CN109837589B - Passive refrigeration crystal, passive refrigeration coating, and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a passive refrigeration crystal, a passive refrigeration coating, a preparation method and an application thereof, wherein the expression of the crystal is CayMg11‑y(HPO3)8(OH)6‑xFx(x is more than or equal to 1 and less than or equal to 6, y is more than or equal to 0.3 and less than or equal to 1), the ultraviolet visible near-infrared band reflectivity is more than 0.95, the emissivity at the atmospheric window is more than 0.90, and certain emission selectivity is shown in the long wave range. Based on magnesium acetate tetrahydrate, calcium acetate monohydrate, sodium fluoride and phosphorous acid as raw materials, cyclohexylamine is added, and the passive refrigeration crystal is prepared by a hydrothermal method. The passive refrigeration coating prepared by the passive refrigeration crystal has the surface temperature lower than the ambient temperature by more than 5 ℃ in the midday of direct solar radiation, and can effectively reduce the surface temperature of the wall surface of a building, and the reduction amplitude reaches more than 7 ℃. The crystal material can relieve the urban heat island effect to a certain extent.
Description
Technical Field
The invention belongs to the field of crystal materials, and particularly relates to a passive refrigeration crystal, a passive refrigeration coating, and preparation methods and applications thereof.
Background
With the continuous advance of urbanization, urban structures are in large numbers and are dense. Because these structures themselves (e.g., concrete, asphalt pavement, building wall) have a low specific heat capacity and absorb heat quickly, particularly in hot summer with sufficient sunlight, the surfaces of these structures absorb a large amount of heat and heat up quickly. The high temperature air flow at the surface enters the atmosphere in the form of turbulence, causing the urban temperature to rise, causing a severe urban heat island effect. Undoubtedly, the urban environment with too high temperature brings inconvenience to the production and life of citizens, such as the energy consumption of urban power supply and refrigeration is increased sharply. The huge consumption of electrical energy directly brings about the accelerated loss of non-renewable energy sources, and simultaneously increases the emission of greenhouse gases. Therefore, it is important to find a replaceable refrigeration mode with no or little energy consumption. A passive refrigeration system that does not require active energy input is receiving increasing attention from various researchers.
The passive refrigeration is a refrigeration mode which can reach the temperature below the environment by means of certain characteristics of the passive refrigeration without external energy input. A class of materials with high reflectivity in the ultraviolet visible near infrared and selective emission characteristics in the infrared region can generally achieve passive refrigeration. This refrigeration is particularly desirable during the daytime.
The Eden Redehaeli designs a passive cooling device with unique micro-morphology, which is made of alpha-quartz, SiC and MgF2，TiO2And Ag layers, which have ultra-low solar absorption and have a strictly selective emission at atmospheric windows. Aaswave P.Raman shows a HfO2And SiO2The overlapping photon radiation cools the device, and the temperature of the device is 4.9 ℃ lower than that of the air under the condition of direct sunlight. Zhai prepared a wrapped random distribution of SiO2When a layer of high-reflection Ag is plated on the back surface of the film, the metamaterial can reach 93W/m at midday when sunlight is directly radiated2Cooling power of (2). Yang proposes a phase inversion based process for producing a single layer graded porous polymer (P (VDF-HFP)) coating having a surface temperature 6 ℃ below ambient temperature in intense sunlight. From the above developments, effective cooling during daytime typically involves a smart combination of a highly reflective layer and a selectively emissive layer. Although the cooling effect is efficient, large area manufacturing and application is difficult to achieve, manufacturing costs are often expensive and materials often appear to be non-corrosive or non-aging.
Disclosure of Invention
In order to overcome the above disadvantages and shortcomings of the prior art, the present invention provides a passive refrigeration crystal and a method for preparing the same. The reflectivity of the passive refrigeration crystal in an ultraviolet visible near-infrared band (0.2-2.5 um) can reach more than 0.95, the emissivity at an atmospheric window (8-13 um) can reach more than 0.90, and the infrared emission spectrum of the crystal material shows emission selectivity in a long wave range.
The invention also aims to provide a passive refrigeration coating and a preparation method thereof, wherein the coating is prepared from raw materials comprising the passive refrigeration crystal.
