EP3319918A1 - Vitrage comprenant un revêtement fonctionnel à base d'argent et d'indium - Google Patents
Vitrage comprenant un revêtement fonctionnel à base d'argent et d'indiumInfo
- Publication number
- EP3319918A1 EP3319918A1 EP16750912.4A EP16750912A EP3319918A1 EP 3319918 A1 EP3319918 A1 EP 3319918A1 EP 16750912 A EP16750912 A EP 16750912A EP 3319918 A1 EP3319918 A1 EP 3319918A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- indium
- functional coating
- silver
- layer
- dielectric
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
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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
- C03C17/3626—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 a nitride, oxynitride, boronitride or carbonitride
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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
- C03C17/3639—Multilayers containing at least two functional metal layers
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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
- C03C17/3647—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 in combination with other metals, silver being more than 50%
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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
- C03C17/3649—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 made of metals other than 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
- C03C17/3657—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
- C03C17/3668—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 electrical properties
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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
- C23C14/0641—Nitrides
- C23C14/0652—Silicon nitride
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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
- C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
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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
- C03C2217/20—Materials for coating a single layer on glass
- C03C2217/25—Metals
- C03C2217/27—Mixtures of metals, alloys
Definitions
- the invention relates to a material and a method for preparing a material, such as glazing, comprising a transparent substrate coated with a stack of thin layers comprising a functional coating acting on infrared radiation.
- a functional coating comprises at least one functional layer.
- the term "functional" layer within the meaning of the present application, the (or) layer (s) of the stack that gives it the essential of its thermal properties.
- the functional layer acts on solar and / or thermal radiation essentially by reflection and / or absorption of near (solar) or far (thermal) infrared radiation.
- dielectric coatings are deposited between coatings based on dielectric materials (hereinafter dielectric coatings) generally comprising several dielectric layers that adjust the optical properties of the stack.
- the functional coatings act on the flow of solar radiation passing through said glazing, as opposed to other dielectric coatings, generally made of dielectric material and having the function of a chemical or mechanical protection of the functional coating.
- the most efficient stacks include a functional layer based on silver (or silver layer). These silver layers are useful for several reasons: by reflecting infrared, thermal or solar radiation, they impart to the material functions of low emissivity or solar control. Conducting electricity, they also make it possible to obtain conductive materials, for example heated windows or electrodes.
- silver layers are, however, very sensitive to corrosion, especially in a humid environment. They should not be exposed to the open air in order to be protected against chemical attacks by agents such as water, sulfur and salt.
- These silver layers are therefore traditionally used inside laminated glass or in multiple glazing such as double glazing, in face 2 or 3, by numbering the faces of the substrate or substrates from the outside to the inside of the window. building or cabin that they equip.
- Such layers are generally not deposited on simple glazing (also called monolithic).
- dielectric layers used in dielectric coatings are also sensitive to wet corrosion such as Zinc oxide-based layers commonly used as a wetting layer below the silver layers to promote their crystallization.
- One proposed solution for improving the chemical resistance is to eliminate the use in the dielectric coatings of any dielectric layers susceptible to corrosion. Although the materials thus formed have improved durability, the corrosion resistance of the stack, when directly exposed to ambient air during long storage or under normal operating conditions, remains insufficient.
- the materials must be able to undergo, once coated with the stack, a heat treatment at high temperature, without significant variation, or at least without degradation, their initial optical and / or energy properties.
- the materials after the heat treatment, the materials must maintain an acceptable light transmission and have emissivity preferably substantially improved, or at least substantially unchanged.
- the invention thus consists in the development of new materials comprising a silver-based functional coating having a high chemical resistance while maintaining the thermal and optical properties of the stack, with a view to to manufacture improved sunscreen glazing including low-emissivity glazing.
- Another object is to provide a material provided with a stack capable of withstanding heat treatments without damage, especially when the carrier substrate of the stack is of the glass type. This results in a lack of variation in its thermal and optical properties before and after heat treatment, especially quench type.
