CN103625032A - Medium-high temperature solar photothermal selective-absorbing coat - Google Patents
Medium-high temperature solar photothermal selective-absorbing coat Download PDFInfo
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- CN103625032A CN103625032A CN201210308290.7A CN201210308290A CN103625032A CN 103625032 A CN103625032 A CN 103625032A CN 201210308290 A CN201210308290 A CN 201210308290A CN 103625032 A CN103625032 A CN 103625032A
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Abstract
The invention relates to a solar energy selective-absorbing coat. The coat is deposited on a metal substrate, and the coat sequentially comprises a bonding transition layer, an infrared high-reflecting layer, a high-metal-content metal-ceramic composite film, a low-metal-content metal-ceramic composite film and a dereflection film which are arranged on the surface of the substrate from bottom to top. The infrared high-reflecting layer is a metallic compound film, the compound film has a high reflectivity in an infrared band and a high absorptivity in a sunlight band, and the compound film has a high hardness and a high oxidation resistance. The metal adopted by the metallic compound film is same to metals adopted by the bonding transition layer and the above metal-ceramic composite films, so the mutual pollution problem among materials is reduced, and the making of the coat is simple. The coat has an absorptivity of above 95% and a hemispherical emittance of below 10% when the atmospheric quality factor AM is 1.5, and the coat also has a good thermal stability.
Description
Technical field
The present invention relates to a kind of new type solar energy photo-thermal coating for selective absorption, is one of key technology in the solar energy heat utilizations such as current solar groove type photo-thermal power generation, solar airconditioning, desalinization.Belong to solar energy heat utilization technical field.
Background technology
The middle high temperature solar thermal utilization of current solar energy is more and more subject to people's attention, and it utilizes mode to comprise solar light-heat power-generation, solar seawater desalination, solar energy heating and dry, solar airconditioning etc.And groove type solar photo-thermal power generation is the Typical Representative of high temperature solar thermal utilization in solar energy, start abroad commercial applications, and be domesticly in the starting stage, commercial applications has a extensive future.And middle high temperature solar photo-thermal coating for selective absorption is groove type solar photo-thermal power generation core component---the key technology of solar energy heat collection pipe.Solar energy optical-thermal coating for selective absorption has the high absorption at 0.3-2.5 μ m, in the high reflection characteristic of 2.5-25 μ m, is directly sunshine to be transformed into heat energy, prevents again the functional film of radiation loss simultaneously.For improving solar thermal utilization efficiency, solar energy utilization just therefrom low temperature (80-300 ℃) develops to middle high temperature (300-600 ℃).
The current middle high temperature solar photo-thermal coating for selective absorption of research and development, infrared reflecting layer mainly adopts high-temperature-phase that Au, Cu, Mo etc. have high reflectance to stable metal material, with operating temperature, improve and prolongation service time, at high temperature easily there is diffusion and oxidation, thereby incidence is raise; Its absorbed layer is the metallic cermet films of infusibility metallic cluster disperse in ceramic dielectric layer, the refractory metal material of selecting is mainly by W, Mo, Au, SS, Pt etc., same refractory metal particle cluster is at high temperature easily oxidized, diffusion etc., thereby cause be at high temperature on active service for a long time its absorbent properties of coating for selective absorption to decline, even lost efficacy; In addition, general solar selectively absorbing coating is that three kinds of above materials form, and for coating manufacturing equipment and preparation technology, has all proposed comparatively strict requirement.We have proposed a kind of novel middle high temperature solar photo-thermal coating for selective absorption for this reason, and the preparation of this coating only needs two kinds of targets, under guaranteeing high temperature high-absorbility and emissivity in, greatly simplified preparation technology.
Summary of the invention
The object of the present invention is to provide a kind of middle high temperature applied solar energy photo-thermal coating for selective absorption, it is applicable to 450 ℃ with interior various solar energy optical-thermal converting systems, as solar light-heat power-generation, solar airconditioning, solar energy drying and heating and desalinization etc.
Middle high temperature solar photo-thermal coating for selective absorption involved in the present invention, is comprised of five tunics to top successively heat absorption substrate surface, and the structure of coating is specific as follows:
Base material is copper or stainless steel material.