It is a further object of the present invention to provide the use of the above passive refrigeration coating.
The purpose of the invention is realized by the following technical scheme:
a passive refrigeration crystal with chemical expression of CayMg11-y(HPO3)8(OH)6-xFx，1≤x≤6，0.3≤y≤1。
Preferably, the passive refrigeration crystal has a chemical formula of CayMg11-y(HPO3)8(OH)6-xFx，x＝1、2、3、4、5、6，y＝0.3、0.5、0.7、1。
Preferably, the reflectivity of the passive refrigeration crystal in an ultraviolet visible near-infrared region is more than 0.95, the emissivity at an atmospheric window is more than 0.90, and long-wave infrared has selective emission.
The preparation method of the passive refrigeration crystal comprises the following steps:
(5) according to the target product CayMg11-y(HPO3)8(OH)6-xFxWeighing magnesium acetate tetrahydrate and calcium acetate monohydrate by a chemical formula that x is more than or equal to 1 and less than or equal to 6 and y is more than or equal to 0.3 and less than or equal to 1, adding water to dissolve, and stirring until a transparent colorless solution is obtained;
(6) weighing sodium fluoride and phosphorous acid according to a target product chemical formula, and respectively dissolving the sodium fluoride and the phosphorous acid in water to prepare a sodium fluoride aqueous solution and a phosphorous acid aqueous solution;
(7) mixing all the solutions prepared in the steps (1) and (2) to obtain a mixed solution, adding cyclohexylamine under the stirring condition, continuously stirring to obtain an emulsion, and transferring the emulsion into a high-pressure reaction kettle for hydrothermal reaction;
(8) and (3) after the reaction in the step (3) is finished and the reaction product is cooled to room temperature, carrying out solid-liquid separation on the reaction product, washing and filtering the obtained solid, drying, grinding and sieving to obtain white powder, namely the passive refrigeration crystal.
Preferably, the ratio of the adding amount of the water in the step (1) to the total mass of the magnesium acetate tetrahydrate and the calcium acetate monohydrate is 4-5: 1.
Preferably, the stirring in the step (1) is specifically: magnetic stirring is adopted, and the rotating speed is 200-400 r/min.
Preferably, the concentration of the aqueous sodium fluoride solution in the step (2) is 0.0069g/ml to 0.0229g/ml, and the concentration of the aqueous phosphorous acid solution is 0.060g/ml to 0.082 g/ml.
Preferably, the volume ratio of the cyclohexylamine to the mixed solution in the step (3) is 1: 6-7.
Preferably, the time for continuing stirring in the step (3) is 30-40 min.
Preferably, the temperature of the hydrothermal reaction in the step (3) is 160-220 ℃, and the time of the hydrothermal reaction is 1400-2200 min.
Preferably, the drying temperature in the step (4) is 80-110 ℃, and the drying time is 2-5 h.
Preferably, the sieve of the step (4) is 100-300 meshes.
Preferably, the room temperature in the step (4) is 20-30 ℃.
The passive refrigeration crystal is applied to the preparation of heat reflection infrared radiation materials.
A preparation method of a passive refrigeration coating comprises the following steps:
(1) adding N-methyl pyrrolidone into the binder to obtain a mixture, heating the mixture, taking out every 10-15 min, and stirring until the binder is completely dissolved to be transparent and bubble-free to obtain transparent viscous liquid;
(2) adding the passive refrigeration crystal into the transparent viscous liquid obtained in the step (1), uniformly stirring, putting a ball mill, fixing a tank body on a ball mill, and carrying out ball milling for 6-8 hours to obtain ink-like slurry with proper viscosity and luster after the ball milling is finished;
(3) and (3) coating the slurry prepared in the step (2) on a substrate to obtain a wet coating tape, and drying the wet coating tape to obtain the passive refrigeration coating.
Preferably, the binder in the step (1) is polyvinylidene fluoride.
Preferably, the mass ratio of the N-methyl pyrrolidone to the binder in the step (1) is 26-33: 1.
Preferably, the heating in step (1) is specifically: and (4) heating in an oven at the temperature of 80-110 ℃.
Preferably, the mass ratio of the passive refrigeration crystal in the step (2) to the binder in the step (1) is 8-9: 2-1.
