EP2646616B1 - Mit einer selbstreinigenden beschichtung bedeckte heizanwendung und herstellungsverfahren dafür - Google Patents

Mit einer selbstreinigenden beschichtung bedeckte heizanwendung und herstellungsverfahren dafür Download PDF

Info

Publication number
EP2646616B1
EP2646616B1 EP11801788.8A EP11801788A EP2646616B1 EP 2646616 B1 EP2646616 B1 EP 2646616B1 EP 11801788 A EP11801788 A EP 11801788A EP 2646616 B1 EP2646616 B1 EP 2646616B1
Authority
EP
European Patent Office
Prior art keywords
self
coating
layer
support
cleaning coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP11801788.8A
Other languages
English (en)
French (fr)
Other versions
EP2646616A1 (de
Inventor
Denis Paccaud
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SEB SA
Original Assignee
SEB SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SEB SA filed Critical SEB SA
Priority to PL11801788T priority Critical patent/PL2646616T3/pl
Publication of EP2646616A1 publication Critical patent/EP2646616A1/de
Application granted granted Critical
Publication of EP2646616B1 publication Critical patent/EP2646616B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
    • C23C18/1208—Oxides, e.g. ceramics
    • C23C18/1216—Metal oxides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/1225—Deposition of multilayers of inorganic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1258—Spray pyrolysis
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1291—Process of deposition of the inorganic material by heating of the substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic material
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
    • D06F75/00—Hand irons
    • D06F75/08—Hand irons internally heated by electricity
    • D06F75/24—Arrangements of the heating means within the iron; Arrangements for distributing, conducting or storing the heat
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06F—LAUNDERING, DRYING, IRONING, PRESSING OR FOLDING TEXTILE ARTICLES
    • D06F75/00—Hand irons
    • D06F75/38—Sole plates
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24C—DOMESTIC STOVES OR RANGES ; DETAILS OF DOMESTIC STOVES OR RANGES, OF GENERAL APPLICATION
    • F24C15/00—Details
    • F24C15/005—Coatings for ovens
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS, OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D5/00—Supports, screens, or the like for the charge within the furnace
    • F27D5/0006—Composite supporting structures