Ground floor is bonding transition zone, and the metal Ti film thick by 2-20nm forms;
The second layer is infrared reflecting layer, and the TiN film thick by 80-200nm forms, and plays the loose layer of barrier material and hydrogen-evolution retardation simultaneously;
The 3rd layer is high tenor absorbed layer, and its composition is comprised of Titanium particle and insulating medium layer, and this insulating medium layer adopts Al
2o
3or SiO
2.The thickness of this layer is 8nm-120nm, and the volume content of Titanium is 30%-60%;
The 4th layer is low-metal content absorbed layer, and its composition is still comprised of Titanium particle and insulating medium layer, and this insulating medium layer still adopts Al
2o
3or SiO
2.The thickness of this layer is 20nm-150nm, and the volume content of Titanium is 10%-30%;
Layer 5 is the antireflection layer that 30-200nm is thick, and this antireflection layer adopts Al
2o
3or SiO
2.
Middle high temperature solar photo-thermal coating for selective absorption involved in the present invention adopts magnetically controlled sputter method preparation.
This coating has the high and low emissivity of high absorptivity and good heat endurance, and preparation technology is easy, is suitable for big batchization and produces.
Advantage of the present invention:
The present invention relates to a kind of new type solar energy coating for selective absorption, in the present invention, infrared reflecting layer adopts TiN film, TiN film has high reflectivity at infrared band, at visible waveband, there is higher absorption simultaneously, TiN film has again high hardness and anti-oxidation characteristics, there is higher high-temperature stability, can play anti-diffusion and hydrogen-evolution retardation; Metal in tack coat and metal-ceramic composite film all adopts Titanium, and ceramic medium material in metallic cermet films and antireflection film all adopts Al
2o
3or SiO
2, whole coating only adopts two kinds of targets in preparation process, and preparation technology is simple, pollution problem each other while having avoided adopting multiple target.
Solar selectively absorbing coating involved in the present invention, is applicable to 450 ℃ with interior middle high-temperature solar thermal-collecting tube.Under air quality factors A M1.5 condition, coating absorptivity of the present invention is greater than 95%, and hemispherical emissivity is less than 10%, and this coating has good heat endurance, can under the vacuum environment in 450 ℃, use for a long time.The present invention has important practical value and wide application prospect at solar energy heat utilization field.
Accompanying drawing explanation
Fig. 1 is coating profile layer structural representation of the present invention.In figure: 1, base material stainless steel (SS 316L or 304), 2, articulamentum Titanium (Ti), 3, TiN infrared reflecting layer, 4, high tenor Ti/Al
2o
3or Ti/SiO
2ceramic composite coating, 5, low-metal content Ti/Al
2o
3or Ti/SiO
2ceramic composite coating, 6, Al
2o
3or SiO
2antireflective coating.
The specific embodiment
A middle high temperature solar photo-thermal coating for selective absorption, is coated in substrate, from substrate surface, is upwards followed successively by tack coat, infrared reflecting layer, high tenor absorbed layer, low-metal content absorbed layer, medium antireflection layer;
Tack coat is metal Ti thin layer;
Infrared reflecting layer is TiN thin layer, plays diffusion impervious layer simultaneously and oozes hydrogen barrier layer effect;
High tenor absorbed layer is comprised of Titanium particle and dielectric, and described high tenor refers to that the volume content of Titanium in absorbed layer is 30%-60%; Insulating medium layer adopts Al2O3 or SiO2;
Low-metal content absorbed layer is comprised of Titanium particle and dielectric, and described low-metal content refers to that the volume content of Titanium in absorbed layer is 15%-30%; Insulating medium layer adopts Al2O3 or SiO2;
Medium antireflection layer is Al2O3 or SiO2.
Base material is the materials such as stainless steel or copper.
