WO2022144519A1 - Solar control glazing comprising a thin film of nickel-chromium alloy and a thin film of sub-stoichiometric silicon nitride in nitrogen - Google Patents
Solar control glazing comprising a thin film of nickel-chromium alloy and a thin film of sub-stoichiometric silicon nitride in nitrogen Download PDFInfo
- Publication number
- WO2022144519A1 WO2022144519A1 PCT/FR2021/052430 FR2021052430W WO2022144519A1 WO 2022144519 A1 WO2022144519 A1 WO 2022144519A1 FR 2021052430 W FR2021052430 W FR 2021052430W WO 2022144519 A1 WO2022144519 A1 WO 2022144519A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- layer
- silicon nitride
- physical thickness
- glass article
- glazing
- Prior art date
Links
- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 71
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title claims abstract description 71
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 title claims description 59
- 229910052757 nitrogen Inorganic materials 0.000 title claims description 29
- 239000010409 thin film Substances 0.000 title 2
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 title 1
- 239000011521 glass Substances 0.000 claims abstract description 108
- 229910001120 nichrome Inorganic materials 0.000 claims abstract description 55
- 239000000758 substrate Substances 0.000 claims abstract description 36
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000010410 layer Substances 0.000 claims description 204
- 229910052710 silicon Inorganic materials 0.000 claims description 19
- 239000010703 silicon Substances 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 10
- 239000011651 chromium Substances 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 5
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 239000011241 protective layer Substances 0.000 claims description 5
- 229910000599 Cr alloy Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000001186 cumulative effect Effects 0.000 claims description 2
- 150000004767 nitrides Chemical class 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 claims description 2
- ZARVOZCHNMQIBL-UHFFFAOYSA-N oxygen(2-) titanium(4+) zirconium(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[Ti+4].[Zr+4] ZARVOZCHNMQIBL-UHFFFAOYSA-N 0.000 claims 1
- 238000010276 construction Methods 0.000 abstract description 3
- 229910018487 Ni—Cr Inorganic materials 0.000 abstract 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 17
- 229910052782 aluminium Inorganic materials 0.000 description 14
- 230000005540 biological transmission Effects 0.000 description 14
- 238000000034 method Methods 0.000 description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 238000000151 deposition Methods 0.000 description 11
- 238000005229 chemical vapour deposition Methods 0.000 description 9
- 230000005855 radiation Effects 0.000 description 9
- 230000008021 deposition Effects 0.000 description 8
- 238000004544 sputter deposition Methods 0.000 description 8
- 238000000576 coating method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 238000004040 coloring Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 6
- 230000007797 corrosion Effects 0.000 description 6
- 238000005260 corrosion Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000475 sunscreen effect Effects 0.000 description 6
- 239000000516 sunscreening agent Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910000906 Bronze Inorganic materials 0.000 description 5
- 239000010974 bronze Substances 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 229910052796 boron Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 239000002346 layers by function Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000004737 colorimetric analysis Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000004297 night vision Effects 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229910004219 SiNi Inorganic materials 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 2
- 230000004438 eyesight Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 230000001976 improved effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000005496 tempering Methods 0.000 description 2
- AZUYLZMQTIKGSC-UHFFFAOYSA-N 1-[6-[4-(5-chloro-6-methyl-1H-indazol-4-yl)-5-methyl-3-(1-methylindazol-5-yl)pyrazol-1-yl]-2-azaspiro[3.3]heptan-2-yl]prop-2-en-1-one Chemical compound ClC=1C(=C2C=NNC2=CC=1C)C=1C(=NN(C=1C)C1CC2(CN(C2)C(C=C)=O)C1)C=1C=C2C=NN(C2=CC=1)C AZUYLZMQTIKGSC-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 208000014451 palmoplantar keratoderma and congenital alopecia 2 Diseases 0.000 description 1
- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
- 239000002985 plastic film Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000005478 sputtering type Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000008093 supporting effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000001429 visible spectrum Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/001—General methods for coating; Devices therefor
- C03C17/002—General methods for coating; Devices therefor for flat glass, e.g. float glass
-
- 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
- C03C17/361—Coatings of the type glass/metal/inorganic compound/metal/inorganic compound/other
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3626—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one layer at least containing a nitride, oxynitride, boronitride or carbonitride
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3642—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating containing a metal layer
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
- C03C17/366—Low-emissivity or solar control coatings
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
- C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
- C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
- C03C17/3681—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating being used in glazing, e.g. windows or windscreens
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/70—Properties of coatings
- C03C2217/78—Coatings specially designed to be durable, e.g. scratch-resistant
Definitions
- Sunscreen glazing comprising a thin layer of nichrome and a thin layer of silicon nitride substoichiometric in nitrogen
- the present invention relates to glass articles for solar control glazing and said glazing, provided with coatings or stacks of layers, at least one of which is "functional", that is to say that it acts on the radiation solar and/or thermal essentially by reflection and/or absorption of near infrared (solar) or far (thermal) radiation.
