CN111076434A - Medium-high temperature solar spectrum selective absorption coating, preparation method thereof and heat collection shell - Google Patents
Medium-high temperature solar spectrum selective absorption coating, preparation method thereof and heat collection shell Download PDFInfo
- Publication number
- CN111076434A CN111076434A CN201911234596.0A CN201911234596A CN111076434A CN 111076434 A CN111076434 A CN 111076434A CN 201911234596 A CN201911234596 A CN 201911234596A CN 111076434 A CN111076434 A CN 111076434A
- Authority
- CN
- China
- Prior art keywords
- layer
- chromium
- aluminum oxide
- absorption layer
- absorption
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- 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
- F24S70/225—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption for spectrally selective absorption
-
- 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
- C23C14/0021—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
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
-
- 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
- C23C14/08—Oxides
-
- 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
- C23C14/10—Glass or silica
-
- 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
- C23C14/14—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
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Thermal Sciences (AREA)
- Combustion & Propulsion (AREA)
- General Engineering & Computer Science (AREA)
- Physical Vapour Deposition (AREA)
- Laminated Bodies (AREA)
Abstract
The invention discloses a medium-high temperature solar spectrum selective absorption coating, a preparation method thereof and a heat collection shell, wherein the selective absorption coating comprises a substrate layer; an infrared reflecting layer, a composite absorbing layer and an antireflection layer are sequentially arranged on the substrate layer from bottom to top; the composite absorption layer sequentially comprises a chromium-aluminum oxide main absorption layer and a chromium-aluminum oxide sub-absorption layer from bottom to top, and the infrared reflection layer, the chromium-aluminum oxide main absorption layer, the chromium-aluminum oxide sub-absorption layer and the antireflection layer are sequentially prepared on the substrate layer by a magnetron sputtering method. Wherein, the content ratio of chromium and aluminum in the main absorbing layer of the chromium-aluminum oxide is high, and the content ratio of chromium and aluminum in the sub-absorbing layer of the chromium-aluminum oxide is low. The absorption layer is made of metal oxide ceramics, so that the diffusion of oxygen in the absorption layer can be slowed down, the thermal stability of the coating in a medium-high temperature atmospheric environment is improved, and the selected material is low in price and easy to use for large-scale production.
Description
Technical Field
The invention relates to a coating, in particular to a medium-high temperature solar spectrum selective absorption coating, a preparation method thereof and a heat collection shell, and belongs to the technical field of coating application.
Background
The structure of the spectrum selective coating film system adopted by the solar thermal collector can be generally summarized as a substrate/an infrared reflecting layer/a solar spectrum absorbing layer/a surface antireflection layer. The infrared reflecting layer is made of high-conductivity metal, has high reflectivity on infrared spectrum and is the main reason for obtaining low radiation performance of the coating; the absorbing layer material can be intrinsic semiconductor, metal oxynitride, metal dielectric interference film system, metal ceramic composite material, etc., wherein the absorbing performance of the metal ceramic composite material, namely the optical performance thereof, can be optimized by regulating and controlling the type and content of metal in the metal ceramic. The reflection of sunlight at the interface between the coating and the air can be reduced by the surface antireflection layer, so that more sunlight energy enters the absorption layer, the absorption rate of a solar spectrum is increased, and the heat collection efficiency is improved. Therefore, the medium-high temperature solar spectrum selective absorption coating, the preparation method thereof and the heat collection shell are provided for solving the problems.
Disclosure of Invention
The invention aims to solve the problems and provide a medium-high temperature solar spectrum selective absorption coating, a preparation method thereof and a heat collection shell.
The invention achieves the aim through the following technical scheme, and provides a medium-high temperature solar spectrum selective absorption coating, a preparation method thereof and a heat collection shell, which comprise a substrate layer; an infrared reflecting layer, a composite absorbing layer and an antireflection layer are sequentially arranged on the substrate layer; the composite absorption layer sequentially comprises a main chromium-aluminum oxide absorption layer and a sub-chromium-aluminum oxide absorption layer from bottom to top, the main chromium-aluminum oxide absorption layer and the sub-chromium-aluminum oxide absorption layer are made of materials with absorption performance on spectrums, and the chromium-aluminum content ratio of the main absorption layer is higher than that of the sub-absorption layer.
