AU2012324662B2 - Insulating glazing having a high light-transmission coefficient - Google Patents
Insulating glazing having a high light-transmission coefficient Download PDFInfo
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- AU2012324662B2 AU2012324662B2 AU2012324662A AU2012324662A AU2012324662B2 AU 2012324662 B2 AU2012324662 B2 AU 2012324662B2 AU 2012324662 A AU2012324662 A AU 2012324662A AU 2012324662 A AU2012324662 A AU 2012324662A AU 2012324662 B2 AU2012324662 B2 AU 2012324662B2
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- 239000011521 glass Substances 0.000 claims abstract description 30
- 230000005540 biological transmission Effects 0.000 claims abstract description 27
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 230000005855 radiation Effects 0.000 claims abstract description 14
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 239000010410 layer Substances 0.000 claims description 102
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 32
- 239000000758 substrate Substances 0.000 claims description 31
- 239000010936 titanium Substances 0.000 claims description 25
- 239000002346 layers by function Substances 0.000 claims description 23
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 21
- 239000010955 niobium Substances 0.000 claims description 19
- 230000003287 optical effect Effects 0.000 claims description 17
- 239000004411 aluminium Substances 0.000 claims description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 6
- 150000004767 nitrides Chemical class 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000002356 single layer Substances 0.000 claims description 4
- 229910017083 AlN Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 description 16
- 238000004737 colorimetric analysis Methods 0.000 description 10
- 238000000034 method Methods 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000014509 gene expression Effects 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 238000005299 abrasion Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 230000006870 function Effects 0.000 description 2
- 238000001755 magnetron sputter deposition Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 1
- 229910052770 Uranium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- OVBPIULPVIDEAO-LBPRGKRZSA-N folic acid Chemical compound C=1N=C2NC(N)=NC(=O)C2=NC=1CNC1=CC=C(C(=O)N[C@@H](CCC(O)=O)C(O)=O)C=C1 OVBPIULPVIDEAO-LBPRGKRZSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- C03C17/34—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
- C03C17/3649—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
- C03C17/3652—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 coating stack containing at least one sacrificial layer to protect the metal from oxidation
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Surface Treatment Of Glass (AREA)
Abstract
The invention relates to transparent single glazing formed by a sheet of glass provided with a coating consisting of a stack of thin layers acting on solar radiation, such that the glazing has a light transmission coefficient greater than or equal to 48% and a heat transmission coefficient (U) less than or equal to 5 W/m
Description
INSULATING GLAZING HAVING A HIGH LIGHT-TRANSMISSION COEFFICIENT
The invention relates to glazings known as solar-control glazings, equipped with stacks of thin layers, at least one of which is functional, that is to say that it acts on solar radiation, The present invention relates more particularly to multilayer glazings, especially those intended mainly for the thermal insulation of buildings.
The term "functional" or else "active" layer is understood within the context of the present ^PP-*~ i cat ion to mean the layer or layers of the stack which give the stack most of its thermal properties. Usually, the stacks of thin layers equipping the glazing give it substantially improved solar-control properties essentially through the intrinsic properties of this active layer. Said layer acts on the flux of solar radiation passing through said glazing, as opposed to the other layers, which are generally made of a dielectric material and have the function of chemically or mechanically protecting said functional layer.
Such glazings equipped with stacks of thin layers act on the incident solar radiation either essentially via cs.bsorptj.on of the incident radiation by the functional layer, or essentially via reflection by this same layer.
They are grouped together under the name of solar-control glazing. They are sold and used essentially - either for essentially ensuring solar-radiation protection of the dwelling and preventing an overheating thereof, such glazings being described in the solar-protection field, “ or essentially for ensuring thermal insulation of the dwelling and preventing heat losses, these glazings being described as insulating glazings.
The expression "solar-protection" is thus understood within the context of the present invention to mean the ability of the glazing to limit energy flux, in particular solar infrared radiation (SIR) passing through it from the outside to the inside of the dwelling or passenger compartment.
The expression "thermally insulating" is understood to mean a glazing equipped with at least one functional layer that gives it an energy loss, measured by the heat transmission coefficient U, of less than 5 W/m2/K.