- the invention relates to a material comprising a transparent substrate coated with a stack of thin layers comprising at least one metallic silver-based functional coating, at least two dielectric coatings comprising at least one dielectric layer, so that each coating metallic functional layer is arranged between two dielectric coatings characterized in that the metallic functional coating comprises, in order of increasing preference, at least 1.0% by mass of indium relative to the mass of silver and indium in the coating functional metal.
- the metallic functional coating comprises, in order of increasing preference:
- the metal functional coating comprises, in order of increasing preference, 1.0 to 5.0%, 1.0 to 4.0%, 1.0 to 3.0%, 1.5 to 3.0%, 2 to 3.5% by weight of indium relative to the mass of silver and indium in the metallic functional coating.
- the stack is located on at least one of the faces of the transparent substrate.
- the proportions of indium in the metallic functional coating are optimized:
- the emissivity of the stack is not significantly increased, in particular following a heat treatment at a high temperature, with respect to the same stack based on a functional coating only at money base.
- the functional coating may comprise a single layer based on an alloy of silver and indium or a sequence of several layers of silver and indium.
- the functional coating can therefore include:
- At least one indium-based metal layer and at least one silver-based metal layer are at least one indium-based metal layer and at least one silver-based metal layer.
- indium as a dielectric layer constituent is known with, in particular, dielectric coatings comprising indium and tin oxide.
- these dielectric layers are susceptible to corrosion and aging.
- What is decisive for improving the chemical resistance of the stacks is the presence of indium at the core of the functional coating either in the form of an alloy with silver or in the form of a silver-indium layer sequence.
- the use of an overlying or underlying indium-based layer in non-metallic form does not allow obtaining the advantageous effects of the invention.
- ⁇ a low emissivity ( ⁇ ), preferably between 1 and 20% and better still between 1 and 10%
- the transparent substrate coated with the stack according to the invention has a light transmission greater than 50%, preferably greater than 60%.
- the stack is deposited by sputtering assisted by a magnetic field (magnetron process). According to this advantageous embodiment, all the layers of the stack are deposited by sputtering assisted by a magnetic field.
- a magnetic field magnetic field
- other deposition methods are possible, for example sputtering and ion beam evaporation.
- the thicknesses discussed herein are physical thicknesses and the layers are thin layers.
- thin layer is meant a layer having a thickness of between 0.1 nm and 100 micrometers.
- the substrate according to the invention is considered laid horizontally.
- the stack of thin layers is deposited above the substrate.
- the meaning of the terms “above” and “below” and “below” and “above” should be considered in relation to this orientation.
- the terms “above” and “below” do not necessarily mean that two layers and / or coatings are arranged in contact with each other.
- a layer is deposited "in contact” with another layer or a coating, this means that there can not be one or more layers interposed between these two layers.
- a metallic silver functional coating comprises, in order of increasing preference, at least 90.0%, at least 95.0%, at least 96.0% at least 97.0%, at least 97.5% in silver mass relative to the mass of the metallic functional coating.
- the metallic functional coating further comprises tin.
- the metal functional coating comprises 0.05 to 5%, 0.05 to 1.0%, 0.1 to 1.0% by weight of tin relative to the weight of silver, and indium and tin in the metallic functional coating.
- the metallic functional coating may also comprise other doping elements, for example, palladium, gold or platinum.
- other doping element non-selected elements among silver, indium and tin.
- these other doping elements represent, in order of increasing preference, less than 10%, less than 5%, less than 1%, less than 0.5% by weight of the functional coating.
- the metal functional coating comprises less than 1.0%, preferably less than 0.5% by weight of other dopants relative to the weight of the silver metal functional coating.
- the silver metal functional coating has, in order of increasing preference, a thickness of 5 to 20 nm, 8 to 18 nm, 10 to 16 nm.
- the functional coating comprises a layer based on an alloy of silver and indium.
- alloy is meant a mixture of several metals.
- the alloy can be obtained by co-depositing from two metal targets, one of indium and the other of silver or by depositing from a target already comprising a silver and indium alloy.
- the thickness of the coating corresponds to the thickness of the layer based on an alloy of silver and indium and is preferably from 5 to 20 nm, 8 to 18 nm or 10 to 16 nm.
