CN102538261A - High-temperature solar photo-thermal conversion functional coating - Google Patents
High-temperature solar photo-thermal conversion functional coating Download PDFInfo
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- CN102538261A CN102538261A CN2012100722812A CN201210072281A CN102538261A CN 102538261 A CN102538261 A CN 102538261A CN 2012100722812 A CN2012100722812 A CN 2012100722812A CN 201210072281 A CN201210072281 A CN 201210072281A CN 102538261 A CN102538261 A CN 102538261A
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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 discloses a high-temperature solar photo-thermal conversion functional coating, which comprises an inner protective layer, an infrared high-reflection layer, an outer protective layer, an absorption layer and an absorption layer which are deposited in turn, wherein the inner protective layer is directly deposited on a substrate; the absorption layer has a four-layer structure and is formed by taking nickel and chromium as targets and oxygen as reaction gas; and from inside to outside of the four-layer structure, the mass of the nickel and chromium is reduced in turn, and the oxygen content is increased in turn. The high-temperature solar photo-thermal conversion functional coating has high solar absorption rate and low infrared emission rate at high temperature, and has excellent stability under antivacuum high temperature conditions.
Description
Technical field
The present invention relates to relate to a kind of high temperature solar photo-thermal translation function coating.
Background technology
The structure of solar energy optical-thermal translation function coating is generally the anti-layer of anti-reflection layer, absorbed layer and infrared height; Be deposited in the substrate successively; The anti-layer of infrared height is nearest apart from substrate, and anti-reflection layer is at the outermost layer of functional layer, and this structure has high solar absorptance and low infrared emission ratio.
The effect of anti-reflection layer is to make the reflection generation destructive interference effect of sunshine on the anti-reflection layer interface and absorbed layer interface, and the reflected energy of being interfered is got in the absorbed layer, thereby improves the solar absorptance of coating.
The effect of absorbed layer is the energy that absorbs in the solar energy spectral limit, and itself is made up of one or more layers nano metal particles and dielectric composite.Nano metal particles is excited by sunshine and transition of electronic energy takes place, and electronics releases energy with thermal-radiating form when returning its orbit, thereby realizes the photo-thermal translation function.
The effect of the anti-layer of infrared height is to reduce the infrared emission ratio, and according to Kirchhoff's law, infrared high reflection characteristic correspondence has low infrared emission ratio.Because the energy in the solar receiver can outwards scatter and disappear with the form of infra-red radiation, can make the least possible being lost to beyond the receiver of energy of absorption through the anti-layer of infrared height.
At present, the anti-reflection layer material of solar energy optical-thermal translation function coating mainly comprises SiO, AlN, AlNO, MgF, MgCF etc.; Absorbing layer materials mainly comprises AlN-Al, AlN-SS, TiAlN etc.; The anti-layer material of infrared height mainly comprises Al, Cu etc.Its performance generally can reach absorptance 0.86-0.96, and emission is than 0.06-0.09 (100 ℃), but temperature is when reaching 400 ℃, and its emission is than generally can surpassing 0.2, and the performance decay fast of absorptance and emission ratio.
Summary of the invention
For this reason, the object of the present invention is to provide a kind of high temperature solar photo-thermal translation function coating, its have high solar absorptance and when high temperature low infrared emission ratio, and under antivacuum hot conditions, also have excellent stability.
The present invention adopts following technical scheme:
This invention high temperature solar photo-thermal translation function coating; Comprise the anti-layer of interior overcoat, infrared height, external protection coating, absorbed layer and the anti-reflection layer of deposition successively; Wherein, interior overcoat directly is deposited in the substrate, and said absorbed layer is a four-layer structure; And absorbed layer is target, is that reaction gas forms with oxygen with nickel and chromium, and the nickel chromium triangle mass percent reduces four-layer structure successively from inside to outside, oxygen content improves successively.
