CN120158203A

CN120158203A - A silver beetle-like multi-level micro-nano structure photon-heat synergistic radiation refrigeration coating and its preparation method

Info

Publication number: CN120158203A
Application number: CN202510312853.7A
Authority: CN
Inventors: 钟正祥; 牛冬寒; 徐洪波; 曹荣耀; 刘江峰; 王文芳; 赵婷玉
Original assignee: Harbin Institute of Technology Shenzhen
Current assignee: Harbin Institute of Technology Shenzhen
Priority date: 2025-03-17
Filing date: 2025-03-17
Publication date: 2025-06-17
Anticipated expiration: 2045-03-17
Also published as: CN120158203B

Abstract

The present invention discloses a silver beetle-like multi-level micro-nano structure photon-heat synergistic radiation refrigeration coating and a preparation method thereof, wherein the coating comprises the following components: 10 to 50 parts of PEEK, 50 to 90 parts of water glass, 1 to 4 parts of surfactant, 1 to 6 parts of dispersant, 0.1 to 3 parts of defoamer, 1 to 3 parts of thickener, 1 to 3 parts of light stabilizer, 1 to 8 parts of film-forming agent, and 1 to 3 parts of leveling agent. The present invention achieves a performance breakthrough of the radiation refrigeration coating through a bionic multi-level structure (nanometer-micrometer cross-scale), a PEEK-silicate composite system, and photon-heat synergistic management, and has both efficient cooling, strong mechanical properties, and long life, filling the technical gap of organic polymer materials in the field of radiation refrigeration. The silver beetle-like multi-level micro-nano structure photon-heat synergistic radiation refrigeration coating of the present invention can still maintain good adhesion within the range of 300 to 800 ° C, and has the prospect of being able to be applied under high temperature conditions.

Description

Silver beetle-like multi-stage micro-nano structure photon-heat synergistic radiation refrigeration coating and preparation method thereof

Technical Field

The invention relates to a radiation refrigeration material, in particular to a silver beetle-imitated multistage micro-nano structure photon-heat synergistic radiation refrigeration coating and a preparation method thereof.

Background

Global climate warming causes energy problems to be continuously focused, and radiation refrigeration is used as a refrigeration technology with zero energy consumption and zero pollution when the climate is deteriorated due to the fact that the climate warming and the carbon emission are increased, so that powerful assistance is provided for the climate warming problem.

In recent years, along with the continuous deep exploration of nature, biomimetic technology is rapidly developed and widely applied, wherein the surface of the silver beetles in the tropical desert is provided with a multi-stage micro-nano structure, and the structures can realize the efficient reflection of solar radiation through the photonic crystal effect, so that the heat absorption is reduced. The surface structure of the silver beetles can realize high-efficiency heat radiation in a middle infrared band, so that heat is dissipated to the outer space in an electromagnetic wave mode. The synergistic effect of the multilevel structure enables the silver beetles to survive in tropical deserts.

Disclosure of Invention

The invention aims to provide a silver beetle-imitated multistage micro-nano structure photon-heat synergistic radiation refrigeration coating and a preparation method thereof. The invention prepares the silver-simulated beetle multistage micro-nano structure photon-heat synergistic radiation refrigeration coating based on nanometer waxy bulges and a micron porous substrate on the desert-simulated silver beetle shell by combining silicate resin with PEEK. The PEEK particles in the coating are orderly arranged through self-assembly in the curing process, and the gaps among the particles form nanometer holes, so that PEEK particles are aggregated in a water glass network structure to form micro-nanometer protrusions. The multilevel structure of the nanometer holes and the micrometer protrusions realizes high-efficiency visible light reflection and middle infrared emission through photonic crystal effect and thermal radiation regulation and control. The coating can realize cooling through the synergistic effect of photon scattering (sunlight reflection) and thermal radiation (infrared emission), and the cross-scale energy management strategy is highlighted. In addition, the coating has good adhesive force in a high-temperature environment, and the coating can still function normally in the high-temperature environment.