Preferably, the refractive indexes of the chromium-aluminum oxide main absorption layer and the chromium-aluminum oxide sub-absorption layer are sequentially reduced; the extinction coefficients of the chromium-aluminum oxide main absorption layer and the chromium-aluminum oxide sub-absorption layer are sequentially reduced.
Preferably, the refractive index of the chromium-aluminum oxide main absorption layer is 2.32-3.87, and the refractive index of the chromium-aluminum oxide sub-absorption layer is 2.18-2.51 in the range of 380-2500 nm; the extinction coefficient of the chromium-aluminum oxide main absorption layer is 1.21-2.08, and the extinction coefficient of the chromium-aluminum oxide sub-absorption layer is 0.29-0.77 in the range of 380-2500 nm.
Preferably, the total thickness of the composite absorption layer is 116-118nm,
wherein:
the material of the chromium-aluminum oxide main absorption layer is Cr70Al30OxThe thickness of the material is 72-73 nm;
the chromium-aluminum oxide sub-absorption layer is made of Cr55Al45OxThe thickness of the material is 44-45 nm.
Preferably, the substrate is made of glass and 304 mirror stainless steel, and the thickness of the substrate layer is 1-6 mm.
Preferably, the material of the infrared reflecting layer has an emissivity of less than 0.04 and is excellent in thermal stability at high temperature, and the infrared reflecting layer has a thickness of 150 nm.
Preferably, the infrared reflecting layer is W.
Preferably, the material of the anti-reflection layer is SiO2、Al2O3、ThO2、Dy2O3、Eu2O3、Gd2O3、Y2O3、La2O3MgO or Sm2O3The thickness of the anti-reflection layer is 50-100 nm.
A preparation method of a medium-high temperature solar spectrum selective absorption coating comprises the steps of preparing an infrared reflection layer, a chromium-aluminum oxide main absorption layer, a chromium-aluminum oxide sub-absorption layer and an antireflection layer on a substrate layer through a magnetron sputtering method in sequence;
al and Cr are deposited on the substrate of glass, aluminum, copper, 304 mirror stainless steel or 316L mirror stainless steel in turn70Al30Ox、Cr55Al45OxAnd SiO2A film;
(1) preparing a substrate, namely selecting a polished 304 stainless steel plate or a polished glass plate, and carrying out radio frequency argon ion cleaning after mechanical cleaning to remove a surface pollution layer and an oxidation layer and improve the surface activity of the substrate;
(2) preparing an infrared reflecting layer, namely preparing a metal infrared reflecting layer on the surface of the substrate layer by sputtering through a (pulse) direct current magnetron sputtering method, wherein the selected target material can be metal tungsten (the purity is more than 99.7 percent), and the working gas is argon;
(3) preparing an absorption layer by reactive sputtering on the infrared reflecting layer by a (pulse) direct current magnetron sputtering method, wherein the selected target materials are respectively a chromium-aluminum alloy target CrAl (purity is 99.9%, Cr: Al =70:30 at%) and a chromium-aluminum alloy target CrAl (purity is 99.9%, Cr: Al =55:45 at%), the reaction gas is oxygen, and the working gas is argon;
(4) preparing the antireflection layer by (pulse) direct current reactive magnetron sputtering on the absorption layer, wherein the selected target material is a silicon-aluminum target (the aluminum content is 0-30 wt%, and the purity is more than 99.7%), the reaction gas is oxygen, and the working gas is argon.
A heat collection shell for a medium-high temperature solar spectrum selective absorption coating comprises a shell, wherein a cover plate is arranged on the shell, a heat absorption layer and a heat insulation layer are arranged below the cover plate, and the heat absorption layer is the medium-high temperature solar spectrum selective absorption coating.
