CN103808048A - High-temperature solar spectrally-selective absorbing coating - Google Patents

High-temperature solar spectrally-selective absorbing coating Download PDF

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Publication number
CN103808048A
CN103808048A CN201210450638.6A CN201210450638A CN103808048A CN 103808048 A CN103808048 A CN 103808048A CN 201210450638 A CN201210450638 A CN 201210450638A CN 103808048 A CN103808048 A CN 103808048A
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China
Prior art keywords
layer
coating
thickness
absorbed layer
spectrally
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CN201210450638.6A
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Chinese (zh)
Inventor
杜淼
刘晓鹏
郝雷
王笑静
蒋利军
米菁
于庆河
王树茂
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Beijing General Research Institute for Non Ferrous Metals
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Beijing General Research Institute for Non Ferrous Metals
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Priority to CN201210450638.6A priority Critical patent/CN103808048A/en
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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

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  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Thermal Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Physical Vapour Deposition (AREA)

Abstract

The invention relates to a high-temperature solar spectrally-selective absorbing coating and a preparation method thereof. The preparation method comprises the following steps of: (1) selecting tungsten, molybdenum, copper or aluminium with a low infrared transmitting rate as a metal infrared high-reflection layer; (2) selecting transition metal nitride with good high-temperature stability as materials of absorbing layers, and obtaining a first absorbing layer and a second absorbing layer by controlling the content of infusible metals in the coating; (3) adopting nitride of Si or oxide of Si as a reflection-reducing layer; controlling the components and the contents of different film-layer materials by controlling the gas flow and the sputtering power; obtaining the spectrally-selective absorbing coating with the four-layer structure. The high-temperature solar spectrally-selective absorbing coating is below 400nm in thickness, has high absorptivity Alpha (0.93-0.96) in the solar spectral range (0.3-2.5mu m), and has very-low emissivity Epsilon (0.04-0.06) in the infrared region (2.5-50mu m).

