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WO2024150244A1 - Vitrage coloré en bronze comprenant un empilement de couches minces présentant une couche absorbante - Google Patents

Vitrage coloré en bronze comprenant un empilement de couches minces présentant une couche absorbante Download PDF

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Publication number
WO2024150244A1
WO2024150244A1 PCT/IN2023/051206 IN2023051206W WO2024150244A1 WO 2024150244 A1 WO2024150244 A1 WO 2024150244A1 IN 2023051206 W IN2023051206 W IN 2023051206W WO 2024150244 A1 WO2024150244 A1 WO 2024150244A1
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WO
WIPO (PCT)
Prior art keywords
glazing
layer
stack
dielectric
layers
Prior art date
Application number
PCT/IN2023/051206
Other languages
English (en)
Inventor
Priyesh DHANDHARIA
Uditendu MUKHOPADHYAY
Original Assignee
Saint-Gobain Glass France
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
Application filed by Saint-Gobain Glass France filed Critical Saint-Gobain Glass France
Publication of WO2024150244A1 publication Critical patent/WO2024150244A1/fr

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Classifications

    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • G02B1/115—Multilayers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10082—Properties of the bulk of a glass sheet
    • B32B17/10091—Properties of the bulk of a glass sheet thermally hardened
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10165—Functional features of the laminated safety glass or glazing
    • B32B17/10174—Coatings of a metallic or dielectric material on a constituent layer of glass or polymer
    • B32B17/1022—Metallic coatings
    • B32B17/10229—Metallic layers sandwiched by dielectric layers
    • 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
    • C03C17/3626—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
    • C03C17/3644—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
    • C03C17/3657—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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/28—Interference filters
    • G02B5/281—Interference filters designed for the infrared light
    • G02B5/282—Interference filters designed for the infrared light reflecting for infrared and transparent for visible light, e.g. heat reflectors, laser protection