By the technical scheme, the medium-high temperature solar spectrum selective absorption coating provided by the invention at least has the following advantages:
a. the absorption layer is made of a chromium-aluminum oxide material, and the atomic ratio of the chromium content to the aluminum content of the main absorption layer is 70:30, the atomic ratio of the content of chromium and aluminum in the sub-absorption layer is 55:45, the oxidation degrees are different, and the dense alumina is adopted to effectively improve the medium-high temperature thermal stability of the coating.
b. The absorption layer of the medium-high temperature solar spectrum selective absorption coating disclosed by the invention comprises a chromium-aluminum oxide main absorption layer and a chromium-aluminum oxide sub-absorption layer, wherein the refractive index and extinction coefficient of the chromium-aluminum oxide main absorption layer and the chromium-aluminum oxide sub-absorption layer are sequentially reduced from bottom to top (adjacent to an infrared reflection layer) and are adjacent to a surface antireflection layer, and the absorption rate of the solar spectrum is higher than 96%, the radiance of the chromium-aluminum oxide sub-absorption layer is lower than 4% at 80 ℃ and the radiance of the chromium-aluminum.
c. In the specific implementation mode of the invention, the infrared metal reflecting layer is made of tungsten, and the absorption rate of the solar spectrum of the coating is further improved by the participation of tungsten in the spectral absorption of the solar band
The foregoing description is only an overview of the technical solutions of the present invention, and in order to make the technical solutions of the present invention more clearly understood and to implement them in accordance with the contents of the description, the following detailed description is given with reference to the preferred embodiments of the present invention and the accompanying drawings.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without inventive exercise.
FIG. 1 is a schematic structural diagram of a medium-high temperature solar spectrum selective absorption coating proposed by the present invention;
FIG. 2 shows the reflection spectrum from the solar band to the infrared band after different annealing times in an atmospheric environment at 400 ℃ according to the present invention.
In the figure: 1. the infrared reflection layer comprises a substrate layer, 2, an infrared reflection layer, 3, a composite absorption layer, 31, a chromium-aluminum oxide main absorption layer, 32, a chromium-aluminum oxide sub-absorption layer, 4 and an antireflection layer.
Detailed Description
In order to make the objects, features and advantages of the present invention more obvious and understandable, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is obvious that the embodiments described below are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "top", "bottom", "inner", "outer", and the like, indicate orientations or positional relationships based on those shown in the drawings, and are used only for convenience in describing the present invention and for simplicity in description, and do not indicate or imply that the referenced devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and thus, are not to be construed as limiting the present invention.
The medium-high temperature spectrum selective absorption coating provided by the embodiment comprises the following components as shown in fig. 1: a base layer 1; an infrared reflecting layer 2, a composite absorbing layer 3 and an antireflection layer 4 are sequentially arranged on the substrate layer; the composite absorption layer sequentially comprises a main chromium-aluminum oxide absorption layer 31 and a sub-chromium-aluminum oxide absorption layer 32 from bottom to top, and the main chromium-aluminum oxide absorption layer and the sub-chromium-aluminum oxide absorption layer are made of materials with absorption performance on spectrums.
The solar spectrum selective absorption coating is a core material for realizing solar photothermal conversion, and on one hand, the solar spectrum selective absorption coating has high absorptivity α in a solar wave band (0.3 mu m-2.5 mu m) and absorbs solar energy as much as possible to convert the solar energy into heat energy, and on the other hand, the infrared wave band (2.0 mu m-48 mu m) in which blackbody radiation occurs after heating has as low emissivity ɛ as possible, so that radiation heat dissipation is effectively inhibited.
The composite absorption layer of the solar spectrum selective absorption coating comprises a chromium-aluminum oxide main absorption layer and a chromium-aluminum oxide sub-absorption layer, wherein the refractive index and the extinction absorption of the chromium-aluminum oxide main absorption layer are sequentially reduced from inside to outside, and the solar spectrum absorption rate is higher than 95%, the emissivity at 80 ℃ is lower than 4%, and the emissivity at 400 ℃ is lower than 10%.
In specific implementation, the refractive indexes of the chromium-aluminum oxide main absorption layer and the chromium-aluminum oxide sub-absorption layer are sequentially reduced; the extinction coefficients of the chromium-aluminum oxide main absorption layer and the chromium-aluminum oxide sub-absorption layer are sequentially reduced. Thereby reducing the reflection of incident light by the selective absorption coating and increasing the absorption of light by the selective absorption coating.
In specific implementation, within the range of 380-2500nm, the refractive index of the main absorption layer of the chromium-aluminum oxide is 2.32-3.87, and the refractive index of the sub-absorption layer of the chromium-aluminum oxide is 2.18-2.51;
the extinction coefficient of the chromium-aluminum oxide main absorption layer is 1.21-2.08, and the extinction coefficient of the chromium-aluminum oxide sub-absorption layer is 0.29-0.77 in the range of 380-2500 nm.
