CN104949362A - Solar spectrum selective absorbing coating - Google Patents
Solar spectrum selective absorbing coating Download PDFInfo
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- CN104949362A CN104949362A CN201410123190.6A CN201410123190A CN104949362A CN 104949362 A CN104949362 A CN 104949362A CN 201410123190 A CN201410123190 A CN 201410123190A CN 104949362 A CN104949362 A CN 104949362A
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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
- F24S70/225—Details of absorbing elements characterised by absorbing coatings; characterised by surface treatment for increasing absorption for spectrally selective absorption
-
- 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 light-thermal solar energy and discloses a solar spectrum selective absorbing coating. The solar spectrum selective absorbing coating comprises an infrared reflecting layer, an absorbing layer and an anti-reflection layer, wherein the infrared reflecting layer, the absorbing layer and the anti-reflection layer are sequentially arranged on the surface of a base plate from inside to outside, the absorbing layer comprises multiple sub-layers, each sub-layer include multiple sub sub-layers, each sub sub-layer include micro sub sub-layers, and each micro sub sub-layer is a metal layer and ceramic layer composite layer. According to the solar spectrum selective absorbing coating, the sub sub-layer absorbing layers in the absorbing layer are exquisite ultra-thin multiple-layer composite material films with metal layers and ceramic layers deposited alternatively and successively, it can be regarded as that metal components are evenly distributed in ceramic, and the sub sub-layer absorbing layers can be regarded as metal ceramic composite films with evenly distributed metal particles. The metal layer component ratio of the micro sub sub-layer absorbing layers and the periodicity of the micro sub sub-layers, namely the thickness of the sub-layers, are mainly considered in a debugging process of the absorbing layer, qualified absorption ratio stipulated by national standard and very low emission rate can be obtained, and metal components and measurement parameters can be very easily determined.
Description
Technical field
The present invention relates to photo-thermal technical field of solar, particularly relate to a kind of coating for selective absorption of sunlight spectrum.
Background technology
Solar energy is a kind of inexhaustible clean energy resource, coating for selective absorption of sunlight spectrum is very high to the absorptivity of visible ray, and self infrared emittance is very low, low-grade solar energy can be converted to high-grade heat energy, enrichment is played to solar energy, the key technology in solar thermal utilization, most important to raising collector efficiency.
The absorption of coating for selective absorption of sunlight spectrum and emitting performance determine the thermal efficiency of solar energy heat collection pipe, coating for selective absorption of sunlight spectrum is primarily of three part compositions as shown in Figure 1: infrared reflecting layer, absorbed layer and anti-reflection layer, adds tack coat and diffusion impervious layer if desired.
Coating for selective absorption of sunlight spectrum commonly uses two kinds of basic structures: gradation type cermet solar energy absorbing coating and interference absorption-type cermet coating for selective absorption of sunlight spectrum, wherein:
Gradation type cermet solar energy absorbing coating as shown in Figure 2, its cermet absorbed layer has many sublayer structures, such as 10-20 layer, and each subgrade interior metal uniform particle distributes, and metal volume content immobilizes.But from gradually from infrared reflecting layer to anti-reflection layer, metal volume content reduces in gradient gradually, the subgrade metal volume content near infrared reflecting layer is maximum, and the subgrade metal volume content near anti-reflection layer is minimum.The metal-cermic coating of different metal volume content, has different refractive index n and extinction coefficient k, has different absorption coefficient and reflectivity R.The multi-layer absorber layer structure of gradation type solar energy absorbing coating effectively can absorb solar radiation.But this coating tuning parameter is many, and absorptance and near infrared emission ratio are not easy to reach ideal value.
Interference absorption-type cermet coating for selective absorption of sunlight spectrum as shown in Figure 3, its cermet absorbed layer has 2 to 3 layers of subgrade, and each subgrade interior metal uniform particle distributes, and metal volume content immobilizes.The coated absorbed inside characteristic of solar radiation and phase interference performance characteristic two aspect absorb.Its modulation parameter is relatively less, but the corresponding a kind of optical constant of the coating of each metal volume content, needs debugging to find out the suitable tenor of two absorbed layers and thicknesses of layers, simultaneously, find proper anti-reflection layer thickness, just can obtain excellent reflectivity R, acquire a certain degree of difficulty.
