CN114349480A - Daytime radiation refrigeration block material with spectral selectivity and preparation method and application thereof - Google Patents
Daytime radiation refrigeration block material with spectral selectivity and preparation method and application thereof Download PDFInfo
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- 238000005057 refrigeration Methods 0.000 title claims abstract description 85
- 239000000463 material Substances 0.000 title claims abstract description 74
- 230000003595 spectral effect Effects 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011241 protective layer Substances 0.000 claims abstract description 29
- 239000002346 layers by function Substances 0.000 claims abstract description 25
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052809 inorganic oxide Inorganic materials 0.000 claims abstract description 15
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 13
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims abstract description 13
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims abstract description 10
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 5
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims abstract description 5
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims abstract description 5
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- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 238000001272 pressureless sintering Methods 0.000 claims description 4
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Abstract
The invention discloses a daytime radiation refrigeration block material with spectral selectivity, a preparation method and application thereof, wherein the daytime radiation refrigeration block material consists of a protective layer and a radiation refrigeration functional layer, and the protective layer is coated on the surface of the radiation refrigeration functional layer; the protective layer is prepared from a macromolecular film forming substance; the radiation refrigeration function layer is prepared from an oxide block material, the oxide block material is prepared from an inorganic oxide, and the inorganic oxide is at least one of magnesium oxide, barium oxide, zirconium oxide, cerium oxide, zinc oxide, aluminum oxide and lithium fluoride. The daytime radiation refrigeration block material has reflectivity of more than 95% in a solar spectrum waveband, high emissivity in an atmospheric window waveband of 8-13 mu m and high reflectivity in wavebands of 2.5-8 mu m and 13-25 mu m. Therefore, the daytime radiation refrigerating material of the invention has less absorption to solar radiation and atmospheric reverse radiation, and can realize better refrigerating effect.
Description
Technical Field
The invention relates to the technical field of daytime radiation refrigeration, in particular to a daytime radiation refrigeration block material with spectral selectivity, and a preparation method and application thereof.
Background
Global warming and energy problems are increasingly highlighted, and the demand for cooling is rapidly increasing, so that the search for new ways to cool the air is urgent. Radiation refrigeration is one of energy-saving cooling modes, and can be combined with cooling modes such as water circulation and the like, so that the energy consumption is remarkably relieved.
Most of the existing day radiation refrigeration materials are infrared wide-band high-emission materials, do not have high emission of 8-13 mu m, have high-reflection spectral selectivity of other bands, and are easy to accept atmospheric radiation input energy, so that the radiation refrigeration performance is reduced. The metamaterial and the composite material are not easy to be simply prepared in a large scale.
Disclosure of Invention
The invention provides a daytime radiation refrigeration block material with spectral selectivity, and a preparation method and application thereof, which are used for overcoming the defects of poor spectral selectivity, complex preparation process and the like in the prior art.
In order to achieve the purpose, the invention provides a daytime radiation refrigeration block material with spectral selectivity, which consists of a protective layer and a radiation refrigeration functional layer, wherein the protective layer is coated on the surface of the radiation refrigeration functional layer;
the protective layer is prepared from a high-molecular film forming substance;
the radiation refrigeration function layer is prepared from an oxide block material, the oxide block material is prepared from an inorganic oxide, and the inorganic oxide is at least one of magnesium oxide, barium oxide, zirconium oxide, cerium oxide, zinc oxide, aluminum oxide and lithium fluoride.
In order to achieve the above object, the present invention further provides a method for preparing a block material for daytime radiation refrigeration with spectral selectivity as described above, comprising the following steps:
s1: weighing inorganic oxide, performing wet ball milling, drying, sieving, performing dry pressing, and sintering to obtain an oxide block material;
s2: weighing a high molecular film forming substance, adding deionized water, mixing to form slurry, coating the slurry on the surface of the oxide block material, leveling and drying to obtain the daytime radiation refrigeration block material.
In order to achieve the purpose, the invention also provides application of the daytime radiation refrigeration block material with spectral selectivity, and the daytime radiation refrigeration block material or the daytime radiation refrigeration block material prepared by the preparation method is applied to buildings, condensation water preparation and thermoelectric power generation.