In specific implementation, the total thickness of the composite absorption layer is 116-118nm, wherein: the material of the chromium-aluminum oxide main absorption layer is Cr70Al30OxThe thickness of the material is 72-73 nm; the chromium-aluminum oxide sub-absorption layer is made of Cr55Al45OxThe thickness of the material is 44-45 nm.
Compared with a solar spectrum selective absorption coating using metal nitrogen oxide as an absorption layer material, the activity and speed of the metal oxidation reaction are far higher than those of the nitridation reaction, so that the process window of the nitrogen-oxygen ratio for obtaining the absorption layer with the optimal performance is narrow, the content of nitrogen and oxygen in the coating process needs to be accurately controlled, the absorption rate and radiance of a film system and even the color of the coating can be obviously changed due to small change of the nitrogen-oxygen ratio, the stability of the coating process is poor, and the requirement on coating equipment is high. The metal material in the absorbing layer is chromium aluminum oxide CrAlOxThe reaction gas is only oxygen, and compared with metal oxynitride, the reactive magnetron sputtering coating process is relatively simple.
In specific implementation, the substrate is made of glass, 304 mirror stainless steel or 316L mirror stainless steel. The substrate can adopt a glass plate with the thickness ranging from 1 mm to 6 mm; the thickness of the substrate layer may also be 1-6mm of a metallic material, such as copper, aluminum or stainless steel. In order to increase the surface activity of the substrate 1, it is necessary to perform rf ion cleaning after mechanical cleaning, so as to remove the contamination layer and the oxidation layer on the surface of the substrate layer.
In specific implementation, the infrared reflecting layer is made of metal tungsten, the emissivity of the metal tungsten at 80 ℃ is lower than 0.04, and the thickness of the infrared reflecting layer is 150 nm.
In specific implementation, the anti-reflection layer is SiO with ideal chemical ratio2The dielectric layer has a refractive index of 1.47-1.43 and an extinction coefficient of less than 0.03 within the wavelength range of 350-2500 nm; the thickness is preferably 80nm to 120 nm. The material of the antireflection layer has a low refractive index, so that the reflection effect of the selective absorption coating on incident light can be reduced, and the absorptivity of the selective absorption coating on the light can be increased.
The above base layer, infrared reflecting layer, composite absorbing layer and antireflection layer are sequentially prepared into films by a coating process, and the coating process is a coating method capable of forming the above materials, such as magnetron sputtering method, electron beam or thermal evaporation method, ion plating method, chemical vapor deposition method, spraying method, and the like.
The method has the advantages of low cost and simple process, but generally has the defects of poor coating adhesion, easy peeling, high emissivity and the like, and has the pollution problem as the electrochemical method, the magnetron sputtering method for preparing the medium-high temperature spectrum selective absorption film can overcome the defects, improve the photothermal conversion efficiency and prolong the service life of the coating, meanwhile, the magnetron sputtering method has the characteristics of high film deposition speed, uniform and compact film layer, convenience for large-area film formation, environmental protection of the process and the like, and is beneficial to building a large-scale horizontal continuous automatic production line, improving the production efficiency and further reducing the cost when preparing the coating of the solar collector plate core.
The following will specifically describe the magnetron sputtering coating method as an example. On the basis of glass, aluminum, copper, 304 mirror stainless steel, 316L mirror stainless steel, etcSequentially depositing Al and Cr on the bottom70Al30Ox、Cr55Al45OxAnd SiO2A film.
Preparing a substrate, namely selecting a polished 304 stainless steel plate or a polished glass plate, and carrying out radio frequency argon ion cleaning after mechanical cleaning to remove a surface pollution layer and an oxidation layer and improve the surface activity of the substrate.
Preparing an infrared reflecting layer, namely sputtering and preparing a metal infrared reflecting layer on the surface of the substrate layer by a (pulse) direct current magnetron sputtering method, wherein the selected target material can be metal tungsten (the purity is more than 99.7 percent), and the working gas is argon.
And (2) preparing the absorption layer by reactive sputtering on the infrared reflecting layer by a (pulse) direct current magnetron sputtering method, wherein the selected target materials are respectively a chromium-aluminum alloy target CrAl (purity is 99.9%, Cr: Al =70:30 at%) and a chromium-aluminum alloy target CrAl (purity is 99.9%, Cr: Al =55:45 at%), the reaction gas is oxygen, and the working gas is argon.
