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
  • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
  • C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
  • C03C17/3435—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising 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
  • C03C2217/00—Coatings on glass
  • C03C2217/90—Other aspects of coatings
  • C03C2217/94—Transparent conductive oxide layers [TCO] being part of a multilayer coating
  • C03C2217/948—Layers comprising indium tin oxide [ITO]

Definitions

• the invention relates to the field of glazing comprising a glass substrate, provided on at least one of its faces with a stack of thin layers.
• a layer with low emissivity property for example a layer of an electrically conductive transparent oxide (TCO) in order to reduce the radiative exchanges with the sky.
• TCO electrically conductive transparent oxide
• the application WO 2007/115796 recommends for example to use a stack comprising a TCO layer (typically oxide fluorine - doped tin), a blocking layer and finally a photocatalytic layer.
• the application WO 2013/132176 also describes anticondensation glazings, and suggests depositing on the face 2, therefore on the face opposite the face carrying the anti-condensation stack, a solar control stack whose purpose is to reduce the solar factor of the glazing. .
• the object of the invention is to improve this type of glazing exhibiting both anti-condensation and solar control functions.
• Another object of the invention is to provide stacks capable of withstanding heat quenching treatments.
• Another object of the invention is to provide stacks with excellent climatic durability.
• Another object of the invention is to provide glazing having a neutral shade in reflection.
• the subject of the invention is a glazing unit comprising a glass substrate provided on a first face, intended to form the face 1 of said glazing in the use position, of a stack of thin layers comprising, from said substrate, an electrically conductive transparent oxide layer, a first dielectric layer, a niobium nitride layer, and a second dielectric layer.
• the inventors have been able to demonstrate that, quite surprisingly, it was possible to combine the antisolar and anti-condensation functions on the same face of the glazing, in this case the face 1, while maintaining satisfactory optical properties, in particular particularly in terms of light reflection and color in reflection.
• the solution obtained proved to be simpler to implement industrially than that proposed by the above-mentioned application WO 2013/132176, consisting in depositing a solar control stack on face 2.
• the expression "based on” is understood to mean that the layer in question preferably comprises at least 60% by weight of the material in question, in particular at least 70%, 80% or 90%.
• face 1 of the glazing is meant, as is the practice in the art, the outer face of the glazing which is intended to be positioned so as to be in contact with the outside of the house.
• the faces of a glazing are numbered starting from the outside, so that the face 2 is the face opposite to the face 1, in other words the other face of the same glass sheet.
• the face 3 is the face of the second glass sheet of the glazing facing the face 2, the face 4 is the face opposite the face 3 etc.
• the glazing according to the invention is preferably a multiple glazing, in particular double or triple, or even more, for example quadruple. These windows have indeed a weak heat transfer coefficient, and are the most affected by the phenomenon of condensation.
• a double glazing generally consists of two glass sheets facing each other and forming a blade of gas, for example air, argon, xenon or krypton.
• a spacer frame in the form of a metal profile, for example made of aluminum, secured to the glass sheets by an adhesive, the periphery of the glazing being sealed to the glass.
• a putty for example silicone, polysulphide or polyurethane, to prevent any entry of moisture into the gas strip.
• a molecular sieve is frequently available in the spacer frame.
• Triple glazing is the same way, except that the number of glass sheets is three.
• At least one other face is preferably coated with a stack with low emissivity properties. It may be in particular stacks of thin layers comprising at least one layer of silver, the or each layer of silver being disposed between dielectric layers.
• low emissivity is meant an emissivity generally of at most 0.1, in particular of at most 0.05.
• two other faces, in particular faces 2 and 5 or faces 3 and 5 are coated with such a stack.
• Other configurations are also possible, but less preferred: faces 2 and 3, 2 and 4, 3 and 4, 4 and 5, faces 2, 3 and 4, faces 2, 3 and 5, faces 2, 4 and 5, faces 2, 3, 4 and 5.