- the present invention relates more particularly to a glass article, preferably so-called “sunscreen” glazing, comprising at least one clear glass substrate on which is deposited a stack of specific layers with specific thicknesses.
- a glass article preferably so-called “sunscreen” glazing
- One of the layers of said stack is a thin layer comprising nichrome, from the glass substrate, above which is deposited at least one thin layer comprising silicon nitride sub-stoichiometric in nitrogen.
- the glass article according to the invention is used as building or automobile glazing, preferably as building glazing, and its main function is to protect buildings from solar radiation in order to avoid overheating; such glazing being qualified in the trade of solar protection.
- the term "functional” or even “active” layer(s), within the meaning of the present application, means the layer(s) of the stack which confers on the stack the essential to its thermal properties. Most often, the stacks of thin layers equipping the glazing give it improved solar control properties essentially by the intrinsic properties of this or these active layer(s). For so-called sunscreen glazing, said layer acts on the flow of solar radiation passing through said glazing, as opposed to the other layers, generally made of dielectric material and essentially having the function of chemical or mechanical protection of the said layer(s). s) functional.
- Such glazing provided with stacks of thin layers act on the incident solar radiation either essentially by absorption of the incident radiation by the functional layer, or essentially by reflection by this same layer.
- “sunscreen” is meant within the meaning of the present invention the ability of the glazing or glass article to limit the energy flow, in particular the solar infrared radiation (1RS) passing through it from the outside to the inside of the dwelling or passenger compartment.
- the solar factor denoted “FS” or “g” is used in the field.
- the solar factor is equal to the ratio of the energy passing through the glazing (that is to say entering the room) and the incident solar energy. More specifically, it corresponds to the sum of the flux transmitted directly through the glazing and the flux absorbed by the glazing (including the stacks of layers possibly present on one of its surfaces) then re-emitted inwards (towards the room) through the glazing.
- low solar factor values indicate good solar protection against undesirable heating due to solar radiation of the room equipped with said glazing.
- a low value of the solar factor indicates that a glass article coated with a stack of layers is capable of keeping a room (a room) relatively cool during the summer months in hot ambient conditions. This is why a low solar factor is desired, particularly in countries with a hot climate.
- T L the visible range
- S the selectivity
- Antisun glazing comprising as functional layer: a layer of silicon oxycarbide deposited on a clear glass substrate. Such a layer allows the glazing to strongly reflect the visible light on the exterior side (side of the glass substrate not coated with layer(s) and which is directed towards the exterior environment).
- this layer of silicon oxycarbide is conventionally deposited on the clear glass substrate by CVD (chemical vapor deposition) methods which pose various problems, among which the following may be mentioned in particular:
- Ni or NiCr nickel denoted Ni or of nichrome denoted NiCr
- Single glazing equipped with these layers generally has good resistance to attacks mechanical and chemical properties compared to single glazing fitted with a stack of silver-based layers.
- the Applicant has therefore sought to provide a durable glass article, in particular a glazing, having solar protection properties and good selectivity, the color of which in external reflection is adjustable, by using a clear glass substrate.
- the applicant has optionally sought to provide a glass article having a good compromise between external reflection and internal reflection (in the visible range) and whose color in internal reflection is acceptable from an aesthetic point of view. Even more preferentially, the applicant has sought to provide a glass article having improved durability and more particularly better resistance to corrosion, especially after tempering.
