EP4182278A1 - Emissionsarmes material mit einer beschichtung mit einem oxidationsgradienten auf titanoxidbasis - Google Patents

Emissionsarmes material mit einer beschichtung mit einem oxidationsgradienten auf titanoxidbasis

Info

Publication number
EP4182278A1
EP4182278A1 EP21749241.2A EP21749241A EP4182278A1 EP 4182278 A1 EP4182278 A1 EP 4182278A1 EP 21749241 A EP21749241 A EP 21749241A EP 4182278 A1 EP4182278 A1 EP 4182278A1
Authority
EP
European Patent Office
Prior art keywords
layer
layers
titanium oxide
material according
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21749241.2A
Other languages
English (en)
French (fr)
Inventor
Denis Guimard
Anne Lelarge
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
Original Assignee
Saint Gobain Glass France SAS
Compagnie de Saint Gobain SA
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from FR2007449A external-priority patent/FR3112545B1/fr
Priority claimed from FR2007448A external-priority patent/FR3112544B1/fr
Application filed by Saint Gobain Glass France SAS, Compagnie de Saint Gobain SA filed Critical Saint Gobain Glass France SAS
Publication of EP4182278A1 publication Critical patent/EP4182278A1/de
Pending legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3657Surface 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
    • C03C17/366Low-emissivity or solar control coatings
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3618Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3681Surface 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
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C17/00Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36Surface 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
    • C03C17/3602Surface 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
    • C03C17/3694Surface 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 having a composition gradient through its thickness
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C2217/00Coatings on glass
    • C03C2217/90Other aspects of coatings
    • C03C2217/91Coatings containing at least one layer having a composition gradient through its thickness

Definitions

  • Low-emissivity material comprising a coating comprising a titanium oxide-based oxidation gradient
  • the invention relates to a material comprising a transparent substrate coated with a stack of thin layers comprising a 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 thermal insulation and/or solar protection glazing.
  • the silver-based functional metal layers have advantageous properties of electrical conduction and reflection of infrared radiation (IR), hence their use in so-called “solar control” glazing aimed at reducing the amount of incoming solar energy and/or in so-called “low-emission” glazing aimed at reducing the amount of energy dissipated outwards from a building or vehicle.
  • IR infrared radiation
  • 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.
  • such materials must undergo heat treatments, intended to improve the properties of the substrate and/or of the stack of thin layers.
  • heat treatments intended to improve the properties of the substrate and/or of the stack of thin layers.
  • it may involve thermal toughening treatment intended to mechanically reinforce the substrate by creating high compressive stresses on its surface.
  • the invention relates more particularly to materials comprising a substrate coated with a stack, intended to undergo a heat treatment at high temperature, having a low emissivity or a low square resistance. Emissivity and resistivity (or resistance) per square vary proportionately. Therefore, it is often possible to assess the emissivity of a material by evaluating its resistance per square.
  • the invention is also concerned with obtaining these materials having a low emissivity without significant modification of the absorption following the heat treatment.
  • the optical and electrical properties such as the emissivity of the materials depend directly on the quality of the silver layers such as their crystalline state, their homogeneity as well as their environment.
  • the term "environment" means the nature of the layers close to the silver layer and the surface roughness of the interfaces with these layers.
  • High temperature heat treatments such as annealing, bending and/or quenching cause changes within the silver layer.
  • dielectric coatings comprising dielectric layers with stabilizing function intended to promote wetting and nucleation of the silver layer.
  • Dielectric layers based on crystallized zinc oxide are notably used for this purpose. Indeed, the zinc oxide deposited by the sputtering process crystallizes without requiring additional heat treatment. The layer based on zinc oxide can therefore serve as an epitaxial growth layer for the silver layer.
  • Another way to prevent the degradation of the silver layers lies in the choice of the layer located above and in contact with the silver layer.
  • the known proposals is the use of so-called blocking layers or dielectric layers based on crystallized zinc oxide.
  • the objective is to protect the functional layers from possible degradation during the deposition of the upper dielectric coating and/or during a heat treatment.
  • the blocking layers are generally based on a metal chosen from nickel, chromium, titanium, niobium, or an alloy of these various metals.
  • the various metals or alloys mentioned can also be partially oxidized, in particular have an oxygen sub-stoichiometry (for example TiOx OR NiCrOx).
  • blocking layers are very thin, normally less than 2 nm thick, and are susceptible at these thicknesses to being partially oxidized during heat treatment.
  • these blocking layers are sacrificial layers, capable of capturing oxygen coming from the atmosphere or from the substrate, thus avoiding the oxidation of the silver layer.
  • this solution also makes it possible to further reduce the resistivity after heat treatment compared with a reference material.
  • the invention therefore relates to a material comprising a transparent substrate coated with a stack of 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 as to that each functional metal layer is placed between two dielectric coatings, characterized in that the stack comprises a coating comprising an oxidation gradient based on titanium oxide located above and in contact with a functional metal layer at silver base, the part of the oxidation gradient coating in contact with the functional layer is less oxidized than the part of this coating further from the functional layer.
