WO2021229165A1 - Matériau bas émissif comprenant une couche épaisse à base d'oxyde de silicium - Google Patents
Matériau bas émissif comprenant une couche épaisse à base d'oxyde de silicium Download PDFInfo
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- WO2021229165A1 WO2021229165A1 PCT/FR2021/050786 FR2021050786W WO2021229165A1 WO 2021229165 A1 WO2021229165 A1 WO 2021229165A1 FR 2021050786 W FR2021050786 W FR 2021050786W WO 2021229165 A1 WO2021229165 A1 WO 2021229165A1
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- 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
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- 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
- C03C17/3602—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 the metal being present as a layer
- C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
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- 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
- C03C17/3602—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 the metal being present as a layer
- C03C17/3636—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 the metal being present as a layer one layer at least containing silicon, hydrogenated silicon or a silicide
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- 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
- C03C17/3602—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 the metal being present as a layer
- C03C17/3644—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 the metal being present as a layer the metal being silver
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- 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
- C03C17/3602—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 the metal being present as a layer
- C03C17/3652—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 the metal being present as a layer the coating stack containing at least one sacrificial layer to protect the metal from oxidation
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- 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
- C03C17/3602—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 the metal being present as a layer
- C03C17/3657—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 the metal being present as a layer the multilayer coating having optical properties
- C03C17/366—Low-emissivity or solar control coatings
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- 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
- C03C17/3602—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 the metal being present as a layer
- C03C17/3681—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 the metal being present as a layer the multilayer coating being used in glazing, e.g. windows or windscreens
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
- C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/10—Glass or silica
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
- C23C14/185—Metallic material, boron or silicon on other inorganic substrates by cathodic sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/34—Sputtering
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
- C23C14/352—Sputtering by application of a magnetic field, e.g. magnetron sputtering using more than one target
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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
- F25D23/00—General constructional features
- F25D23/06—Walls
- F25D23/065—Details
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- 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
- C03C2217/90—Other aspects of coatings
- C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
- C03C2217/944—Layers comprising zinc oxide
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- 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
- C03C2218/00—Methods for coating glass
- C03C2218/10—Deposition methods
- C03C2218/15—Deposition methods from the vapour phase
- C03C2218/154—Deposition methods from the vapour phase by sputtering
- C03C2218/156—Deposition methods from the vapour phase by sputtering by magnetron sputtering
Definitions
- Low emissivity material comprising a thick layer based on silicon oxide
- the invention relates to a material comprising a transparent substrate coated with a stack comprising a functional silver-based metal layer.
- the invention also relates to glazing comprising these materials as well as the use of such materials for manufacturing glazing.
- Functional silver-based metallic layers have advantageous electrical conduction and infrared (IR) radiation reflection properties, hence their use in so-called “solar control” glazing aimed at reducing the amount of incoming solar energy and / or in so-called “low-emissive” glazing aimed at reducing the amount of energy dissipated to the outside of a building, a vehicle or a device.
- IR infrared
- dielectric coatings are deposited between coatings based on dielectric materials generally comprising several dielectric layers (hereinafter “dielectric coatings") making it possible to adjust the optical properties of the stack. These dielectric layers also help protect the silver layer from chemical or mechanical attack.
- the invention relates very particularly to a material used to manufacture a glazing used as a component of a heating or cooling device.
- a heating device comprises an enclosure delimited by one or more walls and heating means so as to allow the enclosure to be heated to a high temperature.
- the heating devices can in particular be chosen from ovens, fireplaces, stoves, etc.
- the heating means are distinct from the stack of thin layers. Heated automotive glazing, the stack of which serves as a heating element that does not correspond to a heating device according to the invention.
- a refrigerating device comprises an enclosure delimited by one or more walls and means making it possible to cool the enclosure to a temperature below the normal temperature (20 ° C).
- the refrigerating devices can in particular be chosen from:
- the glazing used as constituent elements of a refrigerating device of the freezer type (negative cold) are generally monolithic glasses.
- the glazing used as component parts of a refrigerator-type heating or cooling device are generally multiple glazing.
- a multiple glazing comprises at least two substrates kept at a distance so as to delimit a space.
- the faces of the glazing are designated from the inside of the heater or cooler and by numbering the faces of the substrates from the inside (inner face) to the outside (outer face) of the heater or cooler.
- the different substrates are generally arranged side by side in an open space.
- the various substrates are generally interconnected so as to form an airtight cavity between two substrates.
- These glazing help maintain a set temperature inside the device while keeping the exterior surface of the glazing normally cool to the touch for the protection and comfort of users.
