CN110643941B - Solar energy absorbing coating with good heat stability in air and preparation method thereof - Google Patents

Solar energy absorbing coating with good heat stability in air and preparation method thereof Download PDF

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CN110643941B
CN110643941B CN201910965107.2A CN201910965107A CN110643941B CN 110643941 B CN110643941 B CN 110643941B CN 201910965107 A CN201910965107 A CN 201910965107A CN 110643941 B CN110643941 B CN 110643941B
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argon
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高祥虎
刘刚
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Lanzhou Institute of Chemical Physics LICP of CAS
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0676—Oxynitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/081—Oxides of aluminium, magnesium or beryllium
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S70/00—Details of absorbing elements
    • F24S70/20—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption
    • F24S70/25—Coatings made of metallic material
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/40—Solar thermal energy, e.g. solar towers

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Abstract

The invention relates to a solar energy absorbing coating with good heat stability in air, which sequentially comprises a heat absorbing body substrate consisting of a polished stainless steel sheet, an infrared reflecting layer consisting of metal Mo, a main absorbing layer consisting of TiSiCrZrHfN, a secondary absorbing layer consisting of TiSiCrZrHfNO and Al2O3And the formed antireflection layer. The main absorption layer is nitride of TiSiCrZrHf high-entropy alloy prepared by adopting metals of Ti, Si, Cr, Zr and Hf with equal molar ratio through a smelting method; the secondary absorption layer is the oxynitride of TiSiCrZrHf high-entropy alloy prepared by a smelting method by adopting metals of Ti, Si, Cr, Zr and Hf with equal molar ratio. The invention also discloses a preparation method of the coating. The preparation method is simple in preparation process and low in cost, and the prepared coating has the absorption rate of more than or equal to 0.94 and the emissivity of less than or equal to 0.10 under the condition of an atmospheric quality factor AM 1.5; and the coating has good long-term thermal stability at 500 ℃ in air.

Description

Solar energy absorbing coating with good heat stability in air and preparation method thereof
Technical Field
The invention relates to the technical field of high-temperature solar energy absorbing coatings for solar photo-thermal power generation, in particular to a solar energy absorbing coating with good heat stability in air and a preparation method thereof.
Background
Solar photo-thermal power generation is a new energy application technology with the potential of becoming a basic load power supply, and has huge potential. 10.10.2018, the Guanghong group of China announces in Jing that the first large-scale commercial groove type photo-thermal demonstration power station-Zhongguangdong Denja 50MW photo-thermal demonstration project of China is put into operation formally, and therefore, China becomes the 8 th country in the world which masters large-scale photo-thermal technologies. However, the high-temperature heat collecting tubes adopted in the middle-wide core warnaha 50MW trough type photo-thermal power generation photo-thermal demonstration project all depend on the inlet. At present, Xinjiang, Gansu and Qinghai in China are planning and creating ten million kilowatt-level solar photo-thermal power generation bases, and the planned and constructed solar photo-thermal power stations have near billions of investment. However, the lack of key materials and technologies severely restricts the healthy and sustainable development of the solar photo-thermal power generation industry in China.
High temperature solar energy absorbing coating is honored as high temperature thermal-collecting tube and even the "core" material of light and heat power generation system, and its performance plays vital effect to realizing high light and heat conversion efficiency and power station income. In recent years, domestic research on high-temperature solar energy absorption coatings has progressed to a certain extent, but a plurality of bottlenecks still exist in the aspects of high-temperature thermal stability and reliability. The high-temperature solar energy absorption coating reported at present has good thermal stability in vacuum, but the thermal stability in air is poor.
Disclosure of Invention
The invention aims to provide a solar energy absorbing coating with good heat stability in air.
The invention also aims to provide a preparation method of the solar energy absorbing coating with good thermal stability in air.