Generally, all the light and energy characteristics presented in the present description are obtained according to the principles and methods described in the international standards ISO 9050 (2003) and ISO 10292 (1994) or European standards EN 410 (1998) and EN 673 (1998) relating to the determination of the light, solar and energy characteristics of glazings used in glass for construction.
Combined with the glass substrate, these coatings must also be aesthetically pleasing, that is to say that the glazing equipped with its stack must have a colorimetry, in transmission and in external reflection, that is sufficiently neutral so as not to inconvenience the users or alternatively a slightly blue or green shade in particular in the building field. The expressions "neutral colour" or "blue-green shade" are understood within the context of the present invention, in the CIE LAB (L*, a*, b*} colorimetry system, to mean absolute values a* and b* of less than or equal to 10, or even of less than or equal to 5, said values a* and b* preferably being negative.
From the interior side of the building (that is to say from the side of the glazing where the layer is present}, the possible values of the colorimetry are not as restrictive, as for the external face and deeper and more orangey-yellow colours may be accepted.
On the other hand, irrespective of the face of the glazing, this shade must be durable and uniform over the entire surface of the glazing, even if the stack of layers is subjected to premature wear conditions such as abrasion resulting from the cleaning of the panes of glass or else a prolonged exposure to outside humidity and to successive washing operations. The solution to such a problem of durable retaining of the same colorimetry over the entire surface of the glass is particularly pressing when the stack of layers is deposited on a single glazing, in particular on its face 2, that is to say the face intended to be turned towards the inside of the building.
Ideally, these glazings equipped with stacks must also be capable of undergoing a heat treatment of the toughening type without loss of their optical and/or energy properties. In particular, the glazings equipped with layers according to the invention must retain, after the heat treatment, in particular in transmission or in external reflection, the substantially neutral colour or else the blue-green shade described previously.
These coatings are conventionally deposited by sputtering deposition techniques under vacuum and enhanced by a magnetic field from a cathode of the material or of a precursor of the material to be deposited, often referred to as a magnetron sputtering technique in the field. Such a technique is today conventionally used especially when the coating to be deposited consists of a more complex stack of successive layers having thicknesses of a few nanometres or a few tens of nanometres.
The best performing stacks currently sold incorporate at least one metallic layer of silver type functioning essentially on the mode of the reflection of a major portion of the incident IR (infrared) radiation. These stacks are thus mainly used as low-emissivity (or lowe) glazings for the thermal insulation of buildings. These layers are however very sensitive to humidity and are therefore exclusively used in double glazings, on face 2 or 3 thereof in order to be protected from humidify. It is thus not possible to deposit such layers on single glazings (also referred to as monolithic glazings). The stacks according to the invention do not comprise such layers of silver type, or else of gold or platinum type or else in very negligible amounts, in particular in the form of inevitable impurities.
Other metallic layers having a solar-protection function have also been reported in the field, comprising functional layers of metallic or nitrided Nb type, as described for example in application WO 01/21540 or else in application WO 2009/112759. Within such layers, the solar radiation is this time predominantly absorbed non-selectively by the functional layer comprising niobium, the IR radiation (that is to say the radiation for which the wavelength is between around 780 nm and 2500 nm) and the visible radiation (the wavelength of which is between around 38 0 and 78 0 nm) being absorbed indiscriminately by the active layer.
In the least expensive solar-control single glazings, a single functional layer of niobium is deposited on a single glass substrate. As is generally acknowledged, the values of the thermal insulation coefficient U imposed by the standards in force in many countries can however in principle only be easily obtained in such single glazings if the functional layer of niobium is relatively thick, for example of the order of at least 10 nanometres, or even more. Due to the non-selective absorption of this same layer with respect to the incident radiation, the light transmission coefficients of such glazings, within the meaning written in the standard ISO 9050, are in principle very low, generally less than 30-s·, and. usually less than 20%, as can be seen in the examples reported in the aforementioned applications .
