CN113954453B - Colored double-layer radiation refrigerating film and preparation method thereof - Google Patents
Colored double-layer radiation refrigerating film and preparation method thereof Download PDFInfo
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- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
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- B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
- B32B37/12—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by using adhesives
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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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- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/10—Inorganic particles
- B32B2264/105—Metal
- B32B2264/1051—Silver or gold
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- B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
- B32B2264/30—Particles characterised by physical dimension
- B32B2264/302—Average diameter in the range from 100 nm to 1000 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/40—Properties of the layers or laminate having particular optical properties
- B32B2307/416—Reflective
Abstract
The invention discloses a colored double-layer radiation refrigeration film and a preparation method thereof, wherein the colored double-layer radiation refrigeration film comprises a radiation refrigeration bottom layer and a colored layer which are laminated and attached, and the radiation refrigeration bottom layer comprises SiO 2 Microspheres, a thickener and a binder; the color layer comprises Au-Ag nano microspheres, a thickening agent and an adhesive, and the radiation refrigeration bottom layer and the color layer are laminated, attached and adhered through the adhesive. The color double-layer radiation refrigerating film only generates strong absorption on a specific visible light wave band (0.4-0.74 mu m), other wave bands have higher reflectivity, the middle infrared emissivity is higher, and an excellent daytime refrigerating effect can be achieved.
Description
Technical Field
The invention relates to the technical field of passive radiation refrigeration materials, in particular to a colored double-layer radiation refrigeration film and a preparation method thereof.
Background
Due to global warming, the demand for energy for cooling is sharply increasing. However, the compression type cooling system currently in widespread use consumes a large amount of electricity and generates a large amount of gas, which in turn causes various environmental problems, such as urban heat island effect and thermal pollution. Therefore, research and development of alternative cooling technologies with low energy consumption becomes urgent.
Different from the traditional refrigeration technology which transfers heat to the surrounding environment, the radiation refrigeration technology transfers redundant heat to the outer space in a thermal radiation mode, and no energy consumption or pollution is generated in the refrigeration process. At present, the radiation refrigeration technology is gaining the attention of researchers as a refrigeration technology with zero energy consumption and zero pollution. In the daytime, the heat radiation of the sun can reach 1000W/m 2 Therefore, to achieve efficient radiation cooling, the cooling coating needs to be high over the solar spectrum (0.3-2.5 μm)Reflectivity to avoid absorption of solar radiation, and high emissivity in the atmospheric window (8-13 μm) to enhance radiation heat dissipation from the coating surface to space. However, most radiant refrigeration films tend to appear white, which greatly limits the practical application of radiant refrigeration films for aesthetic and eye damage.
Colored radiant refrigeration films achieve the desired color by selectively absorbing sunlight in the visible spectrum (0.4-0.74 μm), which will increase the absorption of solar energy. But better daytime radiation cooling can also be achieved by maintaining high solar reflectance in the near infrared region (0.74-2.5 μm) and high ir emissivity in the atmospheric window (8-13 μm). Plasmonic nanostructures show great potential in colored PDRC coatings because of their inherently narrow and strong absorption capability at the resonance wavelength, and the desired structural color can be generated by structural design, such as silicon nanostructures (e.blandre, r.a).
J.Dr villon, "microscopic surfaces for colored and non-colored sky radial coating," opt.express, vol.28, No.20, p.29703,2020, doi:10.1364/oe.401368.), plasma Ag-SiO 2 Core-shell nanoparticles (R.A.
Blandre, K.Joulin, and J.Drevillon, "Colored radial coating Coatings with nanoparticules," ACS Photonics, vol.7, No.5, pp.1312-1322,2020, doi: 10.1021/acetylionics.0c00513.). However, the preparation of these nanostructured or core-shell spheres is expensive or complicated, so most of these works are performed by numerical simulation.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a color double-layer radiation refrigerating film and a preparation method thereof, the color double-layer radiation refrigerating film only generates strong absorption on a specific visible light waveband (0.4-0.74 μm), other wavebands have higher reflectivity, the middle infrared emissivity is higher, and an excellent daytime refrigerating effect can be achieved.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the colored double-layer radiation refrigeration film comprises a radiation refrigeration bottom layer and a colored layer which are laminated, wherein the radiation refrigeration bottom layer comprises SiO 2 Microspheres, a thickener and a binder; the color layer comprises Au-Ag nano microspheres, a thickening agent and an adhesive.