- Coatings comprising functional silver-based metallic layers (or silver layers) are the most effective for reducing the emissivity of glazing while preserving optical and aesthetic qualities. These coatings provide better user protection, lower energy consumption and greater comfort of use.
- This phenomenon is accentuated when these glazings are used in heating devices, especially when they are subjected to long and repeated heat treatment cycles at high temperatures in a humid environment.
- This coating comprises a single functional silver-based layer protected by an undercoat and a blocking overlay.
- the dielectric coatings surrounding the functional layer essentially consist of oxide-based layers.
- This coating is particularly suitable for refrigeration and heating device applications because it has both:
- the excellent chemical durability may be due to the nature of its dielectrics which are primarily oxides.
- the materials in order to be used in heating or cooling devices, the materials must undergo a high temperature heat treatment such as quenching.
- a high temperature heat treatment such as quenching.
- the functional coating developed by the applicant remains sensitive to overheating, both during its quenching and during its potential use in a heating device. This sensitivity to heat treatment could be due to the nature of its dielectrics, which are composed exclusively of oxides.
- the silver-based functional layer is unstable and dewets during heat treatment at elevated temperature. This dewetting is characterized by the appearance of holes in the silver layer. These holes are called dendritic because of their shape often branched. These holes in the silver layer have two very damaging consequences for the product.
- the product becomes blurry (after quenching, since the edge of the holes in the silver layer diffuses the light).
- this blur corresponds to the appearance of a more or less milky veil.
- This blur can be inhomogeneous because it can reveal defects on the surface of the glass (traces of drying, marks of suction cups handling the glass, etc.).
- the product's emissivity is severely degraded by these holes. Indeed, we can show that in each hole, it is no longer the emissivity of the silver layer (3%, for example) that is to be taken into account, but that of the glass (close to 89%). Thus, if the holes represent only 1% of the area, the emissivity is already degraded by about 1.8 points, going from 3% to almost 5%.
- the solution of the invention consists in placing an intermediate layer based on silicon oxide with a thickness greater than 12 nm between the glass substrate and the first dielectric layer of the stack.
- the solution of the invention has the significant advantage that it does not require any other modification of the stack already developed by the applicant.
- the use of this layer of optical index close to glass does not then require any modification of the stack already developed, because these layers are optically neutral.
- Light interference at the glass / Si02 interface is negligible.
- the use of a 14 nm layer of silicon oxide in a functional coating has an 8 times greater resistance to heating at a temperature of 450 ° C than that of the same functional coating without a layer of silicon oxide.
- the term 8 times greater resistance is understood to mean that the material provided with a stack comprising a 14 nm layer of silicon oxide can be heated at the same temperature for a time 8 times longer than the same stack without an oxide layer. silicon, before exhibiting the same degree of degradation.
- the Applicant has discovered that the use of a silicon oxide layer allows the degradation of the functional coating to be delayed. However, for this degradation delay to be sufficient not to cause degradation:
- a minimum thickness of silicon oxide is required, and in particular a thickness of at least 12 nm.
- the time / temperature pair during heating becomes compatible with a transformation of the glass, such as toughening or bending, without blurring or degradation of emissivity.
- the glazing comprising a functional coating without a thick silicon oxide layer in contact with the substrate shows a haze at time and temperature parameters very close to those necessary to obtain flatness, fragmentation, and an acceptable form.
- Industrial tools used for bending and / or soaking substrates including coatings functionalities may also exhibit variability. A material must therefore be robust enough to accept these process variabilities. The materials of the invention have this additional strength.
- the observed degradation delay severe tens of seconds at 705 ° C is sufficient to ensure that the materials will not be degraded, regardless of the variability of the quenching process.
- the invention therefore relates to a material comprising a transparent substrate coated with a stack comprising at least one functional metallic layer based on silver and at least two dielectric coatings, each dielectric coating comprising at least one dielectric layer, so that each functional metal layer is placed between two dielectric coatings, characterized in that the stack comprises a silicon oxide-based layer with a thickness greater than or equal to 12 nm located directly in contact with the substrate.
- the invention also relates to:
- a glazing comprising a material according to the invention mounted on a device, on a vehicle, in particular a motor vehicle or on a building, and
- glazing according to the invention as solar control glazing and / or low emissivity for the building or vehicles
- the invention also relates to a heating or cooling device comprising heating or cooling means and an enclosure delimited by one or more walls, at least one wall of which comprises at least one glazing comprising a material according to the invention.
- the invention is particularly suitable as a freezer-type refrigerating device.
