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
  • C03C17/3613—Coatings of type glass/inorganic compound/metal/inorganic compound/metal/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
  • C03C17/3639—Multilayers containing at least two functional metal layers
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3644—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the metal being silver
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
  • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
  • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
  • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
  • C03C17/3657—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer the multilayer coating having optical properties
  • C03C17/366—Low-emissivity or solar control coatings
• • C—CHEMISTRY; METALLURGY
  • 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
  • C03C2218/00—Methods for coating glass
  • C03C2218/10—Deposition methods
  • C03C2218/15—Deposition methods from the vapour phase
  • C03C2218/154—Deposition methods from the vapour phase by sputtering
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C2218/00—Methods for coating glass
  • C03C2218/10—Deposition methods
  • C03C2218/15—Deposition methods from the vapour phase
  • C03C2218/154—Deposition methods from the vapour phase by sputtering
  • C03C2218/155—Deposition methods from the vapour phase by sputtering by reactive sputtering
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
  • Y10T428/24942—Structurally defined web or sheet [e.g., overall dimension, etc.] including components having same physical characteristic in differing degree
  • Y10T428/2495—Thickness [relative or absolute]
  • Y10T428/24967—Absolute thicknesses specified
  • Y10T428/24975—No layer or component greater than 5 mils thick
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
  • Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
  • Y10T428/264—Up to 3 mils
  • Y10T428/265—1 mil or less

Definitions

• the present invention relates to low-emissivity glazing in other words glazing that reflects a very large portion of infrared radiation and let the wavelength rays of the visible. More specifically, the invention relates to low emissivity glazings which retain or improve their opto-energetic characteristics when subjected to intense heat treatment such as thermal quenching and / or bending operation.
• Low emissivity and high light transmittance glazing is traditionally obtained by applying to a sheet of glass a thin metal layer, in particular a silver-based layer, which is protected against various possible alterations by dielectric protective layers.
• the layers are applied by a vacuum deposition technique of the so-called "sputtering" type, the material of the layers is obtained from targets bombarded by ionized particles which detach the elements of the target which, possibly after reaction with the components of the atmosphere are deposited on the glass sheet constituting the substrate.
• the barrier layer is implemented essentially to protect the silver metal layer from possible degradation during the application of the dielectric layer II. This is particularly the case when the latter is deposited according to a so-called "reactive" technique in which the deposition is carried out from metal targets in an atmosphere reacting with the deposited metal, in particular an oxidizing or nitriding atmosphere.
• the dielectrics I and II have several functions. They are necessary to constitute an interference filter which makes it possible to reduce the reflection of the visible wavelengths, and consequently makes it possible to increase the light transmission. They are also implemented so that the fraction reflected in the visible leads to a color neutrality as far as possible, and in particular that the reflection does not lead to purple shades to satisfy the preferences of customers on this subject. In addition, the choice of the dielectric layers, or dielectric layer systems, is such that the neutrality in reflection is obtained for the widest range of angles of incidence relative to the glazing.
• the dielectric layers must as far as possible lead to the formation of a metal layer whose properties are optimized.
• the layer can indeed lead to a higher or lower emissivity depending on how it is formed in contact with the dielectric and in particular the dielectric I.
• US Patent 5,110,662 teaches that the use of a thin layer of zinc oxide immediately below the metal layer can significantly improve the properties of the assembly especially with regard to emissivity. This improvement seems to come from the structure of this zinc layer which would have a very regular interface with the deposited metal layer, promoting the growth of the latter in a well controlled structure.
• the glazing with the layer systems must be able to withstand a heat treatment of the bending / tempering type.
• the layer systems can be modified. Depending on the conditions, these modifications may improve certain properties, including emissivity, by what appears to be a transformation of the crystal structure of the silver-based layers. But this requires the very particular choice of layer sets. In the absence of this, the degradation of one or more of the fundamentally sought-after properties of these glazings, for example emissivity, coloring in reflection or the appearance of sail ("haze").
• the systems implemented are the result of difficult selections, as regards the materials of the layers as that of their arrangement in these stacks, the modification of a characteristic to improve a property being able to have a negative effect on the other properties.
