Classifications

• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • 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
• • 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
• • 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
• • 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
  • C03C17/3642—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 containing a metal layer
• • 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
• • 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
• • 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
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/21—Oxides
  • C03C2217/216—ZnO
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/21—Oxides
  • C03C2217/228—Other specific oxides
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/25—Metals
  • C03C2217/251—Al, Cu, Mg or noble metals
  • C03C2217/254—Noble metals
  • C03C2217/256—Ag
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/25—Metals
  • C03C2217/261—Iron-group metals, i.e. Fe, Co or Ni
• • 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
  • C03C2217/262—Light metals other than Al
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2217/00—Coatings on glass
  • C03C2217/20—Materials for coating a single layer on glass
  • C03C2217/28—Other inorganic materials
  • C03C2217/281—Nitrides
• • 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

• the invention relates to a material comprising a transparent substrate coated with a stack of thin layers comprising at least one functional metallic layer based on silver.
• the invention also relates to glazing comprising these materials as well as the use of such materials for manufacturing glazing for thermal insulation and / or sun protection.
• the functional metallic layers based on silver (or silver layers) have advantageous electrical conduction and infrared (IR) reflection properties, hence their use in so-called “solar control” glazing intended to reduce the amount of incoming solar energy and / or in so-called “low-emissivity” glazing aimed at reducing the amount of energy dissipated outside a building or a vehicle.
• 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 make it possible to protect the silver layer from chemical or mechanical attack.
• optical and electrical properties of materials depend directly on the quality of the silver layers such as their crystalline state, their homogeneity and their environment.
• environment is understood to mean the nature of the layers near the silver layer and the surface roughness of the interfaces with these layers.
• dielectric coatings comprising dielectric layers with stabilizing function intended to promote the wetting and nucleation of the silver layer.
• dielectric layers based on crystallized zinc oxide are used for this purpose.
• the zinc oxide deposited by the sputtering process crystallizes without requiring additional heat treatment.
• the zinc oxide layer can therefore serve as an epitaxial growth layer for the silver layer.
• blocking layers located between a functional layer and a dielectric coating, the function of which is to protect these functional layers from possible degradation during deposition of the upper dielectric coating and / or during heat treatment.
• Many possibilities varying in particular by the nature, the number and the position of said blocking layers have been proposed.
• the invention relates more particularly to stacks which have to undergo a heat treatment at high temperature such as annealing, bending and / or quenching.
• stacks comprising, near a silver layer, both blocking layers chosen from certain materials and / or certain thicknesses and dielectric layers comprising zinc, in particular based on oxide of zinc or based on zinc oxide and tin, exhibit, following the heat treatment, advantageously improved scratch resistance properties and disadvantageously degraded resistivity.
• the improvement in scratch resistance could be due to doping of the silver layer with zinc.
• the deterioration in resistivity could be due to the presence of metallic zinc elements or to defects linked to zinc located at the upper or lower interface of the silver layer and / or at the grain boundary of the silver layer. .
• the Applicant has thus surprisingly discovered that the insertion of a zinc-based metal layer not only significantly improves the scratch resistance of the silver stacks, but also drastically reduces hot corrosion and the cold corrosion in humid environments.
• the objective of the present invention is to develop a material which, after a heat treatment (s) at high temperature, has both low resistivity and therefore low emissivity, moderate absorption and excellent mechanical properties resulting in excellent scratch resistance.
• the invention therefore relates to a material comprising a transparent substrate coated with a stack of thin layers 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 each functional metal layer is placed between two dielectric coatings,
• a crystallized dielectric layer based on zinc oxide is located below and in contact with the layer based on nickel oxide.
• the zinc-based metal layer is in a dielectric coating in contact with said functional silver-based metal layer. This means that the zinc-based metal layer is not separated from said metal layer functional based on silver by another functional metallic layer based on silver.
• the migration of metallic zinc elements into the silver layer following the heat treatment makes it possible to improve the scratch resistance after heat treatment regardless of the structure of the stack.
• the zinc-based metal layer therefore improves mechanical resistance.
• the presence of a layer based on nickel oxide makes it possible to completely suppress the degradation of the resistivity and to reduce in part the increase in absorption, normally induced by the metallic layer based on zinc.
• the layer based on nickel oxide makes it possible to restore the degraded properties without losing the advantageous properties induced by the metallic layer based on zinc.
• the solution of the invention makes it possible to significantly improve the scratch resistance of silver stacks, but also to drastically reduce hot corrosion and cold corrosion in wet environments.
• the present invention is suitable for all applications using stacks comprising functional silver-based layers intended to be heat treated and where it is sought to improve the mechanical properties and in particular the scratch resistance.