Definitions

  • the present invention generally relates to heating apparatus or to be heated during use and comprising a self-cleaning coating.
  • heating apparatus is intended to mean any appliance, article or utensil which, during its operation, reaches a temperature of at least 65 ° C. (which is the minimum reheating temperature), and preferably at least 90 ° C.
  • the apparatus can achieve this operating temperature by means of its own, such as a heating base built into the apparatus and provided with heating elements, or by external means.
  • heating elements such as iron insoles, cooking appliances, ovens, grills, and cooking utensils.
  • these heaters some such as iron soles or cooking appliances have qualities of ease of use and efficiency, depending inter alia on the state and nature of the surface of their coating.
  • iron soles they could be improved thanks to the care given to the gliding qualities of the ironing surface, combined with those allowing the easier spreading of the linen.
  • One way of obtaining these qualities is to use enamelled soles with a smooth-looking enamel, possibly with lines of extra thickness to promote the spreading of the fabric during the movement of the iron. It is also known to use metal soles mechanically treated and / or covered or not with a deposit to facilitate sliding.
  • the sole can tarnish by carbonizing more or less diffuse on its surface ironing, and more or less incomplete, various organic fouling (especially in particulate form) that are captured by the sole by friction on the ironed fabrics.
  • the fading of the sole even in a not very visible manner, results in at least a partial loss of its sliding qualities.
  • ironing becomes more difficult.
  • the user apprehends to use a tarnished iron, fearing that he may alter his clothes.
  • the document FR2913682 describes a self-cleaning transparent wall of heating enclosure.
  • the Applicant has previously developed a self-cleaning coating for coating a metal surface of a heater that is more efficient in terms of catalytic activity.
  • This coating is the subject of the French patent FR 2 848 290 , which discloses a heating apparatus comprising a metal support, at least a portion of which is covered with a self-cleaning coating, which comprises an outer layer in contact with ambient air and comprising at least one oxidation catalyst selected from platinum oxide, and at least one inner layer, located between the metal support and the outer layer, comprising at least one catalyst of oxidation chosen from the oxides of the transition elements of the group 1b.
  • this self-cleaning coating has the disadvantage of requiring a large amount of platinum oxide in the outer layer to reach just satisfactory levels of catalytic activity, which in particular results in a significant increase in the cost of coating, and therefore in the end that of the heating device.
  • a heating appliance coating such as a cooking appliance or an iron soleplate, in which the amount of platinoid oxides is appreciably lower, but which is more efficient in terms of Catalytic activity (ie a coating to keep the surface clean of any contamination by organic particles, and not clog up in normal use) without loss of other properties required (glossy appearance, slip and abrasion resistance of the coating).
  • catalytic activity of a coating is meant, in the sense of the present invention, the ability of the outer surface of the self-cleaning coating in contact with the ambient air and with organic soils, to burn these soils, which, a burned, lose adhesion and become detached from the coating.
  • organic soils means any combustible or oxidizable substance in contact with the ambient air, completely or partially.
  • any residue of synthetic fibers as used in textile articles, for example organic polymer such as polyamide or polyester, any organic residue of detergent and optionally softening product, any organic substance such as fats or food projections.
  • the subject of the present invention is a heating apparatus as claimed in claim 1 comprising a metallic support of which at least a part is covered with a self-cleaning coating in contact with the ambient air and comprising at least one catalyst of oxidation chosen from platinum oxide, characterized in that said coating further comprises at least one dopant of said oxidation catalyst selected from rare earth oxides.
  • the heating article according to the invention an apparatus is obtained in which the self-cleaning coating has a particularly excellent catalytic activity and whose adhesion to the metallic support is very good, and which also allows the organic particles in contact with the Self-cleaning coating will be oxidized when the appliance is heated.
  • the organic particles captured by the sole are oxidized. They are somehow burned when the iron is hot, any solid residue loses any adhesion and detaches from the sole. The sole stays clean.
  • a cooking appliance such as an oven for example, the grease projections present on the wall of the oven are oxidized hot, the solid residue is detached from the wall which is kept clean.
  • the catalytic activity of the self-cleaning coating is three to five times greater than that obtained with the coating of FR 2 848 290 with a quantity of platinum oxides of two to four times less.
  • the surface of the coating is regenerated more rapidly than in the coatings described in FR 2 848 290 .
  • platinum is meant, within the meaning of the present application, the elements having properties similar to those of platinum, and in particular, in addition to platinum, ruthenium, rhodium, palladium, osmium and iridium. .