• glazing which may or may not be hardenable, having an emissivity of less than 0.04 met the regulations until recently, the most stringent regulations now require glazing whose emissivity does not exceed 0.038, or, according to the terms of these regulations, in which the coefficient u ⁇ for an insulating glass consisting of two sheets of glass 4mm thick, the layer system being in position 3 and the space between the sheets being 90% argon and 10% of dry air, is such that
• titanium oxide has the advantage, in addition to a relatively low cost, of good light transmission and high chemical stability. For this reason, the use of titanium oxide layers may seem advantageous. This use is indeed for glazing that is not subjected to heat treatment after the formation of the layers. For these windows, the systems therefore often include a more or less thick layer of titanium oxide.
• the inventors have found that the introduction of a layer of titanium among those situated under the silver layer, led to a degradation of the properties of this layer after the glazing has been subjected to a heat treatment of the type bending / tempering. This degradation is observed even though the silver layer is not even in contact with the titanium layer
• This modification which could come from that of the contiguous layers, can also be induced by backlash, by layers which are not in direct contact with the money.
• the first case is that for example in which a layer on which the silver is based has an irregular interface such as that coming from a too marked columnar structure.
• a structure of this type can be found, for example, in zinc oxide layers of excessive thickness, even though a layer of small thickness, as indicated above, is on the contrary very favorable to the growth of a silver layer with good properties.
• titanium oxide is in various structures depending on the conditions under which the layer is formed. Under conditions that affect the structure of this layer, different factors have been identified. The nature of the atmosphere in which the sputtering is carried out, in particular the concentration oxygen in this atmosphere intervenes. The speed with which the deposit is obtained is another previously recognized factor. In all cases, studies on the nature of the layers show that the titanium oxide is either amorphous or in rutile form, or in anatase form, or again, and this is the vast majority of cases, in the form of a mixture of these various forms.
• An object of the invention is therefore, in a system comprising at least one layer based on titanium oxide, to propose means making it possible for the structure of this layer to remain substantially unchanged when subjected to a heat treatment of bending / quenching type.
• Another object of the invention is to provide layer systems comprising at least one silver-based layer under which there is a layer based on oxide or titanium oxy-nitride having this property of substantially maintaining its structure even subject to these treatments.
• Another object of the invention is to propose glazings comprising a set of layers including at least one selectively reflecting infrared reflective silver layer, and dereflective dielectric layers located above and below the silver layer, at the less a layer under the silver being a titanium oxide layer having this property of substantially retain its structure even subject to these heat treatments.
• An object of the invention is also to provide tempered and / or curved glazings comprising the layer systems indicated above.
• titanium oxide or oxynitride layers of TiMOx or TiMOxNy type in which M is metal or several metals or silicon these metals or silicon being introduced in such a quantity that they modify the structure of the layer to render it practically insensitive to heat treatments of the bending / quenching type.
• the inventors starting from the observation that the changes in crystalline structure consecutive to the heat treatments considered induce modifications, especially at the interface of the layers, associate these modifications with the alteration of the properties of the silver layers situated above these layers. based on titanium oxide.
• the inventors also propose to choose the metal (s) or silicon used in the composition of the oxide-based or titanium oxy-nitride layer as a function of their specific contribution to the desired properties for the layer in question. .
• titanium-combined metals in the titanium oxide-based layer is used advantageously according to the invention.
• one or more metals of the group comprising: Zr, Ta, Nb, V Nd, Ce, Hf. , W, Mo, La, Al, Y.
• the preferred metals are those whose oxides have the highest refractive indices, Zr, Ta, Nb is used most readily, alone or in a mixture, and most particularly Zr.
• the choice of additional metals is preferably such that the TiMOx oxides or TiMOxNy oxy-nitrides have a refractive index greater than 2.2 and advantageously greater than 2.3.
• metals or silicon in the layers based on oxide or titanium oxynitride are advantageously introduced from metal or silicon targets, or ceramic targets, corresponding to the desired compositions so that the deposit obtained corresponds to actually to an intimate mixture of metal oxides, or silicon, a mixture which opposes the formation of regular crystallographic structures of significant dimensions.
• the deposit in particular for the oxides, is preferably carried out in an oxidizing atmosphere.
• the atmosphere may be neutral, in particular argon, or slightly oxidizing.
• the atmosphere is oxidizing.