• the invention therefore allows the development of a material comprising a substrate coated with a stack comprising at least one functional metallic layer based on silver having, following a heat treatment of the bending, quenching or annealing type:
• the solution of the invention is suitable in the case of stacks with several functional layers based on silver, in particular stacks with two or three functional layers which are particularly fragile from the point of view of scratches.
• the present invention is also suitable in the case of stacks with a single functional layer based on silver intended for applications where the stacks are highly prone to cold corrosion in a humid environment.
• This is particularly the case with single glazing comprising stacks with a single layer of silver used as glazing for a refrigerator door.
• the invention also relates to:
• - glazing comprising a material according to the invention mounted on a 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 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 “higher” should be considered in relation to this orientation.
• the expressions “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 cannot be one (or more) layer (s) interposed between these two layers (or layer and coating).
• Glazing for the building generally delimits two spaces, a space qualified as “exterior” and a space qualified as “interior”.
• the sunlight entering a building is considered to go from the outside to the inside.
• the light characteristics are measured according to the illuminant D65 at 2 ° perpendicular to the material mounted in a double glazing:
• 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.
• the thicknesses mentioned in this document are physical thicknesses and the layers are thin layers.
• the term “thin layer” is intended to mean a layer having a thickness of between 0.1 nm and 100 micrometers.
• a crystallized dielectric layer based on oxide in particular based on zinc oxide, can be located below the layer based on nickel oxide, preferably in contact.
• the stack can comprise the sequence:
• crystalline oxide-based layer and in particular a zinc oxide-based layer
• a crystallized oxide-based layer located above and in contact with the nickel oxide-based layer.
• This sequence can be found above and / or below the functional silver-based metallic layer.
• the dielectric coating located directly below the functional metallic layer based on silver comprises at least one crystallized dielectric layer based on oxide, in particular based on zinc oxide, optionally doped using at least one other element, such as aluminum.
• the crystallized dielectric layer based on oxide, in particular based on zinc oxide can be located:
• this crystallized layer underlying allows good crystallization of the nickel oxide layer by growth by epitaxy above the crystallized layer.
• nickel oxide unlike zinc oxide, does not crystallize very well when cold under the conditions of deposition of the conventional cathode sputtering, that is to say under vacuum at room temperature, unless it is deposited on a crystallized layer such as a layer of zinc oxide.
• a crystallized layer such as a layer of zinc oxide.
• the first is the decrease in absorption induced by the nickel oxide layer.
• a well crystallized layer is less absorbent.
• the second advantage is that if a crystallized layer is deposited on top of the nickel oxide-based layer, the nickel oxide layer influences to some extent the crystallization of this overlying layer. .
• the nickel oxide-based layer can be located below, preferably in contact with, a crystallized dielectric layer traditionally used as a wetting layer for the functional silver-based layer.
• the nickel oxide-based layer influences to a certain extent the crystallization of this so-called wetting crystallized layer, which layer then in turn influences the crystallization of the overlying silver-based layer.
• the layer based on nickel oxide is located between two crystallized dielectric layers, for example based on zinc oxide.
• the lower crystallized dielectric layer acts as a seed layer for the nickel oxide-based layer, making it less absorbent.
• the nickel oxide layer acts to a lesser extent as a growth layer for the upper crystallized dielectric layer.
• the upper crystallized dielectric layer acts as a growth and wetting layer for the silver layer.
• the solution of the invention makes it possible to obtain low square resistance values in particular of the same order, or even lower, than those obtained for materials not comprising the metallic layer based on zinc.
• the thickness of the layer based on nickel oxide must be optimized as a function of the stack and in particular as a function of the thickness of the metal layer based on zinc and the presence or absence of a layer of blocking.
• the solution of the invention therefore makes it possible to significantly lower the absorption but does not not allow to obtain values as low as those obtained with materials without a metallic layer based on zinc and without a layer based on nickel oxide.
• the presence of a layer of metallic zinc near the silver layer causes during the heat treatment the migration of metallic zinc elements in the silver layer following the heat treatment. As explained above, it is attributed to the migration of these metallic zinc elements in the agent layer during the heat treatment, the improvement of the mechanical resistance and the degradation of the resistivity and of the absorption.
• the layer based on nickel oxide makes it possible to a certain extent to attract to it all or part of the metallic zinc elements having migrated in the silver layer and being at the interfaces or between the grain boundaries of the silver layer. This elimination allows to find excellent resistivity values and to lower the absorption.
• the examples show that excellent scratch resistance is obtained for nickel oxide layer thicknesses between 1 and 3 nm, which results in small widths of scratches.
