阅读说明：本技术 一种彩色太阳能吸收涂层及其制备方法 (Colored solar energy absorbing coating and preparation method thereof ) 是由 高祥虎 刘刚 于 2019-10-11 设计创作，主要内容包括：本发明涉及一种彩色太阳能吸收涂层,该涂层由抛光不锈钢片构成的吸热体基底、金属Al构成的红外反射层、MoNbHfZrTiN构成的主吸收层、MoNbHfZrTiNO构成的次吸收层和SiO<Sub>2</Sub>构成的减反射层组成。主吸收层是指采用等摩尔比的金属Mo、Nb、Hf、Zr、Ti通过熔炼法制备的MoNbHfZrTi高熵合金的氮化物；次吸收层是指采用等摩尔比的金属Mo、Nb、Hf、Zr、Ti通过熔炼法制备的MoNbHfZrTi高熵合金的氮氧化物。本发明还公开了该涂层的制备方法。本发明制备工艺简单、成本较低,所制备的彩色涂层在大气质量因子AM1.5条件下,吸收率≥0.91,发射率≤0.12,同时具有丰富的色彩,在太阳能热利用与建筑一体化领域具有广泛的实用价值和应用前景。(The invention relates to a colorful solar energy absorbing coating, which comprises a heat absorbing body substrate formed by polished stainless steel sheets, an infrared reflecting layer formed by metal Al, a main absorbing layer formed by MoNbHfZrTiN, a secondary absorbing layer formed by MoNbHfZrTiNO and SiO 2 And the formed antireflection layer. The main absorption layer is a nitride of MoNbHfZrTi high-entropy alloy prepared by adopting metals Mo, Nb, Hf, Zr and Ti with equal molar ratio through a smelting method; the secondary absorption layer is a nitrogen oxide of MoNbHfZrTi high-entropy alloy prepared by adopting metals Mo, Nb, Hf, Zr and Ti with equal molar ratio through a smelting method. The invention also discloses the coatingThe preparation method of (1). The preparation method is simple in preparation process and low in cost, and the prepared color coating has the advantages that the absorptivity is more than or equal to 0.91 and the emissivity is less than or equal to 0.12 under the condition of an atmospheric quality factor AM1.5, has rich colors, and has wide practical value and application prospect in the field of solar heat utilization and building integration.)

1. A colored solar absorptive coating characterized by: the coating comprises a heat absorber substrate made of polished stainless steel sheets, an infrared reflecting layer made of metal Al, a main absorbing layer made of MoNbHfZrTiN, a secondary absorbing layer made of MoNbHfZrTiNO and SiO₂The formed antireflection layer; the main absorption layer is a nitride of MoNbHfZrTi high-entropy alloy prepared by adopting metals Mo, Nb, Hf, Zr and Ti with equal molar ratio through a smelting method; the secondary absorption layer is a nitrogen oxide of MoNbHfZrTi high-entropy alloy prepared by adopting metals Mo, Nb, Hf, Zr and Ti with equal molar ratio through a smelting method.

2. The colored solar absorber coating of claim 1, wherein the absorber substrate has a roughness value of 0.5 ~ 3 nm.

3. The colored solar absorptive coating of claim 1, wherein the infrared reflecting layer has a thickness of 20 ~ 50 nm.

4. The colored solar absorbing coating as claimed in claim 1, wherein the thickness of the primary absorbing layer is 30 ~ 60 nm.

5. The colored solar absorbing coating of claim 1, wherein the sub-absorber layer has a thickness of 30 ~ 70 nm.

6. The colored solar absorptive coating of claim 1, wherein the anti-reflective layer has a thickness of 60 ~ 100 nm.

7. A colored solar absorptive coating according to claim 1 wherein: the MoNbHfZrTi high-entropy alloy is prepared by putting Mo, Nb, Hf, Zr and Ti with equal molar ratio into a graphite crucible, then putting the graphite crucible into a vacuum smelting furnace, and vacuumizing to 5 x 10^-6~8×10^-6Torr, melting at 2650 ~ 3000 deg.C, pouring intoMolding, cutting and polishing to obtain the product.