Ultimately, in view of such characteristics, it appears very difficult to obtain, from such stacks, solar-control glazings that combine acceptable heat transfer coefficients U, in particular of less than 5 W/m2/K, while retaining a high enough light trail emission, that is to say of greater than 48% and preferably of greater than 50%, in order to ensure good illumination of the dwelling.
As indicated previously, another constraint is also imposed during the production of the glazing: when the latter consists of a single glass substrate, it must usually undergo one or more heat treatments which may be a bending if it is desired to give it a curve (shop window) but which is usually a toughening, in particular in the building sector where it is desired that it be stronger and less dangerous in the event of impacts. The fact that layers are deposited on the glass before its heat treatment frequently leads to theij. deterioration and to a substantial modification of their properties, especially their optical properties. A contrario, depositing the layers after the heat treatment of the glass proves complex and expensive. As described previously, it is therefore imperative that such glazings equipped with such layers can undergo such heat treatments without significant variation of their initial colorimetric properties,
Furthermore, when the stack comprising the functional layer is deposited on a single glazing, for example on face 2, that is to say on the internal face of the glazing with respect to the building or passenger compartment that it equips, it must have sufficient chemical and mechanical resistance especially to exposure to the ambient atmosphere, in particular such that the colorimetry of the glazing, especially in transmission, remains, in the same way as before, substantially unchanged over the entire surface of the glazing.
The object of the present invention is to propose a single glazing (also referred to as monolithic glazing) simultaneously having sufficient thermal insulation properties, with in particular a heat transmission factor U of less than 5 W/mVK, a high light transmission, that is to say a light transmission factor TL of greater than 48%, preferably of greater than 50%, and which has no or virtually no colorimetric variation during heat treatments, especially of toughening type, or else when it is subjected to chemical or mechanical attach such as an abrasion.
According to the invention, by an appropriate selection of the various constituents of the stack of layers deposited on the initial glass substrate as stated in the claims nereinbelow, a thermally insulating single glazing nas thus been able to be obtained that has, in particular: - a light transmission of greater than 48% and preferably of greater than 50%, - a heat transfer coefficient U of less than s W/m2/K, equivalent to a normal emissivity εη of less than 0.60 (60%), of the single glazing equipped with the solar-control stack, and preferably a normal emissivity εη of less than 0.58, - a good durability especially with regard to tests of chemical/mechanical ageing with retention of the initial colorimetry.
The subject of the invention thus firstly consists of a single transparent insulating glazing, consisting of a sheet of glass equipped with a coating consisting of a stack of thin layers that act on solar radiation, in such a way that the glazing has a light transmission coefficient of greater than or equal to 48% and preferably greater than 50% and a heat transmission coefficient U of less than or equal to 5 W/m2/K, said glazing being characterized in that said coating comprises, from the surface of the substrate: " an underlayer consisting essentially of a nitride or of an oxynitride of aluminium and/or of silicon, having a physical thickness between 30 and 6 0 nm, - a functional layer of niobium Nb, having a physical thickness of between around 6 nm and around 7 nm, - an overlayer for protecting the functional layer with respect to the outside environment, said overlayer consisting either of a single layer consisting essentially of a nitride or of an oxynitride of aluminium and/or of silicon or of an assembly comprising the superposition of a layer essentially of a nitride or of an oxynitride of aluminium and/or of silicon and of a layer of an oxide chosen from silicon oxide and titanium oxide, the total optical thickness of said overlayer being between 80 and 110 nm,
The physical (or geometric) thickness of a layer is understood within the context of the present invention to mean the actual thickness of the layer, such as can be measured in particular by conventional electron microscopy techniques .
The optical thickness is understood conventionally within the context of the present invention to mean the preceding physical thickness multiplied by the refractive index n of the material which constitutes it, measured at 550 nm.