Preferably, the diameter of the ball mill in the step (2) is 1-3 mm, and the ball-milling material-ball ratio is 4-6: 1.
Preferably, the rotating speed of the ball mill in the step (2) is 300-400 r/min.
Preferably, the substrate in step (3) is one of aluminum foil, ceramic tile and plastic plate.
Preferably, the coating amount in the step (3) is 0.02-0.1 g/cm2。
Preferably, the drying temperature in the step (3) is 50-70 ℃, and the drying time is 2-5 h.
Preferably, the drying in the step (3) is specifically as follows: drying for 3h at 60 ℃ in an air drying oven.
The passive refrigeration coating prepared by the preparation method of the passive refrigeration coating.
The passive refrigeration coating is applied to preparing a cooling coating material on the surface of the outer wall of a building.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the crystal material of the invention has the characteristics of higher ultraviolet visible near-infrared high reflectivity and selective infrared emission. The reflectivity of the ultraviolet visible near-infrared band with the wavelength of 0.2-2.5 mu m can reach more than 0.95, the emissivity of the ultraviolet visible near-infrared band at an atmospheric window is more than 0.90, and a certain long-wave infrared emission selectivity is shown.
(2) The preparation method of the crystal material is simple and mature, and the prepared material has stable performance and good repeatability.
(3) The preparation method of the passive refrigeration coating has the advantages of simple process and low cost, and can be manufactured in a large area.
(4) The crystal material can well combine the comprehensive performance of reflection and radiation to prepare a refrigerated coating, and the surface temperature of the coating is lower than the ambient temperature by more than 5 ℃ in the midday of direct solar radiation. The surface temperature of the wall surface of a building can be effectively reduced by more than 7 ℃, and the crystal material can relieve the urban heat island effect to a certain extent.
Drawings
FIG. 1 is an XRD refined spectrum of the passive refrigeration crystal prepared in example 1.
FIG. 2 is a scanning electron micrograph of the passive refrigeration crystals prepared in example 1 at high magnification.
FIG. 3 is a graph showing the reflectance and emissivity in the near-infrared band in the ultraviolet and visible spectrum of the passive refrigeration crystal prepared in example 1.
FIG. 4 is a Fourier infrared absorption spectrum of the passive refrigeration crystal prepared in example 1.
Fig. 5 is a graph showing the real effect of the passive refrigeration coating prepared in example 1 and a comparison graph of a comparison ceramic tile surface, wherein the left side corresponds to example 1 and the right side corresponds to the comparison ceramic tile surface.
FIG. 6 is a graph comparing the surface temperature of the passive refrigeration coating prepared in example 1, the surface temperature of ceramic tiles, and the ambient temperature over time in direct sunlight.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto.
In the embodiment of the invention, the room temperature is 25 ℃, and the mesh number of the screen is 200 meshes.
Example 1
Preparation of passive refrigeration crystal
According to the synthesis of 0.02/11mol of the target product CayMg11-y(HPO3)8(OH)6-xFx(x-3, y-0.5) the mass required for the respective reactants was calculated.
(1) Accurately weighing 4.094g of magnesium acetate tetrahydrate and 0.160g of calcium acetate monohydrate, mixing the two, adding the mixture into a beaker, dissolving the mixture with 20-30 g of water, and stirring the mixture until the mixture is a transparent colorless liquid.
(2) Phosphorous acid solid 1.64g and sodium fluoride solid 0.229g were weighed and dissolved in deionized water to obtain an aqueous phosphorous acid solution having a concentration of 0.082g/ml and an aqueous sodium fluoride solution having a concentration of 0.0114 g/ml.
(3) Mixing all the solutions prepared in the steps (1) and (2) to obtain a mixed solution, adding a magnetic stirrer, adjusting the rotating speed to 300r/min, placing the mixed solution on the magnetic stirrer for continuous stirring, dropwise adding a cyclohexylamine template agent in the stirring process, sealing with a preservative film, wherein the volume ratio of cyclohexylamine to the mixed solution is 1:6.5, continuously stirring for 30min to obtain a uniform emulsion, and quickly transferring the emulsion to a 100mL high-pressure reaction kettle.