- the glazing can be made of the material (monolithic glazing) with preferably the stack located on the face of the substrate in contact with the enclosure.
- the glazing of the invention is also suitable in all applications requiring the use of a stack comprising layers of silver for which the resistance to repeated heat treatments and to corrosion in a hot and cold humid environment are key parameters. .
- the invention also relates to the use of glazing as a constituent element of a cooling device, of a heating device or of a fire door, the glazing comprising a material according to the invention.
- the glazing can be chosen from multiple glazing comprising at least two transparent substrates.
- the glazing can also consist solely of the material according to the invention. In this case, it has only one substrate. It is then a simple glazing or monolithic glazing.
- the substrate according to the invention is considered to be laid horizontally.
- the stack of thin layers is deposited on top of the substrate.
- the meaning of the expressions “above” and “below” and “lower” and “upper” should be considered in relation to this orientation.
- the expressions “above” and “below” do not necessarily mean that two layers and / or coatings are placed in contact with one another.
- a layer is deposited "in contact” with another layer or a coating, this means that there cannot be one (or more) layer (s) interposed between these. two coats (or coat and coating).
- the material that is, the transparent substrate coated with the stack, is intended to undergo heat treatment at elevated temperature. Therefore, the stack and the substrate have preferably been subjected to heat treatment at an elevated temperature such as quenching, annealing or bending.
- the stack is deposited by cathodic sputtering assisted by a magnetic field (magnetron process). According to this advantageous embodiment, all the layers of the stack are deposited by cathodic sputtering assisted by a magnetic field.
- the material and the glazing of the invention are transparent, that is to say not opaque. According to an advantageous embodiment, the material or the glazing according to the invention has a light transmission greater than 35%, greater than 40%, greater than 45% or greater than 50%.
- the thicknesses mentioned in this document are physical thicknesses and the layers are thin layers.
- the term “thin layer” is understood to mean a layer having a thickness of between 0.1 nm and 100 micrometers.
- the stack comprises a silicon oxide-based layer greater than 12 nm thick located directly in contact with the substrate.
- the silicon oxide-based layer has a thickness:
- the silicon oxide-based layer can include other elements. These elements can be selected from aluminum, boron, titanium, and zirconium. Preferably, the elements are selected from aluminum, boron and titanium.
- the silicon oxide-based layer may comprise at least 60%, at least 65%, at least 70% at least 75.0%, at least 80% or at least 90% by mass of silicon relative to the mass of all the elements constituting the silicon oxide-based layer other than oxygen.
- the silicon oxide-based layer comprises at most 35%, at most 30%, at most 20% or at most 10% by mass of elements other than silicon relative to the mass of all elements. constituting the layer based on silicon oxide other than oxygen.
- the layer based on silicon oxide may comprise at least 2%, at least 5.0% or at least 8% by mass of aluminum relative to the mass of all the elements constituting the layer based on silicon oxide. silicon other than oxygen.
- the amounts of oxygen and nitrogen in a layer are determined in atomic percentages relative to the total amounts of oxygen and nitrogen in the layer in question.
- the layers based on silicon oxide essentially comprise oxygen and very little nitrogen.
- Silicon oxide-based layers include greater than 90%, greater than 95% or 100% atomic percent oxygen to oxygen and nitrogen in the silicon oxide based layer.
- the silicon oxide-based layer can be obtained:
- the functional silver-based metal layer before or after heat treatment, comprises at least 95.0%, preferably at least 96.5% and better still at least 98.0% by mass of silver relative to the mass of the functional layer.
- the functional silver-based metal layer before heat treatment comprises less than 5% or less than 1.0% by weight of metals other than silver based on the weight of the functional metal layer based on silver. 'money.
- Functional silver-based layers range in thickness from 5 to 30nm, 5 to 25nm, or 7 to 16nm.
- the stack comprises a single functional layer.
- the stack comprises in this case a single functional layer and two dielectric coatings comprising at least one dielectric layer, so that the functional layer is disposed between two dielectric coatings.
- the stack may include at least two metallic silver-based functional layers and at least three dielectric coatings comprising at least one dielectric layer, such that each functional layer is disposed between two dielectric coatings.
- the stack is located on at least one side of the transparent substrate.
- the stack may include blocking layers located below and / or above the functional silver-based metal layer.
- the stack may include at least one blocking layer, the function of which is to protect the silver layers by preventing possible degradation linked to the deposition of a dielectric coating or linked to a heat treatment.
- These blocking layers are preferably located in contact with the functional silver-based metal layers.