  • oxidation catalysts of the type of platinum oxides are well known in themselves, as well as their methods of obtaining, without there being any need to describe in detail their methods of preparation respectively.
  • platinum oxide IV as an oxidation catalyst (hydrated platinum dioxide PtO 2 -H 2 O or Adams catalyst)
  • its catalytically active form can be obtained by melting hexachloroplatinic acid or its ammonium salt with sodium nitrate, followed by the thermal decomposition of the platinum nitrate obtained in platinum oxide IV.
  • the oxidation catalyst is chosen from palladium oxides, platinum oxides and mixtures thereof.
  • the term "dopant” means an element which is not a catalyst in itself, but which has the effect of increasing and boosting the catalytic activity of said catalyst and of stabilizing the behavior of the catalyst on the catalyst. the substrate.
  • the oxidation catalyst is used as dopant in the self-cleaning coating of at least one rare earth oxide.
  • rare earths is intended to mean lanthanides and yttrium having properties similar to those of lanthanum, and in particular, besides lanthanum, cerium, and yttrium.
  • the dopant is selected from cerium oxides, yttrium oxide and mixtures thereof.
  • any oxidation catalyst and dopant retained according to the present invention must remain sufficiently stable at the operating temperature of the device, and within the limits of the useful life of the device.
  • the self-cleaning coating of the heating article is a monolayer coating comprising at least one platinum oxide doped with yttrium oxide.
  • the self-cleaning coating according to the invention is preferably a coating consisting of an inner layer of cerium or yttrium oxide and an outer layer of palladium oxide.
  • the doping inner layer has a thickness, measured according to the RBS method described in the examples (measuring methods) of the present application, ranging from 50 nm to 100 nm.
  • the catalytic activity increases with the thickness of the inner layer.
  • the outer layer of the coating preferably has a thickness, also measured according to the RBS method described in the examples (measuring methods) of the present application, between 15 and 50 nm.
  • the catalytic activity increases with the thickness of the layer until reaching a threshold effect.
  • the oxidation catalyst is distributed in the outer layer of the self-cleaning coating, which is in contact with the dirt, continuously or discontinuously.
  • the metal support of the apparatus according to the invention can be based on any metal commonly used in the field of heating appliances such as aluminum, steel or titanium.
  • This metal support may itself be covered with a protective layer such as a front enamel layer to be covered by the coating of the present invention.
  • the apparatus comprises an intermediate enamel protective layer between the metal support and the inner layer of the self-cleaning coating, said intermediate protective layer consisting of a material selected from aluminum alloys, enamel and mixtures thereof, so that said protective layer is catalytically inert with respect to oxidation.
  • the intermediate protective layer is enamel with a low porosity and / or roughness, at the micrometric and / or nanometric scale.
  • the enamel is for example a vitreous enamel.
  • the enamel should preferably be hard, have a good glide and resist hydrolysis by hot steam.
  • the heating apparatus is in the form of an iron soleplate comprising an ironing surface and the coating covers the ironing surface.
  • ironing surface is meant, in the sense of the present invention the surface in direct contact with the laundry for the degreasing.
  • the heating apparatus is a cooking appliance comprising walls that are capable of coming into contact with organic soils and the self-cleaning coating covers these walls.
  • the catalyst acts at the operating temperature of the apparatus and the coating is kept clean as and when the use of the apparatus.
  • the latter In a second mode of operation of the heating apparatus according to the invention, during a phase called self-cleaning, before or after the use of the apparatus, the latter is set to a high temperature, equal to or higher than the highest operating temperatures, it is then left on standby for a predetermined time, during which the oxidation catalyst produces its effect.
  • Doping of the oxidation catalyst means, within the meaning of the present invention, an increase in the catalytic activity of the oxidation catalyst, as well as a stabilization of the resistance of the catalyst to the oxidation catalyst. substrate. This is possible thanks to the oxygen available in the rare earth oxide network that can be used by the platinum oxide during the catalysis of the oxidation reaction.
  • hexachloroplatinate acid marketed by Alfa Aesar under the trade name of dihydrogen hexachloroplatinate (IV) hexahydrate, ACS, Premium, 99, 95%, Pt 37.5% min
  • the application on the metal support, covered or not by an enameled layer of the catalytically active layer or layers of the self-cleaning coating is preferably by pyrolysis of an aerosol (technique usually referred to as " thermal spray "). by heating the surface to be coated and then spraying on this hot surface a solution containing a precursor of the oxidation catalyst.
  • the doping of said self-cleaning coating layer is carried out during step ii of the process according to the invention, by adding to the oxidation catalyst precursor solution, a dopant precursor selected from the rare earth salts, so as to form a single-layer self-cleaning coating.
  • dopant precursor means any chemical or physicochemical form of the dopant, which is capable of leading to the dopant as such, or of liberating it by any appropriate treatment, by example by pyrolysis.
