EP4263452A1 - Passive radiant cooler - Google Patents
Passive radiant coolerInfo
- Publication number
- EP4263452A1 EP4263452A1 EP21830683.5A EP21830683A EP4263452A1 EP 4263452 A1 EP4263452 A1 EP 4263452A1 EP 21830683 A EP21830683 A EP 21830683A EP 4263452 A1 EP4263452 A1 EP 4263452A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- layer
- passive
- cooler
- emission layer
- polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
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- 125000001183 hydrocarbyl group Chemical group 0.000 claims description 17
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- HLLICFJUWSZHRJ-UHFFFAOYSA-N tioxidazole Chemical compound CCCOC1=CC=C2N=C(NC(=O)OC)SC2=C1 HLLICFJUWSZHRJ-UHFFFAOYSA-N 0.000 claims 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
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- 238000005259 measurement Methods 0.000 description 2
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- 125000003229 2-methylhexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
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Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/001—General methods for coating; Devices therefor
- C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/3405—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of organic materials
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/38—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal at least one coating being a coating of an organic material
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/42—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating of an organic material and at least one non-metal coating
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/21—Oxides
- C03C2217/212—TiO2
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/25—Metals
- C03C2217/251—Al, Cu, Mg or noble metals
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/25—Metals
- C03C2217/251—Al, Cu, Mg or noble metals
- C03C2217/252—Al
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/25—Metals
- C03C2217/251—Al, Cu, Mg or noble metals
- C03C2217/254—Noble metals
- C03C2217/256—Ag
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
Definitions
- the present invention relates to a passive radiant cooler for cooling objects, in particular buildings.
- Cooling of buildings today is performed using compression based cooling systems such as air conditioners. These cooling systems have a high energy consumption, dissipate energy in the form of heat to the building environment and require polluting coolants.
- compression-based active cooling systems provides for the use of passive radiant coolers (in Engi.: passive daytime radiative cooling). These passive radiant coolers can be arranged in the form of panels on a building roof or serve as facade panels for building cladding. Cooling by such a passive radiation cooler is based on the fact that the passive radiation cooler on the one hand reflects part of the electromagnetic spectrum of incident solar radiation in a wavelength range of approximately 0.3 pm to 2.5 pm and can also emit heat in the form of infrared radiation.
- the reflection of incoming solar radiation prevents the passive radiant cooler and thus the building from heating up.
- the emission of infrared radiation and the resulting release of heat leads to cooling of the surface of the building provided with the passive radiant cooler and consequently also to cooling of the building itself.
- the advantages of these passive radiant coolers are that they do not supply energy in the form of Electricity and no separate, environmentally harmful coolant required. In addition, these passive radiant coolers are largely maintenance-free.
- the infrared radiation emitted can be in an electromagnetic wavelength range which is within at least one so-called atmospheric transmission window.
- a first atmospheric transmission window lies, for example, in a wavelength range from approximately 8 pm to 13 pm.
- Such a passive radiant cooler is disclosed, for example, in US 2017 314 878 A1.
- This passive radiant cooler has a complex multi-layer system of stacked layers of different thicknesses, which alternately consist of magnesium fluoride (MgF?) or titanium dioxide (TiO?).
- MgF magnesium fluoride
- TiO titanium dioxide
- This multilayer system suppresses the absorption of sunlight over the entire solar spectrum and emits infrared radiation in a wavelength range that corresponds to that of the first atmospheric transmission window.
- This passive radiant cooler has the disadvantage that the production of the multi-layer system is complex and therefore expensive.
- WO 2017 151 514 A1 discloses a passive radiation cooler with an emission layer which contains a transparent polymer such as polymethylpentene and a large number of dielectric particles such as silicon dioxide (SiO?) embedded in the polymethylpentene.
- This emission layer is applied to an underlying metallic reflection layer.
- the dielectric particles emit infrared radiation in the wavelength range corresponding to that of the first atmospheric transmission window, allowing heat to be released into cold space.
- an additional protective layer made of polyethylene terephthalate is applied to the emission layer, which protects the emission layer from negative environmental influences.
- the present invention is therefore based on the object of specifying a passive radiant cooler which has improved long-term stability and is easier to manufacture.
- a passive radiation cooler having the features of independent patent claim 1 .
- Advantageous configurations of this passive radiant cooler can be found in the dependent patent claims 2 to 21 .
- a passive radiation cooler according to the invention comprises a layer structure which is applied to a substrate and comprises at least one reflection layer and at least one emission layer. This layer structure can be constructed in such a way that
- the emission layer is applied to the substrate and the reflection layer to the emission layer.
- the latter presupposes that the reflection layer applied to the emission layer is permeable at least to incident infrared radiation and/or infrared radiation emitted by the emission layer.
- this emission layer contains an at least partially crosslinked polymer and/or a ceramic material derived from this polymer, which consists of at least one crosslinkable, silicon-based material to form the emission layer
- Prepolymer are prepared, wherein the prepolymer is composed of at least one type of monomer units according to formula (I):
- A is selected from the group formed by the elements nitrogen, carbon and boron of the periodic table of elements and a carbodiimide group.
- the indices p1, p2, p3, p4, p5 and p6 are independently the numbers 0 or 1.
- m1 and m2 are independently the numbers 0 or 1.
- E is selected from the group formed by the elements oxygen and silicon of the periodic table of the elements.
- D is the element boron of the periodic table of elements.