In order to solve the problems, the solar energy absorbing coating with good heat stability in air is characterized in that: the coating comprises a heat absorber substrate made of polished stainless steel sheets, an infrared reflecting layer made of metal Mo, a main absorbing layer made of TiSiCrZrHfN, a secondary absorbing layer made of TiSiCrZrHfNO and Al in sequence2O3The formed antireflection layer; the main absorption layer is a nitride of TiSiCrZrHf high-entropy alloy prepared by adopting metals of Ti, Si, Cr, Zr and Hf with equal molar ratio through a smelting method; the secondary absorption layer is a nitrogen oxide of TiSiCrZrHf high-entropy alloy prepared by adopting metals of Ti, Si, Cr, Zr and Hf with equal molar ratio through a smelting method.
The roughness value of the heat absorber substrate is 0.5-3 nm.
The thickness of the infrared reflecting layer is 35-70 nm.
The thickness of the main absorption layer is 25-55 nm.
The thickness of the secondary absorption layer is 25-50 nm.
The thickness of the antireflection layer is 35-70 nm.
The TiSiCrZrHf high entropy alloy is prepared by putting Ti, Si, Cr, Zr and Hf metals with equal molar ratio into a graphite crucible, then putting the graphite crucible into a vacuum smelting furnace, and vacuumizing to 3.5 multiplied by 10-6~7×10-6And (3) smelting at 2300-2800 ℃, pouring and molding, and cutting and polishing to obtain the material.
The preparation method of the solar energy absorbing coating with good heat stability in air comprises the following steps:
processing a heat absorbing body substrate;
preparing an infrared reflecting layer on the heat absorber substrate after treatment: mo with the purity of 99.99 percent is taken as a magnetron sputtering target material and is prepared by adopting a direct-current magnetron sputtering method in an argon atmosphere; wherein the working parameters are as follows: pre-vacuum pumping the vacuum chamber to 3.5X 10-6~6.5×10-6Torr; the sputtering power density of the Mo target material is 4.5-7.5W/m-2The air inflow of argon during sputtering deposition is 20-60 sccm, and the thickness of deposited Mo is 35-70 nm;
preparing a main absorption layer on the infrared reflection layer: the TiSiCrZrHf high-entropy alloy with the purity of 99.9 percent is used as a sputtering target material and is prepared by adopting a radio frequency reaction magnetron sputtering method in the atmosphere of argon and nitrogen; wherein the working parameters are as follows: the sputtering power density of the TiSiCrZrHf target material is 3.0-6.5W/cm-2The air inflow of argon is 20-60 sccm during sputtering deposition, the air inflow of nitrogen is 2-6 sccm, and the thickness of the deposited TiSiCrZrHfN is 25-55 nm;
preparing a secondary absorption layer on the primary absorption layer: the TiSiCrZrHf high-entropy alloy with the purity of 99.9 percent is used as a sputtering target material and is prepared by adopting a radio frequency reaction magnetron sputtering method in the atmosphere of argon, nitrogen and oxygen; wherein the working parameters are as follows: the sputtering power density of the TiSiCrZrHf target material is 3.0-6.5W/cm-2The air inflow of argon is 20-60 sccm during sputtering deposition, the air inflow of nitrogen is 3-10 sccm, the air inflow of oxygen is 2-8 sccm, and the thickness of the TiSiCrZrHfNO deposited is 25-50 nm;
preparing an antireflection layer on the secondary absorption layer: al with a purity of 99.99%2O3The target material is prepared by adopting a radio frequency magnetron sputtering method in an argon atmosphere; wherein the working parameters are as follows: al (Al)2O3The sputtering power density of the target material is 5.5-10W/cm-2The air inflow of the argon during sputtering deposition is 20-60 sccm, and the deposition thickness is 35-70 nm.
The heat absorber substrate treatment in the step refers to that after impurities attached to the surface of a polished stainless steel sheet of the substrate are removed, the polished stainless steel sheet is ultrasonically cleaned in acetone and absolute ethyl alcohol for 10-20 minutes respectively, and nitrogen is dried and stored.
