EP2688848A2 - Revêtements pour applications solaires - Google Patents

Revêtements pour applications solaires

Info

Publication number
EP2688848A2
EP2688848A2 EP12721615.8A EP12721615A EP2688848A2 EP 2688848 A2 EP2688848 A2 EP 2688848A2 EP 12721615 A EP12721615 A EP 12721615A EP 2688848 A2 EP2688848 A2 EP 2688848A2
Authority
EP
European Patent Office
Prior art keywords
composition
weight
coating
solar
mixtures
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Withdrawn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
EP12721615.8A
Other languages
German (de)
English (en)
Inventor
Jacob Hormadaly
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.)
Ben Gurion University of the Negev Research and Development Authority Ltd
Original Assignee
Ben Gurion University of the Negev Research and Development Authority Ltd
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 Ben Gurion University of the Negev Research and Development Authority Ltd filed Critical Ben Gurion University of the Negev Research and Development Authority Ltd
Publication of EP2688848A2 publication Critical patent/EP2688848A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/16—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions with vehicle or suspending agents, e.g. slip
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/18—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing free metals
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D1/00—Coating compositions, e.g. paints, varnishes or lacquers, based on inorganic substances
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/32—Radiation-absorbing paints
    • 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
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2207/00—Compositions specially applicable for the manufacture of vitreous enamels
    • C03C2207/04—Compositions specially applicable for the manufacture of vitreous enamels for steel
    • 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
    • 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
    • Y02B—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B10/00—Integration of renewable energy sources in buildings
    • Y02B10/20—Solar thermal
    • 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

  • An ideal solar absorber is a coating with very high absorptance in the solar portion of the spectrum (UV, VIS and near IR) , low emissivity at the working temperature, high chemical durability, good mechanical stability and low cost.
  • Most of the materials in use today have some drawbacks such as thermal degradation at high temperature, instability on exposure to UV radiation, oxidation, and some materials do not protect the steel pipes used in the solar collector from corrosion.
  • solar absorber For solar tower applications and other applications which are based on absorption of the solar energy and its conversion to heat, there is a need for high temperature black material as solar absorber which is compatible with steel such as carbon steel, stainless steel and InconelTM.
  • the solar absorber should also have high absorption in the solar portion of the spectrum (UV, VIS and near IR) , exhibit stability at high temperatures (e.g. 400-700°C), withstand thermal cycling between room temperature to temperatures in the range of 400-700°C and be easily applied onto metal substrates.
  • the inventor has now successfully designed a novel composition that can be used as a coating of a solar absorber, and have successfully shown the application of this coating in solar applications.
  • a coating composition comprising:
  • At least one highly absorbing material selected from the group consisting of ruthenium, iridium and osmium compounds, and mixtures thereof;
  • a ceramic filler comprising metal oxides, metal powders and mixtures thereof;
  • This composition can be formulated as a paste or paint, to be applied on a metal substrate, for example in a solar tower.
  • Suitable metal substrate are made from a metal, such as steel, stainless steel, inconel type alloys and other alloys which can withstand high temperatures in the range of 600-800°C.
  • the coating composition described herein contains a highly absorbing material selected from either a ruthenium compound, an iridium compound or an osmium compound, and mixtures thereof.
  • high absorbing material refers to a component of a ceramic coating which makes the coating to have high absorption (as inferred from reflectance) in 400- 2500nm spectral range (UV, VIS and near IR) of 90-98%. Without being bound to a specific theory, these compounds or mixtures thereof act as the functional (absorbing) phase in the coating composition.
  • the at least one highly absorbing material is selected from the group consisting of ruthenium, iridium and osmium compounds, and mixtures thereof.
  • Suitable Ru, Ir and Os highly absorbing materials include, but are not limited to, the following classes:
  • the highly absorbing material contains at least one Ru compound.
  • Ru compounds include, but are not limited to, Ru0 2 , BaRu03, pyrochlore-like Ru compounds, CaRu0 3 , SrRu03, S ⁇ RuCj and any mixtures thereof.