The Au — Ag nanoparticles in the present invention are defined as one of Au nanoparticles (i.e., Au/Ag — 10/0), Ag nanoparticles (i.e., Au/Ag — 0/10), and Au — Ag alloy nanoparticles.
Preferably, the thickness of the radiation refrigeration bottom layer is 300-500 mu m.
Preferably, the SiO 2 The particle size (radius r) of the microspheres is 0.4-0.5 μm. In the invention, the regulation and control of the particle size is the key to realize high reflectivity of the coating, and as shown in figure 1, the solar reflectivity of the coating is reduced when the particle size is too large or too small.
Preferably, the color layer has a thickness of 8 to 13 μm.
Preferably, the thickener is sodium cellulose, sodium carboxymethyl starch, hydroxypropyl starch, ethyl starch, dextrin or cyclodextrin; the adhesive is styrene butadiene rubber, shellac or epoxy resin.
The invention also provides a preparation method of the colored double-layer radiation refrigeration film, which is characterized in that the radiation refrigeration bottom layer and the colored layer are laminated, attached and adhered through a bonding agent.
Preferably, the specific preparation process of the radiation refrigeration bottom layer comprises the following steps: firstly, the SiO is prepared by a Stober method 2 Microspheres; then SiO 2 Uniformly mixing the microspheres, the thickening agent solution and the binder solution to form white slurry; and finally, coating and drying to obtain the radiation refrigeration bottom layer.
Preferably, the specific preparation process of the color layer is as follows: firstly HAuCl 4 Solution and/or AgNO 3 Mixing with sodium citrate solution to react so as to obtain HAuCl 4 And/or AgNO 3 Completely reducing to obtain Au and/or Ag nano-particle color solution; then, the product is processedUniformly mixing the Au-Ag nano-particle color solution, the thickening agent solution and the binder solution to form color slurry; finally, coating and drying to obtain the color layer.
As shown in fig. 4, the inventors found that Au — Ag nanoparticles have narrow and strong absorption power in the solar spectrum, and as a color layer, by adjusting the ratio of the two, absorption of sunlight can be avoided as much as possible while realizing different colors.
The inventors have further found that, as shown in FIG. 2, due to SiO 2 The interaction between the microspheres and the Au-Ag nanoparticles if the color slurry containing Au-Ag nanoparticles and the SiO-containing SiO nanoparticles are directly mixed 2 White slurry of the microspheres is mixed together, and the solar reflectivity of the prepared color coating can only reach 0.75; if the color slurry containing Au-Ag nano particles is coated on the radiation refrigeration bottom layer formed by drying, the color slurry is filled with SiO 2 The porosity between the microspheres can only reach 0.61 of the reflectivity of the coating. The reflectivity of the colored coating formed by directly adhering the radiation refrigeration bottom layer and the colored layer which are respectively dried and formed can still reach 0.88.
The invention has the advantages that:
the invention optimizes SiO with the grain diameter of 0.4-0.5 mu m 2 White daytime radiation refrigeration film is manufactured by stacking microspheres and drying the formed white SiO 2 The top of the microsphere film is introduced into the dry formed plasmon Au-Ag nanoparticle film in a direct adhesion mode to further realize the color refrigeration film. The colored double-layer radiation refrigeration film has the advantages that the colored layer has selective narrow absorption spectrum in the range of visible light (0.4-0.74 mu m), and the radiation refrigeration bottom layer can reflect sunlight transmitted by the colored layer to the maximum extent. Therefore, the color double-layer radiation refrigeration film is 881W/m 2 The maximum cooling temperatures of lavender and yellow coats can reach 7.5 c and 5.1 c, respectively, as shown in fig. 5. By adjusting different proportions of Au and Ag, the radiation refrigeration films with different colors can be further obtained.
Drawings
FIG. 1 shows comparative example 1 made of SiO with different particle sizes 2 Microspheroidal particlesMaking a spectrogram of the radiation refrigeration bottom layer;
FIG. 2 is a graph comparing the white film (white coating) made in comparative example 1, the color film (two-layer coating) made in example 1, the hybrid coating made in comparative example 2, and the composite coating made in comparative example 3;
FIG. 3 is an electron micrograph and a photograph of a white film obtained in comparative example 1 and a colored film obtained in example 1;
FIG. 4 is a spectrum chart of a white color film obtained in comparative example 1 and color films obtained in examples 1 to 4;
FIG. 5 is a graph showing the outdoor heat dissipation performance results of the colored films obtained in examples 1-2.