In the basic structure of two kinds of coating for selective absorption of sunlight spectrum, in the subgrade of absorbed layer, metallic is uniformly distributed in ceramic material, and its composition determines in real work, all have certain difficulty with location parameter.
In view of the defect of above-mentioned prior art, needing provides convenience to determine and measures the coating for selective absorption of sunlight spectrum of metallic composition in ceramic material.
Summary of the invention
The technical problem to be solved in the present invention is that in the subgrade of the absorbed layer of existing coating for selective absorption of sunlight spectrum, metallic is uniformly distributed in ceramic material, and its composition determines the problem difficult in real work with parametric measurement.
In order to solve the problems of the technologies described above, the invention provides a kind of coating for selective absorption of sunlight spectrum and be included in infrared reflecting layer, absorbed layer and the anti-reflection layer that substrate surface sets gradually from inside to outside, described absorbed layer comprises two sublayers, described subgrade comprises multi-level subgrade, described time subgrade comprises micro-subgrade, and described micro-subgrade is the composite bed of metal level and ceramic layer.
Wherein, described absorbed layer comprises layer 2-3 subgrade, and every layer of subgrade comprises 6-20 level subgrade.
Wherein, the thickness of described absorbed layer is 60-300nm, and the thickness of every layer of subgrade is 30-150nm, and the thickness of every layer of micro-subgrade is less than 5nm.
Wherein, described subgrade is divided into high cermet absorbed layer and low-metal ceramic absorbed layer.
Wherein, the material of described metal level is stainless steel, and the material of described ceramic layer is aluminium nitride.
Wherein, described metal level comprises a kind of metal level or two kinds of metal levels.
Wherein, the material of described infrared reflecting layer is film or the TiAlN of low-infrared radiation rate, and the thickness of described infrared reflecting layer is 80-300nm.
Wherein, the material of described anti-reflection layer is the ceramic material that refractive index is low, and the thickness of described anti-reflection layer is 50-100nm.
Wherein, also comprise tack coat, described tack coat is between described substrate and described infrared reflecting layer, and the material of described tack coat is metal, pottery or ceramic-metal composite, and the thickness of described tack coat is 10-40nm.
Wherein, also comprise diffusion impervious layer, described diffusion impervious layer is between described infrared reflecting layer and described absorbed layer, and the material of described diffusion impervious layer is metal, pottery or ceramic-metal composite, and the thickness of described diffusion impervious layer is 10-40nm.
Technique scheme tool of the present invention has the following advantages: coating for selective absorption of sunlight spectrum provided by the present invention is the meticulous ultra-thin multilayer materials film that metal level ceramic layer replaces successive sedimentation by absorbed layer subgrade absorbed layer, can think that metal component is evenly distributed in pottery, secondary subgrade absorbed layer can think the equally distributed metal-ceramic composite film of metallic.Absorbed layer mainly considers metal level ratio of component and micro-subgrade periodicity and subgrade thickness in micro-subgrade absorbed layer when testing and measuring technology, can obtain the qualified absorptance of national regulations and very low transmitting ratio, be easy to composition and the location parameter of determining metal.
Accompanying drawing explanation
Fig. 1 is the structural representation of background technology coating for selective absorption of sunlight spectrum of the present invention;
Fig. 2 is the absorbed layer metal volume changes of contents schematic diagram of background technology gradation type coating for selective absorption of sunlight spectrum of the present invention;
Fig. 3 is the absorbed layer metal volume changes of contents schematic diagram of background technology interfere type coating for selective absorption of sunlight spectrum of the present invention;
Fig. 4 is the absorbed layer metal volume changes of contents schematic diagram of embodiment of the present invention coating for selective absorption of sunlight spectrum;
Fig. 5 is the reflectivity curve that embodiment of the present invention coating for selective absorption of sunlight spectrum uses spectrophotometer test.
