WO1996002798A1 - Convertisseur de rayonnement pour transformer un rayonnement electromagnetique en chaleur et de la chaleur en rayonnement electromagnetique - Google Patents

Convertisseur de rayonnement pour transformer un rayonnement electromagnetique en chaleur et de la chaleur en rayonnement electromagnetique Download PDF

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Publication number
WO1996002798A1
WO1996002798A1 PCT/EP1995/002753 EP9502753W WO9602798A1 WO 1996002798 A1 WO1996002798 A1 WO 1996002798A1 EP 9502753 W EP9502753 W EP 9502753W WO 9602798 A1 WO9602798 A1 WO 9602798A1
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WIPO (PCT)
Prior art keywords
quasi
converter according
radiation converter
radiation
crystalline
Prior art date
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PCT/EP1995/002753
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German (de)
English (en)
Inventor
Thomas Eisenhammer
Miladin P. Lazarov
Original Assignee
Thomas Eisenhammer
Lazarov Miladin P
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 Thomas Eisenhammer, Lazarov Miladin P filed Critical Thomas Eisenhammer
Priority to AU30784/95A priority Critical patent/AU3078495A/en
Publication of WO1996002798A1 publication Critical patent/WO1996002798A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/12—Alloys based on aluminium with copper as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/12—Alloys based on aluminium with copper as the next major constituent
    • C22C21/16—Alloys based on aluminium with copper as the next major constituent with magnesium
    • 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