Based on said structure, adopted the absorbed layer of four-layer structure, promptly the absorbed layer absorbed layer adopts the composite of refractory metal nickel (Ni) and chromium (Cr) and oxide thereof, comprises 4 secondary layers, and reacting gas adopts oxygen (O
2), it has excellent absorption properties and heat endurance, its performance decays very little under high temperature (400 ℃ ~ 800 ℃) condition, launch lower than very, even if 800 ℃ its emission than also being lower than 0.2.And unexpected discovery is based on the coating of the absorbed layer of above-mentioned four-layer structure and measures its performance in baking under 800 ℃ of non-vacuum conditions again after 24 hours, and its absorptance is merely 0.01 with the decay of emission ratio.
In addition, the absorbed layer layering is coated with, and outer oxygen content is high, Heat stability is good, and the internal layer oxygen content is low, and to external protection, the negative effect of the anti-layer of especially infrared height is low, prevents the oxidation of the anti-layer of infrared height.
Above-mentioned high temperature solar photo-thermal translation function coating, said four-layer structure whenever thick layer by layer at 30-40nm, total bed thickness of absorbed layer is at 130 ~ 155nm.
Above-mentioned high temperature solar photo-thermal translation function coating; Preferable selection is each layer of said four-layer structure; The mol ratio of nickel chromium triangle oxygen (Ni-Cr-O) is respectively 5:3:2/2:1:2/3:1:6/1:1:8 from inside to outside, and outermost layer forms oxide, and heat endurance is fabulous; The internal layer oxygen content is low, is main funtion part.
Above-mentioned high temperature solar photo-thermal translation function coating, said interior overcoat and external protection coating are the chromium layer, and wherein the thickness of interior overcoat is 50 ~ 60nm, and the thickness of external protection coating is 10 ~ 15nm.The selection of interior external protection coating mainly is the protection of the anti-layer of infrared height, and too thick can the influence launched ratio, the too thin protective effect that does not then have essence.
Above-mentioned high temperature solar photo-thermal translation function coating, the anti-layer of said infrared height is a silver layer, and its thickness is 150nm ~ 160nm, and silver layer or silverskin remain selection relatively more commonly used now, adopt relatively reasonable thickness in this programme, can effectively reduce the emission ratio.
Above-mentioned high temperature solar photo-thermal translation function coating, said anti-reflection layer is an alumina layer, and thickness is 60 ~ 70nm, and fine and close pellumina can form further protection.
Description of drawings
Fig. 1 is the structure principle chart according to a kind of high temperature solar photo-thermal translation function coating of the present invention.
Among the figure: the 1-substrate; Overcoat in the 2-; The anti-layer of the infrared height of 3-; The 4-external protection coating; The 5-absorbed layer; The 6-anti-reflection layer.
The specific embodiment
Embodiment 1:
With reference to Figure of description 1; Relate generally to the selection of absorbed layer, other part of coating is done general selection, so according to a kind of high temperature solar photo-thermal translation function coating of the present invention; Comprise anti-layer 3 of interior overcoat 2, infrared height, external protection coating 4, absorbed layer 5 and the anti-reflection layer 6 of deposition successively; Wherein, interior overcoat directly is deposited in the substrate 1, and said absorbed layer 5 is a four-layer structure; And absorbed layer is target, is that reaction gas forms with oxygen with nickel and chromium, and the nickel chromium triangle mass percent reduces four-layer structure successively from inside to outside, oxygen content improves successively.The preferred Cr of interior overcoat and external protection coating (chromium), interior overcoat thickness is 50 ~ 60nm, external protection coating thickness is 10 ~ 15nm; The thickness of selecting for use is preferable selection; Those skilled in the art can adjust as required, and the anti-layer of infrared height then adopts Ag (silver), and thickness is at 150 ~ 160nm; Anti-reflection layer selective oxidation aluminium, thickness is at 60 ~ 70nm.On the basis of above-mentioned general selection; Adopting the best choice structure of absorbed layer is four-layer structure; And the mol ratio of nickel chromium triangle oxygen (Ni-Cr-O) is respectively 5:3:2/2:1:2/3:1:6/1:1:8, and the innermost layer thickness of four-layer structure is 40nm, and other are selected between 30 ~ 32nm.