  • the highly-absorbing material is selected from Ru0 2 , BaRu0 3 , and pyrochlore-like Ru compounds.
  • pyrochlore-like refers to compounds have the same crystal structure as pyrochlore.
  • the pyrochlore-like Ru compound can be Nd 1 . 75 Cuo. 2 5Ru206+5, as exemplified below.
  • the term 6+ ⁇ indicates that in some cases the structure has 6 oxygen units, and in some it has 7 oxygen units.
  • the amount of the highly absorbing material in the aforementioned compositions ranges from 1 to 99.5 % weight of the paste weight.
  • the highly absorbing material concentration ranges from 5 to 50 % weight of the paste weight. More preferably the highly absorbing material concentration ranges from 7 to 30 % weight, on a paste basis.
  • additional black materials having the same crystal structure as Ru0 2 , are also known to a person skilled in the art to have similar properties as Ru0 2 and to therefore can be just as suitable for the purpose of the invention.
  • Some exemplary compounds are hence Ir0 2 and Os0 2 and other compounds of Ir and Os .
  • the coating composition described herein further contains an inorganic glass binder or a precursor thereof.
  • This glass binder phase is preferably a multi-component inorganic glass.
  • the glass component of the coating composition of the invention may be any glass which is compatible with the substrate and has the durability for use in such applications requiring many thermal cycles from room temperature to temperatures in the range of 300-800°C or higher.
  • suitable glasses include, but are not limited to, borosilicates of Na, K, Li, Ca, Sr, Mg, Ba, with or without transition metals oxides; Silicates of Na, K, Li, Ca, Sr, Mg, Ba, with or without transition metals oxides, and boroaluminosilicates of Na, K, Li, Ca, Sr, Mg, Ba, with or without transition metals oxides.
  • the inorganic glass binder or the precursor thereof is selected from borosilicates of Na, K, Li, Ca, Sr, Mg, Ba, with or without transition metals oxides.
  • suitable glasses useful for the invention are identified in the table below (in terms of the glass ingredients and their respective molar concentrations) :
  • alkali oxides within the glass composition may be substituted by the corresponding fluorides, for example, NaF may be a substitute for Na 2 O, LiF may be a substitute for Li 2 0 and KF may be a substitute for K 2 O.
  • the term "metal oxides", as used herein also includes the corresponding metal fluorides .
  • the binder phase of the composition can also be also provided by a precursor of silicon dioxide, which can yield silicon dioxide upon heat treatment.
  • a suitable Si0 2 precursor can be any silicone resin which can be formulated to a paint consistency when combined with the compounds of Ru, Ir, Os, their mixtures and solvents. Examples of silicon resins are polydimethylsiloxanes, polymethydro- dimethylsiloxane copolymer, vinyl terminated silicone polymers and vinyl backbone silicone polymers.
  • the amount of the inorganic glass binder in the aforementioned compositions ranges from 5 to 80 % weight of the paste weight.
  • the glass binder concentration ranges from 10 to 60 % weight of the paste weight. More preferably the glass binder concentration ranges from 15 to 55 % weight of the paste weight.
  • composition of the present invention also includes a ceramic filler, comprising metal oxides, metal powders and mixtures thereof.
  • ceramic coating usually refers to an inorganic, essentially non-metallic protective coating, on metal suitable for use at or above red heat.
  • ceramics both with regard to a ceramic filler, and the cured coating of this invention, includes all engineering materials or products that are chemically inorganic, except metals and metal alloys, and also includes composites, such as ceramic-metal combinations and other combinations of ceramic fillers involving organic materials .
  • the ceramic fillers are, for example, selected from among oxides of groups IVB and VB of the periodic table and transition metal oxides, especially oxides of ZrO 2 , Nb 2 O 5 and CO 3 O 4 .
  • the one or more oxides of groups IVB and VB of the periodic table present in the composition function as nucleating agents, expansion modifiers which, when dissolved in the glass, enhance its durability.
