DK153248B - Coating for selective absorption of solar energy and method for manufacturing such coating - Google Patents
Coating for selective absorption of solar energy and method for manufacturing such coating Download PDFInfo
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- DK153248B DK153248B DK033479AA DK33479A DK153248B DK 153248 B DK153248 B DK 153248B DK 033479A A DK033479A A DK 033479AA DK 33479 A DK33479 A DK 33479A DK 153248 B DK153248 B DK 153248B
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- solar energy
- selective absorption
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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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- Thermal Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Combustion & Propulsion (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Paints Or Removers (AREA)
- Laminated Bodies (AREA)
Description
iin
DK 153248BDK 153248B
Opfindelsen angår en belægning af den i krav l's indledning angivne art.The invention relates to a coating of the kind specified in the preamble of claim 1.
Selektive belægninger må for at være gode solkollektorer, have så lille en lysreflektion som muligt og lille transparens for lys, dvs.In order to be good solar collectors, selective coatings must have as little light reflection as possible and little transparency for light, ie.
5 være så sort som muligt. Imidlertid er det således rent fysisk, at jo større og mørkere et legeme er, desto større er energitabet ved varmestråling.5 be as black as possible. However, it is thus purely physical that the larger and darker a body, the greater the energy loss from heat radiation.
Sort maling har længe været anvendt som en ikke-selektiv belægning, hvis absorption og emission forbliver konstant over det fulde spek-10 trum af solstråling og termisk stråling. Maling kan arbejde op til ca. 100 grader celcius, men over denne temperatur aftager kollekto-rens effektivitet stærkt på grund af de termiske tab ved genudstråling fra kollektoren.Black paint has long been used as a non-selective coating, the absorption and emission of which remains constant over the full spectrum of solar radiation and thermal radiation. Paint can work up to approx. 100 degrees Celsius, but above this temperature, the collector's efficiency decreases greatly due to the thermal losses caused by re-radiation from the collector.
Malinger har endvidere den alvorlige fejl at være baseret på orga-15 niske materialer, som nedbrydes under normale sol- og driftsforhold.Furthermore, paints have the serious flaw to be based on organic materials which decompose under normal solar and operating conditions.
Disse problemer har man forsøgt at undgå ved at anvende forskellige elektrolytiske belægninger.These problems have been tried to avoid by using various electrolytic coatings.
Tidligere beskrevne metoder til fremstilling af selektive belægninger har anvendt metoder og processer med udgangspunkt i U.S. pat.Previously described methods for making selective coatings have employed methods and processes based on U.S. Pat. pat.
20 2.917,817 og 3.129,703.20,917,817 and 3,129,703.
DK 153248BDK 153248B
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De indtil nu anvendte metoder beror på belægninger af sort-nikkel, sort-kobber, sort-zink, sort-sølv og sort-krom samt kombinationer af kemiske, elektrolytiske og varmetekniske behandlinger.The methods used so far are based on coatings of black-nickel, black-copper, black-zinc, black-silver and black-chrome, as well as combinations of chemical, electrolytic and heat-technical treatments.
Andre udførelsesformer af selektive belægninger, består i oxydering 5 af stållegeringer i sure oxyderende opløsninger, som iltende syrer, hvorved det øverste metallag omdannes til et oxidlag med selektive egenskaber, direkte knyttet til den benyttede stållegering.Other embodiments of selective coatings, in oxidation 5, consist of steel alloys in acidic oxidizing solutions, such as oxidizing acids, whereby the upper metal layer is converted into an oxide layer with selective properties, directly linked to the steel alloy used.
En ulempe ved denne metode er, at selektiviteten er knyttet alene til den benyttede stålsort. Endvidere kan der let opstå diffusion 10 mellem oxidlag og stålet, da der mangler et skillelag af et andet materiale.A disadvantage of this method is that the selectivity is related only to the steel used. Furthermore, diffusion 10 can easily occur between the oxide layer and the steel as a separating layer of another material is missing.