In figure: 1: substrate; 2: tack coat; 3: infrared reflecting layer; 4: diffusion impervious layer; 5: absorbed layer; 6: anti-reflection layer; 7: metal level; 8: ceramic layer.
Detailed description of the invention
In describing the invention, except as otherwise noted, the implication of " multiple " is two or more.Term " interior ", " outward ", etc. instruction orientation or position relationship be based on orientation shown in the drawings or position relationship, only the present invention for convenience of description and simplified characterization, instead of indicate or imply that the device of indication or element must have specific orientation, with specific azimuth configuration and operation, therefore can not be interpreted as limitation of the present invention.
Below in conjunction with drawings and Examples, the specific embodiment of the present invention is described in further detail.Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
As shown in Figure 1 and Figure 4, a kind of coating for selective absorption of sunlight spectrum provided by the invention is included in the infrared reflecting layer 3 that substrate 1 surface sets gradually from inside to outside, absorbed layer 5 and anti-reflection layer 6, the material of substrate 1 is glass, the metal of silicon chip or polishing, in the present embodiment, base material 1 adopts the material of polishing stainless steel, absorbed layer 5 comprises multilayer subgrade, each subgrade comprises multi-level subgrade, secondary subgrade comprises micro-subgrade, micro-subgrade is the composite bed of metal level 7 and ceramic layer 8, metal level 7 comprises one or both metal levels, it should be noted that, metal level 7 can be the composite bed of a kind of metal level or two kinds of metal levels, also can be alloying metal layer thus substantially reduce the composition proportion of metal alloy target in magnetron sputtering making difficulty, a kind of coating for selective absorption of sunlight spectrum provided by the invention, its metal volume content is uniformly distributed in ceramic material unlike traditional coating for selective absorption of sunlight spectrum, but metal level ceramic layer in certain ratio of component as volume, thickness and the ratio alternating deposit of time, after depositing certain periodicity, deposit according to another one metal level ceramic layer component ratio.In secondary subgrade, metal level and ceramic layer ratio of component are equal to metal level in subgrade and ceramic layer ratio of component, because each micro-subgrade is very meticulous, each subgrade and subgrade still can be regarded metallic as and be evenly distributed in ceramic material, the metallic content of two subgrades is different, still can have interference effect, its tenor can be converted by metal level in time subgrade and ceramic layer thickness time ratio; Utilize horizontal magnetic control film coating machine on the pipe of polishing metal, deposit the infrared reflecting layer 3 that material is copper successively, material is the ceramic layer 8 of aluminium nitride and material is the absorbed layer 5 that stainless metal level 7 is alternately composited, and material is the anti-reflection layer 6 of aluminum oxynitride.
Metal level 7 and ceramic layer 8 are at least one reacting gas and a kind of inert gas, have the successively continuous sputtering of two kinds of metallic targets to be formed.This metal ingredient can be selected as metal targets sputtering sedimentations in inert gas such as tungsten, nickel, nichrome, platinum, molybdenum, molybdenum alloy, stainless steel obtain.This ceramic component can select pure aluminum target or aluminium alloy target or silicon target sputtering deposition at least one reacting gas is as nitrogen to obtain.
The thickness of absorbed layer 5 is 60-300nm, absorbed layer 5 selects direct current stainless target and intermediate frequency aluminium target to lead to argon gas and nitrogen alternating deposit, the thickness of secondary subgrade is 30-150nm, absorbed layer 5 comprises at least two sublayers cermet absorbed layer, layer 2-3 subgrade cermet absorbed layer is selected in the present embodiment, the secondary subgrade cermet absorbed layer metal level component of each subgrade is identical, when absorbed layer 5 comprises two sublayers cermet absorbed layer, subgrade is respectively high cermet absorbed layer and low-metal ceramic absorbed layer, high cermet absorbed layer thicknesses of layers is 30-150nm, low-metal ceramic absorbed layer thicknesses of layers is 30-150nm, secondary subgrade cermet absorbed layer is made up of 6-20 layer micro-subgrade absorbed layer, the metal level component that the secondary subgrade of different subgrade adopts is different, the thickness of micro-subgrade is less than 5nm, micro-subgrade is metal level 7 and ceramic layer 8 is two-layer is deposited as composite bed.
