US20100155043A1 - Element for emission of thermal radiation - Google Patents
Element for emission of thermal radiation Download PDFInfo
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- US20100155043A1 US20100155043A1 US12/644,985 US64498509A US2010155043A1 US 20100155043 A1 US20100155043 A1 US 20100155043A1 US 64498509 A US64498509 A US 64498509A US 2010155043 A1 US2010155043 A1 US 2010155043A1
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- United States
- Prior art keywords
- radiation
- wavelength range
- cooling
- thermal
- emission
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
- C09K5/08—Materials not undergoing a change of physical state when used
- C09K5/14—Solid materials, e.g. powdery or granular
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B23/00—Machines, plants or systems, with a single mode of operation not covered by groups F25B1/00 - F25B21/00, e.g. using selective radiation effect
- F25B23/003—Machines, plants or systems, with a single mode of operation not covered by groups F25B1/00 - F25B21/00, e.g. using selective radiation effect using selective radiation effect
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D31/00—Other cooling or freezing apparatus
- F25D31/006—Other cooling or freezing apparatus specially adapted for cooling receptacles, e.g. tanks
- F25D31/007—Bottles or cans
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F13/00—Arrangements for modifying heat-transfer, e.g. increasing, decreasing
- F28F13/18—Arrangements for modifying heat-transfer, e.g. increasing, decreasing by applying coatings, e.g. radiation-absorbing, radiation-reflecting; by surface treatment, e.g. polishing
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- G—PHYSICS
- G02—OPTICS
- G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
- G02B5/00—Optical elements other than lenses
- G02B5/20—Filters
- G02B5/26—Reflecting filters
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- E—FIXED CONSTRUCTIONS
- E06—DOORS, WINDOWS, SHUTTERS, OR ROLLER BLINDS IN GENERAL; LADDERS
- E06B—FIXED OR MOVABLE CLOSURES FOR OPENINGS IN BUILDINGS, VEHICLES, FENCES OR LIKE ENCLOSURES IN GENERAL, e.g. DOORS, WINDOWS, BLINDS, GATES
- E06B9/00—Screening or protective devices for wall or similar openings, with or without operating or securing mechanisms; Closures of similar construction
- E06B9/24—Screens or other constructions affording protection against light, especially against sunshine; Similar screens for privacy or appearance; Slat blinds
- E06B2009/2411—Coloured fluid flow for light transmission control
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25D—REFRIGERATORS; COLD ROOMS; ICE-BOXES; COOLING OR FREEZING APPARATUS NOT OTHERWISE PROVIDED FOR
- F25D2331/00—Details or arrangements of other cooling or freezing apparatus not provided for in other groups of this subclass
- F25D2331/80—Type of cooled receptacles
- F25D2331/805—Cans
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F28—HEAT EXCHANGE IN GENERAL
- F28F—DETAILS OF HEAT-EXCHANGE AND HEAT-TRANSFER APPARATUS, OF GENERAL APPLICATION
- F28F2245/00—Coatings; Surface treatments
- F28F2245/06—Coatings; Surface treatments having particular radiating, reflecting or absorbing features, e.g. for improving heat transfer by radiation
Definitions
- the at least one layer may be a part of a multi-layered structure having layer thicknesses that are selected so that the multi-layered structure is arranged for generation of ionic surface plasmon resonances having a wavelength or wavelength range within the atmospheric window wavelength range.
- the particles may be distributed throughout the element of the cooling device, which may also comprise a material that is substantially transmissive for radiation having a wavelength within the atmospheric window range.
- the element of the cooling device may comprise a surface portion, such as a coating, in which the particles are concentrated and which is arranged so that the thermal radiation can be emitted.
- the element of the cooling device may also comprise a membrane which locates the particles.
- the cooling device may also comprise a cover that may be suspended over a body portion of the element or that may be provided in the form of a cover layer that is in direct contact with the body portion.
- the cover typically is transmissive for the thermal radiation and protects the particles from hot breezes and other external influences that could reduce the cooling efficiency.
- the cover typically is arranged for reduction of exchange of thermal energy by convection.
- the cover may comprise a polymeric material such as polyethylene.
- the cover may comprise an oxide or sulphide material, which typically is arranged to block at least a portion of incident UV radiation.
- FIG. 20 shows a cooling device according to a further embodiment of the present invention.
- FIG. 1 shows a cooling element 10 in accordance with an embodiment of the present invention.
- the element 10 may be arranged for cooling a medium that is in thermal contact with a portion of the element 10 .
- the element 10 is arranged so that thermal radiation can be emitted from surface portion 12 to the atmosphere either directly or indirectly.
- the element 10 is arranged so that a portion of the thermal energy received from the medium is emitted by the element 10 in the form of thermal radiation so that cooling of the medium is facilitated by the element 10 .
- FIG. 5 shows a transmission spectrum 34 of the atmosphere of the Earth for substantially cloud free conditions.
- the average transmission is increased to nearly 1 within the range of approximately 7.9 to 13 ⁇ m compared to adjacent wavelength ranges. Further, the average transmission of the atmosphere is increased within a wavelength range of 3-5 ⁇ m. Within these wavelength ranges the atmosphere of the Earth has “windows”.
- Plot 36 is an estimation of the emission spectrum of a black body having a temperature of 100° C., which was calculated using Wein's law and gives an example of the emission spectrum for a medium that may be cooled using the cooling material according to embodiments of the present invention.
- the reflective material 42 has the added advantage that a large portion of incident radiation is reflected away from the element 40 and consequently thermal absorption of radiation having a wavelength within or outside the atmospheric window is reduced, which increases cooling efficiency.
- FIG. 9 shows the cooling system 90 which comprises an object 92 .
- the object may be a container, such as a food container, or a can, such as a beverage can.
- the object 92 includes a top portion 94 to which the above described element for emission of thermal radiation is applied.
- the element may be provided in the form of a coating functioning in the same manner as the elements 40 , 50 and 60 described with reference to FIGS. 6 to 8 .
- FIG. 12 shows another example of the cooling device.
- Cooling device 130 comprises in this case body portion 31 , which is arranged to cool a fluid that is channeled through the body portion 131 .
- the body portion 131 comprises the particles for emission of thermal radiation.
- the cooled fluid is directed by thermally insulated tubes 132 to and from body portion 133 , where heat is absorbed. Consequently, the cooling device 130 functions as heat pump and moves thermal energy from an area within which the body portion 133 is positioned, such as an interior of a building, to the body portion 131 , which may be positioned outside the building.
- cooling device 270 may be provided in various different forms.
- the cooling device 270 may not necessarily be arranged to receive a can, but may alternatively be any other type of object.
- the housing portions 272 and 274 may have any suitable shape.
Abstract
The present disclosure provides an element for emission of thermal radiation. The element comprises particles arranged for receiving thermal energy and emitting at least a portion of the received thermal energy in the form of the thermal radiation. The thermal radiation predominantly has a wavelength or wavelength range within an atmospheric window wavelength range in which the atmosphere of the Earth has a reduced average absorption and emission compared with an average absorption and emission in an adjacent wavelength range whereby absorption by the element of radiation from the atmosphere is reduced.
Description
- The present invention broadly relates to an element for emission of thermal radiation.
- Various methods are used to cool interior spaces of buildings, refrigerate food, condense water or reduce the temperature of objects. These methods have in common that they require relatively large amounts of energy, which typically are provided in the form of electrical energy. For example, in countries which have a relatively warm climate the electrical energy required for cooling often exceeds the available electrical energy, which may result in a breakdown of a power grid. Further, electrical energy is at this time still at least partially generated using non-renewable energy resources, for example by burning coal, which is of concern for the environment and contributes to global warming. Consequently, it would be advantageous if cooling could be achieved in a manner that uses less energy. There is a need for technological advancement.
- The present invention provides an element for emission of thermal radiation, the element comprising particles arranged for receiving thermal energy and emitting at least a portion of the received thermal energy in the form of the thermal radiation, the thermal radiation predominantly having a wavelength or wavelength range within an atmospheric window wavelength range in which the atmosphere of the Earth has a reduced average absorption and emission compared with an average absorption and emission in an adjacent wavelength range whereby absorption by the element of radiation from the atmosphere is reduced.
- Because the atmosphere of the Earth has very low absorption within the atmospheric window wavelength range, only a very small amount of radiation is returned from the atmosphere to the particles within that wavelength range and emitted radiation is largely directed through the atmosphere and into Space where the typical temperature is of the order of 4 Kelvin. As a consequence, thermal energy received by the element is “pumped” away by the element.
- The atmospheric window wavelength range typically includes a minimum of the average absorption of the atmosphere of the Earth. The atmosphere has atmospheric windows within the wavelength ranges of 3 to 5 μm and 7.9 μm to 13 μm. Within these wavelength ranges the emission of the sun is also negligible and often regarded as zero, which has the added advantage that even during daytime the element only absorbs very little radiation from the sun within that wavelength range.
- The element according to embodiments of the present invention and a medium that may be in thermal contact with the element typically is cooled or cooling is facilitated without the need for electrical energy. In particular during the night, or when irradiation by the sun is avoided, cooling well below ambient temperature is possible.