According to preferred embodiments of the invention which may, if necessary, be combined together: - Said coating additionally comprises at least one layer of a material chosen from the group consisting of Ti, Mo, A1 or an alloy comprising at least one of these elements, preferably Ti, positioned with respect to the glass substrate on top of the functional layer and directly in contact therewith, said layer having a physical thickness between around 0 . 2 nm and around 2 nm* Saict coating additionally comprises at least one layer of a material chosen from the group consisting of Ti, Mo, A1 or an alloy comprising at least one of these elements, preferably Ti, positioned with respect to the glass substrate underneath the functional layer and directly in contact therewith, said layer having a physical thickness between around 0,2 nm and around 2 nm. “ The overlayer consists of the succession of a layer consisting essentially of silicon nitride and of a layer of silicon oxide, the physical thickness of the aluminium and/or silicon nitride or oxynitride layer being between 40 and 50 nm and the physical thickness of the silicon oxide layer being between 3 and 10 nm. " The overlayer consists of the succession of a layer consisting essentially of silicon nitride and of a layer of titanium oxide, the physical thickness of the silicon nitride layer being between 30 and 45 nm and the physical thickness of the titanium oxide layer being between 5 and 15 nm. - The overlayer consists of a layer consisting essentially of silicon nitride, additionally optionally comprising aluminium. - The underlayer essentially consists of silicon nitride, additionally optionally comprising1 aluminium, ~ The total optical thickness of said overlayer is between 90 and 105 nm, in particular between 90 and 100 nm. -- The stack of thin layers is positioned on face 2 of the single glazing by numbering the faces of the substrate from the outside to the inside of the building or the passenger compartment that it equips ,
Finally, the present invention also relates oo a facade facing panel of spandrel glass type incorporating at least one glazing as described previously or to a side window, a rear window or a roof for a motor vehicle or other vehicle constituted by or incorporating said glazing.
The coatings according to the invention make it possible to obtain a relatively high value of the light transmission of the substrate, while retaining a significant insulating effect, despite the very small thickness of the functional layer: the measurements carried out indeed show a good compromise between the level of light transmission TL and the heat transfer coefficient U of the multilayer substrate.
The terms "on top of" and "underneath" refer in the present description to the respective position of said layers with respect to the glass substrate supporting the stack of said layers.
Without departing from the scope of the invention, it is possible according to the invention to dope the preceding silicon nitride layers with elements of the following type: Al, Zr, B, etc., so as to modify the colour in transmission and/or in reflection of the glazing, according to techniques that are well known in the art.
Although the application more particularly targeted by the invention is glazing for buildings, it is clear that other applications can be envisaged, especially in the glazings of vehicles (apart from the windscreen where a very high light transmission is required), such as side windows, the sunroof, the rear window.
The invention and its advantages are described in greater detail hereinbelow by means of the non-limiting examples below, which are examples according to the invention and comparative examples. In all the examples and the description, the thicknesses given are physical thicknesses,
All the substrates are made of clear glass having a thickness of 6 mm of Planilux type sold by the company Saint-Gobain Glass France.
All the layers are deposited in a known manner by magnetron sputtering. The layers made of pure metal (Nb, Ti) are deposited from the sputtering of targets made of metal in a reduced and inert (100% argon) atmosphere. The layers made of silicon nitride (subsequently denoted by Si3N4 even if the layer deposited does not necessarily correspond to this assumed stoichiometry) are deposited from a target made of metallic silicon (doped with 8% by weight of aluminium) in a reactive atmosphere containing nitrogen (4 0% Ar and 60% N2) . The layers made of Si3N4 therefore contain a small amount of aluminium. The layers made of silicon oxide (subsequently denoted by Si02 even if the layer deposited does not necessarily correspond to this assumed stoichiometry) are deposited from the metallic target made of silicon in a reactive atmosphere that contains oxygen, according to well-known techniques. The layers made of titanium oxide (subsequently denoted by Ti02 even if the layer deposited does not necessarily correspond to this assumed stoichiometry) are deposited from a metallic target made of titanium in a reactive atmosphere that contains oxygen, according to techniques that are also well known.