• the oxy-nitrides are deposited in an atmosphere comprising nitrogen.
• nitrogen reacts more easily with oxygen than with nitrogen.
• the proportion of nitrogen in the atmosphere of the deposit must be relatively high.
• the ratio N 2 / O 2 will advantageously be greater than 2 to have a significant amount of nitrogen in the atmosphere.
• oxy-nitride This proportion may be up to 3 or 4 to obtain a nitrogen content in the oxynitride of greater than 10%.
• nitrogen in the titanium oxy-nitride tends to make the structural transformation of the titanium oxide during the heat treatment less easy.
• Nitrogen in titanium oxynitride can lead to increase the extinction coefficient of the layer, that is to say to reduce slightly the light transmission, and to promote the appearance of a veil. For these reasons the presence of nitrogen must be well controlled to optimize properties.
• the presence of nitrogen in the modified titanium oxy-nitride does not usually exceed 30% in the ratio N 2 / O 2i and is preferably less than 25% and particularly preferably less than 20%. %.
• additional metal or silicon The higher the content of additional metal or silicon, the more "disorder" in the structure of the titanium oxide is established, and therefore the less titanium oxide is likely to constitute a modifiable network under the effect of a treatment thermal bending type tempering. Conversely, the use of a large proportion of additional metals or silicon tends to lower the refractive index of the assembly, the titanium oxide having the highest index.
• the additional metal or silicon content is at least 10 atomic% with respect to the Ti in the mixture. It is preferably greater than 15% and particularly preferably greater than 20%.
• the atomic proportion of metal or silicon additional is preferably at most 60% and preferably not more than 50%.
• the thickness of the TiMOx or TiMOxNy layer is advantageously at least equal to 6 nm, preferably at least 8 nm and particularly preferably at least 10 nm.
• the TiMOx or TiMOxNy layer or layers used according to the invention to promote the formation of silver-based layers leading to the best properties including electrical conduction or low emissivity, it is advantageous according to the invention to arranging under the layer or layers based on silver, and in contact with this or these layers, a layer based on zinc oxide of limited thickness.
• the layer based on zinc oxide promotes the growth of the silver-based layer as long as its thickness remains such that it does not develop in columnar form.
• the layer based on zinc oxide may comprise "doping" elements in a small amount. These elements are in particular Al, Sn, or Mg. They are advantageously in atomic quantity of less than 15% and preferably less than 10%.
• a particularly preferred layer consists of a zinc oxide comprising between 3 and 6% Sn.
• the thickness of the layer based on zinc oxide is advantageously less than 10 nm, and preferably less than 8 nm.
• the silver-based layers are advantageously protected in the traditional way by a barrier or sacrificial layer.
• the role of this layer is mainly to prevent the degradation of the silver-based layer during the formation of the dielectric layers superimposed on these silver-based layers.
• the barrier layer is formed of a metal that reacts in atmospheres likely to degrade money.
• barrier layers are traditionally those which allow this type of protection and do not significantly reduce the optical properties of the assembly.
• Very thin metal layers are used so as not to reduce light transmission. These layers are furthermore preferably used under conditions such that, in the whole, they are transformed as much as possible into transparent dielectrics, the transformation occurring in particular during the reactive deposition of the layers situated above these barrier layers.
• Preferred metals and alloys for forming these barrier layers include: Ti, Zn, Sn, Zr, Cr, and NiCr.
• the preferred constituents are Ti and NiCr alloys, and for these alloys consist in proportions close to 80/20.
• Titanium-based barriers are preferred in that they offer, once oxidized, a very low light absorption.
• NiCr-based barriers have the advantage of being amenable to relatively precise control of their degree of oxidation.
• These at least partially oxidized barriers are of the TiOw (with w ⁇ 2) or NiCrOv type.
• NiCr barrier in contact with the silver-based layer and superimpose a barrier Ti.
• each of the barrier layers has a thickness of not more than 6 nm.
• composition of the set of interference filter layers intended in particular for the control of the light transmission and the color neutrality especially in reflection, optionally comprises additional dielectric layers located under the TiMOX or TiMOxNy layer, or above that or above and below.
