CN103029365A - Medium-high temperature solar selective absorbing coating - Google Patents
Medium-high temperature solar selective absorbing coating Download PDFInfo
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- CN103029365A CN103029365A CN2011103004975A CN201110300497A CN103029365A CN 103029365 A CN103029365 A CN 103029365A CN 2011103004975 A CN2011103004975 A CN 2011103004975A CN 201110300497 A CN201110300497 A CN 201110300497A CN 103029365 A CN103029365 A CN 103029365A
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- absorbing coating
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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 a solar selective absorbing coating, which is prepared by magnetron sputtering and can stably work at medium-high temperature (greater than 400 DEG C). The solar selective absorbing coating comprises an alloy metal infrared high reflecting layer, a diffusion blocking layer, a selective absorbing layer and an antireflection layer. Different form the double-sub-layer metal ceramic structure of the common solar selective absorbing coating, the coating provided by the invention comprises single-layer metal ceramics, the structure is simple, the alumina layer has the functions of diffusion resistance and antioxidation, and the effect of enhancing the absorption can also be reached through the light interference effect. Under the condition of the atmospheric quality factor being AM1.5, the absorptivity of the coating is greater than or equal to 93 percent, the emissivity at 600 DEG C is smaller than or equal to 13 percent, and the coating has good heat stability and can be used in vacuum environment within 600 DEG C for a long time. The coating has important practical value and wide application prospect in the field of solar heat utilization.
Description
Technical field
The present invention relates to solar energy heat utilization technical field, be specifically related to a kind of coating for selective absorption that under middle hot conditions, uses.
Background technology
In order to improve photo-thermal conversion efficiency, so that the photo-thermal switch technology can become the new bright spot of new energy technology, need the research and development coating for selective absorption.This coating requires the Visible-to-Near InfaRed wave band at the solar spectrum place to have very high absorptivity, and requires to have very high reflectivity at the mid and far infrared wave band at heat radiation place.Sunshine spectrality coating for selective absorption is the key of high-efficiency solar Photo-thermal technology application.Along with the development of solar thermal utilization, solar thermal collector is used (100 ℃-400 ℃) and high temperature application (400 ℃-600 ℃) development from cryogenic applications (less than 100 ℃) Xiang Zhongwen, to satisfy the needs of the applications such as heat generating.Also only have operating temperature is expanded to high temperature, the solar energy optical-thermal switch technology just can become a kind of competitive new forms of energy form.
Current, the absorbed layer of the solar energy selective absorption surface coating of main flow all is that applied metal ceramic material (metal-dielectric material compound) is used as solar absorptive material.The architectural feature of cermet material is that the metal nanoparticle disperse is in dielectric material.After the percent by volume of having controlled certain thickness and metal, it then is transparent in the solar radiation zone to the heat radiation wave band substantially that this kind material shows as strong absorption.Just formed a solar energy selective absorption surface coating system such as this deposition of material at infrared band high reflecting metal coating surface.Used composite system does not possess the stability under the high temperature application conditions now, so can only use when low temperature or middle temperature.
For the heat endurance of coating for selective absorption under the high-temperature service condition in improving, the material systems such as Mo-Al2O3/Cu, SS-AlN/SS have obtained research and development.The present invention has proposed absorbed layer and has used NiCrAl-ZrO2 cermet material system from the intrinsic property of material, by optical design traditional double-level-metal ceramic structure is reduced to individual layer.
Summary of the invention
The purpose of this invention is to provide a kind of solar selectively absorbing coating material system, be applicable to the solar thermal collector of middle hot operation temperature.Coating is high, low, the Heat stability is good of emissivity of absorptivity at high temperature, and preparation technology is simple, is fit to large-scale production.
The middle high-temperature selective absorber coatings that the present invention relates to is provided with successively four-level membrane by substrate and forms to the surface, the feature of every skim is as follows:
The infrared high reflection layer of alloy is formed by NiCr alloy target material and Al target as sputter, Ni:70%-90%, and Cr:5%-15%, Al:5%-15%, its thickness range are 200-600nm.