Compared with the prior art, the invention has the following advantages:
1. the high-entropy alloy has the following characteristics: the Gibbs free energy of a system can be effectively reduced by a thermodynamic high-entropy effect, and the formation of a complex intermetallic compound phase is inhibited; the slow diffusion effect on the kinetics can play a role in hindering diffusion-related reactions such as phase change, recrystallization, grain growth and the like; the alloy performance can be obviously changed by the serious lattice distortion effect on the structure of the alloy, such as the improvement of the strength of the alloy by increasing the solid solution strengthening effect, the reduction of the electrical conductivity, the thermal conductivity and the like; and fourthly, a cocktail effect on the performance. Therefore, the TiSiCrZrHf high-entropy alloy prepared by adopting Si element with excellent oxidation resistance and generating an aggregate effect with Ti, Cr, Zr and Hf not only can effectively improve the thermal stability of the coating in the air, but also expands the application field of the high-entropy alloy and enriches and develops the film system structure of the solar energy absorbing coating.
2. The coating prepared by the invention has the advantages that under the condition that the atmospheric quality factor AM is 1.5, the absorptivity is more than or equal to 0.94, and the emissivity is less than or equal to 0.10; and the coating has good long-term thermal stability at 500 ℃ in air.
3. The invention has simple preparation process and lower cost.
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.
Detailed Description
Example 1 as shown in fig. 1, a solar absorbing coating having excellent thermal stability in air was formed by sequentially forming a heat absorber substrate made of a polished stainless steel sheet having a roughness value of 1.5 nm, an infrared reflecting layer made of metal Mo and having a thickness of 40 nm, a main absorbing layer made of tissicrzrhfn and having a thickness of 38 nm, and a main absorbing layer made of tissicrzrhfno and having a thickness of 35nmSub-absorption layer of nm and Al2O3And an antireflection layer with a thickness of 50 nm. The main absorption layer is nitride of TiSiCrZrHf high-entropy alloy prepared by adopting metals of Ti, Si, Cr, Zr and Hf with equal molar ratio through a smelting method; the secondary absorption layer is the oxynitride of TiSiCrZrHf high-entropy alloy prepared by a smelting method by adopting metals of Ti, Si, Cr, Zr and Hf with equal molar ratio.
Wherein: the TiSiCrZrHf high entropy alloy is prepared by putting Ti, Si, Cr, Zr and Hf metals with equal molar ratio into a graphite crucible, then putting the graphite crucible into a vacuum smelting furnace, and vacuumizing to 3.5 multiplied by 10-6~7×10-6And (3) smelting at 2300-2800 ℃, pouring and molding, and cutting and polishing to obtain the material.
The preparation method of the solar energy absorbing coating with good heat stability in the air comprises the following steps:
the method comprises the following steps of treating a heat absorbing body substrate: 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 15 minutes, and blow-drying and storing the polished stainless steel sheet by nitrogen.
Preparing an infrared reflecting layer on the treated heat absorber substrate: mo with the purity of 99.99 percent is taken as a magnetron sputtering target material and is prepared by adopting a direct-current magnetron sputtering method in an argon atmosphere; wherein the working parameters are as follows: pre-vacuum pumping the vacuum chamber to 5.5X 10-6Torr; the sputtering power density of the Mo target material is 5.0W/m-2The air inflow of argon during sputtering deposition is 35sccm, and the thickness of deposited Mo is 40 nm.
Preparing a main absorption layer on the infrared reflection layer: the TiSiCrZrHf high-entropy alloy with the purity of 99.9 percent is used as a sputtering target material and is prepared by adopting a radio frequency reaction magnetron sputtering method in the atmosphere of argon and nitrogen; wherein the working parameters are as follows: the sputtering power density of the TiSiCrZrHf target material is 5.2W/cm-2The air inflow of argon during sputtering deposition is 35sccm, the air inflow of nitrogen is 4sccm, and the thickness of the TiSiCrZrHfN is 38 nm.