- the functional coating may also include a sequence of silver and indium layers.
- this layer sequence begins with a silver layer and ends with an indium layer or begins with an indium layer and ends with a silver layer.
- the functional coating may therefore comprise at least one indium-based metal layer and at least one silver-based metal layer.
- this layer sequence begins and / or ends with a silver layer.
- the functional coating may therefore comprise at least one indium metal layer and at least two silver-based metal layers, so that each indium metal layer is disposed between two silver-based metal layers.
- this layer sequence begins and ends respectively with an indium layer.
- the functional coating may therefore comprise at least one silver-based metal layer and at least two indium-based metal layers, so that each silver-based metal layer is arranged between two layers. indium-based metal.
- the functional coating comprises at least one indium-based metal layer and at least two silver-based metal layers, so that each indium-based metal layer is disposed between two layers.
- the functional coating may comprise:
- the stacks may comprise functional coatings comprising the following layer sequences:
- each silver-based metal layer is, in order of increasing preference, from 0.5 to 10.0 nm, from 1.0 to 5.0 nm, from 2.0 to 3.0 nm .
- the thickness of each indium-based metal layer is, in order of increasing preference, from 0.05 to 5.0 nm, from 0.1 to 2 nm, from 0.1 to 1 nm, from 0, 1 to 0.5 nm, 0.1 to 0.3 nm.
- the metallic silver-based functional coating may be protected by a metal layer often referred to as a blocking layer.
- the stack of thin layers further comprises at least one blocking layer located in contact with and above and / or below the metallic functional coating.
- 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, Ni, NiN, Cr, CrN, NiCr, NiCrN.
- 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, Ni, NiN, Cr, CrN, NiCr, NiCrN.
- the metallic silver-based functional coating is located in contact and between two blocking layers.
- the blocking layers are preferably selected from metal layers including a nickel alloy and chromium (NiCr).
- Each blocking layer has a thickness of between 0.1 and 5.0 nm.
- the thickness of these blocking layers is preferably:
- the thin film stack may comprise a single functional coating.
- An example of a stack that is suitable according to the invention comprises:
- the functional coatings are deposited between dielectric coatings.
- the dielectric coatings have a thickness greater than 10 nm, preferably between 15 and 100 nm, 20 and 70 nm and more preferably between 30 and 50 nm.
- the dielectric layers have a barrier function.
- Barrier dielectric layers are understood to mean a layer made of a material capable of acting as a barrier to the diffusion of oxygen and water at high temperature from the ambient atmosphere or the substrate. transparent, towards the functional layer.
- the barrier layers may be based on silicon and / or aluminum compounds chosen from oxides such as SiO 2 , TiO 2, nitrides such as silicon nitride Si 3 N 4 and aluminum nitrides AlN, and oxynitrides SiO x Ny, optionally doped with at least one other element such as zirconium, tin or titanium.
- the barrier layers may also be based on tin oxide Sn0 2 or tin oxide and zinc SnZnO x .
- the thin film stack comprises at least one dielectric coating comprising at least one dielectric layer consisting of a nitride or an oxynitride of aluminum and / or silicon or a mixed oxide of zinc and tin, preferably of thickness between 20 and 70 nm.
- the stack may in particular comprise a dielectric layer based on silicon nitride and / or aluminum located below and / or above at least a portion of the functional coating.
- the dielectric layer based on silicon nitride and / or aluminum has a thickness:
- the dielectric coating or coatings located below the functional coating (s) may comprise a single layer consisting of an aluminum or silicon nitride or oxynitride and / or silicon, with a thickness of between 30 and 70 nm, preferably , a layer consisting of silicon nitride, optionally further comprising aluminum.
- the dielectric coating (s) located above the functional coating (s) may comprise at least one layer consisting of a nitride or an oxynitride of aluminum and / or silicon, with a thickness of between 30 and 70 nm, of preferably a layer of silicon nitride, optionally further comprising aluminum.
- the stack of thin layers may optionally comprise a protective layer such as an anti-scratch 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). These layers generally have a thickness of between 2.0 and 10.0 nm, preferably 2.0 and 5.0 nm.