  • the stack comprises a coating comprising an oxidation gradient as deposited. This means that a coating having a gradient is directly deposited of oxidation. The gradient is present from the deposition. The gradient is not obtained following a possible heat treatment or a possible long storage.
  • the improvement in resistivity is obtained without an increase in absorption, before and after heat treatment.
  • the solution of the invention also makes it possible to obtain these advantageous properties, without blurring or the appearance of corrosion points.
  • a significant improvement in the mechanical properties of scratch resistance is also observed following the heat treatment, resulting in:
  • the invention also makes it possible to obtain an improvement in the solar factor.
  • This improvement is partly related to the presence of a high-index layer in contact with the silver layer.
  • the effect on the solar factor makes it possible to obtain:
  • the invention therefore allows the development of a material comprising a substrate coated with a stack comprising at least one functional layer based on silver having, following a heat treatment of the bending, quenching or annealing type, with respect to a reference material with the same silver layer thickness:
  • the invention therefore allows the development of a material comprising a substrate coated with a stack comprising at least one silver-based functional layer having, before or without heat treatment:
  • the coating comprising an oxidation gradient based on titanium oxide is associated with a layer based on particular zinc oxide and tin.
  • This embodiment combining a coating based on titanium oxide with an oxidation gradient and a layer based on zinc and tin oxide makes it possible to obtain the best performance.
  • the invention therefore also relates to a material comprising a transparent substrate coated with a stack of 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 that each functional metal layer is placed between two dielectric coatings, the stack comprises:
  • a coating comprising an oxidation gradient based on titanium oxide located above and in contact with a functional metallic layer based on silver, the part of the coating with an oxidation gradient in contact with the functional layer is less oxidized than the part of this coating furthest from the functional layer,
  • a layer based on zinc oxide and tin comprising at least 20% by mass of tin relative to the total mass of zinc and tin, located above and in contact with the layer based on titanium oxide.
  • the solution of the invention is particularly 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 particularly suitable in the case of stacks with a single functional layer based on silver intended for applications where the stacks are highly subject to hot corrosion.
  • the invention also relates to:
  • - glazing comprising a material according to the invention mounted on a vehicle or on a building, and
  • a glazing according to the invention as solar control and/or low-emission glazing for the building or vehicles
  • the substrate according to the invention is considered laid horizontally.
  • the stack of thin layers is deposited above 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 one another. When it is specified that a layer is deposited "in contact” with another layer or a coating, this means that there cannot be one (or more) interposed layer(s) between these two layers (or layer and coating).
  • Sunlight entering a building is considered to flow from the exterior to the interior.
  • the luminous characteristics are measured according to the D65 illuminant at 2° perpendicular to the material mounted in a double glazing:
  • Rint corresponds to the interior light reflection in the visible in %, observer on the interior space side
  • the materials of the invention can be used both in untempered version and in tempered version.
  • the present invention relates to the unheat-treated coated substrate.
  • the stack may not have undergone heat treatment at a temperature above 500°C, preferably 300°C.
  • the present invention relates to the heat-treated material.
  • the heat treatments are chosen from:
  • the material that is to say the transparent substrate coated with the stack, may have undergone a heat treatment at high temperature.
  • Stacking and substrate may have been subjected to a heat treatment at a high temperature such as quenching, annealing or bending.
  • the stack only may have undergone heat treatment.
  • the stack may have undergone a heat treatment at a temperature above 300°C, preferably 500°C.
  • the heat treatment temperature (at the level of the stack) is greater than 300°C, preferably greater than 400°C, and better still greater than 500°C.
  • Rapid Thermal annealing such as laser or flash lamp annealing.
  • Rapid thermal annealing is for example described in applications WO2008/096089 and WO2015/185848.
  • each point of the stack is brought to a temperature of at least 300 ° C while maintaining a temperature less than or equal to 150 ° C at any point on the side of the substrate opposite to that on which locate the stack.
  • This method has the advantage of heating only the stack, without significant heating of the entire substrate.
  • the coated materials can be treated using a laser line formed from laser sources such as InGaAs diode lasers or Yb:YAG disc lasers. These continuous sources emit at a wavelength between 900 and 1100 nm.
  • the laser line has a length on the order of 3.3 m, equal to the width 1 of the substrate, and an average FWHM half-width between 45 and 100 ⁇ m.
  • the materials are arranged on a roller conveyor so as to scroll along an X direction, parallel to its length.
  • the laser line is fixed and positioned above the coated surface of the substrate with its longitudinal direction Y extending perpendicularly to the running direction X of the substrate, i.e. along the width of the substrate, in extending across that width.
  • the position of the focal plane of the laser line is adjusted to be within the thickness of the functional coating when the substrate is positioned on the conveyor.
  • the surface power of the laser line at the focal plane is less than 100kW/cm2.
  • the substrate was moved under the laser line at a speed of about 8 m/min.
  • the stack may therefore have been subjected to rapid thermal annealing in which each point of the stack is brought to a temperature of at least 300 ° C while maintaining a temperature less than or equal to 150 ° C at any point on the face. of the substrate opposite to that on which the stack is located.
  • heat treatments For example, it is possible to carry out rapid thermal annealing followed by quenching.
  • the stack and the substrate may have been subjected to a heat treatment at a high temperature above 500° C. such as quenching, annealing or bending.