• the glazing according to the invention can be used as any type of glazing. It can be integrated into a facade, a roof, a veranda. It can be arranged vertically or inclined.
• the glazing according to the invention is used as roof glazing, or as veranda roof glazing.
• the glazing according to the invention is in fact particularly useful as roof glazing, in particular porch, to reduce the appearance of condensation of water on the surface of said glazing.
• the appearance of condensation is indeed more important in the case of sloped glazing and on the other hand, the solar control functions are particularly useful in the case of roof glazing, especially for verandas.
• the glazing according to the invention advantageously has at least one of the following optical or energetic properties, according to all the possible combinations:
• Transmission factors and solar factors are calculated according to EN 410.
• the glass substrate can be transparent and colorless (it is then a clear or extra-clear glass). Clear glass typically contains a weight content of iron oxide in the range of 0.05 to 0.2%, while extra clear glass typically contains about 0.005 to 0.03% iron oxide.
• the glass substrate may also be colored, for example blue, green, gray or bronze, so as to further reduce the solar factor of the glazing. We can mention the products of the Applicant called SGG Parsol Green, blue or bronze. It will preferably contain a weight content of iron oxide of the order of 0.4% to 1%, and optionally coloring agents such as cobalt oxide, chromium oxide or selenium.
• the glass is normally inorganic, preferably of the silico-soda-lime type, but it may also be borosilicate or alumino-borosilicate type glass.
• the thickness of the substrate is generally in a range from 0.5 mm to 19 mm, preferably from 0.7 to 9 mm, in particular from 2 to 8 mm, or even from 4 to 6 mm. It is the same, if any, for the other glass sheets of the multiple glazing.
• the glass substrate is preferably of the float type, that is to say likely to have been obtained by a method of pouring the molten glass onto a molten tin bath ("float" bath).
• the stack can be deposited on the "tin” side as well as on the "atmosphere” side of the substrate.
• atmosphere and tin faces means the faces of the substrate having respectively been in contact with the atmosphere prevailing in the float bath and in contact with the molten tin.
• the tin side contains a small surface amount of tin diffusing into the glass structure.
• At least one glass sheet of the glazing unit according to the invention may be thermally hardened or hardened, in order to impart to it improved mechanical strength properties.
• the substrate provided with the stack according to the invention is thermally quenched.
• thermal quenching is useful in order to improve the emissivity properties of the transparent conductive oxide layer (preferably ITO).
• the electrical resistivity of the stack after quenching is at most 2.2 ⁇ 10 -4 ⁇ ⁇ cm, in particular at most 2.1 ⁇ 10 -4 ⁇ ⁇ cm and even at most 2.0 ⁇ 10 -4. Q.cm.
• the emissivity and electrical resistivity properties are closely related.
• At least one glass sheet of the glazing unit can be laminated to another sheet by means of a spacer sheet made of a polymer such as polyvinyl butyral (PVB ) or polyurethane (PU), preferably face more internal than the first face (face 2 etc.).
• PVB polyvinyl butyral
• PU polyurethane
• the electrically conductive transparent oxide is preferably an indium tin oxide (ITO).
• ITO indium tin oxide
• the tin oxide and indium layer is preferably made of ITO.
• the atomic percentage of Sn is preferably in a range from 5 to 70%, especially from 6 to 60%, advantageously from 8 to 12%.
• These layers have good climatic durability, necessary when the stack is disposed in face 1 of the glazing, which is not the case for other low-emissive layers, such as the layer or layers of silver or other low emissivity metal layers such as gold or niobium.
• the latter should preferably be located on an inner face of the multiple glazing, including the face 2 (a double glazing or triple glazing in particular), because placed in front 1 they may impart bad weather resistance glazing.
• the stack of thin layers does not comprise a layer (s) of silver, or even other low emissivity metal layers (in particular under the transparent oxide layer (preferably ITO).
• a layer (thin) disposed on the first face is a silver layer or more broadly a low emissive metal layer.