Detailed Description
Comparative example 1
(1) Adding 2g of sodium cellulose into 75g of deionized water, and stirring for 2 hours on a heating table at 80 ℃ to completely dissolve the sodium cellulose into the deionized water to obtain a thickening agent solution;
(2) SiO with different particle size (radius r is 0.2 μm, 0.3 μm, 0.4 μm, 0.9 μm) is prepared by Stober method 2 Microsphere: firstly, 100mL of ethanol, 30mL of deionized water and 10mL of ammonia water are sequentially added into a flask and stirred at the speed of 500rmp, then 50mL of tetraethyl silicate is uniformly added into the flask and reacted for 6 hours at the temperature of 30 ℃, and then SiO is obtained by centrifugation 2 Microspheres;
(3) mixing 6g of SiO 2 The microspheres are uniformly mixed with 14g of thickener solution and 2g of butadiene styrene rubber solution to form white slurry, a film is coated according to the thickness (t) of 300 mu m, and a radiation refrigeration bottom layer (a white film or a white coating) is obtained after drying.
Example 1
Radiation refrigeration underlayer made by the method of comparative example 1, in which SiO 2 The particle size of the microspheres is 0.4 mu m;
(1) adding 5ml of HAuCl 4 An aqueous solution (10mM) and 100mL of an aqueous sodium citrate solution (5mM) were added to the flask, mixed well and reacted at 100 ℃ for 30 minutes to completely reduce HAuCl 4 Obtaining a color solution;
(2) dissolving 2g of sodium cellulose in 75g of colored aqueous solution to obtain a colored thickener, adding 1g of butadiene styrene rubber solution, uniformly stirring to obtain colored slurry, and finally coating and drying according to the thickness of 10 mu m to obtain a colored layer;
(3) and (3) sticking the colored layer and the radiation refrigeration bottom layer together by using styrene butadiene rubber to obtain the lavender radiation refrigeration film (colored film).
Example 2
Radiation refrigeration underlayer prepared by the method of comparative example 1, in which SiO 2 The particle size of the microspheres is 0.4 mu m;
(1) 2.5ml of AgNO 3 The aqueous solution (10mM) and 100mL of aqueous sodium citrate solution (5mM) were added to the flask, mixed well and reacted at 100 ℃ for 2 hours to completely reduce AgNO 3 Obtaining a color solution;
(2) dissolving 2g of sodium cellulose in 75g of colored aqueous solution to obtain a colored thickener, adding 1g of butadiene styrene rubber solution, uniformly stirring to obtain colored slurry, and finally coating and drying according to the thickness of 10 mu m to obtain a colored layer;
(3) and (3) sticking the color layer and the radiation refrigeration bottom layer together by using styrene butadiene rubber to obtain a yellow radiation refrigeration film (color film).
Example 3
Radiation refrigeration underlayer prepared by the method of comparative example 1, in which SiO 2 The particle size of the microspheres is 0.4 mu m;
(1) 1.75ml of HAuCl 4 Aqueous solution (10mM), 0.75ml AgNO 3 An aqueous solution (10mM) and 100mL of an aqueous sodium citrate solution (5mM) were added to the flask, mixed well and reacted at 100 ℃ for 2 hours to completely reduce HAuCl 4 And AgNO 3 Obtaining a color solution;
(2) dissolving 2g of sodium cellulose in 75g of colored aqueous solution to obtain a colored thickener, adding 1g of butadiene styrene rubber solution, uniformly stirring to obtain colored slurry, and finally coating and drying according to the thickness of 10 mu m to obtain a colored layer;
(3) and (3) adhering the color layer and the radiation refrigeration bottom layer together by using styrene butadiene rubber to obtain the color double-layer radiation refrigeration film (color film).
Example 4
Radiation refrigeration underlayer prepared by the method of comparative example 1, in which SiO 2 The particle size of the microspheres is 0.4 mu m;
(1) 2.25ml of HAuCl 4 Aqueous solution (10mM), 0.25ml AgNO 3 An aqueous solution (10mM) and 100mL of an aqueous sodium citrate solution (5mM) were added to the flask, mixed well and reacted at 100 ℃ for 2 hours to completely reduce HAuCl 4 And AgNO 3 Obtaining a color solution;
(2) dissolving 2g of sodium cellulose in 75g of colored aqueous solution to obtain a colored thickener, adding 1g of butadiene styrene rubber solution, uniformly stirring to obtain colored slurry, and finally coating and drying according to the thickness of 10 mu m to obtain a colored layer;
(3) and adhering the color layer and the radiation refrigeration bottom layer together by using styrene butadiene rubber to obtain the color double-layer radiation refrigeration film (color film).