  • the transition metal oxide e.g., Co 3 0 4
  • the weight of these ceramic fillers is preferably not higher than 30% of the total weight of solids dispersed in the organic medium.
  • the ceramic filler concentration ranges from 0.1wt% to 30wt% of the total weight of solids dispersed in the organic medium.
  • the ceramic filler may also include metals or metal powders.
  • Suitable metals or metal powders to be used as part of the present invention are those metals which have a low emissivity, and also must not oxidize at high temperatures, thereby limiting the choice of appropriate metals to the precious metals only.
  • suitable metal powders include, but are not limited to, Ag powder, Pd powder and their mixtures.
  • Other metals which can be used are Au and Pt but they are more expensive.
  • the ceramic filler is preferably a combination of silver and/or and any of the oxides provided hereinabove.
  • compositions of the invention further comprise a liquid organic vehicle.
  • a liquid organic vehicle any inert liquids can be used.
  • Organic liquid vehicles can be used with or without thickening and/or stabilizing agents and/or other common additives.
  • Suitable organic liquids are aliphatic alcohols or esters thereof, terpens such as pine oil, terpineol and the like, solutions of resins such as the polymethylacrylates of lower alcohols and solutions of ethyl cellulose in solvents such as pine oil and the monobutyl ether of ethylene glycol monoacetate.
  • Preferred liquid organic vehicles are ethyl cellulose solutions in terpineol and butyl ethers of ethylene glycol.
  • the liquid organic vehicle is often a combination of several liquid vehicles.
  • One such combination which is advantageous in its clean burning pattern, is the combination of ethyl cellulose, terpineol and dibutylcarbitol .
  • suitable carriers and/or combinations of carriers may be used, as known to any person skilled in the art.
  • the amount of the liquid organic vehicle ranges from 10-50wt%. Preferably, it ranges from 15 % weight to 40% weight of the total weight of the composition.
  • Some preferred coating compositions of the invention comprise (in Wt% after firing): from 1 to 99.5 Ru0 2 ;
  • a composition comprising from 1 to 99.5 % weight Ru0 2 , from 5 to 80 % weight glass particles, from 0.1 % weight to 30 % weight of the ceramic filler and from 10% weight to 50% weight of the liquid organic vehicle.
  • the chosen ceramic filler in many of the examples contains from 0.1 to 12.0 Co 3 0 4 ;
  • the ceramic filler optionally further contains up to 20% silver powder.
  • compositions of the invention are prepared by combining together at least one of the Ru, Ir, Os compounds, the glass binder component, one or more ceramic fillers comprising oxides of group IVB & VB of the periodic table, or transition metal oxides and/or metal powder (s), and an organic vehicle.
  • the amount and type of the organic vehicle can be adjusted to determine the consistency of the composition, thereby obtaining the specific properties of a coating composition in the form of paste or paint.
  • the working examples below illustrate the preparation of several useful paste or paint compositions.
  • a highly absorbing paste comprising at least one of the Ru, Ir, Os compounds, finely divided glass particles as described hereinabove, dispersed in an organic medium or vehicle, together with additional solids (metal oxides and metal (s) powders) selected according to the intended use of the formulation.
  • the solids dispersed in the organic medium contain from about 0.5 to 80% glass particles, from about 1 to 99.5% particles of the highly absorbing materials, such as the compounds of Ru, Ir and Os, and from about 0.1% to 30.0% of a ceramic filler.
  • composition of the invention can be formulated into a paint, for example, by the addition of suitable solvents.
  • a highly absorbing paint there is provided a highly absorbing paint.
  • paste is considered as a composition with a lower viscosity than paste. By thinning down as paste (having more solvents in the composition) , any composition can be made have paint-like properties and consistency .
  • Both the pastes and paints of the present invention can be used for coating metallic substrates for absorption of solar energy, especially solar applications such as generation of electricity in solar towers, troughs, Stirling engines and as heat absorber in solar collectors for domestic uses.
  • a method of coating a metal substrate comprising applying the coating composition described herein on a metal substrate, and curing it by heating it.