• ITO is also particularly appreciated for its high electrical conductivity, allowing the use of small thicknesses to obtain the same level of emissivity. Easily deposited by a cathodic sputtering method, especially assisted by magnetic field, called “magnetron process", these layers are distinguished by a lower roughness, and therefore a lower fouling. In the manufacture, handling and maintenance of glazing, the rougher layers tend to trap various residues, which are particularly difficult to remove.
• the physical thickness of the TCO layer is adjusted so as to obtain the desired emissivity and thus the desired anti-condensation performance.
• the emissivity of the TCO layer (ITO preferably) is preferably less than or equal to 0.4 better than 0.35 and even 0.3, in particular at most 0.2.
• the physical thickness of the ITO layer is advantageously in a range from 50 to 200 nm, in particular from 60 to 180 nm, and even from 90 to 140 nm, in order to guarantee good anti-condensation properties.
• the stack preferably comprises only one layer of ITO (or more broadly comprises only one emissivity TCO layer of at most 0.4 better of at most 0.3 or even at most 0.2).
• the desired emissivity depends on various factors, including the inclination of the glazing and its coefficient of heat transfer Ug. Typically, glazing sloping and / or low thermal transmittance will require a lower emissivity, and therefore a TCO layer (ITO preferably) thicker.
• the emissivity (of the stack) is preferably at most 0.4 or even 0.3.
• the emissivity (of the stack) is preferably at most 0.3 or even at most 0.2 and even at most 0.18.
• emissivity is meant the normal emissivity at 283 K according to EN 12898.
• the electroconductive transparent oxide may also be another oxide, chosen in particular from fluorine doped tin oxide (SnO 2: F), mixed indium and zinc oxides (IZO), zinc oxide doped with gallium or aluminum, niobium doped titanium oxide, cadmium or zinc stannate, or antimony doped tin oxide. These oxides are, however, less preferred.
• the layer based on niobium nitride is preferably essentially constituted, or even constituted, of niobium nitride.
• niobium nitride does not prejudge the actual stoichiometry of the material, which may be stoichiometric, substoichiometric or super-stoichiometric to nitrogen.
• the physical thickness of the layer based on niobium nitride is preferably in a range from 3 to 30 nm, in particular from 5 to 20 nm, or even 8 to 15 nm. .
• the first dielectric layer is in particular intended to obtain good optical properties in reflection, as well as to protect the niobium nitride layer from a possible migration of alkaline ions from the substrate.
• the first dielectric layer is preferably based, in particular essentially made of a material chosen from silicon nitrides or oxynitrides or zinc tin oxide, which have proved to be the most effective materials.
• the first dielectric layer is preferably a monolayer.
• the second dielectric layer is preferably based on silicon nitride.
• the second dielectric layer is preferably a monolayer. It is even advantageously essentially constituted or even constituted of such a material. Such a layer makes it possible to confer on the stack good properties of climatic durability and resistance to quenching.
• the first and second dielectric layers are based, or even essentially made of silicon nitride, thereby simplifying manufacturing and performance.
• the term "silicon nitride" does not prejudge the actual stoichiometry of the material, which may be stoichiometric, substoichiometric or super-stoichiometric in nitrogen, or any doping.
• the silicon target when these layers are deposited by cathodic sputtering, it is usual to dope the silicon target with an element such as aluminum or even boron or zirconium in order to increase its conductivity.
• the silicon nitride is therefore typically doped with one of these elements.
• the physical thickness of the first and / or second dielectric layer is preferably in a range from 5 to 30 nm, in particular from 6 to 25 nm, or even from 8 to 20 nm.
• the ratio between the physical thicknesses of the first and second dielectric layers is preferably in a range from 0.7 to 1.3, especially from 0.8 to 1.2, and even from 0.9 to 1 1.
• the first dielectric layer (preferably a monolayer) is in direct contact with the layer of TCO (preferably ITO) and / or in direct contact with the layer based on niobium nitride.
• TCO preferably ITO
• direct contact is meant physical contact.