The following refractive indices, as given in the literature, are given: nsi3N4 of the order of 2, nTio2 of the order of 2.3 and nsios of the order of 1.45. EXAMPLE 1 (according to WO 01/21540)
This example has a functional layer made of Nb and an underlayer and over layer made of 813¾ according to the following sequence:
Glass/Si3N4 (10 nm)/Nb (35 nm)/Si3N4 (30 nm)
After the deposition of the layers, the glazing undergoes the following heat treatment: heating at 620°C for 10 minutes followed by toughening, EXAMPLE 2 (according to WO 2009/112750)
This example uses a sequence of layers deposited on the same substrate, a very fine layer of metallic titanium also being deposited on top of and underneath the functional layer, according to the teaching of the publication WO 2009/112759. The stack thus comprises the following succession of layers:
Glass/Si^ (40 nm) /Ti («1 nm) /Nb (10 nm) /Ti («1 nm) /Si3N4 (60 nm)
The glazing according to this example is not in accordance with the present invention with respect to the thickness of the functional layer and the optical thickness of the overlayer (120 nm).
The substrate coated with the stack then undergoes the same heat treatment as described in Example 1. EXAMPLE 3 (comparative)
This example uses a sequence of layers deposited on the same substrate, a very fine layer of metallic titanium also being deposited on top of and underneath the functional layer, according to the teaching of the publication WO 2009/112759. The stack thus comprises the following succession of layers:
Glass/SLNj {40 rm)/Ti {*<1 nm)/Nb {around 8-9 nm)/Ti («1 nrO/Si^ (60 rsm)
The glazing according to this example is not in accordance with the present invention with respect to the thickness of the functional layer and the optical thickness of the overlayer (120 nm).
The substrate coated with the stack then undergoes the same heat treatment as described in Example 1, EXAMPLE 4 (according to the invention)
This example uses a sequence of layers in accordance with the invention, deposited on the same substrate. The stack thus comprises the following succession of layers :
Glass/SiaNj {45 nm)/Ti (=1 nm}/Nb (6 nnt)/Ti (»1 nmJ/SisNj {38 nm)/TiQ> (9 nm)
The optical thickness of the overlayer, consisting of the layers of silicon nitride and of titanium oxide, is of the order of 98 nm.
The substrate coated with the stack then undergoes the same heat treatment as described in the preceding examples . EXAMPLE 5 (according to the invention)
This example uses the same sequence of layers as in the preceding example, deposited on the same substrate, with the exception of the overlayer. The stack thus comprises the following succession of layers:
Glass/SijEi (45 nm) /Ti {*1 ran)/Nb {6 ran) /Ti («1 ran) /Si^ {46 ran)/81¾ (5 ran)
The optical thickness of the overlayer, consisting of the layers of silicon nitride and of silicon oxide, is of the order of 100 nm.
The substrate coated with the stack then undergoes the same heat treatment as described in the preceding examples , EXAMPLE 6 (according to the invention}
This example uses the same sequence of layers as in the preceding example, deposited on the same substrate, with the exception of the overlayer. The stack thus comprises the following succession of layers:
Glass/Si3N4 (45 nm)/Ti («1 nm) /Nb (6 ran)/Ti («1 nm) /Si3N4 (49 nm)
The optical thickness of the overlayer, consisting of the layers of silicon nitride, is of the order of 100 nm.
The substrate coated with the stack then undergoes the same heat treatment as described in the preceding examples. EXAMPLE 2b (comparative)
This example uses the same sequence of layers as Example 2 above, deposited on the same substrate, with the exception of the underlayer of silicon nitride, the thickness of which is optimized to increase the light transmission thereof. The stack thus comprises the following succession of layers:
Glass/Si3N4 (60 nm)/Ti {«1 ran) /Nb (10 nm)/Ti {*1 nm) /Si3N4 (60 nm)
The optical thickness of the overlayer, consisting of the single layer of silicon nitride, is of the order of 123 nm.