Description

A kind of high temperature coating for selective absorption of sunlight spectrum
Technical field
The invention belongs to solar thermal utilization material technology field, specially refer to and use the method for DC reactive sputtering that refractory metal is entrained in to Si 3n 4the coating for selective absorption of sunlight spectrum forming in ceramic matrix.
Background technology
Solar thermal utilization can be divided into low temperature, middle gentle high temperature heat utilization by serviceability temperature difference.China is solar thermal utilization big country, but main application concentrates on low temperature and middle temperature field, such as Al-N/Al gradual change coating and SS-AlN interference absorber coatings, is all widely used.And having high temperature utilization side heat, and also rarely having widely used film structure, subject matter is not have the coating for selective absorption of sunlight spectrum of high-temperature stable.In general, spectral selective absorbing coating need to have high-absorbility (>0.94) and high temperature low-launch-rate (<0.10,400 ℃), because the thermal radiation loss of coating and T4 relation in direct ratio.The high-temperature stability of coating in air and vacuum environment is also very important, and this has determined the operating temperature of coating.
Chinese invention patent CN8510042 relates to a kind of Al-N/Al coating for selective absorption, and this coating can adopt single technology Al target response sputter preparation, and technique is simple, cost is low, and the absorptivity of coating can reach 0.93, emissivity 0.06(100 ℃).On middle low-temperature solar energy vacuum heat collection pipe, be widely applied.But this coating is in the time that higher temperature is worked, and the aluminum particulate activity in coating increases, and the thermal diffusion effect of metallic and dielectric is strengthened, coating structure disorder, coating performance declines, and has affected collecting efficiency and the life-span of vacuum tube.
Chinese invention patent CN96102331.7 relates to a kind of M-AlN(M=SS, W etc.) spectral selective absorbing coating, this coating adopts metallic target at Ar+N 2under atmosphere, reactive sputtering forms.Owing to having adopted two DC reactive sputterings, deposition efficiency increases, and coating heat resistance is improved.But this coating serviceability temperature can not exceed 350 ℃, in hot environment, the diffusion of metallic has caused coating inefficacy.
International monopoly WO2009107157A2 relates to the spectral selective absorbing coating of a kind of metal-ceramic composite coatings as absorbed layer.This coating is used W to be entrained in Al as metallic 2o 3in matrix, wherein W uses metallic target d.c. sputtering to form, Al 2o 3adopt ceramic target radio-frequency sputtering to form or adopt metallic target d.c. sputtering to form.The absorptivity of this coating reaches 0.96,580 ℃ of emissivity and is less than 0.11, is the coating that a kind of performance is very excellent.
Summary of the invention
The object of the invention is the defect for above-mentioned prior art, a kind of high temperature coating for selective absorption of sunlight spectrum and preparation method thereof is proposed, the feature such as that the present invention's coating has is simple in structure, excellent optical performance, heat-resisting ability are strong, aspect preparation technology, be easy to realize and regulate and control simply, be applicable in high-temperature vacuum heat-collecting tube.
The high temperature coating for selective absorption of sunlight spectrum that the present invention proposes is outwards followed successively by the outer high reflection layer of metallic red, absorbed layer and antireflection layer by substrate and forms, and it is characterized in that: described absorbed layer forms by the first absorbed layer containing the high volume fraction of refractory metal with containing the second absorbed layer of the low volume fraction of refractory metal.
High temperature selective solar spectrum absorbed layer of the present invention is that the method for employing DC reactive sputtering is that refractory metal is entrained in ceramic matrix and forms as metallic using high temperature alloy.
What the refractory metal in the present invention was chosen is the one in molybdenum (Mo), tungsten (W), heat resisting steel (321,2520), NiCr alloy (50wt%Ni and 50wt%Cr), and that ceramic material is chosen is Si 3n 4.
Wherein, to refer to content be 50 % by weight Ni and 50 % by weight Cr to NiCr alloy.
One in stainless steel (304 or 316), Cu, Al, glass and the polishing Si sheet of surface finish that what the base material in the present invention was chosen is.
The outer high reflection layer of metallic red in the present invention relates to the one in simple metal W, Mo, Al and Cu, and the target that the outer high reflection layer of this metallic red adopts is W, Mo, Al or Cu simple metal target.Reacting gas and working gas are high-purity Ar, adopt the preparation method of magnetically controlled DC sputtering, and thickness is 50-300 nanometer.