• the second dielectric layer (preferably a monolayer) is advantageously in direct contact with the layer based on niobium nitride.
• the first dielectric layer and respectively the TCO layer (preferably ITO) and the layer based on niobium nitride.
• It can be dielectric layers, oxides and / or metal nitrides or silicon (for example at most two other layers or at most another layer) or blocking layer.
• it is also possible to arrange one or more layers between the second dielectric layer and the niobium nitride layer.
• It can be one or dielectric layers, oxides and / or metal nitrides or silicon (for example at most two other layers or at most another layer) or blocking layer.
• a blocking layer may be disposed between the niobium nitride layer and the second dielectric layer.
• the blocking layer is preferably a metal (M) selected from titanium or chromium or a nickel-chromium alloy.
• M metal selected from titanium or chromium or a nickel-chromium alloy.
• a layer of the same nature that is to say preferably a metal (M) selected from titanium or chromium or an alloy of nickel and chromium (and even of thickness between 1 and 5nm), in particular forming a layer blocker, can also be disposed under and / or on the TCO layer (preferably ITO).
• the second dielectric layer may be the last layer of the stack (preferably the TCO layer of which is an ITO layer), and therefore that in contact with the atmosphere.
• the TCO layer of which is an ITO layer preferably the TCO layer of which is an ITO layer
• at least one other thin layer, preferably dielectric and even metal oxide or silica may be deposited above it.
• a layer, preferably photocatalytic, based on titanium oxide is provided as a last layer deposited on the first face of the substrate.
• the physical thickness of this layer is preferably at most 30 nm, in particular at most 20 nm, or even at most 15 nm and even at most 10 nm.
• Photocatalytic titanium oxide has the particularity, when irradiated by sunlight, of becoming extremely hydrophilic, with contact angles to water of less than 5 ° and even 1 °, which allows the water to flow more easily, eliminating soiling deposited on the surface of the layer.
• the (last) layer is advantageously a layer of titanium dioxide, in particular whose refractive index is included in a range from 2.0 to 2.5.
• the titanium oxide is preferably at least partially crystallized in the anatase form, which is the most active phase from the point of view of photocatalysis. Anatase and rutile phase mixtures have also been found to be very active.
• the titanium dioxide may optionally be doped with a metal ion, for example an ion of a transition metal, or with nitrogen, carbon or fluorine atoms. Titanium dioxide may also be under-treated. stoichiometric or super-stoichiometric.
• the TCO layer (preferably ITO) may be in direct physical contact with the substrate.
• a transparent electro ⁇ conductive oxide preferably ITO
• a neutralizing layer in particular based on silica. It is preferred that the neutralization layer is a monolayer and that this monolayer is in direct contact with the first face and the layer of an electroconductive transparent oxide (preferably ITO). Such a layer has proved effective for
• the physical thickness of the TiO x layer is advantageously at most 15 nm, or even at most 10 nm.
• the examples contain on the glass a silica neutralization layer (for example 3 and 4), the ITO layer, a first silicon nitride dielectric layer, the niobium nitride layer, a second dielectric nitride layer, silicon, and finally the photocatalytic layer made of titanium oxide (for examples 2 and 4).
• the first dielectric layer may also be a layer of zinc tin oxide (SnZnO x )
• the given formulas do not prejudge the actual stoichiometry of the layers, or any doping.
• the silicon nitride and / or the silicon oxide may be doped, for example with aluminum.
• the oxides and nitrides may not be stoichiometric (they can be), hence the use in the formulas of the index "x", which is of course not necessarily the same for all layers.
• the glazing according to the invention is preferably obtained by a multi-step process.
• the layers of the stack are deposited on the glass substrate, which is then generally in the form of a large glass sheet of 3.2 * 6m 2 , or directly on the glass ribbon during or just after the process. float, then the substrate is cut to the final dimensions of the glazing.
• the multiple glazing is then produced by combining the substrate with other glass sheets, themselves optionally optionally provided with functional coatings, for example of the low-emissive type.
