CN113234367A - Colored radiation refrigerating film and preparation method thereof - Google Patents
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Abstract
The invention discloses a colored radiation refrigerating film and a preparation method thereof. The color radiation refrigeration film comprises a radiation refrigeration film layer and a structural color forming layer which are laminated, wherein the radiation refrigeration film layer comprises polyacrylate/waterborne polyvinylidene fluoride resin, inorganic filler and an auxiliary agent, the structural color forming layer is a self-assembled polystyrene microsphere layer, and the structural color forming layer comprises polystyrene microspheres and polyacrylate/waterborne polyvinylidene fluoride resin. The preparation method of the colored radiation refrigerating film comprises the following steps: 1) preparing polystyrene microspheres; 2) preparing a radiation refrigeration film layer; 3) and preparing a structural color forming layer. The colorful radiation refrigeration film has beautiful structural color, can not absorb visible light, has high sunlight reflectivity and high intermediate infrared emissivity, has refrigeration effect and aesthetic characteristics, is simple in preparation process, does not need to be controlled by a precise instrument, and is low in cost.
Description
Technical Field
The invention relates to the technical field of passive radiation refrigeration materials, in particular to a colored radiation refrigeration film and a preparation method thereof.
Background
Under the superposition of urban heat island effect and the big background of global warming, the temperature is high in summer, the demand of an active refrigeration mode represented by an air conditioner is continuously increased, a large amount of energy can be consumed, and the generated greenhouse gas can further aggravate global warming to cause vicious circle.
Radiation refrigeration is a passive refrigeration mode, and the universe with the background temperature of 3K is used as a natural radiator, and the earth surface heat is radiated into the outer space through an atmospheric window (3-5 μm and 8-13 μm) with high transmissivity, so that the temperature can be reduced without energy consumption. Most of energy in daily life comes from the sun, so, in order to realize good refrigeration effect, the material is required to have high radiation performance and high sunlight reflectivity, most of sunlight is reflected out from the surface of the material, and the reflection and the radiation performance are overlapped, so that good refrigeration effect is realized. About 45% of solar energy in sunlight is concentrated in a visible light wave band (0.4-0.76 mu m), and about 52% of solar energy is concentrated in a near infrared wave band (0.76-2.5 mu m), so most radiation refrigeration materials are always white to improve the reflectivity of the visible light wave band and improve the refrigeration effect. However, radiation-cooled materials of a single color have been very limited in practical use, and coloring of the materials is required to improve the aesthetic properties of the radiation-cooled materials.
At present, the radiation refrigeration material is mainly colored by adding pigment to obtain color effect, but the pigment can absorb light with the wavelength ranging from 300nm to 700nm, generate heat and finally cause the cooling performance of the radiation refrigeration material to be reduced, for example: the inorganic-polymer radiation-cooled artificial turf can be prepared by embedding chromium oxide pigment particles into high-density polyethylene, wherein an organic medium provides radiation performance, and the chromium oxide pigment particles make the radiation-cooled artificial turf green, but the absorption of sunlight by the chromium oxide pigment particles can cause the reflectivity of the radiation-cooled artificial turf in a visible light range to be less than 50%, so that the cooling effect is inhibited (Zhangbin Yang, Tiankai Jiang, Jun Zhang. passive synthetic inorganic-polymeric composite decorative lawn for the alternative to the natural lawn [ J ]. Solar Energy Materials Cells, 219). In addition, researchers have also Applied 3D grating structures (Zhu L, Raman a, Fan s.color-preceding digital lighting [ J ]. Applied Physics Letters,2013,103(22):223902) and metal-insulator-metal structures (Wei, Shi, Zhen, et al, photonic thermal management of colored objects [ J ]. Nature communications,2018.) to radiation-cooled materials, these complex structures requiring precise calculation and design of multiple thin films, also requiring precise instruments, complex manufacturing processes, and high costs.