• the preferred additional dielectric layers are in particular at least one layer of zinc oxide or of a mixture of zinc oxide and tin, aluminum or magnesium, in atomic proportions Zn / Sn, Zn / Al , Zn / Mg between
• the thickness of these additional layers is controlled in particular by that of the TiMOx or TiMOxNy layer, to establish the optical path to a satisfactory value to form the interference filter corresponding to the thickness of the chosen silver layer.
• the layer assemblies according to the invention are remarkable for the quality of the silver layers that they make it possible to obtain after heat treatment. This quality results in an emissivity given by the amount of money needed to reach this emissivity. Smaller is this better quantity is the silver layer.
• the content for glazing according to the invention is advantageously between 80 and 160 mg / m 2 , and preferably between 100 and 140 mg / m 2 .
• the glazings according to the invention are advantageously such that after a heat treatment at a temperature which is not less than 650 ° C. for a period of at least 3 minutes, the quality of the silver layer or layers is such that the product of the silver mass per unit area, expressed in mg / m 2 by the emissivity normal (Qx ⁇ ) is less than 5, preferably less than 4.8, and particularly preferably less than 4.6.
• FIG. 1 represents a glazing unit according to the invention comprising a set of layers including an infrared reflective layer
• Figure 2 shows a glazing according to the invention comprising another set of layers including an infrared reflective layer
• FIG. 3 represents a glazing unit according to the invention comprising a set of layers including two infrared reflecting layers.
• FIG. 1 is a schematic sectional view of a glass sheet 1 comprising a layer system, which comprises a silver-based infra-red reflective layer 4.
• the silver-based layer may optionally be "doped" with a metal that promotes its crystalline structure or durability.
• a metal is for example known in palladium platinum, nickel and silicon.
• At least one dielectric layer 2 consists of a mixed oxide or mixed oxy-nitride of titanium and of another metal or silicon of TiOx or TiOxNy type.
• the layer 4 under the silver, when the whole is subjected to a vigorous heat treatment must retain substantially its structure, unlike the behavior of a similar traditional layer based on TiO 2 .
• This layer promotes the growth of the structure of the silver-based layer.
• Relatively thin in comparison with the dielectric layers 2 or 6 conferring most of the filter characteristics in combination with the silver-based layer, this layer 3 vis-à-vis the silver-based layer does not mask the restructuring underlying layers when such changes take place during a heat treatment.
• the layer 2 itself does not have any significant modification of its structure.
• the silver traditionally there is a barrier layer 5 of small thickness, which prevents the oxidation of silver during the deposition of subsequently deposited layers.
• the outermost dielectric layer is a thick layer 6, which completes the interference filter.
• FIG. 2 The structure shown in Figure 2, is similar to the previous one. The similar layers are referenced as in FIG. 1. This structure also comprises layers previously described, a surface layer 7, and a second dielectric 8 in contact with the glass sheet 1.
• the choice of these dielectric is a function of their optical properties: index, transparency etc.
• These dielectrics do not have all the mechanical qualities which guarantee a good resistance of all the layers in the implementation of the glazings. In particular, the layers are not always sufficiently resistant to scratches that may be caused in storage or transport.
• Preferred layers are, for example, titanium oxide.
• the thickness of these layers is limited to what is useful for imparting the desired mechanical strength.
• the dielectric layer 8 contributes to the formation of the optical properties of the assembly. It is usually quite thick. This layer is also used to protect the assembly against the migration of ions from the glass sheet 1, migrations that are facilitated by the heat treatment.
• the order of the layers is not necessarily the one represented, namely a thick layer 8 with a lower index than that of the layer 2 based on TiOMx or TiOMxNy.
• the order of the layers may be reversed, the layer 2 being for example in contact with the glass and covered by the layer 8. Additional layers may still be in the assembly.
• a layer between the layer 2 and the layer 3. This layer is for example of the same nature as the layer 8, but it can also be different.
• the layer 6 can be associated with another dielectric layer situated above or below the layer 6.
• the barrier layer 5 may be simple or itself composed of several layers. In particular, as indicated above, it may be an assembly comprising a first layer of NiCr oxide and a layer of a titanium oxide.
• Figure 3 shows schematically a structure with two silver-based layers 4 and 4 '.
• the utility of double layers of silver is well known in the prior art.
