WO2005102952A2 - Substrat photocatalytique actif sous lumiere visible - Google Patents
Substrat photocatalytique actif sous lumiere visible Download PDFInfo
- Publication number
- WO2005102952A2 WO2005102952A2 PCT/FR2005/050229 FR2005050229W WO2005102952A2 WO 2005102952 A2 WO2005102952 A2 WO 2005102952A2 FR 2005050229 W FR2005050229 W FR 2005050229W WO 2005102952 A2 WO2005102952 A2 WO 2005102952A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- coating
- substrate according
- compound
- type
- glazing
- Prior art date
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Classifications
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- 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
- C03C17/006—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character
- C03C17/007—Surface treatment of glass, not in the form of fibres or filaments, by coating with materials of composite character containing a dispersed phase, e.g. particles, fibres or flakes, in a continuous phase
-
- 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
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
- C03C8/10—Frit compositions, i.e. in a powdered or comminuted form containing lead
- C03C8/12—Frit compositions, i.e. in a powdered or comminuted form containing lead containing titanium or zirconium
-
- 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
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/425—Coatings comprising at least one inhomogeneous layer consisting of a porous layer
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C2217/00—Coatings on glass
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/44—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the composition of the continuous phase
- C03C2217/45—Inorganic continuous phases
-
- 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
- C03C2217/40—Coatings comprising at least one inhomogeneous layer
- C03C2217/43—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase
- C03C2217/46—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase
- C03C2217/47—Coatings comprising at least one inhomogeneous layer consisting of a dispersed phase in a continuous phase characterized by the dispersed phase consisting of a specific material
- C03C2217/475—Inorganic materials
- C03C2217/479—Metals
-
- 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
- C03C2217/71—Photocatalytic coatings
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- 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
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31652—Of asbestos
- Y10T428/31663—As siloxane, silicone or silane
Definitions
- the present invention relates to self-cleaning substrates, by the photocatalytic activity of suitable agents constituting them.
- a coating comprising titanium dioxide crystallized in anatase and / or rutile form which, in sufficient concentrations or thicknesses, has the particularity of forming free radicals under ultraviolet irradiation, and consequently d '' initiate the radical oxidation of any oily or fatty deposit of hydrocarbons.
- This coating is also hydrophilic under ultraviolet. Oily dirt is therefore degraded into shorter molecules under the action of the sun, then the rain is distributed in a uniform film guaranteeing the best possible homogenization of the degradation products as well as any mineral dust.
- TiO 2 crystallized anatase also has a weak photocatalytic activity in the most energetic part of the visible spectrum, so we are looking for an increase in this activity and a shift towards longer wavelengths, for use in (almost) absence of ultraviolet, in particular inside buildings, cockpits or cabins of transport vehicles ... Indeed, glazing in particular lets pass the visible part of the solar radiation, not ultraviolet.
- the photocatalytic activity under visible illumination is also of great interest outdoors, the energy of the solar spectrum being greater in the visible than in the ultraviolet.
- US 2003/144140 describes for this purpose the control of the recombination of electron-hole pairs at the junction of a photocatalytic compound under ultraviolet such as TiO 2 and a mixed oxide such as Ce 2 Zr 2 Oa, photocatalytic under visible light .
- a photocatalytic compound under ultraviolet such as TiO 2
- a mixed oxide such as Ce 2 Zr 2 Oa
- US 2003/232186 also describes the powder mixture of a photocatalytic compound active under ultraviolet and a photocatalytic compound active in the visible. The latter consists of rutile TiO 2 and / or anatase, certain atoms of which are substituted by nitrogen atoms. Obtaining film coatings according to this principle is not described.
- WO 02/92879 describes a thin layer coating on a substrate, in particular glass, and consisting of TiO 2 anatase particles whose photocatalytic activity under ultraviolet light is increased by the fact that these particles are in a binder comprising a semi-metallic metal oxide conductor such as SnO 2 : F.
- SnO 2 : F a semi-metallic metal oxide conductor
- the aim of the present invention is therefore to provide a material with anti-fouling and / or hydrophilic activity which can be used when it receives exclusively visible light, moreover capable of constituting a coating of high mechanical resistance on various substrates, substantially flat, fibrous ...
- the invention relates to a substrate coated with a film of mechanical strength and durability allowing handling by a user, characterized in that the film comprises in intimate association a first compound photocatalytic and a second compound exhibiting an energy jump between the upper level of its valence band and the lower level of its conduction band corresponding to a wavelength in the visible range.