• the zinc-based metal layers are defined as they are obtained during deposition, that is to say before heat treatment. Insofar as the heat treatment induces the migration of metallic zinc elements in the stack, it is not possible to determine with certainty, according to the thicknesses deposited, how this layer of metallic zinc is modified following the heat treatment.
• the term “metallic layer” means a layer comprising not more than 30%, 20% or 10% of oxygen and / or nitrogen in atomic percentage in the layer.
• the layers are deposited in metallic form. Following deposition and before heat treatment, they should not contain more than 10% oxygen and / or nitrogen. However, depending on the nature of the layer deposited directly above, these zinc-based metal layers are liable to undergo partial oxidation which can lead to higher proportions of oxygen or nitrogen. These proportions are however less than 30 or 20%. In any event, at least part of the thickness of these zinc-based metal layers is not oxidized or nitrided.
• Zinc-based metal layers include 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 zinc relative to the mass of the metallic layer based on zinc .
• the zinc-based metal layers can be chosen from:
• the term “metallic zinc layer” is understood to mean metallic layers of pure zinc which may still include some impurities.
• the total mass of zinc represents at least 99% by mass of the mass of the zinc-based metal layer.
• the doped zinc layers comprise at least 90.0%, at least 95%, at least 96%, at least 97%, at least 98% or at least 99% by mass of zinc of the mass of the zinc-based metal layer.
• the doped zinc layers can be chosen from layers based on zinc and at least one element chosen from titanium, nickel, aluminum, tin, niobium, chromium, magnesium, copper, silicon, silver or gold.
• the zinc alloy-based layers comprise at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80% or at least 90% by mass of zinc of the mass of the metallic layer based on zinc.
• the layers based on zinc alloy can be chosen from layers based on zinc and at least one element chosen from titanium, nickel, chromium, tin.
• elements chosen from titanium, nickel, chromium, tin By way of example, mention may be made of binary zinc and titanium alloys such as Zn 2 Ti or ternary alloys based on zinc, nickel and chromium such as ZnNiCr.
• the thickness of the zinc-based metal layer is between 0.2 and 10 nm.
• the thickness of the zinc-based metal layer can be:
• the zinc-based metal layer can be located above and / or below a silver-based functional metal layer, directly in contact or separated by one or more layers from the functional metal-based layer. silver.
• the zinc-based metal layer (s) are located above the functional silver-based metal layer.
• Nickel oxide layers include at least 20%, at least
• 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 total mass of all the elements constituting the layer based on nickel oxide with the exception of oxygen and nitrogen.
• the layers based on nickel oxide can comprise one or more elements chosen from chromium, titanium, aluminum or molybdenum.
• the nickel oxide-based layer may comprise at least 1%, at least 2%, at least 5%, at least 8%, at least 10%, at least 15%, at least 20%, at least 30% , at least 40%, at least 50%, at least 60%, at least 70%, at least 80% by mass of elements other than nickel relative to the total mass of all the elements constituting the base layer d nickel oxide excluding oxygen and nitrogen.
• the layer based on nickel oxide is not nitrided, however traces may exist.
• the nickel oxide-based layer comprises, in ascending order of preference, at least 80%, at least 90%, at least 95%, at least 98%, at least 100%, by mass of oxygen relative to the total mass of oxygen and nitrogen.
• the layer or layers based on nickel oxide have a thickness of between 0.2 and 10.0 nm, or even between 0.6 and 8.0 nm, or even between 1.0 and 5.0 nm.
• the thickness of a layer based on nickel oxide for example can be:
• nm - greater than or equal to 0.2 nm, greater than or equal to 0.5 nm, greater than or equal to 1.0 nm, greater than or equal to 1.2 nm, greater than or equal to 1.5 nm, greater than or equal to 2.0 nm, greater than or equal to 2.5 nm or greater than or equal to 3.0 nm and / or
• the thickness of the single or all the layers separating the layer based on nickel oxide and the functional metallic layer based on silver is between 0.5 and 15.0 nm, or even between 0.7 and 8.0 nm, or even between 1.0 and 6.0 nm.
• the layer based on nickel oxide can be chosen from a layer of nickel and chromium oxide (NiCrOx), a layer of nickel and titanium oxide (NiTiOx) or a layer of nickel oxide and d aluminum (NiAIOx).
• a layer of nickel and chromium oxide comprises, in ascending order of preference, relative to the total mass of all the elements constituting the layer based on nickel oxide excluding oxygen and nitrogen:
• a layer of nickel and titanium oxide comprises, in ascending order of preference, relative to the total mass of all the elements constituting the layer based on nickel oxide excluding oxygen and nitrogen:
• a layer of nickel and aluminum oxide comprises, in ascending order of preference, relative to the total mass of all the elements constituting the layer based on nickel oxide excluding oxygen. and nitrogen:
• the crystallized dielectric layers correspond to the dielectric layers also called “stabilizing layer” or “wetting”.
