying treatment for two hours to obtain the porous radiation refrigeration film.
Example 2:
the preparation of the porous radiation refrigeration film needs the following raw materials: the polymer was polyvinylidene fluoride (weight percent) 19 wt%, the solvent was Dimethylacetamide (DMAC)81 wt%, and the non-solvent was alcohol.
The preparation process of the porous radiation refrigeration film is as follows: fully mixing polyvinylidene fluoride and DMAC according to the mass percentage, and standing for defoaming; after defoaming treatment, the mixed solution is coated on a smooth glass substrate, and then the glass substrate coated with the mixed solution is quickly placed in normal-temperature alcohol. And taking out the mixed solution after the mixed solution is formed into a film and falls off. And finally, putting the taken-out film into an oven at 50 ℃ for drying for one hour to obtain the porous radiation refrigeration film. FIG. 2 is an SEM image of a porous radiation refrigeration film prepared by using DMAC as a solvent in the invention.
Example 3:
the preparation of the porous radiation refrigeration film needs the following raw materials: the polymer is polymethyl methacrylate 17 wt%, the solvent is dimethyl sulfoxide (DMSO)83 wt%, and the non-solvent is methanol.
The preparation process of the porous radiation refrigeration film is as follows: fully mixing polymethyl methacrylate and DMSO according to the mass percentage, and standing for defoaming; after defoaming treatment, the mixed solution is coated on a smooth glass substrate, and then the glass substrate coated with the mixed solution is quickly placed in normal-temperature methanol. And taking out the mixed solution after the mixed solution is formed into a film and falls off. And finally, putting the taken-out film into an oven at 80 ℃ for drying treatment for two hours to obtain the porous radiation refrigeration film. FIG. 3 is an SEM image of a porous radiation refrigerating film prepared by taking DMSO as a solvent in the invention.
Example 4:
the preparation of the porous radiation refrigeration film needs the following raw materials: the polymer is polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) (weight percentage) 13 wt%, the solvent is N-methyl pyrrolidone (NMP)87 wt%, and the non-solvent is acetone.
The preparation process of the porous radiation refrigeration film is as follows: fully mixing PVDF-HFP and NMP according to the mass percentage, and standing for defoaming; after defoaming treatment, the mixed solution is coated on a smooth glass substrate, and then the glass substrate coated with the mixed solution is quickly placed in normal-temperature acetone. And taking out the mixed solution after the mixed solution is formed into a film and falls off. And finally, putting the taken-out film into an oven at 70 ℃ for drying for ten hours to obtain the porous radiation refrigeration film. FIG. 4 is an SEM image of a porous radiation refrigeration film prepared by using NMP as a solvent in the invention.
Example 5:
the preparation of the porous radiation refrigeration film needs the following raw materials: the polymer is polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) (weight percentage) 14 wt%, the solvent is acetone 86 wt%, and the non-solvent is diethyl ether.
The preparation process of the porous radiation refrigeration film is as follows: fully mixing PVDF-HFP and acetone according to the mass percentage, and standing for defoaming; after defoaming treatment, the mixed solution is coated on a smooth glass substrate, and then the glass substrate coated with the mixed solution is quickly placed in normal-temperature ether. And taking out the mixed solution after the mixed solution is formed into a film and falls off. And finally, putting the taken-out film into an oven at 60 ℃ for drying treatment for two hours to obtain the porous radiation refrigeration film. FIG. 5 is an SEM image of a porous radiation refrigerating film prepared by using acetone as a solvent in the invention.
Example 6:
the preparation of the porous radiation refrigeration film needs the following raw materials: the polymer is polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) (weight percentage) 10 wt%, the solvent is N, N-Dimethylformamide (DMF)90 wt%, and the non-solvent is water.
The preparation process of the porous radiation refrigeration film is as follows: fully mixing PVDF-HFP and DMF according to the mass percentage, and standing for defoaming treatment; after defoaming treatment, the mixed solution is sprayed on a smooth metal substrate, and then the glass substrate coated with the mixed solution is quickly placed in normal-temperature water. And taking out the mixed solution after the mixed solution is formed into a film and falls off. And finally, putting the taken-out film into a 60 ℃ hot bench for drying treatment for two hours to obtain the porous radiation refrigeration film.
Example 7:
the preparation of the porous radiation refrigeration film needs the following raw materials: the polymer is polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) (weight percentage) wt 30%, the solvent is N, N-Dimethylformamide (DMF) wt 70%, and the non-solvent is water.
