CN106048535A - High-temperature-resistant and corrosion-resistant solar selective absorption coating - Google Patents
High-temperature-resistant and corrosion-resistant solar selective absorption coating Download PDFInfo
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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
- 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
- C23C14/24—Vacuum evaporation
- C23C14/28—Vacuum evaporation by wave energy or particle radiation
- C23C14/30—Vacuum evaporation by wave energy or particle radiation by electron bombardment
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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
- 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
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
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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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
- C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
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- 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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- 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
Abstract
The invention relates to the technical field of photo-thermal solar energy and discloses a high-temperature-resistant and corrosion-resistant solar selective absorption coating. The coating comprises a reflection substrate layer, a composite absorption layer, an antireflection layer and an organic protection layer which are successively arranged on the surface of a substrate from inside to outside and is characterized in that the reflection substrate layer is prepared by a large-area electric beam evaporation coating process; the coating material used by the coating process is aluminum, copper or silver; the composite absorption layer comprises a first sub-layer and a second sub-layer which are successively arranged from bottom to top; the two sub-layers are double-ceramic films; the antireflection layer comprises a single CuMnOx layer or composite double layers; an inner layer of the composite double layers is a CuMnOx layer, and an outer layer of the composite double layers is an SnO2 layer; the thickness of the organic protection layer is 100-200nm; and the organic protection layer is prepared from tetraethyl orthosilicate, absolute ethyl alcohol and ammonia water. Through the high-temperature-resistant and corrosion-resistant solar selective absorption coating, stress action of the coating in the heat treatment process can be relieved; the absorption-emission ratio of the coating is increased; and the high temperature resistance and the corrosion resistance of the absorption coating are greatly improved.
Description
Technical field
The present invention relates to photo-thermal technical field of solar, the solar selectively being specifically related to a kind of corrosion-and high-temp-resistant is inhaled
Receive coating.
Background technology
Coating for selective absorption of sunlight spectrum has high-selenium corn at the sunlight wave band that wave-length coverage is 0.3 μm-2.5 μm
Rate, has low-E at the infrared band that wave-length coverage is 2.5 μm-50 μm, therefore, and coating for selective absorption of sunlight spectrum
It is widely used in solar thermal collector or thermal-collecting tube, is the core material realizing solar energy hot-cast socket.At present, the existing sun
Spectral selective absorbing coating mainly includes infrared reflecting layer, the absorbed layer being successively set on the substrates such as glass, aluminum, rustless steel
And anti-reflection layer, wherein, the Main Function of infrared reflecting layer is reflection infrared ray, reduces the radiation that heat is outside, works as infrared external reflection
In the case of layer reaches certain thickness, infrared reflecting layer is the finest and close, and infrared external reflection effect is the best, and heat-insulating property is the best；Absorbed layer is used
Absorbing solar energy, temperature raises and is translated into heat energy, and anti-reflection layer is used for reducing at absorbed layer and Air Interface too
Sunlight reflects, so that more sunlight arrives absorbed layer through anti-reflection layer.
Along with solar thermal utilization demand and the development of technology, the range of application of solar energy heat collection pipe is from cryogenic applications
(<100 DEG C) to middle temperature application (100-400 DEG C) and high temperature application (>400 DEG C) development, constantly to meet sea water
The use requirement of high-temperature applications in desalination, solar electrical energy generation etc..But, for solar energy heat collection pipe, operating temperature
The highest, the highest to the thermal stability requirement of coating for selective absorption.Along with the rising of operating temperature, metal component is susceptible to layer
Between phase counterdiffusion, thus cause the solar spectrum absorbance of this coating substantially to reduce, infrared emittance drastically raises, and affects coating
Use temperature and the life-span.