  • chlorides or nitrates sometimes acetates if possible, are used as the dopant or oxidation catalyst salts.
  • the surface of the metal support to be coated is heated in an oven between 250 ° C and 400 ° C.
  • a solution of the precursor of the dopant is then sprayed onto the surface of the metal support. In contact with the surface, the water evaporates, the precursor decomposes and the metal oxide formed is fixed on the support.
  • a layer of thickness between 50 nm and 100 nm is then deposited.
  • the thus cooled support is heated again in the oven or under infrared at a temperature between 250 ° C to 400 ° C for a few seconds.
  • a solution of the precursor of the selected oxidation catalyst is then sprayed over the inner layer.
  • a layer of thickness ranging from 15 to 50 nm is deposited.
  • the thus coated support is then annealed in an oven or under infrared for a few minutes between 400 ° C and 600 ° C, for example for five minutes. This gives a coated support whose self-cleaning properties are particularly good.
  • iron soleplate 1 to iron comprising a metal support 2 covered with an inner layer 3 and an outer layer 4, these inner layers 3 and outer 4 constituting the self-cleaning coating.
  • the sole also comprises a heating base 6 provided with heating elements 7.
  • the support 2 and the base 6 are assembled by mechanical means or by gluing.
  • the inner layer 3 comprises a dopant chosen from rare earth oxides and the outer layer 4 comprises an oxidation catalyst chosen from oxides of PGMs.
  • FIG. 2 there is shown a second example of an iron soleplate 1, which differs from the example shown in FIG. figure 1 by the presence of an intermediate protective layer 5 enamel, covering the support 2 and itself being covered by the inner layer 3 of the self-cleaning coating.
  • FIG. 3 a third example of iron soleplate 1 to be ironed is shown in section comprising a metal support 2 also covered with a self-cleaning coating.
  • this self-cleaning coating 4 is not bilayer, but monolayer. It comprises an oxidation catalyst selected from platinum oxide and a dopant selected from rare earth oxides.
  • the sole also comprises a heating base 6 provided with heating elements 7 and the support 2 and the base 6 are also assembled by mechanical means or by gluing.
  • FIG. 4 there is shown a fourth example of iron soleplate 1, which differs from the example shown in FIG. figure 3 by the presence of an intermediate enamel protective layer 5 covering the support 2 and itself being covered by a self-cleaning monolayer coating 4.
  • the Figures 5 to 8 are discussed in the examples, in the section "Method of determining the abrasion resistance”.
  • the RBS (Rutherford Backscattering Spectroscopy) method is an analytical technique based on the elastic interaction between a 4 He 2+ ion beam and the sample particles.
  • the high energy beam (2MeV) strikes the sample, the backscattered ions are detected at a teta angle.
  • the spectrum thus acquired represents the intensity of the ions detected according to their energy and allows to determine the thickness of the layer. This method is described in WK Chu and G. Langouche, MRS Bulletin, January 1993, p 32 .
  • the principle of this method is to slide a pad covered with a fabric on a part coating during 3000 round trips.
  • the fabric is made of wool and complies with EN ISO 12947-1.
  • the pad mounted at the end of a swingarm and circular shape has a contact area of 2.5 cm 2 and a mass of 1.64 Kg.
  • the apparatus used for the test is the model sold under the trade name Taber® Linear Abrasion Tester Model 5750 by the company Taber Industries.
  • a clean insole of enamelled aluminum iron is placed on a thick aluminum support serving as a heat reservoir to limit temperature variations as much as possible. The whole is heated to 400 ° C in an oven. The sole, with the support, is placed under infrared for a few seconds until reaching a surface temperature between 400 ° C and 600 ° C.
  • aqueous nitrate solution of palladium stabilized with nitric acid is sprayed by means of a pneumatic gun on the soleplate.
  • this single layer is annealed under infrared at 500 ° C for three minutes.
  • An iron soleplate is obtained whose self-cleaning coating adheres to the soleplate and has a catalytic activity, while maintaining its gliding qualities.
  • This iron soleplate corresponds to that illustrated on the figure 4 , which corresponds to an iron soleplate according to the invention with a monolayer self-cleaning coating enamelled support.
  • the only difference (which does not appear in this figure) is related to the absence of an oxidation catalyst in the inner layer of the self-cleaning coating, as is the case according to the present invention.
  • a clean insole of enamelled aluminum iron is placed on a thick aluminum support serving as a heat reservoir to limit temperature variations as much as possible. The whole is heated to 400 ° C in an oven. The sole, with the support, is placed under infrared for a few seconds until reaching a surface temperature between 400 ° C and 600 ° C.
  • Silver nitrate is dissolved in water. This silver nitrate solution is then sprayed with a pneumatic gun on the soleplate. A layer of about 40 nm to 50 nm thick, measured according to the RBS method, is then deposited.
  • the sole is again heated in the oven at 400 ° C and then placed for a few seconds under infrared radiation at a temperature between 400 ° C and 600 ° C.
  • aqueous nitrate solution of palladium stabilized with nitric acid is sprayed by means of a pneumatic gun on the soleplate.
  • the assembly is annealed under infrared at 500 ° C for three minutes.