Preparing a secondary absorption layer on the primary absorption layer: the TiSiCrZrHf high-entropy alloy with the purity of 99.9 percent is used as a sputtering target material and is prepared by adopting a radio frequency reaction magnetron sputtering method in the atmosphere of argon, nitrogen and oxygen; in which workParameters are as follows: the sputtering power density of the TiSiCrZrHf target material is 4.8W/cm-2The air inflow of argon during sputtering deposition is 35sccm, the air inflow of nitrogen is 5sccm, the air inflow of oxygen is 3sccm, and the thickness of the TiSiCrZrHfNO deposited is 35 nm.
Preparing an antireflection layer on the secondary absorption layer: al with a purity of 99.99%2O3The target material is prepared by adopting a radio frequency magnetron sputtering method in an argon atmosphere; wherein the working parameters are as follows: al (Al)2O3The sputtering power density of the target material is 5.5W/cm-2The air inflow of the argon gas during the sputtering deposition is 35sccm, and the deposition thickness is 50 nm.
The coating has an absorptivity of 0.95 and an emissivity of 0.10 under the condition of an atmospheric quality factor AM 1.5.
Example 2 solar absorptive coating with good thermal stability in air consisting of a heat absorber substrate consisting of polished stainless steel sheet with roughness value of 0.5 nm, an infrared reflecting layer with thickness of 35nm consisting of metal Mo, a main absorbing layer with thickness of 25 nm consisting of TiSiCrZrHfN, a sub absorbing layer with thickness of 25 nm consisting of TiSiCrZrHfNO and Al in this order2O3And an antireflection layer with the thickness of 35 nm. The main absorption layer is nitride of TiSiCrZrHf high-entropy alloy prepared by adopting metals of Ti, Si, Cr, Zr and Hf with equal molar ratio through a smelting method; the secondary absorption layer is the oxynitride of TiSiCrZrHf high-entropy alloy prepared by a smelting method by adopting metals of Ti, Si, Cr, Zr and Hf with equal molar ratio.
Wherein: the TiSiCrZrHf high entropy alloy is the same as example 1.
The preparation method of the solar energy absorbing coating with good heat stability in the air comprises the following steps:
the method comprises the following steps of treating a heat absorbing body substrate: 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 minutes, and blow-drying and storing the polished stainless steel sheet by nitrogen.
Preparing an infrared reflecting layer on the treated heat absorber substrate: mo with the purity of 99.99 percent is taken as a magnetron sputtering target material and is prepared by adopting a direct-current magnetron sputtering method in an argon atmosphere; wherein the working parameters are as follows: vacuum chamber forehearthVacuum background to 3.5X 10-6Torr; the sputtering power density of the Mo target material is 4.5W/m-2The air inflow of argon during sputtering deposition is 20sccm, and the thickness of deposited Mo is 35 nm.
Preparing a main absorption layer on the infrared reflection layer: the TiSiCrZrHf high-entropy alloy with the purity of 99.9 percent is used as a sputtering target material and is prepared by adopting a radio frequency reaction magnetron sputtering method in the atmosphere of argon and nitrogen; wherein the working parameters are as follows: the sputtering power density of the TiSiCrZrHf target material is 3.0W/cm-2The air inflow of argon during sputtering deposition is 20sccm, the air inflow of nitrogen is 2sccm, and the thickness of the TiSiCrZrHfN is 25 nm.
Preparing a secondary absorption layer on the primary absorption layer: the TiSiCrZrHf high-entropy alloy with the purity of 99.9 percent is used as a sputtering target material and is prepared by adopting a radio frequency reaction magnetron sputtering method in the atmosphere of argon, nitrogen and oxygen; wherein the working parameters are as follows: the sputtering power density of the TiSiCrZrHf target material is 3.0W/cm-2The air inflow of argon during sputtering deposition is 20sccm, the air inflow of nitrogen is 3sccm, the air inflow of oxygen is 2sccm, and the thickness of the TiSiCrZrHfNO deposited is 25 nm.
Preparing an antireflection layer on the secondary absorption layer: al with a purity of 99.99%2O3The target material is prepared by adopting a radio frequency magnetron sputtering method in an argon atmosphere; wherein the working parameters are as follows: al (Al)2O3The sputtering power density of the target material is 5W/cm-2The air inflow of the argon gas during the sputtering deposition is 20sccm, and the deposition thickness is 35 nm.