The invention aims at realizing the following technical scheme:

The multi-stage micro-nano structured photon-heat synergistic radiation refrigeration coating for the imitation silver beetles comprises, by mass, 10-50 parts of PEEK, 50-90 parts of water glass, 1-4 parts of surfactant, 1-6 parts of dispersing agent, 0.1-3 parts of defoaming agent, 1-3 parts of thickening agent, 1-3 parts of light stabilizer, 1-8 parts of film forming agent and 1-3 parts of leveling agent, wherein:

The water glass is prepared by hydrolyzing silicate powder and distilled water at a high temperature, wherein the preparation condition is that the silicate powder and the distilled water are hydrolyzed for 60-200 min together with an auxiliary agent at a temperature of 40-70 ℃, and the mass ratio of the silicate powder to the distilled water is 1:1-2;

The surfactant is one or more of TEOS (tetraethyl orthosilicate), CTAB (cetyltrimethylammonium bromide), DTAB (dodecyltrimethylammonium bromide), AEO (fatty alcohol polyoxyethylene ether) and SDS (sodium dodecyl sulfate);

the dispersing agent is PEG dispersing agent, preferably one or more of PEG-400, PEG-600, PEG-6000 and PEG-8000, and the specific preparation method comprises mixing one or more of PEG-400, PEG-600, PEG-6000 and PEG-8000 with deionized water according to a mass ratio of 1:1-2, stirring at room temperature for 5min, and performing ultrasonic dispersion for 5min to obtain the PEG dispersing agent;

The film forming agent is one or more of ethylene glycol, alcohol ester-12 and propylene glycol butyl ether;

the defoaming agent is organosilicon 817 defoaming agent;

the leveling agent is Zhongke hongtai K-400;

The thickener is one or more of hydroxyethyl cellulose, carbomer 930 and nano SiO ₂, and the specific preparation method comprises the steps of adding 1-3 parts of one or more of hydroxyethyl cellulose, carbomer 930 and nano SiO ₂ into 100 parts of deionized water in batches, stirring for 30min at 50 ℃, stirring for 10min at 55 ℃, stirring for 10min at 60 ℃, and finally removing bubbles by ultrasonic for 15min to obtain the thickener;

The light stabilizer is one or more of iridescent UV-106, rianlon/Li Anlong UV-622.

A preparation method of a silver beetle-like multi-stage micro-nano structure photon-heat synergistic radiation refrigeration coating comprises the following steps:

Firstly, adding a dispersing agent and a surfactant into water glass by using a high-speed dispersing machine, and stirring for 3-5 min at a rotating speed of 400-600 r/min;

Step two, adding a thickening agent and a defoaming agent, and continuously stirring for 3-5 min at a rotating speed of 400-600 r/min;

Step three, the rotating speed of the high-speed dispersing machine is increased to 600-800 r/min, PEEK powder is slowly added, the rotating speed is continuously increased to 1000-1500 r/min in the adding process, and stirring is carried out for 30-60 min;

step four, reducing the rotating speed of the high-speed dispersing machine to 600-1000 r/min, adding a film forming agent, and stirring for 3-8 min;

Adding a light stabilizer, stirring for 3-8 min, and then adding a leveling agent, stirring for 8-15 min to obtain the radiation refrigeration coating;

And step six, spraying compressed air of 0.6-1.0 MPa for 1-5 times under the conditions that the ambient temperature is 15-30 ℃ and the relative humidity of air is lower than 85%, standing and curing at room temperature after spraying is finished, and thus obtaining the photon-heat synergistic radiation refrigeration coating.

Compared with the prior art, the invention has the following advantages:

1. The silver-simulated beetle multistage micro-nano structure photon-heat synergistic radiation refrigeration coating realizes the performance breakthrough of the radiation refrigeration coating through the bionic multistage structure (nano-micron trans-scale), PEEK-silicate composite system and photon-heat synergistic management, has high-efficiency cooling, strong mechanical property and long service life, and fills the technical blank of the organic polymer material in the radiation refrigeration field.

2. The preparation process of the silver-simulated beetle multistage micro-nano structured photon-heat synergistic radiation refrigeration coating is simple and easy to implement, and the process of room temperature direct curing after spraying is adopted, so that the utilization space of the coating is greatly improved, and the silver-simulated beetle multistage micro-nano structured photon-heat synergistic radiation refrigeration coating can be applied to various fields of aviation thermal control, building energy-saving materials, solar photoelectric photo-thermal systems, power equipment and the like.

3. The silver-simulated beetle multistage micro-nano structured photon-heat synergistic radiation refrigeration coating breaks through the limitation of the traditional refrigeration technology in the aspect of advancement, has multifunctionality and sustainability, and accords with the development concept of green low carbon.

4. The silver-simulated beetle multistage micro-nano structured photon-heat synergistic radiation refrigeration coating can be prepared into a strong infrared selective radiation refrigeration function coating on the surface of a metal, ceramic and other high-reflection base material in a spraying mode and the like, has the advantages of zero energy consumption, temperature reduction and refrigeration, and saves a large amount of energy consumption.