Ground floor is tack coat, and the metal Ti film thick by 2-20nm forms;
The second layer is infrared reflecting layer, and the TiN film thick by 80-200nm forms;
The 3rd layer is high tenor absorbed layer, and its composition is comprised of Titanium particle and insulating medium layer, and this insulating medium layer adopts Al
2o
3or SiO
2.The thickness of this layer is 8nm-80nm, and the volume content of Titanium is 30%-60%;
The 4th layer is low-metal content absorbed layer, and its composition is still comprised of Titanium particle and insulating medium layer, and this insulating medium layer still adopts Al
2o
3or SiO
2.The thickness of this layer is 20nm-80nm, and the volume content of Titanium is 15%-30%;
Layer 5 is the antireflection layer that 30-90nm is thick, and this antireflection layer adopts Al
2o
3or SiO
2.
Described high tenor absorbed layer and low-metal content absorbed layer adopt magnetron sputtering deposition method to prepare, and it adopts cosputtering or many subgrades of alternating deposit method to prepare by Titanium and dielectric, and each subgrade thickness is in 1-10nm; Described dielectric is Al2O3 or SiO2 material.
The present invention relates to a kind of utilize prepared by magnetron sputtering, can be in 450 ℃ the solar selectively absorbing coating of steady operation.This coating deposition can be deposited in the metallic substrates such as stainless steel, copper, aluminium, and coating is upwards followed successively by from substrate surface: bonding transition zone, infrared high reflection layer, the metal-ceramic composite film of high tenor, the metal-ceramic composite film of low-metal content, antireflection film.Different from traditional solar selectively absorbing coating, the infrared high reflection layer that coating for selective absorption involved in the present invention adopts is metal compound film, rather than traditional metallic film, this compound film has high reflectance at infrared band, at sunshine wave band, have high absorptivity, this compound film has high hardness and anti-oxidation characteristics simultaneously.The metal that this metal compound film adopts is same metal with the metal that bonding transition zone, metal-ceramic composite film adopt, reduced and used the mutual pollution problem between multiple material, make coating preparation simple, for simplifying, industrialization coating film production line is significant.
Following examples are implementation method of the present invention, only for the present invention is described, but not for limiting the present invention.
Embodiment:
In conjunction with the coating profile layer shown in Fig. 1, preparation technology of coating flow process is: (1) is used magnetic control sputtering system, selects 99.8% Ti target, 99.99% Al
2o
3target; Matrix is used 316L stainless steel.Before deposition starts, vacuum chamber base vacuum is evacuated to 5 * 10-4Pa.(2) be filled with working gas Ar, adjust flux makes vacustat in sputtering pressure 0.5Pa, opens the intermediate frequency power supply of Ti target, adjusting sputtering current is 6.0A, and dutycycle is 50.0%, and grid bias power supply power is 70w, dutycycle is 30%, has prepared the metal Ti of 10nm as transition tack coat.(3) regulate N
2throughput is 20sccm, then by regulating Ar throughput, making vacuum is due to 0.5Pa, opens intermediate frequency power supply, sputtering current is 10A, and dutycycle is 50%, and same grid bias power supply power is 70w, dutycycle is 30%, and the TiN film of sputter 120nm, as infrared high reflection layer; (3) close N
2, regulate Ar flow and O
2flow is to sputtering pressure 2.0Pa, wherein O
2throughput is 200sccm, opens radio-frequency power supply, regulates radio frequency power output to 2.5KW, sputter Al
2o
3film; The intermediate frequency power supply of opening metal Ti target, adjusting sputtering current is 4A, utilizes the revolution of matrix, successively by two target tops, thereby is deposited as Ti/Al
2o
3sublayer structure alternately.Wherein, the 3rd layer high titanium doped layer, and gross thickness is 8.4nm, the volume content of titanium is that the particle diameter of 43.0%(titanium is determined by the thickness of subgrade, and the thickness of subgrade can be at 1-10nm, and the thickness of its particle diameter and subgrade is suitable), in each cycle, the thickness of Ti is 1.8nm, Al
2o
3thickness be 2.4nm, totally two cycles; The 4th layer low titanium doped layer, gross thickness is 60.2nm, the volume content of titanium is 27%, codeposition Ti/Al
2o
3in 9 cycles, in each cycle, the thickness of Ti is that the particle diameter of 1.8nm(titanium is determined by the thickness of subgrade, and the thickness of subgrade can be at 1-10nm, and the thickness of its particle diameter and subgrade is suitable), Al
2o
3thickness be 4.87nm.(4) close intermediate frequency power supply, proceed Al
2o
3sputter, has prepared the thick Al of 46.9nm
2o
3antireflection layer.