- The particles may be distributed throughout the element, which in this case also comprises a material that is substantially transmissive for radiation having a wavelength within the atmospheric window range. Alternatively, the element may comprise a surface portion, such as a coating, in which the particles are concentrated and which is arranged so that the thermal radiation can be emitted. The element may also comprise a membrane which locates the particles.
- The element may also comprise a cover that may be suspended over a body portion of the element or that may be provided in the form of a cover layer that is in direct contact with the body portion. The cover typically is transmissive for the thermal radiation emitted by the particles and protects the particles from hot breezes and other external influences that could reduce the cooling efficiency. The cover typically comprises a thermally insulating material. For example, the cover may comprise a polymeric material such as polyethylene. Further, the cover may comprise an oxide or sulphide material, which typically is arranged to block at least a portion of incident UV radiation. In one specific example the oxide or sulphide material is positioned on or over the polyethylene material and also protects the polyethylene. This example combines the relative strength of typical polyethylene material with the UV protective function of the sulphide or oxide material, which also increases the lifespan of the polyethylene material. The polymeric material and the oxide or sulphide material typically are arranged so that relatively high transmittance for radiation having a wavelength within the atmospheric window is retained. For example, the oxide or sulphide material may be a layer that is positioned on or over the polymeric material. The sulphide or oxide layer typically has a thickness that is selected so that in use at least the majority of incident UV radiation is blocked and the cover is substantially transmissive for radiation having a wavelength range within the atmospheric window wavelength range. The thickness of the layer typically is within the range of 100 nm-1000 nm, 150 nm-300 nm and typically is of the order of 200 nm.
- The element may further comprise wall portions that define an interior space within which a medium that is to be cooled is in use located. The wall portions typically comprise a reflective material. The element may include thermally insulating materials and may for example form an at least partially thermally insulated container.
- The element may also comprise a structure that has projecting wall portions which are positioned so that, in use, incoming radiation from regions of the atmosphere, which are near the horizon, is substantially blocked off. It is known that for such radiation the atmospheric window is less transmissive, because the atmosphere is “thicker” for radiation traveling closer to the horizon. Being less transmissive, the atmosphere then also radiates more strongly at these wavelengths from directions close to the horizon. Consequently, avoiding that such radiation can reach the particles improves the cooling efficiency of the element. The projecting wall portions typically are reflective for the thermal radiation emitted by the particles. The structure may also comprise the above-described cover.
- The projecting wall portions typically are reflective for the thermal radiation emitted by the particles and may be positioned so that, in use, thermal radiation emitted by the particles or reflected by the projecting wall portions is directed in a direction towards Space and in a direction away from the horizon. The projecting wall portions typically are formed from a material that has low thermal emittance.
- In one specific embodiment the element comprises a concentrator such as a “CPC” concentrator or a parabolic dish or trough concentrator. In this case the projecting wall portions typically form a portion of the concentrator. The concentrator typically is arranged so that radiation emitted form substantially all regions of the conduit is directed towards the sky by the concentrator. Further, the projecting wall portion has the added advantage that heating of the particles, and/or of the medium that is to be cooled by the particles, by a hot breeze that may in use pass over the element is reduced.
- In another specific embodiment the element forms a part of, or is provided in the form of, an object and is arranged for cooling of the object and/or a medium that is in thermal contact with the object.
- The element may be in contact with the portion of the object and may also be adhered to, formed on or otherwise applied to the portion of the object.
- In one specific embodiment the object includes a container, such as a can, in which for example food or a liquid may be located.
- For example, the object may be a container, such as a food container or a container for transportation or storage of medicine, organs, blood, or anything else that is to be cooled. Further, the object may be an electronic device and the element may be arranged for cooling of the electronic device or may form a part of any means for transportation including automobiles, trucks, train carriages and shipment containers and the like, which require cooling of an interior portion.
- The element may also be a part of a structure, such as a building or a house. For example, the element may be provided in the form of a window, roof tile, roof sheet or skylight. For example if the element is provided in a form that is substantially transparent for visible light, the element may comprise a substantially transparent polymeric material that comprises the particles for emission of the thermal radiation. The element may in this embodiment also comprise a honeycomb-like structure that provides additional strength. The element may further comprise a material, such as a further type of particles, that is arranged for absorbing incoming radiation in the near infrared wavelength range. In this case the element may be arranged so that the incoming near infrared radiation is absorbed and the resulting absorbed thermal energy is at least partially re-emitted in the form of thermal radiation by the particles arranged for emission of radiation having a wavelength within the atmospheric window wavelength range.
- A person skilled in the art will appreciate that there are many additional examples of objects which may comprise the element or which the element may form.
- In embodiments of the present invention the element is arranged to enable cooling to temperatures that are 5°, 10°, 20° below an ambient temperature or even lower.
- The element may also be arranged to extract heat at a finite rate at a temperature below ambient. The element may be arranged so that cooling rates such as 40, 60, 80 W per m2 of cooling material area are possible at temperatures that are 5°, 10° or more below ambient temperature.
- The particles may be arranged for generation of ionic surface plasmon resonances having a wavelength or wavelength range within the atmospheric window wavelength range.
- Throughout this specification the term “ionic surface plasmon” is used for an excitation that involves movement of ions (and consequently relates to surface phonons), such as that often referred to as “Fröhlich resonance”.
- The particles typically are arranged so that at least some, typically the majority or all, of the ionic surface plasmons have a wavelength within the wavelength range from 1-7 μm, 2-6 μm, or 3-5 μm, and/or any one of 5-16 μm, 7-14 μm, 8-13 μm and 7.9-13 μm.
- However, it is to be appreciated that at least a portion of the particles may also be arranged so that the ionic surface plasmons are generated at a wavelength range that is partially outside the atmospheric window wavelength range. Further, the atmospheric window wavelength range may be one of a plurality of atmospheric window ranges, such as the wavelength range of 3-5 μm and 7.9 to 13 μm.
- In one specific embodiment of the present invention the particles comprise, or are entirely composed of, SiC or another suitable material.
- At least a portion of the particles may also be arranged for emission of radiation by a physical mechanism other than that associated with the generation of ionic surface plasmons. The particles may be composed of any suitable material that is arranged for emission of radiation having a wavelength within the atmospheric window wavelength range. Alternatively or additionally, the element may comprise a material that is arranged for emission of radiation having a wavelength outside the atmospheric window range.
- The element may comprise a polymeric material, such as a coating, that is transmissive for radiation of a predetermined range of wavelength. For example, the particles may be embedded in the polymeric material or may be located adjacent the polymeric material.
- The element may also be arranged to reflect at least some incident radiation, such as radiation from the atmosphere and/or from the sun in the daytime. The element may comprise a reflective material that is provided in the form of a layer positioned below the particles and may be arranged to reflect at least a portion of incident radiation. Alternatively or additionally, the element may comprise reflective particles that are dispersed within an at least partially transparent material, such as the above-described polymeric material.
- In one embodiment the element comprises at least one channel for a fluid whereby the element is arranged for cooling the fluid.
- It is to be appreciated that in variations of the above-described embodiments the element may not necessarily comprise particles that are arranged for emission of thermal radiation having a wavelength within the atmospheric window wavelength range, but the particles may be replaced by at least one layer that is arranged for emission of thermal radiation having a wavelength within the atmospheric window wavelength range. For example, the at least one layer may comprise a granular structure, a porous structure or may have a surface that is profiled so that the at least one layer is arranged for generation of ionic surface plasmon resonances having a wavelength or wavelength range within the atmospheric window wavelength range. Alternatively, the at least one layer may be a part of a multi-layered structure that is arranged for generation of ionic surface plasmon resonances having a wavelength or wavelength range within the atmospheric window wavelength range.
- The present invention provides in a second aspect an element for emission of thermal radiation, the element comprising at least one layer that is arranged for receiving thermal energy and emitting at least a portion of the received thermal energy in the form of the thermal radiation, the thermal radiation predominantly having a wavelength or wavelength range within an atmospheric window wavelength range in which the atmosphere of the Earth has a reduced average absorption and emission compared with an average absorption and emission in an adjacent wavelength range whereby absorption by the element of radiation from the atmosphere is reduced.
- The atmospheric window wavelength range typically is a wavelength range from 3 to 5 μm and/or from 7.9 μm to 13 μm.
- The at least one layer typically is arranged for generation of ionic surface plasmon resonances having a wavelength or wavelength range within the atmospheric window wavelength range.
- The at least one layer may have a structural property that is selected so that the at least one layer is arranged for generation of ionic surface plasmon resonances having a wavelength or wavelength range within the atmospheric window wavelength range. For example, the at least one layer may comprise grains, or may at least in part be of a porous structure and the structural property may be associated with a grain size or a thickness of residual solid between pores, respectively. Further, the at least one layer may have a surface roughness and the structural property may be associated with thickness or width of surface features of the at least one layer. The grain size, the thickness of residual solid between pores and the thickness or width of surface features of the at least one layer typically are within the range of 50 nm-150 nm.
- Alternatively, the at least one layer may be a part of a multi-layered structure having layer thicknesses that are selected so that the multi-layered structure is arranged for generation of ionic surface plasmon resonances having a wavelength or wavelength range within the atmospheric window wavelength range.