Disclosure of Invention
The invention aims to provide a color radiation refrigeration film and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a colored radiation refrigeration film comprises a radiation refrigeration film layer and a structural color forming layer which are laminated; the radiation refrigeration film layer comprises the components of polyacrylate/waterborne polyvinylidene fluoride resin, inorganic filler and auxiliary agent; the structural color forming layer is a self-assembled polystyrene microsphere layer, and the components of the structural color forming layer comprise polystyrene microspheres and polyacrylate/aqueous polyvinylidene fluoride resin.
Preferably, the thickness of the radiation refrigeration film layer is 50-150 μm.
Preferably, the structural color forming layer has a thickness of 2 to 20 μm.
Preferably, the diameter of the polystyrene microsphere is 167nm to 336 nm.
Preferably, the inorganic filler is at least one of titanium dioxide, silicon dioxide, calcium carbonate, aluminum phosphate and magnesium hydrogen phosphate.
The preparation method of the colored radiation refrigerating film comprises the following steps:
1) mixing styrene and an emulsifier with water, emulsifying, adding an initiator, and polymerizing to obtain polystyrene microspheres;
2) mixing polyacrylate emulsion or aqueous polyvinylidene fluoride resin, inorganic filler and an auxiliary agent, performing ball milling to prepare slurry, and coating and drying to obtain a radiation refrigeration film layer;
3) and adding water into the polystyrene microspheres for dispersion, adding polyacrylate emulsion or aqueous polyvinylidene fluoride resin to prepare polystyrene microsphere dispersion, coating the polystyrene microsphere dispersion on the radiation refrigeration film layer, performing gravity settling self-assembly, and drying to obtain the colored radiation refrigeration film.
Preferably, the emulsifier in step 1) is at least one of sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate and sodium allyloxy hydroxypropyl sulfonate.
Preferably, the dosage of the emulsifier in the step 1) is 0.2-1% of the mass of the styrene.
Preferably, the initiator in the step 1) is at least one of ammonium persulfate and potassium persulfate.
Preferably, the amount of the initiator in the step 1) is 0.5-2% of the mass of the styrene.
Preferably, the polymerization in the step 1) is carried out at 70-90 ℃ for 4-8 h.
Preferably, the mass ratio of the polyacrylate emulsion to the inorganic filler in the step 2) is 2: 1-2: 5.
Preferably, the mass ratio of the aqueous polyvinylidene fluoride resin in the step 2) to the inorganic filler is 2: 1-2: 5.
Preferably, the dosage of the auxiliary agent in the step 2) is 8-12% of the mass of the slurry.
Preferably, the auxiliary agent in the step 2) is composed of a dispersing agent, a defoaming agent, a flatting agent and a film forming agent according to a mass ratio of 5: 1-2: 3.
Preferably, the dosage of the polyacrylate emulsion in the step 3) is 50-300% of the mass of the polystyrene microsphere.
Preferably, the amount of the aqueous polyvinylidene fluoride resin in the step 3) is 50-300% of the mass of the polystyrene microsphere.
Preferably, the coating amount of the polystyrene microsphere dispersion liquid in the step 3) on the radiation refrigeration film layer is 3L/m2～15L/m2。
The invention has the beneficial effects that: the colored radiation refrigeration film can generate physical effects such as interference, diffraction and the like on incident light through a periodic three-dimensional photonic crystal structure, generates beautiful structural color, cannot absorb visible light, has high sunlight reflectivity and high intermediate infrared emissivity, has refrigeration effect and aesthetic characteristics, is simple in preparation process, does not need to be controlled by a precise instrument, and is low in cost.