- the groups R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , R 7 and R 8 are independently selected from the group formed by the element hydrogen of the periodic table of the elements, a linear saturated or branched saturated hydrocarbon group, a linear unsaturated or branched unsaturated hydrocarbon group, a functionalized linear or a functionalized branched hydrocarbon group, an unsaturated cyclic or a saturated cyclic hydrocarbon group, and a hydroxy group.
- prepolymer is to be understood as meaning a macromolecule that is formed from a plurality of individual monomer units and serves as the starting material or educt for the at least partially crosslinked polymer that is formed and/or the ceramic material derived from this polymer.
- the prepolymer can be composed either of a plurality of identical, ie one type of monomer units or of different, ie of several types of monomer units. In the latter case, the prepolymer is a so-called hybrid polymer whose different monomer units can have, for example, the same polymer backbone with groups R 1 , R 2 , R 3 , R 4 , R 5 and/or R 6 differing from one another.
- the prepolymer is in particular a polysilazane, a polysilylcarbodiimide, a polyborosilazane, a polyborosilane, a polyborosiloxane or a polycarbosilane, the monomer units of which have the general structural formulas listed in the table below:
- the emission layer can also be produced from two or more structurally different prepolymers according to formula (I).
- the at least partially crosslinked polymer is a copolymer.
- crosslinking means the formation of covalent polymer bridge bonds within a polymer chain or between two polymer chains, as a result of which a three-dimensional polymer network can be formed.
- the at least partial crosslinking of the prepolymer in the emission layer to be formed can be achieved either by passive drying of the prepolymer at room temperature or by thermal treatment at temperatures above room temperature over a defined period of time. This thermal treatment preferably takes place in a temperature range between 0.degree. C. and 2000.degree.
- the degree of crosslinking ie the number of covalent polymer bridge bonds formed within the polymer chains or between the polymer chains of the prepolymer, is dependent on the selected drying process. temperature, drying time and/or the molecular structure of the prepolymer.
- Crosslinking of the prepolymer during manufacture of the polymer can result in partial or even complete crosslinking of the prepolymer.
- the at least partially crosslinked polymer is produced from the crosslinkable, silicon-based prepolymer in the emission layer that forms, ie on the reflection layer or the substrate.
- the passive drying or the thermal treatment of the prepolymer is carried out in an oxygen, air or nitrogen atmosphere, then air, oxygen (O2) and/or nitrogen (N2) are stored in the emission layer.
- the oxygen (O2) can react with the prepolymer during the passive drying or the thermal treatment and be involved in the formation of the covalent polymer bridge bonds, so that Si-O-Si polymer bridge bonds can be formed, for example.
- the formation of the three-dimensional polymer network and thus the emission layer means that the emission layer is at least partially or even completely permeable or transparent to incident solar radiation, so that the solar radiation can penetrate the emission layer. At least a portion of the electromagnetic spectrum of the incident solar radiation is reflected on and/or within the reflection layer. As a result, the passive radiant cooler and the object on which the passive radiant cooler can be applied do not heat up unnecessarily.
- the wording “at least a portion of the electromagnetic spectrum of the incident solar radiation” means that not all incident solar radiation has to be reflected by the reflection layer.
- a portion of the electromagnetic spectrum of the incident solar radiation in the infrared radiation wavelength range that is not reflected by the reflection layer can be absorbed by the emission layer and re-emitted.
- the Si-A, AE, ED and/or D-Si bonds contained in a polymer backbone of the at least partially crosslinked polymer of the emission layer and/or the covalent polymer bridge bonds formed can be excited to vibrate by absorption of infrared radiation and/or by heat whereupon the vibrational energy is at least partially re-emitted as infrared radiation.
- This emission of Infrared radiation and reflection of solar radiation have the advantage that the passive radiant cooler can cool an object without the supply of energy.
- the layer structure of the passive radiant cooler is so stable that an additional protective layer is not absolutely necessary in order to ensure sufficient long-term stability against environmental influences. Further advantages consist in the simple construction of the layered structure of the passive radiant cooler and the large number of possible substrates or objects on which the passive radiant cooler can be applied for cooling.
- the thermal treatment of the crosslinkable, silicon-based prepolymer is carried out at high temperatures, for example at temperatures above 500° C.
- the previously described formation of the three-dimensional polymer network of the at least partially crosslinked polymer takes place first.
- an at least partially thermally induced decomposition of this polymer into the ceramic material derived from this polymer in Engi, polymer derived ceramics (abbr.: PDC)
- PDC polymer derived ceramics
- This decomposition can take place via molecular restructuring, condensation reactions and/or free-radical chain reactions of the at least partially crosslinked polymer.
- the polymer-derived ceramic material can have, for example, the composition of silicon carbide (SiC), silicon oxycarbide (SiO x C y ), silicon nitride (SiaN.*), silicon carbonitride (Si 3+ xN 4 Cx + y), or silicon oxynitride (SiO x N y ).
- SiC silicon carbide
- SiO x C y silicon nitride
- SiaN.* silicon carbonitride
- Si 3+ xN 4 Cx + y silicon oxynitride
- SiO x N y silicon oxynitride
- the emission layer containing this ceramic material is also transparent in the first spectral wavelength range.
- the reflection layer can be applied in a desired layer thickness to the substrate or the emission layer using an electron beam evaporator (e-beam deposition process), by sputtering, by chemical vapor deposition or by electroplating (Engl .: electroplating) are applied.