Additionally, though the most common anti-reflection layer can increase the transmitance of visible region, but to the protected effect of coating not
Ideal, and how restricted in the selection of material, it is difficult to obtain satisfied effect；The coating of multiple structure is deposited in sintering process
In the phenomenon that surface stress increases so that crackle occurs in the coating phase after sintering, affect the final optics of coating and select absorbability
Energy.Simultaneously as the thermal coefficient of expansion difference of interlayer materials is relatively big, therefore between coated film layer, interfacial stress is relatively big, causes film
Layer occurs, during high/low temperature experiment and use, the probability come off.
The form of light thermo-power station starts variation at present, and conventional coating is used on vacuum heat collection pipe and is also possible, can
It is that the application of present naked pipe also begins to more and more extensive, it is therefore desirable to coating not only can have good heatproof in a vacuum
Performance and decay resistance, also must have in air (including steam, salt fog, soda acid) etc. more excellent heat resistance and
Decay resistance, can meet the use demand in power station.
Summary of the invention
The invention aims to solve the problem of above-mentioned existence, for realizing object above, technical scheme
For:
The solar selectively absorbing coating of a kind of corrosion-and high-temp-resistant, be included in that substrate surface sets gradually from inside to outside is anti-
Penetrate basal layer, composite absorption layer, anti-reflection layer and organic protection coating, it is characterised in that: described reflective substrate layer uses large area
Electron beam evaporation deposition technique is prepared from, and the Coating Materials that coating process is used is aluminum, copper or silver；Described compound suction
Receiving layer to be made up of the first subgrade the most from bottom to up and the second subgrade, two subgrades are double ceramic membrane；Described anti-reflection layer by
Monolayer CuMnOxLayer composition, or be CuMnO by internal layerxLayer, outer layer are SnO2The composite double layer composition of layer；Described organic protection
Layer thickness is 100 ~ 200nm, and it is prepared from by following method: tetraethyl orthosilicate is added dehydrated alcohol, the solution being made into
In, tetraethyl orthosilicate is 15% ~ 25% with the percent by volume of dehydrated alcohol；Ammonia is added dehydrated alcohol, in the solution being made into,
Ammonia is 3% ~ 7% with the percent by volume of dehydrated alcohol；The two kinds of mixed solutions obtained by aforesaid operations mix and stir
Mixing, after 20 ~ 28 hours stand, use sol-gal process, the colloid formed after standing is coated uniformly on anti-reflection layer surface.
As preferred technical scheme, described substrate is aluminium strip, stainless steel band or copper strips.
As preferred technical scheme, the lower surface of described reflective substrate layer is coated with thin film coating, and its purpose exists
In the tack and/or the corrosion resistance that improve and improve selective solar heat absorption coating.
As preferred technical scheme, the composition of described film coating is at least one metal, at least one burning
Thing, at least one metal nitride, at least one metal oxynitride or above metal, metal-oxide, metal nitride
Combination in any with metal oxynitride.
As preferred technical scheme, described film coating uses DC magnetron sputtering technique or AC magnetron sputtering work
Skill is sputtered at the lower surface of described reflective substrate layer.
As preferred technical scheme, the thickness of described reflective substrate layer is 50nm ~ 1000nm.
As preferred technical scheme, the upper surface of described reflective substrate layer is coated with one layer of TiN, AlN, Al2O3、
TiO2、 SiO2Si3N4Or Cr2O3Diffusion impervious layer, thickness is 50 ~ 100nm.
As preferred technical scheme, described pair of ceramic membrane is SiO2+TiO2Film, SiO2+ NiO film, Si3N4+Ni3N2
Film, Si3N4+ TiN film, NiO+TiO2Film or Ni3N2+ TiN film, described first subgrade and the thickness of described second subgrade
It is 50 ~ 100nm.