Definitions

  • the invention relates to radiation converters for converting electromagnetic radiation into heat (absorber) or from heat into electromagnetic radiation (emitter).
  • Radiation converters are used in several areas. They are used as absorbers, particularly in the production of thermal energy from solar radiation.
  • the radiation can be concentrated, for example with the help of parabolic mirrors.
  • High optical absorption grades a s > 0.85 for the solar spectral range ie wavelength ⁇ * 300-2000 nm
  • these absorbers must additionally be selective, ie the absorber must have the highest possible degrees of reflection, ie low emissivities, in the spectral range of the thermal emission.
  • the low hemispherical emissivity (e ⁇ ⁇ 0.1) is intended to reduce losses in the solar radiation obtained through re-emission in the infrared spectral range.
  • Non-selective absorbers with high solar absorption levels and high spherical emission levels are e.g. available on the basis of simple coats.
  • Rough metal layers made of small particles, e.g. Black-chrome or black-cobalt are common. These materials have high degrees of solar absorption; the hemispherical emission level is around 0.2 (J. Spitz, T.V. Danh, A. Aubert, Solar Energy Materials I (1979), 189-200) and is therefore too high for many applications.
  • Such a coating is TiN ⁇ (US Pat. No. 4,098,956) with a thickness of approximately 50 nm. Amorphous, ⁇ -CH carbon doped with hydrogen is also used (DR McKenzie et al. In Solar Energy Materials 9 (1983), 113). ⁇ -
  • Cermets are small metallic particles with a diameter of approx. 2 - 40 ⁇ m, which are embedded in a dielectric matrix.
  • Many different material combinations have been discussed and investigated, for example Au-Si0 2 , stainless steel in -C: H etc. (for example LK Thomas and T. Chunhe, Solar Energy Materials IS (1989), 117-126).
  • the commercially used nickel-pigmented aluminum oxide also belongs to the cermets. Such layers are partially provided with additional dielectric anti-reflection layers (A. Anderson et al., J. Appl. Phys. _L (1980), 754).
  • the volume fraction of the metallic particles can also be varied as a function of the location within the thickness of the layer.
  • the optical constants of the cermet are also variable and allow an increase in the degree of solar absorption (GL Harding et al., J. Vac. Sei. Teclinol. I £ (1979), 2105).
  • thermophotovoltaics as emitters (RM Swanson, Proc. IEEE _ ⁇ (1979), 446). Heat is converted into electromagnetic radiation and then into electricity using a photocell. A body is heated to temperatures in the range of 600 - 900 ° C. In order to achieve maximum conversion of the thermal radiation emitted by the body, the band gap of the material of the photocell must be set appropriately. It is of great importance that the wavelength characteristics of the emitter and the photocell are matched to one another and that as little radiation as possible is emitted in wavelength ranges far from the band gap becomes. It is therefore useful to coat the emitter suitably and selectively.
  • Ideal quasi-crystalline materials have a long-range order which does not correspond to a translation symmetry, but can be described by other well-defined mathematical methods (see, for example, "Quasicristals", C. Janot, Oxford University Press, Oxford, 1992, chap. 1, Section 2.4).
  • quasi-crystalline materials are also understood to mean materials which only approximate an ideal quasi-crystalline order. They consist of microcrystalline areas, the microcrystals being arranged in a quasi-crystalline form (C. Janot, ibid., Chapter 2.5). Like ideal quasicrystals, these materials show diffraction patterns with "forbidden” symmetries, i.e. Those that are actually impossible for crystals.
  • Radiation converters must meet a number of requirements at the same time.
  • selective absorbers they must have high levels of solar absorption. Their emissivity must be very low, especially at high absorber temperatures. They must be chemically stable at high absorber temperatures and must not show any other signs of aging, e.g. by diffusion of substrate material into the layers or by diffusion within the different layers.
  • the selective absorbers 5 used and known today do not sufficiently meet all requirements.
  • the invention is therefore based on the object of providing a radiation converter which fully meets the requirements for thermal and chemical stability and whose spectral optical properties can be set in the form desired for the particular application.
  • the radiation converter contains at least one quasi-crystalline material or at least one quasi-crystalline material is used as a component of an inhomogeneous material.
  • quasi-crystalline regions occur in an otherwise amorphous or crystalline environment (phase).
  • the material that forms a quasi-crystalline phase can also contain amorphous or crystalline phases.
  • the quasi-crystalline phase of this material exceeds a volume fraction of 30%, preferably 50%, very preferably 80%.
  • thermodynamically stable quasi-crystalline material ie a material whose thermodynamically stable structure is not crystalline.
  • quasi-crystalline materials are preferably made of two or more elements, these being selected from aluminum, boron, chromium, iron, gallium. Germanium, hafnium, carbon, copper, magnesium, Molybdenum, manganese. Nickel, niobium, osmium, palladium. Rhenium, ru ⁇ thenium, silicon, tantalum, titanium, vanadium, bismuth, tungsten, yttrium, zinc or zirconium can be used. Materials that meet the following formulas are particularly preferably used:
  • X means an impurity such as e.g. Na, O or N or one or more of the elements listed in the paragraph above.