8. A method of making a colored solar absorptive coating as claimed in claim 1, comprising the steps of:

⑴ treating the heat sink substrate;

⑵ preparing infrared reflecting layer on the heat absorber substrate, wherein the infrared reflecting layer is prepared by using Al with purity of 99.99% as magnetron sputtering target material and adopting DC magnetron sputtering method in argon atmosphere, and the working parameters are that the vacuum chamber is pre-pumped to be vacuum to 3.0 × 10^-6~7.0×10^-6Torr, the sputtering power density of the Al target material is 3 ~ 7W/m^-2The air inflow of argon during sputtering deposition is 20 ~ 50sccm, and the thickness of deposited Al is 20 ~ 50 nm;

⑶ preparing a main absorption layer on the infrared reflection layer, wherein the main absorption layer is prepared by taking MoNbHfZrTi high-entropy alloy with the purity of 99.9% as a sputtering target and adopting a radio frequency reaction magnetron sputtering method in an argon and nitrogen atmosphere, and the working parameter is that the sputtering power density of the MoNbHfZrTi target is 2 ~ 6W/cm^-2The air inflow of argon during sputtering deposition is 20 ~ 50sccm, the air inflow of nitrogen is 0.5 ~ 5sccm, and the thickness of the deposited MoNbHfZrTiN is 30 ~ 60 nm;

⑷ preparing a secondary absorption layer on the main absorption layer, wherein the secondary absorption layer is prepared by taking MoNbHfZrTi high-entropy alloy with the purity of 99.9% as a sputtering target and adopting a radio frequency reaction magnetron sputtering method in the atmosphere of argon, nitrogen and oxygen, and the working parameter is that the sputtering power density of the MoNbHfZrTi target is 2 ~ 6W/cm^-2The air inflow of argon during sputtering deposition is 20 ~ 50sccm, the air inflow of nitrogen is 5 ~ 12sccm, the air inflow of oxygen is 2 ~ 6sccm, and the thickness of the deposited MoNbHfZrTiNO is 30 ~ 70 nm;

⑸ preparing an anti-reflective layer on the secondary absorbing layer with SiO having a purity of 99.99%₂The target material is prepared by adopting a radio frequency magnetron sputtering method in an argon atmosphere; wherein the working parameters are as follows: SiO 2₂The sputtering power density of the target is 5 ~ 10W/cm^-2The air inflow of the argon gas during the sputtering deposition is 20 ~ 50sccm, and the deposition thickness is 60 ~ 100 nm.

9. The method of claim 8, wherein the step ⑴ of processing the substrate of the heat absorbing body comprises removing impurities attached to the surface of the polished stainless steel sheet, ultrasonic cleaning in acetone and absolute ethanol for 10 ~ 20 minutes, and storing by nitrogen drying.

Technical Field

The invention relates to the technical field of solar energy absorbing coatings, in particular to a colored solar energy absorbing coating and a preparation method thereof.

Background

Sun of the sunThe solar-thermal utilization is the most direct and effective way for human to utilize solar energy. The solar spectrum selective absorption coating is a core material for realizing photothermal conversion, and generally requires high absorptivity and low emissivity. In recent years, transition metal nitride and oxynitride systems have been extensively studied in the construction of solar energy absorbing coating film systems, such as: WSiAlN_x/WSiAlO_yN_x/SiAlO_x，WAlN/WAlON/Al₂O₃，ZrSiN/ZrSiON/SiO₂，NbMoN/NbMoON/SiO₂，Cr/CrN_x/CrN_xO_y/SiO₂，TiAlSiN/TiAlSiON/SiO₂And CrN/AlCrNO/AlCrO. With the development of solar building integration, the colored solar energy absorbing coating layer is widely concerned. However, the current research on the construction of solar energy absorbing coatings using transition metal nitride and oxynitride systems focuses more on the high temperature performance and little research on the color thereof.

The high-entropy alloy is one of the important discoveries in the field of metal materials in recent years. Compared with the traditional metal material, which mainly uses one element (such as titanium alloy and steel), the high-entropy alloy generally comprises at least four alloy elements with similar proportions, and the unique alloy design concept can embody the collective effect of various elements, often has a novel structure and excellent comprehensive performance, and has been widely concerned in key fields of aerospace, ships, nuclear energy, automobiles, electronics and the like. As a brand new alloy, high-entropy alloy has been widely paid attention to due to its excellent properties such as high strength, high wear resistance, high corrosion resistance and high temperature softening resistance. However, no report is found on the research of applying the high-entropy alloy to the colored solar energy absorption coating.

Disclosure of Invention

The invention aims to provide a colored solar energy absorbing coating.

The invention also provides a preparation method of the colored solar energy absorption coating.

In order to solve the above problems, the present invention provides a color solar energy absorbing coating, which is characterized in that: the coating is formed by polishingA heat absorber substrate made of light stainless steel sheet, an infrared reflecting layer made of metal Al, a main absorbing layer made of MoNbHfZrTiN, a secondary absorbing layer made of MoNbHfZrTiNO and SiO₂The formed antireflection layer; the main absorption layer is a nitride of MoNbHfZrTi high-entropy alloy prepared by adopting metals Mo, Nb, Hf, Zr and Ti with equal molar ratio through a smelting method; the secondary absorption layer is a nitrogen oxide of MoNbHfZrTi high-entropy alloy prepared by adopting metals Mo, Nb, Hf, Zr and Ti with equal molar ratio through a smelting method.

The roughness value of the absorber substrate was 0.5 ~ 3 nm.