• the different layers of the stack can be deposited on the glass substrate by any type of thin film deposition process. It may for example be sol-gel type processes, pyrolysis (liquid or solid), chemical vapor deposition (CVD), including plasma-assisted (APCVD), possibly under atmospheric pressure (APPECVD), evaporation.
• sol-gel type processes pyrolysis (liquid or solid), chemical vapor deposition (CVD), including plasma-assisted (APCVD), possibly under atmospheric pressure (APPECVD), evaporation.
• the layers of the stack are obtained by sputtering, in particular assisted by a magnetic field (magnetron process).
• a plasma is created under a high vacuum near a target comprising the chemical elements to be deposited.
• the active species of the plasma by bombarding the target, tear off said elements, which are deposited on the substrate forming the desired thin layer.
• This process is called "reactive" when the layer consists of a material resulting from a chemical reaction between the elements torn from the target and the gas contained in the plasma.
• the major advantage of this process lies in the possibility of depositing on the same line a very complex stack of layers by successively scrolling the substrate under different targets, usually in a single device.
• the magnetron method has a disadvantage when the substrate is not heated during deposition: the TCO (and optionally titanium oxide) layers thus obtained are weakly crystallized, so that their respective properties of emissivity and activity photocatalytic are not optimized. A heat treatment is then necessary.
• This heat treatment intended to improve the crystallization of the TCO layer, in particular of ITO (and optionally the photocatalytic layer), is preferably chosen from quenching, annealing and rapid annealing treatments.
• the improvement of the crystallization can be quantified by an increase in the crystallization rate (the mass or volume proportion of crystallized material) and / or the size of the crystalline grains (or the size of coherent diffraction domains measured by diffraction methods X-ray or Raman spectroscopy).
• This improvement in crystallization can also be verified indirectly, by improving the properties of the layer.
• the emissivity decreases, preferably by at least 5% in relative or even at least 10% or 15%, as well as its absorption. luminous and energetic.
• the improvement in crystallization results in an increase in the photocatalytic activity.
• the activity is generally evaluated by following the degradation of model pollutants, such as stearic acid or methylene blue.
• the quenching or annealing treatment is generally carried out in an oven, respectively tempering or annealing.
• the entire substrate is heated to a high temperature of at least 300 ° C in the case of annealing, and at least 500 ° C or 600 ° C in the case of quenching.
• Fast annealing is preferably carried out using a flame, a plasma torch or laser radiation or from at least one flashlamp.
• the substrate In this type of process, it comes to create a relative movement between the substrate and the device (flame, laser, flash lamps, plasma torch). Generally, the device is fixed, and the coated substrate is scrolled with respect to the device so as to treat its surface. These methods make it possible to bring a high energy density to the coating to be treated in a very short time, thus limiting the diffusion of heat towards the substrate, and thus the heating of said substrate.
• the temperature of the substrate is generally at most 100 ° C, or even 50 ° and even 30 ° C during the treatment.
• Each point of the thin layer is subjected to fast annealing treatment for a period generally less than or equal to 1 second, or even 0.5 seconds.
• the fast annealing heat treatment is implemented using a laser radiation emitting in the infrared or the visible.
• the wavelength of the radiation is preferably in a range from 530 to 1200 nm, or from 600 to 1100 nm, in particular from 700 to 1100 nm, or even from 800 to 1100 nm.
• Laser diodes emitting for example at a wavelength of the order of 808 nm, 880 nm, 915 or 940 nm or 980 nm, or fiber lasers, in particular disc lasers emitting at different frequencies, are preferably used. wavelengths of about 1000 nm (for example 1030 nm for a Yb: YAG laser).
• the surface powers at the level of the coating to be treated are preferably greater than 20 kW / cm 2 , or even 30 kW / cm 2 .
• the laser radiation is preferably in the form of a line (called "laser line” in the rest of the text) which simultaneously irradiates all or part of the width of the substrate.