- the stack may comprise at least one blocking layer, located below and (directly) in contact with a functional silver-based metal layer (under blocking layer) and / or at least one blocking layer located above and (directly) in contact with a functional silver-based metal layer (on blocking layer).
- a blocking layer on top of a functional silver-based metal layer is called a blocking overcoat.
- a blocking layer below a functional silver-based metal layer is called a blocking sublayer.
- the blocking layers are chosen from metal layers based on a metal or a metal alloy, metal nitride layers, metal oxide layers and metal oxynitride layers of one or more elements chosen from titanium, nickel, chromium, tantalum and niobium such as Ti, TiN, TiOx, Nb, NbN, NbOx, Ni, NiN, NiOx, Cr, CrN, CrOx, NiCr, NiCrN, NiCrOx.
- these blocking layers When these blocking layers are deposited in metallic, nitrided or oxynitrided form, these layers may undergo partial or total oxidation depending on their thickness and the nature of the layers which surround them, for example, at the time of deposition of the next layer or by oxidation. in contact with the underlying layer.
- the blocking layers can be chosen from metallic layers, in particular of an alloy of nickel and chromium (NiCr) or of titanium.
- the blocking layers are metallic layers based on nickel.
- the nickel-based metal blocking layers can comprise, (before heat treatment), at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99% or 100% by mass of nickel relative to the mass of the metallic base layer nickel.
- the nickel-based metal layers can be chosen from:
- Nickel alloy metal layers can be nickel chromium alloy based.
- Each blocking layer has a thickness between 0.1 and 5.0 nm.
- the thickness of these blocking layers can be:
- dielectric coating within the meaning of the present invention, it should be understood that there may be a single layer or several layers of different materials inside the coating.
- a “dielectric coating” according to the invention mainly comprises dielectric layers. However, according to the invention these coatings can also comprise layers of another nature, in particular absorbent layers, for example metallic.
- dielectric layer within the meaning of the present invention, it should be understood that from the point of view of its nature, the material is “non-metallic", that is to say is not a metal. In the context of the invention, this term denotes a material exhibiting an n / k ratio over the entire visible wavelength range (from 380 nm to 780 nm) equal to or greater than 5.
- n denotes the index of actual refraction of the material at a given wavelength and k represents the imaginary part of the refractive index at a given wavelength; the ratio n / k being calculated at a given wavelength identical for n and for k.
- the thickness of a dielectric coating corresponds to the sum of the thicknesses of the layers constituting it.
- the dielectric coatings have a thickness greater than 15 nm, preferably between 15 and 200 nm.
- They have a thickness greater than 2 nm, preferably between 2 and 100 nm.
- the silver-based functional layer is located above a dielectric layer called a stabilizing or wetting layer made of a material capable of stabilizing the interface with the functional layer.
- a stabilizing or wetting layer made of a material capable of stabilizing the interface with the functional layer.
- These layers are generally zinc oxide based.
- the silver-based functional layer is located below a dielectric layer called a stabilizing or wetting layer made of a material capable of stabilizing the interface with the functional layer.
- a stabilizing or wetting layer made of a material capable of stabilizing the interface with the functional layer.
- These layers are generally zinc oxide based.
- the zinc oxide-based layers may comprise, at least 80%, at least 90% by mass of zinc relative to the total mass of all the elements constituting the zinc oxide-based layer, excluding oxygen and nitrogen.
- the zinc oxide-based layers can comprise one or more elements chosen from aluminum, titanium, niobium, zirconium, magnesium, copper, silver, gold, silicon, molybdenum, nickel, chromium, platinum, indium, tin and hafnium, preferably aluminum.
- Zinc oxide-based layers can optionally be doped with at least one other element, such as aluminum.
- the zinc oxide-based layer is not nitrided, however traces may exist.
- the zinc oxide-based layer comprises, in increasing order of preference, at least 80%, at least 90%, at least 95%, at least 98%, at least 100%, by weight of oxygen relative to the total mass of oxygen.
- the dielectric coating located between the substrate and the first functional metallic layer and / or one or each dielectric coating located above the first functional silver-based layer located comprises a zinc oxide-based layer comprising at least 80 % by mass of zinc relative to the mass of all elements other than oxygen.
- each dielectric coating comprises a zinc oxide-based layer comprising at least 80% by mass of zinc relative to the mass of all elements other than oxygen.
- the dielectric coating located directly below the functional metal layer based on silver comprises at least one dielectric layer based on zinc oxide, optionally doped with at least one other element, such as aluminum.
- the metallic functional layer deposited on top of a zinc oxide-based layer is either directly in contact or separated by a blocking layer.