• stabilizing layer is meant a layer made of a material capable of stabilizing the interface with the functional layer.
• These layers are generally based on zinc oxide.
• Zinc oxide layers may include 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 zinc relative to the total mass of all the elements constituting the zinc oxide-based layer excluding oxygen and l 'nitrogen.
• the zinc oxide-based layers advantageously comprise at least 80%, or even at least 90% by mass of zinc relative to the total mass of all the elements constituting the base layer zinc oxide excluding oxygen and nitrogen.
• the layers based on zinc oxide 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.
• the zinc oxide 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 mass of oxygen relative to the total mass of oxygen and nitrogen.
• the thickness of a layer based on zinc oxide can for example be:
• the crystalline oxide-based dielectric layer in particular based on zinc oxide, may be in contact with the nickel oxide layer and / or in contact with the functional metallic layer based on silver.
• the metallic functional layers based on silver can be “protected” by a layer qualified as a blocking layer.
• a blocking layer above a functional silver-based metal layer is called a blocking overlay.
• a blocking layer below a functional silver-based metallic layer is called a blocking undercoat.
• the stack can comprise at least one blocking overlay, preferably located immediately in contact with the functional metallic layer based on silver.
• the stack may comprise at least one blocking under layer, preferably located immediately in contact with the functional metallic layer based on silver.
• the blocking layers are chosen from metallic layers based on a metal or a metal alloy, metallic nitride layers, metallic oxide layers and metallic 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.
• these blocking layers When these blocking layers are deposited in metallic, nitrided or oxynitrided form, these layers can 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 on contact with the underlying layer.
• the blocking layers can be chosen from metallic layers, in particular an alloy of nickel and chromium (NiCr) or titanium.
• the blocking layers are metallic layers based on nickel.
• Nickel-based metallic blocking layers may include, (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 of nickel.
• the nickel-based metal layers can be chosen from:
• the metal layers based on nickel alloy can be based on alloy of nickel and chromium.
• Each blocking layer has a thickness of between 0.1 and
• These blocking layers can be:
• the metallic layer based on zinc and the layer based on nickel oxide can be:
• the zinc-based metal layer (s) are located above a silver layer and above a blocking overlay.
• the zinc-based metal layer is located above the functional silver-based metal layer and is separated from this layer by at least one blocking overlay.
• the zinc-based metal layer can be located:
• the metallic zinc layer is in contact with the functional metallic layer based on silver (Ag / Zn sequence),
• the metallic zinc layer is separated from the functional metallic layer based on silver by at least one blocking overlay (sequence Ag // Blocking layer // Zn),
• the layer of metallic zinc is in contact with the functional metallic layer based on silver (sequence Ag / Zn / Crystallized layer),
• the layer of metallic zinc is separated from the functional metallic layer based on silver by at least one overlayer blocking (Ag sequence // Blocking layer // Zn // Crystallized layer),
• the crystallized dielectric layer is optionally separated from the functional metallic layer based on silver by at least a blocking overlay (Ag sequence // possibly Blocking layer // Crystallized layer / Zn),
• the metallic zinc layer is in contact with the functional metallic layer based on silver (Zn / Ag sequence),
• the metallic zinc layer is separated from the functional metallic layer based on silver by at least one blocking under layer (sequence Zn // Blocking layer / / Ag),
• the layer of metallic zinc is in contact with the functional metallic layer based on silver (layer sequence crystallized / Zn / Ag),
• the layer of metallic zinc is separated from the functional metallic layer based on silver by at least one blocking under layer (sequence Crystallized layer / Zn // Blocking layer // Ag),
• the crystallized dielectric layer is in contact with or separated from the functional metallic layer based on silver by at least one blocking sublayer (Zn sequence / crystallized layer // possibly blocking layer.//Ag).
• the thickness of all the possible layers separating the layer based on metallic zinc and the functional layer is between 0 and 15.0 nm, even between 0 and 10 nm, even between 0 and 5 nm.
• the thickness of all the layers separating the functional metallic layer based on silver from the metallic layer based on zinc can be:
• nm - greater than or equal to 0.2 nm, greater than or equal to 0.4 nm, greater than or equal to 0.5 nm, greater than or equal to 1 nm, greater than or equal to 2 nm, greater than or equal to 3 nm, greater or equal to 4 nm, greater than or equal to 5 nm, greater than or equal to 6 nm, greater than or equal to 7 nm, greater than or equal to 8 nm or greater than or equal to 9 nm and / or
• nm less than or equal to 25 nm, less than or equal to 20 nm, less than or equal to 15 nm, less than or equal to 13 nm, less than or equal to 12 nm, less than or equal to 11 nm, less than or equal to 10 nm , less than or equal to 9 nm or less than or equal to 8 nm, less than or equal to 7 nm, less than or equal to 6 nm, less than or equal to 5 nm, less than or equal to 4 nm, less than or equal to 3 nm, less than or equal to 2 nm, less than or equal to 1.5 nm.