Definitions

  • the present disclosure relates, in general to a glazing comprising a transparent substrate, on the surface of which a stack of thin layers is deposited which comprises a single functional layer based on silver making it possible to act on the solar and/or infrared radiation likely to strike said surface. More specifically the invention relates to a glazing having an absorber layer comprised in the stack of thin layers for achieving low visible light transmission and bronze external reflection color while maintaining good selectivity.
  • Solar control coatings comprise a plurality of stacks that are optimized for desired specific requirements based on geography and/or aesthetics and/or optical behavior and/or durability and/or functionality.
  • the thickness of the metallic layers in the stack can be increased. But, this essentially increases the internal and external light reflections on the coating side and glass side, respectively.
  • a low internal reflection is desirable to enables a clear view of the outside to a viewer positioned inside the building.
  • Patent FR-2751 666 it is proposed to insert, between the glass and the first dielectric layer, an absorbent layer based on iron oxide.
  • Patent FR-2 708 262 it is proposed to insert an absorbent layer of the titanium nitride type, in contact with and above the silver layer.
  • these solutions have a drawback in both cases if the stack of thin layers undergoes a heat treatment of the annealing, bending or toughening type: the absorbent layer will be significantly changed optically and/or make the multilayer stack in its entirety change optically.
  • Similar solutions are also found in Patent Application US 2008070044 and Patent US 729440 which suffer from the above mentioned drawback.
  • Patent documents US 11027527, US 10947153, US 7166360 US 10266446 and US 8507099 are all referenced herein for teachings related to coating comprising absorber layer for increasing durability and obtaining desirable external reflection colors viz., grey or silver, low visible transmission, desirable external reflectance values, desirable transmission color and more desirable internal reflective b* values, low SF and SHGC value(s).
  • the objective of the invention is therefore to develop a glazing having: low internal reflection while maintaining good selectivity; low light transmission; exceptional solar control properties and enhanced aesthetic appearance; capable of heat treatment without losing the solar control and aesthetic properties; low sheet resistance; and
  • the complexity of the stacks comprising silver-based functional layers makes it difficult to improve the thermal performance and reflection properties without adversely affecting the other properties of the stack.
  • the Applicant has surprisingly discovered that by optimizing the thicknesses of the barrier layers sandwiching the silver functional layer, inserting a thin absorbent layer between the first and second dielectric layers and engineering the thickness of the first, second and third dielectric layers, a layer stack capable of exhibiting the desired properties is obtained.
  • the solution of the invention represents an excellent compromise between the optical performance, thermal performance, transparency and aesthetic appearance.
  • the invention uses a coating stack having a single silver layer to obtain all the above mentioned properties thereby offering an economic solution. It is thus a purpose of this disclosure to help achieve all the said characteristics, detail of which will become apparent to the skilled artisan once given the following disclosure.
  • Certain example embodiments of this disclosure relate to a glazing that has visible light transmission of less than 30%; internal and external reflection of less than 20%; solar factor of less than 0.25 and selectivity up to 1.3
  • the glazing exhibits a bronze coloration in external reflection.
  • the glazing is durable having an increased thermal stability and mechanical performance while retaining desired optical characteristics of the article.
  • a glazing comprising a transparent substrate with a stack of thin layers.
  • the stack of thin layers comprises moving away from the transparent substrate: a first dielectric layer, an absorber layer consisting of niobium nitride or nickel chromium, a second dielectric layer, a first barrier layer, an IR reflecting layer based on silver or silver containing alloys, a second barrier layer and a third dielectric layer.
  • the second barrier layer is thicker than the first barrier layer, wherein the ratio of physical thickness of the second barrier layer to that of the first barrier layer is >3. It is characterized in that, the ratio of physical thickness of the third dielectric layer to the combined physical thickness of the first and second dielectric layer is greater than 0.6 and less than 1.5.
  • FIG. 1 illustrates a stack of thin layers deposited on a transparent glass substrate, according to one embodiment of the present disclosure
  • FIG. 2 illustrates a stack of thin layers deposited on a transparent glass substrate, according to one other embodiment of the present disclosure
  • FIG. 3 illustrates a stack of thin layers deposited on a transparent glass substrate, according to a particular embodiment of the present disclosure.
  • Embodiments disclosed herein are related to a bronze colored glazing comprising an absorber layer sandwiched in between the first and second dielectric layers underlying the silver functional layer sandwiched on either sides in direct contact with barrier layers, whose thickness in combination with the thicknesses of the first, second and third dielectric layers enable low visible light transmission, low internal and external reflection of less than 20%; solar factor of less than 0.25 and selectivity up to 1.3. Further the glazing exhibits bronze external reflection color and improved aesthetics for use in the context of insulating glass (IG) window units, vehicle windows, other types of windows, or in any other suitable application.