  • the coated substrate of the stack can be bent or tempered glass.
  • the stack is deposited by cathode sputtering assisted by a magnetic field (magnetron process). According to this advantageous embodiment, all the layers of the stack are deposited by cathodic sputtering assisted by a magnetic field.
  • the thicknesses referred to in this document 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 stack comprises a coating comprising a titanium oxide-based oxidation gradient located above and in contact with a silver-based functional metal layer, the part of the oxidation gradient coating in contact with the functional layer is less oxidized than the part of this coating furthest from the functional layer.
  • the titanium oxide coating is described as it is deposited, that is to say before any heat treatment or before any long storage.
  • a heat treatment at high temperature or a long storage can generate modifications within layers or coating. These modifications may in particular correspond to a rearrangement of the oxygen atoms within the coating, making it more difficult to observe the gradient.
  • the oxidation gradient coating has a thickness:
  • nm less than or equal to 30 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 10 nm, less than or equal to 8 nm.
  • the oxidation gradient coating may include:
  • the layers based on titanium oxide comprise at least 50%, at least 60%, at least 70%, at least 80%, at least 95.0%, at least 96.5% and better still at least 98.0 % by mass of titanium relative to the mass of all the elements constituting the layer based on titanium oxide other than oxygen.
  • the layers based on titanium oxide can comprise or consist of elements other than titanium and oxygen. These elements can be chosen from silicon, chromium and zirconium. Preferably, the elements are chosen from zirconium. Preferably, the layer based on titanium oxide comprises at most 35%, at most 20% or at most 10% by mass of elements other than titanium relative to the mass of all the elements constituting the layer based on titanium oxide other than oxygen.
  • the layers based on titanium oxide can have a thickness:
  • nm less than or equal to 30 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 10 nm, less than or equal to 8 nm, less than or equal to 4 nm.
  • the layers based on titanium oxide can be obtained:
  • the deposition atmosphere includes significant proportions of oxygen.
  • the layers based on titanium oxide are preferably obtained from a ceramic target of titanium oxide, preferably under stoichiometric in oxygen, in an atmosphere comprising oxygen or without oxygen.
  • the quantity of oxygen in the deposition atmosphere can be adapted according to the desired properties.
  • a layer based on titanium oxide is deposited from a ceramic target, in particular sub-stoichiometric, in a controlled atmosphere comprising oxygen.
  • the layer based on titanium oxide can be deposited from a ceramic target of TiO x with x between 1.5 and 2.
  • the layer based on titanium oxide can be deposited from a ceramic target of TiO x under stoichiometric, where x is a number different from the stoichiometry of titanium oxide T1O2, i.e. different of 2 and preferably less than 2, in particular between 0.75 times and 0.99 times the normal stoichiometry of the oxide.
  • TiOx may in particular be such that 1.5 ⁇ x ⁇ 1.98 or 1.5 ⁇ x ⁇ 1.7, or even 1.7 ⁇ x ⁇ 1.95.
  • the layer based on titanium oxide can be deposited in an atmosphere not containing oxygen or in a controlled atmosphere comprising oxygen.
  • controlled atmosphere comprising oxygen means an atmosphere comprising an optimized quantity of oxygen to obtain, after heat treatment, a gain in resistivity without harming the absorption on the one hand, and the brush resistance before and after annealing (EBT), on the other hand.
  • the deposition atmosphere comprises a mixture of noble gases (He, Ne, Xe, Ar, Kr) and oxygen.
  • the noble gas is preferably argon. The following parameters are used to define the conditions for sputtering deposition:
  • the pressure in the deposition chamber is between 1 and 15 pbar, preferably 2 and 10 pbar or 2 and 8 pbar,
  • the deposition atmosphere comprises a mixture of argon and oxygen.
  • the controlled atmosphere making it possible to obtain the advantageous effects of the invention was obtained with a percentage by volume flow of oxygen of between 0 and 10%, between 0.1 and 10%, between 0.1 and 5%, between 0.1 and 4%, between 0.5 and 3%, between 1 and 2.5% or between 1.5 and 2.0%.
  • the maximum oxygen threshold may vary to some extent depending on, for example:
  • the volume flow quantities of oxygen that can be used during the deposition will be lower because the TiOx is deposited more slowly and is therefore more likely to oxidize.
  • a person skilled in the art is able to define a satisfactory controlled atmosphere by varying these parameters to some extent.
  • a person skilled in the art is in particular perfectly able to determine the power to be applied to the target and the volume flow rates of oxygen and noble gases.
  • the oxidation gradient coating may comprise at least one layer based on titanium oxide deposited from a ceramic target, in particular substoichiometric, in a controlled atmosphere comprising oxygen, preferably in a controlled atmosphere comprising oxygen.
  • the layer based on titanium oxide can be deposited with a percentage of oxygen in volume flow representing between 0.1 and 10%.
  • the oxidation gradient coating can comprise at least two layers of titanium oxide each comprising different proportions of oxygen, that is to say different degrees of oxidation.