• laser line a line
• the in-line laser beam can in particular be obtained using high-power laser diode systems associated with focusing optics or using fiber lasers.
• the thickness (width) of the line is preferably at least 35 microns, especially in a range from 40 to 100 microns or 40 to 70 microns.
• the length of the line is typically between 50 mm and 3 m.
• the profile of the line may in particular be a Gauss curve or a slot.
• the laser line simultaneously radiating all or part of the width of the substrate may be composed of a single line (then radiating the entire width of the substrate), or of several lines, possibly disjointed. When multiple lines are used, it is preferable that they be arranged so that the entire surface of the stack is processed.
• the or each line is preferably arranged perpendicular to the direction of travel of the substrate, or disposed obliquely.
• the different lines can process the substrate simultaneously, or in a time-shifted manner. The important thing is that the entire surface to be treated is.
• the substrate can thus be placed in displacement, in particular in translation translation with respect to the fixed laser line, generally below, but possibly above the laser line. This embodiment is particularly appreciable for a continuous treatment.
• the substrate can be fixed and the laser can be mobile.
• the difference between the respective speeds of the substrate and the laser is greater than or equal to 1 meter per minute, or even 4 and even 6, 8, 10 or 15 meters per minute, in order to ensure a high processing speed.
• the substrate can be set in motion by any mechanical conveying means, for example using strips, rollers, trays in translation.
• the conveyor system controls and controls the speed of travel.
• the laser may also be moved to adjust its distance to the substrate, which may be useful especially when the substrate is curved, but not only. Indeed, it is preferable that the laser beam is focused on the coating to be treated so that the latter is located at a distance less than or equal to 1 mm of the focal plane.
• the rapid annealing heat treatment is implemented using at least one flash lamp.
• Such lamps are generally in the form of glass or quartz tubes sealed and filled with a rare gas, provided with electrodes at their ends. Under the effect of a short-term electrical pulse, obtained by discharging a capacitor, the gas ionizes and produces a particularly intense incoherent light.
• the emission spectrum generally comprises at least two emission lines; it is preferably a continuous spectrum having a maximum emission in the near ultraviolet.
• the lamp is preferably a xenon lamp. It can also be a lamp with argon, helium or krypton.
• the emission spectrum preferably comprises several lines, especially at wavelengths ranging from 160 to 1000 nm.
• the duration of the flash is preferably in a range from 0.05 to 20 milliseconds, in particular from 0.1 to 5 milliseconds.
• the repetition rate is preferably in a range from 0.1 to 5 Hz, in particular from 0.2 to 2 Hz.
• the radiation may be from several lamps arranged side by side, for example 5 to 20 lamps, or 8 to 15 lamps, so as to simultaneously treat a wider area. In this case, all lamps can emit flashes simultaneously.
• the or each lamp is preferably arranged transversely to the longer sides of the substrate.
• the or each lamp has a length preferably of at least 1 m in particular 2 m and even 3 m so as to be able to process large substrates.
• the capacitor is typically charged at a voltage of 500 V to 500 kV.
• the current density is preferably at least 4000 A / cm 2 .
• the total energy density emitted by the flash lamps, relative to the surface of the coating is preferably between 1 and 100 J / cm 2 , in particular between 1 and 30 J / cm 2 , or even between 5 and 20 J / cm. 2 .
• the laser radiation device or the flash lamp may be integrated in a layer deposition line, for example a magnetic field assisted sputtering deposition line (magnetron process), or a chemical vapor deposition line (CVD) , especially plasma assisted (PECVD), under vacuum or at atmospheric pressure (APPECVD).
• a layer deposition line for example a magnetic field assisted sputtering deposition line (magnetron process), or a chemical vapor deposition line (CVD) , especially plasma assisted (PECVD), under vacuum or at atmospheric pressure (APPECVD).
• Rapid annealing is normally such that the power and energy densities used make it possible to heat the stack of thin layers (coating) very rapidly, without heating the substrate significantly.