Compared with the prior art, the invention has the beneficial effects that:
1. the daytime radiation refrigeration block material with spectral selectivity provided by the invention consists of a protective layer and a radiation refrigeration functional layer, wherein the protective layer is coated on the surface of the radiation refrigeration functional layer; the protective layer is prepared from a macromolecular film forming substance; the radiation refrigeration function layer is prepared from an oxide block material, the oxide block material is prepared from an inorganic oxide, and the inorganic oxide is at least one of magnesium oxide, barium oxide, zirconium oxide, cerium oxide, zinc oxide, aluminum oxide and lithium fluoride. The daytime radiation refrigeration block material has reflectivity of more than 95% in a solar spectrum waveband, high emissivity in an atmospheric window waveband of 8-13 mu m and high reflectivity in wavebands of 2.5-8 mu m and 13-25 mu m. The reason is that the residual reflection band strength is high due to the large grain size of the surface of the block material, the reflectivity of the wave band of 13-25 mu m is high, and the pores are used as scattering centers to enhance the reflection of the solar spectrum. Therefore, the daytime radiation refrigeration block material has high reflectivity in a solar spectrum waveband, has high emissivity in an atmosphere window with the thickness of 8-13 mu m, can emit heat of an object to the space with the temperature of minus 270 ℃ in the form of infrared waves, is completely spontaneous, and does not need external energy input. Therefore, the daytime radiation refrigerating material of the invention has less absorption to solar radiation and atmospheric reverse radiation, and can realize better refrigerating effect.
2. The preparation method of the daytime radiation refrigeration block material with the spectrum selectivity provided by the invention has the advantages of simple process, short period and low cost, and is suitable for mass production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the structures shown in the drawings without creative efforts.
FIG. 1 is a block diagram of a spectrally selective daytime radiation refrigeration bulk material provided in accordance with the present invention;
FIG. 2 is a surface topography of the radiation refrigerating function layer in example 1;
fig. 3 is a graph of the spectral absorption (emission) rate of the daytime radiation refrigeration bulk material with spectral selectivity of example 1.
The reference numbers illustrate: 1, a protective layer; 2: radiation refrigeration functional layer.
The implementation, functional features and advantages of the objects of the present invention will be further explained with reference to the accompanying drawings.
Detailed Description
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 only a part of the embodiments of the present invention, and not all of the embodiments. 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.
In addition, the technical solutions in the embodiments of the present invention may be combined with each other, but it must be based on the realization of those skilled in the art, and when the technical solutions are contradictory or cannot be realized, such a combination of technical solutions should not be considered to exist, and is not within the protection scope of the present invention.
The drugs/reagents used are all commercially available without specific mention.
The invention provides a daytime radiation refrigeration block material with spectral selectivity, which is composed of a protective layer 1 and a radiation refrigeration functional layer 2 as shown in figure 1, wherein the protective layer 1 is coated on the surface of the radiation refrigeration functional layer 2;
the protective layer 1 is prepared from a high-molecular film forming substance;
the radiation refrigeration functional layer 2 is prepared from an oxide bulk material, the oxide bulk material is prepared from an inorganic oxide, and the inorganic oxide is at least one of magnesium oxide, barium oxide, zirconium oxide, cerium oxide, zinc oxide, aluminum oxide and lithium fluoride.
The dispersion relation indicates that some ion crystals have a frequency band in the infrared that cannot propagate through the crystal due to the surface phonon polariton effect, and is called a residual reflection band (restahlen band). The reflection of sunlight can be enhanced by preserving a volume size of the pores. Based on the optical characteristics of the residual reflection band of the oxide, the invention can realize the spectral selectivity of high emission of 8-13 mu m and high reflection of other wave bands by using a single material.
Preferably, the daytime radiation refrigeration block material has the porosity of 2.5-3%, the pore diameter is mainly distributed about 100nm, and the grain size is larger than or equal to 5 microns.