Specifically, the method comprises the following steps:
1) the color radiation refrigeration film provided by the invention has the advantages that the photonic crystal with the periodic micro-nano size structure is used for carrying out physical interaction such as interference and diffraction on incident light, visible light cannot be absorbed, the sunlight reflectivity is higher, more required aesthetic characteristics are met in practical application, the color regulation and control are simple, the control of a precise instrument is not needed, and the cost is low;
2) according to the colored radiation refrigeration film, a certain proportion of polyacrylate emulsion or aqueous polyvinylidene fluoride resin can be added according to the components of the radiation refrigeration film layer to adjust the components of the three-dimensional photonic crystal structure, so that the colored radiation refrigeration film has better stability, the special three-dimensional photonic crystal structure and the radiation refrigeration film layer interface can generate good adhesive force, the structure is not easy to damage, and the color is more durable;
3) the color radiation refrigeration film has strong absorption in the middle infrared band, and can be prepared into a color radiation refrigeration film with high emissivity and high reflectivity even if titanium dioxide filler with low emissivity is used;
4) the sunlight reflectivity of the colored radiation refrigeration film reaches 99.86 percent, and the emissivity of an atmospheric window (8-13 mu m) reaches 0.90 percent.
Drawings
FIG. 1 is an SEM image of polystyrene microspheres from example 1.
Fig. 2 is an SEM image of the color radiation refrigeration film of example 1.
FIG. 3 is a graph showing the reflectance of the color-radiation-based refrigeration films of examples 1 to 3.
FIG. 4 is a graph comparing the emissivity of the colored radiation refrigeration films of examples 1-3.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
a preparation method of a colored radiation refrigeration film comprises the following steps:
1) adding 12g of styrene and 0.03g of sodium dodecyl sulfate into 130mL of deionized water, placing the mixture in a nitrogen atmosphere, adjusting the stirring speed to 200rpm, stirring for 1h, adding 0.1g of ammonium persulfate, heating to 70 ℃, reacting for 4h, and centrifuging to obtain polystyrene microspheres;
2) mixing 20g of polyacrylate emulsion with the solid content of 50%, 10g of titanium dioxide, 1.5g of dispersant BYK-2015, 0.3g of defoamer Tego-810, 0.3g of flatting agent BYK-348 and 0.9g of film-forming agent alcohol ester twelve, adding zirconia balls for milling, preparing slurry, coating by taking an aluminum foil as a substrate, and drying at 30 ℃ to obtain a radiation refrigeration film layer, wherein the thickness of the film is 50 mu m;
3) adding 1g of polystyrene microsphere into 9mL of deionized water, adding 3.3g of polyacrylate emulsion with the solid content of 10% to prepare polystyrene microsphere dispersion, and dripping the dispersion on a radiation refrigeration film layer with the coating amount of 3L/m2And performing gravity settling self-assembly and drying at 30 ℃ to obtain the colored radiation refrigeration film.
The SEM image of the polystyrene microspheres in step 1) of this example is shown in fig. 1, and the SEM image of the color radiation refrigeration film prepared in this example is shown in fig. 2.
As can be seen from fig. 1: the polystyrene microspheres have uniform particle size of 285-294 nm.
As can be seen from fig. 2: the surface of the colored radiation refrigeration film forms a regular three-dimensional photonic crystal structure, and can generate interference and diffraction interaction on visible light in a specific area to form a bright color.
Example 2:
a preparation method of a colored radiation refrigeration film comprises the following steps:
1) adding 15g of styrene and 0.05g of sodium dodecyl sulfate into 130mL of deionized water, placing the mixture in a nitrogen atmosphere, adjusting the stirring speed to 350rpm, stirring the mixture for 1h, adding 0.15g of ammonium persulfate, heating the mixture to 80 ℃, reacting the mixture for 6h, and centrifuging the mixture to obtain polystyrene microspheres;
2) mixing 10g of aqueous polyvinylidene fluoride resin with the solid content of 50%, 15g of calcium carbonate, 1.25g of dispersant BYK-2015, 0.5g of defoamer Tego-810, 0.25g of flatting agent BYK-348 and 0.75g of film-forming agent alcohol ester twelve, adding zirconia balls for milling, preparing slurry, coating by taking an aluminum foil as a substrate, and drying at 45 ℃ to obtain a radiation refrigeration film layer, wherein the thickness of the film layer is 100 mu m;
3) adding 3g of polystyrene microspheres into 7mL of deionized water, adding 0.7g of aqueous polyvinylidene fluoride resin with the solid content of 10% to prepare polystyrene microsphere dispersion, and dripping the polystyrene microsphere dispersion on a radiation refrigeration film layer with the coating amount of 9L/m2And performing gravity settling self-assembly and drying at 50 ℃ to obtain the colored radiation refrigeration film.