(4) The reaction kettle is placed into a forced air drying oven (also called an oven), and the temperature of the drying oven is set to be 200 ℃ for 2000 min. And (3) after the reaction is finished and the reaction product is cooled to room temperature, taking out the reaction product, pouring out the supernatant, washing and filtering the precipitate for multiple times, and then drying the precipitate in an oven at 105 ℃ for 3 hours. And after drying, grinding and sieving to obtain white solid powder with uniform particle size, namely the passive refrigeration crystal, which is referred to as CFM for short.
Preparation of passive refrigeration coating
(1) Adding N-methyl pyrrolidone into polyvinylidene fluoride to obtain a mixture, wherein the mass ratio of the N-methyl pyrrolidone to the polyvinylidene fluoride is 30: 1, placing the mixture in a drying oven at 100 ℃, taking out the mixture every 10min, and stirring the mixture until the binder is completely dissolved until the binder is transparent and bubble-free, so as to obtain transparent viscous liquid;
(2) adding the passive refrigeration crystal into the transparent viscous liquid obtained in the step (1), uniformly stirring, then putting a ball mill with the diameter of 2mm, wherein the material-ball ratio is 6:1, sealing and fixing the ball mill on the ball mill for ball milling for 6 hours, the rotating speed is 360r/min, obtaining ink-like slurry with proper viscosity and luster after the ball milling is finished, and the mass ratio of the passive refrigeration crystal to the polyvinylidene fluoride obtained in the step (1) is 8.5: 1.5;
(3) coating the slurry prepared in the step (2) on the ceramic tile, wherein the coating amount is 0.02g/cm2And drying the wet coating tape in a 60 ℃ blast drying oven for 3 hours to obtain the passive refrigeration coating.
The graphs of the reflectivity and the infrared emissivity of the ultraviolet-visible near-infrared band of the passive refrigeration crystal prepared in example 1 are shown in fig. 3. As can be seen from fig. 3: the reflectivity of the passive refrigeration crystal at an ultraviolet visible near-infrared band (0.2-2.5 um) is 0.98, the emissivity at an atmosphere transparent window (8-13 um) is 0.91, and the selectivity is shown in a long wave range.
FIG. 1 is the XRD refined spectrum of the passive refrigeration crystal prepared in example 1, and FIG. 1 is the sample and Co in ICSD database11(HPO3)8(OH)6Contrast pattern of diffraction. The comparison shows that: the crystal phase and Co of the sample are obtained by the synthesis11(HPO3)8(OH)6The crystal phase of the crystal is highly consistent and belongs to a hexagonal crystal system, and the space group is P63And mc. The matching factors Rwp and Rp obtained by the Rietveld refinement method are 7.54 percent and 6.23 percent, and both values are less than 10 percent, which indicates that the fitting reliability is high. The crystal phase and Co are synthesized by a reasonable fine modification mode11(HPO3)8(OH)6A new substance with highly matched crystal phase is obtained, and a new crystal material with the chemical formula of Ca is obtainedyMg11-y(HPO3)8(OH)6-xFx(x＝3,y＝0.5)。
FIG. 2 is a scanning electron micrograph of the passive refrigeration crystals prepared in example 1 at high magnification. Clearly seen from the photograph: a large number of fine grains are grown on the surface of the single spherical particle, and the size of the grains is about 10 nm. According to Rayleigh scatteringTheory: when the particle size is smaller than 1/10 or less of the wavelength of light, strong rayleigh scattering between the light wave and the particle occurs, the stronger the scattering, the stronger the reflection, and the shorter the wavelength, the stronger the scattering. Therefore, CayMg11-y(HPO3)8(OH)6-xFx(x-3, y-0.5) has a very high uv-vis-nir reflectance, especially in the short wavelength range, which is verified in fig. 3.
FIG. 4 is a Fourier infrared absorption spectrum of the passive refrigeration crystal prepared in example 1, from which it can be seen that: at 1100cm-1On the other hand, the crystal exhibits very strong infrared absorption. A good absorber is a good emitter according to kirchhoff's law. And the strong infrared absorption band is just positioned in an atmospheric transparent window (8-13 um), so that the sample has higher infrared emissivity at the atmospheric window. Furthermore, the substitution of part of the hydroxyl groups in the structure by fluorine results in a lower absorption, i.e. a lower emissivity, of the short-wave infrared part, which is also verified in fig. 3.