- The present invention provides in a third aspect a cooling system comprising the above-described element in accordance with the first or second aspect of the present invention, the element forming a part of an object and the cooling system comprising a thermally insulating wall portion for reducing exchange of thermal energy between a portion of the object an environment of the cooling system.
- The element may be in contact with the portion of the object and may also be adhered to, formed on or otherwise applied to the portion of the object.
- The object may include a container, such as a can, in which for example food or a liquid may be located.
- The thermally insulating wall portion typically is arranged so that the element of the object is in use enabled to emit thermal radiation in a direction away from the cooling system. The cooling system typically is also arranged so that the object is positionable in, and removable from, an interior formed by the thermally insulating wall portion.
- The cooling system may further comprise a removable lid-portion and a base portion that together with the thermally insulating wall portion form an enclosure in which in use the object is positioned, the lid-portion being formed from a material that is transmissive for thermal radiation emitted by the particles of the element.
- The present invention provides in a fourth aspect a cooling device for cooling a medium, the cooling device comprising an element for emission of thermal radiation, the element comprising particles arranged for receiving thermal energy and emitting at least a portion of the received thermal energy in the form of the thermal radiation, the thermal radiation predominantly having a wavelength or wavelength range within an atmospheric window wavelength range in which the atmosphere of the Earth has a reduced average absorption and emission compared with an average absorption and emission in an adjacent wavelength range whereby absorption by the element of radiation from the atmosphere is reduced.
- For example, the cooling device may comprise the element for emission of thermal radiation in accordance with the first aspect of the present invention.
- The atmospheric window wavelength range typically includes a minimum of the average absorption of the atmosphere of the Earth. The atmosphere has atmospheric windows within the wavelength ranges of 3 to 5 μm and 7.9 μm to 13 μm. Within these wavelength ranges the emission of the sun is also negligible and often regarded as zero, which has the added advantage that even during daytime the element of the cooling device only absorbs very little radiation from the sun within that wavelength range.
- The cooling device may be arranged so that the medium is in direct or indirect thermal contact with the element.
- The medium typically is in use cooled or cooling is facilitated without the need for electrical energy. In particular during the night, or when irradiation by the sun is avoided, cooling well below ambient temperature is possible.
- For example, the cooling device may be an air-conditioning device or a refrigerator or the like. The element of the cooling device may be in thermal contact, ether directly or indirectly, with a fluid, such as a liquid or gaseous medium, and may be arranged for cooling of the fluid or facilitating cooling of the fluid.
- The cooling device may also be arranged to facilitate operation of another device. For example, the cooling device may be arranged to correspond with the other cooling device and may be mountable on, or in the proximity of the other device so that a “hybrid” device is formed. In one specific embodiment the cooling device is arranged to facilitate operation of an air-conditioning device or refrigerator. For example, the cooling device may be arranged to cool a fluid, especially during the night, which is then used to facilitate heat exchange of the other cooling device, such as the refrigerator or the air-conditioning device. In one variation the cooling device is arranged to store the cooled fluid for a period of time, for example during the night.
- In one specific embodiment the cooling device is arranged so that in use the element receives thermal energy from a fluid. In this embodiment the cooling device comprises a conduit that is arranged for directing the fluid to and from the proximity of the element of the cooling device so that in use the cooling device results in cooling of the fluid. The cooling device is arranged so that the element receives thermal energy directly or indirectly from the fluid. In this embodiment the conduit may provided in the form of a tubular portion and at least a portion of the conduit may be arranged for mounting at an exterior surface of a building or structure. Further, the cooling device may be arranged so that in use at least a portion of an interior of the building or structure is cooled by the cooling device and the cooling device may be arranged so that the fluid is directed in a closed cycle along the proximity of the element and along a portion from which the fluid in use absorbs thermal energy from the interior of the building or structure. In one example the conduit comprises a region at which in use the element is enabled to emit the thermal radiation in a direction away from the cooling device. The conduit may further comprise a thermally insulated region that is arranged to reduce exchange of thermal energy between the fluid and an environment of the conduit. The cooling device may further be arranged so that the region at which in use the element is enabled to emit the thermal radiation is oriented so that the thermal radiation is emitted in a direction directly towards Space.
- In another example the cooling device is provided in the form of an evaporative cooling device and the cooling device may be arranged for cooling of a liquid prior to evaporation of the liquid or may otherwise facilitate cooling of the evaporative cooling device. The cooling device may also be provided in the form of a radiator or heat exchanger and the element may enable or facilitate the cooling.
- The particles may be distributed throughout the element of the cooling device, which may also comprise a material that is substantially transmissive for radiation having a wavelength within the atmospheric window range. Alternatively, the element of the cooling device may comprise a surface portion, such as a coating, in which the particles are concentrated and which is arranged so that the thermal radiation can be emitted. The element of the cooling device may also comprise a membrane which locates the particles.
- The cooling device may also comprise a cover that may be suspended over a body portion of the element or that may be provided in the form of a cover layer that is in direct contact with the body portion. The cover typically is transmissive for the thermal radiation and protects the particles from hot breezes and other external influences that could reduce the cooling efficiency. The cover typically is arranged for reduction of exchange of thermal energy by convection. For example, the cover may comprise a polymeric material such as polyethylene. Further, the cover may comprise an oxide or sulphide material, which typically is arranged to block at least a portion of incident UV radiation.
- In one specific example the oxide or sulphide material is positioned on or over the polyethylene material and also protects the polyethylene. This example combines the relative strength of typical polyethylene material with the UV protective function of the sulphide or oxide material, which also increases the lifespan of the polyethylene material. The polymeric material and the oxide or sulphide material typically are arranged so that relatively high transmittance for radiation having a wavelength within the atmospheric window is retained. For example, the oxide or sulphide material may be a layer that is positioned on or over the polymeric material. The sulphide or oxide layer typically has a thickness that is selected so that in use at least the majority of incident UV radiation is blocked and the cover is substantially transmissive for radiation having a wavelength range within the atmospheric window wavelength range. The thickness of the layer typically is within the range of 1000 nm-100 nm, 300 nm-150 nm and typically is of the order of 200 nm.
- The cooling device may further comprise wall portions that define an interior space within which a medium that is to be cooled is in use located. The cooling device may include thermally insulating materials and may for example form an at least partially thermally insulated container.
- Further, the cooling device may comprise a closure that is removable so that the medium is locatable within the interior space and the interior space is closable. The cooling device may also be arranged to cool the medium that after removal from the cooling device, is used to cool another medium. For example, the medium may comprise a phase change material.
- The cooling device may also comprise a conduit for guidance of emitted radiation from the particles to a remote location. For example, the conduit may be provided in the form of a hollow tube with reflective interior wall portions that are arranged to reflect the emitted thermal radiation and thereby guide the thermal radiation to an end-portion of the conduit that may be open or covered with a suitable material that is substantially transmissive for the thermal radiation.
- The cooling device may also form a part of, or may be provided in the form of, a water condenser. The water condenser may be arranged so that water is generated by condensation of water vapour in air, for example in an environment that has insufficient supply of fresh water, including, but not limited to, remote areas and areas on or near an ocean. The water condenser may form a part of a water desalination device in which the cooling by the element facilitates condensation of water.
- In one specific embodiment the cooling device forms a part of a water purifier. In this case the cooling device may comprise a first layer that includes the particles for emission of thermal radiation and a second layer that is spaced apart from the first layer. The second layer comprises in this embodiment a material that is arranged for absorbing a portion of incoming solar radiation and thereby increasing the temperature of the second layer. The cooling device typically is arranged so that the first layer is in use positioned over the second layer. A fluid, such as water containing impurities, may be directed through the space formed between the first and the second layer. The water will be heated in the proximity of the second layer and, as the first layer is cooled by the particles for emission of the thermal radiation, developed water vapour will condense at the first layer. The water formed by condensation of water vapour at the first layer typically is substantially free of the impurities, such as salt in the case of sea water.
- The cooling device may also comprise a structure that has projecting wall portions which are positioned so that, in use, incoming radiation from regions of the atmosphere, which are near the horizon, is substantially blocked off. It is known that for such radiation the atmospheric window is less transmissive, because the atmosphere is “thicker” for radiation traveling closer to the horizon. Being less transmissive, the atmosphere then also radiates more strongly at these wavelengths from directions close to the horizon. Consequently, avoiding that such radiation can reach the particles improves the cooling efficiency of the cooling device. The structure may also comprise the above-described cover.
- The projecting wall portions typically are reflective for the thermal radiation emitted by the particles and may be positioned so that, in use, thermal radiation emitted by the particles or reflected off the projecting wall portions is directed in a direction towards Space and in a direction away from the horizon. The projecting wall portions typically are formed from a material that has low thermal emittance.
- In one specific embodiment the cooling device comprises a concentrator such as a “CPC” concentrator or a parabolic dish or trough concentrator. In this case the projecting wall portions typically form a portion of the concentrator. For example, the cooling device may comprise a conduit for fluid that is positioned at or near a focal region of the concentrator. The conduit may comprise the particles that emit in use the thermal radiation. A fluid may be directed through the conduit so that in use the fluid is cooled. The concentrator typically is arranged so that radiation emitted form substantially all regions of the conduit is directed towards the sky by the concentrator. Further, the projecting wall portion has the added advantage that heating of the particles, and/or of the medium that is to be cooled by the particles, by a hot breeze that may in use pass over the is reduced.