The substrate coated with the stack then undergoes the same heat treatment as described in the preceding examples . EXAMPLE 3b (comparative)
This example uses the same sequence of layers as Example 3 above, deposited on the same substrate, with the exception of the two layers of silicon nitride, which are optimized in order to increase the light transmission thereof, The stack thus comprises the following succession of layers *
Glass/Si3N4 (60 nm)/Ti {*1 nm) /Nb (8-9 run) /Ti («1 nm) /Si3N4 (60 ran)
The optical thickness of the overlayer and of the underlayer, each consisting of the single layer of silicon nitride, xs of the order of 120 nm,
The substrate coated with the stack then undergoes the same heat treatment as described in the preceding examples ,
Table 1
The data listed in Table 1 show that Examples 1, 2 and 3 according to the prior art do not make it possible to obtain the desired criteria, namely a light transmission greater than or equal to 48% and preferably greater than or equal to 50% and a coefficient U of less than 5 w/m^/K (corresponding to a normal emissivity of less than 58%).
It can be seen that such objectives may nevertheless be achieved by a person skilled in the art starting from the stack of Example 3b by optimizing the optical thickness of the overlayer and the underlayer, so as to increase the light transmission. Examples 4, 5 and 6 according to the invention also make it possible to directly obtain such criteria owing to the very small thickness of the functional layer. On the other hand, a glazing equipped with a niobium layer having a thickness greater than or equal to 10 nm cannot have a light transmission of greater than 48% as shown by Example 2b, for which the respective thicknesses of the various layers have however been optimized in order to maximize the light transmission of the glazing.
The chemical resistance properties of the glazings according to Examples 6 (according to the invention) and 3b (comparative) were measured by an HH test, the experimental conditions of which are given below:
The glazings are placed in a chamber maintained at atmospheric pressure, under a temperature of 50°C in an atmosphere comprising 95% relative humidity.
The test is carried out on a portion of the glazing on two samples according to the same protocol for a same duration of 14 days, the rest of the glazing being protected from the humidity. The objective is to characterize the possible variations of colour in transmission, internal reflection and external refxection which would degrade the aesthetics of the giazings with respect to their original appearance, particularly if the chemical attacks are localized and give rise to marks of a visibly different colour. The quantity chosen for characterizing this change is, in the Clt. (L*, a*, b*} colorimetric system, the quantity ΔΕ* conventionally defined by the equation:
Table 2 below gives, for each of the two samples, the colorimetric differences, in transmission and in internal and external reflection, between the region of the glazing that has not undergone the chemical treatment and the treated region of the glazing.
Table 2
It is observed that the quantities measured ΔΕΤ and £ERLext between a region subjected to the HH test and a region that has not been treated is small for the two glazings according to Examples 6 and 3b, which indicates a substantially constant colorimetry of the glazings subjected to environment attacks, when they are observed from the outside.
On the contrary, examination of the colorimetry between a region subjected to the HH test and a region that has not been treated on the inner face of the glazing (that is to say the face turned towards the inside of the building) as measured by the quantity hERLint, shows very large colorimetric variations of the glazing according to comparative Example 3b. On the contrary, the glazing from Example 6 according to the invention is characterized by a much smaller colorimetric variation.
Ultimately, only the glazing coated with a stack according to the invention can therefore undergo the accelerated ageing test without its colorimetric properties, and also the desired optical and energy properties, being substantially modified thereby.
The same HH tests were also carried out on glazings according to Example 5 according to the invention. The results obtained are given in Table 3 below:
Table 3
Here too, it can be seen that between a region subjected to the HH test and a region that has not been treated, the glazings of Example 5 according to the invention are characterized by a very small colorimetric variation, as measured by the quantity ^^RLint ·
In conclusion, the solar-protection glazings according to the invention appear highly advantageous and not very expensive in particular for equipping buildings, without however excluding applications in motor vehicles and all vehicles: side windows, rear windows, sunroof, which may furthermore have enamelled coatings.
The stacks of layers according to the invention make it possible to obtain solar-control glazings having the desired TL and thermal insulation values and the colorimetry of which remains substantially constant, under the effect of the various treatments and chemical attacks to which they may be subjected during their manufacture and their use.
By application of the present invention, it is thus possible to manufacture solar-control glazings that allow improved vision and that also have a very good chemical durability, without significant variation of their colorimetry over time.
Without departing from the scope of the invention, it is also possible to make spandrel glass containing enamelled layers, rather than lacquered layers, which is industrially very advantageous, since the enamelling is carried out during the toughening process, whereas lacquering requires an additional manufacturing step.