Dette giver en mindre stabil belægning ved langvarig drift, tfed vacuumpådampning kan der fremstilles interferensbelægninger baseret på halvtransparente tynde metallag belagt med halvleden-15 de interferenslag. Disse to lag er udfældet på et poleret aluminiumsubstrat, med det halvledende lag øverst.This provides a less stable coating for long-term operation, because of vacuum evaporation, interference coatings based on semi-transparent thin metal layers coated with semiconductor interference layers can be produced. These two layers are deposited on a polished aluminum substrate, with the semiconducting layer at the top.
På grund af de gentagne reflektioner gennem lagene opnås selektiviteten.Due to the repeated reflections through the layers, selectivity is achieved.
Disse fremstillingsmetoder er dog langsomme og kostbare ved store 20 flader, da de anvendte materialer skal være af stor renhed. Metoden anvendes derfor fortrinsvis til optiske filtre og i rumfartsteknik.However, these manufacturing methods are slow and expensive at large 20 surfaces, as the materials used must be of high purity. Therefore, the method is preferably used for optical filters and in aerospace engineering.
Disse processer har været vanskelige at reproducere, alt for kostbare, eller forholdet mellem solabsorbtionen ύζ , og emissionen 25 , har været utilfredsstillende.These processes have been difficult to reproduce, overly expensive, or the relationship between solar absorption ύζ and emission 25 has been unsatisfactory.
DK 153248BDK 153248B
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Opfindelsen adskiller sig fra kendte principper og processer, hvor selektiviteten er knyttet til underlaget, som kendt fra dansk patent ansøgning nr. 4184/76 , og tysk offentliggørelsesskrift 2.702.079 , hvor selektiviteten alene frembringes ved interferens-5 virkninger i et eller flere lag, og fremstillingsmetoderne er henholdsvis kemisk oxydation og højvacuumpådampning.The invention differs from known principles and processes in which the selectivity is linked to the substrate, as known from Danish Patent Application No. 4184/76, and German Publication No. 2,702,079, wherein the selectivity is produced only by interference effects in one or more layers. and the methods of preparation are chemical oxidation and high vacuum evaporation respectively.
Opfindelsen bryder med ovennævnte principper og processer ved indførelse af elektrolytiske dispersionsbelægninger i solteknologi.The invention breaks with the above principles and processes of introducing electrolytic dispersion coatings in solar technology.
Det bliver derved muligt i højere grad at styre pore strukturen 10 ved at tilsætte uopløselige stoffer med veldefineret komstørrel-se, som udfældes sammen med den elektrokemiske belægning bestående af metaloxider, metalsulfider og metal.It thus becomes more possible to control the pore structure 10 by adding insoluble substances with well-defined grain size which are precipitated together with the electrochemical coating consisting of metal oxides, metal sulfides and metal.
Derved muliggøres fremstilling af en kontrolleret belægning med såkaldte 'sorte huller1. Ved en kombination af halvlederegenskaber 15 i såvel den elektrokemiske grundbelægning, som i de faste stoffer der indlejres, og selektive strukturegenskaber øges selektiviteten væsentligt.This makes it possible to make a controlled coating with so-called 'black holes1. By a combination of semiconductor properties 15 in both the electrochemical primer and in the solids embedded, and selective structural properties, the selectivity is significantly increased.
Fremstillingsmetoderne er billige og egnet til masseproduktion.The manufacturing methods are inexpensive and suitable for mass production.
Belægningen af den indledningsvis angivne art er ejendommelig ved 20 det i krav l's kendetegnende del angivne.The coating of the type initially specified is peculiar to the characterizing part of claim 1.
Herved opnås en overflade med halvledende dielektriske egenskaber, og optræder med en dendritisk overfladestruktur og mikrohulrum i størrelsesorden o,2- 2^tm. Det er endvidere karakteristisk, at lagtykkelsen er veldefineret, og i størrelsesorden 500-3000 Ångstrøm.This results in a surface having semiconducting dielectric properties and having a dendritic surface structure and micro cavities of the order of 2 - 2 µm. Furthermore, it is characteristic that the layer thickness is well defined, and in the order of 500-3000 Angstroms.