• the thickness of all the layers separating the functional metallic layer based on silver from the metallic layer based on zinc can be between 0.2 and 5 nm, between 0.5 and 3 nm, between 0, 8 and 1.5 nm.
• All the configurations according to which the metallic layer based on zinc is situated above and not directly in contact with the functional metallic layer based on silver have, for an optimized thickness, a resistivity before heat treatment not degraded compared to a stack not comprising the zinc-based metal layer.
• an undegraded resistivity is understood to mean a variation in resistivity due to the presence of the zinc layer not more than 15%, preferably not more than 10%.
• the configuration that the zinc-based metal layer is located above and separated from the silver-based functional metal layer by a blocking overlay appears to give the best results.
• the configuration in which the zinc-based metal layer is located above and separated from the silver-based functional metal layer by a blocking overlay and a crystallized layer also gives good results.
• a blocking under layer it is also possible to use in these configurations a blocking under layer.
• the use of a blocking underlay allows to improve the mechanical resistance.
• a blocking sublayer situated below a silver layer and a zinc-based metallic layer situated above and directly in contact with said silver layer or separated from the silver layer are then combined. by a crystallized layer and / or by a blocking overlay.
• the silver layers are polycrystalline layers, that is to say composed of a plurality of monocrystalline grains of silver. During the heat treatment, a rearrangement takes place leading to a decrease in the number of grains and an increase in the size of the grains.
• the blocking layer could act as a barrier and slow down the diffusion of metallic zinc elements. This would keep metallic zinc elements in the silver layer when the higher silver layer rearrangement temperatures are reached. The metallic zinc elements would then be retained near the silver layer. This would explain the significant impact of the presence of the blocking layer on the mechanical properties and on the resistivity.
• a blocking underlayer also performs the function of preventing the diffusion of metallic zinc elements and confining them near the silver layer. Configurations according to this embodiment can be advantageous.
• the configurations in which the zinc-based metal layer is located below and near the silver-based functional metal layer have a resistivity before degraded heat treatment.
• One possible explanation is that the zinc layer under the silver layer increases the roughness of the lower interface of the silver layer. This is observed when the zinc-based metal layer is located in contact with a functional silver-based metal layer or separated from this functional silver-based metal layer by at least one blocking sublayer.
• the term “layer located near” means a layer located, in order of preferably increasing within 15 nm, within 10 nm, within 5 nm, within 4 nm, at less than 3 nm, less than 2 nm from another layer.
• the zinc-based metal layer is located near the silver layer and / or
• the metallic layer based on zinc and the layer based on nickel oxide are separated by the silver layer, and / or
• the zinc-based metal layer is located above the silver layer
• the zinc-based metal layer is located above the silver layer and the nickel oxide-based layer is located below the silver layer.
• Zinc-based metal layers to be effective, must allow the diffusion of metallic zinc elements towards the silver layer. It is likely that if these zinc layers are separated from the silver layer:
• dielectric layers which are too thick, for example layers of zinc oxide and tin which are too thick and / or
• dielectric layers with barrier function such as layers of silicon nitrides and / or aluminum and / or zirconium
• zinc-based metal layers are separated from the silver layer by blocking layers and / or crystallized layers.
• the stack comprises at least one functional metallic layer based on silver.
• the functional metallic layer based on silver, 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 metallic layer based on silver before heat treatment comprises less than 1.0% by mass of metals other than silver relative to the mass of the functional metallic layer based on silver.
• the functional metallic layer based on silver is likely to include a proportion of zinc.
• a measurement of the zinc doping can be carried out for example by microprobe analysis of Castaing (ElectroProbe MicroAnalyzer or EPMA in English) or by measurement by atomic tomographic probe ("Atom Probe Tomography").
• the thickness of the silver-based functional layer is from 5 to 25 nm.
• the stack of thin layers comprises at least one functional layer and at least two dielectric coatings comprising at least one dielectric layer, so that each functional layer is placed between two dielectric coatings.
• the stack of thin layers can comprise at least two functional metallic layers based on silver and at least three dielectric coatings comprising at least one dielectric layer, so that each functional layer is placed between two dielectric coatings.
• the stack of thin layers can comprise at least three functional layers and at least four dielectric coatings comprising at least one dielectric layer, so that each functional layer is placed between two dielectric coatings.