  • An iron soleplate is obtained whose self-cleaning coating adheres to the soleplate and has a catalytic activity, while maintaining its gliding qualities.
  • This iron soleplate corresponds to that illustrated on the figure 2 , which corresponds to an iron soleplate according to the invention with a two-layer self-cleaning coating enamelled support.
  • the only difference (which does not appear in this figure) is related to the nature of the oxidation catalyst of the inner layer of the self-cleaning coating which is a silver oxide in this example and not a rare earth oxide, such as is the case according to the present invention.
  • a clean insole of enamelled aluminum iron is placed on a thick aluminum support serving as a heat reservoir to limit temperature variations as much as possible. The whole is heated to 300 ° C in an oven. The sole, with the support, is placed under infrared for a few seconds until reaching a surface temperature between 400 ° C and 600 ° C.
  • Acetate or copper nitrate is dissolved in the water. This solution of acetate or copper nitrate, stabilized respectively with acetic acid or nitric acid, is then sprayed by means of a pneumatic gun on the sole. A layer of about 40 nm to 50 nm thick, measured according to the RBS method, is then deposited.
  • the sole is again heated in the oven at 400 ° C and then placed for a few seconds under infrared radiation at a temperature between 400 ° C and 600 ° C.
  • the assembly is annealed under infrared at 500 ° C for three minutes.
  • An iron soleplate is obtained whose self-cleaning coating adheres to the soleplate and has a catalytic activity, while maintaining its gliding qualities.
  • This iron soleplate corresponds to that illustrated on the figure 2 , which is that of an iron soleplate according to the invention with a two-layer self-cleaning coating enamelled support.
  • the only difference (which does not appear in this figure) is related to the nature of the oxidation catalyst of the inner layer of the self-cleaning coating, which is a silver oxide in this example and not a rare earth oxide, such as this is the case according to the present invention.
  • a clean insole of enamelled aluminum iron is placed on a thick aluminum support serving as a heat reservoir to limit temperature variations as much as possible.
  • the whole is heated in an oven at a temperature of 300 ° C.
  • the sole, with the support, is placed for a few seconds under infrared radiation until a surface temperature of between 300 ° C and 350 ° C.
  • Cerium nitrate is dissolved in water. This solution of cerium nitrate is then sprayed by means of a pneumatic gun on the sole. A layer of about 50 nm to 100 nm thick, measured according to the RBS method, is then deposited.
  • the sole is heated in the oven at 250 ° C, and then placed for a few seconds under infrared radiation at a temperature between 280 ° C and 350 ° C.
  • aqueous nitrate solution of palladium stabilized with nitric acid is sprayed by means of a pneumatic gun on the soleplate.
  • the assembly is annealed under infrared radiation at a temperature of 480 ° C for 4 minutes.
  • An iron sole is obtained whose self-cleaning coating adheres particularly well to the sole and has a very good catalytic activity, while maintaining its gliding qualities.
  • a clean insole of enamelled aluminum iron is placed on a thick aluminum support serving as a heat reservoir to limit temperature variations as much as possible.
  • the whole is heated in an oven at a temperature of 300 ° C.
  • the sole, with the support, is placed for a few seconds under infrared radiation until a surface temperature of between 300 ° C and 350 ° C.
  • Yttrium nitrate is dissolved in water. This solution of yttrium nitrate is then sprayed with a pneumatic gun on the soleplate. A layer of about 50 nm to 100 nm thick, measured according to the RBS method, is then deposited.
  • the sole is heated in the oven at 250 ° C, and then placed for a few seconds under infrared radiation at a temperature between 280 ° C and 350 ° C.
  • aqueous nitrate solution of palladium stabilized with nitric acid is sprayed by means of a pneumatic gun on the soleplate.
  • the assembly is annealed under infrared radiation at a temperature of 500 ° C for 4 minutes.
  • An iron sole is obtained whose self-cleaning coating adheres particularly well to the sole and has a very good catalytic activity, while maintaining its gliding qualities.
  • This iron soleplate is also illustrated on the figure 2 .
  • a clean insole of enamelled aluminum iron is placed on a thick aluminum support serving as a heat reservoir to limit temperature variations as much as possible.
  • the whole is heated in an oven at a temperature of 250 ° C.
  • the sole, with the support, is placed for a few seconds under infrared radiation until a surface temperature between 280 ° C and 350 ° C.
  • the assembly is annealed under infrared radiation at a temperature of 500 ° C for 4 minutes.
  • An iron sole is obtained whose self-cleaning coating adheres particularly well to the sole and has a very good catalytic activity, while maintaining its gliding qualities.
  • This iron soleplate is also illustrated on the figure 4 .
  • the catalytic activity of the self-cleaning coating was determined according to the method described above for each of the coatings of Comparative Examples 1 to 3 and Examples 1 to 3.
  • the abrasion resistance of the self-cleaning coating was determined, according to the test described above according to EN ISO 12947-1, for each of the coatings of Comparative Examples 1 to 3 and Examples 1 to 3.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Ceramic Engineering (AREA)
  • Catalysts (AREA)