As preferred technical scheme, in described first subgrade, SiO2+TiO2In SiO2Account for percent by volume be 30 ~
50%, remaining is TiO2；SiO2SiO in+NiO2Accounting for percent by volume is 30 ~ 50%, and remaining is NiO；Si3N4+Ni3N2
In Si3N4Accounting for percent by volume is 30 ~ 50%, and remaining is Ni3N2；Si3N4TiN in+TiN account for percent by volume be 30 ~
50%, remaining is Si3N4；NiO+ TiO2In TiO2Accounting for percent by volume is 30 ~ 50%, and remaining is NiO；Ni3N2In+TiN
TiN to account for percent by volume be 30 ~ 50%, remaining is Ni3N2；In described second subgrade, SiO2+TiO2In SiO2Account for volume hundred
Proportion by subtraction is 50 ~ 75%, and remaining is TiO2；SiO2SiO in+NiO2Accounting for percent by volume is 50 ~ 75%, and remaining is NiO；
Si3N4+Ni3N2In Si3N4Accounting for percent by volume is 50 ~ 75%, and remaining is Ni3N2；Si3N4TiN in+TiN accounts for volume hundred
Proportion by subtraction is 50 ~ 75%, and remaining is Si3N4；NiO+ TiO2In TiO2Accounting for percent by volume is 50 ~ 75%, and remaining is NiO；
Ni3N2It is 50 ~ 75% that TiN in+TiN accounts for percent by volume, and remaining is Ni3N2。
As preferred technical scheme, described CuMnOxLayer is by CuMnOxComplex sol is prepared from, described CuMnOx
Complex sol is by nano-solid granule and CuMnOxColloidal sol is blended prepares gained.Described nano-solid granule is rare-earth oxidation
Thing or silicon compound, described rare earth oxide is terbia. Diterbium trioxide, cerium oxide or strontium oxide, and described silicon compound is silicon oxide.Wherein
Described CuMnOxThe surface roughness of layer is 50 ~ 80nm.
Compared to the prior art, what the present invention produced has the beneficial effects that:
1, the present invention designs ingenious, practical, by using a kind of Investigation of Large Area Electron Beam evaporation coating technique to prepare selection
The reflective substrate layer of property solar heat absorber coatings, can increase the thickness of reflective substrate layer, and these thicker coatings can
Selective solar heat absorption coating is made to have lower infrared emission ratio easily.Having the same of lower infrared emission ratio
Time, selective solar heat absorption coating is affected the least by base material condition.Meanwhile, of a relatively high production can had
In the case of ability, it is achieved the improvement to the reflective substrate layer quality of selective solar heat absorption coating, and then can help
Improve and improve the serviceability of solar thermal collector.
2, the present invention uses sol-gal process to prepare copper manganese colloidal sol, and nano-solid granule is joined copper manganese by a certain percentage
In colloidal sol, form solid-liquid solid solution；The pinning effect of nano-solid granule can alleviate colloidal sol should in heat treatment process
The phenomenon that power is excessive, prevents the generation of crackle, makes coating finer and close.
3, owing to adding organic protection coating so that it is high temperature resistant and the performance of atmospheric corrosion resistance is greatly reinforced so that this
Plant new structure high-temperature selective absorber coatings and there is good high high-temp stability and weatherability.
Accompanying drawing explanation
For the technical scheme being illustrated more clearly that in the embodiment of the present invention, in embodiment being described below required for make
Accompanying drawing be briefly described, it should be apparent that, below describe in accompanying drawing be only some embodiments of the present invention, for
From the point of view of those of ordinary skill in the art, on the premise of not paying creative work, it is also possible to obtain other according to these accompanying drawings
Accompanying drawing, wherein:
Fig. 1 is the structural representation of the present invention.
Detailed description of the invention
Below in conjunction with the accompanying drawing in present example, the technical scheme in the embodiment of the present invention is carried out clear, complete
Ground describes.Obviously, described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based on sending out
Embodiment in bright, the every other enforcement that those of ordinary skill in the art are obtained under not making creative work premise
Example, broadly falls into the scope of protection of the invention.