The left side of fig. 5 is the real effect diagram of the prepared passive refrigeration coating, and the right side is the comparison ceramic tile surface, and as can be seen from the diagram, the coating surface is white, smooth and has no obvious flaws.
FIG. 6 is a graph comparing the surface temperature of the passive refrigeration coating prepared in example 1, the surface temperature of ceramic tiles, and the ambient temperature over time in direct sunlight.
The testing steps are as follows:
(1) the ceramic tiles coated with passive refrigeration coating of example 1, produced by Jiali ceramics Inc. and having a size of 200x300mm, and ceramic tiles (blank) were laid flat on an insulating foam (foam thickness 5cm) with the coating side facing up.
(2) Temperature probes (a type of K-type thermocouple equipped with a multi-channel temperature measuring instrument) are respectively arranged on the surface of the passive refrigeration coating, the surface of the ceramic tile blank group and the ambient air, wherein the height of an ambient temperature detection point is equal to the height of the surface of the coating.
(3) Starting a multi-channel temperature measuring instrument (model: AT4208, produced by Anbai precision instruments Co., Ltd., Changzhou), recording the temperature of three detection points in real time, wherein the test point is a five-layer high building rooftop (Guangzhou, China, the height is 16m), and the test time is 9:00 am-17: 40pm in the daytime.
By comparison, it can be seen that: the ceramic tile has serious sunlight absorption, and the surface temperature of the ceramic tile is always higher than the ambient temperature under the direct sunlight; the surface temperature of the ceramic tile coated with the passive refrigeration coating is the lowest, the whole testing time period is lower than the environmental temperature, taking 12:00am at noon as an example, the surface temperature of the passive refrigeration coating is lower than the environmental temperature by 5.1 ℃ and lower than the surface temperature of the ceramic tile by 7.3 ℃, and the coating prepared by the method has a good passive refrigeration effect.
Example 2
According to the synthesis of 0.02/11mol of the target product CayMg11-y(HPO3)8(OH)6-xFx(x-2, y-0.5), the mass required for each of the reactants can be calculated from the stoichiometric ratio. The synthesis route of the target product and the preparation method of the passive refrigeration coating are the same as those of the embodiment 1, and are not described again.
The reflectivity of an ultraviolet visible near-infrared band (0.2-2.5 um) of the passive refrigeration crystal prepared in the embodiment 2 is 0.96, the emissivity at an atmosphere transparent window (8-13 um) is 0.91, and certain emission selectivity is shown in an infrared long-wave range.
The refrigeration test results of the passive refrigeration coating prepared in this example are similar to those of example 1, and are not repeated herein.
Example 3
According to the synthesis of 0.02/11mol of the target product CayMg11-y(HPO3)8(OH)6-xFx(x-3, y-1), the mass required for each of the reactants can be calculated from the stoichiometric ratio. The synthesis route of the target product and the preparation method of the passive refrigeration coating are the same as those of the embodiment 1, and are not described again.
The reflectivity of an ultraviolet visible near-infrared band (0.2-2.5 um) of the passive refrigeration crystal prepared in the embodiment 3 is 0.97, the emissivity at an atmosphere transparent window (8-13 um) is 0.90, and a certain emission selectivity is shown in an infrared long-wave range.
The refrigeration test results of the passive refrigeration coating prepared in this example are similar to those of example 1, and are not repeated herein.
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 passive refrigeration crystal is characterized in that the chemical expression of the passive refrigeration crystal is CayMg11-y(HPO3)8(OH)6-xFx，1≤x≤6，0.3≤y≤1。
2. A method for preparing a passive refrigeration crystal of claim 1 comprising the steps of:
(1) according to the target product CayMg11-y(HPO3)8(OH)6-xFxWeighing magnesium acetate tetrahydrate and calcium acetate monohydrate by a chemical formula that x is more than or equal to 1 and less than or equal to 6 and y is more than or equal to 0.3 and less than or equal to 1, adding water to dissolve, and stirring until a transparent colorless solution is obtained;
(2) weighing sodium fluoride and phosphorous acid according to a target product chemical formula, and respectively dissolving the sodium fluoride and the phosphorous acid in water to prepare a sodium fluoride aqueous solution and a phosphorous acid aqueous solution;
(3) mixing all the solutions prepared in the steps (1) and (2) to obtain a mixed solution, adding cyclohexylamine under the stirring condition, continuously stirring to obtain an emulsion, and transferring the emulsion into a high-pressure reaction kettle for hydrothermal reaction;
(4) and (3) after the reaction in the step (3) is finished and the reaction product is cooled to room temperature, carrying out solid-liquid separation on the reaction product, washing and filtering the obtained solid, drying, grinding and sieving to obtain white powder, namely the passive refrigeration crystal.