Secondary subgrade is the meticulous ultra-thin multilayer materials film that metal level ceramic layer replaces successive sedimentation, can think that metal component is evenly distributed in pottery, adjacent time subgrade absorbed layer metal component is different, adjacent time subgrade absorbed layer metal level component reduces to anti-reflection layer 6 from rete gradually near infrared-emitting layer 3, identical with each micro-subgrade metal level component in a subgrade absorbed layer.
Secondary subgrade absorbed layer can think the equally distributed metal-ceramic composite film of metallic, the metallic content of two subgrades is different, different metal content metal-ceramic composite film, there is different optical constant refractive index n and extinction coefficient k, there is different absorption characteristics and reflection characteristic, laminated film rete reduces near infrared-emitting layer 3 gradually to anti-reflection layer 6 tenor, and there is obvious interface in the tenor between the adjacent two cermet absorbed layers of different average metal content, the destructive interference of sunshine can be produced, increase rete to the absorption of solar radiation.
Absorbed layer 5 mainly considers metal level ratio of component and micro-subgrade periodicity and subgrade thickness in micro-subgrade absorbed layer when testing and measuring technology, when total metal component is not very large, just can obtain the qualified absorptance of national regulations and very low transmitting ratio, be easy to composition and the location parameter of determining metal.At high temperature, such as 400 DEG C-500 DEG C, radianting capacity is little for this rete, under also can be applicable to middle warm air condition, as can be applicable to 300 DEG C air conditions under.
The coating for selective absorption of sunlight spectrum that the present embodiment provides also comprises tack coat 2, tack coat 2 is between substrate 1 and infrared reflecting layer 3, tack coat 2 is deposited directly on base material 1, tack coat 2 material can select metal, pottery or ceramic-metal composite, such as can select molybdenum, aluminium nitride, aluminium oxide or aluminum oxynitride, or wherein a kind of cermet formed with pottery, tack coat 2 selects intermediate frequency aluminium target to lead to argon gas and nitrogen reaction preparation, and the thicknesses of layers of tack coat 2 is 10-40nm.
The coating for selective absorption of sunlight spectrum that the present embodiment provides also comprises diffusion impervious layer 4, diffusion impervious layer 4 is deposited between infrared reflecting layer 3 and absorbed layer 5, the material of diffusion impervious layer 4 can select metal, pottery or ceramic-metal composite, as can molybdenum be selected, aluminium nitride, aluminium oxide or aluminum oxynitride, or wherein a kind of cermet formed with pottery, diffusion impervious layer 4 selects intermediate frequency aluminium target to lead to argon gas and nitrogen reaction preparation, diffusion impervious layer 4 is for stopping metallic in infrared reflecting layer 3 and the metallic phase counterdiffusion in absorbed layer 5, the thickness of diffusion impervious layer 4 is 10-40nm.
The material of infrared reflecting layer 3 is that film such as the metallic film materials such as aluminium, copper, gold, silver or the TiAlN thin-film material of low-infrared radiation rate is formed by magnetron sputtering deposition, the thickness range of infrared reflecting layer 3 is 80-300nm, infrared reflecting layer 3 can improve the reflection infrared spectrum rate of coating for selective absorption of sunlight spectrum, reduces the reflectivity under high temperature.
The material of anti-reflection layer 6 is the ceramic material that refractive index is low, and as aluminium nitride, aluminium oxide, aluminum oxynitride or the composition such as silica, silicon nitride, anti-reflection layer 6 selects intermediate frequency aluminium target to lead to argon gas and nitrogen and oxygen reaction preparation, adopts reacting gas N
2or O
2, or N
2and O
2mist.Anti-reflection layer 6 have anti-reflection, antireflective, wear-resisting, anti-oxidant, improve the advantages such as heat endurance, the thickness 50-100nm of anti-reflection layer 6.