As it is shown in figure 1, the present invention proposes the solar selectively absorbing coating of a kind of corrosion-and high-temp-resistant, it is included in base
On sheet, six tunics of preparation, are followed successively by: film coating, reflective substrate layer, diffusion impervious layer, composite absorption from bottom surface to surface
Layer, anti-reflection layer, organic protection coating, wherein:
Substrate is aluminium strip, stainless steel band or copper strips material；
Film coating is at least one metal, at least one metal-oxide, at least one metal nitride, at least one metal
Nitrogen oxides or the combination in any of above metal, metal-oxide, metal nitride and metal oxynitride.It uses DC
Magnetron sputtering technique or AC magnetron sputtering technique are sputtered at the lower surface of high reflective substrate layer, select for improving and improving
The tack of property solar heat absorber coatings and/or corrosion resistance.
Reflective substrate layer uses Investigation of Large Area Electron Beam evaporation coating technique to be prepared from, the plating that this coating process is used
Membrane material is aluminum, copper or silver, and its thickness is 50nm ~ 1000nm.
Diffusion impervious layer is nitride or oxide membranous layer, specially TiN, AlN, Al2O3、 TiO2、 SiO2Si3N4Or
Person Cr2O3, thickness is 50 ~ 100nm.
Composite absorption layer includes that the first subgrade and the second subgrade, two subgrades are double ceramic membrane, specially SiO2+TiO2
Film, SiO2+ NiO film, Si3N4+Ni3N2Film, Si3N4+ TiN film, NiO+TiO2Film or Ni3N2+ TiN film, first
The thickness of subgrade and the second subgrade is 50 ~ 100nm.In first subgrade, SiO2+TiO2In SiO2Accounting for percent by volume is
30 ~ 50%, remaining is TiO2；SiO2SiO in+NiO2Accounting for percent by volume is 30 ~ 50%, and remaining is NiO；Si3N4+
Ni3N2In Si3N4Accounting for percent by volume is 30 ~ 50%, and remaining is Ni3N2；Si3N4TiN in+TiN accounts for percent by volume
30 ~ 50%, remaining is Si3N4；NiO+ TiO2In TiO2Accounting for percent by volume is 30 ~ 50%, and remaining is NiO；Ni3N2+TiN
In TiN to account for percent by volume be 30 ~ 50%, remaining is Ni3N2；In described second subgrade, SiO2+TiO2In SiO2Account for volume
Percentage ratio is 50 ~ 75%, and remaining is TiO2；SiO2SiO in+NiO2Accounting for percent by volume is 50 ~ 75%, and remaining is NiO；
Si3N4+Ni3N2In Si3N4Accounting for percent by volume is 50 ~ 75%, and remaining is Ni3N2；Si3N4TiN in+TiN accounts for volume hundred
Proportion by subtraction is 50 ~ 75%, and remaining is Si3N4；NiO+ TiO2In TiO2Accounting for percent by volume is 50 ~ 75%, and remaining is NiO；
Ni3N2It is 50 ~ 75% that TiN in+TiN accounts for percent by volume, and remaining is Ni3N2。
Anti-reflection layer is by monolayer CuMnOxLayer composition, or be CuMnO by internal layerxLayer, outer layer are SnO2The composite double layer of layer
Composition.
At preparation CuMnOxDuring layer, first, with Cu salt and Mn salt for metal cation source, ethanol is solvent, according to Cu
Ion: the mol ratio of Mn ion is the proportions solution A of 1:1；Citric acid is dissolved in dehydrated alcohol and forms solution B；Will
The pH value regulating mixed solution after solution A and solution B mix homogeneously is 5.5 ~ 6.5, the more concentrated concentration that obtains is 0.