  • the coating is obtained by depositing at least two consecutive layers based on titanium oxide. This deposition in several stages makes it possible to obtain mainly in the coating a layer of titanium oxide with a large quantity of oxygen, while protecting the functional layer based on silver from a first layer of titanium oxide weakly oxidized. The absorption of the stack before heat treatment is then greatly reduced.
  • the oxidation gradient coating can also comprise a first layer deposited from a ceramic target, in particular sub-stoichiometric, in an oxygen-free atmosphere.
  • the oxidation gradient coating may comprise a first layer based on titanium oxide deposited from a ceramic target, in particular sub-stoichiometric, in a non-oxidizing or oxidizing atmosphere whose percentage by volume flow rate of oxygen represents between 0 and 5%, between 0 and 4%, between 0.1 and 4%, between 0.5 and 4%, between 0 and 3%, between 0.1 and 3%, between 0.5 and 3%, between 0.1 and 2.5% or between 0.5 and 2%.
  • This first layer based on titanium oxide is in contact with the functional layer based on silver.
  • the amount of oxygen in the first layer based on titanium oxide must be relatively low so as not to degrade the functional layer based on silver.
  • using a little oxygen contributes to a better resistance to the brush test without inducing too great a penalty in absorption, especially before heat treatment.
  • the thickness of the first layer based on titanium oxide can be as thin as that of a standard blocking layer ( ⁇ 1nm), as long as the functional layer based on silver does not prove to be degraded by the oxygen present during the deposition of the next layer based on titanium oxide, deposited with more oxygen than the first.
  • the first layer has a thickness between 0.2 and 4 nm.
  • the first layer can have a thickness of less than 3 nm, less than 2 nm, less than 1 nm or less than 0.5 nm.
  • the oxidation gradient coating comprises a second layer based on titanium oxide deposited from a ceramic target, in particular sub-stoichiometric, in an atmosphere comprising higher proportions of oxygen than that used for the first layer.
  • the second layer based on titanium oxide can be deposited from a metal target or a ceramic target.
  • the second layer based on titanium oxide can be deposited from a ceramic target, in particular sub-stoichiometric, in an oxidizing atmosphere whose percentage of oxygen in volume flow represents between 1 and 10%, between 1.5 and 8%, between 2 and 5%.
  • the second layer based on titanium oxide has a thickness between 0.2 and 30 nm, between 2 and 20 nm or between 5 and 15 nm.
  • the second layer based on titanium oxide can have a thickness:
  • the oxidation gradient coating can also comprise a single layer of titanium oxide comprising an oxygen gradient.
  • a coating based on titanium oxide comprising a single layer with an oxygen gradient can be obtained:
  • the volume flow rate of oxygen in the deposition atmosphere is gradually increased as the layer based on titanium oxide is deposited.
  • the part of the oxidation gradient coating in contact with the functional layer is less oxidized than the part of this coating further from the functional layer.
  • the proportions of oxygen in the deposition atmosphere can vary from 0% to 10%, preferably from 0 to 5%.
  • the stack comprises at least one functional metallic layer based on silver.
  • the silver-based functional metallic layer before or after heat treatment, comprises at least 95.0%, preferably at least 96.5% and better still at least 98.0% by mass of silver with respect to the mass of the functional layer.
  • the silver-based functional metal layer before heat treatment comprises less than 1.0% by mass of metals other than silver relative to the mass of the silver-based functional metal layer.
  • the thickness of the silver-based functional layer is between 5 to 25 nm, 8 to 20 nm or 8 to 15 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 metallic functional 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 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.
  • these coatings can also comprise layers of another nature, in particular absorbent layers or metallic layers other than functional layers based on silver.
  • the coating farthest from the substrate may comprise a protective layer deposited in metallic form.
  • dielectric layer within the meaning of the present invention, it should be understood that from the point of view of its nature, the material is “non-metallic", that is to say is not a metal.
  • this term designates a material having an n/k ratio over the entire visible wavelength range (from 380 nm to 780 nm) equal to or greater than 5.
  • n designates the index of real refraction of the material at a given wavelength and k represents the imaginary part of the refractive index at a given wavelength; the ratio n/k being calculated at a given wavelength identical for n and for k.
  • the thickness of a dielectric coating corresponds to the sum of the thicknesses of the layers constituting it.
  • the layers based on titanium oxide form part of a dielectric coating.
  • the thickness of these layers is taken into consideration.
  • the dielectric coatings have a thickness greater than 10 nm, greater than 15 nm, between 15 and 200 nm, between 15 and 100 nm or between 15 and 70 nm.
  • nm preferably between 2 and 100 nm, between 5 and 50 nm or between 5 and 30 nm.
  • barrier layer a layer made of a material capable of forming a barrier to the diffusion of oxygen and water at high temperature, coming from the ambient atmosphere or from the substrate. transparent, towards the functional layer.
  • barrier layer is meant a layer made of a material capable of forming a barrier to the diffusion of oxygen and water at high temperature, coming from the ambient atmosphere or from the substrate. transparent, towards the functional layer.
  • Such dielectric layers are chosen from:
  • the material may comprise a layer based on zinc oxide and tin comprising at least 20% by mass of tin relative to the total mass of zinc and tin, located above and in contact with the layer based on titanium oxide.