- the substrate or the substrate coated with the reflection layer can be coated with a prepolymer solution by dip coating using a dip coater.
- the substrate or the substrate coated with the reflective layer is slowly immersed in the prepolymer solution and, after a defined period of time, pulled out of the solution again at a defined speed.
- the thickness of the liquid prepolymer layer and thus also the thickness of the emission layer to be produced is dependent on the speed at which the substrate coated with the reflection layer is pulled out of the solution again.
- the emission layer by means of spray coating (Engl .: spray-coating), by a sol-gel process, by spin coating (Engl .: spin coating), plasma-enhanced chemical vapor deposition (Engl .: chemical vapor deposition) or by Squeegees (Engi .: doctor-blading) are applied to the substrate or the substrate coated with the reflection layer.
- the still liquid prepolymer layer is then either passive at room temperature, i.e. without external intervention, or by thermal treatment in a drying cabinet in a temperature range between 0 °C and 2000 °C, preferably between 25 °C and 600 °C and particularly preferably between 100 °C and 300 °C and dried over a defined period of time.
- the at least partial crosslinking of the still liquid prepolymer layer and/or the decomposition into the ceramic material by means of a treatment
- radiation in particular with vacuum ultraviolet radiation, ultraviolet radiation, visible radiation, infrared radiation or X-ray radiation;
- the passive radiation cooler according to the invention has the advantage over the multi-layer system known from the prior art that only two layers, namely the reflection layer and the emission layer, are required to prevent the reflection of a sub-range of the electromagnetic spectrum of the incident solar radiation with simultaneous emission of infrared radiation and the to allow the heat to be released as a result. This significantly simplifies the manufacturability of the passive radiant cooler and is less expensive.
- linear saturated or branched saturated hydrocarbon group includes hydrocarbon groups having one or more carbon atoms. These include, in particular, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, 2,2-dimethylpropyl, n-hexyl, isohexyl , 2-ethylhexyl, n-heptyl, iso-heptyl, n-octyl, iso-octyl, n-nonyl, n-decyl and the like.
- linear unsaturated or branched unsaturated hydrocarbon group includes unsaturated linear or unsaturated branched hydrocarbon groups having two or more carbon atoms, the hydrocarbon groups having at least one C-C double bond and/or at least one C-C triple bond.
- the term “functionalized linear or functionalized branched hydrocarbon group” encompasses functionalized linear or functionalized branched hydrocarbon groups having one or more carbon atoms and having at least one functional group.
- This functional group is selected from the group formed is composed of a hydroxy group (-OH), an amine group (-NR2) and the elements chlorine (-Cl), bromine (-Br) and iodine (-I). If the functionalized linear or functionalized branched hydrocarbon group has at least two or more carbon atoms, this hydrocarbon group can have at least one CC double bond and/or at least one CC triple bond.
- the term “unsaturated cyclic hydrocarbon group or a saturated cyclic hydrocarbon group” includes cyclic, saturated hydrocarbon groups or cyclic, unsaturated hydrocarbon groups having at least three carbon atoms, the cyclic, unsaturated hydrocarbon groups containing at least one C-C double bond. This includes cyclopropyl, cyclobutyl, cyclobutenyl, cyclopentyl, cyclopentenyl, phenyl, cyclohexyl, cyclohexenyl, aryl and the like. These unsaturated cyclic hydrocarbon groups and saturated cyclic hydrocarbon groups may also contain at least one of the aforementioned functional groups.
- this reflective layer can optimally reflect at least part of the electromagnetic spectrum of the incident solar radiation, this reflective layer can have a reflectivity of 0.60 to 1.00, preferably 0.90, in a first spectral wavelength range.
- R(A) is the spectral reflectance of the reflective layer or sample measured with a UV-VIS-NIR spectrometer became.
- This UV-VIS-NIR spectrometer is the "Cary 500" model from Agilent Technologies, Inc. from the USA. However, any other UV-VIS-NIR spectrometer can also be used for this measurement.
- T(A) corresponds to the transmission of the reflective layer, which has the value 0 since the reflective layer is impermeable or opaque.
- the first spectral wavelength range which corresponds to the portion of the electromagnetic spectrum of the incident solar radiation that can be reflected by the reflection layer, is between 200 nm and 3000 nm, preferably between 300 nm and 2500 nm. The reflection in this spectral wavelength range can prevent unnecessary heating of the passive radiant cooler can be prevented.
- the reflection layer is made of a metal selected from the group formed by silver (Ag), aluminum (Al), rhodium (Rh) and magnesium (Mg). Studies have shown that the metals rhodium, silver and magnesium have very good reflection properties.
- the reflection layer can also be made of a metal alloy such as steel, an aluminum-magnesium alloy or an aluminum-zinc alloy or of a metal oxide selected from the group formed by titanium dioxide in the form of TiO? and TiO x and barium sulfate (BaSOzi). Titanium dioxide in the form of TiO? and TiO x has the advantage that it can be brushed or sprayed onto the substrate like a wall paint.
- the reflection layer is formed from a polymer, in particular a microporous polymer.
- This polymer can be a polymer based on tetrafluoroethylene-hexafluoropropylene copolymer or polytetrafluoroethylene.
- the reflection layer can have a layer thickness in the range from 20 nm to 1 mm, preferably 50 nm to 2 ⁇ m, more preferably from 100 nm to 500 nm, particularly preferably 180 nm.