- the substrate of the invention is a glass, a ceramic, a ceramic glass, a metal (steel, stainless steel), a building material (interior wall possibly coated / painted ...), a mineral material, wood, a plastic material.
- said first photocatalytic compound generally has a minimum activation energy in a more energetic field than visible light; this is the case with ZrO. KtaO 3 , Nb 2 O 5 , SnO 2 . Although this minimum energy, for TiO 2 , is located in the most energetic part of the visible spectrum, it must be specified that the photocatalytic activity of TiO 2 under exclusively visible light is very low, and much more important and usable for a anti-fouling functionality, under ultra-violet.
- titanium dioxide crystallized in particular at least in part in anatase form, known for constituting durable and abrasion resistant coatings on transparent substrates for which high optical quality is required, is of course at the heart of the 'invention. Indeed, by the association of said second well-chosen compound, the photocatalytic activity of TiO 2 in the visible is increased and becomes usable. On the other hand, in the context of the invention, the cases where said first photocatalytic compound would have a minimum activation energy in a less energetic field than visible light, such as for example Si, are not excluded.
- the inherent ability of the photocatalytic compound to initiate radical oxidations results in particular from its characteristics of lifetime of electron-hole pairs, quantity of these pairs generated, diffusion of these; on the contrary, the insufficiency in some of these characteristics results in weaker to almost zero anti-fouling and / or hydrophilic functionality, which may justify excluding the compound from certain applications requiring a high photocatalytic activity.
- said second compound taken in isolation although generator of electron-hole pairs under visible light, will not necessarily, in general, have a durability, quantity or diffusion of these pairs making it possible to qualify it as a photocatalytic compound.
- the inventors have established that it can make it photocatalytically active - or at least increase its photocatalytic activity - under visible light by displacement of the electrons, respectively holes generated in said second compound on the strip. conduction, respectively valence of the first photocatalytic compound. Even if, in a first case, the energy jump between the upper level of the valence band and the lower level of the conduction band of the second compound is less than the excitation energy of the first photocatalytic compound required to to obtain the maximum activity, the first photocatalytic compound acquires an activity which it had little or no visible light.
- the energy jump between the upper level of the valence band and the lower level of the conduction band of the second compound is on the contrary greater than or equal to the excitation energy of the first photocatalytic compound required for obtain the maximum activity, and this exhibits a still increased photocatalytic activity under visible light.
- the above values correspond to the extreme wavelengths of the visible spectrum, that is to say 800 and 380 nm.
- the second compound can thus be chosen from GaP, CdS, KTao.77Nbo.23O3, CdSe, SrTiO 3 , TiO 2 , ZnO, Fe 2 O 3 . WO 3l Nb 2 O 5 . V 2 O 5 , Eu 2 O 3 .
- the substrate is transparent, and its anti-fouling / hydrophilic functionality is such as to maintain its initial transparency and high optical quality under exclusively visible light.
- Organic pollution is then degraded into smaller, less adherent and less fatty molecules, which are more easily eliminated, in particular by water in the form of a film having regard to the hydrophilic property of the coating. It can be envisaged to combine a more or less regular spraying means. In the absence of water, organic degradation products can be removed with a cloth as easily as mineral dust; a chemically active agent such as a detergent is superfluous.
- transparent substrate in particular a plastic material such as polycarbonate, polymethyl methacrylate, polypropylene, polyurethane, polyvinyl butyral, poly (ethylene terephthalate), poly (butylene tetphthalate), ionomer resin such as ethylene / acid copolymer (neth) acrylic neutralized by a polyamine, cycloolefinic copolymer such as ethylene / norbornene or ethylene / cyclopentadiene, polycarbonate / polyester copolymer, ethylene / vinyl acetate copolymer and the like, alone or in mixtures.
- the transparent substrate is made of glass of which at least a surface part oriented towards said coating is dealkalized.
- the alkalis contained in the glass migrate to the surface under the effect of heating in particular, and affect the photocatalytic activity of the coating.
- a dealkalization consists in that at least in a zone of its surface oriented towards said coating, the substrate does not contain alkaline and alkaline-earth oxides in total proportion exceeding 15% by weight, nor sodium oxide in proportion exceeding 10% by weight.
- Silosodocalcium glass thus dealkalized is obtained by treatments using various techniques, in particular electrical such as corona discharge, as described in documents WO 94/07806-A1 and WO 94/07807-A1.
- said coating has a (meso) porous structure, in accordance with the teaching of WO 03/087002-A1 in particular.
- Such a structure is distinguished by a large contact surface and a network of pores communicating with each other, and finally by a particularly strong photocatalytic activity.