  • IG insulating glass
  • FIG. 1 illustrates a structure of a stack of thin layers having an absorber layer 100 deposited on a transparent substrate 10.
  • the absorber layer 100 is positioned between dielectric coatings 20 (first dielectric coating) and 40 (second dielectric coating) such that: the absorber layer 100, starting from the substrate, is positioned between the dielectric coatings 20 and 40.
  • a functional layer 150 is deposited above the absorber layer 100 and is in direct contact with a first barrier layer 51 below and a second barrier layer 52 above the functional layer 150.
  • the third dielectric coating 60 is deposited above the functional layer 150.
  • the dielectric coatings 20, 40, 60 each include at least one dielectric layers viz., 21, 41, 61.
  • Each dielectric layer includes a dielectric material.
  • the functional layer 150 comprises a noble material which preferably is silver or an alloy of silver.
  • the absorber layer 100 consist of either niobium nitride or nickel chromium.
  • the barrier layers 51, 52 comprise nickel chromium.
  • the stack of thin layers deposited on the transparent substrate 10 comprises moving away from the transparent substrate 10 outwardly the following layers: 21/ 100/ 41/ 51/ 150/ 52/ 61.
  • the layers 21, 100 ,41, 51, 150, 52 and 61 are deposited through magnetron sputtering or other types of sputtering or other suitable deposition techniques.
  • Other layers may be provided between illustrated layers in certain other embodiments of the present disclosure as shown in FIG. 2.
  • certain illustrated layers may be absent.
  • the stack of thin layers thereof shown in FIG. 1 are considered to be "on" the substrate 10 even when other layer(s) (not shown) are provided there between.
  • the stack of thin layers may further comprise as shown in FIG. 2 at least one overcoat layer 200.
  • the stack of thin layers may comprise more than one barrier layers (51a, 5 lb) deposited as under layers in contact with the functional layer; and/ or more than one barrier layers (52a, 52b) deposited as over layers in contact with the functional layer.
  • the presence of silver functional layer 150 makes the glazing 101 reflective and hence the absorber layer 100 is introduced to control reflection values.
  • the transparency of the glazing 101 may be controlled so as to obtain visible light transmission TL below 30%.
  • This range is particularly suitable for glazing’s intended to be used in high-sunshine regions.
  • the major advantage of the invention is that of achieving the satisfactory visual appearance while reducing both internal and external reflection values to as low as less than 20% and still retaining low sheet resistance and good selectivity.
  • This is attributable to the insertion of the thin absorber layer 100 chosen from a niobium nitride layer or a nickel chromium layer. More particularly significant is all these properties do not take place to the detriment of the solar protection performance.
  • the excellent energy performance is maintained without requiring substantial modifications of the other parameters of the stack such as the nature, the thickness and the sequence of the layers forming it.
  • the label “first”, “second”, “third” for the dielectric coatings are defined starting from the substrate bearing the stack and with reference to the layers or coatings having the same function.
  • the dielectric coating closest to the substrate is the first dielectric coating
  • the next one moving away from the substrate is the second dielectric coating etc.
  • Thicknesses stated in the present document with no other specifications are physical, real or geometric thicknesses and are expressed in nanometers (and not optical thicknesses).
  • the thickness of the dielectric coatings is represented as T. Tl, T2 and T3 according to the specific dielectric coating they refer to.
  • the three dielectric coatings 20, 40 and 60 satisfy the condition: the dielectric coatings 20, 40 and 60 each have a thickness Tl, T2 and T3, wherein the thickness Tl of the dielectric coating 20 ranges between 10 nm to 60 nm and/or thickness T2 of the dielectric coating 40 ranges between 5 nm to 25 nm and/or thickness T3 of the dielectric coating 60 ranges between 10 nm to 60 nm, inclusive of all said values mentioned for Tl, T2 and T3; and the ratio of physical thickness of the third dielectric layer to the combined physical thickness of the first and second dielectric layer is greater than 0.6 and less than 1.5, inclusive of the said value.
  • These thickness ranges for the dielectric coatings 20, 40 and 60 are the ranges for which the best results are obtained for a light transmission less than 30%, internal and external reflection as low as less than 20%, and external bronze reflection color values: a*g between 0 to +4 & b*g between +6 and +12 in combination with selectivity values up to 1.3 and solar factor less than 0.25.
  • the role of the barrier layer 52 deposited over the functional layer 150 is conventionally to protect the layers underneath from a possible degradation during the deposition of the upper dielectric coating and during an optional high- temperature heat treatment of the annealing, bending and/or tempering type.
  • the role of barrier layer 51 below the functional layer 150 is to promote adhesion and improve the mechanical durability during transport and processing.
  • the barrier layers 51, 52 are made of nickel chromium. When these barrier layers are deposited in metallic, nitride or oxide form, these layers may undergo a partial or complete oxidation depending on their thickness and the nature of the layers that surround them, for example, at the time of the deposition of the next layer or by oxidation in contact with the underlying layer.