- This layer thickness can be determined with a profilometer or with a scanning electron microscope. Layer thicknesses used in the case of the present invention were determined using a Vecco Instruments Inc. Dektak 150 profilometer. This achieves optimal reflection and long-term stability of the reflective layer can be, the layer thickness can be selected depending on the material used for the reflection layer.
- the passive radiant cooler can also have a plurality of reflective layers of the same or different materials arranged one on top of the other (multilayer structures).
- the emission layer is arranged either on the uppermost of these reflection layers or between these reflection layers and the substrate.
- the layer thicknesses and/or a refractive index of the individual reflective layers arranged one above the other are preferably selected such that the reflective layers reflect the incident radiation in the first electromagnetic spectral wavelength range. This is preferably a so-called dielectric mirror.
- Such multilayer reflection layers can be formed from metal oxides or polymers, for example.
- An example of such multi-layer reflection layers is the commercially available 3MTM Enhanced Specular Reflector (abbr.: 3M ESR) from 3M, USA, which consists of several Ren polymer layers is formed. 3M ESR has very good reflection properties.
- the reflection layer contains at least one additive.
- This additive can be a pigment or a dye. If the reflective layer is made of a polymer, then the additive is embedded in the polymer. The embedding of this additive in the reflective layer causes a further part of the electromagnetic spectrum of the incident solar radiation to be absorbed by the pigment or dye and re-emitted, with the radiation emitted by the pigment or dye being in the visible region of the electromagnetic spectrum and is colored. This further part of the electromagnetic spectrum of the incident solar radiation is preferably in a wavelength range between 200 nm and 1000 nm.
- the embedding of the pigment or the dye has the advantage that the passive radiation cooler appears colored as a result. This allows the color of the passive radiant cooler to be matched to the color of the object to which it is applied.
- the emission layer has an emissivity in the range from 0.50 to 1.00, preferably from 0.70 to 0.95, particularly preferably 0.87, in a second electromagnetic spectral wavelength range.
- This second electromagnetic spectral wavelength range is preferably in the range from 7 pm to 14 pm, particularly preferably in the range from 8 pm to 13 pm.
- the emission layer can have an emissivity in the range from 0.20 to 1.00, preferably from 0.25 to 0.90, particularly preferably 0.30.
- the third electromagnetic spectral wavelength range is preferably in a range from 16 pm to 26 pm, particularly preferably in a range from 20 pm to 25 pm.
- the respective emissivity E in the second and third electromagnetic spectral wavelength range was calculated with the following equation (C):
- R(A) is the spectral reflectance of the reflective layer or sample measured with an FTIR spectrometer model “Vertex 80V” manufactured by Bruker GmbH of Germany or with an FTIR spectrometer with the model designation "Spectrum 400 Series" from the company PerkinElmer, Inc. from the USA was measured.
- T(A) corresponds to the transmission of the reflective layer, which has the value 0 since the reflective layer is impermeable or opaque.
- E(A)biackbody corresponds to the spectral intensity of a blackbody at a temperature of 300 K.
- the value 8 pm and the value 14 pm can be used for A2.
- the value 20 pm can be used for Ai and the value 25 pm for A2 in the aforementioned equation (C).
- the prepolymer according to formula (I) is a polysilazane.
- A is the element nitrogen and p1 is the number 1 in the formula (I).
- p2, m1 , p3, p4, m2, p5 and p6 are the number 0.
- This polysilazane is composed of one kind of monomer units represented by the following formula (IV):
- a in the formula (I) is the element nitrogen, p1 is the number
- the prepolymer can also be composed of two types of monomer units according to the following formulas (II) and (III):
- This prepolymer is a polysilazane in the form of a hybrid polymer.
- the monomer units according to the formulas (II) and (III) are preferably evenly distributed in this hybrid polymer, depending on their respective proportions y and z.
- a prepolymer which is made up of the two monomer units of the formulas (II) and (III) and in which y is 0.8 and z is 0.2 is available under the brand name “Durazane 1800” from Merck KGaA Germany available for purchase.
- the aforementioned polysilazanes having the monomer units represented by the formulas (II), (III), (IV), (V) and (VI) have a Si-N polymer backbone.
- the Si-N-Si bonds present in the polymer backbone can be excited to vibrate by absorption of infrared radiation and/or by heat, whereupon the vibrational energy is re-emitted, at least in part, as infrared radiation having a wavelength of about 11 pm.
- This infrared radiation lies in the first atmospheric transmission window and is therefore not or only hardly absorbed by the earth's atmosphere, but rather emitted directly into cold space.
- the passive radiant cooler can emit heat in the form of infrared radiation to cold space without the earth's atmosphere heating up.
- the polymer of the emission layer is made from a prepolymer with two types of monomer units according to the formulas (II) and (III), then covalent Si-CH2-CH2-Si polymer bridge bonds can form between the polysilazanes.
- These covalent Si-CH2-CH2-Si polymer bridge bonds can be excited to vibrate by absorption of infrared radiation, whereupon the vibrational energy is at least partially re-emitted as infrared radiation having a wavelength of approximately 12.5 pm.
- oxygen (O2) can react with the prepolymer and/or the polymer and participate in the formation of the polymer covalent bonds, leading to the formation of Si-O-Si covalent polymer bonds can come.