Example 3:
a preparation method of a colored radiation refrigeration film comprises the following steps:
1) adding 18g of styrene and 0.07g of sodium dodecyl sulfate into 130mL of deionized water, placing the mixture in a nitrogen atmosphere, adjusting the stirring speed to 500rpm, stirring the mixture for 1h, adding 0.22g of ammonium persulfate, heating the mixture to 80 ℃, reacting the mixture for 8h, and centrifuging the reaction product to obtain polystyrene microspheres;
2) 8g of aqueous polyvinylidene fluoride resin with the solid content of 50 percent, 20g of magnesium phosphite, 1.4g of dispersant BYK-2015, 0.28g of defoamer Tego-810, 0.28g of flatting agent BYK-348 and 0.84g of film-forming agent alcohol ester twelve, then adding zirconia balls for milling, preparing slurry by ball milling, coating by taking an aluminum foil as a substrate, and drying at 60 ℃ to obtain a radiation refrigeration film layer, wherein the film thickness of the film layer is 150 mu m;
3) adding 5g of polystyrene microspheres into 5mL of deionized water, and then adding 0.5g of solid content10% of aqueous polyvinylidene fluoride resin is prepared into polystyrene microsphere dispersion liquid, and the polystyrene microsphere dispersion liquid is dripped on a radiation refrigeration film layer, wherein the coating amount is 15L/m2And performing gravity settling self-assembly and drying at 70 ℃ to obtain the colored radiation refrigeration film.
And (3) performance testing:
the reflectivity contrast graph of the colored radiation refrigeration film of the examples 1-3 is shown in fig. 3, the emissivity contrast graph is shown in fig. 4, and the reflectivity and emissivity data are shown in the following table:
table 1 reflectance and emissivity data for colored radiation refrigeration films
As can be seen from fig. 3 and table 1: the colored radiation refrigeration films of the embodiments 1 to 3 all have a peak of about 500nm, which is because the interference effect of the three-dimensional photonic crystal structure on part of visible light corresponds to blue-green, and the visible light band still maintains higher reflectivity, the reflectivity of the visible light band of the colored radiation refrigeration film of the embodiment 1 is as high as 99.86%, the reflectivity of the solar spectrum band is as high as 97.44%, the reflectivity of the visible light band of the colored radiation refrigeration film of the embodiment 2 is as high as 99.79%, the reflectivity of the solar spectrum band is as high as 96.45%, the reflectivity of the visible light band of the colored radiation refrigeration film of the embodiment 3 is as high as 98.53%, and the reflectivity of the solar spectrum band is as high as 94.90%; therefore, the energy of the solar spectrum accounts for about 45% in the visible light wave band and 52% in the near infrared wave band, so that the colorful radiation refrigeration film can reflect most of sunlight out and reduce the surface temperature of the material.
As can be seen from fig. 4 and table 1: the emissivity of the color radiation refrigeration film of the embodiment 1 in the atmospheric window of 8-13 μm is 0.90, the emissivity of the color radiation refrigeration film of the embodiment 2 in the atmospheric window of 8-13 μm is 0.89, and the emissivity of the color radiation refrigeration film of the embodiment 3 in the atmospheric window of 8-13 μm is 0.91, so that a good radiation refrigeration effect can be realized.