Preparing the antireflection layer by (pulse) direct current reactive magnetron sputtering on the absorption layer, wherein the selected target material is a silicon-aluminum target (the aluminum content is 0-30 wt%, and the purity is more than 99.7%), the reaction gas is oxygen, and the working gas is argon.
The preparation of the examples was carried out according to the above preparation method, with the following specific operating steps:
1) cleaning a 304 mirror stainless steel substrate: firstly, a neutral cleaning solution is adopted to primarily clean a glass substrate; then bombarding the surface of the stainless steel substrate in a film plating equipment film feeding chamber by a radio frequency ion source to carry out secondary cleaning, wherein the process parameters are set as follows: the sputtering power of the radio frequency power supply is 200W, the flow rate of the working gas Ar (the purity is 99.99%) is 45 sccm, and the working pressure is 9.8 multiplied by 10-2mTorr, sputtering time 360 s.
2) Conveying the 304 mirror surface stainless steel substrate into a sputtering chamber through a film coating device, wherein the background vacuum of the sputtering chamber is better than 6 x 10-6Torr。
3) Preparing an infrared reflecting layer W on a 304 mirror surface stainless steel substrate: a metal W film is deposited on a 304-mirror stainless steel substrate by bombarding a metal tungsten target (with the purity of 99.9%) by adopting a pulse direct-current power magnetron sputtering method. The process parameters are set as follows: the sputtering power of a pulse direct current power supply is 1500W, the working pressure is 3 mTorr, the flow of working gas Ar (the purity is 99.99%) is 30sccm, the transmission rate of the substrate is 1m/min, the glass substrate reciprocates 5 times below the metal aluminum target, and the temperature of the substrate is 300 ℃.
4) Preparation of a Main absorber layer Cr on (W/304 SS)70Al30Ox: depositing Cr on (W/304 SS) by bombarding an alloy CrAl target (purity 99.9%, Cr: Al =70:30 at%) by pulsed DC magnetron sputtering70Al30OxAnd (3) a membrane. The process parameters are set as follows: the sputtering power of the pulse direct current power supply is 1500w, the working pressure is 3 mTorr, the flow rate of the working gas Ar (the purity is 99.99%) is 30sccm, and O2(purity 99.99%) flow rate is 1 sccm, substrate 1m/min, round trip 2 times, substrate temperature is room temperature.
5) In (Cr)70Al30OxPreparation of a sub-absorber Cr layer on/W/304 SS)55Al45Ox: bombard alloy CrAl target (purity 99.9%, Cr: Al =55:45 at%) by adopting pulse direct current power magnetron sputtering method70Al30Ox/W/304 SS) deposition of Cr55Al45OxAnd (3) a membrane. The process parameters are set as follows: the sputtering power of the pulse direct current power supply is 1500W, the working pressure is 3 mTorr, the flow of the working gas Ar (the purity is 99.99%) is 30sccm, O2(purity 99.99%) flow rate is 1.5 sccm, substrate 1m/min, round trip 1 time, substrate temperature is room temperature.
6) In (Cr)55Al45Ox/Cr70Al30OxPreparation of antireflection layer SiO on/W/304 SS)2: adopts a pulse direct-current power supply oxidation reaction magnetron sputtering silicon-aluminum target (the aluminum content is 30 wt percent, the purity is 99.7 percent) method (Cr)55Al45Ox/Cr70Al30Ox/W/304 SS) deposition of SiO2And (3) a membrane. The parameters of the coating process are as follows: the sputtering power of the pulse direct current power supply is 2000W, and the working gasPressure of 5mTorr, flow rate of working gas Ar (purity 99.99%) of 30sccm, and O2(purity 99.99%) flow rate is 14 sccm, substrate transmission rate is 0.6 m/min, base glass reciprocates 6 times under the silicon-aluminum target, and substrate temperature is room temperature.
8) After the preparation steps are completed, the sample is cooled for 20min, and then the machine is stopped.