- a porosity of 70 to 90% defined by the percentage of the theoretical density of TiO 2 which is approximately 3.8, is favorable.
- This doping can also be done by surface doping only of titanium oxide or of the entire coating, surface doping carried out by covering at least part of the coating with a layer of oxides or metal salts, the metal being chosen from iron, copper, ruthenium, cerium, molybdenum, vanadium and bismuth.
- the photocatalytic phenomenon can be amplified by increasing the yield and / or the kinetics of the photocatalytic reactions, by covering the titanium oxide, or at least part of the coating which incorporates it, with a noble metal in the form of a thin layer.
- a noble metal in the form of a thin layer.
- platinum, rhodium, silver, palladium type platinum, rhodium, silver, palladium type.
- Such a catalyst for example deposited by a vacuum technique, makes it possible in fact to increase the number and / or the lifetime of the radical entities created by titanium oxide, and thus to favor the chain reactions leading to the degradation of organic products.
- the thickness of the coating according to the invention is variable, it is preferably between 2 nm and 1 ⁇ m, in particular between 5 and 100 nm, preferably not exceeding 80 nm.
- This thickness is adapted according to the envisaged application, because the photocatalytic activity increases at constant thickness.
- an increased thickness can be chosen to limit possible alkalis of an underlying glass in the depth of the coating, and to prevent them from reaching the most superficial active part.
- the coating can be chosen to have a more or less smooth surface.
- a certain roughness can indeed be advantageous: - it makes it possible to develop a larger active photocatalytic surface and therefore it induces a greater photocatalytic activity, - it has a direct influence on wetting. The roughness indeed enhances the wetting properties.
- a smooth hydrophilic surface will be even more hydrophilic when roughened.
- the substrate and the coating according to the invention it is possible to have one or more other layers with an antistatic, thermal, optical function, or promoting the crystal growth of TiO 2 in anatase or rutile form, in addition layers according to the invention forming a barrier to the migration of certain elements originating from the substrate, in particular forming a barrier to alkalis and very particularly to sodium ions when the substrate is made of glass. It is also possible to envisage a stack of “anti-reflection” layers alternating thin layers with high and low indices, the coating according to the invention constituting the last layer of the stack. In this case, it is preferable that the coating has a relatively low refractive index, which is the case when it consists of a mixed oxide of titanium and silicon.
- the layer with an antistatic and / or thermal function can in particular be chosen based on a conductive material of the metal type, such as silver, or of the metal oxide type doped such as indium oxide doped with tin ITO, tin oxide doped with a halogen of the fluorine type SnO 2 : F, or with antimony SnO 2 : Sb , or zinc oxide doped with indium ZnO: ln, fluorine ZnO.F, aluminum ZnO: AI or tin ZnO.Sn. It can also be metal oxides substoichiometric in oxygen, such as SnO 2 .
- the antistatic function layer preferably has a square resistance value of 20 to 1000 ohms / square. Provision may be made for supplying current in order to polarize it (supply voltages for example between 5 and 100 V). This controlled polarization makes it possible in particular to combat the deposit of dust of size on the order of a millimeter capable of being deposited on the coating, in particular dry adherent dust only by electrostatic effect: by abruptly reversing the polarization of the layer, we "eject" This dust.
- the thin layer with an optical function can be chosen in order to reduce the light reflection and / or make the color in reflection of the substrate more neutral.
- this thin layer has an index of refraction close to the square root of the product of -, squares of the indices of refraction of the two materials which surround it, that is ie the substrate and the coating according to the invention.
- the thin layer with an optical function is advantageously absorbent in the yellow.
- the thin layer with an alkali barrier function can be chosen in particular based on silicon oxide, nitride, oxynitride or oxycarbide, in aluminum oxide containing fluorine AI 2 O: F, or also in nitride. aluminum.
- the substrate is made of glass, because the migration of sodium ions into the coating according to the invention can, under certain conditions, alter its photocatalytic properties.
- the nature of the substrate or of the sub-layer also has an additional advantage: it can promote the crystallization of the photocatalytic layer which is deposited, in particular in the case of CVD deposition.
- a crystallized SnO 2 : F sublayer promotes the growth of Ti0 2 in predominantly rutile form, in particular for deposition temperatures of the order of 400 ° to 500 ° C.
- the surface of a soda-lime glass or a silicon oxycarbide sublayer rather induces anatase growth, in particular for deposition temperatures of the order of 400 ° to 600 ° C.
- All of these optional thin layers can, in known manner, be deposited by vacuum techniques of the sputtering type, in particular assisted by magnetic field (magnetron) or by other techniques of the thermal decomposition type such as pyrolysis in solid, liquid or gas phase. .