  • metal substrate refers to any substrate that can be used in such applications which requires many thermal cycles from room temperature to temperatures in the range of 300-800°C or higher.
  • thermal cycle refers to heating to 300-800°C and cooling to room temperature.
  • the coating In the presently sought thermal applications, such as solar towers, Stirling engines and troughs, the coating must withstand at least 5 years of service, i.e. at least 1800 cycles .
  • the temperature is lower (around 100°C or less), and therefore the cycles required should be at least 3600 (about 10 years of service).
  • the metal substrate is selected from carbon steel, stainless steel, inconel type alloys and other alloys which can be used in the range of 300-800°C.
  • the metal substrate is steel, such as carbon steel or stainless steel.
  • the metal substrate is InconelTM.
  • InconelTM (a registered trademark of Special Metals Corporation) refers to a family of high-performance alloys (or superalloys ⁇ where nickel and chromium are the two primary metals. There are many variations of Inconcel, all with high strength and high temperature resistance, corrosion resistance, and oxidation resistance.
  • InconelTM 625" refers to a super alloy material comprising at least 58% nickel, 20-23% chromium, 0.1% carbon, 0.5% manganese, 0.5% silicon, no more than 5.0% iron, no more than 0.015% sulfur, no copper, no more than 0.40% aluminum, no more than 0.40% titanium, no more than 0.015% lead, no more than 1% cobalt, 3.15-4.15% niobium, no boron , and 8.0-10.0% molybdenum.
  • InconelTM 718 refers to a super alloy material comprising 50-55% nickel and cobalt, 17-21% chromium, 4.75- 5.5% niobium and tantalum, 2.8-3.3% molybdenum, 0.65 - 1.15 % titanium, 0.2-0.8% aluminum, balance* iron (*Reference to the 'balance' of a composition does not guarantee this is exclusively of the element mentioned but that it predominates and others are present only in minimal quantities).
  • super alloy refers to an alloy both inert and non- inert that provides resistance to abrasion and corrosion and that has a low iron content.
  • a low iron content means an alloy having an iron content of less than 25%.
  • the super alloy contains 10-30% chromium and less than 30% molybdenum.
  • Nickel comprises at least 40% of the super alloy and is the highest element percentage. Examples are materials having the names InconelTM and Hastelloy®.
  • the present compositions can be used as an efficient coating for the metallic parts which contain and shield the fluid.
  • the fluid can be water or steam, molten salt or other fluids which can survive high temperatures.
  • Parabolic trough power stations feature a large number of collectors, which have long concentrators with a small lateral dimension, and thus possess not a focal point, but rather a focal line; this fundamentally differentiates this design from that of the dish-Sterling and solar tower power stations.
  • thermo oil or superheated stream comes into consideration as the transport medium; this circulates in the absorber pipework.
  • a trough collector is preferably designed as a parabolic trough collector
  • trough collectors with spherical or only approximately parabolic designs of concentrators are often used, since an exact parabolic concentrator with the dimensions cited above can only be manufactured with great effort that is not really justified economically.
  • the cured compositions and some or the absorbing materials may be useful as absorbing materials in the multilayer of materials used to fabricate the coating of the central pipe of any trough as described hereinabove.
  • Stirling Engines are constructed of a hot and cold modules. The present coatings can be applied on the hot component of the engine, to absorb the sun energy and convert it to heat.
  • compositions of this invention can be applied onto the substrates by brushing, dipping, automatic printing or a hand printing employing conventional techniques.
  • the printed pattern is then dried at below 200°C, preferably at about 150°C, for 5-15 minutes before heating it.
  • Heating of the composition can be done either by firing in a box furnace, or by natural curing, for example by using solar power .
  • the temperature used for heating and curing of the composition depends on the heating method, but should generally be at least 600°C, as shown hereinbelow.