Anti-diffusion layer is Al
2O
3, being formed by Al simple substance target reactive sputtering, its thickness range is 20-60nm.
Absorbed layer is the single-layer metal ceramic structure, and its material is M-ZrO
2(M is the NiCrAl metal nanoparticle) cermet material.The volume fraction of metal nanoparticle is 15%-50%, and thickness is 20-60nm.Absorbed layer adopts metal and ZrO
2The mode of the many subgrades of alternating deposit prepares.Wherein metal adopts the mode of NiCrAl alloy target material d.c. sputtering to prepare, and ZrO
2Mode with radio-frequency sputtering prepares.NiCrAl target Cr mass content is 5%-20%, and the Al mass content is 5%-20%, surplus Ni.
Antireflection layer is Al
2O
3, by Al
2O
3Simple substance target reactive sputtering forms, and its thickness range is that thickness is 50-100nm.
Substrate is nickel base superalloy or stainless steel.
The present invention relates to utilize the magnetron sputtering preparation, can be at the solar selectively absorbing coating of middle high temperature (＞400 ℃) steady operation.Comprise: the infrared high reflection layer of alloying metal, diffusion impervious layer, selectively absorbing layers and antireflection layer.Wherein: the alloy reflecting layer is the NiCrAl alloy; Diffusion barrier material is Al
2O
3The absorbed layer material is NiCrAl alloy nanoparticle and ZrO
2The cermet that mixes; The antireflection layer material is Al
2O
3Different from two subgrade cermet structures of common solar selectively absorbing coating, coating involved in the present invention only comprises the single-layer metal pottery, and is simple in structure; Alumina layer had both not only had anti-diffusion, oxidation resistant function, can also reach by optical interference effect to strengthen the effect that absorbs.Under air quality factors A M1.5 condition, this coating absorptivity 〉=93%, 600 ℃ emissivity≤13%, this coating has good heat endurance, can use under the vacuum environment in 600 ℃ for a long time.The present invention has important practical value and wide application prospect at solar energy heat utilization field.
Description of drawings
Fig. 1 coating for selective absorption of sunlight spectrum structural representation.
The specific embodiment
Following examples are the specific embodiment of the present invention, only are used for explanation the present invention, but not are used for restriction the present invention.
Embodiment 1:
In conjunction with coating profile layer shown in Figure 1, the preparation technology of coating flow process is: (1) to substrate surface polish, decontamination and cleaning, place among the magnetron sputtering apparatus; (2) use magnetic control sputtering system, select 99.9% NiCrAl (Ni87.9Cr5.5A16.4) target, 99.99% Al
2O
3Target and 99.99% ZrO
2Target.Matrix uses stainless steel.Before the deposition beginning, the vacuum chamber base vacuum is evacuated to 4 * 10
-4Pa.(3) regulate the Ar flow to sputtering pressure 0.1Pa, open the dc sputtering power of NiCrAl target, regulation voltage is to 400V, and electric current 0.1A prepares the thick infrared high reflection layer of NiCrAl alloy of 280nm.(4) be filled with working gas Ar, adjust flux so that vacustat in sputtering pressure 0.1Pa.Open Al
2O
3The radio-frequency sputtering power supply of target, regulating power are to 500W, and voltage is 2000V, to Al
2O
3Carry out radio-frequency sputtering, prepared the thick Al of 45nm
2O
3Anti-diffusion layer.(5) be filled with working gas Ar, adjust flux so that vacustat in sputtering pressure 0.1Pa.Open ZrO
2The radio-frequency sputtering power supply of target, regulating power are to 500W, and voltage is 2000V, to ZrO
2Carry out reactive sputtering; Open the dc sputtering power of NiCrAl target, regulation voltage is to 400V, and electric current 0.1A carries out d.c. sputtering to NiCrAl.Utilize the revolution of substrate, successively by two target tops, thereby be deposited as M/ZrO
2Sublayer structure (M=NiCrAl) alternately.By regulating the speed of matrix revolution, the thickness of regulating M in each cycle is 3nm, ZrO
2Thickness be 7nm.The gross thickness of absorbed layer is that 30nm (6) is filled with working gas Ar, adjust flux so that vacustat in sputtering pressure 0.1Pa.Open Al
2O
3The radio-frequency sputtering power supply of target, regulating power are to 500W, and voltage is 2000V, to Al
2O
3Carry out radio-frequency sputtering, prepared the thick Al of 75nm
2O
3Antireflection layer.