25 Dette kan således opnås på et metallisk eller metalliseret substrat med lille hemisfærisk udstråling,£ Z 0,1 , og ved bølgelængder i området 0,35-12julm.Thus, this can be achieved on a metallic or metallized substrate with small hemispherical radiance, £ Z 0.1, and at wavelengths in the range of 0.35-12 µm.
DK 153248BDK 153248B
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Derved bliver forholdet mellem absorbtionsfaktoren for solenergi θ< og emissionsfaktoren £ , større end 9 og differencen o^— £ bliver større end eller lig 0,7.Thus, the ratio between the absorption factor of solar energy θ <and the emission factor £ becomes greater than 9 and the difference o ^ - £ becomes greater than or equal to 0.7.
Der opnås således, at overfladen absorberer størst mulig solenergi 5 og udstråler mindst mulig varme. Derved opnås den maksimale virkningsgrad af en solfanger ved den højeste arbejdstemperatur.It is obtained so that the surface absorbs as much solar energy as possible 5 and radiates as little heat as possible. This results in the maximum efficiency of a collector at the highest operating temperature.
Den forøgede selektivitet, opnås ved en kombination af struktur-og halvlederegenskaber. Mikrohulrummene kan dannes ved en kombineret teknik bestående af ætsning af overfladen med syre, og belægning 10 med en elektrolytisk dispersionsbelægning. Ved en dispersions belægning forstås en udfældning af metal, plus faste uopløselige stoffer, son udfældes samtidigt f. eks. ved elektrolyse som i dette tilfælde.The increased selectivity is achieved by a combination of structural and semiconductor properties. The micro-cavities can be formed by a combined technique consisting of etching the surface with acid and coating 10 with an electrolytic dispersion coating. By a coating dispersion is meant a precipitation of metal, plus solid insoluble matter, which is simultaneously precipitated, for example, by electrolysis as in this case.
Tidligere har man fremstillet slibeskiver af nikkel med diamantpul-15 ver indfældet, samt selvsmørende lejer af nikkel med grafitpulver ved dispersionsbelægning. Opfindelsen angår ligeledes en fremgangsmåde til fremstilling af en sådan belægning, der er ejendommelig ved det i krav 4's kendetegnende del angivne, belyses nærmere ved de efter følgende eksempler.Previously, nickel abrasive discs with diamond powder have been manufactured, as well as self-lubricating bearings of nickel with graphite powder by dispersion coating. The invention also relates to a process for making such a coating, which is characterized by the characterizing part of claim 4, which is further illustrated by the following examples.
20 Den forbedrede belægning er opnået med tynde belægninger af kolloid natur med en sammensætning vist ved følgende eksempler.The improved coating is obtained with thin coatings of colloidal nature with a composition shown by the following examples.
EKS. 1 : .Nikkel - nikkeloxid- nikkelsulfid - zinksulfid r .. blysulfid.EKS. 1: Nickel - nickel oxide- nickel sulphide - zinc sulphide r .. lead sulphide.
EKS. 2 : Nikkel- nikkeloxid- koboltoxid.EKS. 2: Nickel-nickel oxide-cobalt oxide.
25 EKS. 3 : Nikkel- nikkeloxid- molybdænoxid.EKS. 3: Nickel-nickel oxide-molybdenum oxide.
Derudover indeholder belægningen kom af et eller flere af følgende stoffer: Karbider ,nitrider , silicider , borider , siliciumoxid, aluminiumoxid , chalkonenide glasser , kulstof , titanater .In addition, the coating contains one or more of the following substances: Carbides, nitrides, silicides, borides, silica, alumina, chalconenide glasses, carbon, titanates.
Den procentiske sammensætning varieres som følger.The percent composition is varied as follows.