  • Firing the treated substrate to effect sintering of both the inorganic binder and the finely divided particles of compounds of Ru, Ir and Os is preferably done in a box furnace with a temperature profile that will allow burnout of the organic matter at about 300 o C-450 o C, lasting about 5-15 minutes, followed by a controlled ramp to temperature in the range of 650-1000 °C lasting 10-60 minutes and cool-down cycle.
  • Natural curing of the treated substrate can take place for example when the metallic parts of a solar tower (such as pipes and plates) , which contain fluid, are coated by the composition of the invention, and are let to dry by the sun. Then the solar tower is allowed to operate ⁇ to be heated by the sun) . During the warm up process the solar tower itself can reach temperatures in the range of 600-700°C. In this temperature range the composition cures to obtain the cured ceramic coating. Some examples conducted by the inventors have shown that during heat treatment in the temperatures range of 600°C to 700°C, a ceramic coating was obtained even after 30 minutes at 600-700 °C range.
  • the heating is conducted at a temperature which is lower than 750°C.
  • Another aspect of the invention therefore relates to a coated substrate, wherein the coating present on the substrate comprises the fired (or cured) form of the composition set forth above, namely, a ceramic coating comprising crystallized glass, one or more ruthenium, iridium and osmium compounds, one or more oxides of groups IVB and VB of the periodic table and transition metal oxide and metal (s) powder.
  • the substrate is preferably steel, such as carbon steel, stainless steel and InconelTM.
  • the invention also provides a coated substrate in a solar collector comprising a steel substrate coated with the ceramic coating set forth above.
  • the parts of the solar tower to be coated include pipes and other parts of the solar tower which are exposed to concentrated solar power.
  • the following examples are given for the purpose of illustration, and are not intended to limit the scope of the invention .
  • a Hegman gauge was used to determine the state of dispersion of the particles in the paste. This instrument consists of a channel in a block of steel that was 25 Dm deep (1 mil ⁇ on one end and ramps up to 0" depth at the other end. A blade is used to draw down paste along the length of the channel. Scratches will appear in the channel where the agglomerates' diameter is greater than the channel depth. A satisfactory dispersion will give a fourth scratch point of 10-18 ⁇ m typically. A fourth scratch measurement of >10 ⁇ indicates a poorly dispersed suspension.
  • the reflection was measured on USB 4000 miniature fiber optic spectrometer and the emissivity was measured in emissiometer ⁇ manufactured by Devices and Services Company, USA) .
  • Refection spectrum and emissivity of the fired samples were measured in the range 400-1100 nm.
  • Reflectometer and emissiometer (Surface Optics Corporation) . These were used also to measure reflectance in the range of 400-2500nm and emissivity at room temperature
  • Glass compositions coded Glass A, Glass B and Glass C were prepared in a platinum crucible at 1300°C.
  • the compositions of the three glasses are specified below (in terms of mole% of each ingredient present in the glass) :
  • One method for preparing the glasses consists of mixing together in the desired proportions the oxide or fluoride precursors, melting the mixture and pouring the molten composition into water to form the frit.
  • An oxide or fluoride precursor may, of course, be any compound that will yield the desired oxide or fluoride under the usual conditions of frit production.
  • boric oxide will be obtained from boric acid; silicon dioxide will be produced from flint; barium oxide will be produced from barium carbonate; etc.
  • the glass was preferably milled in a ball mill with water to reduce the particle size.
  • melting was conducted at a peak temperature and for a time such that the melt becomes entirely liquid and homogeneous.
  • the components were premixed by shaking in a polyethylene jar with plastic balls, and were then melted in a platinum or a high purity alumina crucible at the desired temperature.
  • the melt was maintained at a peak temperature of 1100°C-1400°C for a period of 1.5 - 3.0 hours.
  • the melt was then poured into cold water.
  • the maximum temperature of the water during quenching was kept as low as possible by increasing the volume of water to melt ratio.
  • the crude frit after separation from water was freed from residual water by drying in air, or by displacing the water by rinsing with methanol.
  • the crude frit was then ball milled for 3-24 hours in alumina containers using alumina balls.