• the presence of two layers of silver makes it possible on the one hand to further improve the emissivity of the glazings and to better control the neutrality of color in reflection.
• FIG. 3 shows, with regard to the additional layers (2 ', 3', 4 ', 5', 6 ') as previously an assembly comprising layers (2' and 3 ') favoring the formation of a layer of silver presenting an adequate structure to present in particular the best quality in terms of conduction and emissivity, one or more barrier layers (5 ') protecting the silver-based layer (4') against a possible degradation during the deposition of the layers which are superimposed on it, and one or more dielectric layers (6 ') to complete the filter.
• the order of the essentially optical function layers can be changed as can the number of layers used.
• the layer systems comprising or not the oxide or oxynitride layers, TiOMx or TiOMxNy, have been compared for both their emissivity and their neutrality in reflection. .
• the thicknesses of the layers are expressed in Angstrom for dielectrics and in mg / m 2 for silver.
• the deposits are carried out in an oxidizing atmosphere from metal targets for the dielectrics, and in a neutral atmosphere (argon) for the silver layer and for the TiOw barrier layer.
• a similar set of layers is deposited by reducing the first ZnSnO layer (50/50) to 180 Angstrom, and depositing on this layer in a weakly oxidizing atmosphere, from a ceramic target made of titanium oxide. , a layer of 100 Angstroms.
• the structure of this system is accordingly: ZnSnO (50/50) / TiO 2 / ZnSnO (90/10) / Ag / TiOw /
• the systems are subjected to heat treatment at 650 ° C. for three minutes in a preheated oven and in an air atmosphere.
• the measurements of normal emissivity, sail (haze) and colorimetry in reflection according to the CIE-LAB system are indicated in the following table:
• TiO 2 under the silver causes a significant alteration of the emissivity of this layer (and thus also of its electrical conduction). This alteration is attributed to the change in the crystallographic nature of the TiO 2 layer when it is subjected to heat treatment.
• the procedure is analogous in that the 100 Angstrom layer of TiO 2 is replaced by a layer of the same thickness consisting of a mixed oxide of titanium and zirconium.
• the deposition of this layer is carried out in a weakly oxidizing atmosphere, from a ceramic target made up in weight percentage of 50% of TiO, 46% of ZrO and 4% YO.
• the structure of the system then becomes:
• this layer with a high refractive index does not substantially affect the quality of the emissivity when the glazing is subjected to heat treatment.
• Example 2 A similar test to that of Example 1 is carried out this time by depositing the layer based on titanium and zirconium (50%) in a nitrogen atmosphere. Using the ceramic target, the deposit obtained in these conditions is an oxy-nitride, the oxygen of the target entering mainly in the composition of the layer.
• the ceramic target consists of a mixture of titanium and silicon (8% by weight).
• the mixed oxide layer of titanium and niobium like that of titanium and zirconium, is very stable to the thermal test.
• the silver layer retains good properties, and the reflection coloration is very neutral.
• the first system consists of the following way starting from the glass:
• the second system is of the same composition but the mixed oxide layer of titanium and niobium is only 80 thick instead of 100.
• the presence of the layer based on zinc oxide under silver can be omitted without the heat treatment significantly affecting the performance of the silver layer or the colorimetric characteristics in reflection.

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• 2007
  • 2007-03-19 EP EP07104429A patent/EP1980539A1/fr not_active Withdrawn
• 2008
  • 2008-03-17 EP EP08717902.4A patent/EP2137116B2/fr active Active
  • 2008-03-17 EA EA200901252A patent/EA020682B1/ru not_active IP Right Cessation
  • 2008-03-17 ES ES08717902T patent/ES2814249T5/es active Active
  • 2008-03-17 PL PL08717902.4T patent/PL2137116T5/pl unknown
  • 2008-03-17 US US12/532,318 patent/US8105695B2/en active Active
  • 2008-03-17 WO PCT/EP2008/053166 patent/WO2008113786A1/fr not_active Ceased
  • 2008-03-17 CN CN200880014802.0A patent/CN101675011B/zh not_active Expired - Fee Related
  • 2008-03-17 JP JP2010500200A patent/JP5553746B2/ja not_active Expired - Fee Related
  • 2008-03-17 HU HUE08717902A patent/HUE050289T2/hu unknown

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