The thickness of the infrared reflecting layer is 20 ~ 50 nm.

The thickness of the main absorption layer is 30 ~ 60 nm.

The thickness of the secondary absorption layer is 30 ~ 70 nm.

The thickness of the antireflection layer is 60 ~ 100 nm.

The MoNbHfZrTi high-entropy alloy is prepared by putting Mo, Nb, Hf, Zr and Ti with equal molar ratio into a graphite crucible, then putting the graphite crucible into a vacuum smelting furnace, and vacuumizing to 5 x 10^-6~8×10^-6And (4) smelting at 2650 ~ 3000 ℃ by using a Torr, pouring and molding, and cutting and polishing to obtain the material.

The preparation method of the colored solar energy absorption coating comprises the following steps:

⑴ treating the heat sink substrate;

⑵ preparing infrared reflecting layer on the heat absorber substrate, wherein the infrared reflecting layer is prepared by using Al with purity of 99.99% as magnetron sputtering target material and adopting DC magnetron sputtering method in argon atmosphere, and the working parameters are that the vacuum chamber is pre-pumped to be vacuum to 3.0 × 10^-6~7.0×10^-6Torr, the sputtering power density of the Al target material is 3 ~ 7W/m^-2The air inflow of argon during sputtering deposition is 20 ~ 50sccm, and the thickness of deposited Al is 20 ~ 50 nm;

⑶ preparing a main absorption layer on the infrared reflection layer, wherein the main absorption layer is prepared by taking MoNbHfZrTi high-entropy alloy with the purity of 99.9% as a sputtering target and adopting a radio frequency reaction magnetron sputtering method in the atmosphere of argon and nitrogen, and the working parameters are MoNbHfZrTiThe sputtering power density of the target is 2 ~ 6W/cm^-2The air inflow of argon during sputtering deposition is 20 ~ 50sccm, the air inflow of nitrogen is 0.5 ~ 5sccm, and the thickness of the deposited MoNbHfZrTiN is 30 ~ 60 nm;

⑷ preparing a secondary absorption layer on the main absorption layer, wherein the secondary absorption layer is prepared by taking MoNbHfZrTi high-entropy alloy with the purity of 99.9% as a sputtering target and adopting a radio frequency reaction magnetron sputtering method in the atmosphere of argon, nitrogen and oxygen, and the working parameter is that the sputtering power density of the MoNbHfZrTi target is 2 ~ 6W/cm^-2The air inflow of argon during sputtering deposition is 20 ~ 50sccm, the air inflow of nitrogen is 5 ~ 12sccm, the air inflow of oxygen is 2 ~ 6sccm, and the thickness of the deposited MoNbHfZrTiNO is 30 ~ 70 nm;

⑸ preparing an anti-reflective layer on the secondary absorbing layer with SiO having a purity of 99.99%₂The target material is prepared by adopting a radio frequency magnetron sputtering method in an argon atmosphere; wherein the working parameters are as follows: SiO 2₂The sputtering power density of the target is 5 ~ 10W/cm^-2The air inflow of the argon gas during the sputtering deposition is 20 ~ 50sccm, and the deposition thickness is 60 ~ 100 nm.

The step ⑴ of processing the heat absorber substrate refers to removing impurities attached to the surface of the polished stainless steel sheet of the substrate, respectively ultrasonically cleaning the polished stainless steel sheet in acetone and absolute ethyl alcohol for 10 ~ 20 minutes, and drying and storing the polished stainless steel sheet in nitrogen.

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

1. according to the invention, nitrides and nitrogen oxides of high-entropy alloy (MoNbHfZrTi) prepared from metals Mo, Nb, Hf, Zr and Ti with equal molar ratios are selected as basic materials, and a color solar energy absorbing coating is prepared by utilizing the collective effect of various metal elements, so that the application field of the high-entropy alloy is greatly expanded, and the film system structure of the solar energy absorbing coating is enriched and developed.

2. The absorptivity of the prepared color coating is more than or equal to 0.91 and the emissivity is less than or equal to 0.12 under the condition of an atmospheric quality factor AM 1.5.

3. The preparation method is simple in preparation process and low in cost, and the prepared coating has high absorptivity and low emissivity, has rich colors, and has wide practical value and application prospect in the field of solar heat utilization and building integration.

Drawings

The following describes embodiments of the present invention in further detail with reference to the accompanying drawings.

FIG. 1 is a block diagram of the present invention.

Fig. 2 is a digital photograph of a bluish solar absorbing coating of the invention.

Fig. 3 is a digital photograph of an orange solar absorptive coating of the invention.

Fig. 4 is a digital photograph of a yellowish solar energy absorbing coating of the present invention.

Fig. 5 is a digital photograph of a deep blue solar absorbing coating of the present invention.

Detailed Description