In conclusion: according to the colored radiation refrigeration film, the photonic crystal with the periodic micro-nano size structure is used for carrying out physical interaction such as interference and diffraction on incident light to generate beautiful colors, and absorption of visible light is avoided, so that the excellent high reflection performance of the colored radiation refrigeration film is ensured, a better refrigeration effect is realized, and meanwhile, the beautiful colors can improve visual attraction, meet aesthetic characteristics and provide more possibility for application of radiation refrigeration materials.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A colored radiation refrigeration film characterized by: the color radiation refrigeration film comprises a radiation refrigeration film layer and a structural color forming layer which are laminated; the radiation refrigeration film layer comprises the components of polyacrylate/waterborne polyvinylidene fluoride resin, inorganic filler and auxiliary agent; the structural color forming layer is a self-assembled polystyrene microsphere layer, and the components of the structural color forming layer comprise polystyrene microspheres and polyacrylate/aqueous polyvinylidene fluoride resin.
2. A colored radiation chilling film according to claim 1, wherein: the thickness of the radiation refrigeration film layer is 50-150 mu m.
3. A colored radiation chilling film according to claim 1 or 2, wherein: the thickness of the structural color formation layer is 2 μm to 20 μm.
4. A colored radiation chilling film according to claim 3, wherein: the diameter of the polystyrene microsphere is 167 nm-336 nm.
5. A colored radiation chilling film according to claim 1 or 2, wherein: the inorganic filler is at least one of titanium dioxide, silicon dioxide, calcium carbonate, aluminum phosphate and magnesium hydrogen phosphate.
6. The method for preparing the colored radiation refrigerating film as claimed in any one of claims 1 to 5, which is characterized by comprising the following steps:
1) mixing styrene and an emulsifier with water, emulsifying, adding an initiator, and polymerizing to obtain polystyrene microspheres;
2) mixing polyacrylate emulsion or aqueous polyvinylidene fluoride resin, inorganic filler and an auxiliary agent, performing ball milling to prepare slurry, and coating and drying to obtain a radiation refrigeration film layer;
3) and adding water into the polystyrene microspheres for dispersion, adding polyacrylate emulsion or aqueous polyvinylidene fluoride resin to prepare polystyrene microsphere dispersion, coating the polystyrene microsphere dispersion on the radiation refrigeration film layer, performing gravity settling self-assembly, and drying to obtain the colored radiation refrigeration film.
7. The method for preparing a colored radiation refrigerating film according to claim 6, wherein the method comprises the following steps: the emulsifier in the step 1) is at least one of sodium dodecyl sulfate, sodium dodecyl sulfonate, sodium dodecyl benzene sulfonate and allyloxy hydroxypropyl sodium sulfonate.
8. The method for preparing a colored radiation refrigerating film according to claim 6 or 7, wherein the method comprises the following steps: the initiator in the step 1) is at least one of ammonium persulfate and potassium persulfate.
9. The method for preparing a colored radiation refrigerating film according to claim 6 or 7, wherein the method comprises the following steps: the polymerization in the step 1) is carried out at 70-90 ℃, and the reaction time is 4-8 h.
10. The method for preparing a colored radiation refrigerating film according to claim 6 or 7, wherein the method comprises the following steps: the auxiliary agent in the step 2) is composed of a dispersing agent, a defoaming agent, a flatting agent and a film forming agent according to a mass ratio of 5: 1-2: 3.
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Cited By (6)
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| CN112984858A (en) * | 2021-03-18 | 2021-06-18 | 哈尔滨工业大学 | Preparation method and application of microstructure radiation refrigeration device |
| CN113954453A (en) * | 2021-12-07 | 2022-01-21 | 中南大学 | Colored double-layer radiation refrigerating film and preparation method thereof |
| CN114801403A (en) * | 2022-03-08 | 2022-07-29 | 深圳大学 | Radiation refrigeration composite flexible membrane with structural color |
| CN114801378A (en) * | 2022-05-21 | 2022-07-29 | 南开大学 | Flexible color radiation refrigerating device below room temperature and preparation method thereof |
| CN115434151A (en) * | 2022-08-15 | 2022-12-06 | 浙江理工大学 | Colorful passive radiation refrigeration coating fabric and preparation method thereof |
| CN115627088A (en) * | 2022-10-12 | 2023-01-20 | 三峡大学 | Radiation refrigeration film of tricyclodecane dimethanol diacrylate (DMDA) light-cured monomer |
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