- These covalent Si-O-Si polymer bridge bonds can also be excited to vibrate by absorbing infrared radiation, whereupon the vibrational energy is at least partially re-emitted as infrared radiation in a wavelength range of approximately 7.5 pm to 10.5 pm. This infrared radiation is also in the first atmospheric transmission window and is thus emitted directly into cold space.
- the crosslinkable, silicon-based prepolymer can also be a polycarbosilane.
- polycarbosilanes Compared to polysiloxanes and polycarbosiloxanes, polycarbosilanes have the advantage that the polymer backbone of the polycarbosilanes, which consists of Si—C bonds, is significantly more stable to nucleophilic attack by water, for example, than the Si—O bonds of the polysiloxanes and polycarbosiloxanes.
- An emission layer that contains an at least partially crosslinked polymer that is produced from the polycarbosilane to form the emission layer is therefore significantly more stable than an emission layer based on a polysiloxane or polycarbosiloxane.
- polycarbosilanes have very good heat stability. Such polycarbosilanes can be produced as described in the following scientific publications:
- crosslinkable, silicon-based prepolymer can also be a polyborosiloxane.
- the production of such polyborosiloxanes is evident from US4824730A and US4405687A.
- the emission layer is microstructured.
- the emission layer can be microstructured by means of nano-embossing lithography, by stamping or by laser inscription.
- the above-mentioned crosslinking of the prepolymer during production of the polymer can result in a volume reduction of the emission layer.
- This reduction in volume which is also referred to as polymer shrinkage, is caused, among other things, by the reduction in the distance between adjacent polymer strands during crosslinking or the formation of covalent polymer bridge bonds. This shrinkage can lead to the formation of cracks in the emissive layer containing or formed from the polymer.
- the layer thickness of the emission layer should not exceed a critical layer thickness, depending on the polymer used.
- the emission layer contains at least one filler which is embedded in the at least partially crosslinked polymer.
- This filler is preferably selected from the group formed by silicon dioxide (SiO?), titanium dioxide (TiO?), barium sulfate (BaSCh), aluminum oxide (AI2O3), boron nitride (BN), polytetrafluoroethylene (PTFE), zirconium oxide (ZrO?) , magnesium oxide (MgO) and cerium oxide (CeC ).
- the emissive layer can also contain a mixture of these fillers.
- the filler can be in the form of nanoparticles and/or microparticles. In addition to increased long-term stability, these fillers can also impart other properties to the emission layer. For example, nanoparticles or microparticles made of silicon dioxide (SiO2), aluminum oxide (AI2O3) or titanium dioxide (TiÜ2) can also emit infrared radiation and thus contribute to passive cooling.
- the emission layer has a layer thickness in the range from 0.1 ⁇ m to 600 ⁇ m, preferably from 0.5 ⁇ m to 20.0 ⁇ m, more preferably from 1 ⁇ m to 10 ⁇ m, particularly preferably from 2 up to 6 pm.
- the filler described above can be added to the emission layer.
- a further advantage of the reflection layer and the emission layer is that they can be applied both to solid, inflexible surfaces such as the glass substrate or to flexible surfaces such as a film. This significantly increases the possible uses of the passive radiant cooler.
- the substrate is therefore a glass substrate, a silicon wafer, a flexible foil, in particular a metal foil or a ceramic foil, a metal sheet or a ceramic plate.
- the metal foil and the metal sheet can be made of aluminum or copper, for example. The use of the metal foil or metal sheet enables high thermal conductivity between the object on which the passive radiant cooler can be applied and the passive radiant cooler, whereby the heat can be dissipated by emitting infrared radiation.
- an intermediate layer can be arranged either between the substrate and the reflection layer or between the substrate and the emission layer.
- This intermediate layer can be made of silicon dioxide (SiO?), germanium (Ge), chromium (Cr), titanium (Ti), a transparent, conductive oxide, in particular zinc oxide (ZnO) and doped variants of zinc oxide (AI:ZnO, Ga:ZnO) , an inorganic oxide or the like.
- the intermediate layer can improve the adhesion of the reflection layer or the emission layer on the substrate and/or prevent a reaction and/or mixing of the material of the reflection layer or the emission layer with the material of the substrate.
- a metal foil made of aluminum is used as the substrate and a metallic reflection layer made of silver, for example, is applied to it, a mixture of silver and aluminum atoms can occur at the silver-aluminium interface, which can influence the reflection properties of the reflection layer.
- This mixing of silver and aluminum atoms can be prevented by an intermediate layer made of, for example, silicon dioxide.
- FIG. 1 shows a first exemplary embodiment of a passive radiation cooler in a schematic side view
- FIG. 2 shows a second exemplary embodiment of a passive radiation cooler in a schematic side view
- FIG. 3 shows the extinction of electromagnetic radiation in the range from 4,000 cm -1 to 500 cm' 1 through an emission layer
- FIG. 4 shows the absorption coefficient of the emission layer and the radiation power of solar radiation, each as a function of the wavelength
- FIG. 5 shows the atmospheric transmissivity and the emissivity of the first exemplary embodiment of the passive radiation cooler 1 from FIG. 1, each as a function of the wavelength;
- FIG. 6 shows a third exemplary embodiment of the passive radiation cooler in a schematic side view
- FIG. 7 shows a fourth exemplary embodiment of the passive radiation cooler in a schematic side view
- FIG. 8 shows a fifth exemplary embodiment of the passive radiation cooler in a schematic side view
- FIG. 9 shows a sixth exemplary embodiment of the passive radiation cooler in a schematic side view
- FIG. 10 shows a seventh exemplary embodiment of the passive radiation cooler in a schematic side view
- FIG. 11 shows an eighth exemplary embodiment of the passive radiation cooler in a schematic side view
- FIG. 12 shows a ninth exemplary embodiment of the passive radiant cooler in a schematic side view
- FIG. 13 shows a tenth exemplary embodiment of the passive radiation cooler in a schematic side view
- FIG. 14 shows a building in the form of a high-rise building in a schematic perspective representation
- FIG. 15 shows the cooling by a passive radiation cooler as part of an outdoor experiment.