Comparative example 2
A white slurry (in which SiO was obtained) was obtained by the method of comparative example 1 2 Microsphere size of 0.4 μm) and the color slurry obtained by the method of example 1, and then directly mixing the color slurry and the white slurry to form a mixed coating, as shown in fig. 2, the solar reflectance can only reach 0.75.
Comparative example 3
Radiation refrigeration bottom layer (in which SiO is obtained) by the method of comparative example 1 2 The particle size of the microspheres is 0.4 μm) and a color slurry is obtained by the method of example 1, and then the color slurry is coated on a radiation-cooled substrate formed by drying to form a composite coating, the color slurry is filled with SiO 2 The solar reflectance of the voids between the microspheres, as shown in FIG. 2, can only reach 0.61.
Claims (7)
1. A colored double-layer radiation refrigerating film is characterized in that: the colored double-layer radiation refrigerating film comprises a radiation refrigerating bottom layer and a colored layer which are laminated, wherein the radiation refrigerating bottom layer comprises SiO 2 Microspheres, a thickener and a binder; the color layer comprises Au-Ag nano microspheres, a thickening agent and an adhesive;
the Au-Ag nano-microspheres are one of Au nano-particles, Ag nano-particles and Au-Ag alloy nano-particles;
the colored double-layer radiation refrigeration film is obtained by laminating, adhering and adhering a radiation refrigeration bottom layer and a colored layer through an adhesive.
2. The colored bi-layer radiation refrigerating film according to claim 1, wherein: the thickness of the radiation refrigeration bottom layer is 300-500 mu m.
3. The colored bi-layer radiation refrigerating film according to claim 1, wherein: the SiO 2 The radius of the microspheres is 0.4-0.5 μm.
4. The colored bi-layer radiation refrigerating film according to claim 1, wherein: the thickness of the color layer is 8-13 mu m.
5. The colored bi-layer radiation refrigerating film according to claim 1, wherein: the thickening agent is sodium cellulose, sodium carboxymethyl starch, hydroxypropyl starch, ethyl starch, dextrin or cyclodextrin; the adhesive is styrene butadiene rubber, shellac or epoxy resin.
6. The colored bi-layer radiation refrigerating film according to claim 1, wherein: the specific preparation process of the radiation refrigeration bottom layer comprises the following steps: firstly, the SiO is prepared by adopting a Sto ̈ ber method 2 Microspheres; then SiO 2 Uniformly mixing the microspheres, the thickening agent solution and the binder solution to form white slurry; and finally, coating and drying to obtain the radiation refrigeration bottom layer.
7. The colored bi-layer radiation refrigerating film according to claim 1, wherein: the specific preparation process of the color layer comprises the following steps: firstly HAuCl 4 Solution and/or AgNO 3 Mixing with sodium citrate solution to react to obtain HAuCl 4 And/or AgNO 3 Completely reducing to obtain Au-Ag nano particle color solution; uniformly mixing the Au-Ag nano particle color solution, the thickening agent solution and the binder solution to form color slurry; finally, coating and drying to obtain the color layer.
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| CN205017440U (en) * | 2015-07-27 | 2016-02-03 | 珠海拾比佰彩图板股份有限公司 | TV set metal backplate of utensil heat dissipation cooling function |
| KR102225793B1 (en) * | 2020-04-20 | 2021-03-11 | 고려대학교 산학협력단 | Coloured radiative cooling device using nanomaterials |
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| CN103168259A (en) * | 2010-10-20 | 2013-06-19 | 3M创新有限公司 | Wide band semi-specular mirror film incorporating nanovoided polymeric layer |
| CN104693513A (en) * | 2014-09-05 | 2015-06-10 | 中国热带农业科学院农产品加工研究所 | Method for preparing gold and silver nano particle/ colored natural rubber nano composite material |
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| CN113234367A (en) * | 2021-04-08 | 2021-08-10 | 华南理工大学 | Colored radiation refrigerating film and preparation method thereof |
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