Claims (10)

  1. Heizvorrichtung (1), die einen metallischen Träger (2) umfasst, von dem mindestens ein Teil mit einer selbstreinigenden Beschichtung überzogen ist, die mit der Umgebungsluft in Kontakt steht, wobei die Beschichtung mindestens einen Oxidationskatalysator umfasst, der aus Oxiden der Platingruppe ausgewählt ist, und mindestens ein Dotierungsmittel des Oxidationskatalysators, das aus Oxiden seltener Erden ausgewählt ist,
    dadurch gekennzeichnet, dass die selbstreinigende Beschichtung eine zweischichtige Beschichtung ist, die umfasst:
    - eine innere Schicht (3) einer Dicke im Bereich zwischen 50 nm und 100 nm, die den metallischen Träger (2) mindestens teilweise überzieht und das Dotierungsmittel umfasst, und
    - eine äußere Schicht (4) einer Dicke im Bereich zwischen 15 nm und 50 nm, die mit der Umgebungsluft in Kontakt steht und den Oxidationskatalysator umfasst, und
    dadurch, dass die äußere Schicht (4) auf der inneren Schicht (3) angeordnet ist.
  2. Vorrichtung nach Anspruch 1, dadurch gekennzeichnet, dass das Dotierungsmittel aus Ceroxiden, Yttriumoxiden und deren Gemischen ausgewählt ist.
  3. Vorrichtung nach den Ansprüchen 1 oder 2, dadurch gekennzeichnet, dass der Oxidationskatalysator aus Palladiumoxiden, Platinoxiden und deren Gemischen ausgewählt ist.
  4. Vorrichtung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass die selbstreinigende Beschichtung eine zweischichtige Beschichtung ist, die sich aus einer inneren Schicht 3 aus Cer- oder Yttriumoxid und einer äußeren Schicht 4 aus Palladiumoxid zusammensetzt.
  5. Vorrichtung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass sie weiterhin eine Zwischen-Schutzschicht (5) umfasst, die zwischen dem metallischen Träger (2) und der inneren Schicht (3) der selbstreinigenden Beschichtung angeordnet ist, wobei die Zwischen-Schutzschicht (5) aus einem Material gebildet ist, das aus Aluminiumlegierungen, Emaille und deren Gemischen ausgewählt ist, um einen Träger zu bilden, der, was die Oxidation betrifft, katalytisch inert ist.
  6. Vorrichtung nach Anspruch 5, dadurch gekennzeichnet, dass die Zwischen-Schutzschicht (5) aus Emaille ist.
  7. Vorrichtung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass sie sich in der Form einer Bügeleisensohle zeigt, die eine Bügelfläche umfasst, und dass die selbstreinigende Beschichtung die Bügelfläche überzieht.
  8. Vorrichtung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass sie sich in Form einer Kochvorrichtung zeigt, die Wände umfasst, die mit organischem Schmutz in Kontakt kommen können, wobei die selbstreinigende Beschichtung diese Wände überzieht.
  9. Verfahren zur Herstellung einer Heizvorrichtung (1), die einen metallischen Träger (2) umfasst, von dem mindestens ein Teil mit einer selbstreinigenden Beschichtung überzogen ist, die aus einer inneren Schicht (3) und einer äußeren Schicht (4) gebildet ist, wobei das Verfahren dadurch gekennzeichnet ist, dass es die folgenden Schritte umfasst:
    i. Erhitzen der zu überziehenden Fläche des metallischen Trägers (2) in einem Ofen oder unter Infrarotstrahlung auf eine Temperatur im Bereich zwischen 250 °C und 400 °C;
    ii. Aufsprühen einer Lösung eines Dotierungsmittel-Vorläufers, der aus Salzen der seltenen Erden ausgewählt ist, auf die zu überziehende Fläche des metallischen Trägers (2), die sich auf einer Temperatur im Bereich zwischen 250 °C und 400 °C befindet, um die innere Schicht (3) einer Dicke im Bereich zwischen 50 nm und 100 nm Beschichtung zu formen, die ein Dotierungsmittel umfasst, das aus Oxiden der seltenen Erden ausgewählt ist;
    iii. erneutes Erhitzen der von der inneren Schicht (3) überzogenen Fläche des metallischen Trägers (2) in einem Ofen oder unter Infrarotstrahlung auf eine Temperatur im Bereich zwischen 250 °C und 400 °C;
    iv. Aufsprühen einer Lösung eines Oxidationskatalysator-Vorläufers auf die Fläche der inneren Schicht (3), um die äußere Schicht (4) einer Dicke im Bereich zwischen 15 nm und 50 nm zu formen, wobei der Oxidationskatalysator-Vorläufer aus Salzen der Platingruppe ausgewählt ist, um die selbstreinigende Beschichtungsschicht zu erhalten;
    v. Kochen der mit der selbstreinigenden Beschichtung überzogenen Fläche des metallischen Trägers (2) während einiger Minuten bei einer Temperatur im Bereich zwischen 400 °C und 600 °C in einem Ofen oder unter Infrarotstrahlung.
  10. Verfahren nach Anspruch 9, dadurch gekennzeichnet, dass die Dotierungsmittel- oder Oxidationskatalysator-Salze Acetate, Chloride oder Nitrate sind.
EP11801788.8A 2010-11-29 2011-11-29 Mit einer selbstreinigenden beschichtung bedeckte heizanwendung und herstellungsverfahren dafür Active EP2646616B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
PL11801788T PL2646616T3 (pl) 2010-11-29 2011-11-29 Urządzenie grzewcze pokryte powłoką samoczyszczącą i sposób jego wytwarzania