- FIG. 1 shows a first exemplary embodiment of a passive radiation cooler 1 in a schematic side view.
- This radiation cooler 1 comprises a reflection layer 3 applied to a substrate 2 and an emission layer 4 applied to the reflection layer 3.
- the substrate 2 is a glass substrate.
- the reflection layer 3 applied to the glass substrate 2 is made of silver (Ag) and has a layer thickness of 300 nm.
- the emission layer 4 applied to the reflective layer 3 comprises a partially crosslinked polymer made of the crosslinkable silicon-based prepolymer composed of two kinds of monomer units represented by the formulas (II) and (III), where y is 0 ,8 and z is 0.2 in the formulas (II) and (III).
- This prepolymer in the form of a polysilazane can be purchased under the brand name “Durazane 1800” from Merck KGAA of Germany.
- the emission layer has a layer thickness of 3 ⁇ m.
- the procedure for producing the first exemplary embodiment of the passive radiant cooler 1 is as follows:
- the reflection layer 3 made of silver is applied to the glass substrate 2 with a layer thickness of 300 nm using an electron beam evaporator (DREVA LAB 450, VTD Vakuumtechnik Dresden GmbH, Germany).
- the crosslinkable, silicon-based prepolymer which is composed of two types of monomer units according to the formulas (II) and (III), wherein y is 0.8 and z is 0.2, with the Di-n-butyl ether solvent is mixed to form a liquid solution containing 50 percent by weight (wt%) of the prepolymer.
- the glass substrate 2 coated with the reflective layer 3 made of silver is coated with the solution produced in the second process step using a dip coater manufactured by the applicant.
- the glass substrate 2 coated with the reflective layer 3 made of silver is slowly immersed in a trough of the dip coater filled with the solution, which is coated with the reflective layer 3 silver-coated glass substrate 2 is held in the trough for a defined period of 10 seconds, so that the silver-coated glass substrate 2 with the reflective layer 3 is surrounded by the solution.
- the glass substrate 2 coated with the solution and the silver reflection layer 3 is slowly withdrawn from the trough of the dip coater at a speed of 0.5 m/min.
- the glass substrate coated with the liquid layer of the prepolymer and the reflection layer 3 is dried for one hour in an air atmosphere at a temperature of 180° C. in a drying cabinet.
- This thermal treatment leads to crosslinking of the prepolymer with simultaneous evaporation of the di-n-butyl ether solvent, as a result of which covalent polymer bridge bonds are formed between individual polysilazane molecules and also within a polysilazane molecule.
- FIG. 2 shows a second exemplary embodiment of the passive radiant cooler 1 in a schematic side view.
- This second exemplary embodiment of the passive radiant cooler 1 differs from the first exemplary embodiment from FIG. 1 in that the substrate 2 is an aluminum sheet (Alanod GmbH & Co. KG, Germany) with a thickness of 0.04 cm. This aluminum sheet has good thermal conductivity. Another difference is that the reflection layer 3 has a layer thickness of 230 nm.
- FIG. 3 shows a diagram in which the extinction of electromagnetic radiation in the range from 4,000 cm -1 to 500 cm -1 through the emission layer 4 is shown.
- This emission layer 4 comprises the at least partially wetted polymer made from the previously described polysilazane called "Durazane 1800" to form the emission layer 4 and applied directly to a substrate 2 in the form of a silicon wafer, i.e. without a reflection layer 3 arranged between the emission layer 4 and the substrate 2 (so-called PSZ coated silicon wafer).
- This layer structure serves to analyze the extinction properties of the emission layer 4 . Peaks or local maxima in the spectrum indicate the extinction that is caused, among other things, by absorption of infrared radiation by covalent bonds in the partially crosslinked polymer of emission layer 4 .
- This infrared radiation is absorbed either by a polymer backbone Si-N-Si of the polymer, by covalent polymer bonds Si-O-Si or by other covalent bonds NH, CH, Si-H and Si-CHa. This absorption of infrared radiation stimulates the respective bonds to vibrate. In Figure 3, each peak is labeled with the associated vibration.
- FIG. 4 shows a diagram in which the insolation power of solar radiation is shown as a function of the wavelength (dashed line; denoted as AM1.5G insolation power).
- the absorption coefficient of the second exemplary embodiment of the passive radiation cooler 1 from FIG. 2 is also shown as a function of the wavelength (solid line, referred to as absorption factor of PSZ-coated sample).
- the wavelength range between 300 nm and 2,500 nm shown in the diagram corresponds to the first electromagnetic spectral wavelength range.
- This diagram shows that the emission layer 4 absorbs solar radiation only to a very small extent in this first spectral wavelength range. This is because the emission layer 4 is transparent in this first spectral wave range.