- The cooling device may be arranged so that cooling is facilitated by the element. Alternatively, the cooling device may be arranged so that cooling is effected solely by the element.
- In another specific embodiment the cooling device forms a part of an object and is arranged for cooling of the object and/or a medium that is in thermal contact with the object.
- For example, the object may be a container, such as a food container or a container for transportation or storage of medicine, organs, blood, or anything else that is to be cooled. Further, the object may be an electronic device and the cooling device may be arranged for cooling of the electronic device or may form a part of any means for transportation including automobiles, trucks, train carriages and shipment containers and the like, which require cooling of an interior portion.
- The following will describe a selection of further possible features and the function of the cooling device in more detail.
- In embodiments of the present invention the cooling device is arranged to enable cooling to temperatures that are 5°, 10°, 20° below an ambient temperature or even lower.
- The cooling device may also be arranged to extract heat at a finite rate at a temperature below ambient. The cooling device may be arranged so that cooling rates such as 40, 60, 80 W/m2 of cooling material area are possible at temperatures that are 5°, 10° or more below ambient temperature.
- The particles may be arranged for generation of ionic surface plasmon resonances having a wavelength or wavelength range within the atmospheric window wavelength range.
- The particles typically are arranged so that at least some, typically the majority or all, of the ionic surface plasmons have a wavelength within the wavelength range from 1-7 μm, 2-6 μm, or 3-5 μm, and/or any one of 5-16 μm, 7-14 μm, 8-13 μm and 7.9-13 μm.
- It is to be appreciated, however, that at least a portion of the particles may also be arranged so that the ionic surface plasmons are generated at a wavelength range that is partially outside the atmospheric window wavelength range. Further, the atmospheric window wavelength range may be one of a plurality of atmospheric window ranges, such as the wavelength range of 3-5 μm and 7.9 to 13 μm.
- In one specific embodiment of the present invention the particles comprise, or may be entirely composed of, SiC or another suitable material.
- At least a portion of the particles may also be arranged for emission of radiation by a physical mechanism other than that associated with the generation of ionic surface plasmons. The particles may be composed of any suitable material that is arranged for emission of radiation having a wavelength within the atmospheric window wavelength range. Alternatively or additionally, the cooling device may comprise a material that is arranged for emission of radiation having a wavelength outside the atmospheric window range.
- The element of the cooling device may comprise a polymeric material, such as a coating, that is transmissive for radiation of a predetermined range of wavelength. For example, the particles may be embedded in the polymeric material or may be located adjacent the polymeric material.
- The cooling device may also be arranged to reflect at least some incident radiation, such as radiation from the atmosphere and/or from the sun in the daytime. The cooling device may comprise a reflective material that is provided in the form of a layer positioned below the particles and may be arranged to reflect at least a portion of incident radiation. Alternatively or additionally, the element may comprise reflective particles that are dispersed within an at least partially transparent material, such as the above-described polymeric material.
- In one embodiment the cooling device comprises at least one channel for a fluid whereby the cooling device is arranged for cooling the fluid.
- It is to be appreciated that in variations of the above-described embodiments the element may not necessarily comprise particles that are arranged for emission of thermal radiation having a wavelength within the atmospheric window wavelength range, but the particles may be replaced by at least one layer that is arranged for emission of thermal radiation having a wavelength within the atmospheric window wavelength range. For example, the at least one layer may comprise a granular structure, a porous structure or have a surface that is profiled so that the at least one layer is arranged for generation of ionic surface plasmon resonances having a wavelength or wavelength range within the atmospheric window wavelength range. Alternatively, the at least one layer may be a part of a multi-layered structure that is arranged for generation of ionic surface plasmon resonances having a wavelength or wavelength range within the atmospheric window wavelength range.
- The present invention provides in a fifth aspect a cooling device for cooling a medium, the cooling device comprising an element for emission of thermal radiation, the element comprising at least one layer arranged for receiving thermal energy and emitting at least a portion of the received thermal energy in the form of the thermal radiation, the thermal radiation predominantly having a wavelength or wavelength range within an atmospheric window wavelength range in which the atmosphere of the Earth has a reduced average absorption and emission compared with an average absorption and emission in an adjacent wavelength range whereby absorption by the element of radiation from the atmosphere is reduced.
- The atmospheric window wavelength range typically is a wavelength range from 3 to 5 μm and/or from 7.9 μm to 13 μm.
- The at least one layer typically is arranged for generation of ionic surface plasmon resonances having a wavelength or wavelength range within the atmospheric window wavelength range.
- In one example the at least one layer has a structural property that is selected so that the at least one layer is arranged for generation of ionic surface plasmon resonances having a wavelength or wavelength range within the atmospheric window wavelength range. For example, the at least one layer may comprise grains, or may at least in part be of a porous structure and the structural property may be associated with a grain size or a thickness of residual solid between pores, respectively. Further, the at least one layer may have a surface roughness and the structural property may be associated with thickness or width of surface features of the at least one layer. The grain size, the thickness of residual solid between pores and the thickness or width of surface features of the at least one layer typically within the range of 50 nm-150 nm.
- Alternatively, the at least one layer may be a part of a multi-layered structure having layer thicknesses that are selected so that the multi-layered structure is arranged for generation of ionic surface plasmon resonances having a wavelength or wavelength range within the atmospheric window wavelength range.
- The present invention provides in a sixth aspect a cooling system comprising the above-described cooling device, the cooling device comprising wall portions that define an interior space within which a medium that is to be cooled is in use located, the cooling system further comprising a cooling container that is arranged to receive the medium cooled by the cooling device so that the cooled medium is enabled to cool an interior portion of the cooling container.
- The cooling device typically includes thermally insulating materials.
- Further, the cooling container may comprise a closure that is removable so that the cooled medium is locatable within the interior of the cooling container and the cooling container is closable.
- The present invention provides in a seventh aspect a method of cooling a medium comprising the steps of:
-
- receiving thermal energy by a medium;
- directing the thermal energy to a remote location;
- receiving the thermal energy by an element positioned at the remote location; and
- emitting at least a portion of the thermal energy received by the element in the form of the thermal radiation predominantly having a wavelength or wavelength range within an atmospheric window wavelength range in which the atmosphere of the Earth has a reduced average absorption and emission compared with an average absorption and emission in an adjacent wavelength range.
- The method typically comprises moving the medium so that the thermal energy received by the medium transported to the element.
- The invention will be more fully understood from the following description of specific embodiments of the invention. The description is provided with reference to the accompanying drawings.
-
FIG. 1 shows an a device incorporating an element for emission of thermal radiation according to an embodiment of the present invention; -
FIGS. 2 , 3 (a), 3(b) and 4 show objects incorporating an element for emission of thermal radiation according to an embodiment of the present invention; -
FIG. 5 shows a transmission spectrum of the atmosphere of the Earth as a function of wavelength; -
FIGS. 6-8 show elements for emission of thermal radiation according to embodiments of the present invention; -
FIG. 9 shows a cooling system according to a specific embodiment of the present invention; -
FIG. 10 shows an a cooling device according to an embodiment of the present invention; -
FIGS. 11 and 12 show cooling devices according to embodiments of the present invention; -
FIGS. 13-18 show further examples of cooling devices according to embodiments of the present invention; -
FIG. 19 shows a cooling system according to a embodiment of the present invention; and -
FIG. 20 shows a cooling device according to a further embodiment of the present invention. - Generally, the element comprises particles that are arranged for emission of radiation having a wavelength within a range referred to as the “atmospheric window wavelength range”. The atmospheric window wavelength range is a wavelength range within which the absorption and emission of radiation by the atmosphere of the Earth is strongly reduced or zero. Radiation emitted from the element within that wavelength range is largely transmitted through the atmosphere to Space where the average temperature is 4 Kelvin. Further, as within that wavelength range typically very little or no radiation is received by the element, the element functions as a pump of thermal energy.