Its preparation method does; Be fixed on 316 stainless steel substrates that are of a size of 40mm * 40mm * 1mm on the substrate frame of magnetron sputtering experimental machine; The experimental machine cavity diameter is 700mm, highly is 500mm, and there are 4 rotary magnetron sputtering targets at the center; Its material is respectively silver (Ag), nickel (Ni), chromium (Cr), aluminium (Al), and substrate is 90mm to the distance of sputtering target.With oil-sealed rotary pump and molecular pump vacuum in the cavity is extracted into 5 * 10
-3Pa, the controllable register valve charges into 30sccm argon gas (Ar), makes the interior pressure of cavity reach 4 * 10
-1Pa.Starting chromium (Cr) target stops after 6 minutes with the sputter of 5kW power; Start silver (Ag) target and stop after 15 minutes, restart chromium (Cr) target, start nickel (Ni) target then simultaneously with 5kW power sputter 1 minute with the sputter of 5kW power; Power is 5kW, and pours 10sccm oxygen (O
2) sputter 3 minutes, oxygen (O then
2) be increased to the 18sccm sputter 3 minutes, oxygen (O
2) be increased to the 33sccm sputter again 4 minutes, last oxygen (O
2) be increased to the 40sccm sputter and stop after 5 minutes, starting aluminium (Al) target, power is 3kW, charges into (O simultaneously
2) the 30sccm sputter stops after 28 minutes, the coating preparation is accomplished.
The solar absorptance that uses ultraviolet-visible-near infrared spectrometer and infrared spectrometer to measure this functional coating is 0.958; The emission ratio of different temperatures is respectively 0.04 (100 ℃)/0.09 (400 ℃)/0.16 (800 ℃); Its special feature is that emission is lower than very, particularly under high-temperature condition, still keeps lower emission ratio.More surprisingly this coating is measured its performance in baking under 800 ℃ of non-vacuum conditions after 24 hours again, and its absorptance decays to 0.01 with the emission ratio.
Embodiment 2:
Equipment, substrate and vacuum condition are with embodiment 1; Starting chromium (Cr) target stops after 8 minutes with the sputter of 5kW power; Start silver (Ag) target and stop after 18 minutes, restart chromium (Cr) target, start nickel (Ni) target then simultaneously with 5kW power sputter 2 minutes with the sputter of 5kW power; Power is 5kW, and pours 10sccm oxygen (O
2) sputter 4 minutes, oxygen (O then
2) be increased to the 18sccm sputter 4 minutes, oxygen (O
2) be increased to the 33sccm sputter again 5 minutes, last oxygen (O
2) be increased to the 40sccm sputter and stop after 6 minutes, starting aluminium (Al) target, power is 3kW, charges into (O simultaneously
2) the 30sccm sputter stops after 30 minutes, the coating preparation is accomplished.
The solar absorptance that uses ultraviolet-visible-near infrared spectrometer and infrared spectrometer to measure this functional coating is 0.96; The emission ratio of different temperatures is respectively 0.05 (100 ℃)/0.1 (400 ℃)/0.18 (800 ℃); This coating is measured its performance in baking under 800 ℃ of non-vacuum conditions after 24 hours again, and its absorptance decays to 0.012 with the emission ratio.
Embodiment 3:
Equipment, substrate and vacuum condition are with embodiment 1; Starting chromium (Cr) target stops after 4 minutes with the sputter of 5kW power; Start silver (Ag) target and stop after 12 minutes, restart chromium (Cr) target, start nickel (Ni) target then simultaneously with 5kW power sputter 1 minute with the sputter of 5kW power; Power is 5kW, and pours 10sccm oxygen (O
2) sputter 2 minutes, oxygen (O then
2) be increased to the 18sccm sputter 2 minutes, oxygen (O
2) be increased to the 33sccm sputter again 3 minutes, last oxygen (O
2) be increased to the 40sccm sputter and stop after 5 minutes, starting aluminium (Al) target, power is 3kW, charges into (O simultaneously
2) the 30sccm sputter stops after 25 minutes, the coating preparation is accomplished.