- This protective layer may be chosen from a layer of titanium, zirconium, hafnium, zinc and / or tin, or these metals being in metallic, oxidized or nitrided form.
- the protective layer is based on titanium oxide.
- the thickness of the titanium oxide layer being between 2 and 10 nm.
- the transparent substrates according to the invention are preferably in a mineral rigid material, such as glass, or organic based on polymers (or polymer).
- the transparent organic substrates according to the invention can also be made of polymer, rigid or flexible.
- suitable polymers according to the invention include, in particular:
- polyesters such as polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polyethylene naphthalate (PEN);
- polyacrylates such as polymethyl methacrylate (PMMA);
- fluorinated polymers such as fluoroesters such as ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene chlorotrifluoroethylene (ECTFE), fluorinated ethylene-propylene copolymers (FEP);
- fluoroesters such as ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluoroethylene (PCTFE), ethylene chlorotrifluoroethylene (ECTFE), fluorinated ethylene-propylene copolymers (FEP);
- photocurable and / or photopolymerizable resins such as thiolene, polyurethane, urethane-acrylate, polyester-acrylate and
- the substrate is preferably a glass or glass-ceramic sheet.
- the substrate is preferably transparent, colorless (it is then a clear or extra-clear glass) or colored, for example blue, gray or bronze.
- the glass is preferably of the silico-soda-lime type, but it may also be of borosilicate or alumino-borosilicate type glass.
- the substrate advantageously has at least one dimension greater than or equal to 0.5 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, especially between 2 and 8 mm, or even between 4 and 6 mm.
- the substrate may be flat or curved, or even flexible.
- the material that is to say the transparent substrate coated with the stack, is intended to undergo a heat treatment at high temperature selected from an annealing, for example by flash annealing such as laser or flame annealing, quenching and / or bending.
- the temperature of the heat treatment may be greater than 200 ° C., 400 ° C., 450 ° C. or even greater than 500 ° C.
- the substrate coated with the stack can therefore be curved and / or tempered.
- the material may be in the form of monolithic glazing or single glazing, laminated glazing or multiple glazing including double glazing or triple glazing.
- the invention therefore also relates to a transparent glazing unit comprising at least one material according to the invention. These materials are preferably glazing mounted on a building or a vehicle.
- the stack is preferably deposited in face 2, that is to say, it is on the substrate defining the outer wall of the glazing and more specifically on the inner face of this substrate.
- a monolithic glazing has 2 faces, the face 1 is outside the building and therefore constitutes the outer wall of the glazing, the face 2 is inside the building and therefore constitutes the inner wall of the glazing.
- a double glazing has 4 faces, the face 1 is outside the building and therefore constitutes the outer wall of the glazing, the face 4 is inside the building and therefore constitutes the inner wall of the glazing, the faces 2 and 3 being inside the double glazing.
- the stack can also be deposited in face 4.
- the material can be for:
- the building such as a glazing, a partition or part of a glazed door
- - electronic equipment particularly as a screen for protection or visualization or display, such as a television or computer screen, a touch screen, particularly as an electrode holder or OLED ("Organic Light -Emitting Diode ").
- a screen for protection or visualization or display such as a television or computer screen
- a touch screen particularly as an electrode holder or OLED ("Organic Light -Emitting Diode ").
- the invention also relates to a method for preparing a material comprising a transparent substrate coated with a thin film stack deposited by cathodic sputtering possibly assisted by a magnetic field, the method comprises the following sequence of steps:
- At least one dielectric coating comprising at least one dielectric layer is deposited on the transparent substrate
- a silver-based metallic functional coating is deposited on top of the dielectric coating comprising at least 1.0% by weight of indium relative to the mass of silver and indium in the metallic functional coating, and then a dielectric coating comprising at least one dielectric layer is deposited on top of the metallic silver-based functional coating,
- This heat treatment may be carried out at a temperature greater than 200 ° C., greater than 300 ° C. or greater than 400 ° C., preferably greater than 500 ° C.
- the heat treatment is preferably chosen from quenching, annealing and rapid annealing treatments.