  • the layer based on zinc oxide and tin comprises by mass of tin relative to the total mass of zinc and tin:
  • the layer based on zinc oxide and tin has a thickness:
  • the stack may comprise at least one layer comprising silicon.
  • Each dielectric coating may include at least one layer comprising silicon.
  • Layers comprising silicon are extremely stable to heat treatments. For example, no migrations of the constituent elements are observed. Therefore, these elements are not likely to alter the silver layer. Layers comprising silicon therefore also contribute to the non-alteration of the silver layers and therefore to obtaining a low emissivity after heat treatment.
  • the layers comprising silicon can be chosen from layers based on oxide, based on nitride or based on silicon oxynitride such as layers based on silicon oxide, layers based on silicon nitride and layers based on silicon oxynitride.
  • each coating comprises a layer comprising silicon
  • these layers are not necessarily of the same nature.
  • the layers comprising silicon can comprise or consist of elements other than silicon, oxygen and nitrogen. These elements can be chosen from among aluminum, boron, titanium, and zirconium.
  • the layers comprising silicon can comprise at least 50%, at least 60%, at least 65%, at least 70% at least 75.0%, at least 80% or at least 90% by mass of silicon with respect to the mass of all the elements constituting the layer comprising silicon other than nitrogen and oxygen.
  • the layer comprising silicon comprises at most 35%, at most 20% or at most 10% by mass of elements other than silicon relative to the mass of all the elements constituting the layer comprising silicon other than oxygen and nitrogen.
  • the layers comprising silicon comprise less than 35%, less than 30%, less than 20%, less than 10%, less than 5% or less than 1% by mass of zirconium with respect to the mass of all the elements constituting the layer based on silicon oxide other than oxygen and nitrogen.
  • the layer comprising silicon may comprise at least 2%, at least 5.0% or at least 8% by mass of aluminum relative to the mass of all the elements constituting the layer based on silicon oxide other than oxygen and nitrogen.
  • the amounts of oxygen and nitrogen in a layer are determined in atomic percentages relative to the total amounts of oxygen and nitrogen in the layer under consideration.
  • - layers based on silicon oxynitride include a mixture of oxygen and nitrogen.
  • the silicon oxide layers include at least 90 atomic percent oxygen relative to the oxygen and nitrogen in the silicon oxide layer.
  • the silicon nitride based layers include at least 90% atomic percent nitrogen relative to the oxygen and nitrogen in the silicon oxide based layer.
  • the layers based on silicon oxynitride include 10 to 90% (limits excluded) in atomic percentage of nitrogen relative to the oxygen and nitrogen in the layer based on silicon oxide.
  • the layers based on silicon oxide are characterized by a refractive index at 550 nm, less than or equal to 1.55.
  • the layers based on silicon nitride are characterized by a refractive index at 550 nm, greater than or equal to 1.95.
  • the layers based on silicon oxynitride are characterized by a refractive index at 550 nm intermediate between a layer of non-nitrided oxide and a layer of non-oxidized nitride.
  • the layers based on silicon oxynitride preferably have a refractive index at 550 nm greater than 1.55, 1.60 or 1.70 or between 1.55 and 1.95, 1.60 and 2.00 , 1.70 and 2.00 or 1.70 and 1.90.
  • refractive indices may vary to some extent depending on the deposition conditions. Indeed, by playing on certain parameters such as the pressure or the presence of dopants, it is possible to obtain more or less dense layers and therefore a variation in refractive index.
  • the layers comprising silicon can be layers of silicon and aluminum nitride and optionally of zirconium. These layers of silicon nitride and aluminum and/or zirconium can also, by weight relative to the weight of silicon, aluminum and zirconium:
  • the sum of the thicknesses of all the layers comprising silicon in each dielectric coating is greater than or equal to 5 nm, greater than or equal to 10 nm, or even greater than or equal to 15 nm.
  • These layers comprising silicon have, in increasing order of preference, a thickness:
  • At least one dielectric coating comprises a layer comprising silicon chosen from layers based on silicon nitride and/or aluminum.
  • each dielectric coating comprises a layer comprising silicon chosen from layers based on silicon and/or aluminum nitride.
  • the dielectric coatings may comprise layers other than these layers comprising silicon.
  • the sum of the thicknesses of all the layers comprising silicon in the dielectric coating located between the substrate and the first layer of silver can be greater than 30%, greater than 35%, greater than 50%, greater than 60% greater than 70 %, greater than 75% of the total thickness of the dielectric coating.
  • the sum of the thicknesses of all the layers comprising silicon based on silicon nitride in the dielectric coating located between the substrate and the first layer of silver can be greater than 30%, greater than 35%, greater than 50%, greater than at 60% greater than 70%, greater than 75% of the total thickness of the dielectric coating.
  • the sum of the thicknesses of all the layers comprising silicon in each dielectric coating located above the first silver-based functional metal layer may be greater than 30%, greater than 35%, greater than 50%, greater than 60% greater than 70% greater than 75% of the total thickness of the dielectric coating.
  • the sum of the thicknesses of all the layers comprising silicon based on silicon nitride in each dielectric coating located above the first functional metal layer based on silver can be greater than 30%, greater than 35% , greater than 50%, greater than 60% greater than 70%, greater than 75% of the total thickness of the dielectric coating.