The first absorbed layer of the present invention is that metallic volume integral number is that the volume fraction that refractory metal is high is 0.3-0.8, and thickness is 30-150nm, and solar spectrum is had to stronger absorbability, is main absorbed layer.The second absorbed layer is that metallic volume integral number is that the volume fraction that refractory metal is low is 0.05-0.3, thickness is 20-150nm, refractive index size is between the first absorbed layer and antireflection layer, with antireflection layer and a film structure that refractive index gradually changes of the common composition of the first absorbed layer, the interference of generation absorbs the absorptivity that has further increased coating.
Antireflection layer in the present invention is mainly the nitride of Si or the oxide of Si, comprises Si 3n 4or SiO 2.The target that this layer adopts is Si target.Reacting gas and working gas are high-purity Ar and high-purity N 2, or high-purity Ar and high-purity O 2, the preparation method of employing magnetically controlled DC sputtering, thickness is 20-200 nanometer.
The present invention is directed to different film materials and control each thicknesses of layers and composition by flow and the sedimentation time of adjusting sputtering power, nitrogen-oxygen-argon.
High temperature coating for selective absorption of sunlight spectrum and preparation method thereof in one of the present invention, the solution of its key technology is:
(1) base material ultrasonic cleaning is inserted after vacuum chamber after drying, and argon ion bombardment 20 ~ 30min is carried out in its surface;
(2) depositing pure gold belongs to infrared high reflection layer, by selecting suitable metal to obtain low infrared emittance;
(3) deposition the first absorbed layer, rete forms (metallic volume integral number is 0.5-0.8) by the cermet composite coating of high metal volume mark.
(4) deposition the second absorbed layer, rete forms (metallic volume integral number is 0.1-0.5) by the cermet composite coating of low metal volume mark.
(5) last depositing nitride or oxide antireflection layer;
(6) in order to guarantee the integrality of every tunic growth and to prevent that the atom between each layer from spreading, plate every layer between interval 5 ~ 15min, take out sample after being finally cooled to room temperature.
The present invention is a kind of coating for selective absorption of sunlight spectrum and preparation method thereof, its advantage is: coating has higher absorptivity α (0.93 ~ 0.96) in solar spectrum scope (0.3～2.5 micron), there is very low emissivity ε (0.04 ~ 0.06) at region of ultra-red (2.5～50 microns), there is high-temperature stability simultaneously, meet the requirement that solar energy high temperature utilizes.This preparation technology of coating is simple, and cost is low
Accompanying drawing explanation
Fig. 1 is the microstructure models of coating of the present invention, wherein 1 is substrate, and 2 is the outer high reflection layer (W, Mo, Al, Cu) of metallic red, and 3 is the first absorbed layer containing volume fraction 0.3-0.8 refractory metal, 4 is the second absorbed layer containing volume fraction 0.05-0.3 refractory metal, and 5 is antireflection layer (Si 3n 4, SiO 2).
The specific embodiment
Embodiment 1
With Mo-Si 3n 4film is example, and as shown in Figure 1, coating for selective absorption of sunlight spectrum of the present invention is divided into 4 layers from below to up from substrate 1, is followed successively by outer high reflection layer 2, the first absorbed layer 3, the second absorbed layers 4 and the antireflection layers 5 of metallic red.In coating machine, pass into argon gas, adopt molybdenum target sputter in argon gas atmosphere to be coated with Mo film, as the outer high reflection layer 2 of metallic red, thickness is 100nm; Adopt molybdenum target and silicon target reactive sputtering in the mist of argon gas and nitrogen, form Mo-Si 3n 4form the first absorbed layer 3, the volume fraction containing Mo of this layer is 0.4, and thickness is 75nm; Adopt molybdenum target and silicon target reactive sputtering in the mist of argon gas and nitrogen, form Mo-Si 3n 4form the second absorbed layer 4, the volume fraction containing Mo of this layer is 0.1, and thickness is 55nm; Adopt silicon target reactive sputtering in the mist of argon gas and nitrogen, form silicon nitride (Si 3n 4) forming antireflection layer 5, the thickness of this layer is 50nm.
Prepared coating absorptivity can reach 0.95, emissivity ε≤0.05(82 ℃), ε≤0.08(400 ℃).
Embodiment 2
With W-Si 3n 4film is example, and coating for selective absorption of sunlight spectrum of the present invention is divided into 4 layers from below to up from substrate.Except substrate, the 1st layer is the outer high reflection layer of metallic red, adopts the sputter in argon gas of W target to be coated with W film, and thickness is 120nm; The 2nd layer is the first absorbed layer of high W content, adopts tungsten target and silicon target reactive sputtering in the mist of argon gas and nitrogen, forms W-Si 3n 4the first absorbed layer forming, the volume fraction containing W of this layer is 0.55, thickness is 80nm; The 3rd layer is the second absorbed layer of low W content, adopts tungsten target and silicon target reactive sputtering in the mist of argon gas and nitrogen, forms W-Si 3n 4the second absorbed layer forming, the volume fraction containing W of this layer is 0.15, thickness is 45nm; The 4th layer is antireflection layer, adopts silicon target reactive sputtering in the mist of argon gas and oxygen, forms silica (SiO 2) forming antireflection layer, the thickness of this layer is 35nm;
Prepared coating absorptivity can reach 0.94, emissivity ε≤0.04(80 ℃), ε≤0.09(400 ℃).
Above-described embodiment is only for the present invention is described, rather than restriction the present invention.

Claims (4)

1. a high temperature coating for selective absorption of sunlight spectrum, it is characterized in that, this absorber coatings is outwards followed successively by the outer high reflection layer of metallic red, absorbed layer and antireflection layer by substrate, wherein, absorbed layer forms by ceramic material the first absorbed layer containing 0.3-0.8 volume fraction refractory metal with containing ceramic material second absorbed layer of 0.053-0.3 volume fraction refractory metal.
2. high temperature coating for selective absorption of sunlight spectrum according to claim 1, is characterized in that, the refractory metal in absorbed layer is the one in Mo, W, 321 heat resisting steel, 2520 heat resisting steel, NiCr alloy, and ceramic material is Si 3n 4; Infrared high reflection layer is the one in simple metal W, Mo, Cu and Al; Antireflection layer is Si 3n 4or SiO 2.
3. high temperature coating for selective absorption of sunlight spectrum according to claim 1, it is characterized in that: infrared high reflection layer thickness is 50 ~ 300 nanometers, the thickness of the first absorbed layer is 30 ~ 150nm, and the second absorber thickness is 20 ~ 150nm, and antireflection layer thickness is 20 ~ 200 nanometers.
4. according to high temperature coating for selective absorption of sunlight spectrum described in any one in claim 1,2,3, it is characterized in that, described absorber coatings is by adjusting sputtering power, high-purity Ar, high-purity N 2with high-purity O 2in one or more flow and sedimentation time control thickness and the composition of each absorber coatings.
CN201210450638.6A 2012-11-12 2012-11-12 High-temperature solar spectrally-selective absorbing coating Pending CN103808048A (en)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106052171A (en) * 2016-06-21 2016-10-26 华中科技大学 Selective absorption film
CN106568207A (en) * 2016-10-26 2017-04-19 中国大唐集团科学技术研究院有限公司 High-temperature solar spectrum selective absorbing coating and preparation method thereof
CN106756899A (en) * 2016-11-28 2017-05-31 江南大学 A kind of preparation method of high temperature resistant spectral selective absorbing coating
CN107560200A (en) * 2017-09-06 2018-01-09 广东五星太阳能股份有限公司 A kind of stable solar selectively absorbing coating under high temperature atmospheric environment
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
CN109234675A (en) * 2018-08-31 2019-01-18 江苏京展能源科技有限公司 A kind of solar energy vacuum tube coating for selective absorption and preparation method thereof
CN109371364A (en) * 2018-12-03 2019-02-22 蓝思科技（长沙）有限公司 A kind of evaporation process that glass is non-discolouring

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1323858A (en) * 2001-05-29 2001-11-28 清华大学 Selective solar spectrum absorbing coating
US20050258030A1 (en) * 2004-04-27 2005-11-24 Finley James J Effects of methods of manufacturing sputtering targets on characteristics of coatings
US20070196670A1 (en) * 2006-02-21 2007-08-23 Harish Chandra Barshilia solar selective coating having higher thermal stability useful for harnessing solar energy and a process for the preparation thereof
CN200968738Y (en) * 2006-11-22 2007-10-31 江苏太阳雨太阳能有限公司 Middle- and high-temperature solar thermal-collecting tube
CN101294749A (en) * 2007-04-24 2008-10-29 梁美意 Heat-collecting tube with solar energy selective absorption coating and manufacturing method thereof
CN102121757A (en) * 2010-01-28 2011-07-13 北京有色金属研究总院 Non-vacuum solar spectrum selective absorption coating and preparation method thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1323858A (en) * 2001-05-29 2001-11-28 清华大学 Selective solar spectrum absorbing coating
US20050258030A1 (en) * 2004-04-27 2005-11-24 Finley James J Effects of methods of manufacturing sputtering targets on characteristics of coatings
US20070196670A1 (en) * 2006-02-21 2007-08-23 Harish Chandra Barshilia solar selective coating having higher thermal stability useful for harnessing solar energy and a process for the preparation thereof
CN200968738Y (en) * 2006-11-22 2007-10-31 江苏太阳雨太阳能有限公司 Middle- and high-temperature solar thermal-collecting tube
CN101294749A (en) * 2007-04-24 2008-10-29 梁美意 Heat-collecting tube with solar energy selective absorption coating and manufacturing method thereof
CN102121757A (en) * 2010-01-28 2011-07-13 北京有色金属研究总院 Non-vacuum solar spectrum selective absorption coating and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106052171A (en) * 2016-06-21 2016-10-26 华中科技大学 Selective absorption film
CN106568207A (en) * 2016-10-26 2017-04-19 中国大唐集团科学技术研究院有限公司 High-temperature solar spectrum selective absorbing coating and preparation method thereof
CN106756899A (en) * 2016-11-28 2017-05-31 江南大学 A kind of preparation method of high temperature resistant spectral selective absorbing coating
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
CN107560200A (en) * 2017-09-06 2018-01-09 广东五星太阳能股份有限公司 A kind of stable solar selectively absorbing coating under high temperature atmospheric environment
CN109234675A (en) * 2018-08-31 2019-01-18 江苏京展能源科技有限公司 A kind of solar energy vacuum tube coating for selective absorption and preparation method thereof
CN109371364A (en) * 2018-12-03 2019-02-22 蓝思科技（长沙）有限公司 A kind of evaporation process that glass is non-discolouring

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Application publication date: 20140521