- the dielectric coating closest to the substrate is called the bottom coating and the dielectric coating farthest from the substrate is called the top coating.
- Stacks with more than one silver layer also include intermediate dielectric coatings located between the bottom and top coatings.
- the lower or intermediate coatings comprise a dielectric layer based on zinc oxide located below and directly in contact with a metallic layer based on silver or separated from this layer by a blocking sublayer.
- the dielectric coating located directly above the functional metal layer based on silver comprises at least one dielectric layer based on zinc oxide, optionally doped with at least one other element, such as aluminum.
- the metallic functional layer deposited below a zinc oxide-based layer is either directly in contact or separated by a blocking layer.
- the intermediate or top coatings comprise a zinc oxide-based dielectric layer located above and directly in contact with the silver-based metallic layer or separated from this layer by a blocking overlay.
- Zinc oxide layers have a thickness:
- the dielectric layers can have a barrier function.
- barrier layer is understood to mean a layer made of a material capable of forming a barrier to the diffusion of oxygen and water at high temperature, originating from the ambient atmosphere or from the substrate. transparent, towards the functional layer.
- Such dielectric layers are chosen from the layers:
- oxides such as Si02, nitrides such as silicon nitride Si3N4 and aluminum nitrides AIN, and oxynitrides SiOxNy, optionally doped using at least one other element,
- the material comprises one or more layers based on zinc oxide and tin.
- Zinc and tin oxide layers contain at least 20% by mass of tin based on the total mass of zinc and tin.
- the layer based on zinc and tin oxide comprises, with respect to the total mass of zinc and tin, at least 20%, at least 30%, at least 40%, at least 50%, at least 60% or at least 80% by mass of tin.
- the zinc-tin oxide layer comprises 40-80% by weight of tin based on the total weight of zinc and tin.
- the zinc-tin oxide-based layer has a thickness:
- the dielectric coating located between the substrate and the first functional metal layer and / or each dielectric coating located above the first functional silver-based layer located comprises a zinc oxide-based layer and tin comprising at less 20% by mass of tin relative to the total mass of zinc and tin.
- Each dielectric coating may include a zinc-tin oxide-based layer comprising at least 20% by mass of tin based on the total mass of zinc and tin.
- the sum of the thicknesses of all the zinc and tin oxide-based layers located in the dielectric coating located between the substrate and the first silver layer is greater than 30%, greater than 40%, greater 50% or greater than 60% of the total thickness of the dielectric coating.
- the sum of the thicknesses of all the zinc and tin oxide based layers located in the dielectric coating located above a functional silver based layer is greater than 50%, greater than 60 %, greater than 70% or greater than 75% of the total thickness of the dielectric coating.
- the sum of the thicknesses of all the oxide-based layers present in the dielectric coating located between the substrate and the first functional metal layer and / or in each dielectric coating located above the first functional layer based on The silver is greater than 50%, greater than 60%, greater than 70%, greater than 80% or greater than 90% of the total thickness of the dielectric coating.
- the dielectric coating located between the substrate and the first functional metal layer and / or one or each dielectric coating located above the first silver-based functional layer may consist of an oxide layer only.
- the stack comprises at least one dielectric layer based on zinc oxide and one layer based on zinc oxide and tin.
- the dielectric coating located directly below the functional silver-based metal layer has at least one zinc oxide-based dielectric layer and one zinc-tin oxide-based layer.
- one or each dielectric coating located above the functional metal layer based on silver comprises at least one dielectric layer based on zinc oxide and one layer based on zinc oxide and tin.
- each dielectric coating comprises at least one dielectric layer based on zinc oxide and one layer based on zinc oxide and tin.
- the stack of thin layers may optionally include a protective layer.
- the protective layer is preferably the last layer of the stack, that is to say the layer furthest from the substrate coated with the stack (before heat treatment).
- the dielectric coating furthest from the substrate may include a protective layer. These layers generally have a thickness of between 0.5 and 10 nm, preferably 1 and 5 nm.
- This protective layer can be chosen from a layer based on titanium, zirconium, hafnium, silicon, zinc and / or tin and their mixture, this or these metals being in metallic, oxidized or nitrided form.
- the protective layer is based on zirconium and / or titanium oxide, preferably based on zirconium oxide, titanium oxide or titanium and zirconium oxide.
- the stack comprises:
- a dielectric coating located above the functional silver-based metal layer optionally comprising a protective layer.