Utilize the tack coat 2 of horizontal magnetic control film coating machine deposit aluminum nitride successively on the pipe of polishing metal, material is the infrared reflecting layer 3 of copper, material is the diffusion impervious layer 4 of aluminum oxynitride, the anti-reflection layer 6 of material to be the absorbed layer 5 of the metal level of ceramic layer and aluminium nitride and material be aluminum oxynitride.
The concrete grammar preparing this solar spectrum Selective absorber coating is: select matrix, select polishing stainless steel sheet or direct plating on polishing stainless steel straight pipe, when utilizing horizontal magnetic control film coating machine to deposit on the pipe of polishing metal, metal tube rotation, and track revolution, metal tube revolution autobiography ratio is 12.5.When vacuum reaches 5 × 10-3Pa, applying argon gas Ar and nitrogen N
2, operating pressure is 0.3-0.4Pa, and medium frequency magnetron sputtering aluminium target carries out reactive sputter-deposition tack coat 2 aluminium nitride AlN, and power is 16KW, and the time 4 is minute, and thickness is 23nm; Turn off N
2with aluminium target, only fill Ar, operating pressure is 0.2-0.3Pa, and infrared reflecting layer 3 prepared by magnetically controlled DC sputtering copper target, and infrared reflecting layer 3 is layers of copper, and power is 15KW, and the time is 15 minutes, and the thickness of infrared reflecting layer 3 is 120nm; Open N
2with aluminium target, with tack coat 2 technique same deposition diffusion impervious layer 4, the thickness of diffusion impervious layer 4 is 24nm; Open stainless steel target, steel target and aluminium target replace successive sedimentation cermet absorbed layer, and operating pressure is 0.3-0.4Pa, and high low-metal ceramic absorbed layer steel target power output is respectively 7kw and 3kw, and aluminium target power output is 22kw, each 10 minutes of time, and thickness is 92cm altogether; Close steel target, working vacuum degree 0.4-0.5Pa, mid frequency sputtering aluminium target, power is 20kw, time is 40 minutes, and the thickness of anti-reflection layer 6 is 67cm, observes depositional coating, treat that Film color reddens through flavescence, when finally becoming blue, close target power supply and each road gas, terminate plated film.
Use German tester to draw absorptance and the transmitting ratio of coating for selective absorption of sunlight spectrum, its absorptivity is 95.6%, temperature be 200 DEG C, 300 DEG C, 400 DEG C and 500 DEG C time emissivity be respectively 7.7%, 9.0%, 10.1% and 10.5%; The absorptivity using spectrophotometer test reflectivity curve to calculate is 94.5% as shown in Figure 5.
When coating for selective absorption of sunlight spectrum of the present invention uses, tack coat 2 is for stopping metallic in substrate 1 and the metallic phase counterdiffusion in infrared reflecting layer 3, infrared reflecting layer 3 can improve the reflection infrared spectrum rate of coating for selective absorption of sunlight spectrum, reduce the reflectivity under high temperature, in absorbed layer 5, time subgrade absorbed layer is the meticulous ultra-thin multilayer materials film that metal level 7 and ceramic layer 8 replace successive sedimentation, solar radiation is absorbed, diffusion impervious layer 4 is for stopping metallic in infrared reflecting layer 3 and the metallic phase counterdiffusion in absorbed layer 5, anti-reflection layer 6 has anti-reflection, antireflective, wear-resisting, anti-oxidant, improve the advantages such as heat endurance.