  • the quasi-crystalline material very preferably has the following empirical formulas: Al 65 Cu 20 Ru 15 , Al 62 Cu 20 Co 15 Si 3 , Al 635 Cu 245 Fe 12> Al ⁇ Cu ⁇ Fe ⁇ , Al ⁇ Cu ⁇ Fe, ⁇ Al 60 Cu 10 Li 30 Al 65 Cu 20 Co 15 , Ga 16 Mg 32 Zn 52 or Al 70 Mn Pd 21 .
  • the required optical properties are achieved for the different applications by different techniques and measures in the sense of the invention.
  • the quasi-crystalline material already has unusually good optical properties that can be used for a radiation converter.
  • These optical properties can be further expanded by using inhomogeneous materials.
  • Preferred dielectric materials are amorphous carbon; dielectric oxides, dielectric nitrides, dielectric halides or dielectric sulfur compounds of any main group and sub group elements or a mixture of these materials, very preferably A1 2 0 3 , Y 2 0 3 , Hf0 2 , Sn0 2 , ln 2 0 3 , Bi 2 0 3 , Ta ⁇ g, Si 3 N 4 or ZnS.
  • Other useful matrix materials are semiconductors, such as doped silicon or germanium, and metals, such as iron or copper.
  • the material component that forms a largely coherent structure is referred to as the matrix in the sense used above.
  • the embedded particles are largely separated from one another.
  • the optical properties of such inhomogeneous materials can often be described using effective media theories.
  • the properties of the matrix material determine the optical properties. This applies both to the case in which the quasi-crystalline material represents the matrix and to the case in which the quasi-crystalline material is embedded in the form of particles in a different type of matrix.
  • absorption occurs due to so-called geometric resonances, which does not occur in homogeneous materials.
  • the fill factor ie the volume fraction of the particles in one inhomogeneous material, determines the spectral shape and the strength of these resonances.
  • the fill factor is in the range of 2-80%, preferably in the range of 5-40%. This means that the matrix fills the interspaces between the separate particles. However, there may be contact between the particles.
  • the matrix can be quasi-crystalline or made of another material.
  • the fill factor can be spatially varied in order to reduce reflection losses on the surface and, for example, to increase the degree of solar absorption.
  • the particles or voids in the matrix are formed regularly or regularly unre ⁇ and preferably have volumes in the range of 0.2 nm 3 to 10 / in 3, preferably in the range of 2 nm 3 to 1 /.m 3, most preferably in the range from 5 nm 3 to 30000 nm 3 .
  • the diameters of the particles are in the range from 0.5-2000 nm, preferably 1-500 nm and very preferably 2-30 nm.
  • the quasi-crystalline material in addition to the quasi-crystalline phase, can also contain ' amorphous or crystalline phases, the volume fraction of which is below 70% overall. This means that the quasi-crystalline phase must exceed 30% by volume, preferably 50%, very preferably 80%.
  • the quasi-crystalline material or the inhomogeneous material containing the quasi-crystalline material is preferably applied to a substrate in the form of one or more layers with a thickness of 1 nm to mm, preferably 5-5000 nm, very preferably 10-500 nm.
  • the substrate is a highly reflective metal, such as aluminum and copper. Silver, gold, molybdenum, titanium, iron or an alloy of these materials, such as steel or brass. However, a serve a thin layer of the aforementioned metals or alloys on another substrate customary in the art. These are temperature-stable materials, preferably ceramics.
  • the substrate can also have a roughness in order to reduce the short-wave reflection.
  • the roughness of the substrate surface is characterized by a statistical distribution of the deviations from a medium level and the standard deviation of this distribution (RMS roughness) is in the range from 0 to 1500 nm, with a lateral correlation length of 10- 1000 nm.
  • RMS roughness the standard deviation of this distribution
  • the design as thin layers enables the realization of optical interference filters with certain properties, for example the properties of a selective absorber.
  • homogeneous quasi-crystalline layers In order to implement a selective absorber, homogeneous quasi-crystalline layers must be relatively thin (1 nm - 200 nm), since the emissivity of a solid quasi-crystalline material is too high, approx. 40%. Only thin quasi-crystalline layers are sufficiently transparent in the infrared spectral range, so that the emissivity is determined by the highly reflective metallic substrate underneath.
  • dielectric anti-reflection layers with thicknesses of 10-1000 nm are used.
  • Any layer systems can be formed from dielectric layers and layers with quasi-crystalline materials.
  • a preferred layer sequence consists of substrate / dielectric layer / quasi-crystalline layer / dielectric layer.
  • Another preferred layer sequence consists of substrate / inhomogeneous material containing quasi-crystalline particles (cermet) / dielectric layer. The choice of the dielectric depends on the selected layer sequence, as well as on the type of layer containing the quasi-crystalline material. It II -
  • both break-through dielectrics preferably Sn0 2 , In 2 0 3 , Bi 2 0 3 , Ta 2 0 5 , ZnS, ZnO, Ti0 2 , as well as low-refraction materials, preferably A1 2 0 3 , Si0 2 , or materials with medium refractive index, preferably Y 2 0 3 , Hf0 2 , Si 3 N 4 .
  • the layer sequence and the Schichtdic ⁇ can ken for the respective application are optimized numerically, preferably using genetic algorithms (T. iron Hammer et al., Appl. Opt. 32 (1993), 6310-6315). However, any other layer with anti-reflective properties that is known to the person skilled in the art is also possible. These layers can also serve as a diffusion barrier.