- the stack comprises:
- a dielectric coating located below the functional silver-based metallic layer comprising the silicon oxide-based layer, a zinc-tin oxide-based layer, an oxide-based layer zinc,
- a dielectric coating located above the functional silver-based metal layer comprising a zinc oxide-based layer, a zinc-tin oxide-based layer and optionally a protective layer.
- the substrate coated with the stack or the stack only may be intended to undergo a heat treatment.
- the substrate coated with the stack may be curved and / or soaked.
- the present invention also relates to the untreated heat treated coated substrate.
- the stack may not have undergone a heat treatment at a temperature above 500 ° C, preferably 300 ° C.
- the stack may have undergone heat treatment at a temperature above 300 ° C, preferably 500 ° C.
- the heat treatments are chosen from annealing, for example by rapid thermal annealing ("Rapid Thermal Process”) such as laser or flash lamp annealing, hardening and / or bending. Rapid thermal annealing is for example described in application WO2008 / 096089.
- Rapid Thermal annealing is for example described in application WO2008 / 096089.
- the heat treatment temperature (at the stack) is greater than 300 ° C, preferably greater than 400 ° C, and better still greater than 500 ° C.
- the substrate coated with the stack is preferably a tempered glass, especially when it forms part of a glazing used as a constituent element of a cooling device, of a heating device or of a fire door.
- the transparent substrates according to the invention are preferably made of a rigid mineral material, such as glass, or organic based on polymers (or polymer).
- the organic transparent substrates according to the invention can also be made of polymer, rigid or flexible.
- polymers suitable according to the invention include, in particular:
- PET polyethylene terephthalate
- PBT polybutylene terephthalate
- PEN polyethylene naphthalate
- PMMA polymethyl methacrylate
- fluorinated polymers such as fluoroesters such as ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene ethylene (ECTFE), fluorinated ethylene-propylene copolymers (FEP);
- fluoroesters such as ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), chlorotrifluoroethylene ethylene (ECTFE), fluorinated ethylene-propylene copolymers (FEP);
- - photocrosslinkable and / or photopolymerizable resins such as thiolene, polyurethane, urethane-acrylate, polyester-acrylate resins and
- the substrate is preferably a sheet of glass or ceramic glass.
- the substrate is preferably transparent, colorless (this is then a clear or extra-clear glass) or colored, for example blue, gray or bronze.
- the glass is preferably of the soda-lime-silicate type, but it can also be of the borosilicate or alumino-borosilicate type glass.
- the substrate is made of glass, in particular soda-lime silica, or of polymeric organic material.
- the substrate advantageously has at least one dimension greater than or equal to 1 m, or even 2 m and even 3 m.
- the thickness of the substrate generally varies between 0.5 mm and 19 mm, preferably between 0.7 and 9 mm, in particular between 2 and 8 mm, or even between 2.8 and 6 mm.
- the substrate can be flat or curved, or even flexible.
- the invention also relates to a glazing comprising at least one material according to the invention.
- the invention relates to glazing which may be in the form of monolithic, laminated or multiple glazing, in particular double glazing or triple glazing.
- the glazing can be a monolithic glazing comprising 2 faces.
- the glazing can be a multiple glazing comprising two, three or four substrates.
- the glazing comprises a material according to the invention, comprising in particular a substrate and one, two, three additional substrates.
- Multiple glazing comprises at least one material according to the invention and at least one additional substrate.
- the material and the additional substrate are either side by side or separated by at least one intermediate gas sheet.
- Double glazing has two substrates, an exterior substrate and an interior substrate and 4 sides.
- a triple glazing has three substrates, an outer substrate, a central substrate and an inner substrate, and 6 sides.
- face 1 is outside the building and therefore constitutes the outer wall of the glazing. All the other faces are numbered successively. The face inside the building has the highest number.
- a laminated glazing comprises at least one structure of the first substrate / sheet (s) / second substrate type.
- the polymeric sheet may in particular be based on polyvinyl butyral PVB, ethylene vinyl acetate EVA, polyethylene terephthalate PET, polyvinyl chloride PVC.
- the stack of thin layers is positioned on at least one side of one of the substrates.
- These glazing can be mounted on a building or a vehicle. These glazings can be mounted on heating or cooling devices such as oven or refrigerator doors.
- the glazing may include at least one transparent substrate coated with a functional coating other than a stack comprising at least one functional silver-based metal layer such as a coating comprising a transparent conductive oxide ("TCO").
- TCO transparent conductive oxide
- the coating comprising a transparent conductive oxide can be chosen from a material based on indium tin oxide (ITO), based on zinc oxide doped with aluminum (ZnO: Al) or doped with boron. (ZnO: B), or else based on tin oxide doped with fluorine (SnO 2: F).