The CuMnOx colloidal sol of 2mol/L ~ 0. 5mol/L；Then, by CuMnOxColloidal sol and ethanol mix according to the ratio of 1:3 ~ 1:4,
Stirring in water bath is completely dissolved to colloidal sol, obtains solution C, is slowly added to nano-solid granule to solution C, and constant temperature stirs to solid
Granule is completely dispersed, and is subsequently adding chelating agent, continues constant temperature stirring, until the viscosity of colloidal sol is 4 ~ 5 mPa s, obtains
CuMnOxComplex sol；Finally, CuMnO is carried outxThe lifting coating film treatment of complex sol, repeats to lift coating film treatment technique 2 ~ 5
Secondary, after drying, annealing heat treatment, obtain monolayer CuMnOxLayer, the roughness on its surface is 50 ~ 80nm.Wherein the above
Cu, Mn slaine be one or more in chlorate, nitrate and acetate；Described chelating agent is OP10 and poly-second
One or both in glycol；Described nano-solid granule is rare earth oxide or silicon compound, and described rare earth oxide is oxygen
Changing terbium, cerium oxide or strontium oxide, described silicon compound is silicon oxide.
And at preparation SnO2During layer, first, stannic chloride pentahydrate being dissolved in deionized water, regulation solution pH value is
3.5 ~ 4.5, prepare the SnO that concentration is 0.5mol/L2Colloidal sol, then carries out SnO2Colloidal sol lifting coating film treatment, then warp
After flash baking, annealing heat treatment, obtain SnO2Layer.
When preparing organic protection coating, tetraethyl orthosilicate is added dehydrated alcohol, in the solution being made into, tetraethyl orthosilicate with
The percent by volume of dehydrated alcohol is 15% ~ 25%；Ammonia is added dehydrated alcohol, in the solution being made into, ammonia and dehydrated alcohol
Percent by volume be 3% ~ 7%；The two kinds of different mixed solutions obtained by aforesaid operations carry out mixing and stirring, through 20 ~ 28
Obtaining colloid after hour standing, finally use sol-gal process that colloid is coated uniformly on anti-reflection layer surface, thickness is 100 ~
200nm.It is as protective layer, and Main Function is atmospheric corrosion resistance, including steam, salt fog, soda acid etc..
Embodiment 1
As it is shown in figure 1, the present embodiment provides one to have SiO2And TiO2The solar energy of the air corrosion-and high-temp-resistant of structure
Coating for selective absorption, wherein substrate is aluminium strip, and film coating selects metallic aluminium, and reflective substrate layer uses aluminum as plated film material
Material, thickness is 500 nm, and diffusion impervious layer is TiO2Film, thickness is 50nm, and composite absorption layer is SiO2+TiO2Film, gross thickness
For 140nm, wherein the first subgrade SiO2+TiO2Film thickness is 80nm, the second subgrade SiO2+TiO2Film thickness is 60nm,
SiO in first subgrade2Percent by volume be 40%, remaining is TiO2；Second subgrade SiO2Percent by volume be
60%, remaining is TiO2；Anti-reflection layer is monolayer CuMnOxLayer, its surface roughness is 50 nm；Organic protection layer thickness is
150nm。
Embodiment 2
As it is shown in figure 1, the present embodiment provides one to have Si3N4And Ni3N2The air corrosion-and high-temp-resistant solar energy of structure
Coating for selective absorption.Wherein, substrate is stainless steel band, and film coating selects metallic aluminium and copper, and reflective substrate layer uses copper to make
For Coating Materials, thickness is 800 nm, and diffusion impervious layer is Si3N4Film, thickness is 60nm, composite absorption layer Si3N4+ Ni3N2
Film, gross thickness is 160nm, and wherein the first subgrade thickness is 100nm, and the second subgrade thickness is 60nm, Si in the first subgrade3N4
Percent by volume be 40%, remaining is Ni3N2；Second subgrade Si3N4Percent by volume be 60%, remaining is
Ni3N2；Anti-reflection layer is CuMnO by internal layerxLayer, outer layer are SnO2The composite double layer composition of layer, CuMnOxThe surface roughness of layer
It is 80 nm；The thickness of organic protection coating is 130mm.