• the invention is not limited to the insertion of a single metallic layer based on zinc. It is obviously possible to have a metallic layer based on zinc near at least two functional layers based on silver, or even each functional layer based on silver.
• a stack can therefore comprise one or more metallic layers based on zinc.
• a stack comprising at least two metallic functional layers based on silver may comprise at least two metallic layers based on zinc near at least two metallic functional layers based on silver.
• each silver-based metallic functional layer is in proximity to a zinc-based metallic functional layer.
• the stack is located on at least one of the faces of the transparent substrate.
• 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 other nature, in particular absorbent layers, for example metallic layers.
• dielectric layer in the sense 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 designates a material having an n / k ratio over the entire wavelength range of the visible (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 n / k ratio being calculated at a given given given wavelength for n and for k.
• the thickness of a dielectric coating corresponds to the sum of the thicknesses of the constituent layers.
• the coatings have a thickness greater than 15 nm, preferably between 15 and 200 nm.
• the dielectric layers of the coatings have the following characteristics, alone or in combination:
• They have a thickness greater than or equal to 2 nm, preferably between 2 and 100 nm.
• the dielectric coating located directly below the functional metallic layer based on silver comprises at least one crystallized dielectric layer as defined above, in particular based on zinc oxide, optionally doped using at least one other element, such as aluminum.
• the dielectric coating closest to the substrate is called the bottom coating and the dielectric coating furthest from the substrate is called the top coating.
• Stacks with more than one silver layer also include intermediate dielectric coatings located between the upper and lower coating.
• the lower or intermediate coatings comprise a crystallized dielectric layer based on zinc oxide situated directly in contact with the metallic layer based on silver or separated by a blocking under layer.
• the intermediate or upper coatings comprise a crystallized dielectric layer based on zinc oxide situated directly in contact with the metallic layer based on silver or separated by a blocking overlay.
• the zinc oxide layers have a thickness:
• the dielectric layers can have a barrier function.
• barrier layer a layer 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,
• each coating comprises at least one dielectric layer consisting of:
• each dielectric coating comprises at least one dielectric layer with a barrier function based on an aluminum nitride and / or silicon and / or zirconium.
• the sum of the thicknesses of all the barrier function dielectric layers based on an aluminum nitride and / or silicon and / or zirconium in each dielectric coating is greater than or equal to 15 nm, or even greater than or equal at 20 nm.
• These dielectric layers have, in increasing order of preference, a thickness:
• 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). 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 of titanium, zirconium, hafnium, silicon, zinc and / or tin, this or these metals being in metallic, oxidized or nitrided form.
• the protective layer is based on zirconium oxide and / or titanium, preferably based on zirconium oxide, titanium oxide or titanium oxide and zirconium.
• the substrate coated with the stack or the stack only is intended to undergo a heat treatment.
• the present invention also relates to the coated substrate which is not heat treated.
• the stack may not have undergone a heat treatment at a temperature above 500 ° C, preferably 300 ° C.
• the stack may have been heat treated 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 annealing or flash lamp, quenching 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 may be a curved or tempered glass.
• the transparent substrates according to the invention are preferably made of a rigid mineral material, such as glass, or organic polymers (or polymer).
• the transparent organic 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), polychlorotrifluorethylene (PCTFE), chlorotrifluorethylene ethylene (ECTFE), fluorinated ethylene-propylene copolymers (FEP);
• fluoroesters such as ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluorethylene (PCTFE), chlorotrifluorethylene 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 glass ceramic.
• the substrate is preferably transparent, colorless (it is then a clear or extra-clear glass) or colored, for example in blue, gray or bronze.
• the glass is preferably of the soda-lime-silica type, but it can also be made of borosilicate or alumino-borosilicate type glass.
• the substrate is made of glass, in particular silica-soda-lime or of polymeric organic material.
• the substrate advantageously has at least one dimension greater than or equal to 1 m, 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 4 and 6 mm.
• the substrate can be flat or curved, or even flexible.
• the invention also relates to a glazing unit comprising at least one material according to the invention.
• the invention relates to glazing which can be in the form of monolithic, laminated or multiple glazing, in particular double glazing or triple glazing.
• a monolithic glazing has 2 faces, the face 1 is outside the building and therefore constitutes the exterior wall of the glazing, the face 2 is inside the building and therefore constitutes the interior wall of the glazing.
• Multiple glazing comprises at least one material according to the invention and at least one additional substrate, the material and the additional substrate are separated by at least one interlayer of gas.
• the glazing creates a separation between an exterior space and an interior space.
• Double glazing has 4 sides, side 1 is outside the building and therefore constitutes the outer wall of the glazing, side 4 is inside the building and therefore constitutes the inner wall of the glazing, sides 2 and 3 being inside the double glazing.