  • the barrier layers 51, 52 satisfy the condition: the second barrier layer 52 is thicker than the first barrier layer 51; the ratio of physical thickness of the second barrier layer to that of the first barrier layer is >3.
  • the first barrier layer 51 has a thickness greater than 1 nm and less than 3 nm.
  • the second barrier layer 52 has a thickness greater than 4.5 nm and less than 10 nm.
  • the ratio of the physical thickness of the second barrier layer to that of the first barrier layer being >3 allows to reduce the internal reflection of the glazing while having a desired low TL value of less than 30% and a good selectivity, all the said properties with the use of just one silver layer in the coating stack.
  • Said ration of the first and second barrier layers is additionally advantageous for achieving all desirous optical and performance characterizes of the present invention using a single absorption layer as against all existing prior art that preferentially propose a coating stack comprising two absorption layers. Furthermore, the coating stack of the present invention comprising just a single absorption layer adds to the simplicity of working with the coating stack.
  • the absorber layer 100 is inserted between the first dielectric coating 20 and the second dielectric coating 40 and is made of niobium nitride layer or a nickel chromium layer.
  • the niobium nitride material is entirely nitrided. In many embodiments, fully or partially oxidized niobium is not desired.
  • the absorber layer 100 is made of niobium nitride which contributes to achieving bronze external reflection color by way of a*g ranging between 0 and +4 and b*g ranging between +6 and +12.
  • Thickness of the absorbent layer 100 is in the range of 1 nm and 5 nm. While the absorber layer is not restricted to NbN and NiCr, similar materials performing in a similar manner to substantially result in similar or substantially similar properties when used in the specifically claimed stack is considered to also fall within the scope of the invention.
  • the position of the absorber layer between the first and second dielectric coating 20, 40 provides for a better control over reflection values both in the external glass side and the internal coating side. Further this configuration of the absorber layer provides for achieving a bronze external reflection color.
  • Each of the three dielectric coatings 20, 40, 60 comprise at least one dielectric layer comprising one of silicon nitride or silicon zirconium nitride.
  • the dielectric material is silicon nitride.
  • each of the three dielectric coatings 20, 40, 60 each comprise a dielectric layer each viz., 21; 41 and
  • each of the three dielectric coatings 20, 40, 60 comprise at least one dielectric layer comprising one of silicon nitride or silicon zirconium nitride and at least one other dielectric layer comprising one of silicon nitride or silicon zirconium nitride.
  • the first dielectric coating 20 includes a dielectric layer 21 made of silicon nitride.
  • the second dielectric coating 40 includes a dielectric layer 41 made of silicon nitride and the third dielectric coating 60 includes a dielectric layer 61 made of a silicon nitride.
  • the dielectric layers 20, 40 placed in the immediate vicinity of the absorbent layer 100 both above and below comprise of a metallic nitride material which includes one of silicon nitride or silicon zirconium nitride.
  • the absorbent layer 100 is sandwiched between two dielectric layers made of silicon nitride.
  • the first dielectric coating 20 comprising the dielectric layer 21 is positioned below the functional layer 150; the dielectric layer 21 has a barrier function and is based on most preferably silicon nitride optionally doped with zirconium.
  • the third dielectric coating 60 comprising the dielectric layer 61 is positioned above the absorber layer 100; the dielectric layer 61 has a barrier function and is based on most preferably silicon nitride optionally doped with zirconium.
  • the second dielectric coating 40 comprises dielectric layer 41 positioned between the functional layer 150 and the absorbent layer 100.
  • the dielectric layer 41 has a barrier function and is based most preferably on silicon nitride.
  • the second dielectric coating 40 may comprise at least two dielectric layers having a barrier function; and/or a stabilizing function; and/or a smoothing function.
  • Dielectric layer having a barrier function should be understood as a layer made of a material capable of forming a barrier to the diffusion of sodium, oxygen and/or water at high temperature, originating from either the transparent substrate or the ambient atmosphere towards the functional layer.
  • the constituent materials of the dielectric layer having a barrier function thus must not undergo chemical or structural modification at high temperature which would result in a modification to their optical properties.
  • the layer or layers having a barrier function are preferably also selected from a material capable of forming a barrier to the constituent material of the functional layer.
  • the dielectric layers having a barrier function thus allow the stack to be subjected to heat treatments of the annealing, tempering or bending type, without excessively significant optical change.
  • the stack of thin layers comprises at least one overcoat layer 200 deposited farthest from the surface capable of being in contact with the atmosphere based on titanium zirconium nitride or oxynitride or titanium zirconium oxide.
  • the stack of thin layers comprises at least two overcoat layers disposed farthest from the surface capable of being in contact with the atmosphere one layer based on titanium zirconium nitride or oxynitride or titanium zirconium oxide and another layer based on Carbon.
  • the overcoat layer generally has a thickness of less than 5 nm, more preferably less than 4 nm.