  • the sum of the thicknesses of all the layers comprising silicon in each dielectric coating can be greater than 30%, greater than 35%, greater than 50%, greater than 60%, greater than 70%, greater than 75% of the total thickness dielectric coating.
  • the stack does not include a metallic blocking layer or one based on titanium oxide below and in contact with the functional metallic layer based on silver.
  • the silver-based functional metallic layer is located above and in contact with a dielectric layer of the dielectric coating.
  • this dielectric layer is a stabilizing or wetting layer made of a material capable of stabilizing the interface with the functional layer.
  • the metallic functional layer can therefore be deposited above and in contact with a layer based on zinc oxide.
  • the layers based on zinc oxide can comprise, 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 by mass total of all the elements constituting the layer based on zinc oxide with the exclusion of oxygen and nitrogen.
  • the layers based on zinc oxide advantageously comprise at least 80%, even at least 90% by mass of zinc relative to the total mass of all the elements constituting the layer based zinc oxide excluding oxygen and nitrogen.
  • the layers based on zinc oxide can comprise one or more elements chosen from among aluminum, titanium, niobium, zirconium, magnesium, copper, silver, gold, silicon, molybdenum, nickel, chromium, platinum, indium, tin and hafnium, preferably aluminum.
  • Layers based on zinc oxide can optionally be doped with at least one other element, such as aluminum.
  • the layer based on zinc oxide is not nitrided, however traces may exist.
  • the layer based on zinc oxide 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 with respect to the total mass of oxygen and nitrogen.
  • the dielectric coating located directly below the silver-based functional metal layer comprises at least one crystallized dielectric layer, in particular based on zinc oxide, optionally doped with at least one other element, such as aluminum.
  • the metallic functional layer is deposited above and in contact with a layer based on zinc oxide.
  • the zinc oxide-based layer is deposited from a ceramic target, with or without oxygen or from a metal target.
  • the dielectric coating located between the substrate and the first silver layer can only consist of layers comprising silicon and layers based on zinc oxide.
  • Dielectric coatings can only consist of layers comprising silicon and layers based on zinc oxide.
  • 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 bottom and top coating.
  • the lower or intermediate coatings comprise a crystallized dielectric layer based on zinc oxide located directly in contact with the metallic layer based on silver.
  • the zinc oxide layers have a thickness:
  • the sum of the thicknesses of all the oxide-based layers present in the dielectric coating located below the first functional metal layer may be less than 70%, less than 60%, less than 50%, less than 40%, less than 30%, less than 25% of the total thickness of the dielectric coating.
  • the sum of the thicknesses of all the oxide-based layers present in the dielectric coating(s) located above the first functional metallic layer may be less than 50%, less than 40%, less than 30%, less than 25% the total thickness of the dielectric coating.
  • the sum of the thicknesses of all the oxide-based layers present in each dielectric coating located above the first functional metal layer can be less than 70%, less than 60%, less than 50%, less than 40% at 30%, less than 25% of the total thickness of the dielectric coating.
  • the stack of thin layers can optionally include a protective layer.
  • the protective layer is preferably the last layer of the stack, that is to say the layer farthest from the coated substrate of the stack (before heat treatment). These layers generally have a thickness of between 0.5 and 10 nm, between 1 and 5 nm, between 1 and 3 nm or between 1 and 2.5 nm.
  • This protective layer can be chosen from among 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 thickness of the protective layer is taken into account.
  • the material of the invention may include:
  • the material of the invention may include:
  • the transparent substrates according to the invention are preferably made of a rigid mineral material, such as glass, or organic based on polymers (or polymer).
  • the organic transparent substrates according to the invention can also be made of polymer, rigid or flexible.
  • polymers suitable according to the invention include, in particular:
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PEN polyethylene naphthalate
  • PMMA polymethyl methacrylate
  • fluorinated polymers such as fluoroesters such as ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluorethylene (PCTFE), ethylene chlorotrifluorethylene (ECTFE), fluorinated ethylene-propylene copolymers (FEP);
  • fluoroesters such as ethylene tetrafluoroethylene (ETFE), polyvinylidene fluoride (PVDF), polychlorotrifluorethylene (PCTFE), ethylene chlorotrifluorethylene (ECTFE), fluorinated ethylene-propylene copolymers (FEP);
  • photocrosslinkable 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 soda-lime-silico type, but it can also be of borosilicate or alumino-borosilicate type glass.
  • the substrate is made of glass, in particular silico-sodo-lime or of polymeric organic material.
  • the substrate advantageously has at least one dimension greater than or equal to 1 m, or even 2 m and even 3 m.
  • the thickness of the substrate generally varies between 0.5 mm and 19 mm, preferably between 0.7 and 9 mm, in particular between 2 and 8 mm, or even between 4 and 6 mm.
  • the substrate can be flat or curved, even flexible.
  • the invention also relates to a glazing comprising at least one material according to the invention.
  • the invention relates to glazing which may be in the form of monolithic, laminated and/or multiple glazing, in particular double glazing or triple glazing.