Embodiment 3
As it is shown in figure 1, the present embodiment provides one to have TiO2With the selection of corrosion-and high-temp-resistant in the air of NiO structure
Property absorber coatings, wherein, substrate is copper strips, and film coating selects metallic copper, reflective substrate layer use copper as Coating Materials, thick
Degree is 1000 nm, and diffusion impervious layer is TiO2 Film, thickness is 80nm；Composite absorption layer includes two sublayer structures, two Asias
Layer is TiO2+ NiO film, the thickness of the first subgrade and the second subgrade is 75nm, TiO in the first subgrade2Volume basis
Ratio is 60%, and remaining is NiO；TiO in second subgrade2Percent by volume be 40%；Remaining is NiO；Anti-reflection layer is by internal layer
For CuMnOxLayer, outer layer are SnO2The composite double layer composition of layer, CuMnOxThe surface roughness of layer is 80 nm；Organic protection coating
Thickness be 140mm.
Embodiment 4
As it is shown in figure 1, the present embodiment provides one to have NiO and SiO2In air, the solar energy of corrosion-and high-temp-resistant selects
Property absorber coatings, wherein, substrate is stainless steel band, film coating select metallic aluminium, reflective substrate layer use aluminum as plated film material
Material, thickness is 100 nm, and diffusion impervious layer is NiO, and thickness is 70nm；Composite absorption layer includes two sublayer structures, two Asias
Layer is NiO+SiO2Film, the thickness of the first subgrade and the second subgrade is 100nm, the volume basis of NiO in the first subgrade
Ratio is 40%, and remaining is SiO2；The percent by volume of the second subgrade NiO is 70%, and remaining is SiO2；Anti-reflection layer is by internal layer
For CuMnOxLayer, outer layer are SnO2The composite double layer composition of layer, CuMnOxThe surface roughness of layer is 50 nm；Organic protection coating
Thickness be 140mm.
Above example only in order to technical scheme to be described, is not intended to limit；Although with reference to previous embodiment
The present invention is described in detail, it will be understood by those within the art that: it still can be to aforementioned each enforcement
Technical scheme described in example is modified, or wherein portion of techniques feature is carried out equivalent；And these amendment or
Replace, do not make the essence of appropriate technical solution depart from the spirit and scope of various embodiments of the present invention technical scheme.
Claims (10)
1. a solar selectively absorbing coating for corrosion-and high-temp-resistant, is included in what substrate surface set gradually from inside to outside
Reflective substrate layer, composite absorption layer, anti-reflection layer and organic protection coating, it is characterised in that: described reflective substrate layer uses big face
Long-pending electron beam evaporation deposition technique is prepared from, and the Coating Materials that coating process is used is aluminum, copper or silver；Described is compound
Absorbed layer is made up of the first subgrade the most from bottom to up and the second subgrade, and two subgrades are double ceramic membrane；Described anti-reflection layer
By monolayer CuMnOxLayer composition, or be CuMnO by internal layerxLayer, outer layer are SnO2The composite double layer composition of layer；Described organic anti-
Covering thickness is 100 ~ 200nm, and it is prepared from by following method: tetraethyl orthosilicate is added dehydrated alcohol, the solution being made into
In, tetraethyl orthosilicate is 15% ~ 25% with the percent by volume of dehydrated alcohol；Ammonia is added dehydrated alcohol, the solution being made into
In, ammonia is 3% ~ 7% with the percent by volume of dehydrated alcohol；Two kinds of mixed solutions that aforesaid operations is obtained carry out mixing and
Stirring, after 20 ~ 28 hours stand, uses sol-gal process, and the colloid formed after standing is coated uniformly on anti-reflection layer
Surface.
The solar selectively absorbing coating of corrosion-and high-temp-resistant the most according to claim 1, it is characterised in that: described base
Sheet is aluminium strip, stainless steel band or copper strips.
The solar selectively absorbing coating of corrosion-and high-temp-resistant the most according to claim 1, it is characterised in that: described instead
The lower surface penetrating basal layer is coated with thin film coating.