- These materials are deposited chemically, such as for example by chemical vapor deposition (“CVD”), optionally improved by plasma (“PECVD”) or physically, such as for example by vacuum deposition by cathode sputtering, optionally assisted by magnetic field (“Magnetron”).
- CVD chemical vapor deposition
- PECVD plasma
- Magnetron magnetic field
- the non-stack functional coating comprising at least one functional silver-based metal layer may be on the same substrate.
- the non-stack functional coating comprising at least one silver-based functional metal layer may be on a different substrate than that coated with a stack comprising a silver-based functional metal layer.
- the glazing is a multiple glazing.
- the glazing can therefore include a functional coating other than a stack comprising a functional silver-based metallic layer such as a coating comprising a transparent conductive oxide located:
- the heating device allows the enclosure to be heated to a high temperature, in particular greater than 50, 100, 200, 300, 400, 500 or 600 ° C.
- the heating device further comprises heating means. These heating means allow the enclosure to be heated to a high temperature, in particular greater than 50, 100, 200, 300, 400, 500 or 600 ° C.
- Magnetic cathode sputtering the conditions for depositing the layers deposited by sputtering (so-called “magnetron cathode sputtering”) are summarized in Table 1 below.
- the materials Cp-1 to Cp-5 and lnv-1 and lnv-2 comprise a layer of SiO2 deposited in a single zone.
- the SiO 2 layer is deposited in two different zones.
- Table 3 below lists the materials and the physical thicknesses in nanometers (unless otherwise indicated) of each layer or coating which constitutes the stacks as a function of their positions with respect to the substrate carrying the stack. [Table 3] RD: Dielectric coating; CB: Blocking layer; CF: Functional layer
- a quench type heat treatment is performed on the coated substrates at 705 ° C for 180 seconds.
- the level of blur is evaluated as follows.
- the tempered glass is placed on a desk tilted 20 degrees from the vertical, in a room with black walls. It is lit by a powerful lamp placed vertically over the desk.
- the observer stands in front of the desk, 1 m away.
- a fuzzy sample shows a marked milky appearance: it scatters the light from the lamp away from its specular reflection zone on the glass.
- a sample that does not present a blur does not scatter any light in the direction of the observer, so it appears dark.
- the following assessment indicators were used:
- the chemical durability is evaluated by a high humidity test before (HH) and after heat treatment (TT-HH).
- the humidity test (HH) consists of storing samples for 56 days at 90% relative humidity and 60 ° C and observing the possible presence of defects such as pitting corrosion.
- the following assessment indicators were used:
- FIG. 2 groups together two images taken under a microscope, on the left the material Cp-1 and on the right the material lnv-2.
- Table 5 summarizes the observations. [Table 5]
- Table 6 shows the delay in degradation of the solution of the invention. For this, we compare the duration of the heat treatment in seconds for which we obtain 2 points of degradation of the emissivity between the material Cp-1 and respectively the materials Cp-3 and Cp-4 as well as the materials of the invention lnv-2, lnv-3 and lnv-4.
- the delay is too short to be really useful.
- the time / temperature pair during heating becomes compatible with a transformation of the glass, such as tempering or bending without blurring, or degradation of emissivity.
- the Cp-1 glazing showed a blurring at time and temperature parameters very close to those necessary to obtain an acceptable flatness, a fragmentation, and an acceptable shape.
- Industrial tools used to bend and / or toughen coated glazing which may exhibit variability. A glazing must therefore be sufficiently robust to accept these process variabilities.
- the materials lnv-2, lnv-3, and lnv-4 have this added strength.