- the quenching or annealing treatment is generally carried out in an oven, respectively quenching or annealing.
- the entire material, including therefore the substrate, can be raised to a high temperature, at least 200 ° C or at least 300 ° C in the case of annealing, and at least 500 ° C or 600 ° C in the case of quenching.
- Thin film stacks defined below are deposited on substrates of soda-lime clear glass with a thickness of 3.9 mm.
- the stacks are deposited, in known manner, on a cathode sputtering line (magnetron process) in which the substrate comes under different targets.
- Atomic wt weight; * : at 550 nm.
- Table 2 lists the materials and physical thicknesses in nanometers (unless otherwise indicated) of each layer or coating that constitutes the stacks as a function of their position vis-à-vis the carrier substrate of the stack (last line at the bottom of the table). ). The thicknesses given in this table correspond to the thicknesses before quenching. Tab. 2: Comparative Invention Materials
- NiCr blocking layer (0.17 nm) NiCr (0.17 nm)
- NiCr blocking layer (0.35 nm) NiCr (0.35 * or 0.17 ** nm)
- the functional coatings of the materials according to the invention comprise at least one silver layer and one indium layer. Each silver layer and each indium layer of the same functional coating are respectively chosen of the same thickness.
- the densities of indium and tin are 7.31 and the density of silver is
- the indium and tin layers comprise 90% by weight of indium and 10% by weight of tin.
- the masses of silver and indium per cm 2 in the functional coating were determined.
- the substrates coated with the stacks undergo thermal heat-quenching treatment for 10 minutes at a temperature of 640 ° C (TT).
- the high moisture resistance test In order to evaluate the chemical resistance of the stack, an accelerated aging test called the high moisture resistance test was performed. This test consists in placing a material in an oven heated to 120 ° C for 480 minutes with a relative humidity of 100% (hr). Visual observation of the material according to the invention after heat treatment makes it possible to observe the absence of blur.
- the resistivity per square (Rsq), measured in Ohm at Nagy, corresponds to the resistance of a sample of width equal to the length (for example 1 meter) and of any thickness.
- the resistivity per square is measured:
- an adhesion test corresponding to the grid test according to EN ISO 2409 has been performed ("tape test" or T. ad.). This test involves making a grid with the cutter and then applying a standard piece of adhesive that is removed after a certain time. Inspection of the gridded surface after removal of the adhesive allows, depending on the quantity of thin layers torn off, to characterize the holding of the stack. According to the invention, the test is qualified as:
- - RL indicates the light reflection in the visible in%, measured according to the illuminant A at 2 °, Observer on the side of the inner face, the face 2;
- TL indicates the light transmission in the visible in%, measured according to the illuminant A at 2 ° Observer;
- the functional coating comprises a sequence of several layers of silver and indium, better results are obtained when this layer sequence begins and / or ends with a layer of silver.
- the functional coating comprises less than 5% by mass of indium.
- Examples In.5, In.6 and In.7 show high square resistivity values.
- the functional coatings comprise at least 3% by weight of indium
- This tendency is not systematically observed when the coatings functional elements comprise less than 3% by mass of indium because the resistivity values per square are then very low and in particular less than 10 ohm per square.
- the functional coatings comprise proportions of less than 4% and better still 1 to 3% by mass of indium relative to the mass of indium and of silver
- the resistivity per square is not increased significantly because of the addition of indium by comparison to the same stack based on a functional coating solely based on silver.
- In.10 and In.1 examples 1 comprising less than 2.5% by mass of indium with respect to the mass of indium and silver resistivities per square less than 10 Ohm before heat treatment.
- the resistivity is generally proportional to the emissivity, it means that the excellent thermal performances are not modified because of the addition of indium.
- Comparative example (cp.14) does not include indium in the functional coating present after aging a resistivity per square much higher than that of the example according to the invention In.10 (1 1, 3 Ohm for cp .14 and 6.4 or 7.9 Ohm for In.10).
- the comparative material is therefore less efficient than the material of the invention after aging.
- the functional coating according to the invention makes it possible to maintain high light transmission values after heat treatment, despite the significant proportions of indium used.