- This diagram was recorded using a UV-VIS-NIR spectrometer (Cary 500, Agilent Technologies, Inc., USA).
- Figure 5 is a graph showing atmospheric transmissivity as a function of wavelength (dotted line labeled atmospheric transmissivity).
- the emissivity of the second exemplary embodiment of the passive radiation cooler 1 from FIG. 2 (continuous line, referred to as PSZ-coated substrate (with Ag reflector)) is shown in the same diagram as a function of the wavelength.
- the atmospheric transmissivity corresponds to the permeability of the earth's atmosphere for electromagnetic radiation lung.
- the earth's atmosphere has two atmospheric transmission windows.
- a first transmission window is in the second electromagnetic spectral wave range between 8 pm and 14 pm.
- the earth's atmosphere is also transparent to infrared radiation between approximately 16 pm and 25 pm.
- infrared radiation emitted by the emission layer 4 can be emitted into cold space without the earth's atmosphere being heated in the process.
- the emission layer 4 of the second exemplary embodiment of the passive radiation cooler 1 emits infrared radiation in the second electromagnetic spectral wavelength range between 8 pm and 14 pm and in a third electromagnetic spectral wavelength range between 20 pm and 25 pm.
- These second and third electromagnetic spectral wavelength ranges lie within the first and second atmospheric transmission windows, respectively.
- FIG. 6 shows a third exemplary embodiment of the passive radiant cooler 1.
- This third exemplary embodiment differs from the first exemplary embodiment of the passive radiant cooler 1 shown in FIG. 1 in that the emission layer 4 is microstructured. This microstructuring of the emission layer 4 was applied to the reflection layer 3 by stamping.
- FIG. 7 shows a fourth exemplary embodiment of the passive radiant cooler 1.
- This fourth exemplary embodiment differs from the second exemplary embodiment shown in FIG. 2 in that the emission layer 4 is formed from a partially crosslinked polymer made from a crosslinkable polycarbosilane.
- This emission layer 4 made of polycarbosilane has a layer thickness of 4 ⁇ m.
- FIG. 8 shows a fifth exemplary embodiment of the passive radiation cooler 1.
- This fifth exemplary embodiment differs from the fourth exemplary embodiment of the passive radiation cooler shown in FIG. 7 in that an intermediate layer 5 made of silicon oxide (SiO?) is arranged between the substrate 2 and the reflection layer 3.
- This intermediate layer 5 can prevent the mixing of silver and aluminum atoms at an interface between the substrate 2 and the reflection layer 3 .
- FIG. 9 shows a sixth exemplary embodiment of the passive radiation cooler 1 in a schematic side view.
- This sixth exemplary embodiment differs from the fifth exemplary embodiment of the passive radiant cooler 1 from FIG. 8 in that the emission layer 4 contains a filler 6 which is embedded in the partially crosslinked polymer and is in the form of silicon dioxide particles (SiC).
- silicon dioxide particles are in the form of microparticles with a diameter of 10 ⁇ m ⁇ 5 ⁇ m. They serve to prevent cracking in the emission layer 4 when the critical layer thickness is exceeded. Because of this, the emission layer 4 in the sixth exemplary embodiment has a greater layer thickness than the emission layer 4 shown in the second exemplary embodiment, namely 60 ⁇ m. These silicon dioxide particles are also able to emit heat in the form of infrared radiation.
- FIG. 10 shows a seventh exemplary embodiment of the passive radiant cooler 1 in a schematic side view.
- This seventh exemplary embodiment differs from the second exemplary embodiment of the passive radiation cooler 1 shown in FIG. 2 in that the reflection layer 5 is made of tetrafluoroethylene-hexafluoropropylene copolymer and contains an additive 7 that is a pigment.
- This pigment 7 is embedded in the reflection layer 5 in the form of nanoparticles.
- the embedding of this pigment 7 in the reflective layer 5 means that a portion of the first spectral wavelength range of the incident solar radiation is not reflected by the reflective layer 5, but rather is absorbed by the pigment.
- the pigment 7 emits electromagnetic radiation in the visible range of the electromagnetic spectrum, so that the reflection layer 5 is colored.
- the embedding of the pigment 7 in the reflection layer 5 has the advantage that the passive radiation cooler 1 appears colored as a result. This allows the color of the passive radiant cooler 1 to be matched to the color of the object on which it is to be attached.
- Figure 1 1 shows an eighth embodiment of the passive radiation cooler 1 in a schematic side view.
- This eighth exemplary embodiment differs from the first exemplary embodiment of the passive radiation cooler 1 shown in FIG. 1 in that the passive radiation cooler 1 has several re, stacked reflection layers 31, 32, 33, 34 comprises a dielectric material.
- the layer thicknesses of the individual reflection layers 31, 32, 33, 34 arranged one above the other are chosen such that the reflection layers 31, 32, 33, 34 reflect the incident radiation in the first electromagnetic spectral wavelength range.
- FIG. 12 shows a ninth exemplary embodiment of the passive radiant cooler 1 in a schematic side view.
- This ninth exemplary embodiment differs from the first exemplary embodiment of the passive radiant cooler 1 shown in FIG. 1 in that the substrate 2 is a metal sheet made of copper with a thickness of 0.2 cm.