5. The silver-simulated beetle multistage micro-nano structured photon-heat synergistic radiation refrigeration coating can still keep good cohesiveness in the temperature range of 300-800 ℃, and has the prospect of being applied under the high-temperature condition.

Drawings

Fig. 1 is an apparent physical diagram of the silver beetle-like multi-stage micro-nano structure photon-heat synergistic radiation refrigeration coating provided in example 1 on the surfaces of different materials.

Fig. 2 is an apparent physical diagram of the silver-simulated beetle multi-stage micro-nano structure photon-heat synergistic radiation refrigeration coating provided in example 1 after being ablated for 30s on the surfaces of different materials by using a card type spray gun.

Fig. 3 is an SEM image (20000 times) of the multi-stage micro-nano structured photon-heat synergistic radiation refrigeration coating of the silver-imitated beetles provided in example 4.

Fig. 4 is an SEM image (10000 times) of the multi-stage micro-nano structured photon-heat synergistic radiation refrigeration coating of the silver-imitated beetles provided in example 4.

Fig. 5 is a photograph of a nano waxy bump and a micro porous substrate on a silver beetle shell.

Fig. 6 is an infrared emission spectrum chart of the silver beetle-like multi-stage micro-nano structure photon-heat synergistic radiation refrigeration coating provided in example 1 in a wave band of 2.5-16 μm.

Fig. 7 is an infrared emission spectrum chart of the silver beetle-like multi-stage micro-nano structure photon-heat synergistic radiation refrigeration coating provided in example 2 in a wave band of 2.5-16 μm.

Fig. 8 is an infrared emission spectrum chart of the silver beetle-like multi-stage micro-nano structure photon-heat synergistic radiation refrigeration coating provided in example 3 in a wave band of 2.5-16 μm.

Fig. 9 is an infrared emission spectrum chart of the silver beetle-like multi-stage micro-nano structure photon-heat synergistic radiation refrigeration coating provided in example 4 in a wave band of 2.5-16 μm.

Detailed Description

The following description of the present invention is provided with reference to the accompanying drawings, but is not limited to the following description, and any modifications or equivalent substitutions of the present invention should be included in the scope of the present invention without departing from the spirit and scope of the present invention.

The amounts of the raw materials used in the following examples were all parts by mass.

Example 1

The embodiment provides a preparation method of a silver beetle-imitated multistage micro-nano structure photon-heat synergistic radiation refrigeration coating, which comprises the following steps:

Adding sodium silicate and distilled water into a single-neck flask according to a mass ratio of 1:1.5, adding a reaction auxiliary agent, hydrolyzing at 60 ℃ for 60min, hydrolyzing at 70 ℃ to a proper viscosity, and cooling to obtain the water glass. 2 parts of PEG-6000 dispersant and 1 part of DTAB surfactant are added into 90 parts of water glass by using a high-speed dispersing machine, and stirred at a rotating speed of 500r/min for 3min for dissolution.

And step two, adding 1 part of hydroxyethyl cellulose thickener and 0.3 part of 817 defoamer, and continuously stirring at a rotation speed of 500r/min for 5min for dissolution.

And thirdly, increasing the rotating speed of the high-speed dispersing machine to 700r/min, slowly adding 15 parts of PEEK powder, continuously increasing the rotating speed to 1250r/min in the adding process, and continuously stirring the dispersion system for 40min to realize uniform dispersion.

And fourthly, reducing the rotating speed of the high-speed dispersing machine to 800r/min, and then adding 2 parts of alcohol ester-12 film forming agent, and continuously stirring for 5min to realize uniform dispersion.

And fifthly, adding 3 parts of UV-106 light stabilizer, continuously stirring for 5min to realize uniform dispersion, and adding 1 part of leveling agent K-400, and stirring for 10min to realize uniform dispersion to obtain the photon-heat synergistic radiation refrigeration coating.

And step six, adopting compressed air with the pressure of 0.8MPa to spray for 2 times under the conditions that the ambient temperature is 15-30 ℃ and the relative humidity of air is lower than 85%, standing and curing at room temperature after the spraying is finished, and obtaining the photon-heat synergistic radiation refrigeration coating. The resulting coating performance index is shown in table 1.

TABLE 1

Index (I)	Numerical value	Test index
			Reflectivity of	0.94	ASTM/C1549-09(2014)
Infrared emissivity of radiation	0.94	GB/T6040-2019
			High temperature resistance	≤800	HG/T4565-2013
Refrigerating performance	5~10°C	GB/T4893.7-1985

According to the graph 1, the coating can be perfectly coated on the ceramic sheet and the metal sheet, the integrity and the adhesive force of the coating are good, according to the graph 2, the coating can be perfectly adhered on the ceramic sheet and the metal sheet after being ablated for 30 seconds by the clip type spray gun, the adhesive force is good, according to the graph 6, the emissivity of the coating in the wave band of an air window (8-14 mu m) is 93.62% on average, which is far superior to that of the traditional coating (85%), and the performance is excellent.