  • the glazing 101 is provided with a temporary protective coating conventionally known in the art in order as the furthest layer from the substrate to protect the underlying stack of thin layers during heat treatment. As is known from the conventional processes this temporary protective layer is burned off during the heat treatment.
  • a glazing 101 having the stack of thin layers comprises starting from the glass substrate 10, as illustrated in FIG. 3: a first dielectric coating 20 comprising at least one dielectric layer having a barrier function 21 made of SislS ; an absorber layer 100 made of NbN; a second dielectric coating 40 comprising at least one dielectric layer one having a barrier function 41 made of SislS ; a first barrier layer 51 made of NiCr; a functional layer 150 made of Silver; a second barrier layer 52 made of NiCr; a third dielectric coating 60 comprising at least one lower dielectric layer having a barrier function 61 made of SislS ; and optionally one overcoat layer 200 made of TiZrN.
  • the transparent substrates according to the present invention are preferably made of an inorganic rigid material, such as glass, or an organic material based on polymers (or made of polymer).
  • the substrate is preferably a sheet of glass or of glass-ceramic.
  • the substrate is preferably transparent, colorless (it is then a clear or extra-clear glass) or colored, for example colored blue, grey, green or bronze.
  • the glass is preferably of soda-lime-silica type, but it may also be made of glass of borosilicate or alumino-borosilicate type.
  • 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 12 mm, or even between 4 and 10 mm.
  • the substrate may be flat or curved, or even flexible.
  • the material may undergo a high-temperature heat treatment such as an annealing, for example a flash annealing such as a laser or flame annealing, a tempering and/or a bending.
  • a high-temperature heat treatment such as an annealing, for example a flash annealing such as a laser or flame annealing, a tempering and/or a bending.
  • the temperature of the heat treatment is greater than 500° C, preferably greater than 550° C, and better still greater than 600° C.
  • the substrate coated with the stack may therefore be curved and/or tempered.
  • the invention also relates to a glazing comprising a material according to the invention.
  • the faces of a glazing are denoted starting from the outside of the building and by numbering the faces of the substrates from the outside towards the inside of the passenger compartment or room that it equips. This means that the incident solar light passes through the faces in the increasing order of their number.
  • the stack is preferably positioned in the glazing so that the incident light coming from outside passes through the first dielectric coating before passing through the absorber layer.
  • the stack is not deposited on the face of the substrate that defines the external wall of the glazing but on the inner face of this substrate.
  • the stack is therefore advantageously positioned on face 2, face 1 of the glazing being the outermost face of the glazing, as is customary.
  • the material may be intended for applications that require the substrate coated with the stack to have undergone a heat treatment at a high temperature such as a tempering, an annealing or a bending.
  • the glazing of the invention may be in the form of monolithic, laminated or multiple glazing, in particular double glazing or triple glazing.
  • the stack is preferably deposited on face 2, that is to say that it is on the substrate that defines the external wall of the glazing and more specifically on the inner face of this substrate.
  • a monolithic glazing comprises 2 faces; face 1 is on the outside of the building and therefore constitutes the external wall of the glazing, face 2 is on the inside of the building and therefore constitutes the internal wall of the glazing.
  • a multiple glazing comprises at least two substrates kept at a distance so as to delimit a cavity filled by an insulating gas (e.g., dry air, Ar, Kr or their mixture).
  • an insulating gas e.g., dry air, Ar, Kr or their mixture.
  • the materials according to the invention are very particularly suitable when they are used in double glazings with enhanced thermal insulation (ETI).
  • a double glazing comprises 4 faces; face 1 is outside of the building and therefore constitutes the external wall of the glazing, face 4 is inside the building and therefore constitutes the internal wall of the glazing, faces 2 and 3 being on the inside of the double glazing.
  • a triple glazing comprises 6 faces; face 1 is outside of the building (external wall of the glazing), face 6 is inside the building (internal wall of the glazing) and faces 2 to 5 are on the inside of the triple glazing.
  • a laminated glazing comprises at least one structure of first substrate/sheet(s)/second substrate type. The stack of thin layers is positioned on at least one of the faces of one of the substrates. The stack may be on the face of the second substrate not in contact with the, preferably polymer, sheet. This embodiment is advantageous when the laminated glazing is assembled as double glazing with a third substrate.
  • the glazing according to the invention used in a multiple glazing e.g., a double glazing unit, has neutral internal reflection color.
  • the glazing has a bronze external reflective coloration.
  • the external color is not too dull at the same time is not too reflective.
  • the glazing of the invention has colors in reflection on the external side in the L*a*b* color measurement system: a*ext between 0 and 4, preferably between 1 to 3; in a particular exemplary embodiment a* ext is 2.1; b* ext between +6 and +12, preferably less than 7 to 11; in a particular exemplary embodiment b* ext is 10.5.