  • the radiation converters according to the invention can be used as selective absorbers in concentrating systems, for example with parabolic trough mirrors.
  • the absorber layers are applied to a cylindrical tube.
  • Another possible application is in flat and tube collectors, which are often, but not necessarily, evacuated to avoid heat transfer.
  • the low emissivities allow the use of relatively high absorber temperatures (200 ° C and higher).
  • the radiation converter preferably has high degrees of absorption for electromagnetic radiation in the solar wavelength range ( ⁇ approx. 300- 1200 nm) and high reflectance for electromagnetic radiation in the spectral range of the thermal emission ( ⁇ > approx. 2000 nm).
  • the design of the radiation converter as an emitter in combination with a photocell enables the conversion of heat into electricity without the use of moving parts.
  • interesting applications in power plant technology and the automotive industry require high temperatures (approx. 900 ° C) and selective properties of the emitter.
  • the radiation converter is preferably heated with electric current for generating infrared or visible electromagnetic radiation, by burning fossil fuels or by thermal coupling to hot gaseous, liquid or solid media.
  • Fig.l Representation of the spectral reflectance of a radiation converter from a simple layer of Al 70 Mn 9 Pd 2 , (quasi-crystalline material) on a copper substrate.
  • Fig.2 Representation of the reflectance of a radiation converter, which consists of a layer system made of Ti0 2 / Al 7 () MnyPd 2
  • Fig.3 Representation of the reflectance of a radiation converter, which consists of a layer system made of Y 2 ⁇ 3 / Al 7ü Mn 9 Pd 21 / Y 0 3 on a copper substrate .
  • Fig.4 Representation of the reflectance of a radiation converter from a cermet, which has a quasi-crystalline material (Al ⁇ Mn ⁇ Pd ⁇ ) and Hf0 2 as a dielectric, as well as an additional anti-reflection layer (AIF-.O) on a copper substrate.
  • Fig.5 Representation of the reflectance of a radiation converter from a cermet which has Al 70 Mn 9 Pd 21 as quasi-crystalline material and Y 7 0 3 as dielectric and A1F-.0 as an additional antireflection layer on a copper substrate.
  • Fig.6 Representation of the reflectance of a radiation converter from a cermet, which has Al 70 Mn 9 Pd 71 as quasi-crystalline material and A1 2 0 3 as dielectric and AlF ⁇ O y as an additional antireflection layer on a copper substrate.
  • Example 1 shows the optical properties of a thin quasi-crystalline layer on a highly reflective Metal substrate.
  • Examples 2 to 6 show selective absorbers based on quasi-crystalline materials.
  • the corresponding table shows the solar absorption levels for an AM 1.5 spectrum with vertical incidence and hemispherical emission levels at 250 ° C. and 400 ° C.
  • the numbers given in brackets in the "Layer system” column are the respective layer thicknesses in nm.
  • a simple layer of a quasi-crystalline material made of Al 70 Mn 9 Pd 21 on a copper substrate has, with a thickness of the layer of, for example, 40 nm, an almost constant degree of absorption of about 55% in the wavelength range from 300 nm to almost 2 ⁇ .
  • the quasi-crystalline material becomes transparent for longer wavelengths, and the degree of reflection rises sharply due to the copper substrate lying under the quasi-crystalline material, ie the degree of absorption decreases sharply.
  • the spectral reflectance is shown in Figure 1.
  • the optical behavior of other quasi-crystalline materials, e.g. Al ⁇ Cu ⁇ Fe ⁇ , is comparable.
  • One application is the generation of a thermal emission spectrum with a reduced infrared portion. This is annoying when simulating solar radiation with conventional, largely gray emitters high proportion of the emission in the infrared spectral range, which is largely suppressed in the example described here.
  • the degree of solar absorption of a single quasi-crystalline layer is not sufficient for solar thermal applications.
  • the degree of solar absorption can be significantly increased, for example, with a layer system made of TiO 2 / quasi-crystalline material / Y 2 O 3 on a copper substrate.
  • Figure 2 shows the spectral reflectance of such a layer system (TiO 2 / Al 70 Mn 9 Pd 21 / Y 2 O 3 ).
  • the solar degree of absorption is 0.86, while the hemispherical degree of emissivity for a temperature of 250 ° C is 0.043 (see table, line 1).
  • the optimal properties can also be optimized for applications at low absorber temperatures.
  • a higher degree of solar absorption is necessary here, while the hemispherical emissivity is of less importance.
  • a layer system Y 2 O 3 / Al 70 Mn 9 21 Pd / Y 2 O 3 with the copper layer thicknesses of 60/14/55 nm has a solar absorptance of 0.92, the hemispherical emissivity at 100 C C is 0.045.
  • Figure 3 shows the spectral reflectance of this layer system. l ( ⁇
  • cermets made of a quasi-crystalline material and various dielectric materials are very well suited for use as a selective absorber.
  • the table shows some examples of layers with a fill factor of 30% and an additional dielectric antireflection layer with a low refractive index (AlF ⁇ O »; GL Harding, Solar Energy Materials 12 (1985), 169-186) .
  • a solar degree of absorption of 0.89 with a hemispherical emissivity of 0.037 is achieved with a cermet with Hf0 2 as a dielectric.
  • a solar absorption level of 0.92 with a hemispherical emission level of 0.042 is achieved with a cermet with Y 2 0 3 as the dielectric.
  • a degree of solar absorption of 0.91 with a hemispherical degree of emission of 0.043 is achieved with a cermet with A1 2 0 3 as dielectric.
  • the spectral reflectance is shown in Figure 6.