• the maximum temperature experienced by each point of the coating during the heat treatment is preferably at least 300 ° C, especially 350 ° C, or even 400 ° C, and even 500 ° C or 600 ° C.
• the maximum temperature is normally experienced when the point of the coating under consideration passes under the radiation device, for example under the laser line or under the flash lamp.
• the points of the surface of the coating located under the radiation device (for example under the laser line) and in its immediate vicinity (for example less than a millimeter) are normally at a temperature of minus 300 ° C.
• the coating temperature is normally at most 50 ° C, and even 40 ° C or 30 ° C.
• Each point of the coating undergoes the heat treatment (or is brought to the maximum temperature) during a period advantageously in a range from 0.05 to 10 ms, in particular from 0.1 to 5 ms, or from 0.1 to 2 ms. ms.
• this time is set by both the width of the laser line and the relative speed of movement between the substrate and the laser line.
• this duration corresponds to the duration of the flash.
• the optional photocatalytic layer can also be obtained from a layer of metallic titanium, which is oxide and crystallizes during rapid annealing, as taught by WO 2011/039488.
• the invention therefore also relates to a glass substrate provided on a first face of a stack of thin layers comprising, from said substrate, an electrically conductive transparent oxide layer (preferably ITO), a first dielectric layer, a layer based on niobium nitride, then a second dielectric layer, and then a layer of metallic titanium.
• an electrically conductive transparent oxide layer preferably ITO
• a first dielectric layer a layer based on niobium nitride
• a second dielectric layer a layer of metallic titanium.
• Such an intermediate product is particularly suitable for the process according to the invention.
• the various characteristics mentioned above for the glazing also apply to this intermediate product (no low emissivity metal layer on the first face, the aforementioned preferred choices for the first and second dielectric layers, for the TCO layer).
• this intermediate product no low emissivity metal layer on the first face, the aforementioned preferred choices for the first and second dielectric layers, for the TCO layer.
• the crystallization of the photocatalytic layer is also improved by the addition, especially above the titanium oxide layer, an energy-providing layer such as an overcoat of carbon or preferably of titanium, as taught by the application WO 2009136110.
• Magnetic sputtering was deposited on a clear glass substrate 4 mm thick, sold by the Applicant under the name SGG Planilux® stacks constituted, starting from the substrate of a layer of ITO, then a silicon nitride layer, then a layer of niobium nitride, then a layer of silicon nitride, and finally a layer of titanium oxide.
• the silicon nitride layers are deposited using aluminum-doped silicon targets (2 to 8 atomic%), so that they contain a small (undetermined) amount of this element. The exact stoichiometry of the nitride layers has not been determined either.
• Table 1 below indicates the physical thicknesses (in nm) of each of the layers for the three stacks according to the invention.
• the glass sheets thus obtained were then thermally quenched in known manner, heating the glass at about 700 ° C for a few minutes before cooling it rapidly with the aid of air nozzles.
• the solar factor and the transmission and light reflection factors are calculated according to the EN410 standard from transmission and reflection spectra measured with a spectrophotometer.
• the colorimetric coordinates are calculated taking into account the reference illuminant D65 and the CIE-1931 reference observer.
• Table 2 The glass sheets obtained can be integrated with glazing (double glazing, triple glazing), the coated face being located in front of said glazing, in particular for veranda roofs.
• the glazings thus obtained have remarkable properties in terms of both solar control and suppression of condensation.

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)
• Laminated Bodies (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=51688196

Family Applications (1)

Country Status (4)

Families Citing this family (12)

Family Cites Families (3)

• 2014
  • 2014-06-24 FR FR1455829A patent/FR3022539A1/fr active Pending
• 2015
  • 2015-06-23 EP EP15738739.0A patent/EP3160917A1/de not_active Withdrawn
  • 2015-06-23 WO PCT/FR2015/051671 patent/WO2015197969A1/fr active Application Filing
  • 2015-06-23 CA CA2952751A patent/CA2952751A1/fr not_active Abandoned

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events