- the solution of the invention therefore makes it possible to obtain a stability of the characteristics of the glazing before and after the heat treatment.
- the excellent chemical stability of the stack according to the invention allows the use of the material with the stack positioned indifferently on an outer face, that is to say in contact with the ambient air, or internal to a substrate.
Landscapes
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (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)
- Laminated Bodies (AREA)
- Surface Treatment Of Glass (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR1556369A FR3038595A1 (fr) | 2015-07-06 | 2015-07-06 | Vitrage comprenant un revetement fonctionnel a base d'argent et d'indium |
PCT/FR2016/051644 WO2017006026A1 (fr) | 2015-07-06 | 2016-06-30 | Vitrage comprenant un revêtement fonctionnel à base d'argent et d'indium |
Publications (1)
Publication Number | Publication Date |
---|---|
EP3319918A1 true EP3319918A1 (fr) | 2018-05-16 |
Family
ID=54199844
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16750912.4A Withdrawn EP3319918A1 (fr) | 2015-07-06 | 2016-06-30 | Vitrage comprenant un revêtement fonctionnel à base d'argent et d'indium |
Country Status (11)
Country | Link |
---|---|
US (1) | US20180208503A1 (fr) |
EP (1) | EP3319918A1 (fr) |
JP (1) | JP2018528140A (fr) |
KR (1) | KR20180026440A (fr) |
CN (1) | CN107709264A (fr) |
BR (1) | BR112017027149A2 (fr) |
CO (1) | CO2017012949A2 (fr) |
FR (1) | FR3038595A1 (fr) |
MX (1) | MX2017016707A (fr) |
RU (1) | RU2717490C2 (fr) |
WO (1) | WO2017006026A1 (fr) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP6566433B2 (ja) * | 2016-07-20 | 2019-08-28 | 三菱重工コンプレッサ株式会社 | 可変速増速機 |
US10921495B2 (en) * | 2017-12-29 | 2021-02-16 | Vitro Flat Glass Llc | Solar control coatings and methods of forming solar control coatings |
KR102509032B1 (ko) * | 2018-05-09 | 2023-03-09 | 쌩-고벵 글래스 프랑스 | 다층 코팅이 구비된 투명 기판 및 이를 포함하는 단열 유리 유닛 |
FR3110159A1 (fr) * | 2020-05-12 | 2021-11-19 | Saint-Gobain Glass France | Matériau bas émissif comprenant une couche à base de nitrure ou d'oxynitrure de silicium et une couche à base d'oxyde de zinc et d'étain |
CN113724918B (zh) * | 2021-07-29 | 2023-06-23 | 富士新材(深圳)有限公司 | 一种金属化碳纤维板及其制备方法 |
Family Cites Families (21)
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US5510173A (en) * | 1993-08-20 | 1996-04-23 | Southwall Technologies Inc. | Multiple layer thin films with improved corrosion resistance |
JP3404165B2 (ja) * | 1994-03-30 | 2003-05-06 | 日本板硝子株式会社 | 熱線遮蔽ガラス |
US6007901A (en) * | 1997-12-04 | 1999-12-28 | Cpfilms, Inc. | Heat reflecting fenestration products with color corrective and corrosion protective layers |
US7232615B2 (en) * | 2001-10-22 | 2007-06-19 | Ppg Industries Ohio, Inc. | Coating stack comprising a layer of barrier coating |
ES2627198T5 (es) * | 2002-05-03 | 2020-08-21 | Vitro Flat Glass Llc | Sustrato que tiene revestimiento de gestión térmica para una unidad de vidrio aislante |
US7572517B2 (en) * | 2002-07-08 | 2009-08-11 | Target Technology Company, Llc | Reflective or semi-reflective metal alloy coatings |
US7241506B2 (en) * | 2003-06-10 | 2007-07-10 | Cardinal Cg Company | Corrosion-resistant low-emissivity coatings |