FIG. 2 shows the reflection spectrum of the high-temperature solar spectrum selective absorption coating material in the invention at 0.3-48 μm waveband without heat treatment and under the annealing time of 100 hours at 400 ℃ in atmospheric environment, the reflection spectrum of 0.3-2.5 μm waveband is obtained by Hitachi U-4100 spectrophotometer test, and the reflection spectrum of 2.5-48 μm waveband is obtained by Bruker's Tensor27 Fourier infrared spectrometer test.
The solar spectrum selective absorption coating provided by the invention has the following advantages:
(1) the adopted film system structure comprises a metal W film, a chromium-aluminum oxide main absorption layer, a chromium-aluminum oxide sub-absorption layer and an anti-reflection layer SiO from bottom to top in sequence2The refractive index of each layer is sequentially decreased, and the extinction coefficient is sequentially decreased, thereby reducing the reflection of incident light by the selective absorption coating and increasing the absorption of light by the selective absorption coating, the absorption α of the resulting coating>95% emissivity ε<4%（80）。
(2) The absorption layer is made of a chromium-aluminum oxide composite material, so that the diffusion of oxygen among layers at high temperature is slowed down, and the thermal stability of the coating in a medium-high temperature atmospheric environment is improved.
(3) The absorption layer adopts metal CrAl oxide, and exists in the form of compounds, and the used materials are low in price, simple to prepare and easy to produce in a large scale.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way, and any simple modification, equivalent change and modification made to the above embodiment according to the technical spirit of the present invention are still within the scope of the technical solution of the present invention.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A medium-high temperature solar spectrum selective absorption coating is characterized in that: comprises a substrate layer; an infrared reflecting layer, a composite absorbing layer and an antireflection layer are sequentially arranged on the substrate layer; the composite absorption layer sequentially comprises a main chromium-aluminum oxide absorption layer and a sub-chromium-aluminum oxide absorption layer from bottom to top, the main chromium-aluminum oxide absorption layer and the sub-chromium-aluminum oxide absorption layer are made of materials with absorption performance on spectrums, and the chromium-aluminum content ratio of the main absorption layer is higher than that of the sub-absorption layer.
2. Solar spectrum selective absorbing coating according to claim 1, characterized in that: the refractive indexes of the chromium-aluminum oxide main absorption layer and the chromium-aluminum oxide sub-absorption layer are sequentially reduced; the extinction coefficients of the chromium-aluminum oxide main absorption layer and the chromium-aluminum oxide sub-absorption layer are sequentially reduced.
3. Solar spectrum selective absorbing coating according to claim 2, characterized in that: in the range of 380-2500nm, the refractive index of the chromium-aluminum oxide main absorption layer is 2.32-3.87, and the refractive index of the chromium-aluminum oxide sub-absorption layer is 2.18-2.51; the extinction coefficient of the chromium-aluminum oxide main absorption layer is 1.21-2.08, and the extinction coefficient of the chromium-aluminum oxide sub-absorption layer is 0.29-0.77 in the range of 380-2500 nm.
4. Solar spectrum selective absorbing coating according to claim 1, characterized in that: the total thickness of the composite absorption layer is 116-118nm,
wherein:
the material of the chromium-aluminum oxide main absorption layer is Cr70Al30OxThe thickness of the material is 72-73 nm;
the chromium-aluminum oxide sub-absorption layer is made of Cr55Al45OxThe thickness of the material is 44-45 nm.
5. The medium-high temperature solar spectrum selective absorbing coating according to claim 1, characterized in that: the substrate is made of glass and 304 mirror stainless steel, and the thickness of the substrate layer is 1-6 mm.
6. The medium-high temperature solar spectrum selective absorbing coating according to claim 1, characterized in that: the emissivity of the material of the infrared reflecting layer is lower than 0.04, the thermal stability at high temperature is excellent, and the thickness of the infrared reflecting layer is 150 nm.
7. The medium-high temperature solar spectrum selective absorbing coating according to claim 6, characterized in that: the infrared reflecting layer is W.
8. The medium-high temperature solar spectrum selective absorbing coating according to claim 1, characterized in that: the material of the anti-reflection layer is SiO2、Al2O3、ThO2、Dy2O3、Eu2O3、Gd2O3、Y2O3、La2O3MgO or Sm2O3The thickness of the anti-reflection layer is 50-100 nm.