- the object of the present invention is first of all to propose a glass article provided with a stack of layers having a good compromise between its light transmission and its thermal insulation properties, which results in good selectivity. .
- Another objective of the present invention is to be able to provide the glass article on its exterior face with an adjustable exterior color (that is to say on the face facing the outside of the building that it equips), c. i.e. values of the parameters a* ext and b*ext adjustable in the international La*b* system.
- one of the aims of the present invention is to obtain a specific color in external reflection (glass side), in particular a blue, gray or bronze coloration. According to the invention and advantageously in particular economically, it becomes possible to modify at will said colors in external reflection of a glass article by simply varying the thicknesses of the layers constituting a stack as described in the remainder of this request, in particular in the same sputtering device.
- a glass article is sought having good reflection on the side intended to be exposed towards the outside of the building (called external reflection in the present description), that is to say on the face of the glass article not covered with the stack of thin layers acting on solar radiation.
- the glazing in addition to the antisun properties previously explained, in the field of construction, in night vision, that is to say when the exterior luminosity is lower than the interior luminosity, the glazing may have the disadvantage of presenting a mirror effect for a observer placed inside the building, if the internal reflection of the glazing is too important and much higher than the external reflection. Such a mirror effect is undesirable because it prevents the observer placed inside the building from seeing the outside of the building.
- another advantage of the present invention is to be able to provide a glass article limiting the mirror effect indoors, in particular thanks to a limited reflection on the interior side (face of the glazing on which the stack is deposited) and in particular preferably lower or at least close to that of the exterior side (face of the glazing not covered). It is thus, according to the invention, to provide a glass article having a good compromise between the external reflection and the internal reflection.
- a stack of layers deposited on a clear glass substrate and specifically comprising the following succession of layers from the surface of said clear glass substrate made it possible to impart to the glass article the desired optical and thermal properties, said layers being the following:
- a first layer comprising silicon nitride in which the N/Si atomic ratio is greater than 1.25 and having a physical thickness of between 5 and 100 nm,
- nichrome of formula NiCr having a physical thickness of between 2 and 12 nm
- a second layer comprising silicon nitride in which the N/Si atomic ratio is less than 1.25 and having a physical thickness of between 2 and 15 nm, and
- a third layer comprising silicon nitride in which the ratio atomic N/Si is greater than 1.25 and has a physical thickness between 5 and 100 nm.
- T L a light transmission "T L " greater than or equal to 25%, preferably greater than 30%, and more preferably greater than 35%
- external light reflection “RLext” in the visible range is meant the light reflected towards the external environment and by internal light reflection “RLint” in the visible range, the light reflected towards the interior of a building or a vehicle.
- a reflection on the exterior side corresponds to the reflection on the face of the uncovered glass article and a reflection on the interior side (or called “interior reflection”) corresponds to the reflection on the face of the glass article on which the stack of layers is deposited.
- external face (or “external) and “inner face” or (“internal”) therefore refer to the position of the glass article or glazing when it equips the building or the vehicle that it equips, within the meaning of the present invention.
- stack side or “layer side” is meant the face of the glass article on which the stack is deposited.
- glass side is meant the face of the glass article opposite to that on which the stack is deposited, in principle not covered.
- the object of the present invention is to propose a glass article making it possible to solve the technical problems described above.
- the present invention relates to a glass article comprising at least one clear glass substrate on which is deposited a stack of layers, said stack of layers comprising the succession of the following layers from the surface of said clear glass substrate:
- first layer comprising silicon nitride, said layer possibly comprising at least one other element chosen from Al, Zr and B, in which the atomic ratio N/Si is greater than 1.25, the physical thickness of said layer being between 5 and 100 nm,
- NiCr nichrome of formula NiCr, optionally nitrided, the physical thickness of said NiCr layer being between 2 and 12 nm,
- a second layer comprising silicon nitride, said layer optionally comprising at least one other element chosen from Al, Zr and B, in which the atomic ratio N/Si is less than 1.25, the physical thickness of said layer being between 2 and 15 nm, and
- a third layer comprising silicon nitride, said layer optionally comprising at least one other element chosen from Al, Zr and B, in which the atomic ratio N/Si is greater than 1.25, the physical thickness of said layer being between 5 and 100 nm.