Preferably, the median diameter of the inorganic oxide is 0.5 to 1 μm
Preferably, the thickness of the radiation refrigeration functional layer is 2-4 mm. The thickness is too small, sintering is easy to deform, the thickness prepared by the same process is small, density is high, and solar spectrum and 8-13 micron transmittance are high. The thickness is too large, isostatic pressing treatment is needed, if isostatic pressing treatment is not needed, the density is low, and the strength of the residual reflection band is reduced.
Preferably, the thickness of the radiation refrigeration functional layer is 2-3 mm.
Preferably, the thickness of the protective layer is 8-45 μm. Too thick or too thin affects the light transmittance.
Preferably, the thickness of the protective layer is 10-20 μm.
Preferably, the polymer film-forming material is one of polyethylene oxide, aqueous polyurethane and polyvinylidene fluoride-hexafluoropropylene. The selected film forming material has good film forming property, high solar spectrum and infrared transmittance and high environmental protection.
Preferably, the oxide bulk material is prepared from magnesium oxide. The radiation refrigeration functional layer prepared by using the pure magnesium oxide has better refrigeration performance.
The invention also provides a preparation method of the daytime radiation refrigeration block material with the spectrum selectivity, which comprises the following steps:
s1: weighing inorganic oxide, ball-milling by a wet method, drying, sieving, molding by dry pressing, and sintering to obtain the oxide block material.
And performing wet ball milling to enable the particle size of the powder to reach submicron level.
S2: weighing a high molecular film forming substance, adding deionized water, mixing to form slurry, coating the slurry on the surface of the oxide block material, leveling and drying to obtain the daytime radiation refrigeration block material.
Preferably, the proportion of the grinding balls, raw materials and solvent of the wet ball milling is 1: 1: 1, the solvent is absolute ethyl alcohol, and the median diameter of the powder obtained after ball milling is 0.5-1 mu m;
the pressure intensity range of the dry pressing is 40-55 MPa;
the sintering is pressureless sintering or hot-pressing sintering; the pressureless sintering is that the temperature is increased to 1500 ℃ at the temperature rising speed of 10 ℃/min under the air atmosphere, the temperature is preserved for 0.5h at 1500 ℃, and the temperature is reduced to 800 ℃ from 1500 ℃ at the temperature reducing speed of 10 ℃/min, and then the temperature is reduced to room temperature along with the furnace; the hot-pressing sintering pressure range is 30-50 MPa, the temperature range is 800-1000 ℃, and the hot-pressing sintering time is 0.5 h. Hot press sintering is a sintering method in which powder is placed in a mold cavity and heated while being pressurized in a uniaxial direction.
The invention also provides an application of the daytime radiation refrigeration block material with spectral selectivity, and the daytime radiation refrigeration block material or the daytime radiation refrigeration block material prepared by the preparation method is applied to buildings, condensation water and thermoelectric power generation.
Example 1
The embodiment provides a daytime radiation refrigeration block material with spectral selectivity, which consists of a protective layer and a radiation refrigeration functional layer, wherein the protective layer is coated on the surface of the radiation refrigeration functional layer.
The protective layer was 10 μm thick polyethylene oxide.
The radiation refrigeration functional layer is a high-density magnesium oxide block body with the thickness of 3.31 mm. The purity of the magnesium oxide powder was 99%.
In the embodiment, the porosity of the daytime radiation refrigeration block material is 2.5-3%, the pore diameter is mainly distributed about 100nm, and the grain size is more than or equal to 5 microns.
Fig. 2 is a surface topography of the radiation refrigeration functional layer in the embodiment, and it can be known that the grain size exceeds 5 μm.
FIG. 3 is a graph showing the spectral absorption (emission) rate of the daytime radiation refrigeration bulk material with spectral selectivity in this embodiment, and it can be seen from the graph that the sample has spectral selectivity, high emission at 8-13 μm, high reflection at 13-25 μm. In the embodiment, the reflectivity (0.25-2.5 mu m) of the daytime radiation refrigeration block material in a solar spectrum waveband is more than 95%, the emissivity in an atmosphere window with the thickness of 8-13 mu m is more than 90%, and the reflectivity in the range of 13-25 mu m is about 30%.