9. The method for preparing the medium-high temperature solar spectrum selective absorbing coating according to any one of claims 1 to 8, wherein the method comprises the following steps: preparing an infrared reflecting layer, a chromium-aluminum oxide main absorbing layer, a chromium-aluminum oxide sub-absorbing layer and an antireflection layer on a substrate layer sequentially by a magnetron sputtering method;
al and Cr are deposited on the substrate of glass, aluminum, copper, 304 mirror stainless steel or 316L mirror stainless steel in turn70Al30Ox、Cr55Al45OxAnd SiO2A film;
(1) preparing a substrate, namely selecting a polished 304 stainless steel plate or a polished glass plate, and carrying out radio frequency argon ion cleaning after mechanical cleaning to remove a surface pollution layer and an oxidation layer and improve the surface activity of the substrate;
(2) preparing an infrared reflecting layer, namely preparing a metal infrared reflecting layer on the surface of the substrate layer by sputtering through a (pulse) direct current magnetron sputtering method, wherein the selected target material can be metal tungsten (the purity is more than 99.7 percent), and the working gas is argon;
(3) preparing an absorption layer by reactive sputtering on the infrared reflecting layer by a (pulse) direct current magnetron sputtering method, wherein the selected target materials are respectively a chromium-aluminum alloy target CrAl (purity is 99.9%, Cr: Al =70:30 at%) and a chromium-aluminum alloy target CrAl (purity is 99.9%, Cr: Al =55:45 at%), the reaction gas is oxygen, and the working gas is argon;
(4) preparing the antireflection layer by (pulse) direct current reactive magnetron sputtering on the absorption layer, wherein the selected target material is a silicon-aluminum target (the aluminum content is 0-30 wt%, and the purity is more than 99.7%), the reaction gas is oxygen, and the working gas is argon.
10. The heat collection shell for the medium-high temperature solar spectrum selective absorption coating obtained by the medium-high temperature solar spectrum selective absorption coating according to claim 1 is characterized in that:
the solar heat-absorbing coating comprises a shell, wherein a cover plate is arranged on the shell, a heat-absorbing layer and a heat-insulating layer are arranged below the cover plate, and the heat-absorbing layer is the medium-high temperature solar spectrum selective absorption coating.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911234596.0A CN111076434A (en) | 2019-12-05 | 2019-12-05 | Medium-high temperature solar spectrum selective absorption coating, preparation method thereof and heat collection shell |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911234596.0A CN111076434A (en) | 2019-12-05 | 2019-12-05 | Medium-high temperature solar spectrum selective absorption coating, preparation method thereof and heat collection shell |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111076434A true CN111076434A (en) | 2020-04-28 |
Family
ID=70313020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911234596.0A Pending CN111076434A (en) | 2019-12-05 | 2019-12-05 | Medium-high temperature solar spectrum selective absorption coating, preparation method thereof and heat collection shell |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111076434A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102734956A (en) * | 2012-06-26 | 2012-10-17 | 四川中科百博太阳能科技有限公司 | Solar medium and high-temperature selective heat absorption coating |
| CN102734961A (en) * | 2012-06-26 | 2012-10-17 | 四川中科百博太阳能科技有限公司 | Solar medium-temperature and high-temperature selective absorption coating layer |
| WO2012172148A1 (en) * | 2011-06-16 | 2012-12-20 | Consejo Superior De Investigaciones Científicas (Csic) | Covering that selectively absorbs visible and infrared radiation, and method for the production thereof |
| CN103255377A (en) * | 2013-05-20 | 2013-08-21 | 武汉大学 | Nano composite Cr-Al-O (chromium-aluminum-oxygen) solar spectrum selective absorption coating and preparation method thereof |
| CN104294270A (en) * | 2014-10-16 | 2015-01-21 | 太原理工大学 | Novel process of preparing solar selective absorption coating |
| CN106288462A (en) * | 2016-08-26 | 2017-01-04 | 中国建筑材料科学研究总院 | A kind of solar selectively absorbing coating and preparation method thereof |
| CN107588569A (en) * | 2017-09-26 | 2018-01-16 | 中国建筑材料科学研究总院 | Double absorption layer spectral selective absorbing coating and preparation method thereof |