- each of said layers is in direct contact with the previous one.
- said first and third layers in which the N/Si ratio is greater than 1.25 are layers based on silicon nitride which are substantially stoichiometric or over-stoichiometric in nitrogen.
- the N/Si ratio of said first and third layers comprising silicon nitride of the glass article according to the invention may be greater than or equal to 1.33, and preferably is between 1.33 and 1, 60, terminals included.
- said first and third layers are substantially stoichiometric in silicon nitride.
- stoichiometric it is meant that the N/Si ratio is equal to 1.33 for these silicon-based nitride layers, corresponding to the Si 3 N 4 compound.
- substantially stoichiometric it is meant for example that the value measured for this Si 3 N 4 compound differs by less than 5% from this theoretical value.
- the layers comprising silicon nitride according to the invention are obtained by a magnetron-assisted sputtering process from a metallic silicon target which may comprise a minor quantity of another element such as aluminium, most often around 8 atomic %, in a reactive atmosphere containing nitrogen.
- Said second layer in which the N/Si ratio is less than 1.25 is itself a layer based on silicon nitride substoichiometric in nitrogen.
- the N/Si ratio of said second layer comprising silicon nitride of the glass article according to the invention may be less than or equal to 1.00, preferably less than or equal to 0.80 and more preferably between 0.20 and 1.00, terminals included.
- said second layer comprising silicon nitride substoichiometric in nitrogen is deposited specifically above the layer comprising nichrome, in the stack of layers.
- the layer comprising silicon nitride substoichiometric in nitrogen is in direct contact with said layer comprising nichrome.
- said second layer comprising silicon nitride substoichiometric in nitrogen placed above the layer comprising nichrome allows the glass article to be more durable, in particular to be more resistant to mechanical and chemical attack. , especially more resistant to corrosion.
- the inventors have also found that the use of this second layer comprising silicon nitride substoichiometric in nitrogen deposited above the layer comprising nichrome also made it possible to greatly reduce the unpleasant red coloration of the glass article in interior reflection .
- the first, second and third layers comprising silicon nitride mainly comprise silicon and nitrogen as main constituents.
- silicon and nitrogen together represent more than 50%, more than 60% or even more than 70% or even more than 80% of the atoms present in the layer, or even more than 90% of the atoms present in the layer.
- said layers comprising silicon nitride consist essentially of silicon and nitrogen and optionally of at least one element chosen from among aluminum, boron or zirconium, preferably aluminum, apart from the inevitable impurities.
- Said layers comprising silicon nitride are in principle free of oxygen except for inevitable impurities, for example they comprise less than 5% molar of elemental oxygen, in particular less than 1% molar of elemental oxygen.
- the stack of layers according to the invention does not comprise layers based on Ag, Au, Pt, Cu, or stainless steel.
- the contents of the various elements present in the layers described previously and in particular the N/Si ratio, can be measured according to any known technique.
- any known technique By way of example, mention may be made of energy-dispersive X-ray spectroscopy (or Energy-dispersive X-ray Spectroscopy: EDS or EDXS, in English) or the technique of photoelectron spectrometry by X-rays (or X- Ray Photoelectron Spectrometry: XPS, in English).
- the nichrome of the layer is preferably an alloy of nickel and chromium, comprising between 70% and 90% nickel and between 30% and 10% chromium.
- the layer comprising nichrome may also comprise nitrogen, preferably in an amount less than or equal to 20 atomic % of the sum of the nickel and chromium atoms, more preferably still less than 10 atomic % and more preferably less than 5 atomic % of the sum of nickel and chromium atoms.
- nitrogen preferably in an amount less than or equal to 20 atomic % of the sum of the nickel and chromium atoms, more preferably still less than 10 atomic % and more preferably less than 5 atomic % of the sum of nickel and chromium atoms.
- the additional presence of nitrogen in the layer comprising nichrome could affect the resistance of the glass article, in particular its chemical resistance, in particular if the glazing had to be subjected to a heat treatment such as quench.