  • the glazing of the invention in the form of a double glazing comprising the stack positioned on face 2 makes it possible to achieve, in particular, the following performances: a solar factor less than or equal to 25%, preferably less than or equal to 22%, and/or a high selectivity, in order of increasing preference, of at least 1.0, or at least 1.2, and/or a low emissivity, in particular of less than 0.07, and/or sheet resistance no greater than 6 Q/square, and/or a light reflection on the external side of less than or equal to 20%, preferably less than or equal to 18%, and/or a light reflection on the internal side of less than or equal to 20%, preferably less than or equal to 18%, and/or bronze in external reflection.
  • the stack is deposited by magnetron sputtering.
  • all the layers of the stack are deposited by magnetron sputtering.
  • Stack of thin layers are deposited on substrates made of clear soda-lime glass with a thickness of 6 mm.
  • the functional layer is a layer of silver (Ag)
  • the absorber layer is based on niobium nitride (NbN)
  • the barrier layers are metallic layers made of nickel -chromium alloy (NiCr)
  • the dielectric layers are based on silicon nitride (SisN ⁇
  • the overcoat layers are made of titanium zirconium oxide (TiZrNx).
  • Table 1 lists the materials and thicknesses in nanometers for each layer of coating that forms the stacks as a function of their position with respect to the substrate bearing the stack (final line at the bottom of the table).
  • the “Ref.” numbers correspond to the references from FIG. 3.
  • Comparative samples were also prepared by constructing the stack of thin layers as shown in Table 2.
  • Table 2 Stack of thin layers - Comparative Sample
  • Table 3 lists the main optical characteristics measured when the glazings are part of double glazing having a 6/12/6 structure: 6 mm glass/12 mm interlayer space filled with 100% air/6 mm glass, the stack being positioned on face 2 (face 1 of the glazing being the outermost face of the glazing, as is customary).
  • face 1 of the glazing being the outermost face of the glazing, as is customary.
  • TL indicates: the light transmission in the visible region in %, measured according to the illuminant D65 Obs 2; a*T and b*T indicate the a* and b* colors in transmission in the L*a*b* system measured according to the illuminant D65 Obs 2 and measured perpendicularly to the glazing;
  • Rext indicates: the light reflection in the visible region in %, measured according to the illuminant D65 Obs 2 on the side of the outermost face, face 1; a*Rext and b*R ex t indicate the a* and b* colors in reflection in the L*a*b* system measured according to the illuminant D65 Obs 2 on the side of the outermost face and thus measured perpendicularly to the glazing;
  • Rint indicates: the light reflection in the visible region in %, measured according to the illuminant D65 Obs 2 on the side of the internal face, face 4; a*Rint and b*Rint indicate the a* and b* colors in reflection in the L*a*b* system measured according to the illuminant D65 Obs 2 on the side of the internal face and thus measured perpendicularly to the glazing.
  • the samples according to the present invention all have bronze color in external reflection, less than 20% internal and external reflection and light transmission less than 30%.
  • the examples presented are particularly advantageous since they have the desired aesthetic appearance, in addition to low solar factor and a good selectivity, using coating stack comprising only one silver layer and one absorber layer.
  • the proposed invention therefore makes it possible to achieve combined desired solar performance, optical and aesthetic properties using a single silver layered coating stack.
  • the comparative sample 1 was prepared with the third dielectric layer having an increased thickness, such that the ration of third dielectric layer thickness to the sum of the thicknesses of the first and second dielectric layers was 1.8 (outside the claimed ration of 0.3 to 1.5).
  • comparative sample 1 exhibits increased external reflection Rg 28% and a negative a*g (-2.5).
  • comparative sample 2 was prepared with first and second barriers layers having same thickness value, which resulted in increased internal reflection of 23%.
  • the glazing described in the present disclosure finds application as a glazed element in building.
  • the glazing may form a double or triple glazing with the coating side of the glass arranged facing the closed space inside the multiple glazing.
  • the glazing may also form a laminated glazing whose stack of layers may be in contact with the thermoplastic adhesive material connecting the substrates, in general PVB.
  • the glazing according to the invention is, however, particularly useful when the multilayer stack is facing the outer environment, whether it is an insulated glazing or laminated glazing, but also optionally a multiple glazing.
  • the glazing may also be enameled.
  • the glazing of the present disclosure can also be annealed, strengthened, toughened, tempered or curved and/or bent.
  • the tempered glazing can also be used in building wall cladding panel of curtain walling for interior applications. Further an also be used as a side window, rear window or sunroof for an automobile or other vehicle.
  • the terms “comprises,” “comprising,” “includes,” “including,” “has,” “having” or any other variation thereof, are intended to cover a non-exclusive inclusion.
  • a method, article, or apparatus that comprises a list of features is not necessarily limited only to those features but may include other features not expressly listed or inherent to such method, article, or apparatus.
  • “or” refers to an inclusive-or and not to an exclusive-or. For example, a condition A or B is satisfied by any one of the following: A is true (or present) and B is false (or not present), A is false (or not present) and B is true (or present), and both A and B are true (or present).