- the reflection layer 2 includes titanium dioxide in the form of TiOs
- FIG. 13 shows a tenth exemplary embodiment of the passive radiation cooler 1 in a schematic side view. This tenth exemplary embodiment differs from the eighth exemplary embodiment of the passive radiation cooler 1 shown in FIG of the emission layer 4 are arranged.
- FIG. 14 shows a building 9 in the form of a high-rise building in a schematic perspective representation.
- the second exemplary embodiment of the passive radiation cooler 1 from Figure 2 is arranged on a building roof 10 of this building 9 and is used to cool the building 9.
- the cooling by the passive radiation cooler 1 is based on the passive radiation cooler 1 on the one hand absorbing incident solar radiation in the first electromagnetic spectral wavelength range reflect and additionally emit heat in the form of infrared radiation in the second and third spectral wavelength range.
- the reflection of incident solar radiation prevents the passive radiant cooler 1 and thereby the building 9 from heating up.
- the emission of infrared radiation and the resulting release of heat leads to a cooling of the building roof 10 provided with the passive radiant cooler 1 and consequently also to a cooling of the building 9 itself.
- FIG. 15 shows a diagram that shows the cooling of the building 9 as an example using an outdoor experiment.
- a simple uncovered Petri dish was covered with a thin polyethylene (PE) kitchen sheet 13 ⁇ m thick, which served as a convective barrier.
- the PE kitchen foil ensures limited convection losses between a sample to be examined placed in the Petri dish and the atmosphere outside the Petri dish.
- the sample inside the was fixed to a small styrofoam block with a small piece of double-sided tape to ensure minimal convection losses.
- the sample is the second exemplary embodiment of the passive radiant cooler 1 from FIG. 2.
- a first calibrated class A Pt100 sensor with a 4-wire configuration [Heraeus Nexensos M222, Kleinostheim, Germany] was used to carry out continuous outside temperature measurements , also called Pt100 temperature sensor.
- the first Pt100 sensor was placed between the styrofoam block and the sample.
- some thermal compound was applied between the first Pt100 sensor and the sample.
- the ambient temperature was measured by a second Pt100 sensor that was placed freely hanging next to the sample in the Petri dish.
- the Pt100 sensors were connected to an Agilent 34972A LXI data acquisition unit, which reads the temperature every 5 seconds.
- the data acquisition unit was connected to a laptop running a Python script to collect and store the measured temperature from all sensors.
- the petri dish was then secured to an inverted glass beaker, ie, to the bottom of the inverted glass beaker, with double-sided adhesive tapes to keep it off any surface.
- the petri dish was arranged so that its bottom was oriented parallel to the sky, without any solar tracking, shielding, or radiating fixtures.
- Several measurements were carried out on a building roof of the German Aerospace Center (DLR), Institute for Networked Energy Systems (N53°09'05.1 "E8°10'01 .1 ”) on October 10, 2020. A clean and clear sky day was chosen for the continuous temperature measurements.
- DLR German Aerospace Center
- N53°09'05.1 Institute for Networked Energy Systems
- the global horizontal solar irradiance was collected by a pyranometer from DLR's permanent weather station, located 166 m from where we used the present open-air experiment was carried out.
- the diagram from FIG. 15 shows the ambient temperature measured by the second Pt1 OO sensor as a function of the time during the field experiment (thick dotted line, denoted as ambient temperature).
- this diagram shows the sample temperature of the sample measured by the first Pt100 sensor as a function of the time during the field experiment (dash-dot line, referred to as sample temperature).
- the diagram shows the irradiance of the solar radiation as a function of time during the field experiment (thin dotted line, denoted as solar irradiance).
- the difference between the ambient temperature and the sample temperature is also shown in the diagram as a function of the time during the field experiment (solid line, referred to as temperature difference) and makes it clear that the sample, i.e. the second exemplary embodiment of the passive radiant cooler 1 from Figure 2, has an average temperature of 5 °C colder than the surrounding area. At its maximum, the sample, ie the second exemplary embodiment of the passive radiation cooler 1 from FIG. 2, had a maximum temperature of 6.8° C. lower than the environment.
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Abstract
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DE102020134437.6A DE102020134437A1 (en) | 2020-12-21 | 2020-12-21 | Passive radiant cooler |
PCT/EP2021/085509 WO2022136001A1 (en) | 2020-12-21 | 2021-12-13 | Passive radiant cooler |
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EP (1) | EP4263452A1 (en) |
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DE3213247A1 (en) | 1981-04-13 | 1982-12-02 | Showa Electric Wire & Cable Co., Ltd., Kawasaki, Kanagawa | POLYBORSILOXANE COATING AND INSULATED ELECTRICAL LADDER |
KR900009035B1 (en) | 1986-09-19 | 1990-12-17 | 마쯔시다덴기산교 가부시기가이샤 | Coating composition |
CN103180257B (en) * | 2010-11-17 | 2016-02-17 | 3M创新有限公司 | Reduce the electromigratory method of silver and goods prepared therefrom |
US9709349B2 (en) | 2012-11-15 | 2017-07-18 | The Board Of Trustees Of The Leland Stanford Junior University | Structures for radiative cooling |
FR3045034B1 (en) * | 2015-12-15 | 2019-06-07 | Saint-Gobain Glass France | THERMAL CONTROL GLAZING WITH PROTECTIVE POLYMER FILM |
AU2017225866B2 (en) | 2016-02-29 | 2021-10-07 | The Regents Of The University Of Colorado, A Body Corporate | Radiative cooling structures and systems |
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