| CN108611610A (en) * | 2016-12-02 | 2018-10-02 | 北京有色金属研究总院 | A kind of dual dielectric layer selective solar spectrum absorbing membrane and preparation method thereof |
-
2019
- 2019-12-05 CN CN201911234596.0A patent/CN111076434A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2012172148A1 (en) * | 2011-06-16 | 2012-12-20 | Consejo Superior De Investigaciones Científicas (Csic) | Covering that selectively absorbs visible and infrared radiation, and method for the production thereof |
| CN102734956A (en) * | 2012-06-26 | 2012-10-17 | 四川中科百博太阳能科技有限公司 | Solar medium and high-temperature selective heat absorption coating |
| CN102734961A (en) * | 2012-06-26 | 2012-10-17 | 四川中科百博太阳能科技有限公司 | Solar medium-temperature and high-temperature selective absorption coating layer |
| CN103255377A (en) * | 2013-05-20 | 2013-08-21 | 武汉大学 | Nano composite Cr-Al-O (chromium-aluminum-oxygen) solar spectrum selective absorption coating and preparation method thereof |
| CN104294270A (en) * | 2014-10-16 | 2015-01-21 | 太原理工大学 | Novel process of preparing solar selective absorption coating |
| CN106288462A (en) * | 2016-08-26 | 2017-01-04 | 中国建筑材料科学研究总院 | A kind of solar selectively absorbing coating and preparation method thereof |
| CN108611610A (en) * | 2016-12-02 | 2018-10-02 | 北京有色金属研究总院 | A kind of dual dielectric layer selective solar spectrum absorbing membrane and preparation method thereof |
| CN107588569A (en) * | 2017-09-26 | 2018-01-16 | 中国建筑材料科学研究总院 | Double absorption layer spectral selective absorbing coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN204345956U (en) | The continuously adjustable coating for selective absorption of sunlight spectrum of a kind of ABSORPTION EDGE | |
| Cao et al. | A review of cermet-based spectrally selective solar absorbers | |
| AU662360B2 (en) | Photovoltaic device | |
| CN105299935B (en) | A kind of coating for selective absorption of sunlight spectrum and preparation method thereof and heat collector | |
| CN201218622Y (en) | Selective solar energy absorbing coating | |
| US20150316289A1 (en) | Solar spectrum selective absorption coating and its manufacturing method | |
| CN105222381B (en) | A kind of double absorption layer coating for selective absorption of sunlight spectrum and preparation method thereof | |
| CN102122006A (en) | Solar spectrum selective absorbing coating and preparation method thereof | |
| CN102501459B (en) | Preparation method of medium-and-high-temperature solar selective absorption coating | |
| US20150316290A1 (en) | Solar spectrum selective absorption coating and its manufacturing method | |
| CN204535163U (en) | A kind of coating for selective absorption of sunlight spectrum and heat collector | |
| CN109457219B (en) | Medium-low temperature solar spectrum selective absorption coating and preparation method thereof | |
| CN105970175B (en) | A kind of titanium carbide-titanium carbide zirconium high temperature solar energy selective absorption coating and preparation method thereof | |
| CN102108491A (en) | High-temperature solar selective absorbing coating and preparation method thereof | |
| CN110595084A (en) | Metal gradual-change high-temperature solar energy absorption coating and preparation method thereof | |
| CN204478557U (en) | A kind of double absorption layer coating for selective absorption of sunlight spectrum | |
| CN110643942B (en) | Spectrum-selective high-temperature solar energy absorption coating and preparation method thereof | |
| CN106011746A (en) | Laser protective film for satellite solar battery array and preparation method thereof | |
| CN109341116B (en) | Cr-Si-N-O solar selective absorption coating and preparation method thereof | |
| CN108917210A (en) | A kind of nano combined photothermal conversion coating of auto-dope and preparation method thereof | |
| CN109338297B (en) | Hafnium diboride-zirconium diboride-based high-temperature solar energy absorption coating and preparation method thereof | |
| CN104034071A (en) | Dark green solar spectral selection absorbing coating and preparation method and application thereof | |
| CN209484869U (en) | Double transition zone composite absorption type coating for selective absorption of sunlight spectrum | |
| CN116123741A (en) | Solar spectrum selective absorption coating for groove type thermal power generation high-temperature vacuum heat collecting tube and preparation method thereof | |
| CN105276846B (en) | Coating for selective absorption of sunlight spectrum that ABSORPTION EDGE is continuously adjusted and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200428 |
|
| RJ01 | Rejection of invention patent application after publication |