After having prepared, use Lamada 950 ultraviolets/visible/near infrared spectrophotometer and TJ270-300 infrared spectrophotometer respectively to coating within the scope of solar spectrum the reflectivity of (0.3 ~ 3um) and infra-red radiation wave band (2.5 ~ 25um) test, passing through the absorptivity that calculates the present embodiment coating is 95.2%; Hemispherical emissivity is 10.8%.
Under atmospheric condition, after 450 ℃ of constant temperature of 48 hours are processed, coating is without coming off and crack performance, and the absorptivity of rete and emissivity do not change.
From the present embodiment, can see, solar energy coating involved in the present invention has high absorptance and low-launch-rate, high high-temp stability is good, production technology is simple, is easy to organize large-scale production; For example: after being attached in substrate, it can be used for the surface selectivity absorber coatings of middle high-temperature solar thermal-collecting tube.Have broad application prospects.
Claims (4)
1. high temperature solar photo-thermal coating for selective absorption in a kind; be prepared in metallic substrates; from substrate surface, be upwards followed successively by superimposed bonding transition zone, infrared reflecting layer, high tenor absorbed layer, low-metal content absorbed layer, antireflection layer; it is characterized in that: described absorber coatings is comprised of five tunics to top successively the substrate surface that absorbs heat; ground floor, for bonding transition zone, is comprised of metal Ti film; The second layer is infrared reflecting layer, TiN film, consists of; The 3rd layer is high tenor absorbed layer, and its composition alternately consists of successively Titanium particle subgrade and dielectric subgrade, and this insulating medium layer adopts Al
2o
3or SiO
2, the volume content of Titanium is 30%-60%; The 4th layer is low-metal content absorbed layer, and its composition still its composition alternately consists of successively Titanium particle subgrade and dielectric subgrade, and this insulating medium layer still adopts Al
2o
3or SiO
2, the volume content of Titanium is 10%-30%; Layer 5 is antireflection layer, and this antireflection layer adopts Al
2o
3or SiO
2.
2. middle high temperature solar photo-thermal coating for selective absorption as claimed in claim 1, is characterized in that: base material is aluminium, copper or stainless steel material, is coated with and is deposited upon in metallic substrates.
3. middle high temperature solar photo-thermal coating for selective absorption as claimed in claim 1, is characterized in that: ground floor is bonding transition zone, and the metal Ti film thick by 2-20nm forms; The second layer is infrared reflecting layer, and the TiN film thick by 80-200nm forms, and plays the loose layer of barrier material and hydrogen-evolution retardation simultaneously; The 3rd layer is high tenor absorbed layer, and its composition alternately consists of successively Titanium particle subgrade and dielectric subgrade, and this insulating medium layer adopts Al
2o
3or SiO
2material; The thickness of this layer is 8nm-120nm, and the volume content of Titanium is 30%-60%; The 4th layer is low-metal content absorbed layer, and its composition still its composition alternately consists of successively Titanium particle subgrade and dielectric subgrade, and this insulating medium layer still adopts Al
2o
3or SiO
2material; The thickness of this layer is 20nm-150nm, and the volume content of Titanium is 10%-30%; Layer 5 is the antireflection layer that 30-200nm is thick, and this antireflection layer adopts Al
2o
3or SiO
2material.
4. the middle high temperature solar photo-thermal coating for selective absorption as described in claim 1,2 or 3, it is characterized in that: described high tenor absorbed layer and low-metal content absorbed layer adopt magnetron sputtering deposition method to prepare, it adopts cosputtering or many subgrades of alternating deposit method to prepare by Titanium and dielectric, and each subgrade thickness is in 1-10nm; Described dielectric is Al
2o
3or SiO
2material.