• a laminated glazing unit comprises at least one structure of the first substrate / sheet (s) / second substrate type.
• the polymer sheet can 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 of the faces of one of the substrates.
• These glazings can be mounted on a building or a vehicle.
• These glazings can be mounted on devices such as oven or refrigerator doors.
• devices such as oven or refrigerator doors.
• the following examples illustrate the invention.
• Stacks of thin layers defined below are deposited on clear soda-lime glass substrates with a thickness of 2 or 4 mm.
• the functional layers are silver layers (Ag),
• the blocking layers are metallic layers of nickel and chromium alloy (NiCr),
• the layers based on nickel oxide NiOx are based on nickel and chromium
• the dielectric layers are based on silicon nitride, doped with aluminum (Si 3 N 4 : Al) and zinc oxide (ZnO).
• the square resistance Rsq corresponding to the resistance reported on the surface, is measured by induction with a Nagy SMR-12.
• the square resistance and the absorption were measured before heat treatment (BT) and after heat treatments at a temperature of 650 ° C for 10 min (AT).
• the variation in resistivity was determined as follows:
• ARsq (AT vs. BT) (RsqAT-RsqBT) / RsqBT X 100. a. Influence of the thickness of the nickel oxide-based layer
• the table below shows the square resistance results obtained for coated substrates, after heat treatment at 650 ° C., as a function of the thickness of the layer based on nickel oxide.
• the resistivity gradually decreases for thicknesses of layer of nickel oxide between 1 and 3 nm. Then, these values remain almost constant for greater thicknesses.
• the table below shows the results of square resistance and absorption obtained for coated substrates, before and after quenching.
• the material ref. 1 (without a zinc-based metal layer and without a nickel-oxide layer) has an equal resistivity gain of around 30% after heat treatment at 650 ° C.
• the material ref. 2 (with a zinc-based metal layer and without a nickel oxide-based layer) has an emissivity and absorption that is severely degraded following the heat treatment.
• the comparison of materials Ref.1 and Ref.2 shows a loss of resistivity. This results in negative ARsq values and represents a fall from +30% to -12%. Absorption increases from 7 to 13%.
• the Emp.1-1 material has a resistivity gain of 12%.
• the Emp.1-3 material has a gain of around 30%.
• the gain and the square resistance are equivalent to those of Ref. 1.
• the solution of the invention makes it possible to obtain low resistivity values, in particular as low as those obtained with materials without a layer of metallic zinc and without a layer based on nickel oxide.
• the absorption decreases gradually for increasing thicknesses of nickel oxide-based layers.
• the material Emp.1-3 has an absorption of 10%, a decrease of 3% compared to Ref.2.
• the solution of the invention makes it possible to significantly lower the absorption but does not make it possible to obtain values as low as those obtained with materials without a metallic layer based on zinc and without a layer based on nickel oxide.
• the layer based on nickel oxide allows to a certain extent to attract to it all or part of the metallic zinc elements having migrated in the silver layer and being at the interfaces or between the joints of grain of the silver layer. This elimination makes it possible to find excellent resistivity values and to lower the absorption.
• vs. Stacks with a sub-blocking layer The table below shows the results of square resistance and absorption obtained for coated substrates, before and after quenching.
• the stack comprises a blocking under layer and comprises a metallic layer based on zinc (Ref. 4).
• a gain in resistivity of 4% is observed.
• the example Ref. 3 comprising a blocking under layer and not comprising a zinc layer has a gain of 33%.
• the resistivity is however significantly less degraded when the stack comprises a blocking under layer. Indeed, in the presence of a blocking under layer, the impact of the incorporation of a zinc-based metal layer is less severe on the resistivity after heat treatment (comparison Ref. 2 and Ref. 3, ARsq respectively 4% and -12%)
• the layer based on nickel oxide makes it possible to completely recover the gain in resistivity (Ref. 3 and Emp. 2, ARsq of 33%).
• This test consists in applying a point (Van Laar point, steel ball) at a given force (in Newton) to make a scratch in the stack and possibly to transfer the width of the stripes.
• the EST test (without any other qualifier) is carried out without heat treatment.
• This test consists in carrying out an EST test followed by a heat treatment under the following conditions: Applied force: 0.3 N, 0.5 N, 0.8 N, 1 N, 3 N or 5 N ; Heat treatment, 10 minutes at a temperature of 650 ° C,
• - TT-EST This test consists of carrying out a heat treatment followed by an EST test under the following conditions: Heat treatment, 10 minutes at a temperature of 650 ° C; Applied force: 0.3 N, 0.5 N, 0.8 N, 1 N, 3 N or 5 N. a. Stacks without a blocking layer The table below shows the results of the TT-EST Test after a heat treatment at 650 ° C and reports the measurements of the width of the scratches in pm with an applied force of 0.8 N.