It is to be understood that, if any prior art publication is referred to herein, such reference does not constitute an admission that the publication forms a part of the common general knowledge in the art, in Australia or any other country.
In the claims which follow and in the preceding description of the invention, except where the context requires otherwise due to express language or necessary implication, the word "comprise" or variations such as "comprises" or "comprising" is used in an inclusive sense, i.e. to specify the presence of the stated features but not to preclude the presence or addition of further features in various embodiments of the invention.
Claims (13)
1. Single transparent glazing, consisting of a sheet of glass equipped with a coating consisting of a stack of thin layers that act on solar radiation, in such a way that the glazing has a light transmission coefficient of greater than or equal to 48% and a heat transmission coefficient U of less than or equal to 5 W/m2/K, said glazing being characterized in that said coating comprises, from the surface of the substrate: - an underlayer consisting essentially of a nitride or of an oxynitride of aluminium and/or of silicon, having a physical thickness between 30 and 60 nm, - a functional layer of niobium Nb, the physical thickness of which is between around 6 nm and around 7 nm, - an overlayer for protecting the functional layer with respect to the outside environment, said overlayer consisting either of a single layer consisting essentially of a nitride or of an oxynitride of aluminium and/or of silicon or of an assembly comprising the superposition of a layer essentially of a nitride or of an oxynitride of aluminium and/or of silicon and of a layer of an oxide chosen from silicon oxide and titanium oxide, the total optical thickness of said overlayer being between 80 and 110 nm.
2. Glazing according to Claim 1, in which said coating additionally comprises at least one layer of a material chosen from the group consisting of Ti, Mo, A1 or an alloy comprising at least one of these elements, positioned with respect to the glass substrate on top of the functional layer and in contact therewith, said layer having a physical thickness between around 0.2 nm and around 2 nm.
3. Glazing according to either of Claims 1 and 2, in which said coating additionally comprises at least one layer of a material chosen from the group consisting of Ti, Mo, A1 or an alloy comprising at least one of these elements, positioned with respect to the glass substrate on top of and underneath the functional layer and in contact therewith, said layer having a physical thickness between around 0.2 nm and around 2 nm.
4. Glazing according to either of Claims 2 and 3, in which said material is Ti.
5. Glazing according to one of the preceding claims, in which the overlayer consists of the succession of a layer consisting essentially of silicon nitride and of a layer of silicon oxide, the physical thickness of the aluminium and/or silicon nitride or oxynitride layer being between 40 and 50 nm and the physical thickness of the silicon oxide layer being between 3 and 10 nm.
6. Glazing according to one of Claims 1 to 4, in which the overlayer consists of the succession of a layer consisting essentially of silicon nitride and of a layer of titanium oxide, the physical thickness of the silicon nitride layer being between 30 and 45 nm and the physical thickness of the titanium oxide layer being between 5 and 15 nm.
7. Glazing according to one of Claims 1 to 4, in which the overlayer consists of or comprises a layer consisting essentially of silicon nitride, additionally optionally comprising aluminium.
8. Glazing according to one of the preceding claims, in which the underlayer essentially consists of silicon nitride, additionally optionally comprising aluminium.
9. Glazing according to one of the preceding claims, in which the total optical thickness of said overlayer is between 90 and 105 nm.
10. Glazing according to claim 9, in which the total optical thickness of said overlayer is between 90 and 100 nm.
11. Single glazing incorporating the substrate according to one of the preceding claims, the stack of thin layers being positioned on face 2 of the single glazing by numbering the faces of the substrate from the outside to the inside of the building or the passenger compartment that it equips .