The preparation process of the porous radiation refrigeration film is as follows: fully mixing PVDF-HFP and DMF according to the mass percentage, and standing for defoaming treatment; after defoaming treatment, the mixed solution is coated on a smooth plastic substrate by blade coating, and then the glass substrate coated with the mixed solution is quickly put into normal-temperature water. And taking out the mixed solution after the mixed solution is formed into a film and falls off. And finally, putting the taken-out film into a 60 ℃ tubular furnace for drying treatment for two hours to obtain the porous radiation refrigeration film.
The foregoing embodiments are merely illustrative of the principles of this invention and its efficacy, rather than limiting it, and various modifications and variations can be made by those skilled in the art without departing from the spirit and scope of the invention, which is defined in the appended claims.
Claims (10)
1. The preparation method of the porous radiation refrigeration film is characterized by comprising the following steps:
(1) mutually dissolving a material with the infrared electromagnetic wave radiation capability corresponding to a radiation atmosphere window and a first solvent to form a uniform mixed solution;
(2) forming the mixed solution on a substrate;
(3) and forming a second solvent which does not dissolve the material with the radiation atmosphere window corresponding to the infrared electromagnetic wave radiation capacity on the substrate with the mixed solution to obtain the porous radiation cooling film, wherein the second solvent is mutually soluble with the first solvent.
2. The method for preparing a porous radiation refrigerating film according to claim 1, characterized in that step (4) is further included during or after step (3): carrying out curing or natural air drying treatment on the film;
preferably, the curing comprises putting the film into a heating device at 50-80 ℃ for drying treatment for 1-10 hours;
preferably, the heating means comprises an oven, a hot plate or a tube furnace.
3. The method for preparing a porous radiation refrigerating film according to claim 1, wherein the method for forming the mixed solution on a substrate comprises the following steps: at least one of spin coating, spray coating, blade coating and roll coating;
preferably, the method of forming the second solvent that does not dissolve the material having the ability to radiate the infrared electromagnetic wave radiation corresponding to the atmospheric window on the substrate on which the mixed solution is formed includes: putting the substrate into the second solvent, or spraying the second solvent on the substrate, wherein the second solvent is sprayed on one side of the substrate with the mixed solution;
preferably, the weight percentage of the first solvent in the mixed solution is 70-90%.
4. The method for preparing a porous radiation refrigeration film according to claim 1, wherein the material having the capacity of radiating the infrared electromagnetic wave radiation corresponding to the atmospheric window comprises at least one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polymethyl methacrylate, polystyrene, ethyl cellulose, cellulose acetate and the like; the first solvent comprises at least one of acetone, dimethyl ammonium formate, dimethyl acetamide, dimethyl sulfoxide, N-methyl pyrrolidone, N, N-dimethyl formamide, triethyl phosphate, toluene, xylene and the like; the second solvent comprises at least one of water, alcohol, methanol, acetone, diethyl ether, etc.
5. The method for preparing a porous radiation refrigeration film according to claim 4, wherein the material having the capacity of radiating the infrared electromagnetic wave radiation corresponding to the atmospheric window comprises powder, particles or liquid.
6. The method for preparing a porous radiation refrigerating film according to claim 1, wherein a defoaming treatment is performed after the mixed solution is formed.
7. The method of claim 1, wherein the substrate comprises glass, metal, wood or plastic.
8. The method for preparing a porous radiation refrigerating film according to claim 1, wherein the film obtained in the step (3) is in an attached state or an independent state.
9. The preparation method of the porous radiation refrigeration film according to claim 1, wherein the thickness of the porous radiation refrigeration film is not less than 50 μm, and the pore diameter is 0.02-8 μm.
10. A porous radiation refrigerating film prepared by the method of any one of claims 1 to 9.
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| CN115232418A (en) * | 2022-06-27 | 2022-10-25 | 上海交通大学 | Method for preparing porous radiation refrigeration coating by pickling particles |
| CN115264993A (en) * | 2022-07-19 | 2022-11-01 | 南京工业大学 | Novel radiation refrigeration material |
| CN115260740A (en) * | 2022-08-26 | 2022-11-01 | 电子科技大学长三角研究院(湖州) | High-mechanical-property radiation refrigeration film with composite aperture, preparation method and application thereof |
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