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|---|---|---|---|
| CN201210308290.7A CN103625032A (en) | 2012-08-27 | 2012-08-27 | Medium-high temperature solar photothermal selective-absorbing coat |
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|---|---|---|---|
| CN201210308290.7A CN103625032A (en) | 2012-08-27 | 2012-08-27 | Medium-high temperature solar photothermal selective-absorbing coat |
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| CN103625032A true CN103625032A (en) | 2014-03-12 |
Family
ID=50206654
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| CN201210308290.7A Pending CN103625032A (en) | 2012-08-27 | 2012-08-27 | Medium-high temperature solar photothermal selective-absorbing coat |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105444443A (en) * | 2014-08-14 | 2016-03-30 | 北京桑达太阳能技术有限公司 | Solar selective absorbing coating and preparation method thereof |
| CN105568238A (en) * | 2015-12-30 | 2016-05-11 | 中国建材国际工程集团有限公司 | Preparation method for film system provided with solar selective absorption thin film |
| CN106091446A (en) * | 2016-06-15 | 2016-11-09 | 中国科学院兰州化学物理研究所 | A kind of titanium nitride base solar coating for selective absorption and preparation method thereof |
| CN108617161A (en) * | 2018-07-02 | 2018-10-02 | 白国华 | A kind of ultra-thin anti-EMI filter film and preparation method thereof |
| CN108613423A (en) * | 2016-12-02 | 2018-10-02 | 北京有色金属研究总院 | A kind of high temperature 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 |
| CN110029347A (en) * | 2019-04-04 | 2019-07-19 | 南京邮电大学 | A kind of high thermal stability solar energy optical-thermal switching film and preparation method thereof |
| CN110422345A (en) * | 2019-07-26 | 2019-11-08 | 中国电子科技集团公司第三十三研究所 | A kind of OSR thermal control coating based on photonic crystal |
| CN110592533A (en) * | 2019-10-11 | 2019-12-20 | 中国科学院兰州化学物理研究所 | Solar energy absorbing coating with anti-diffusion and anti-oxidation performance and preparation method thereof |
| CN114196980A (en) * | 2021-12-09 | 2022-03-18 | 北京大学深圳研究生院 | Composite material and composite substrate thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105444443A (en) * | 2014-08-14 | 2016-03-30 | 北京桑达太阳能技术有限公司 | Solar selective absorbing coating and preparation method thereof |
| CN105444443B (en) * | 2014-08-14 | 2018-02-16 | 北京桑达太阳能技术有限公司 | Solar selectively absorbing coating and preparation method thereof |
| CN105568238A (en) * | 2015-12-30 | 2016-05-11 | 中国建材国际工程集团有限公司 | Preparation method for film system provided with solar selective absorption thin film |
| CN105568238B (en) * | 2015-12-30 | 2020-11-13 | 中国建材国际工程集团有限公司 | Preparation method of film system with solar selective absorption film |
| CN106091446A (en) * | 2016-06-15 | 2016-11-09 | 中国科学院兰州化学物理研究所 | A kind of titanium nitride base solar coating for selective absorption and preparation method thereof |
| CN108613423A (en) * | 2016-12-02 | 2018-10-02 | 北京有色金属研究总院 | A kind of high temperature selective solar spectrum absorbing membrane and preparation method thereof |
| CN108617161A (en) * | 2018-07-02 | 2018-10-02 | 白国华 | A kind of ultra-thin anti-EMI filter film 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 |
| CN110029347A (en) * | 2019-04-04 | 2019-07-19 | 南京邮电大学 | A kind of high thermal stability solar energy optical-thermal switching film and preparation method thereof |
| CN110422345A (en) * | 2019-07-26 | 2019-11-08 | 中国电子科技集团公司第三十三研究所 | A kind of OSR thermal control coating based on photonic crystal |
| CN110592533A (en) * | 2019-10-11 | 2019-12-20 | 中国科学院兰州化学物理研究所 | Solar energy absorbing coating with anti-diffusion and anti-oxidation performance and preparation method thereof |
| CN114196980A (en) * | 2021-12-09 | 2022-03-18 | 北京大学深圳研究生院 | Composite material and composite substrate thereof |
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Application publication date: 20140312 |