12. Facade facing panel of spandrel glass type incorporating at least one glazing according to one of Claims 1 to 11.
13. Use of glazing according to one of Claims 1 to 11 for the thermal insulation of buildings.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
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FR1159478A FR2981645B1 (en) | 2011-10-20 | 2011-10-20 | INSULATING GLAZING WITH HIGH COEFFICIENT OF LIGHT TRANSMISSION |
FR1159478 | 2011-10-20 | ||
PCT/FR2012/052362 WO2013057424A1 (en) | 2011-10-20 | 2012-10-17 | Insulating glazing having a high light-transmission coefficient |
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AU2012324662A1 AU2012324662A1 (en) | 2014-06-05 |
AU2012324662B2 true AU2012324662B2 (en) | 2016-06-09 |
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AU2012324662A Ceased AU2012324662B2 (en) | 2011-10-20 | 2012-10-17 | Insulating glazing having a high light-transmission coefficient |
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EP (1) | EP2768783B1 (en) |
KR (1) | KR102042587B1 (en) |
CN (1) | CN103946174B (en) |
AU (1) | AU2012324662B2 (en) |
ES (1) | ES2776134T3 (en) |
FR (1) | FR2981645B1 (en) |
HU (1) | HUE048100T2 (en) |
IN (1) | IN2014CN03421A (en) |
MX (1) | MX360954B (en) |
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FR3011836B1 (en) * | 2013-10-10 | 2015-10-23 | Saint Gobain | THERMAL CONTROL GLAZING |
CR20160407A (en) | 2014-02-10 | 2017-01-02 | Vidrio Plano Mexico Sa De Cv | COATING WITH SOLAR CONTROL PROPERTIES FOR A GLASS SUBSTRATE |
EP3722265B1 (en) * | 2019-04-11 | 2023-07-19 | Saint-Gobain Glass France | Method for assessing the sensitivity of a glass panel to forming quench marks |
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US20110027554A1 (en) * | 2008-02-27 | 2011-02-03 | Saint-Gobain Glass France | Solar-protection glazing having an improved light transmission coefficient |
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FR2799005B1 (en) | 1999-09-23 | 2003-01-17 | Saint Gobain Vitrage | GLAZING PROVIDED WITH A STACK OF THIN FILMS ACTING ON THE SOLAR RADIATION |
FR2869606B1 (en) * | 2004-04-28 | 2007-02-23 | Saint Gobain | GLAZING PROVIDED WITH A STACK OF THIN LAYERS ACTING ON SOLAR RADIATION |
FR2928913B1 (en) * | 2008-03-18 | 2011-05-20 | Saint Gobain | SUBSTRATE PROVIDED WITH A STACK WITH THERMAL PROPERTIES |
FR2949774B1 (en) * | 2009-09-08 | 2011-08-26 | Saint Gobain | MATERIAL COMPRISING A GLASS SUBSTRATE COATED WITH A THIN FILM STACK |
US8445111B2 (en) * | 2010-10-14 | 2013-05-21 | Guardian Industries Corp. | Gadolinium oxide-doped zirconium oxide overcoat and/or method of making the same |
US8703281B2 (en) * | 2011-01-11 | 2014-04-22 | Guardian Industries Corp. | Heat treatable coated article with breaker layer |
JP2014503461A (en) * | 2011-01-11 | 2014-02-13 | エージーシー グラス ユーロップ | Solar control plate glass |
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2011
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US20110027554A1 (en) * | 2008-02-27 | 2011-02-03 | Saint-Gobain Glass France | Solar-protection glazing having an improved light transmission coefficient |
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CN103946174A (en) | 2014-07-23 |
IN2014CN03421A (en) | 2015-07-03 |
MX2014004554A (en) | 2014-08-01 |
HUE048100T2 (en) | 2020-05-28 |
FR2981645A1 (en) | 2013-04-26 |
EP2768783B1 (en) | 2019-12-11 |
CN103946174B (en) | 2017-10-31 |
AU2012324662A1 (en) | 2014-06-05 |
FR2981645B1 (en) | 2013-11-01 |
PL2768783T3 (en) | 2020-05-18 |
EP2768783A1 (en) | 2014-08-27 |
KR102042587B1 (en) | 2019-11-11 |
MX360954B (en) | 2018-11-23 |
KR20140088521A (en) | 2014-07-10 |
WO2013057424A1 (en) | 2013-04-25 |
ES2776134T3 (en) | 2020-07-29 |
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