- the first layer comprising silicon nitride has a physical thickness of between 70 and 100 nm, preferably between 75 and 90 nm,
- the layer comprising nichrome of formula NiCr has a physical thickness comprised between 4 and 12 nm, preferably comprised between 6.5 and 9.5 nm,
- the second layer comprising silicon nitride has a physical thickness comprised between 6 and 14 nm, preferably comprised between 8 and 12 nm, and
- the third layer comprising silicon nitride has a physical thickness comprised between 10 and 50 nm, preferably comprised between 15 and 35 nm.
- the first layer comprising silicon nitride has a physical thickness of between 5 and 25 nm, preferably between 10 and 20 nm,
- the layer comprising nichrome of formula NiCr has a physical thickness comprised between 4 and 10 nm, preferably comprised between 5.5 and 8 nm,
- the second layer comprising silicon nitride has a physical thickness comprised between 2 and 10 nm, preferably comprised between 2 and 6 nm, and
- the third layer comprising silicon nitride has a physical thickness comprised between 10 and 40 nm, preferably comprised between 15 and 30 nm.
- the first layer comprising silicon nitride has a physical thickness comprised between 15 and 45 nm, preferably comprised between 25 and 35 nm,
- the layer comprising nichrome of formula NiCr has a physical thickness of between 5 and 10 nm, preferably between 6.5 and 8.5 nm,
- the second layer comprising silicon nitride has a physical thickness comprised between 6 and 11 nm, preferably comprised between 8 and 10 nm
- - the third layer comprising silicon nitride has a physical thickness comprised between 70 and 100 nm, preferably comprised between 75 and 85 nm.
- the layer comprising nichrome and the second layer comprising silicon nitride, of the glass article according to the invention have a cumulative thickness of between 6 and 25 nm, preferably between 10 and 20 nm.
- the first layer comprising silicon nitride is deposited directly on the glass substrate and is in contact with it
- the stack is formed by the succession of said first layer comprising silicon nitride, of the layer comprising nichrome, of said second and third layers comprising silicon nitride, and optionally of said outer protective layer .
- the layers or coatings according to the invention are deposited by deposition techniques of the magnetic field-assisted vacuum sputtering type of a cathode of the material or of a precursor of the material to be deposited, often called the technique of magnetron sputtering in the field. .
- deposition techniques of the magnetic field-assisted vacuum sputtering type of a cathode of the material or of a precursor of the material to be deposited often called the technique of magnetron sputtering in the field.
- Such a technique is conventionally used today, in particular when the coating to be deposited consists of a stack of successive layers with thicknesses of a few nanometers or a few tens of nanometers.
- This layer deposition technique makes it possible to avoid the problems existing with the other CVD deposition techniques set out above.
- the glass articles according to the invention are durable over time, in the sense that their initial properties, in particular their coloring and their properties optical, vary only very slightly under chemical attack, such as corrosion, or under the mechanical attack to which they are subjected during their intended use.
- Laminated or laminated glazing conventionally means glazing comprising at least two glass substrates united by a plastic sheet, for example of the polyvinyl butyral (PVB) or polyurethane (PU) type.
- PVB polyvinyl butyral
- PU polyurethane
- the glass article comprises a stack of layers capable of undergoing a heat treatment such as tempering, bending or more generally a heat treatment at temperatures between 600° C. and 750° C., preferably between 680°C and 715°C, without loss of its optical and thermal properties.
- a heat treatment such as tempering, bending or more generally a heat treatment at temperatures between 600° C. and 750° C., preferably between 680°C and 715°C, without loss of its optical and thermal properties.
- the glass article, according to the invention can thus be heat-tempered and/or bent.
- the invention also relates to building glazing comprising a glass article as defined above.
- the application more particularly targeted by the invention is glazing for the building, it is clear that other applications are possible, in particular in the glazing of vehicles (apart from the windshield where one requires a very high light transmission), such as the side windows, the car roof or the rear window.
- the invention also relates to a method for manufacturing a glass article according to the invention, comprising for example the following steps:
- the level of nitrogen present in the second layer comprising silicon nitride is controlled in particular, by limiting the percentage of the nitrogen gas introduced into the sputtering chamber in the ixh/gas mixture, serving as plasma gas.