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Abstract

L'invention concerne un convertisseur de rayonnement qui permet de transformer un rayonnement électromagnétique en chaleur (absorbeur) ou de la chaleur en rayonnement électromagnétique (émetteur). Ledit convertisseur de rayonnement contient au moins un matériau quasicristallin. L'invention concerne en outre l'utilisation des convertisseurs de rayonnement comme absorbeurs ou comme émetteurs.
PCT/EP1995/002753 1994-07-15 1995-07-13 Convertisseur de rayonnement pour transformer un rayonnement electromagnetique en chaleur et de la chaleur en rayonnement electromagnetique WO1996002798A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU30784/95A AU3078495A (en) 1994-07-15 1995-07-13 Radiation converter for converting electromagnetic radiation into heat and vice versa

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4425140A DE4425140C1 (de) 1994-07-15 1994-07-15 Strahlungswandler zur Umsetzung von elektromagnetischer Strahlung in Wärme und von Wärme in elektromagnetische Strahlung
DEP4425140.8 1994-07-15

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WO1996002798A1 true WO1996002798A1 (fr) 1996-02-01

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DE (1) DE4425140C1 (fr)
WO (1) WO1996002798A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011057972A3 (fr) * 2009-11-11 2012-02-09 Almeco-Tinox Gmbh Système multicouche optiquement actif pour absorption solaire

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FR2744839B1 (fr) * 1995-04-04 1999-04-30 Centre Nat Rech Scient Dispositifs pour l'absorption du rayonnement infrarouge comprenant un element en alliage quasi-cristallin
AU5810796A (en) * 1995-05-22 1996-12-11 Thomas Eisenhammer Process for producing selective absorbers
US6177628B1 (en) * 1998-12-21 2001-01-23 Jx Crystals, Inc. Antireflection coated refractory metal matched emitters for use in thermophotovoltaic generators
US6271461B1 (en) * 2000-04-03 2001-08-07 Jx Crystals Inc. Antireflection coated refractory metal matched emitters for use in thermophotovoltaic generators
DE10043295C1 (de) * 2000-09-02 2002-04-25 Rheinzink Gmbh Heliothermischer Flachkollektor-Modul
DE102004019061B4 (de) * 2004-04-20 2008-11-27 Peter Lazarov Selektiver Absorber zur Umwandlung von Sonnenlicht in Wärme, ein Verfahren und eine Vorrichtung zu dessen Herstellung
US20050275936A1 (en) * 2004-06-14 2005-12-15 Anurag Gupta Bandpass reflector with heat removal
SE530464C2 (sv) * 2005-08-02 2008-06-17 Sunstrip Ab Nickel-aluminiumoxid-belagd solabsorbator

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EP0104708A2 (fr) * 1982-09-24 1984-04-04 Energy Conversion Devices, Inc. Dispositif photothermique
WO1992013111A1 (fr) * 1991-01-18 1992-08-06 Centre National De La Recherche Scientifique Alliages d'aluminium, les substrats revetus de ces alliages et leurs applications
JPH04338733A (ja) * 1991-05-15 1992-11-26 Ricoh Co Ltd 準結晶の超微粒子を含有する非線形光学材料
FR2693185A1 (fr) * 1992-07-03 1994-01-07 France Grignotage Revêtement composite à base de quasi-cristaux et son procédé de fabrication.
EP0587186A1 (fr) * 1992-09-11 1994-03-16 Ykk Corporation Alliage à base d'aluminium à haute résistance et résistance à la chaleur
US5312521A (en) * 1992-06-30 1994-05-17 Fraas Arthur P Compact DC electric power generator using low bandgap thermophotovoltaic cell strings with a hydrocarbon gas burner fitted with a regenerator

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US4098956A (en) * 1976-08-11 1978-07-04 The United States Of America As Represented By The Secretary Of The Interior Spectrally selective solar absorbers
US4772370A (en) * 1987-06-23 1988-09-20 The United States Of America As Represented By The Secretary Of Commerce Process for producing icosahedral materials
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WO1992013111A1 (fr) * 1991-01-18 1992-08-06 Centre National De La Recherche Scientifique Alliages d'aluminium, les substrats revetus de ces alliages et leurs applications
JPH04338733A (ja) * 1991-05-15 1992-11-26 Ricoh Co Ltd 準結晶の超微粒子を含有する非線形光学材料
US5312521A (en) * 1992-06-30 1994-05-17 Fraas Arthur P Compact DC electric power generator using low bandgap thermophotovoltaic cell strings with a hydrocarbon gas burner fitted with a regenerator
FR2693185A1 (fr) * 1992-07-03 1994-01-07 France Grignotage Revêtement composite à base de quasi-cristaux et son procédé de fabrication.
EP0587186A1 (fr) * 1992-09-11 1994-03-16 Ykk Corporation Alliage à base d'aluminium à haute résistance et résistance à la chaleur

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2011057972A3 (fr) * 2009-11-11 2012-02-09 Almeco-Tinox Gmbh Système multicouche optiquement actif pour absorption solaire
EP2759783A1 (fr) * 2009-11-11 2014-07-30 Almeco GmbH Système multicouches à effet optique pour absorption solaire
US9222703B2 (en) 2009-11-11 2015-12-29 Almeco Gmbh Optically active multilayer system for solar absorption

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AU3078495A (en) 1996-02-16

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