After preparation is finished, using the Lamada950 spectrophotometer to test the reflectivity spectral line of in the solar spectrum scope (0.3-3um), is 91.3% through the absorptance that calculates the present embodiment coating; By the reflectivity ratio of this coating of TJ270-300 infrared spectrophotometer test infrared band (2.5-25um), the hemispherical emissivity that calculates coating is 4.21% (80 ℃), 9.41% (450 ℃).(model: PHI-5400) the depth profiling NiCrAl alloy ratio that obtains institute's sputter is Ni88.5-Cr 5.7-Al-5.6 to use XPS.Under the atmospheric condition, 450 ℃ of lower 48 hours constant temperature are processed, and coating is intact, and absorptivity and emissivity are unchanged.
Can see that from present embodiment solar energy coating involved in the present invention has high absorptance and low-launch-rate.And the thermal coefficient of expansion gap of every layer of this coating system is little.NiCrAl alloy oxidation behavior at high temperature is extremely at the interface preferential oxidation generation aluminium oxide of Al Elements Diffusion.This just provides protection for film bulk, and the aluminium oxide that generates can also be repaired the crackle that thermal cycle causes, the further diffusion of prevention oxygen in coating.This mechanism is just so that this coating has extraordinary heat endurance.The material system of this coating is simple, and less demanding to the control accuracy of preparation, the single-layer system film thickness errors reaches 6%, and spectral response does not still significantly change, and is easy to organize large-scale production.
Claims (7)
1. high temperature solar energy selective absorption coating in a kind, be deposited in the substrate, upwards formed by the infrared high reflection layer of alloy, anti-diffusion layer, absorbed layer and antireflection layer successively from substrate surface, it is characterized in that: absorbed layer is the cermet absorbed layer, described cermet absorbed layer can be expressed as NiCrAl-ZrO2, and the cermet absorbed layer is comprised of NiCrAl alloy nanoparticle and ZrO2.
2. solar selectively absorbing coating according to claim 1, it is characterized in that: the infrared high reflection layer of described alloy is NiCrAl alloy firm layer, and its weight item consists of Ni:70%-90%, Cr:5%-15%, Al:5%-15%, its thickness range are 200-600nm.
3. solar selectively absorbing coating according to claim 1, it is characterized in that: described anti-diffusion layer is Al
2O
3Thin layer, its thickness range is: 20-60nm.
4. solar selectively absorbing coating according to claim 1, it is characterized in that: described cermet absorbed layer is the single-layer metal pottery, metal nanoparticle is embedded among the ZrO2 pottery, the volume fraction of its NiCrAl metal nanoparticle is 15%-50%, NiCrAl target Cr mass content is 5%-20%, the Al mass content is 5%-20%, surplus Ni; Thickness is 20-60nm.
5. solar selectively absorbing coating according to claim 1, it is characterized in that: described antireflection layer is Al
2O
3Thin layer, thickness are 50-100nm.
6. according to claim 1 or 4 described solar selectively absorbing coatings, it is characterized in that: the preparation of metals target that described cermet absorbed layer adopts is the NiCrAl alloy target material, NiCrAl target Cr mass content is 5%-20%, and the Al mass content is 5%-20%, surplus Ni.
7. solar selectively absorbing coating according to claim 1 is characterized in that:
The employed substrate of coating is nickel-base high-temperature alloy material or stainless steel material.