DK 153248BDK 153248B
5 EKS. 1 : Nikkel : 23-50%5 EX. 1: Nickel: 23-50%
Zink : 7-48"Zinc: 7-48 "
Svovl : 8-15"Sulfur: 8-15 "
Kvælstof : 0-3,5" 5 Ilt : 0-5 "Nitrogen: 0-3.5 "5 Oxygen: 0-5"
Kulstof : 0-4,5"Carbon: 0-4.5 "
Bly : 0-10" EKS. 2 : Nikkel : 0-50%Lead: 0-10 "EX. 2: Nickel: 0-50%
Kobolt : 0-50" 10 Ilt : 0-50" EKS. 3 : Nikkel : 5-25%Cobalt: 0-50 "10 Oxygen: 0-50" EX. 3: Nickel: 5-25%
Molybdæn : 10-60"Molybdenum: 10-60 "
Ilt : 20-40"Oxygen: 20-40 "
Bly : 0-10” 15 EKS. 1 : Udfældes fra bade bestående af nikkel sulfat, nikkelammoniumsulf at, zinksulfat, thiocyanater.og blyforbindelser.Lead: 0-10 ”15 EX. 1: Precipitated from baths consisting of nickel sulfate, nickel ammonium sulfate, zinc sulfate, thiocyanates and lead compounds.
EKS. 2 : Nikkelklorid, zinkklorid , thiocyanater og blyforbindelser, ved ph 5-6,5 og strømtætheder fra 0,1-1 Arap/dnt2 og tempe-20 raturer fra 18- 60 grader celcius.EKS. 2: Nickel chloride, zinc chloride, thiocyanates and lead compounds, at pH 5-6.5 and current densities of 0.1-1 Arap / dnt2 and temperatures of 18-60 degrees Celsius.
EKS. 3 : Udfældes fra bad indeholdende nikkelsulfater, molybda-ter og blyforbindelser ved samme betingelser som eks. 1 og 2 .EKS. 3: Precipitated from baths containing nickel sulphates, molybdates and lead compounds under the same conditions as Examples 1 and 2.
• $ 6• $ 6
DK 153248BDK 153248B
Opfindelsen forklares i det følgende nærmere under henvisning til den skematiske tegning, hvor fig. 1 viser en enkel udførelsesform for en selektiv belægning, fig. 2 viser en forstørrelse af den selektive belægnings struktur.The invention is explained in more detail below with reference to the schematic drawing, in which fig. 1 shows a simple embodiment of a selective coating; FIG. 2 shows an enlargement of the selective coating structure.
5 fig. 3 viser en forstørrelse af fig. 2, til illustration af re-f lektionsforholdene i et såkaldt 'absolut sort hul' .5 FIG. 3 shows an enlargement of FIG. 2, to illustrate the reflection conditions in a so-called 'absolute black hole'.
FIG.l viser en metalplade (1) belagt med et lag elektrolytisk udfældet metal (2) og derover yderligere et lag metal eller metaloxid (3) og yderst den selektive sorte belægning (4) , som 10 bestråles af sollys (5) .FIG. 1 shows a sheet of metal (1) coated with a layer of electrolytically precipitated metal (2) and, further, a layer of metal or metal oxide (3) and extremely the selective black coating (4) which is irradiated by sunlight (5).
FIG. 2 viser en forstørrelse af den selektiv sorte belægnings struktur (4) som danner 'absolut sorte huller' (6), i det følgende skal dette forklares nærmere.FIG. 2 shows an enlargement of the selective black coating structure (4) which forms 'absolutely black holes' (6), hereinafter this will be explained in more detail.
Hullernes størrelsesorden er 0,2- 2yu'm. Derved øges absorbtionen 15 i området op til 2yttm, og samtidig fungerer hullerne son reflekter for det infrarøde område over 2yUm.The size of the holes is 0.2 - 2 µm. Thereby, the absorption 15 in the region is increased up to 2 µm, and at the same time the holes function as reflectors for the infrared region above 2 µm.