- all the layers comprising silicon nitride, according to the invention can comprise a minimal part of another element, in particular aluminum, useful during the process from vacuum deposition to sputtering of the silicon layer forming the cathodic target in the installation.
- silicon targets comprising 8 atomic % aluminum are conventionally used at present to improve their conductivity.
- the thicknesses given are physical. All the substrates are made of 4 mm thick glass of the Planilux® type marketed by the company Saint-Gobain Glass France. Examples 1a, 2a, 3a (prior art, clear glass substrate) In the following examples 1a, 2a and 3a, according to the prior art, the properties of highly reflective sunscreen glazings currently marketed by the applicant company under the reference Reflectasol®. These are glazings for buildings comprising a clear glass substrate on which is deposited by CVD deposition a stack of layers based on silicon oxycarbide.
- Examples 1b, 2b, 3b (prior art, tinted glass substrate)
- the properties of reflective sunscreen glazings currently marketed by the applicant company under the reference Reflectasol were measured. ®. These are windows for buildings comprising a tinted glass substrate: either blue (1b), gray (2b), or bronze (3b) on which is deposited by CVD deposition a stack of layers based on silicon oxycarbide.
- Example 1c, 2c, 3c (according to the invention)
- the clear glass substrate was covered with a stack of layers comprising the succession of the following layers to from the surface of said clear glass substrate: - a first layer comprising so-called “substantially stoichiometric" silicon nitride (N/Si ratio ⁇ 1.33 > 1.25), denoted Si 3 N 4 , - a layer comprising nichrome, which is an alloy of nickel and chromium comprising 80% nickel and 20% chromium, denoted NiCr, - a second layer comprising silicon nitride called "sub- stoichiometric” in nitrogen (N/Si ratio ⁇ 1.25), denoted SiN y and
- the layer stack sequence is therefore as follows: Clear glass / Si 3 N 4 (1 st layer) / NiCr / SiN y (2 nd layer) / Si 3 N 4 (3 rd layer)
- the thicknesses of the different layers are adjusted so as to obtain a building glazing with a blue color in external reflection in the visible range (glass side), which results in a value of b* in external reflection less than -15.
- the thicknesses of the different layers are adjusted so as to obtain a building glazing with a gray color in external reflection in the visible range (glass side), which results in a value of a* in external reflection between -4 and 4 and a value of b* in external reflection greater than 0.
- the thicknesses of the different layers are adjusted so as to obtain building glazing with a bronze color in external reflection in the visible range (glass side), which results in an a* value in reflection between 5 and 10 and a value of b* in external reflection between 10 and 25.
- Table 0 groups together the information concerning the constitution of the solar protection stacks 1c, 2c, 3c, according to the invention:
- All the layers according to these examples are deposited by sputtering assisted by magnetic field (often called magnetron), on a clear glass substrate.
- the different successive layers are deposited in the successive compartments of the sputtering device, each compartment being provided with a specific metal target in Si, or in NiCr, under conditions chosen for the deposition of a specific layer of the stack.
- the first and the third layer comprising silicon nitride, according to the invention, called “substantially stoichiometric” (N/Si ratio ⁇ 1.33 > to 1.25) are deposited in compartments of the device from silicon targets metal (doped with 8% aluminum mole), in a reactive atmosphere containing argon and nitrogen (60% Ar and 40% N2 by volume).
- silicon targets metal doped with 8% aluminum mole
- argon and nitrogen 60% Ar and 40% N2 by volume.
- These silicon nitride layers therefore contain a little aluminum, and are denoted Si 3 N 4 for convenience, knowing that the actual stoichiometry may be significantly different, in particular due to this doping (see the explanations previously provided in the description of the this application).
- the layer comprising nichrome is deposited from the sputtering of a target of an alloy of nickel and metallic chromium (80% Ni and 20% Cr) in a reactive atmosphere containing 100% argon.
- the second layer comprising silicon nitride called "sub-stoichiometric" in nitrogen (N/Si ratio ⁇ 1.25) is deposited above the layer comprising nichrome by means of another compartment of the device from the same target of metallic silicon doped with 8% by mole of aluminum, in a reactive atmosphere depleted in nitrogen and containing 95% Ar and 5% N2 by volume.