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| CN2011103004975A CN103029365A (en) | 2011-09-30 | 2011-09-30 | Medium-high temperature solar selective absorbing coating |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104149410A (en) * | 2014-07-08 | 2014-11-19 | 中国人民解放军国防科学技术大学 | Inorganic high-temperature-resistant low-infrared-emissivity composite coating and preparation method thereof |
| CN105698416A (en) * | 2016-03-01 | 2016-06-22 | 江苏贝德莱特太阳能科技有限公司 | Selective solar absorbing coating for flat-plate solar collector |
| CN107828997A (en) * | 2017-11-21 | 2018-03-23 | 广西超星太阳能科技有限公司 | A kind of panel solar aluminum alloy coating and preparation method thereof |
| CN108273994A (en) * | 2018-03-30 | 2018-07-13 | 东莞市晟日电子科技有限公司 | The preparation facilities and method of high-density molybdenum niobium alloy target |
| CN108273994B (en) * | 2018-03-30 | 2024-04-19 | 江苏理成科技有限公司 | Preparation device and method of high-density molybdenum-niobium alloy target |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101177772A (en) * | 2007-12-10 | 2008-05-14 | 北京矿冶研究总院 | Nickel-chromium-aluminum/nickel-graphite composite powder material and preparation method thereof |
| CN101294749A (en) * | 2007-04-24 | 2008-10-29 | 梁美意 | Heat-collecting tube with solar energy selective absorption coating and manufacturing method thereof |
| CN101600915A (en) * | 2006-11-10 | 2009-12-09 | 第三专利投资有限两合公司 | The preparation method of the thin layer of metal-ceramic composite material |
| CN101886847A (en) * | 2009-05-11 | 2010-11-17 | 范天方 | Medium-high temperature solar thermal collector tube |
| CN201652952U (en) * | 2010-04-08 | 2010-11-24 | 常州龙腾太阳能热电设备有限公司 | Inner pipe of solar thermal collecting pipe |
-
2011
- 2011-09-30 CN CN2011103004975A patent/CN103029365A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101600915A (en) * | 2006-11-10 | 2009-12-09 | 第三专利投资有限两合公司 | The preparation method of the thin layer of metal-ceramic composite material |
| CN101294749A (en) * | 2007-04-24 | 2008-10-29 | 梁美意 | Heat-collecting tube with solar energy selective absorption coating and manufacturing method thereof |
| CN101177772A (en) * | 2007-12-10 | 2008-05-14 | 北京矿冶研究总院 | Nickel-chromium-aluminum/nickel-graphite composite powder material and preparation method thereof |
| CN101886847A (en) * | 2009-05-11 | 2010-11-17 | 范天方 | Medium-high temperature solar thermal collector tube |
| CN201652952U (en) * | 2010-04-08 | 2010-11-24 | 常州龙腾太阳能热电设备有限公司 | Inner pipe of solar thermal collecting pipe |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104149410A (en) * | 2014-07-08 | 2014-11-19 | 中国人民解放军国防科学技术大学 | Inorganic high-temperature-resistant low-infrared-emissivity composite coating and preparation method thereof |
| CN104149410B (en) * | 2014-07-08 | 2016-03-02 | 中国人民解放军国防科学技术大学 | Inorganic high-temperature resistant low infrared emissivity composite coating and preparation method thereof |
| CN105698416A (en) * | 2016-03-01 | 2016-06-22 | 江苏贝德莱特太阳能科技有限公司 | Selective solar absorbing coating for flat-plate solar collector |
| CN107828997A (en) * | 2017-11-21 | 2018-03-23 | 广西超星太阳能科技有限公司 | A kind of panel solar aluminum alloy coating and preparation method thereof |
| CN108273994A (en) * | 2018-03-30 | 2018-07-13 | 东莞市晟日电子科技有限公司 | The preparation facilities and method of high-density molybdenum niobium alloy target |
| CN108273994B (en) * | 2018-03-30 | 2024-04-19 | 江苏理成科技有限公司 | Preparation device and method of high-density molybdenum-niobium alloy target |
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Application publication date: 20130410 |