FIG.3 viser et 'absolut sort hul' (6) .FIG.3 shows an 'absolute black hole' (6).
Ingen materiel flade udgør et absolut sort legeme, men et hul i en væg eller overflade, kan betragtes som et absolut sort legeme.No material surface constitutes an absolute black body, but a hole in a wall or surface can be considered an absolute black body.
20 Den stråling (7) , scan trænger ind gennem hullet, reflekteres fra de indre vægge, men kun en forsvindende del finder vej ud igen. Emissionsspektret fra et absolut sort legeme fastlægges helt og holdent af hulrummets temperatur.20 The radiation (7) the scan penetrates through the hole is reflected from the inner walls, but only a vanishing part finds its way out again. The emission spectrum of an absolutely black body is determined entirely by the temperature of the cavity.
Dette medfører forøget selektiv absorbtion i området 0,35- 2,5yum 25 ( solens spektrum ) og minimal emission i det infrarøde område for bølgelænder over 2ytt.ni.This results in increased selective absorption in the range of 0.35-2.5 µm (solar spectrum) and minimal emission in the infrared region for wavelengths above 2 ms.
Selektiviteten er karakteriseret ved forholdet , hvor er absorbtionen, og £ er emissionen. Jo større dette forhold er, des større er selektiviteten. Absorbtionen skal dog være i 30 størrelsesorden > 0,9 , da o( indgår i solfangerligningen med større vægt end £ , for at der kan opnås fuld nytte af effekten.The selectivity is characterized by the ratio, where is the absorption, and £ is the emission. The greater this ratio, the greater the selectivity. However, the absorbance must be in the order of> 0.9, since o (is included in the collector equation with greater weight than £) in order for full benefit of the effect to be obtained.
Claims (4)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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DK033479A DK153248C (en) | 1979-01-26 | 1979-01-26 | COATING FOR SELECTIVE ABSORBTION OF SOLAR ENERGY AND A PROCEDURE FOR THE PREPARATION OF SUCH COATING |
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DK33479 | 1979-01-26 | ||
DK033479A DK153248C (en) | 1979-01-26 | 1979-01-26 | COATING FOR SELECTIVE ABSORBTION OF SOLAR ENERGY AND A PROCEDURE FOR THE PREPARATION OF SUCH COATING |
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DK33479A DK33479A (en) | 1980-07-27 |
DK153248B true DK153248B (en) | 1988-06-27 |
DK153248C DK153248C (en) | 1988-11-21 |
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DK033479A DK153248C (en) | 1979-01-26 | 1979-01-26 | COATING FOR SELECTIVE ABSORBTION OF SOLAR ENERGY AND A PROCEDURE FOR THE PREPARATION OF SUCH COATING |
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017054780A1 (en) * | 2015-09-29 | 2017-04-06 | 淄博环能海臣环保技术服务有限公司 | High-temperature-resistant selective-absorption functional film formed by etching |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2702079A1 (en) * | 1976-01-19 | 1977-08-04 | Centre Nat Etd Spatiales | SUN ABSORBERS |
DK152624B (en) * | 1975-09-22 | 1988-03-28 | Yazaki Corp | SELECTIVE ABSORPTION SURFACE FOR A SUN AND MAKING PROCEDURE |
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1979
- 1979-01-26 DK DK033479A patent/DK153248C/en not_active IP Right Cessation
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
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DK152624B (en) * | 1975-09-22 | 1988-03-28 | Yazaki Corp | SELECTIVE ABSORPTION SURFACE FOR A SUN AND MAKING PROCEDURE |
DE2702079A1 (en) * | 1976-01-19 | 1977-08-04 | Centre Nat Etd Spatiales | SUN ABSORBERS |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2017054780A1 (en) * | 2015-09-29 | 2017-04-06 | 淄博环能海臣环保技术服务有限公司 | High-temperature-resistant selective-absorption functional film formed by etching |
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DK153248C (en) | 1988-11-21 |
DK33479A (en) | 1980-07-27 |
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