- This layer is denoted SiN y for convenience.
- the N/Si ratio in the layers comprising substantially stoichiometric silicon nitride Si 3 N 4 , as evaluated by X-ray photoelectron spectrometry (XPS) is of the order of 1.4, on the basis of the compounds defined AIN and Si 3 N 4 , and close to the theoretical value.
- the N/Si ratio in the layer comprising silicon nitride sub-stoichiometric in nitrogen SiN y is of the order of 0.6.
- the colorimetry parameters a* ext and b* ext in exterior reflection as well as the colorimetry parameters a*int and b*int in interior reflection are measured according to the international colorimetry model (L, a*, b*).
- the thermal insulation properties of the glazing are evaluated by determining the solar factor g, according to the conditions described in standard NF EN 410 (2011), and the selectivity S being the Ti_/g ratio.
- RLint 21.1%
- Such a characteristic makes such glazing suitable for use allowing vision from the interior to the exterior of the building, whatever the exterior lighting conditions.
- the glazing according to the invention 1c has a slightly red coloring in internal reflection.
- the glazing according to the invention 2c has a higher light transmission and better selectivity (S > 0.8) compared to the glazing according to the prior art 2a and 2b, while maintaining good external reflection (RLext > 20%).
- the color of the glazing according to the invention 2c in internal reflection is not red, but slightly blue.
- Example 4 comparativative
- Example 4 which follows, is deposited, according to the conventional magnetron technique described above, on a clear glass substrate of the Planilux® type marketed by the applicant company, the following stack of layers from the glass substrate clear: Si 3 N 4 (85 nm) / NiCr (10.6 nm) / Si 3 N 4 (30 nm).
- Example 1c (according to the invention) is identical to Example 4, except that an additional layer comprising silicon nitride called sub-stoichiometric in nitrogen (N/Si ratio ⁇ 1.25), denoted SiN y is deposited above the NiCr layer by means of another compartment of the device from the same metallic silicon target doped with 8% by mole of aluminum, in a reactive atmosphere depleted in nitrogen and containing 95% of Ar and 5% of N2, by volume (as indicated previously).
- an additional layer comprising silicon nitride called sub-stoichiometric in nitrogen (N/Si ratio ⁇ 1.25), denoted SiN y is deposited above the NiCr layer by means of another compartment of the device from the same metallic silicon target doped with 8% by mole of aluminum, in a reactive atmosphere depleted in nitrogen and containing 95% of Ar and 5% of N2, by volume (as indicated previously).
- the sequence of the layer stacks according to the invention is as follows starting from the clear glass substrate: Si 3 N 4 (1 st layer of 80 nm) / NiCr (8.0 nm) / SiN y (2 nd layer of 10 nm) / Si 3 N 4 (3rd layer of 25 nm).
- the N/Si ratio in the layers comprising substantially stoichiometric silicon nitride Si 3 N 4 ( 1st layer and 3rd layer ), as evaluated by X-ray photoelectron spectrometry (XPS), is order of 1.4 (based on the defined compounds AIN and Si 3 N 4 ) and close to the theoretical value.
- the N/Si ratio in the layer comprising silicon nitride sub-stoichiometric in nitrogen SiN y (2 nd layer) is of the order of 0.6.
- the single glazing prepared in accordance with the invention (example 1c) has thermal properties equivalent to those of the glazing of the comparative example (example 4) (same order of magnitude for g and S), as well as properties optics such as equivalent light transmission and exterior reflection.
- the use of an additional layer based on silicon nitride substoichiometric in nitrogen (deposited above the layer comprising nichrome) according to the invention makes it possible to lower the values of the parameters a*int and b*int in internal reflection (side of the glazing on which the stack of layers is deposited), and in particular the value of the parameter b*int, which makes it possible to obtain glazing that does not exhibit an intense red coloring in internal reflection.
- a monolithic solar glazing according to example 4 clear glass/Si 3 N 4 /NiCr/Si 3 N 4 (comparative example) and a monolithic solar glazing according to example 1 c (example according to the invention): clear glass/Si 3 N 4 /NiCr/SiN y /Si 3 N 4 , are subjected to the Cupro-acetic Salt Spray test “BSC” (or “CASS”: Copper Accelerated Salt Spray test, in English) according to the conditions described in standard EN ISO 9227: 2017. The results of the test show corrosion after 56 days almost 4 times higher for a glazing according to example 4, in particular on the coating side, in comparison with a glazing according to the invention (example 1 c).