The solar selectively absorbing coating of corrosion-and high-temp-resistant the most according to claim 3, it is characterised in that: described thin
The composition of membrane coat is at least one metal, at least one metal-oxide, at least one metal nitride, at least one metal
Nitrogen oxides or the combination in any of above metal, metal-oxide, metal nitride and metal oxynitride.
The solar selectively absorbing coating of corrosion-and high-temp-resistant the most according to claim 3, it is characterised in that: described thin
Membrane coat uses DC magnetron sputtering technique or AC magnetron sputtering technique to be sputtered at the lower surface of described reflective substrate layer.
6. according to the solar selectively absorbing coating of the corrosion-and high-temp-resistant described in claim 1, it is characterised in that: described
The thickness of reflective substrate layer is 50nm ~ 1000nm.
7. according to the solar selectively absorbing coating of the corrosion-and high-temp-resistant described in claim 1, it is characterised in that: described
The upper surface of reflective substrate layer is coated with one layer of TiN, AlN, Al2O3、 TiO2、 SiO2Si3N4Or Cr2O3Diffusion barrier
Layer, thickness is 50 ~ 100nm.
8. according to the solar selectively absorbing coating of the corrosion-and high-temp-resistant described in claim 1, it is characterised in that: described
Double ceramic membranes are SiO2+TiO2Film, SiO2+ NiO film, Si3N4+Ni3N2Film, Si3N4+ TiN film, NiO+TiO2Film or
Person Ni3N2+ TiN film, the thickness of described first subgrade and described second subgrade is 50 ~ 100nm.
The solar selectively absorbing coating of corrosion-and high-temp-resistant the most according to claim 8, it is characterised in that:
In described first subgrade, SiO2+TiO2In SiO2Accounting for percent by volume is 30 ~ 50%, and remaining is TiO2；SiO2+
SiO in NiO2Accounting for percent by volume is 30 ~ 50%, and remaining is NiO；Si3N4+Ni3N2In Si3N4Accounting for percent by volume is
30 ~ 50%, remaining is Ni3N2；Si3N4It is 30 ~ 50% that TiN in+TiN accounts for percent by volume, and remaining is Si3N4；NiO+
TiO2In TiO2Accounting for percent by volume is 30 ~ 50%, and remaining is NiO；Ni3N2TiN in+TiN account for percent by volume be 30 ~
50%, remaining is Ni3N2；
In described second subgrade, SiO2+TiO2In SiO2Accounting for percent by volume is 50 ~ 75%, and remaining is TiO2；SiO2+NiO
In SiO2Accounting for percent by volume is 50 ~ 75%, and remaining is NiO；Si3N4+Ni3N2In Si3N4Account for percent by volume be 50 ~
75%, remaining is Ni3N2；Si3N4It is 50 ~ 75% that TiN in+TiN accounts for percent by volume, and remaining is Si3N4；NiO+TiO2In
TiO2Accounting for percent by volume is 50 ~ 75%, and remaining is NiO；Ni3N2TiN in+TiN account for percent by volume be 50 ~
75%, remaining is Ni3N2。
10. according to the solar selectively absorbing coating of the corrosion-and high-temp-resistant described in claim 1, it is characterised in that: institute
State CuMnOxLayer is by CuMnOxComplex sol is prepared from, described CuMnOxComplex sol be by nano-solid granule with
CuMnOxColloidal sol is blended prepares gained, and described nano-solid granule is rare earth oxide or silicon compound, described rare earth oxide
For terbia. Diterbium trioxide, cerium oxide or strontium oxide, described silicon compound is silicon oxide；Described CuMnOxThe surface roughness of layer is 50 ~
80nm。
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| CN108286833A (en) * | 2018-01-05 | 2018-07-17 | 山东省圣泉生物质石墨烯研究院 | Dark volume absorption-type coating, photothermal conversion component and solar water heater comprising it |
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Application publication date: 20161026 |