  • Monolithic glazing has 2 faces, face 1 is outside the building and therefore constitutes the outer wall of the glazing, face 2 is inside the building and therefore constitutes the inner wall of the glazing.
  • a multiple glazing unit 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 spacer gas layer.
  • the glazing creates a separation between an exterior space and an interior space.
  • Double glazing has 4 faces, face 1 is outside the building and therefore constitutes the outer wall of the glazing, face 4 is inside the building and therefore constitutes the inner wall of the glazing, faces 2 and 3 being inside the double glazing.
  • a laminated glazing comprises at least one structure of the first substrate/sheet(s)/second substrate type.
  • the polymer sheet may in particular be based on polyvinyl butyral PVB, ethylene vinyl acetate EVA, polyethylene terephthalate PET, polyvinyl chloride PVC.
  • the stack of thin layers is positioned on at least one of the faces of one of the substrates.
  • These glazings can be mounted on a building or a vehicle.
  • Stacks of thin layers defined below are deposited on clear soda-lime glass substrates with a thickness of 2 or 4 mm.
  • 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 layers of silver (Ag),
  • the dielectric layers are based on silicon nitride, doped with aluminum (S1 3 N 4 : Al), zinc oxide and tin and zinc oxide (ZnO).
  • TiOx titanium oxide layers are deposited from a TiOx ceramic target with or without oxygen in the deposition atmosphere.
  • the stacks were made with titanium oxide-based coatings comprising different thickness ratios for a total thickness of 5 nm.
  • Titanium oxide based layers are deposited from a TiOx ceramic target with or without oxygen in the deposition atmosphere.
  • the stacks of the invention include a titanium oxide-based oxygen gradient coating above and in contact with the silver layer.
  • the oxygen-gradient titanium oxide-based coatings of stacks 1-1, 1-2 and 1-3 comprise a first layer based on titanium oxide deposited from an oxygen-free ceramic target in the deposit atmosphere.
  • the coatings based on titanium oxide with an oxygen gradient of stacks 2-1 and 2-2 comprise a first layer based on titanium oxide deposited from a ceramic target in an oxidizing atmosphere comprising 1.7 % oxygen.
  • the zinc oxide layers below and in contact with the silver layer are deposited from a ZnO ceramic target with 5% Ü2 in the deposition atmosphere.
  • the stacks 12-1, 12-2 and 12-3 comprise coatings based on titanium oxide (oxygen gradient coating) comprising at least two layers of titanium oxide comprising different proportions of oxygen.
  • the first layer is deposited in contact with the silver layer and in an oxygen-free atmosphere with a thickness of 5 nanometers. This layer is therefore under-oxidized.
  • the second layer based on titanium oxide is deposited in an atmosphere with 3.3% oxygen by volume flow and has a thickness varying from 0 to 15 nanometers. This layer is therefore more oxidized than the first.
  • Stacks 13 and 13-1 comprise an oxygen gradient coating comprising at least two layers of titanium oxide comprising different proportions of oxygen. Both layers are deposited from a ceramic target with oxygen. The second layer is more oxidized than the first.
  • the square resistance and absorption were measured before heat treatment (BT) and after heat treatments at a temperature of 650°C for 10 min (AT).
  • the square resistance variation was determined as follows:
  • ARsq(n-p) (RsqRef-RsqEmp(n-p)) / RsqRef X 100.
  • the gain is positive when the resistance per sheet is improved and negative when the resistance per sheet is deteriorated following the heat treatment.
  • the square resistance of the stacks of the invention Emp.1-1, 1-2 and 1-3 is lower than that of the reference stack.
  • a gradient coating with a first layer of TiOx deposited without oxygen therefore makes it possible to obtain a gain in Rsq before and after heat treatment.
  • the square resistance decreases compared to the reference stack when the thickness of the first layer comprising titanium oxide deposited without oxygen increases or when the thickness of the second layer comprising titanium oxide.
  • titanium deposited with oxygen decreases (3.06 W/p > 3.00 W/D > 2.96 W/m).
  • the supply of oxygen in the second layer of titanium oxide makes it possible to lower the absorption of the stacks.
  • the absorption, before and after heat treatment, of the stacks with a coating based on titanium oxide comprising a gradient is similar to that of a reference material and better than or equal to that of stacking with titanium oxide without gradient.
  • the thickness of the first layer of TiOx deposited without oxygen e.g., 1 nm, or even less
  • the square resistance of the stacks is not improved, but identical or even degraded, compared to the reference structure.
  • the supply of oxygen in the first layer of titanium oxide (1.7%) degrades the silver layer during deposition.
  • the gain in square resistance compared to the reference is at least 14%.
  • the layer based on zinc oxide and tin is directly in contact with the layer based on under-oxidized titanium oxide.
  • the Rsq remains high for emp.12-0 comprising a layer of SnZnO in direct contact with a layer of under-oxidized TiOx with a gain between the square resistance obtained AT vs. Low BT.
  • the over-oxidized titanium oxide layer with a thickness of 15 nm associated with the layer based on zinc and tin oxide makes it possible to significantly reduce absorption: 5.4% vs. 7.7%.