In sum, coating for selective absorption of sunlight spectrum provided by the present invention is the meticulous ultra-thin multilayer materials film that metal level ceramic layer replaces successive sedimentation by absorbed layer subgrade absorbed layer, can think that metal component is evenly distributed in pottery, secondary subgrade absorbed layer can think the equally distributed metal-ceramic composite film of metallic.Absorbed layer mainly considers metal level ratio of component and micro-subgrade periodicity and subgrade thickness in micro-subgrade absorbed layer when testing and measuring technology, can obtain the qualified absorptance of national regulations and very low transmitting ratio, be easy to composition and the location parameter of determining metal.
Above embodiment only in order to technical scheme of the present invention to be described, is not intended to limit; Although with reference to previous embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that: it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature; And these amendments or replacement, 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 coating for selective absorption of sunlight spectrum, be included in infrared reflecting layer (3), absorbed layer (5) and anti-reflection layer (6) that substrate (1) surface sets gradually from inside to outside, it is characterized in that: described absorbed layer (5) comprises multilayer subgrade, described subgrade comprises multi-level subgrade, described time subgrade comprises micro-subgrade, and described micro-subgrade is the composite bed of metal level (7) and ceramic layer (8).
2. coating for selective absorption of sunlight spectrum according to claim 1, is characterized in that: described absorbed layer (5) comprises layer 2-3 subgrade, and every layer of subgrade comprises 6-20 level subgrade.
3. coating for selective absorption of sunlight spectrum according to claim 2, is characterized in that: the thickness of described absorbed layer (5) is 60-300nm, and the thickness of every layer of subgrade is 30-150nm, and the thickness of every layer of micro-subgrade is less than 5nm.
4. coating for selective absorption of sunlight spectrum according to claim 1, is characterized in that: described subgrade is divided into high cermet absorbed layer and low-metal ceramic absorbed layer.
5. coating for selective absorption of sunlight spectrum according to claim 1, is characterized in that: the material of described metal level (7) is stainless steel, and the material of described ceramic layer (8) is aluminium nitride.
6. coating for selective absorption of sunlight spectrum according to claim 1, is characterized in that: described metal level (7) comprises a kind of metal level or two kinds of metal levels.
7. coating for selective absorption of sunlight spectrum according to claim 1, is characterized in that: the material of described infrared reflecting layer (3) is film or the TiAlN of low-infrared radiation rate, and the thickness of described infrared reflecting layer (3) is 80-300nm.
8. coating for selective absorption of sunlight spectrum according to claim 1, is characterized in that: the material of described anti-reflection layer (6) is the ceramic material that refractive index is low, and the thickness of described anti-reflection layer (6) is 50-100nm.
9. coating for selective absorption of sunlight spectrum according to claim 1, it is characterized in that: also comprise tack coat (2), described tack coat (2) is positioned between described substrate (1) and described infrared reflecting layer (3), the material of described tack coat (2) is metal, pottery or ceramic-metal composite, and the thickness of described tack coat (2) is 10-40nm.
10. coating for selective absorption of sunlight spectrum according to claim 1, it is characterized in that: also comprise diffusion impervious layer (4), described diffusion impervious layer (4) is positioned between described infrared reflecting layer (3) and described absorbed layer (5), the material of described diffusion impervious layer (4) is metal, pottery or ceramic-metal composite, and the thickness of described diffusion impervious layer (4) is 10-40nm.
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| CN106091444A (en) * | 2016-06-06 | 2016-11-09 | 南宁可煜能源科技有限公司 | A kind of coating for selective absorption of sunlight spectrum |
| 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 |
| CN109282514A (en) * | 2018-09-18 | 2019-01-29 | 岭南师范学院 | A kind of high temperature resistant solar selectively absorbing coating and preparation method thereof |
| EP3400408A4 (en) * | 2016-01-04 | 2019-08-21 | Uniqan OY | Product for heating |
| CN110895058A (en) * | 2018-09-13 | 2020-03-20 | 康楚钒 | Novel high-temperature solar selective absorption coating |
| EP3410030B1 (en) * | 2016-01-29 | 2021-05-19 | Kabushiki Kaisha Toyota Jidoshokki | Solar heat collection tube and production method therefor |
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Application publication date: 20150930 |