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR1059868A FR2968016B1 (fr) 2010-11-29 2010-11-29 Appareil chauffant recouvert d'un revetement autonettoyant
PCT/FR2011/052809 WO2012072944A1 (fr) 2010-11-29 2011-11-29 Appareil chauffant recouvert d'un revetement autonettoyant et son procede de fabrication

Publications (2)

Publication Number Publication Date
EP2646616A1 EP2646616A1 (de) 2013-10-09
EP2646616B1 true EP2646616B1 (de) 2017-08-02

Family

ID=43983972

Family Applications (1)

Application Number Title Priority Date Filing Date
EP11801788.8A Active EP2646616B1 (de) 2010-11-29 2011-11-29 Mit einer selbstreinigenden beschichtung bedeckte heizanwendung und herstellungsverfahren dafür

Country Status (8)

Country Link
US (1) US8745904B2 (de)
EP (1) EP2646616B1 (de)
CN (1) CN103237938B (de)
FR (1) FR2968016B1 (de)
HK (1) HK1185388A1 (de)
PL (1) PL2646616T3 (de)
RU (1) RU2568086C2 (de)
WO (1) WO2012072944A1 (de)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8720325B2 (en) 2010-04-29 2014-05-13 Whirlpool Corporation Food processor with a lockable adjustable blade assembly
US10449685B2 (en) 2010-04-29 2019-10-22 Whirlpool Corporation Food processor with adjustable blade assembly
JP6219970B2 (ja) * 2013-02-06 2017-10-25 コーニンクレッカ フィリップス エヌ ヴェＫｏｎｉｎｋｌｉｊｋｅ Ｐｈｉｌｉｐｓ Ｎ．Ｖ． 衣類処置機器のための処置プレート
US10085599B2 (en) 2014-12-19 2018-10-02 Whirlpool Corporation Multi-cook and food processing prep product
FR3039091B1 (fr) * 2015-07-20 2017-07-21 Seb Sa Inclusion d'oxydes de terres rares dans un revetement a base de resine fluorocarbonee
FR3039053B1 (fr) 2015-07-21 2018-02-02 Seb S.A. Article culinaire comprenant une couche d'oxyde de terre rare
EP3222770A1 (de) * 2016-03-21 2017-09-27 Koninklijke Philips N.V. Behandlungsplatte für eine kleidungsbehandlungsanwendung

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1197069A (en) * 1967-06-28 1970-07-01 Du Pont Catalytic Coatings for Cooking Devices
US3566855A (en) * 1969-10-21 1971-03-02 Fedders Corp Self-cleaning cooking apparatus
US3738350A (en) * 1972-05-12 1973-06-12 A Stiles Fibrous catalyst structures for oven walls
US4029603A (en) 1973-03-26 1977-06-14 Imperial Chemical Industries Limited Catalytic coating composition and a method for making a coated surface for an oven
JPS5436320A (en) 1977-08-24 1979-03-17 Matsushita Electric Ind Co Ltd Articles having selffcleanable coated layer
DE3676975D1 (en) 1985-12-24 1991-02-21 Braun Ag Buegeleisensohle.
US5411771A (en) * 1993-04-29 1995-05-02 Tsai; Tung-Hung Method for coating metal cookware
US20010026838A1 (en) * 1996-06-21 2001-10-04 Engelhard Corporation Monolithic catalysts and related process for manufacture
US6054173A (en) * 1997-08-22 2000-04-25 Micron Technology, Inc. Copper electroless deposition on a titanium-containing surface
GB9917583D0 (en) * 1999-07-28 1999-09-29 Marconi Electronic Syst Ltd Hydrocarbon fuel processor catalyst
US6245390B1 (en) * 1999-09-10 2001-06-12 Viatcheslav Baranovski High-velocity thermal spray apparatus and method of forming materials
FR2825385B1 (fr) * 2001-06-01 2003-09-12 Seb Sa Fer a repasser a semelle auto-nettoyante
TW200304503A (en) * 2002-03-20 2003-10-01 Asahi Chemical Ind Electrode for generation of hydrogen
US20050265920A1 (en) * 2002-11-11 2005-12-01 Conocophillips Company Supports and catalysts comprising rare earth aluminates, and their use in partial oxidation
FR2848290B1 (fr) * 2002-12-05 2005-01-07 Seb Dev Appareil chauffant recouvert d'un revetement autonettoyant
US7524531B2 (en) * 2005-04-27 2009-04-28 Ferro Corporation Structured self-cleaning surfaces and method of forming same
FR2913682B1 (fr) * 2007-03-12 2010-10-29 Saint Gobain Paroi transparente autonettoyante d'enceinte chauffante
US8652993B2 (en) * 2011-08-18 2014-02-18 University Of Central Florida Research Foundation, Inc. Doped palladium containing oxidation catalysts
WO2014025356A1 (en) * 2012-08-10 2014-02-13 Empire Technology Development Llc Inorganic hydrophilic self-cleaning coatings