The coating has an absorptivity of 0.95 and an emissivity of 0.09 under the condition of an atmospheric quality factor AM 1.5.
Example 3 solar absorptive coating with good thermal stability in air consisting of a heat absorber substrate consisting of polished stainless steel sheet with roughness value of 3 nm, an infrared reflecting layer with thickness of 70nm consisting of metal Mo, a main absorbing layer with thickness of 55 nm consisting of TiSiCrZrHfN, a sub absorbing layer with thickness of 50nm consisting of TiSiCrZrHfNO and Al in this order2O3And an antireflection layer with a thickness of 70 nm. The main absorption layer is TiSiCrZrHf high prepared by a smelting method by adopting metals of Ti, Si, Cr, Zr and Hf with equal molar ratioA nitride of an entropy alloy; the secondary absorption layer is the oxynitride of TiSiCrZrHf high-entropy alloy prepared by a smelting method by adopting metals of Ti, Si, Cr, Zr and Hf with equal molar ratio.
Wherein: the TiSiCrZrHf high entropy alloy is the same as example 1.
The preparation method of the solar energy absorbing coating with good heat stability in the air comprises the following steps:
the method comprises the following steps of treating a heat absorbing body substrate: removing impurities attached to the surface of the polished stainless steel sheet of the substrate, respectively ultrasonically cleaning in acetone and absolute ethyl alcohol for 20 minutes, and blow-drying and storing by nitrogen.
Preparing an infrared reflecting layer on the treated heat absorber substrate: mo with the purity of 99.99 percent is taken as a magnetron sputtering target material and is prepared by adopting a direct-current magnetron sputtering method in an argon atmosphere; wherein the working parameters are as follows: pre-vacuum pumping the vacuum chamber to 6.5X 10-6Torr; the sputtering power density of the Mo target material is 7.5W/m-2The air inflow of argon during sputtering deposition is 60sccm, and the thickness of deposited Mo is 70 nm.
Preparing a main absorption layer on the infrared reflection layer: the TiSiCrZrHf high-entropy alloy with the purity of 99.9 percent is used as a sputtering target material and is prepared by adopting a radio frequency reaction magnetron sputtering method in the atmosphere of argon and nitrogen; wherein the working parameters are as follows: the sputtering power density of the TiSiCrZrHf target material is 6.5W/cm-2The air inflow of argon during sputtering deposition is 60sccm, the air inflow of nitrogen is 6sccm, and the thickness of the TiSiCrZrHfN is 55 nm.
Preparing a secondary absorption layer on the primary absorption layer: the TiSiCrZrHf high-entropy alloy with the purity of 99.9 percent is used as a sputtering target material and is prepared by adopting a radio frequency reaction magnetron sputtering method in the atmosphere of argon, nitrogen and oxygen; wherein the working parameters are as follows: the sputtering power density of the TiSiCrZrHf target material is 6.5W/cm-2The air inflow of argon is 60sccm during sputtering deposition, the air inflow of nitrogen is 10sccm, the air inflow of oxygen is 8sccm, and the thickness of the TiSiCrZrHfNO deposited is 50 nm.
Preparing an antireflection layer on the secondary absorption layer: al with a purity of 99.99%2O3The target material is prepared by adopting a radio frequency magnetron sputtering method in an argon atmosphere; it is composed ofThe middle working parameters are as follows: al (Al)2O3The sputtering power density of the target material is 10W/cm-2The air inflow of the argon gas during the sputtering deposition is 60sccm, and the deposition thickness is 70 nm.
The coating has an absorptivity of 0.94 and an emissivity of 0.10 under the condition of an atmospheric quality factor AM 1.5.