Example 2

And fourthly, reducing the rotating speed of the high-speed dispersing machine to 800r/min, and then adding 2 parts of glycol film forming agent and continuously stirring for 5min to realize uniform dispersion.

And step six, adopting compressed air with the pressure of 0.8MPa to spray for 2 times under the conditions that the ambient temperature is 15-30 ℃ and the relative humidity of air is lower than 85%, standing and curing at room temperature after the spraying is finished, and obtaining the photon-heat synergistic radiation refrigeration coating. The resulting coating performance index is shown in table 2.

TABLE 2

Index (I)	Numerical value	Test index
			Reflectivity of	0.95	ASTM/C1549-09(2014)
Infrared emissivity of radiation	0.94	GB/T6040-2019
			High temperature resistance	≤800	HG/T4565-2013
Refrigerating performance	5~10°C	GB/T4893.7-1985

As shown in FIG. 7, the emissivity of the coating in the air window (8-14 μm) wave band is on average 94.53%, which is far superior to that of the traditional coating (85%), and the performance is excellent.

Example 3

Adding sodium silicate and distilled water into a single-neck flask according to a mass ratio of 1:1.5, adding a reaction auxiliary agent, hydrolyzing at 60 ℃ for 60min, hydrolyzing at 70 ℃ to a proper viscosity, and cooling to obtain the water glass. 2 parts of PEG-6000 dispersant and 1 part of CTAB surfactant are added into 90 parts of water glass by using a high-speed dispersing machine, and stirred at a rotating speed of 500r/min for 3min for dissolution.

And step six, adopting compressed air with the pressure of 0.8MPa to spray for 2 times under the conditions that the ambient temperature is 15-30 ℃ and the relative humidity of air is lower than 85%, standing and curing at room temperature after the spraying is finished, and obtaining the photon-heat synergistic radiation refrigeration coating. The resulting coating performance index is shown in table 3.

TABLE 3 Table 3

As shown in FIG. 8, the emissivity of the coating in the band of the atmospheric window (8-14 μm) is 93.62% on average, which is far superior to that of the traditional coating (85%).

Example 4

And step six, adopting compressed air with the pressure of 0.8MPa to spray for 2 times under the conditions that the ambient temperature is 15-30 ℃ and the relative humidity of air is lower than 85%, standing and curing at room temperature after the spraying is finished, and obtaining the photon-heat synergistic radiation refrigeration coating. The resulting coating performance index is shown in table 4.

TABLE 4 Table 4

As shown in FIG. 9, the emissivity of the coating in the air window (8-14 μm) wave band is on average 94.31%, which is far superior to that of the traditional coating (85%). As can be seen from fig. 3, fig. 4 and fig. 5, the microstructure on the coating layer shows a dense arrangement of concave-convex units, which are highly similar to the micro scale and nano hole composite structure of the shell of the silver beetle, both can increase the surface area and destroy the surface smoothness, enhance the radiation emission efficiency of the mid-infrared band (8-14 μm), scatter the sunlight of the short-wave band, and reduce the heat absorption.

Example 5

Adding potassium silicate and distilled water into a single-neck flask according to a mass ratio of 1:1.5, adding a reaction auxiliary agent, hydrolyzing at 60 ℃ for 60min, hydrolyzing at 70 ℃ to a proper viscosity, and cooling to obtain the water glass. 3.5 parts of PEG-8000 dispersant and 2 parts of TEOS surfactant were added to 60 parts of water glass by using a high-speed disperser and stirred at 500r/min for 3min for dissolution.

And step two, adding 2 parts of nano SiO ₂ thickener and 1.5 parts of 817 defoamer, and continuously stirring at a rotating speed of 500r/min for 5min for dissolution.

And thirdly, increasing the rotating speed of the high-speed dispersing machine to 700r/min, slowly adding 45 parts of PEEK powder, continuously increasing the rotating speed to 1250r/min in the adding process, and continuously stirring the dispersion system for 40min to realize uniform dispersion.

And fourthly, reducing the rotating speed of the high-speed dispersing machine to 800r/min, and then adding 5 parts of the propylene glycol butyl ether film forming agent, and continuously stirring for 5min to realize uniform dispersion.