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
None *

Also Published As

Publication number Publication date
EP2646616A1 (de) 2013-10-09
HK1185388A1 (en) 2014-02-14
CN103237938B (zh) 2015-09-16
FR2968016B1 (fr) 2013-05-03
WO2012072944A1 (fr) 2012-06-07
FR2968016A1 (fr) 2012-06-01
CN103237938A (zh) 2013-08-07
RU2568086C2 (ru) 2015-11-10
RU2013123485A (ru) 2015-01-10
US20130247430A1 (en) 2013-09-26
PL2646616T3 (pl) 2017-10-31
US8745904B2 (en) 2014-06-10

Similar Documents

Publication Publication Date Title
EP2646616B1 (de) Mit einer selbstreinigenden beschichtung bedeckte heizanwendung und herstellungsverfahren dafür
EP1567807B1 (de) Mit einer selbstreinigenden beschichtung beschichtetes heizgerät
EP2320776B1 (de) Kulinarischer artikel mit einer antihaftbeschichtung mit verbesserten antihafteigenschaften
FR2915205A1 (fr) Revetement antiadhesif a proprietes hydrophobes ameliorees
EP2783022B1 (de) Fleckenbeständige kochfläche und kochartikel oder elektrisches haushaltsgerät mit einer solchen kochfläche
FR2904206A1 (fr) Article culinaire presentant des proprietes hydrophobes ameliorees et procede de fabrication d'un tel article
WO2002097185A1 (fr) Fer a repasser a semelle auto-nettoyante
FR2702208A1 (fr) Verre portant un revêtement et procédé de fabrication d'un tel verre.
CH676463A5 (de)
EP3589597B1 (de) Artikel für einen feuchtraum mit hydrophober verglasung
FR3110591A1 (fr) Revêtement anti-adhésif amélioré
FR3110463A1 (fr) Caractérisation d’un composé thermochrome pour indicateur de température
FR3138283A1 (fr) Revêtement non-fluoré hybride sol-gel/résine silicone
JP2002363774A (ja) キッチン用ホーロー材及びその製造方法、並びにその使用方法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20130423

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: SEB S.A.

17Q First examination report despatched

Effective date: 20160929

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

RIC1 Information provided on ipc code assigned before grant

Ipc: C23C 18/12 20060101ALI20170428BHEP

Ipc: F27D 5/00 20060101ALI20170428BHEP

Ipc: D06F 75/38 20060101AFI20170428BHEP

Ipc: D06F 75/24 20060101ALI20170428BHEP

Ipc: F24C 15/00 20060101ALI20170428BHEP

INTG Intention to grant announced

Effective date: 20170518

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: AT

Ref legal event code: REF

Ref document number: 914602

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170815

REG Reference to a national code

Ref country code: RO

Ref legal event code: EPE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602011040229

Country of ref document: DE

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 914602

Country of ref document: AT

Kind code of ref document: T

Effective date: 20170802

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171102

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171103

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171102

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20171202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602011040229

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

26N No opposition filed

Effective date: 20180503

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171130

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171129

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20171129

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20111129

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20170802

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20191015

Year of fee payment: 9

Ref country code: CZ

Payment date: 20191021

Year of fee payment: 9

Ref country code: RO

Payment date: 20191031

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: PL

Payment date: 20191029

Year of fee payment: 9

Ref country code: BE

Payment date: 20191126

Year of fee payment: 9

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20191122

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20170802

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20201201

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20201129

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201129

Ref country code: RO

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201129

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20201130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201129

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20201129

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: TR

Payment date: 20231115

Year of fee payment: 13

Ref country code: FR

Payment date: 20231124

Year of fee payment: 13

Ref country code: DE

Payment date: 20231107

Year of fee payment: 13