Claims (3)

1. The solar energy absorbing coating with good heat stability in air is characterized in that: the coating comprises a heat absorber substrate made of polished stainless steel sheets, an infrared reflecting layer made of metal Mo, a main absorbing layer made of TiSiCrZrHfN, a secondary absorbing layer made of TiSiCrZrHfNO and Al in sequence2O3The formed antireflection layer; the main absorption layer is a nitride of TiSiCrZrHf high-entropy alloy prepared by adopting metals of Ti, Si, Cr, Zr and Hf with equal molar ratio through a smelting method; the secondary absorption layer is a nitrogen oxide of TiSiCrZrHf high-entropy alloy prepared by adopting metals of Ti, Si, Cr, Zr and Hf with equal molar ratio through a smelting method; the roughness value of the heat absorber substrate is 0.5-3 nm; the thickness of the infrared reflecting layer is 35-70 nm; the thickness of the main absorption layer is 25-55 nm; the thickness of the secondary absorption layer is 25-50 nm; the thickness of the antireflection layer is 35-70 nm; the TiSiCrZrHf high entropy alloy is prepared by putting Ti, Si, Cr, Zr and Hf metals with equal molar ratio into a graphite crucible, then putting the graphite crucible into a vacuum smelting furnace, and vacuumizing to 3.5 multiplied by 10-6~7×10-6And (3) smelting at 2300-2800 ℃, pouring and molding, and cutting and polishing to obtain the material.
2. The method for preparing a solar energy absorbing coating with good thermal stability in air according to claim 1, comprising the steps of:
processing a heat absorbing body substrate;
preparing an infrared reflecting layer on the heat absorber substrate after treatment: mo with the purity of 99.99 percent is taken as a magnetron sputtering target material and is prepared by adopting a direct-current magnetron sputtering method in an argon atmosphere; wherein the working parameters are as follows: pre-vacuum pumping the vacuum chamber to 3.5X 10-6~6.5×10-6Torr; sputtering power density of Mo target materialThe degree of the alloy is 4.5 to 7.5W/m2The air inflow of argon during sputtering deposition is 20-60 sccm, and the thickness of deposited Mo is 35-70 nm;
preparing a main absorption layer on the infrared reflection layer: the TiSiCrZrHf high-entropy alloy with the purity of 99.9 percent is used as a sputtering target material and is prepared by adopting a radio frequency reaction magnetron sputtering method in the atmosphere of argon and nitrogen; wherein the working parameters are as follows: the sputtering power density of the TiSiCrZrHf target material is 3.0-6.5W/cm2The air inflow of argon is 20-60 sccm during sputtering deposition, the air inflow of nitrogen is 2-6 sccm, and the thickness of the deposited TiSiCrZrHfN is 25-55 nm;
preparing a secondary absorption layer on the primary absorption layer: the TiSiCrZrHf high-entropy alloy with the purity of 99.9 percent is used as a sputtering target material and is prepared by adopting a radio frequency reaction magnetron sputtering method in the atmosphere of argon, nitrogen and oxygen; wherein the working parameters are as follows: the sputtering power density of the TiSiCrZrHf target material is 3.0-6.5W/cm2The air inflow of argon is 20-60 sccm during sputtering deposition, the air inflow of nitrogen is 3-10 sccm, the air inflow of oxygen is 2-8 sccm, and the thickness of the TiSiCrZrHfNO deposited is 25-50 nm;
preparing an antireflection layer on the secondary absorption layer: al with a purity of 99.99%2O3The target material is prepared by adopting a radio frequency magnetron sputtering method in an argon atmosphere; wherein the working parameters are as follows: al (Al)2O3The sputtering power density of the target material is 5.5-10W/cm2The air inflow of the argon during sputtering deposition is 20-60 sccm, and the deposition thickness is 35-70 nm.
3. The method for preparing a solar energy absorbing coating having good thermal stability in air according to claim 2, wherein: the heat absorber substrate treatment in the step refers to that after impurities attached to the surface of a polished stainless steel sheet of the substrate are removed, the polished stainless steel sheet is ultrasonically cleaned in acetone and absolute ethyl alcohol for 10-20 minutes respectively, and nitrogen is dried and stored.
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