US20050238923A1 (en) * | 2004-04-27 | 2005-10-27 | Thiel James P | Hybrid coating stack |
US7311975B2 (en) * | 2004-06-25 | 2007-12-25 | Centre Luxembourgeois De Recherches Pour Le Verre Et La Ceramique S.A. (C.R.V.C.) | Coated article having low-E coating with ion beam treated IR reflecting layer and corresponding method |
ES2720602T3 (es) * | 2005-05-11 | 2019-07-23 | Agc Glass Europe | Apilamiento para protección solar |
JP2010513942A (ja) * | 2006-12-14 | 2010-04-30 | ナムローゼ・フェンノートシャップ・ベーカート・ソシエテ・アノニム | 太陽光制御フィルム |
FR2924231B1 (fr) * | 2007-11-22 | 2010-05-28 | Saint Gobain | Substrat muni d'un empilement a proprietes thermiques |
KR101550946B1 (ko) * | 2007-12-28 | 2015-09-07 | 쓰리엠 이노베이티브 프로퍼티즈 컴파니 | 태양광 조절 및 그 외의 용도의 적외선 반사 필름 |
BE1019346A3 (fr) * | 2010-05-25 | 2012-06-05 | Agc Glass Europe | Vitrage de controle solaire. |
BE1019345A3 (fr) * | 2010-05-25 | 2012-06-05 | Agc Glass Europe | Vitrage de controle solaire a faible facteur solaire. |
US8790783B2 (en) * | 2011-03-03 | 2014-07-29 | Guardian Industries Corp. | Barrier layers comprising Ni and/or Ti, coated articles including barrier layers, and methods of making the same |
US20140170434A1 (en) * | 2012-12-14 | 2014-06-19 | Intermolecular Inc. | Two Layer Ag Process For Low Emissivity Coatings |
ES2873178T3 (es) * | 2013-08-16 | 2021-11-03 | Guardian Industries | Artículo recubierto con recubrimiento de baja E que tiene baja transmisión visible |
GB2518899A (en) * | 2013-10-07 | 2015-04-08 | Pilkington Group Ltd | Heat treatable coated glass pane |
CN104401062B (zh) * | 2014-12-03 | 2017-01-04 | 张家港康得新光电材料有限公司 | 一种窗膜及其制备方法 |
US10233531B2 (en) * | 2017-03-01 | 2019-03-19 | Guardian Glass, LLC | Coated article with low-E coating having protective doped silver layer for protecting silver based IR reflecting layer(s), and method of making same |
-
2015
- 2015-07-06 FR FR1556369A patent/FR3038595A1/fr not_active Withdrawn
-
2016
- 2016-06-30 MX MX2017016707A patent/MX2017016707A/es unknown
- 2016-06-30 RU RU2018103077A patent/RU2717490C2/ru active
- 2016-06-30 BR BR112017027149-4A patent/BR112017027149A2/pt not_active IP Right Cessation
- 2016-06-30 CN CN201680039907.6A patent/CN107709264A/zh active Pending
- 2016-06-30 KR KR1020187000103A patent/KR20180026440A/ko unknown
- 2016-06-30 WO PCT/FR2016/051644 patent/WO2017006026A1/fr active Application Filing
- 2016-06-30 JP JP2018500305A patent/JP2018528140A/ja active Pending
- 2016-06-30 EP EP16750912.4A patent/EP3319918A1/fr not_active Withdrawn
- 2016-06-30 US US15/741,962 patent/US20180208503A1/en not_active Abandoned
-
2017
- 2017-12-15 CO CONC2017/0012949A patent/CO2017012949A2/es unknown
Also Published As
Publication number | Publication date |
---|---|
JP2018528140A (ja) | 2018-09-27 |
KR20180026440A (ko) | 2018-03-12 |
CN107709264A (zh) | 2018-02-16 |
RU2018103077A3 (fr) | 2019-09-23 |
BR112017027149A2 (pt) | 2018-08-14 |
US20180208503A1 (en) | 2018-07-26 |
RU2717490C2 (ru) | 2020-03-24 |
WO2017006026A1 (fr) | 2017-01-12 |
FR3038595A1 (fr) | 2017-01-13 |
CO2017012949A2 (es) | 2018-03-20 |
MX2017016707A (es) | 2018-03-09 |
RU2018103077A (ru) | 2019-08-06 |
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