- The element comprises a cooling material that is disclosed in Australian provisional patent application No 2007903673 and U.S. patent application Ser. No. 11/765,217. These patent applications are hereby incorporated by cross-reference. Further details of the function of the element will be discussed with reference to
FIGS. 4-7 . - Referring initially to
FIGS. 1-3 , examples of elements and objects incorporating the element according to specific embodiments of the present invention are now described. -
FIG. 1 shows acooling element 10 in accordance with an embodiment of the present invention. For example, theelement 10 may be arranged for cooling a medium that is in thermal contact with a portion of theelement 10. Theelement 10 is arranged so that thermal radiation can be emitted fromsurface portion 12 to the atmosphere either directly or indirectly. Theelement 10 is arranged so that a portion of the thermal energy received from the medium is emitted by theelement 10 in the form of thermal radiation so that cooling of the medium is facilitated by theelement 10. - The
cooling element 10 may form a part of an evaporative cooling device. In this case theelement 10 typically is arranged to cool a liquid, typically water, prior to evaporation. Alternatively, theelement 10 may form a part of any other type of air-conditioning device and theelement 10 may be arranged for facilitating cooling of a fluid that in use circulates though portions of the air-conditioning unit. - Further, the
element 10 may form a part of be a radiator, heat exchanger, or refrigerator or any other type of cooling device. A person skilled in the art will appreciate that there are numerous examples of cooling devices in which theelement 10 may be incorporated. -
FIG. 2 shows an example of astructure 14 in which an element for emission of the thermal radiation according to embodiments of the present invention is incorporated. Thestructure 14 is in this embodiment a house or building or the like and includes roof-covering and/or other external coverings that are provided in the form ofobjects 16. For example, eachobject 16 may be a roof tile or a roof-sheet which comprises a metallic, ceramic or polymeric material. Theobject 16 comprises a surface portion that incorporates the particles for emission of the thermal radiation and is positioned over the metallic, ceramic or polymeric material. For example, the particles may be embedded in a coating material that is applied by painting or otherwise to the metallic, ceramic or polymeric material of theobject 16. The coating material is substantially transmissive for radiation having a wavelength within the atmospheric window wavelength range. Alternatively, the particles may be positioned on a surface portion of theobject 16 without being embedded in a coating material. - The
object 16 is arranged so that thermal radiation is emitted which results in cooling of a roof space of the house orbuilding 14. This particular application has significant advantages in particular for warmer regions of the Earth. During hot summer days roof spaces gain a substantial amount of thermal energy and often maintain a substantial portion of that thermal energy during the night. Theelement 16 facilitates cooling of the roof space and thereby improves comfort of living in the house orbuilding 14. In one specific embodiment of the present invention large portions of the external surface, such as the roof area of a house or building 14, are covered by theobject 16. - Referring again to
FIG. 2 , thestructure 14 may also include further objects that incorporate an element for emission of the thermal radiation and that are provided in the form of windows, such aswindow 18. Thewindow 18 is arranged so that a portion of near-infrared radiation is blocked. - Referring now to
FIG. 3 (a), a further example of an object that incorporates theelement 10 for emission of thermal radiation is now described. Theobject 20 is in this example a container for containing food, medical articles, blood or organs and the like or any other objects or matter that requires cooling. An external surface portion of theobject 20 comprises the particles arranged for emission of thermal radiation. Emission of the thermal radiation results in cooling of thecontainer 20 and an interior portion thereof. -
FIG. 3 (b) shows an example of a further variation of a container that includes theelement 12. In this case thecontainer 22 haswall portions 24 that are composed of a thermally insulating material. Thecontainer 22 also comprises atop portion 26 that is composed of a material that is substantially transmissive for the thermal radiation having a wavelength range within the atmospheric window wavelength range. The top portion may also have thermally insulating properties and may for example comprise iron oxide or ZnS. A medium that is to be cooled is positioned adjacent theelement 12. This embodiment has the added advantage that the thermally insulating wall portions further increase the cooling efficiency. Further, theelement 10 and the medium that is to be cooled are protected from any hot breezes that may also reduce the cooling efficiency. - A person skilled in the art will appreciate that there are numerous examples of objects in which the element for emission of thermal radiation maybe incorporated. For example, the element may form a portion of an electronic device, such as an integrated electronic device, and may be arranged for cooling of the electronic device.
-
FIG. 4 shows astructure 28 that is largely transmissive for visible radiation and may be used as a roof-sheet, window or sky light and the like. Thestructure 28 comprises afirst layer 30 and asecond layer 32. Thefirst layer 30 and thesecond layer 32 are connected bymembers 34 so that a honey-comb like structure is formed that is relatively stabile. Thestructure 28 comprises a polymeric material and has particles incorporated within that material so that thestructure 28 has advantages analogous to those of the above-discussed element. - A person skilled in the art will also appreciate that the cooling element has numerous applications for cooling objects, or fluids. If an object or fluid is to be cooled, the cooling element may be arranged to cool the object or fluid directly. Alternatively, the cooling element may be arranged for cooling the object or fluid indirectly by cooling another fluid of material, which then cools the fluid or object that is to be cooled.
- Referring now to
FIGS. 5 and 6 , the function of the element for emission of thermal radiation according to a specific embodiment of the present invention are now described in further detail.FIG. 5 shows atransmission spectrum 34 of the atmosphere of the Earth for substantially cloud free conditions. The average transmission is increased to nearly 1 within the range of approximately 7.9 to 13 μm compared to adjacent wavelength ranges. Further, the average transmission of the atmosphere is increased within a wavelength range of 3-5 μm. Within these wavelength ranges the atmosphere of the Earth has “windows”.Plot 36 is an estimation of the emission spectrum of a black body having a temperature of 100° C., which was calculated using Wein's law and gives an example of the emission spectrum for a medium that may be cooled using the cooling material according to embodiments of the present invention. -
FIG. 6 shows a secondary electron microscopy micrograph of a surface portion of the element according to a specific embodiment of the present invention. - The
element 40 comprises a reflectivemetallic layer 42, which in this embodiment is provided in the form of an aluminum layer positioned on a substrate. Further, theelement 40 comprisesSiC particles 44, which are positioned on themetallic layer 42. TheSiC particles 44 have an average diameter of approximately 50 nm and are deposited using suitable spin coating procedures. - The
SiC particles 44 are in this embodiment nano-particles and the majority of the surface of theparticles 44 is exposed to air. Theparticles 44 show resonantly enhanced absorption and emission of radiation at a wavelength range of 10 to 13 μm. Within that wavelength range ionic surface plasmons are generated. The wavelength range of resonant ionic surface plasmon emission is within the above-described atmospheric window wavelength range. For that wavelength range the average absorption of the atmosphere of the Earth is very low and consequently very little radiation in this wavelength range is transferred from the atmosphere to theelement 40. - The energy associated with the emitted radiation is largely drawn from the thermal energy of the
particles 44 and/or from a medium that is in thermal contact with theparticles 44. Due to the atmospheric window, the emitted radiation is largely transmitted through the atmosphere and directed to Space where the temperature typically is 4 Kelvin. Consequently, theelement 40 functions as a pump of thermal energy even if the cooling material, or a medium that is in thermal contact with the cooling material, has a temperature below ambient temperature. - The
reflective material 42 has the added advantage that a large portion of incident radiation is reflected away from theelement 40 and consequently thermal absorption of radiation having a wavelength within or outside the atmospheric window is reduced, which increases cooling efficiency. - In variations of the above-described embodiment the
particles 44 may be composed of other suitable materials that show ionic surface plasmon resonances, such as BN and BeO. Further, theparticles 44 may also be composed of materials that are not arranged for ionic plasmon generation at a wavelength within the atmospheric window wavelength range, but may be arranged for emission of radiation within that wavelength range by any other possible mechanism. For example, SiO, silicon oxynitride particles exhibit relatively strong emissions within that wavelength range. - The
reflective material 42 improves the cooling efficiency. However, it is to be appreciated that the element may not necessarily comprise a reflective material. Further, theparticles 44 may be embedded in a transparent material, such as a suitable polymeric material that is positioned upon thereflective material 42. For example, the polymeric material may comprise polyethylene or a fluorinated material. - Referring now to
FIG. 7 , an element according to a second specific embodiment of the present invention is now described. - In this embodiment the
element 50 also comprises the above-describedparticles 44. In this example, however, theparticles 44 are positioned within a matrix of apolymeric material 54 that is largely transparent to thermal radiation within a black body wavelength range, such as radiation having a wavelength within the range of 3-28 μm, or a wavelength range outside one or both of 3-5 and 7.9-13 μm, or most of solar spectral range in addition to the black body radiation range. For example, thepolymeric material 54 may comprise polyethylene or a fluorinated polymeric material. - In contrast to the
element 40, incident radiation is not reflected, but largely transmitted through the coolingmaterial 50, which also reduces thermal absorption of radiation directed to theelement 50 and thereby improves the cooling efficiency. - In addition, the