The embodiment also provides a preparation method of the daytime radiation refrigeration block material with the spectral selectivity, which comprises the following steps:
s1: weighing 24g of magnesium oxide powder with the purity of 99% and the median diameter of 4.483 mu m, carrying out wet ball milling for 4h (using agate balls with the diameter of 3mm and 8mm and the gradation of 1: 1), drying and sieving to obtain the magnesium oxide powder with the median diameter of 0.738 mu m. Forming under 50MPa, drying in a forced air drying oven at 100 ℃ for 24h, heating to 1500 ℃ in a muffle furnace at a heating rate of 10 ℃/min in the air atmosphere, preserving heat for 0.5h, cooling to 800 ℃ at a cooling rate of 10 ℃/min, and cooling to room temperature along with the furnace to obtain a magnesium oxide block material;
s2: weighing 1g of polyoxyethylene, adding 9g of deionized water, adding a small amount of hydrophobic agent, performing ultrasonic treatment for 2h to obtain polyoxyethylene dispersion, coating the polyoxyethylene dispersion on the surface of the magnesium oxide block material, leveling and drying to obtain the daytime radiation refrigeration block material.
Example 2
The embodiment provides a daytime radiation refrigeration block material with spectral selectivity, which consists of a protective layer and a radiation refrigeration functional layer, wherein the protective layer is coated on the surface of the radiation refrigeration functional layer.
The protective layer is aqueous polyurethane with the thickness of 45 mu m.
The radiation refrigeration functional layer is a 4mm high-density zinc oxide block. The purity of the zinc oxide powder was 99%.
In the embodiment, the porosity of the daytime radiation refrigeration block material is 2.5-3%, the pore diameter is mainly distributed about 100nm, and the grain size is more than or equal to 5 microns.
The embodiment also provides a preparation method of the daytime radiation refrigeration block material with the spectral selectivity, which comprises the following steps:
s1: 24g of zinc oxide powder with the purity of 99 percent and the median diameter of 4.750 mu m is weighed, ball-milled for 3.5h by a wet method (agate balls with the diameter of 3mm and 8mm are adopted, the grading is 1: 1), and the zinc oxide powder with the median diameter of 1.0 mu m is obtained by drying and sieving. Molding by dry pressure of 55MPa, placing in a forced air drying oven, drying at 100 ℃ for 24h, placing in a muffle furnace, heating to 1500 ℃ at a heating rate of 10 ℃/min under air atmosphere, keeping the temperature for 0.5h, cooling to 800 ℃ at a cooling rate of 10 ℃/min, and then cooling to room temperature along with the furnace to obtain a zinc oxide block material;
s2: weighing 1g of waterborne polyurethane, adding 9g of deionized water, adding a small amount of hydrophobing agent, performing ultrasonic treatment for 2h to obtain polyurethane dispersion, coating the polyurethane dispersion on the surface of the zinc oxide block material, leveling and drying to obtain the daytime radiation refrigeration block material.
Example 3
The embodiment provides a daytime radiation refrigeration block material with spectral selectivity, which consists of a protective layer and a radiation refrigeration functional layer, wherein the protective layer is coated on the surface of the radiation refrigeration functional layer.
The protective layer is aqueous polyurethane with the thickness of 8 mu m.
The radiation refrigeration function layer is a 2mm high-density alumina block. The purity of the alumina powder was 99%.
In the embodiment, the porosity of the daytime radiation refrigeration block material is 2.5-3%, the pore diameter is mainly distributed about 100nm, and the grain size is more than or equal to 5 microns.