- each of the pre-mentioned layers can combine several functions, but they can also be superimposed.
- the sublayer barrier to the migration of alkalis is directly in contact with the glass, and itself directly covered with the thin layer with an optical function, which in turn is connected to the coating of the invention via of the layer with antistatic and / or thermal function.
- the subject of the invention is also: - anti-fouling and / or hydrophilic (anti-fog) glazing, monolithic, multiple of the double-glazing or laminated type incorporating the substrate described above; the application of this substrate to the manufacture of self-cleaning, hydrophilic and / or anti-fouling glazing, of the organic and / or mineral fouling type, in particular glazing for the building of the double glazing type, glazing for vehicles of the barrier type -brise, rear or side glasses of automobile, train, plane, water transport vehicle, or utility glazing such as aquarium glasses, display cases, greenhouse, verandas, interior furnishings such as table, tablet, step stair, walls of all positions, possibly with surface irregularities, in particular printed matter, textures, satin, sanded, or even lacquered, varnish, ophthalmic glass, glazing of street furniture, mirrors, television, telephone or similar screens, glazing with controlled absorption electronically, lamp covers of the flat lamp type, tunnel lamp, or any architectural material of the facade, cladding, roofing material such as tiles,
- a sputtering assisted by magnetic field is implemented with the following characteristics: - Pressure 2 ⁇ bar - Gas 15 sccm Ar, 12 sccm O 2 - Power 2 kW - Target Si: Al (8% by weight) 50 cm x 15 cm
- On cut samples of 30 cm x 30 cm of glass + 150nm Si0 2 into smaller ones of 10 cm x 15 cm which are coated with a layer of TiO 2 of 100 nm by sputtering assisted by magnetic field with the following characteristics: - Pressure 24 ⁇ bar - Gas 47 sccm Ar, 5 sccm O 2 - Power 1 kW - Metal target: Ti at 99.96% 20 cm x 9 cm
- a layer of TiO 2 is formed containing various proportions of Nb 2 Os by gluing one or more Nb
- the photocatalytic activity of the different samples is evaluated under low residual UV.
- the samples are cut into 2.5 cm x 2.5 cm.
- a solution of 0.1 g of stearic acid in 10 ml of ethanol is prepared, and the mixture is stirred for 40 minutes.
- the sample is cleaned with UV - ozone for 40 minutes.
- 60 ⁇ l of stearic acid solution are deposited by spin coating on each sample.
- the amount of stearic acid is evaluated by FTIR analysis initially, then after two hours of illumination by a fluorescent lamp essentially delivering visible light (low residual UVA of 1.4 W / m 2 ). The proportion of stearic acid degraded by the layer is thus deduced therefrom.
- a proportion of degraded stearic acid of 15% is measured for a layer of pure TiO 2 , and this proportion reaches a maximum of 18% for a proportion of atom of Nb divided by the sum of atoms of Nb and Ti, in%, of 2.6 atomic%.
- This result shows the increase in photocatalytic activity under visible light of TiO2 by the intimate association of Nb 2 O 5 .
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- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Dispersion Chemistry (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
- Surface Treatment Of Glass (AREA)
- Securing Of Glass Panes Or The Like (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Physical Vapour Deposition (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US11/578,035 US20080261056A1 (en) | 2004-04-13 | 2005-04-12 | Photocatalytic Substrate Active Under a Visible Light |
JP2007507824A JP2007532462A (ja) | 2004-04-13 | 2005-04-12 | 可視光下で活性な光触媒性基材 |
EP05746932A EP1737801A2 (fr) | 2004-04-13 | 2005-04-12 | Substrat photocatalytique actif sous lumiere visible |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0403824 | 2004-04-13 | ||
FR0403824A FR2868792B1 (fr) | 2004-04-13 | 2004-04-13 | Substrat photocatalytique actif sous lumiere visible |
Publications (2)
Publication Number | Publication Date |
---|---|
WO2005102952A2 true WO2005102952A2 (fr) | 2005-11-03 |
WO2005102952A3 WO2005102952A3 (fr) | 2006-08-24 |
Family
ID=34948417