element 50 comprisesparticles 56. In general, theparticles 56 have a spectrally selective property that complements a spectrally selective property of theparticles 44. In this example, theparticles 56 are arranged for generation of electronic surface plasmons in the near infrared (NIR) wavelength range. Within that wavelength range theparticles 56 absorb radiation, such as radiation originating from the sun. This inhibits transmission of a portion of incident radiation, which facilitates the cooling. In this embodiment the coolingmaterial 50 is arranged so that the thermal energy, that is present as a consequence of the absorbed solar radiation, is emitted by theparticles 44. - For example, the
element 50 may be provided in the form of a skylight or a window, such aswindow element 18. In this case the coolingmaterial 50 typically is arranged so that a large portion of the visible light originating from the sun can penetrate through theelement 50. Theparticles 44 emit radiation within the atmospheric window wavelength range, which results in cooling, and theparticles 56 partially “block” thermal radiation originating from the sun which facilitates the cooling. - For example, the
particles 56 may comprise indium tin oxide, tin oxide, LaB6, SbSn oxide, or aluminium doped ZnO. - It is to be appreciated, however, that in variations of the above-described embodiment the
particles 56 may also be arranged for generation of electronic surface plasmons at any other suitable wavelength range. - In addition, the
element 50 may comprise a layered structure of dielectric and/or metallic materials having layer thicknesses that are selected to effect reflection of thermal radiation, such as thermal radiation originating from the atmosphere, which further facilitates cooling. - Further, the
element 30 may also comprise a layer structured material that is arranged so that a portion of light within the visible wavelength range is reflected and light that is transmitted though theelement 50 is of a particular colour, which has advantageous applications for aesthetic purposes. - With reference to
FIG. 8 anelement 60 according to another specific embodiment of the present invention is now described. Theelement 60 corresponds to theelement 50 shown inFIG. 7 and described above, but is in this embodiment positioned on a reflective layer 62. Theelement 60 is particularly suited for cooling a medium that may be in thermal contact with the coolingmaterial 60. In this embodiment the reflective layer 62 is a metallic layer that is arranged to reflect radiation having a wide wavelength range and originating, for example, from the sun. - For example, the reflective layer 62 may be arranged to reflect the majority of thermal radiation and visible radiation originating from the sun and from the atmosphere, which facilitates cooling of the cooling
material 60. The reflective material may comprise for example Al, Cu, Ag, Au, Ni, Cr, Mo, W or steel including stainless steel. - In a variation of the embodiment shown in
FIG. 8 , the reflective material may not be provided in form of a layer, but may be provided in form of reflective particles that are incorporated in thematerial 54. - The
elements cooling device 10 orobjects element 60 has particularly advantageous applications as window or skylight, such aswindow 18 - Referring now to
FIG. 9 , a cooling system in accordance with an embodiment of the present invention is now described.FIG. 9 shows thecooling system 90 which comprises anobject 92. For example, the object may be a container, such as a food container, or a can, such as a beverage can. Theobject 92 includes atop portion 94 to which the above described element for emission of thermal radiation is applied. For example, the element may be provided in the form of a coating functioning in the same manner as theelements FIGS. 6 to 8 . - In this embodiment, the
cooling system 90 comprises a thermally insulating housing 96 in which theobject 92 is positioned. Further, thecooling system 90 comprises a lid-portion 98 which is composed of material that is transmissive for thermal radiation emitted by the particles of theelement 94. Further, thecooling system 90 comprises a base portion on which the housing portion 96 and theobject 92 are positioned. In this embodiment, the housing portion 96 is taller than theobject 92 so that in use the likelihood of incidence of direct sunlight on theobject 92 is reduced. Further, the housing portion 96 is sufficiently tall so that in use incoming radiation from the atmosphere, which is incident at angles which are closer to the horizon than to the zenith, is substantially blocked off. The housing portion 96 is reflective for the thermal radiation emitted by the particles and is in use positioned so that thermal radiation emitted by the particles is directed in a direction towards Space and in a direction away from the horizon. Interior wall portions of the housing portion 96 comprise a material that has low thermal emittance. - The lid-
portion 98 creates a barrier for transfer of heat by convection and, at the same time, is transmissive for thermal energy emitted by the particles of theelement 94. - In use, the particles of
element 94 absorb thermal energy from an adjacent portion of theobject 92 and emit the absorbed thermal energy in the form of thermal radiation having a wavelength range within the atmospheric wavelength range. The housing portion 96 and thebase portion 100 provide thermal insulation and consequently facilitate cooling of theobject 92. Thecooling system 90 is arranged so that the object is removable from an interior of the housing portion 96. - It is to be appreciated, however, that the
cooling system 90 may be provided in various different forms. For example, theobject 92 may not necessarily be a container for food or liquid, but may alternatively be any other type of object. Further, theelement 94 may be applied to any side portion of the object and may also be in indirect thermal contact to the object. In addition, the housing portion 96 may have any suitable shape. - Further, it will be appreciated by those skilled in the art that the particles of the element, such as
element FIGS. 7 and 8 , may also be positioned in a membrane that has openings which a suitably sized to locate one or more of the particles. In addition, the element may also comprise projecting wall portions, which may or may not be reflective and which are arranged so that in use it is avoided that radiation that penetrated to atmospheres at regions near the horizon. - Further, it is to be appreciated that in variations of the above-described embodiments the element may not necessarily comprise particles that are arranged for emission of thermal radiation having a wavelength within the atmospheric window wavelength range, but the particles may be replaced by at least one layer, such as a multi-layered structure, that is arranged for emission of thermal radiation having a wavelength within the atmospheric window wavelength range. The layers of the multi-layered structure typically have thicknesses that are selected so that in use ionic surface plasmon resonances are generated and the ionic surface plasmon resonances have a wavelength or wavelength range within the atmospheric window wavelength range. For example, the multi-layered structure may comprise SiO and SiC layers having a thickness of the order of 50-150 nm.
- Alternatively, the particles may be replaced by grains of a layer having a granular structure, such as a suitable SiC layer. In this case the average diameter of the grains is selected so that the layer is arranged for emission of thermal radiation having a wavelength within the atmospheric window wavelength range. The particles may also be replaced by a porous layer or a layer having a rough surface, such as a suitable SiC layer. In this case an average pore spacing or surface profile, respectively, is selected so that the layer is arranged for emission of thermal radiation having a wavelength within the atmospheric window wavelength range.
- In addition, it is to be appreciated that the element may comprise the above-described particles in addition to the above-described at least one layer. The at least one layer and the particles may both be arranged for emission of thermal radiation having a wavelength range within the atmospheric window wavelength range.
- Referring now to
FIGS. 10-12 , examples of cooling devices according to specific embodiments of the present invention are now described. Generally, the cooling device may comprise the above-described element for emission of thermal radiation. -
FIG. 10 shows acooling device 110 that incorporates theelement 112. For example, the cooling device may be an air-conditioning device, a radiator, or any other type of cooling device. Thecooling device 110 may be arranged for cooling a medium that is in thermal contact with a portion of thecooling device 110. Theelement 112 is arranged so that thermal radiation can be emitted fromsurface portion 114 to the atmosphere either directly or indirectly. Thecooling device 110 is arranged so that a portion of the thermal energy received from the medium is emitted by theelement 112 in the form of thermal radiation so that cooling of the medium is facilitated by theelement 112. - The
cooling device 110 may for example be provided in the form of an evaporative cooling device. In this case theelement 112 typically is arranged to cool a liquid, typically water, prior to evaporation. Alternatively, thecooling device 110 may be any other type of air-conditioning device and theelement 112 may be arranged for facilitating cooling of a fluid that in use circulates though portions of the air-conditioning unit. - Further, the
cooling device 110 may be a radiator, heat exchanger, or refrigerator or any other type of cooling device. A person skilled in the art will appreciate that there are numerous examples of cooling devices in which theelement 112 may be incorporated. - For example, the
cooling device 112 may be provided in the form of a container for containing food, medical articles, blood or organs and the like or any other objects or matter that requires cooling. A person skilled in the art will appreciate that there are numerous further examples of cooling devices in which the cooling device may be incorporated. For example, the cooling device may form a portion of an electronic device, such as an integrated electronic device, and may be arranged for cooling of the electronic device. - Referring now to
FIG. 11 , another specific example of a cooling device is now described. In this embodiment thecooling device 127 comprises abody portion 128 which includes particles for emission of the thermal radiation. Further, thecooling device 127 comprises aconduit 129. Theconduit 129 is a hollow tubular portion with reflective internal wall portions that are arranged to reflect the radiation and thereby guide the radiation to a distal end-portion of the conduit. Theconduit 129 is used to channel thermal radiation emitted by the particles of thebody portion 128 to the distal end-portion of theconduit 129 that is exposed to the atmosphere. - For example, the
body portion 128 may comprise a thermally absorptive material that is also arranged to reflect the thermal radiation having a wavelength within the atmospheric window wavelength range. This would ensure that radiation generated by the particles of thecooling device 127 is largely directed into theconduit 129. - It is to be appreciated that the conduit may be provided in any suitable form and may also comprise bent portions.