And fifthly, continuously adding 1 part of UV-106 light stabilizer, stirring for 5min to uniformly disperse, and adding 3 parts of leveling agent K-400, stirring for 10min to uniformly disperse to obtain the photon-heat synergistic radiation refrigeration coating.

And step six, adopting compressed air with the pressure of 0.8MPa to spray for 2 times under the conditions that the ambient temperature is 15-30 ℃ and the relative humidity of air is lower than 85%, standing and curing at room temperature after the spraying is finished, and obtaining the photon-heat synergistic radiation refrigeration coating.

Example 6

Adding calcium silicate and distilled water into a single-neck flask according to a mass ratio of 1:1.5, adding a reaction auxiliary agent, hydrolyzing at 60 ℃ for 60min, hydrolyzing at 70 ℃ to a proper viscosity, and cooling to obtain the water glass. 5 parts of PEG-400 dispersant and 3 parts of AEO surfactant were added to 75 parts of water glass by means of a high-speed disperser and stirred at 500r/min for 3min for dissolution.

Step two, adding 3 parts of Carbomer 930 thickener and 2.5 parts of 817 defoamer, and stirring at 500r/min for 5min for dissolution.

Step three, the rotating speed of the high-speed dispersing machine is increased to 700r/min, 30 parts of PEEK powder is slowly added, the rotating speed is continuously increased to 1250r/min in the adding process, and the dispersion system is continuously stirred for 40min to realize uniform dispersion.

And fourthly, reducing the rotating speed of the high-speed dispersing machine to 800r/min, and then adding 7 parts of alcohol ester-12 film forming agent, and continuously stirring for 5min to realize uniform dispersion.

And fifthly, adding 2 parts of UV-622 light stabilizer, continuously stirring for 5min to realize uniform dispersion, and adding 2 parts of leveling agent K-400, and stirring for 10min to realize uniform dispersion to obtain the photon-heat synergistic radiation refrigeration coating.

Claims

1. The multi-stage micro-nano structured photon-heat synergistic radiation refrigeration coating for the imitation silver beetles is characterized by comprising, by mass, 10-50 parts of PEEK, 50-90 parts of water glass, 1-4 parts of a surfactant, 1-6 parts of a dispersing agent, 0.1-3 parts of a defoaming agent, 1-3 parts of a thickening agent, 1-3 parts of a light stabilizer, 1-8 parts of a film forming agent and 1-3 parts of a leveling agent.

2. The silver beetle-like multi-stage micro-nano structured photon-heat synergistic radiation refrigeration coating is characterized in that the water glass is prepared by hydrolyzing silicate powder and distilled water at a high temperature, the hydrolysis temperature is 40-70 ℃, the hydrolysis time is 60-200 min, the mass ratio of the silicate powder to the distilled water is 1:1-2, and the silicate is one or more of sodium silicate, potassium silicate, calcium silicate, lithium silicate and ammonium silicate.

3. The multi-stage micro-nano structured photon-heat synergistic radiation refrigeration coating for imitation silver beetles according to claim 1, wherein the surfactant is one or more of TEOS, CTAB, DTAB, AEO, SDS.

4. The silver beetle-like multi-stage micro-nano structured photon-heat synergistic radiation refrigeration coating according to claim 1, wherein the dispersing agent is a PEG dispersing agent.

5. The multi-stage micro-nano structured photon-heat synergistic radiation refrigeration coating for imitating silver beetles according to claim 4, wherein the PEG dispersing agent is one or more of PEG-400, PEG-600, PEG-6000 and PEG-8000.

6. The silver beetle-like multi-stage micro-nano structured photon-heat synergistic radiation refrigeration coating according to claim 1, wherein the film forming agent is one or more of ethylene glycol, alcohol ester-12 and propylene glycol butyl ether.

7. The silver beetle-like multi-stage micro-nano structured photon-heat synergistic radiation refrigeration coating according to claim 1, wherein the defoamer is an organosilicon 817 defoamer and the flatting agent is K-400.

8. The multi-stage micro-nano structured photon-heat synergistic radiation refrigeration coating for imitating silver beetles according to claim 1, wherein the thickener is one or more of hydroxyethyl cellulose, carbomer 930 and nano SiO ₂.

9. The silver beetle-like multi-stage micro-nano structured photon-heat synergistic radiation refrigeration coating according to claim 1, wherein the light stabilizer is one or two of UV-106 and UV-622.

10. A method for preparing the silver beetle-like multi-stage micro-nano structured photon-heat synergistic radiation refrigeration coating according to any one of claims 1 to 9, which is characterized by comprising the following steps: