EP2245208A2 - Procédé de production d'un revêtement spectralement sélectif à base de cermet pour le tube de réception d'un concentrateur solaire, et matériau ainsi obtenu - Google Patents

Procédé de production d'un revêtement spectralement sélectif à base de cermet pour le tube de réception d'un concentrateur solaire, et matériau ainsi obtenu

Info

Publication number
EP2245208A2
EP2245208A2 EP09715629A EP09715629A EP2245208A2 EP 2245208 A2 EP2245208 A2 EP 2245208A2 EP 09715629 A EP09715629 A EP 09715629A EP 09715629 A EP09715629 A EP 09715629A EP 2245208 A2 EP2245208 A2 EP 2245208A2
Authority
EP
European Patent Office
Prior art keywords
metal
layer
cermet
coating material
reflective
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09715629A
Other languages
German (de)
English (en)
Inventor
Alessandro Antonaia
Salvatore Esposito
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Agenzia Nazionale per le Nuove Tecnologie lEnergia e lo Sviluppo Economico Sostenibile ENEA
Original Assignee
Agenzia Nazionale per le Nuove Tecnologie lEnergia e lo Sviluppo Economico Sostenibile ENEA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Agenzia Nazionale per le Nuove Tecnologie lEnergia e lo Sviluppo Economico Sostenibile ENEA filed Critical Agenzia Nazionale per le Nuove Tecnologie lEnergia e lo Sviluppo Economico Sostenibile ENEA
Publication of EP2245208A2 publication Critical patent/EP2245208A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0688—Cermets, e.g. mixtures of metal and one or more of carbides, nitrides, oxides or borides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C23C14/0084—Producing gradient compositions
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S20/00—Solar heat collectors specially adapted for particular uses or environments
    • F24S20/20—Solar heat collectors for receiving concentrated solar energy, e.g. receivers for solar power plants
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S70/00—Details of absorbing elements
    • F24S70/30—Auxiliary coatings, e.g. anti-reflective coatings
    • 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

Definitions

  • the present invention relates to the sector of solar plants for the production of energy and in particular an innovative material to be used as surface coating for the receiver tube of a solar plant, preferably of the type with linear parabolic mirrors, suitable for operating at a high temperature.
  • the receiver tube positioned along the focal line of the parabolic mirrors, must perform the function of absorbing the maximum amount of concentrated solar radiation and, at the same time, dispersing outwards the minimum amount of the heat stored.
  • the materials suitable for use as surface coatings of the receiver tube are the ones that behave in an optically selective way, i.e., those materials the optical properties of reflectance, absorbance, and hemispherical emissivity of which are modified appreciably with the wavelength of the radiation passing from the region of irradiance of the solar spectrum to the region of the thermal infrared.
  • the coating to be made must have a behaviour as close as possible to the ideal one : zero reflectance (unit absorbance) in the spectral region of solar radiation (wavelength 0.3-2.0 ⁇ m) and unit reflectance (zero absorbance and emissivity) in the region of the thermal infrared (wavelength 2.0-40 ⁇ m) , with a step passage between the two regions.
  • CERMETs are ceramic-metal composite materials, where metal nano-particles are dispersed in a ceramic matrix.
  • CERMETs are materials that meet the requisites referred to above, presenting a high absorption in the region of the solar spectrum and being transparent in the region of the thermal infrared. Furthermore, they prove quite stable when used at a high temperature.
  • the interest in these composite materials dates back to 1950, when Tabor, Gier and Dunkle presented the their first results on the use of CERMETs as coating materials for selective absorption of solar radiation.
  • the first composite materials produced as selective absorbers were constituted by a layer of CERMET, with a homogeneous volumetric fraction of metal, inserted between a metal layer that functioned as reflector for the infrared and a layer of anti-reflective material that enabled an improvement in the absorption of the solar spectrum.
  • This structure presented an absorption of 0.87 , with an emissivity of 0.07 at 100 0 C.
  • Structures of this sort were produced, and each time it was possible to reduce the emissivity by accepting lower values of absorption or else improve the absorption by accepting higher values of emissivity. In any case, the values of absorption obtained with this type of structure were not sufficiently high to be used in the production of coating materials for thermo-electric applications. In addition, when the working temperature rose above 300 °C the emissivity increased drastically, degrading the performance of the coating.
  • the first structure developed and produced was the one with variable content of metal dispersed in the ceramic matrix. Numerous works conducted starting from 1977 demonstrated the benefits that were obtained by inserting between the metal reflector and the anti-reflective layer a CERMET with volumetric fraction ofmetal that decreased passing fromthe metal reflector to the anti-reflective layer. The studies conducted in those years by I. T. Ritche and B. Window highlighted that between the various possible profiles that described the content of the metal in the ceramic matrix the linear one was the one that maximized solar absorption.
  • Qi-Chu Zhang proposed an alternative structure constituted by a series of layers of CERMET set on top of one another, each with different volumetric fractions of metal inserted between a metal reflector and an anti-reflective layer.
  • both of the structures i.e., the one with the multilayer CERMET and the one with CERMET with continuously variable profile
  • the temperature of use of the coatings does not exceed 400 0 C so that the performance of the systems is comparable irrespective of the structure used as coating.
  • one of the major limits of currently known CERMET coatings is the value of the maximum temperature at which they can work at the same time guaranteeing good performance and a good stability over time.
  • a useful parameter for comparing the performance of solar concentrators of thermoelectric plants is the photothermal-conversion efficiency ( ⁇ pt ) : ⁇ T 2 ⁇ pt -a- ⁇ h — where ⁇ is the absorbance, ⁇ h is the emissivity, ⁇ is the Stefan-Boltzmann constant, T is the temperature of the coating, I is the irradiance of the direct component of the solar spectrum evaluated' at AM 1.5, and C is the factor of concentration (aperture of the mirror/circumference of the receiver tube) .
  • a first purpose of the invention is to provide a coating material for receiver tubes having a good chemical, structural, and mechanical stability over the entire range of operating temperatures, in particular up to 380 0 C in traditional solar plants that use diathermic oil as heat-exchange fluid, up to 58O 0 C in innovative solar plants that use molten salts as heat-exchange fluid.
  • a second purpose of the invention is to make available a coating material of the aforesaid type designed to provide a high absorbance in the spectral region of the solar radiation (wavelength 0.3-2.0 ⁇ m) .
  • a third purpose of the invention is to make available a coating material of the aforesaid type, designed to provide a low emissivity up to the maximum operating temperature, preferably 580 0 C, in a solar plant for the production of energy with linear-parabolic-mirror technology.
  • a fourth purpose of the invention is to make available a coating material of the aforesaid type, designed to provide excellent performance in terms of high absorbance and low emissivity in the entire range of variation of the operating temperature (300 to 580 0 C) along the linear collector usually made of steel (the length of which is, for example, 0 to 600 m) , which results in the possibility of producing just one type of material as coating with evident technological and economic benefits in the stage of construction of the plant.
  • a fifth purpose of the invention consists in providing a process of production of the layers constituting the coating, characterized by high reliability and reproducibility of deposition, by means of the use of techniques of deposition, such as those of DC sputtering and RF sputtering and those of reactive sputtering.
  • a multilayer coating material according to Claim 1 comprising a bottom metal layer that is highly reflective in the infrared and a top layer of anti-reflective material, provided between which is a layer of an innovative composite ceramic-metal (CERMET) material of a graded type, in the case in point with a volumetric fraction of metal that decreases passing from the metal reflector to the anti-reflective layer.
  • CERMET composite ceramic-metal
  • the first optically active layer of the selective coating is the reflector in the infrared (back reflector) and is constituted by tungsten deposited via DC sputtering in the crystalline form ⁇ , which represents the structure of tungsten with higher reflectivity in the infrared.
  • a preventive deposition of a matching layer constituted by a layer of W-Al 2 O 3 CERMET with constant metal content is provided: the deposition of said matching layer, by producing both a rise in temperature of the steel substrate and incorporation of the "poisoning" species (such as, for example, H 2 O, CO 2 ) for W, prevents germination of grains of phase ⁇ and favours the direct growth of W of phase ⁇ .
  • the "poisoning" species such as, for example, H 2 O, CO 2
  • the tungsten of type ⁇ thus produced constitutes: i) an excellent optical reflector in the infrared even for very contained thicknesses of deposition ( ⁇ 0.15 ⁇ m) ; ii) a material with high chemico-physical stability when used at a high temperature; iii) an excellent barrier layer that prevents any polluting elemental diffusion (C, Ni) from the steel to the CERMET.
  • the ceramic matrix of the CERMET is made up of aluminium oxide (Al 2 Os) deposited by means of RF sputtering or else by means of reactive sputtering in an environment with argon-oxygen mixture, whilst the metal particles dispersed in the ceramic matrix are constituted by tungsten (W) deposited by means of DC sputtering.
  • the global process for producing CERMET hence proves to be a DC-RF co-sputtering or else a DC-reactive co-sputtering, whilst the deposition of a graded type, in the case in point characterized by a metal content that decreases as the thickness increases, is obtained by means of continuous variation of the cathode power during the time of production of the CERMET.
  • the W-Al 2 O 3 CERMET of a graded type thus produced proves to be a very stable material at a high temperature and with the best performance in terms of high absorption of the solar spectrum.
  • the anti-reflective layer is constituted by aluminium oxide (AI 2 O 3 ) or silicon oxide (SiO 2 ) and is produced by means of RF sputtering or else by means of reactive sputtering.
  • Figure 1 shows the structure of the coating according to the invention, with regard to the preferred embodiment in which the first layer deposited is a matching material of a CERMET type, the second is a layer of ⁇ -phase tungsten, the third is a W-Al 2 O 3 CERMET of a graded type, and the fourth is an alumina or silica layer, for a total of four thin layers; and
  • Figure 2 is a diagram that shows the experimental spectral reflectance of a coating obtained in the laboratory according to the invention, as well as the experimental data regarding the photothermal parameters of interest, in particular solar absorbance ⁇ and hemispherical emissivity ⁇ evaluated at two different operating temperatures (400 and 580 0 C) .
  • the coating comprises four layers, which, starting from the bottom substrate made of steel, are respectively represented by:
  • a matching layer 4 constituted by a material made of W-Al 2 O 3 CERMET with constant metal content, having a thickness of from 0.06 to 0.13 ⁇ m, preferably 0.09 ⁇ m;
  • a layer of tungsten 1 with crystalline phase ⁇ having a thickness of from 0.05 to 0.25 ⁇ m, preferably 0.12 ⁇ m;
  • the present invention stems from the need to provide an innovative material, the selective properties of which in wavelength of the solar radiation will enable it to be used as coating for the receiver tubes of the linear-concentration system of a thermoelectric solar plant operating at medium-to-high temperature (with heat-exchange fluid up to 55O 0 C) .
  • the need to provide processes of production of said coating that will be reliable and perfectly repeatable.
  • this is a coating the selective structure of which uses a metal-ceramic composite material, CERMET (W-Al 2 O 3 ) , that is highly stable and ensures, at a maximum temperature of operation of the plant of 55O 0 C, efficiencies of photothermal conversion higher than 0.75 for a factor of solar concentration higher than 50.
  • This selective structure is preferably made up of four layers that are produced, preferably, using the DC-sputtering technique and the RF-sputtering technique, or else the reactive-sputtering technique, starting from metal and ceramic targets or else from just metal targets.
  • the possibility of producing, via DC sputtering and with excellent repeatability, layers of tungsten with crystalline structure in phase ⁇ without using particularly costly and demanding measures, such as direct heating of the substrate and an ultra-high-vacuum pumping system, is a factor that renders the use of tungsten itself as optical reflector for the infrared economically and technologically very advantageous.
  • the coating material according to the invention is designed to be used for coating a solar collector that develops along the focal line of the concentrators and that reaches a maximum temperature of approximately 58O 0 C, ensuring a temperature of the fluid at outlet substantially equal to 550 0 C
  • the thermoelectric efficiency of the plant coated with the material according to the invention is advantageously higher than that of the systems obtained up to now, which work at lower temperatures ( ⁇ 400°C) or which resort to further heating operations of a traditional type of the fluid to bring it up to the optimal working temperature.
  • the use of higher temperatures of the fluid enables high efficiencies in the turbine to be obtained because it is not necessary to heat the fluid prior to its entry into the impeller. From what has been said above, it emerges that also forming a subject of the present invention is the method of production of the multilayer coating for solar collectors.
  • Said method substantially comprises the followxng steps:

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Optical Elements Other Than Lenses (AREA)
  • Physical Vapour Deposition (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne un matériau de revêtement de surface pour tubes de réception d'installations solaires, en particulier du type à miroirs paraboliques linéaires, formé d'une structure multicouche qui comprend une couche de base en métal (réflecteur arrière) qui réfléchit fortement l'infrarouge et une couche supérieure en matériau anti-réfléchissant, avec entre elles une couche d'un composite innovant en matériau céramique-métallique (CERMET) du type échelonné, dans le cas présent avec une fraction volumétrique décroissante de métal du réflecteur métallique vers la couche anti-réfléchissante. En particulier : i) la matrice céramique du CERMET est constituée d'oxyde d'aluminium (Al2O3), tandis que les particules métalliques dispersées dans la matrice céramique sont constituées de tungstène (W); ii) le réflecteur arrière est en tungstène sous forme cristalline α et iii) la couche anti-réfléchissante est en oxyde d'aluminium ou en oxyde de silicium.
EP09715629A 2008-02-29 2009-01-28 Procédé de production d'un revêtement spectralement sélectif à base de cermet pour le tube de réception d'un concentrateur solaire, et matériau ainsi obtenu Withdrawn EP2245208A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
IT000113A ITRM20080113A1 (it) 2008-02-29 2008-02-29 Metodo per la fabbricazione di un rivestimento spettralmente selettivo a base cermet per il tubo ricevitore di un concentratore solare e materiale cosi ottenuto
PCT/IT2009/000021 WO2009107157A2 (fr) 2008-02-29 2009-01-28 Procédé de production d'un revêtement spectralement sélectif à base de cermet pour le tube de réception d'un concentrateur solaire, et matériau ainsi obtenu

Publications (1)

Publication Number Publication Date
EP2245208A2 true EP2245208A2 (fr) 2010-11-03

Family

ID=40291938

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Application Number Title Priority Date Filing Date
EP09715629A Withdrawn EP2245208A2 (fr) 2008-02-29 2009-01-28 Procédé de production d'un revêtement spectralement sélectif à base de cermet pour le tube de réception d'un concentrateur solaire, et matériau ainsi obtenu

Country Status (3)

Country Link
EP (1) EP2245208A2 (fr)
IT (1) ITRM20080113A1 (fr)
WO (1) WO2009107157A2 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9803891B2 (en) 2011-12-15 2017-10-31 Council Of Scientific & Industrial Research Solar selective coating having high thermal stability and a process for the preparation thereof
CN102721206A (zh) * 2012-06-29 2012-10-10 苏州嘉言能源设备有限公司 中高温太阳能集热器集热管
CN102721218A (zh) * 2012-06-29 2012-10-10 苏州嘉言能源设备有限公司 太阳能中温选择性吸收涂层
ITMI20121572A1 (it) * 2012-09-21 2014-03-22 Eni Spa Procedimento per la produzione di un rivestimento otticamente selettivo di un substrato per dispositivi ricevitori solari ad alta temperatura e relativo materiale ottenuto
ITVI20130006A1 (it) * 2013-01-16 2014-07-17 Fond Bruno Kessler Rivestimento multistrato a elevato assorbimento di energia solare e a bassa emissività termica, un relativo composito cermet, un suo uso e procedimenti per la loro produzione
JP6207224B2 (ja) * 2013-05-01 2017-10-04 デクセリアルズ株式会社 エッチング製品の製造方法
FR3023362A1 (fr) * 2014-07-04 2016-01-08 Commissariat Energie Atomique Absorbeur solaire selectif a couche epaisse de passivation anticorrosion et barriere thermique pour des applications hautes temperatures et son procede de realisation.
ES2689556B1 (es) * 2016-12-22 2019-09-09 Consejo Superior Investigacion Recubrimiento solar selectivo
JP6691084B2 (ja) * 2017-09-05 2020-04-28 デクセリアルズ株式会社 熱吸収材
JP6826138B2 (ja) * 2019-02-13 2021-02-03 デクセリアルズ株式会社 熱吸収材

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
WO2009107157A2 (fr) 2009-09-03
WO2009107157A3 (fr) 2010-01-14
ITRM20080113A1 (it) 2009-09-01

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