-
FIG. 12 shows another example of the cooling device.Cooling device 130 comprises in this case body portion 31, which is arranged to cool a fluid that is channeled through thebody portion 131. Thebody portion 131 comprises the particles for emission of thermal radiation. The cooled fluid is directed by thermally insulatedtubes 132 to and frombody portion 133, where heat is absorbed. Consequently, thecooling device 130 functions as heat pump and moves thermal energy from an area within which thebody portion 133 is positioned, such as an interior of a building, to thebody portion 131, which may be positioned outside the building. - A person skilled in the art will appreciate that the
cooling device 130 has numerous applications. For example, thebody portion 131 may be positioned at the exterior of a shipping container and thebody portion 133 may be positioned so that an interior portion of the shipping container is cooled. In this case thecooling device 130 may also be arranged for cooling a relatively small area of the interior of the container, such as the interior of a refrigeration box, within which relatively low temperatures can be achieved. -
FIG. 13 shows a variation of the cooling device that forms a water purifier.FIG. 13 shows astructure 200 that comprises afirst layer 202 and a second layer 102. Thefirst layer 204 and thesecond layer 204 are coupled bymembers 206. Thelayer 202 is in this example corrugated and comprises theparticles 44. Theparticles 56 are separated from theparticles 44 and are distributed in thesecond layer 204. A fluid is in use directed along thesecond layer 204 and in channels that are formed by themembers 206. Theparticles 56 increase the temperature of thesecond layer 204 by absorbing near-infrared radiation and theparticles 44 of thefirst layer 202 cool thesecond layer 202, which results in formation of water vapour and condensation of the water vapour at thefirst layer 202. The condensed water is substantially free of impurities, such as salt, that the water may contain. Because of the corrugation of thefirst layer 202, the condensed water is collected inchannels 208 and available for use. - It is to be appreciated that the first and second layer of the
element 200 may alternatively be mechanically coupled by any other suitable arrangement. - Referring now to
FIG. 14 , a cooling device according to a further embodiment of the present invention is now described.Cooling device 210 comprisesreflectors 212, which in this embodiment are shaped so that a “CPC” concentrator is formed. Thecooling device 210 comprises atube 214 through which in use a fluid is conducted. Thetube 214 is coated with a material comprising theparticles 44 for emission of thermal radiation having a wavelength within the atmospheric window wavelength range and which in use cool the fluid. The emitted thermal radiation is directed by thereflector portions 212 throughcover 216, which is transmissive for the radiation and may be comprise iron oxide or ZnS. - The concentrator has a number of practical advantages. The concentrator is in use oriented so that it is substantially avoided that incoming radiation, that is emitted by regions of the atmosphere near the horizon, can reach the
tube 214. It is known that the atmospheric window is becoming less transmissive for radiation which travels through the atmosphere at a longer distance, such as radiation that is directed through the atmosphere near the horizon. Consequently, avoiding that that radiation can reach the particles improves the cooling efficiency. Further, the shape of thereflector portions 212 allows that the thermal radiation emitted from a lower portion of thetube 214 is directed to the atmosphere. - In addition, the
reflector portion 212 comprise projecting wall portions that, together with thetop cover 216, avoid heating of the particles and the fluid by a hot breeze that may in use pass over theelement 210. In a variation of this embodiment theelement 210 does not comprise thecover 216 and consequently the projecting wall portions of thereflector portions 212 will then alone have that function. - The cooling device according to any one of the described embodiments may also comprise a cover that may be suspended over a body portion or that is provided in the form of a cover layer that is in direct contact with the body portion. The cover is transmissive for the thermal radiation and protects the particles from hot breezes and other external influences that would reduce the cooling efficiency. The cover may also comprise a thermally insulating material. In one specific example, the cover comprises polyethylene and oxide or sulphide material, such as ZnS or iron oxide, which is positioned over the polyethylene material and also protects the polyethylene.
- It will be appreciated that the alternatively the
reflector portions 212 may have any other suitable shape, such as a parabolic dish and trough shape. - Referring now to
FIG. 15 , a further example of a cooling device in accordance with a specific embodiment of the present invention is now described.FIG. 15 (a) shows a cross-sectional view of a portion of acooling device 220 andFIG. 15 (b) shows a perspective view of a portion of thecooling device 220.FIG. 15 (c) shows a front view of the portion of thecooling device 220. - In this embodiment, the portion of the
cooling device 220 is arranged for mounting on a surface, such as an exterior surface of a building or structure. Thecooling device 220 comprisestubular portions 222 which are arranged for directing a fluid. Further, thecooling device 220 comprises a thermally insulatingmaterial 224 which is arranged to reduce exchange of thermal energy between the fluid and an exterior of the portion of thecooling device 220. The cooling device 120 also includeselements 226 for emission of thermal radiation. In this embodiment, the elements are provided in the form of coatings and are of the type as described above. - The
cooling device 220 comprises further tubular portions (not shown) that direct the fluid to an interior portion of the building or structure where the fluid is enabled to absorb thermal energy. A pump (not shown) then directs the fluid from the interior portion of the building or structure to the exterior portion or structure where theelements 226 receive the thermal energy from the fluid and emit the received thermal energy in the form of thermal radiation. Consequently, the fluid is cooled by theelements 226. The cooled fluid is then directed back into the interior of the building or structure and consequently results in cooling of the interior of the building or structure. - It is to be appreciated that the
cooling device 220 may be used to cool the interior of shipping containers, office buildings, domestic buildings or any other type of structure building of structure. The portion of thecooling device 220 typically is mounted to the exterior portion of the building or structure so that theelements 226 are enabled to emit thermal radiation towards the sky. -
FIGS. 16 and 17 show examples of portions of coolingdevices cooling devices cooling device 220. However, the coolingdevices tubular portions tubular portions 232 comprise elements for emission of thermal energy at top surfaces of thetubular portions 232, which are slightly angled so that the elements are enabled to emit thermal radiation towards the sky. - The
tubular portions 242 of thecooling device 242 also comprise elements for emission of thermal radiation at top surfaces of the tubular portions, but in this case, the tubular portions are not angled and are located at differing distances relative to awall 244 in a manner such that overshadowing by upper tubular portions is reduced. - The portions of the
cooling devices -
FIG. 18 (a) shows components of acooling device 250 according to an embodiment of the present invention andFIG. 18 (b) shows assembled components and a further component of thecooling device 250. Thecooling device 250 comprises ametallic body portion 252 and a lid-portion 254. The lid-portion 254 comprises an element for emission of thermal radiation as described above. Thebody portion 252 is shaped so that a cavity is formed in which an article may be positioned and which is closed by the lid-portion 254 and aclosure 256. Thebody portion 252 is positioned in a thermally insulating shell 158. - The cooling device further comprises a
concentrator portion 255 which is in use positioned over the lid-portion 254. In this example theconcentrator portion 255 has a plurality of projecting wall portions that are arranged so that a plurality of smaller and substantially square concentrator areas are formed. The projecting wall portions are formed from a material that has a low thermal emittance and is reflective for the thermal radiation emitted by the particles. The projecting wall portions are arranged so that in use the thermal radiation is predominantly directed towards the Sky in a direction away from the horizon. Further, the projecting wall portions are positioned so that, in use, incoming radiation from regions of the atmosphere, which are near the horizon, is substantially blocked off. - For example, the
cooling device 250 may be used for cooling food, liquids or any other matter that requires cooling. The articles are positioned in the cavity of thebody portion 252, which is then closed by the lid-portion 256. The cooling device then cools the article by absorbing thermal energy from the article, which is then emitted by the element of the lid-portion 254. -
FIG. 19 shows components of a cooling system in accordance with an embodiment of the present invention. Thecooling system 260 comprises of thecooling device 250. Further, thecooling system 260 comprises acooling container 262 having a lid-portion 264. In this embodiment thecooling device 250 is arranged to cool liquid-filledelements 266. For example, the liquid-filledelements 266 may be provided in the form of water-filled containers or bags. Thecooling device 250 is then used to cool the liquid-filledelements 266 so that ice is formed within theelements 266. Theelements 266 are then removed from thecooling device 250 and positioned in cavities of thefood container 262. Articles that require cooling, such as food items, may then be positioned in thecooling container 262 which is then closed by the lid-portion 264. - Referring now to
FIG. 20 , a cooling device in accordance with another embodiment of the present invention is now described.FIG. 20 shows acooling device 270 which compriseshousing portions housing portions wall portions housing portions portion housing portions housing portion 272 further comprises anelement 284 having particles for emission of thermal radiation within the atmospheric window wavelength range. Theelement 284 is of the type as described above. Further, thehousing portion 272 comprises a projectingwall portion 286 that is in this embodiment composed of a metallic material, such as aluminium, which has a relatively high thermal conductivity. - The
wall portion 286 is arranged to receive a container, such as a beverage can. The can is in use positioned within the projectingwall portion 286, which in turn is located within thehousing portion 274 when thehousing portions element 284 and thewall portion 286. Theelement 284 is arranged to cool thewall portion 286 and the can. Once the can has been cooled, thehousing portion 272 is separated from thehousing portion 274 in a manner such that the can remains in thehousing portion 274, which continues to provide thermal insulation. - In this embodiment, the
housing portion 272 is taller than the can and theelement 284 is positioned below an upper portion of thehousing portion 272 so that in use the likelihood of incidence of direct sunlight onto theelement 284 is reduced. Further, thehousing portion 272 is sufficiently tall so that in use incoming radiation from regions of the atmosphere, which are near the horizon, is substantially blocked off. Thehousing portion 272 also comprises aninterior wall portion 288 that is reflective for the thermal radiation emitted by the particles and is in use positioned so that thermal radiation emitted by the particles is directed in a direction towards Space and in a direction away from the horizon. Interior wall portions of thehousing portion 274 comprise a material that has low thermal emittance. - In use, the particles of the
element 284 absorb thermal energy from the can positioned at theelement 284 and within the projectingwall portion 286. The absorbed thermal energy is emitted in the form of thermal radiation having a wavelength range within the atmospheric wavelength range. Thehousing portions - It is to be appreciated, however, that the
cooling device 270 may be provided in various different forms. For example, thecooling device 270 may not necessarily be arranged to receive a can, but may alternatively be any other type of object. In addition, thehousing portions - Although the invention has been described with reference to particular examples, it will be appreciated by those skilled in the art that the cooling device may also be arranged to facilitate operation of another device so that a “hybrid” device is formed. The cooling device may be arranged to cool a fluid, especially during the night, which is then used to facilitate heat exchange of a refrigerator or an air-conditioning device. In one variation the cooling device is arranged to store the cooled for a period of time, for example during the night.