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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Combustion & Propulsion (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Surface Treatment Of Glass (AREA)
- Laminated Bodies (AREA)
Abstract
Description
Claims
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MX2022014175A MX2022014175A (es) | 2020-05-12 | 2021-05-07 | Material de baja emisividad que comprende una capa gruesa a base de oxido de silicio. |
BR112022021996A BR112022021996A2 (pt) | 2020-05-12 | 2021-05-07 | Material de baixa emissão compreendendo uma camada espessa à base de óxido de silício |
EP21732439.1A EP4149897A1 (fr) | 2020-05-12 | 2021-05-07 | Matériau bas émissif comprenant une couche épaisse à base d'oxyde de silicium |
US17/924,837 US20230212065A1 (en) | 2020-05-12 | 2021-05-07 | Low-e material comprising a thick layer based on silicon oxide |
CONC2022/0016074A CO2022016074A2 (es) | 2020-05-12 | 2022-11-10 | Material de baja emisividad que comprende una capa gruesa a base de óxido de silicio |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR2004679A FR3110160B1 (fr) | 2020-05-12 | 2020-05-12 | Matériau bas émissif comprenant une couche épaisse à base d'oxyde de silicium |
FRFR2004679 | 2020-05-12 |
Publications (1)
Publication Number | Publication Date |
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WO2021229165A1 true WO2021229165A1 (fr) | 2021-11-18 |
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Family Applications (1)
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PCT/FR2021/050786 WO2021229165A1 (fr) | 2020-05-12 | 2021-05-07 | Matériau bas émissif comprenant une couche épaisse à base d'oxyde de silicium |
Country Status (7)
Country | Link |
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US (1) | US20230212065A1 (fr) |
EP (1) | EP4149897A1 (fr) |
BR (1) | BR112022021996A2 (fr) |
CO (1) | CO2022016074A2 (fr) |
FR (1) | FR3110160B1 (fr) |
MX (1) | MX2022014175A (fr) |
WO (1) | WO2021229165A1 (fr) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6040056A (en) * | 1996-06-07 | 2000-03-21 | Nippon Sheet Glass Co., Ltd. | Transparent electrically conductive film-attached substrate and display element using it |
EP1480920A1 (fr) | 2002-03-01 | 2004-12-01 | Cardinal CG Company | Revetement a couches minces presentant une couche de base transparente |
EP1527028A2 (fr) * | 2002-07-31 | 2005-05-04 | Cardinal CG Company | Revetements a performance d'ombrage elevee trempables |
WO2008096089A2 (fr) | 2007-01-05 | 2008-08-14 | Saint-Gobain Glass France | Procede de depot de couche mince et produit obtenu |
WO2009103929A2 (fr) * | 2008-02-18 | 2009-08-27 | Saint-Gobain Glass France | Cellule photovoltaique et substrat de cellule photovoltaique |
EP3033311A1 (fr) * | 2013-08-16 | 2016-06-22 | Pilkington Group Limited | Panneau de verre revêtu thermotraitable |
US20160273265A1 (en) * | 2015-03-20 | 2016-09-22 | Cardinal Cg Company | Nickel-aluminum blocker film multiple cavity controlled transmission coating |
-
2020
- 2020-05-12 FR FR2004679A patent/FR3110160B1/fr active Active
-
2021
- 2021-05-07 WO PCT/FR2021/050786 patent/WO2021229165A1/fr unknown
- 2021-05-07 MX MX2022014175A patent/MX2022014175A/es unknown
- 2021-05-07 US US17/924,837 patent/US20230212065A1/en active Pending
- 2021-05-07 EP EP21732439.1A patent/EP4149897A1/fr active Pending
- 2021-05-07 BR BR112022021996A patent/BR112022021996A2/pt unknown
-
2022
- 2022-11-10 CO CONC2022/0016074A patent/CO2022016074A2/es unknown
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6040056A (en) * | 1996-06-07 | 2000-03-21 | Nippon Sheet Glass Co., Ltd. | Transparent electrically conductive film-attached substrate and display element using it |
EP1480920A1 (fr) | 2002-03-01 | 2004-12-01 | Cardinal CG Company | Revetement a couches minces presentant une couche de base transparente |
EP1527028A2 (fr) * | 2002-07-31 | 2005-05-04 | Cardinal CG Company | Revetements a performance d'ombrage elevee trempables |
WO2008096089A2 (fr) | 2007-01-05 | 2008-08-14 | Saint-Gobain Glass France | Procede de depot de couche mince et produit obtenu |
WO2009103929A2 (fr) * | 2008-02-18 | 2009-08-27 | Saint-Gobain Glass France | Cellule photovoltaique et substrat de cellule photovoltaique |
EP3033311A1 (fr) * | 2013-08-16 | 2016-06-22 | Pilkington Group Limited | Panneau de verre revêtu thermotraitable |
US20160273265A1 (en) * | 2015-03-20 | 2016-09-22 | Cardinal Cg Company | Nickel-aluminum blocker film multiple cavity controlled transmission coating |
Also Published As
Publication number | Publication date |
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FR3110160A1 (fr) | 2021-11-19 |
US20230212065A1 (en) | 2023-07-06 |
MX2022014175A (es) | 2022-12-02 |
FR3110160B1 (fr) | 2023-10-27 |
BR112022021996A2 (pt) | 2022-12-13 |
EP4149897A1 (fr) | 2023-03-22 |
CO2022016074A2 (es) | 2022-12-09 |
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