  • Table 7 presents the sheet resistance and absorption measurements in the case of material comprising an oxygen gradient coating with two layers of TiOx deposited with oxygen.
  • the Rsq is neither improved nor degraded compared to the reference stack (4.50 W/p vs. 4.55 W/D).
  • the Rsq is lower in the case of the stack of the invention Emp.13-1 comprising the sequence Ag/TiOx_1.7%/TiOx_5%/SnZnO (3.20 W/p) compared to Emp.13 not comprising a layer of SnZnO (3.42 W/D).
  • the absorption is lower in the case of Ag/TiOx_1.7%/TiOx_5%/SnZnO stacking, before (7.8% vs. 8.5%) and after heat treatment (5.4% vs. 6.5%).
  • the two layers of TiOx are deposited with oxygen and are therefore not very absorbent. This low absorption of the two TiOx layers is also visible in the Ag/TiOx_1.7%/TiOx_5% stack compared to the reference Ag/ZnO: 6.2% vs. 6.5%.
  • the thickness of the first layer of TiOx deposited with 02 eg, 1 nm, or even less like the thickness of a TiOx blocker
  • the morphology of the stacks is analyzed by optical microscopy (x50 magnification) after heat treatment.
  • Figure 1 shows these images taken under an optical microscope. The images were taken after heat treatment.
  • the stacks of the invention do not exhibit any blurring either.
  • the presence of the titanium oxide layer on top of the layer in contact with the silver prevents the presence of blurring.
  • Each sample is observed after a certain number of cycles: 50, 100, 200, 300.
  • the Ok boxes indicate good resistance to the EBT or TT-EBT test after 300 cycles.
  • the figure beside corresponds to the number of cycles to which the sample was subjected.
  • the Nok boxes indicate poor resistance to the EBT or TTEBT test after 300 cycles.
  • the number indicated next corresponds to the number of cycles from which the test becomes bad (Nok).
  • the stacks according to the invention all make it possible to obtain good results in the brush test, whereas this is not the case either for the reference (Ref.) or for the stack without gradient.
  • the presence of oxygen is crucial for obtaining a good TT_EBT.
  • the EBT test is not good with examples 1-1, 1-2 and 1-3, i.e. with a first layer of TiOx deposited without 02.
  • the EBT test is drastically improved for 2-1 and 2-2 stacks comprising a first layer of weakly oxidized titanium oxide.
  • Figures 3 explained by table 12 represent images taken under a microscope (x50 magnification) of the scratches made at 5N. This highlights the corrosion of the scratches after heat treatment for the reference stack and the absence of corrosion for the stack of the invention Emp.13-1.
  • the coated materials were processed using a laser line formed from a disc laser.
  • the following conditions were used: - disc laser source: Yb:YAG,
  • the laser treatment was carried out on the following stacks: Emp.0-1, EmpO-2, Emp.1-1, Emp.1-2, Emp.1-3, Emp.2-1, Emp. 2-2, Emp.12-1, Emp.12-2, Emp.12-3, Emp.13, Emp.13-1.
  • the examples of the invention show that an oxidation gradient coating based on titanium oxide makes it possible to obtain after heat treatment:
  • the oxidation gradient also allows:

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Surface Treatment Of Glass (AREA)
EP21749241.2A 2020-07-16 2021-07-13 Emissionsarmes material mit einer beschichtung mit einem oxidationsgradienten auf titanoxidbasis Pending EP4182278A1 (de)

Applications Claiming Priority (3)

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FR2007449A FR3112545B1 (fr) 2020-07-16 2020-07-16 Matériau à faible émissivité comprenant une couche à base d'oxyde de titane épaisse et une couche à base d'oxyde de zinc et d'étain
FR2007448A FR3112544B1 (fr) 2020-07-16 2020-07-16 Matériau à faible émissivité comportant un revêtement comprenant un gradient d'oxydation à base d'oxyde de titane
PCT/FR2021/051297 WO2022013496A1 (fr) 2020-07-16 2021-07-13 Matériau à faible émissivité comportant un revêtement comprenant un gradient d'oxydation à base d'oxyde de titane

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FR3131742A1 (fr) * 2022-01-10 2023-07-14 Saint-Gobain Glass France Vitrage contrôle solaire
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PL1833768T3 (pl) * 2004-12-21 2012-10-31 Agc Glass Europe Tafla szkła z naniesioną powłoką wielowarstwową
PL1888476T3 (pl) * 2005-05-11 2019-06-28 Agc Glass Europe Stos przeciwsłoneczny
FR2893023B1 (fr) * 2005-11-08 2007-12-21 Saint Gobain Substrat muni d'un empilement a proprietes thermiques
FR2911130B1 (fr) 2007-01-05 2009-11-27 Saint Gobain Procede de depot de couche mince et produit obtenu
EP3702337B1 (de) * 2008-03-20 2023-10-04 AGC Glass Europe Verglasung mit dünnschichtbeschichtung
BRPI0911918A2 (pt) * 2008-04-30 2015-10-06 Agc Glass Europe vitrificação para controle solar
FR3021967B1 (fr) 2014-06-06 2021-04-23 Saint Gobain Procede d'obtention d'un substrat revetu d'une couche fonctionnelle
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