- Further, it is to be appreciated that in variations of the above-described embodiments the element of the cooling device may not necessarily comprise particles that are arranged for emission of thermal radiation having a wavelength within the atmospheric window wavelength range, but the particles may be replaced by at least one layer, such as a multi-layered structure, that is arranged for emission of thermal radiation having a wavelength within the atmospheric window wavelength range. The layers of the multi-layered structure typically have thicknesses that are selected so that in use ionic surface plasmon resonances are generated and the ionic surface plasmon resonances have a wavelength or wavelength range within the atmospheric window wavelength range. For example, the multi-layered structure may comprise SiO and SiC layers having a thickness of the order of 50-150 nm. Alternatively, the particles may be replaced by grains of a layer having a granular structure, such as a suitable SiC layer. In this case an average diameter of the grains is selected so that the layer is arranged for emission of thermal radiation having a wavelength within the atmospheric window wavelength range. The particles may also be replaced by a porous layer or a layer having a rough surface such as a suitable SiC layer. In this case an average pore spacing or a surface profile, respectively, is selected so that the layer is arranged for emission of thermal radiation having a wavelength within the atmospheric window wavelength range.
- In addition, it is to be appreciated that the element of the cooling device may comprise the above-described particles in addition to the above-described at least one layer. The at least one layer and the particles may both be arranged for emission of thermal radiation having a wavelength range within the atmospheric window wavelength range.
Claims (20)
1. An element for emission of thermal radiation, the element comprising a component arranged for receiving thermal energy and emitting at least a portion of the received thermal energy in the form of the thermal radiation, the thermal radiation predominantly having a wavelength or wavelength range within an atmospheric window wavelength range in which the atmosphere of the Earth has a reduced average absorption and emission compared with an average absorption and emission in an adjacent wavelength range whereby absorption by the element of radiation from the atmosphere is reduced.
2. The element of claim 1 wherein the atmospheric window wavelength range includes a minimum of the average absorption of the atmosphere of the Earth.
3. The element of claim 1 wherein the atmospheric window wavelength range is a wavelength range from 3 to 5 μm and/or from 7.9 μm to 13 μm.
4. The element of claim 1 wherein the element comprises particles arranged for receiving thermal energy and emitting at least a portion of the received thermal energy in the form of the thermal radiation.
5. The element of claim 1 wherein the element comprises a layer arranged for receiving thermal energy and emitting at least a portion of the received thermal energy in the form of the thermal radiation.
6. The element of claim 4 wherein the particles are distributed throughout the element and the element also comprises a material that is substantially transmissive for radiation having a wavelength within the atmospheric window range.
7. The element of claim 1 comprising a cover that is substantially transmissive for the thermal radiation and that is arranged for reduction of exchange of thermal energy by convection.
8. The element of any claim 7 comprising wall portions that define an interior space within which a medium that is to be cooled is in use located.
9. The element of claim 8 wherein the wall portions comprise a reflective material.
10. The element of claim 8 wherein at least some of the wall portions are thermally insulating.
11. The element of claim 1 comprising a structure that has projecting wall portions which are positioned so that, in use, incoming radiation from regions of the atmosphere, which are near the horizon, is substantially blocked off.
12. The element of claim 1 comprising a structure that has projecting wall portions that are reflective for the thermal radiation emitted by the component arranged for receiving thermal energy and emitting at least a portion of the received thermal energy in the form of the thermal radiation.
13. The element of claim 12 wherein the projecting wall portions are positioned so that in use the emitted thermal radiation is directed in a direction towards Space and in a direction away from the horizon.
14. The element of claim 1 any one of comprising a concentrator for concentrating radiation.
15. The element of claim 1 wherein the element is substantially transparent for visible light.
16. The element of claim 1 wherein the element comprises a substantially transparent polymeric material that comprises the component for emission of the thermal radiation and wherein the element is arranged so that in use at least a portion of the incoming near infrared radiation is absorbed and the resulting absorbed thermal energy is at least partially re-emitted in the form of thermal radiation by the component arranged for emission of radiation having a wavelength within the atmospheric window wavelength range.
17. The element of claim 1 wherein the element forms a part of an object.
18. A cooling system comprising thermally insulating wall portions and comprising the element of claims 1 wherein the cooling system is arranged for cooling an object that is positionable in, and removable from, an interior formed by the thermally insulating wall portion.
19. A cooling device for cooling a medium, the cooling device comprising an element for emission of thermal radiation, the element comprising particles arranged for receiving thermal energy and emitting at least a portion of the received thermal energy in the form of the thermal radiation, the thermal radiation predominantly having a wavelength or wavelength range within an atmospheric window wavelength range in which the atmosphere of the Earth has a reduced average absorption and emission compared with an average absorption and emission in an adjacent wavelength range whereby absorption by the element of radiation from the atmosphere is reduced.
20. The cooling device of claim 19 wherein the cooling device is arranged so that the medium is in indirect thermal contact with the element.
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2007202832A AU2007202832A1 (en) | 2007-06-19 | 2007-06-19 | A cooling material |
AU2007202832 | 2007-06-19 | ||
AU2007221733 | 2007-09-28 | ||
AU2007221733A AU2007221733A1 (en) | 2007-06-19 | 2007-09-28 | An element for emission of thermal radiation |
PCT/AU2008/000893 WO2008154693A1 (en) | 2007-06-19 | 2008-06-19 | A cooling device |
PCT/AU2008/000892 WO2008154692A1 (en) | 2007-06-19 | 2008-06-19 | An element for emission of thermal radiation |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
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PCT/AU2008/000892 Continuation-In-Part WO2008154692A1 (en) | 2007-06-19 | 2008-06-19 | An element for emission of thermal radiation |
Publications (1)
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US20100155043A1 true US20100155043A1 (en) | 2010-06-24 |
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US12/644,985 Abandoned US20100155043A1 (en) | 2007-06-19 | 2009-12-22 | Element for emission of thermal radiation |
Country Status (8)
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US (1) | US20100155043A1 (en) |
EP (1) | EP2162688A1 (en) |
KR (1) | KR20100062993A (en) |
CN (1) | CN101784845A (en) |
AU (1) | AU2007202832A1 (en) |
MX (1) | MX2009014110A (en) |
WO (2) | WO2008154693A1 (en) |
ZA (1) | ZA201000330B (en) |
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US20140131023A1 (en) * | 2012-11-15 | 2014-05-15 | The Board Of Trustees Of The Leland Stanford Junior University | Structures for radiative cooling |
US8739859B2 (en) | 2010-10-04 | 2014-06-03 | Toyota Motor Engineering & Manufacturing North America, Inc. | Reversible thermal rectifiers, temperature control systems and vehicles incorporating the same |
US20160268464A1 (en) * | 2013-11-13 | 2016-09-15 | The Board Of Trustees Of The Leland Stanford Junior University | Illumination and radiative cooling |
WO2017066795A3 (en) * | 2015-10-16 | 2017-05-18 | Stc. Unm | Microsphere-based coatings for radiative cooling under direct sunlight |
WO2017151514A1 (en) * | 2016-02-29 | 2017-09-08 | The Regents Of The University Of Colorado, A Body Corporate | Radiative cooling structures and systems |
WO2018027034A1 (en) * | 2016-08-03 | 2018-02-08 | Schott Gemtron Corp. | Oven having a dielectrically coated glass substrate that absorbs electromagnetic radiation and emits heat radiation |
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US10502505B2 (en) * | 2016-02-29 | 2019-12-10 | The Regents of the Univeristy of Colorado, a body corporate | Radiative cooling structures and systems |
CN110873870A (en) * | 2018-08-29 | 2020-03-10 | 罗伯特·博世有限公司 | Device and method for producing a device |
US10591652B2 (en) | 2015-11-20 | 2020-03-17 | Schott Gemtron Corp. | Multi-layer coated glass substrate |
JP2021521768A (en) * | 2018-04-16 | 2021-08-26 | ロミー エム. ファイン, | Manufacturing methods, structures, and uses for passive radiative cooling |
US11215407B2 (en) * | 2014-05-21 | 2022-01-04 | The Board Of Trustees Of The Leland Stanford Junior University | Radiative cooling with solar spectrum reflection |
US11274859B2 (en) * | 2017-12-11 | 2022-03-15 | University Of Kansas | Active daytime radiative cooling for air conditioning and refrigeration systems |
US11359841B2 (en) | 2019-04-17 | 2022-06-14 | SkyCool Systems, Inc. | Radiative cooling systems |
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JP2021521768A (en) * | 2018-04-16 | 2021-08-26 | ロミー エム. ファイン, | Manufacturing methods, structures, and uses for passive radiative cooling |
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Also Published As
Publication number | Publication date |
---|---|
CN101784845A (en) | 2010-07-21 |
AU2007202832A1 (en) | 2009-01-15 |
WO2008154692A1 (en) | 2008-12-24 |
WO2008154693A1 (en) | 2008-12-24 |
KR20100062993A (en) | 2010-06-10 |
ZA201000330B (en) | 2010-09-29 |
MX2009014110A (en) | 2010-08-02 |
EP2162688A1 (en) | 2010-03-17 |
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