3. The preparation method of the passive refrigeration crystal as claimed in claim 2, wherein the ratio of the addition amount of the water in the step (1) to the total mass of the magnesium acetate tetrahydrate and the calcium acetate monohydrate is 4-5: 1;
the concentration of the sodium fluoride aqueous solution in the step (2) is 0.0069 g/ml-0.0229 g/ml, and the concentration of the phosphorous acid aqueous solution is 0.060 g/ml-0.082 g/ml;
the volume ratio of the cyclohexylamine to the mixed solution in the step (3) is 1: 6-7.
4. The preparation method of the passive refrigeration crystal according to claim 2 or 3, wherein the time for continuing stirring in the step (3) is 30-40 min;
the temperature of the hydrothermal reaction in the step (3) is 160-220 ℃, and the time of the hydrothermal reaction is 1400-2200 min;
and (4) drying at the temperature of 80-110 ℃ for 2-5 h.
5. A method for preparing a passive refrigeration coating by using the passive refrigeration crystal as claimed in claim 1, which comprises the following steps:
(1) adding N-methyl pyrrolidone into the binder to obtain a mixture, heating the mixture, taking out every 10-15 min, and stirring until the binder is completely dissolved to be transparent and bubble-free to obtain transparent viscous liquid;
(2) adding the passive refrigeration crystal into the transparent viscous liquid obtained in the step (2), uniformly stirring, putting a ball mill into the transparent viscous liquid, fixing the ball mill on a ball mill, and performing ball milling for 6-8 hours to obtain slurry after the ball milling is finished;
(3) and (3) coating the slurry prepared in the step (2) on a substrate to obtain a wet coating tape, and drying the wet coating tape to obtain the passive refrigeration coating.
6. The method for preparing the passive refrigeration coating according to claim 5, wherein the mass ratio of the N-methylpyrrolidone to the binder in the step (1) is 26-33: 1;
the heating in the step (1) is specifically as follows: heating in an oven at the temperature of 80-110 ℃;
the mass ratio of the passive refrigeration crystal in the step (2) to the binder in the step (1) is 8-9: 2-1.
7. The method for preparing a passive refrigeration coating according to claim 5 or 6, wherein the binder of step (1) is polyvinylidene fluoride;
the diameter of the ball mill in the step (2) is 1-3 mm, and the material-ball ratio of the ball mill is 4-6: 1;
and (3) the rotating speed of the ball mill in the step (2) is 300-400 r/min.
8. The method for preparing a passive refrigeration coating according to claim 5 or 6, wherein the substrate of the step (3) is one of aluminum foil, ceramic tile and plastic plate;
the coating amount in the step (3) is 0.02-0.1 g/cm2；
And (4) drying at the temperature of 50-70 ℃ for 2-5 h.
9. The passive refrigeration coating prepared by the method for preparing the passive refrigeration coating according to any one of claims 5 to 8.
10. Use of the passive refrigeration coating according to claim 9 for the production of a cooling coating material for the outer wall surface of a building.
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| CN108193268A (en) * | 2017-12-15 | 2018-06-22 | 华南理工大学 | A kind of crystalline material and its preparation method and application |
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| CN106752526A (en) * | 2016-12-23 | 2017-05-31 | 沈阳化工研究院有限公司 | A kind of aqueous light reflection industrial heat preservation coating and preparation method thereof |
| CN108193268A (en) * | 2017-12-15 | 2018-06-22 | 华南理工大学 | A kind of crystalline material and its preparation method and application |
| CN108795108A (en) * | 2018-05-07 | 2018-11-13 | 华南理工大学 | A kind of radiation refrigeration coating and preparation method thereof, test device |
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