  • the glass obtained was suitable for use in the preparation of the coating compositions of the invention, as described in the following examples.
  • Powders of the title glasses were formulated to pastes which were used to prepare the solar absorbing coatings. Typical compositions of pastes are provided in Table 3 below.
  • the preparation of the paste formulations according to the present invention was carried as follows.
  • the particulate inorganic solids were mixed with the organic liquids and dispersed with suitable equipment, such as a Muller, to form a suspension, resulting in a composition for which the viscosity was in the range of about 100-150 pascalseconds at a shear rate of 4 sec -1 .
  • the organic liquid used was a mixture of diethylene glycol dibutyl ether, terpineol, and ethyl cellulose.
  • the ingredients of the formulation minus about 5 weight percent of the organic components, were weighed together in a container.
  • the components were then vigorously mixed to form a uniform blend; then the blend was passed through dispersing equipment, such as a Muller, to achieve a good dispersion of particles.
  • the remaining 5% consisting of organic components of the paste was then added, and the resin content was adjusted to bring the viscosity, when fully formulated, to between 140 and 200 Pa . s at a shear rate of 4 sec -1 .
  • the composition was then applied onto a substrate, such as carbon steel, stainless steels and InconelTM substrate, usually by the process of screen printing, brushing or dipping to the desired thickness, typically to 5-100 um.
  • the nine coated substrates of inconelTM 718 were fired at 700°C, 900°C and 1000°C for 30 minutes at peak temperature, three coated substrates were used for each temperature. Ramp was 20°C/minute to peak temperature and cool down was 20°C /minute .
  • the coated substrates were tested for their reflectivity and emissivity, showing that the samples fired at 1000°C had the highest reflectivity (lowest absorption) and emissivity of 82% for the paste fired on InconelTM 718. Fired samples at 700°C had the lowest reflectivity, lower than Pyromark® 2500 and emissivity of 83% for the paste fired on InconelTM 718.
  • Samples 5 (reference JH-041-114) composition was printed on InconelTM 718 and fired at 750°C; 800 Q C & 850°C peak
  • Ramp was 20°C/minute to reach peak temperature, kept at peak temperature for 30 minutes and cooled down to room temperature at 20°C/minute
  • composition of Sample 5 when fired in the 750-850°C range has very high solar absorptivity.
  • Sample 5 composition was printed on InconelTM 718 substrates, fired at peak temperature of 900°C for 30 minutes (ramp 20°C/min, held 30 minutes at 900°C then cool down to room temperature 20°C/min) .
  • One fired part (Sample 9) was subjected to temperature cyclings (from room temperature to 700°C, in a box furnace, air atmosphere) and storage at 700°C. Total number of cyclings was 16 and the total time at 700°C was
  • Example 10 Another fired part (Sample 10) was kept at room temperature as a reference. Solar absorptivities of the above two samples (Samples 9 and 10) were measured by 410 - Solar , reflectometer and emissiometer . Cycled sample (Sample 9) absorptivity was 94.6% and the reference (Sample 10)
  • Samples 11 & 12 compositions were printed on InconelTM 718 substrates and fired in air at 700°C, 750°C, 800°C and 900°C. Firings schedules were: ramp of 20°C/minute to peak temperature, hold 30 minutes at peak temperature and cool down room temperature 20°C/minute.
  • Absorptivities of fired compositions of Samples 11 and 12 at 4 peak firing temperatures 700°C, 750°C, 800°C and 900°C were measured by 410 - Solar reflectometer and emissiometer,
  • compositions (Samples 21& 22, ) , similar to Sample 5 were prepared, printed on InconelTM 718 and fired at peak
  • Table 7 shows that useful absorptivities > 93.0% that can be obtained by using less ruthenium oxide.
  • Sample 22 was also tested in field trials on a trough, for 2 months at a maximal temperature of 350 C, showing no change in both solar absorptivity and emissivity.
  • compositions- Samples 23 and 24 were formulated with pyrochlore taught in US patent No. 6,989,111, having the general formula Ndi.75 CU o . 25 Ru 2 0 6+ 8, Compositions and solar absorptivity are given in table 8.