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  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
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  • Surface Treatment Of Glass (AREA)

Abstract

Selon l'invention, un empilement de couches minces sur un substrat transparent comprend une couche fonctionnelle d'argent présentant des propriétés de réflexion dans la plage de rayonnement infrarouge et/ou solaire, qui est prise en sandwich entre un premier et un second revêtement diélectrique. Une couche d'absorbeur mince prise en sandwich de chaque côté par une couche barrière est placée sous la couche fonctionnelle d'argent pour réaliser une couleur de réflexion externe de bronze, moins de 20 % de réflexion externe et interne, une transmission visible inférieure à 30 %, une bonne sélectivité et un faible facteur solaire.
PCT/IN2023/051206 2023-01-10 2023-12-21 Vitrage coloré en bronze comprenant un empilement de couches minces présentant une couche absorbante WO2024150244A1 (fr)

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IN202341002142 2023-01-10

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019111273A1 (fr) * 2017-12-08 2019-06-13 Saint-Gobain Glass France Article en verre de contrôle solaire
WO2020089545A1 (fr) * 2018-10-30 2020-05-07 Saint-Gobain Glass France Materiau comprenant un substrat muni d'un empilement de couches minces a proprietes thermiques
IN202041055494A (fr) * 2020-12-21 2022-02-24

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019111273A1 (fr) * 2017-12-08 2019-06-13 Saint-Gobain Glass France Article en verre de contrôle solaire
WO2020089545A1 (fr) * 2018-10-30 2020-05-07 Saint-Gobain Glass France Materiau comprenant un substrat muni d'un empilement de couches minces a proprietes thermiques
IN202041055494A (fr) * 2020-12-21 2022-02-24

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