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR2005/050229 WO2005102952A2 (fr) | 2004-04-13 | 2005-04-12 | Substrat photocatalytique actif sous lumiere visible |
Country Status (6)
Country | Link |
---|---|
US (1) | US20080261056A1 (fr) |
EP (1) | EP1737801A2 (fr) |
JP (1) | JP2007532462A (fr) |
CN (1) | CN1968905A (fr) |
FR (1) | FR2868792B1 (fr) |
WO (1) | WO2005102952A2 (fr) |
Cited By (6)
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WO2007121211A2 (fr) * | 2006-04-11 | 2007-10-25 | Cardinal Cg Company | Revêtements photocatalytiques dotés de propriétés améliorées permettant un entretien minime |
WO2009036284A1 (fr) * | 2007-09-14 | 2009-03-19 | Cardinal Cg Company | Revêtements à faible entretien et procédés de production de revêtements à faible entretien |
FR2932796A1 (fr) * | 2008-06-19 | 2009-12-25 | Saint Gobain | Verre ancien autonettoyant |
WO2011003974A1 (fr) * | 2009-07-09 | 2011-01-13 | Saint-Gobain Glass France | Procede de depôt par pulverisation cathodique, produit obtenu et cible de pulverisation |
US9738967B2 (en) | 2006-07-12 | 2017-08-22 | Cardinal Cg Company | Sputtering apparatus including target mounting and control |
US10604442B2 (en) | 2016-11-17 | 2020-03-31 | Cardinal Cg Company | Static-dissipative coating technology |
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EP1765740B1 (fr) | 2004-07-12 | 2007-11-07 | Cardinal CG Company | Revêtements à entretien minime |
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FR2950878B1 (fr) | 2009-10-01 | 2011-10-21 | Saint Gobain | Procede de depot de couche mince |
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JP2001025666A (ja) * | 1999-07-14 | 2001-01-30 | Nippon Sheet Glass Co Ltd | 積層体およびその製造方法 |
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- 2005-04-12 US US11/578,035 patent/US20080261056A1/en not_active Abandoned
- 2005-04-12 WO PCT/FR2005/050229 patent/WO2005102952A2/fr active Application Filing
- 2005-04-12 EP EP05746932A patent/EP1737801A2/fr not_active Withdrawn
- 2005-04-12 CN CNA2005800194222A patent/CN1968905A/zh active Pending
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WO2007121211A2 (fr) * | 2006-04-11 | 2007-10-25 | Cardinal Cg Company | Revêtements photocatalytiques dotés de propriétés améliorées permettant un entretien minime |
WO2007121215A1 (fr) * | 2006-04-11 | 2007-10-25 | Cardinal Cg Company | Revêtements photocatalytiques dotés de propriétés améliorées permettant un entretien minime |
WO2007121211A3 (fr) * | 2006-04-11 | 2007-12-13 | Cardinal Cg Co | Revêtements photocatalytiques dotés de propriétés améliorées permettant un entretien minime |
US9738967B2 (en) | 2006-07-12 | 2017-08-22 | Cardinal Cg Company | Sputtering apparatus including target mounting and control |
EP2261186A3 (fr) * | 2007-09-14 | 2012-07-11 | Cardinal CG Company | Technologie de revêtement à faible entretien |
WO2009036263A3 (fr) * | 2007-09-14 | 2009-06-04 | Cardinal Cg Co | Technologie de revêtement à faible entretien |
WO2009036263A2 (fr) * | 2007-09-14 | 2009-03-19 | Cardinal Cg Company | Technologie de revêtement à faible entretien |
WO2009036284A1 (fr) * | 2007-09-14 | 2009-03-19 | Cardinal Cg Company | Revêtements à faible entretien et procédés de production de revêtements à faible entretien |
FR2932796A1 (fr) * | 2008-06-19 | 2009-12-25 | Saint Gobain | Verre ancien autonettoyant |
WO2011003974A1 (fr) * | 2009-07-09 | 2011-01-13 | Saint-Gobain Glass France | Procede de depôt par pulverisation cathodique, produit obtenu et cible de pulverisation |
FR2947816A1 (fr) * | 2009-07-09 | 2011-01-14 | Saint Gobain | Procede de depot par pulverisation cathodique, produit obtenu et cible de pulverisation |
US10604442B2 (en) | 2016-11-17 | 2020-03-31 | Cardinal Cg Company | Static-dissipative coating technology |
US11325859B2 (en) | 2016-11-17 | 2022-05-10 | Cardinal Cg Company | Static-dissipative coating technology |
Also Published As
Publication number | Publication date |
---|---|
US20080261056A1 (en) | 2008-10-23 |
FR2868792B1 (fr) | 2006-05-26 |
CN1968905A (zh) | 2007-05-23 |
WO2005102952A3 (fr) | 2006-08-24 |
JP2007532462A (ja) | 2007-11-15 |
FR2868792A1 (fr) | 2005-10-14 |
EP1737801A2 (fr) | 2007-01-03 |
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