The solar absorptance that uses ultraviolet-visible-near infrared spectrometer and infrared spectrometer to measure this functional coating is 0.95; The emission ratio of different temperatures is respectively 0.04 (100 ℃)/0.08 (400 ℃)/0.15 (800 ℃); This coating is measured its performance in baking under 800 ℃ of non-vacuum conditions after 24 hours again, and its absorptance decays to 0.012 with the emission ratio.
Claims (7)
1. high temperature solar photo-thermal translation function coating; Comprise interior overcoat (2), the anti-layer of infrared height (3), external protection coating (4), absorbed layer (5) and the anti-reflection layer (6) of deposition successively; Wherein, interior overcoat directly is deposited in the substrate (1), it is characterized in that: said absorbed layer (5) is a four-layer structure; And absorbed layer is target, is that reaction gas forms with oxygen with nickel and chromium, and the nickel chromium triangle mass percent reduces four-layer structure successively from inside to outside, oxygen content improves successively.
2. high temperature solar photo-thermal translation function coating according to claim 1 is characterized in that: said four-layer structure whenever thick in layer by layer 30-40nm.
3. high temperature solar photo-thermal translation function coating according to claim 2 is characterized in that: each of said four-layer structure layer, thickness reduces successively from inside to outside.
4. according to the arbitrary described high temperature solar photo-thermal translation function coating of claim 1 to 3, it is characterized in that: each of said four-layer structure layer, the mol ratio of nickel chromium triangle oxygen (Ni-Cr-O) is respectively 5:3:2/2:1:2/3:1:6/1:1:8 from inside to outside.
5. high temperature solar photo-thermal translation function coating according to claim 1 is characterized in that: overcoat (2) and external protection coating are the chromium layer in said, and wherein the thickness of interior overcoat is 50 ~ 60nm, and the thickness of external protection coating is 10 ~ 15nm.
6. high temperature solar photo-thermal translation function coating according to claim 1 is characterized in that: the anti-layer of said infrared height (3) is a silver layer, and its thickness is 150nm ~ 160nm.
7. high temperature solar photo-thermal translation function coating according to claim 1, it is characterized in that: said anti-reflection layer is an alumina layer, thickness is 60 ~ 70nm.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105299935A (en) * | 2015-04-03 | 2016-02-03 | 中国建筑材料科学研究总院 | Solar spectrum selective absorbing coating layer and preparation method thereof and heat collector |
| CN108603693A (en) * | 2016-01-29 | 2018-09-28 | 株式会社丰田自动织机 | Solar energy heat collection pipe |
| US10586879B2 (en) | 2015-04-03 | 2020-03-10 | China Building Materials Academy | Spectrally selective solar absorbing coating and a method for making it |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105299935A (en) * | 2015-04-03 | 2016-02-03 | 中国建筑材料科学研究总院 | Solar spectrum selective absorbing coating layer and preparation method thereof and heat collector |
| CN105299935B (en) * | 2015-04-03 | 2017-07-07 | 中国建筑材料科学研究总院 | A kind of coating for selective absorption of sunlight spectrum and preparation method thereof and heat collector |
| US10586879B2 (en) | 2015-04-03 | 2020-03-10 | China Building Materials Academy | Spectrally selective solar absorbing coating and a method for making it |
| CN108603693A (en) * | 2016-01-29 | 2018-09-28 | 株式会社丰田自动织机 | Solar energy heat collection pipe |
| CN108603693B (en) * | 2016-01-29 | 2020-10-30 | 株式会社丰田自动织机 | Solar heat collecting pipe |
| US11009264B2 (en) | 2016-01-29 | 2021-05-18 | Kabushiki Kaisha Toyota Jidoshokki | Solar heat collector tube |
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Application publication date: 20120704 |