• Materials ref. 1 (without zinc-based metal layer and without nickel-oxide-based layer) and ref. 2 (with a zinc-based metal layer and without a nickel-oxide layer) have a stripe width of 20 ⁇ m and 14 ⁇ m respectively in the 0.8 N TT-EST test. A similar trend for the width of the scratches are also observed in the TT-EST 3 N test. A decrease in the visibility of scratches is also observed (comparison Ref. 1 and Ref. 2). The use of a zinc-based metal layer significantly improves the scratch resistance.
• the solution of the invention combining a layer of metallic zinc and a layer based on nickel oxide makes it possible to obtain excellent scratch resistance.
• the TT-EST and EST-TT tests were performed for Emp.2 stacking. The results are similar to those obtained with the Emp stack. 1-3. Consequently, the use of a blocking under layer does not harm the obtaining of the positive effect of the insertion of a metallic layer based on zinc.
• the morphology of the layers is analyzed by light microscopy. Images of the scratches after EST at 1 and 5 N and heat treatment at 650 ° C (EST-TT) were taken.
• Figures 1-a, 1 -b, 1-c, 1 -d, 1-e, 1-f are images taken under the microscope of scratches made after indentation with a force of 1 or 5 N followed by heat treatment.
• the scratches, when present, are much finer for the material comprising a metallic layer based on zinc (Ref. 2 and Emp.1-3) than for the material Ref. 1. Above all, the scratches of the materials comprising a metallic layer based on zinc are not corroded at all.
• the addition of the layer based on nickel oxide does not prevent the advantageous effects linked to the presence of the metal layer based on zinc.
• the images following the EST-TT test clearly show that the striped parts of the stack comprising both a layer based on nickel oxide and a metal layer based on zinc are not corroded.
• HH test High humidity tests
• FIG. 2 includes optical images showing the visibility of corrosion after 5 and 20 days of HH test on non-heat treated materials and after 20 days of HH test on heat treated materials.
• FIG. 3 includes optical images showing the defects due to corrosion after 5 days of HH test for the reference material Ref. 1 not heat treated (3-a) and heat treated (3-b).
• the Ref. 1 stack without heat treatment has corrosion defects visible to the eye after 5 days of HH test (Fig. 2-a and 3-a).
• the density of the corrosion points increases after 20 days of HH test (Fig. 2-b).
• the presence of a zinc-based metal layer prevents the formation of haze linked to cold corrosion.
• the addition of a layer based on nickel oxide makes it possible to maintain the excellent resistance to cold corrosion observed in the presence of a metallic layer based on zinc (comparison with Ref. 2).
• the materials according to the invention treated or not heat treated, have little or no corrosion or haze points (fig. 2-h, 2-i) unlike the material of Ref. 1 (fig. 2-b, 2-c). Thanks to the incorporation of a zinc-based metal layer, a significant improvement in the resistance to cold corrosion is observed both on heat-treated and non-heat-treated materials.
• the solution of the invention makes it possible to obtain low resistivity values, in particular of the same order as those obtained for materials not comprising the layer based on zinc oxide (comparison of Ref. 1 and Emp. 1-3) .
• the layer based on nickel oxide should preferably have a thickness greater than or equal to 0.5 nm, greater than or equal to 1 nm, 2 nm, 2.5 nm, or 3 nm.
• improvement could be observed for smaller ranges of nickel oxide layer thickness.
• the solution of the invention makes it possible to significantly lower the absorption but does not make it possible to obtain values as low as those obtained with materials without a layer of metallic zinc and without a layer based on nickel oxide (comparison Emp. 1-3, and ref. 1 Ref. 2).
• the solution of the invention makes it possible both to obtain excellent scratch resistance but also to completely restore low resistivity and to obtain moderate absorption.
• the addition of a layer based on nickel oxide makes it possible to retain the advantageous mechanical properties observed in the presence of a metallic layer based on zinc (comparison with Ref. 2).
• the solution of the invention makes it possible to significantly improve the resistance to hot corrosion. Indeed, the observation following the EST-TT test clearly shows that the striped parts of the stack comprising both a layer based on nickel oxide and a metal layer based on zinc are not corroded. The beneficial effect of the zinc-based metal layer on the resistance to hot corrosion is maintained even when a layer of nickel oxide is added to the stack.
• the solution of the invention makes it possible to significantly improve the resistance to cold corrosion.
• the addition of a layer based on nickel oxide makes it possible to maintain the excellent resistance to cold corrosion observed in the presence of a metallic layer based on zinc.
• the materials according to the invention, treated or not heat treated, have little or no corrosion or blurring.

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