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- Geochemistry & Mineralogy (AREA)
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Abstract
Description
Claims
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
MX2023007895A MX2023007895A (en) | 2020-12-31 | 2021-12-22 | Solar control glazing comprising a thin film of nickel-chromium alloy and a thin film of sub-stoichiometric silicon nitride in nitrogen. |
CONC2023/0008679A CO2023008679A2 (en) | 2020-12-31 | 2023-06-30 | Solar control glazing comprising a thin film of nickel-chromium alloy and a thin film of substoichiometric silicon nitride in nitrogen |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FRFR2014303 | 2020-12-31 | ||
FR2014303A FR3118441B1 (en) | 2020-12-31 | 2020-12-31 | Sunscreen glazing comprising a thin layer of nichrome and a thin layer of silicon nitride substoichiometric in nitrogen |
Publications (1)
Publication Number | Publication Date |
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WO2022144519A1 true WO2022144519A1 (en) | 2022-07-07 |
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Application Number | Title | Priority Date | Filing Date |
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PCT/FR2021/052430 WO2022144519A1 (en) | 2020-12-31 | 2021-12-22 | Solar control glazing comprising a thin film of nickel-chromium alloy and a thin film of sub-stoichiometric silicon nitride in nitrogen |
Country Status (4)
Country | Link |
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CO (1) | CO2023008679A2 (en) |
FR (1) | FR3118441B1 (en) |
MX (1) | MX2023007895A (en) |
WO (1) | WO2022144519A1 (en) |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0779255A1 (en) * | 1995-12-14 | 1997-06-18 | Guardian Industries Corp. | Matchable, heat treatable durable, IR-reflecting sputter-coated glasses and method of making same |
WO2004076174A1 (en) * | 2003-02-21 | 2004-09-10 | Guardian Industries Corp. | Heat treatable coated article with niobium chromium nitride ir reflecting layer and method of making same |
WO2012096771A1 (en) * | 2011-01-11 | 2012-07-19 | Centre Lexumbourgeois De Recherches Pour Le Verre Et La Ceramique S.A. (C.R.V.C.) | Heat treatable coated article with breaker layer with extended coloring possibilities |
WO2018129125A1 (en) * | 2017-01-05 | 2018-07-12 | Guardian Glass, LLC | Heat treatable coated article having titanium nitride and nickel chrome based ir reflecting layers |
-
2020
- 2020-12-31 FR FR2014303A patent/FR3118441B1/en active Active
-
2021
- 2021-12-22 WO PCT/FR2021/052430 patent/WO2022144519A1/en active Application Filing
- 2021-12-22 MX MX2023007895A patent/MX2023007895A/en unknown
-
2023
- 2023-06-30 CO CONC2023/0008679A patent/CO2023008679A2/en unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0779255A1 (en) * | 1995-12-14 | 1997-06-18 | Guardian Industries Corp. | Matchable, heat treatable durable, IR-reflecting sputter-coated glasses and method of making same |
WO2004076174A1 (en) * | 2003-02-21 | 2004-09-10 | Guardian Industries Corp. | Heat treatable coated article with niobium chromium nitride ir reflecting layer and method of making same |
WO2012096771A1 (en) * | 2011-01-11 | 2012-07-19 | Centre Lexumbourgeois De Recherches Pour Le Verre Et La Ceramique S.A. (C.R.V.C.) | Heat treatable coated article with breaker layer with extended coloring possibilities |
WO2018129125A1 (en) * | 2017-01-05 | 2018-07-12 | Guardian Glass, LLC | Heat treatable coated article having titanium nitride and nickel chrome based ir reflecting layers |
Also Published As
Publication number | Publication date |
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MX2023007895A (en) | 2023-07-10 |
FR3118441B1 (en) | 2022-12-23 |
CO2023008679A2 (en) | 2023-08-28 |
FR3118441A1 (en) | 2022-07-01 |
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