  • compositions of Samples 23 and 24 were printed on InconelTM 718 and fired at peak temperature of 800°C using the same firing schedule of: ramp 20°C/minute to 800°C, hold 30 minutes at
  • compositions containing ruthenium compounds and silver powder are exemplified by Samples 25-27 which are given in table 8. These compositions were formulated with larger amounts of organic materials to form paint like consistency. Samples 25- 27 compositions were applied to Inconel ® 718 and stainless steel 347 by a brush and fired at peak temperature of 700°C; firing schedule was ramp of 20°C/minute to 700°C, hold 30 minutes at 700°C and cool down 20°C/minute to room temperature. Visual inspection shows that black coating were obtained with no cracks.
  • compositions taught in this application mature to a ceramic coating by thermal treatment in the range of 600-700°C. Because of the low temperature required to form mature ceramics, these formulations can be applied directly on the metallic part of solar tower and mature during the operation of the solar tower.
  • Preparation Example 10 Compositions containing ruthenium compounds and larger concentration of silver powder are also exemplified by Samples 28-30 which are given in table 10.
  • Samples 28- 30 compositions were applied to stainless steel 347 by a brush and fired at peak temperature of 700°G; firing schedule was ramp of 20°C/minute to 700°C, hold 30 minutes at 700°C and cool down 20°C/minute to room temperature. Visual inspection shows that black - gray coatings were obtained for Samples 28, 29 and black coating for Sample 30. All Samples 28-30 formed good coatings with no cracks and very good adhesion to the stainless steel substrate

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Abstract

La présente invention concerne des compositions de revêtement comprenant : I) au moins un matériau extrêmement absorbant sélectionné dans le groupe comprenant des composés de ruthénium, d'iridium et d'osmium et des mélanges de ceux-ci; II) un liant verre inorganique ou un précurseur de celui-ci; III) une charge céramique comprenant des oxydes métalliques, des poudres métalliques et des mélanges de ceux-ci et IV) et un véhicule organique liquide. L'invention concerne également des procédés de préparation de ces revêtements et leurs utilisations dans des applications solaires.
EP12721615.8A 2011-03-24 2012-03-25 Revêtements pour applications solaires Withdrawn EP2688848A2 (fr)

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JP5176159B1 (ja) * 2011-07-19 2013-04-03 日立化成株式会社 ｎ型拡散層形成組成物、ｎ型拡散層の製造方法、及び太陽電池素子の製造方法
EP2947179A1 (fr) * 2014-05-21 2015-11-25 Areva Renouvelables Procédé de fabrication d'un substrat revêtu
WO2016027269A1 (fr) 2014-08-18 2016-02-25 B.G. Negev Technologies And Applications Ltd., At Ben-Gurion University Compositions de revêtement pour applications solaires
WO2016027268A1 (fr) * 2014-08-18 2016-02-25 B.G. Negev Technologies And Applications Ltd., At Ben-Gurion University Revêtements pour applications solaires
ES2574553B1 (es) * 2014-12-18 2017-04-05 Arraela, S.L. Procedimiento para la realización de un recubrimiento para bases sometidas a la incidencia de energía en el espectro de 10-7 < lambda < 10-4 m. y recubrimiento obtenido por dicho procedimiento
CN107532015A (zh) * 2016-04-21 2018-01-02 亮源产业（以色列）有限公司 具有防腐保护的高温吸光涂层及其使用方法
RU2631713C1 (ru) * 2016-09-12 2017-09-26 Юлия Алексеевна Щепочкина Керамический пигмент зеленый
CN106441590A (zh) * 2016-09-26 2017-02-22 渤海大学 金属‑陶瓷太阳能选择性吸收涂层多光谱发射率测量方法
EP3527911A1 (fr) 2018-02-16 2019-08-21 Cockerill Maintenance & Ingenierie S.A. Revêtement absorbeur appliqué par pulvérisation thermique de haute performance

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