The embodiment also provides a preparation method of the daytime radiation refrigeration block material with the spectral selectivity, which comprises the following steps:
s1: 24g of alumina powder with the purity of 99 percent and the median diameter of 5.123 mu m is weighed, wet ball milling is carried out for 4.2h (agate balls with the diameters of 3mm and 8mm are adopted, the grading is 1: 1), and the alumina powder with the median diameter of 1.0 mu m is obtained after drying and sieving. Dry pressing at 40MPa, drying in an air drying oven at 100 deg.C for 24 hr, and hot pressing at 900 deg.C under 40MPa for 0.5 hr to obtain alumina block material;
s2: weighing 1g of polyvinylidene fluoride-hexafluoropropylene, adding 9g of deionized water, adding a small amount of a hydrophobizing agent, carrying out ultrasonic treatment for 2 hours to obtain a polyvinylidene fluoride-hexafluoropropylene dispersion, coating the polyvinylidene fluoride-hexafluoropropylene dispersion on the surface of the alumina block material, leveling and drying to obtain the daytime radiation refrigeration block material.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention, and all modifications and equivalents of the present invention, which are made by the contents of the present specification and the accompanying drawings, or directly/indirectly applied to other related technical fields, are included in the scope of the present invention.
Claims (10)
1. A daytime radiation refrigeration block material with spectral selectivity is characterized by comprising a protective layer and a radiation refrigeration functional layer, wherein the protective layer is coated on the surface of the radiation refrigeration functional layer;
the protective layer is prepared from a high-molecular film forming substance;
the radiation refrigeration function layer is prepared from an oxide block material, the oxide block material is prepared from an inorganic oxide, and the inorganic oxide is at least one of magnesium oxide, barium oxide, zirconium oxide, cerium oxide, zinc oxide, aluminum oxide and lithium fluoride.
2. The daytime radiation refrigerating block material according to claim 1, wherein the daytime radiation refrigerating block material has a porosity of 2.5-3% and a grain size of not less than 5 μm.
3. The daytime radiation refrigeration bulk material according to claim 1, wherein the inorganic oxide has a median diameter of 0.5 to 1 μm.
4. The daytime radiation refrigeration bulk material according to claim 1, wherein the thickness of the radiation refrigeration functional layer is 2-4 mm.
5. The daytime radiation refrigeration bulk material according to claim 1, wherein the protective layer has a thickness of 8 to 45 μm.
6. The daytime radiation refrigeration bulk material according to claim 5, wherein the protective layer has a thickness of 10 to 20 μm.
7. The daytime radiation refrigerating block material according to claim 1, wherein the polymer film-forming substance is one of polyethylene oxide, aqueous polyurethane and polyvinylidene fluoride-hexafluoropropylene.
8. A method for preparing a block material for daytime radiation refrigeration with spectral selectivity according to any one of claims 1 to 7, comprising the following steps:
s1: weighing inorganic oxide, performing wet ball milling, drying, sieving, performing dry pressing, and sintering to obtain an oxide block material;
s2: weighing a high molecular film forming substance, adding deionized water, mixing to form slurry, coating the slurry on the surface of the oxide block material, leveling and drying to obtain the daytime radiation refrigeration block material.
9. The method of claim 8, wherein in step S1, the ratio of the wet ball milled grinding balls to the raw materials to the solvent is 1: 1: 1, the solvent is absolute ethyl alcohol, and the median diameter of the powder obtained after ball milling is 0.5-1 mu m;
the pressure intensity range of the dry pressing is 40-55 MPa;
the sintering is pressureless sintering or hot-pressing sintering; the pressureless sintering is that the temperature is increased to 1500 ℃ at the temperature rising speed of 10 ℃/min under the air atmosphere, the temperature is preserved for 0.5h at 1500 ℃, and the temperature is reduced to 800 ℃ from 1500 ℃ at the temperature reducing speed of 10 ℃/min, and then the temperature is reduced to room temperature along with the furnace; the hot-pressing sintering pressure range is 30-50 MPa, the temperature range is 800-1000 ℃, and the hot-pressing sintering time is 0.5 h.
10. Application of the daytime radiation refrigeration block material with spectral selectivity is characterized in that the daytime radiation refrigeration block material according to any one of claims 1 to 7 or the daytime radiation refrigeration block material prepared by the preparation method according to claim 8 or 9 is applied to buildings, condensation water and thermoelectric power generation.
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| CN117385492A (en) * | 2023-12-07 | 2024-01-12 | 天津包钢稀土研究院有限责任公司 | Hollow cooling fiber modified by lanthanum and cerium natural distribution product and preparation method thereof |
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