EP1567807A1 - Heating device coated with a self-cleaning coating - Google Patents

Heating device coated with a self-cleaning coating

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Publication number
EP1567807A1
EP1567807A1 EP03786028A EP03786028A EP1567807A1 EP 1567807 A1 EP1567807 A1 EP 1567807A1 EP 03786028 A EP03786028 A EP 03786028A EP 03786028 A EP03786028 A EP 03786028A EP 1567807 A1 EP1567807 A1 EP 1567807A1
Authority
EP
European Patent Office
Prior art keywords
layer
metal support
oxidation catalyst
oxides
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.)
Granted
Application number
EP03786028A
Other languages
German (de)
French (fr)
Other versions
EP1567807B1 (en
Inventor
Stéphanie PESSAYRE
Henry Boulud
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
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Filing date
Publication date
Application filed by SEB SA filed Critical SEB SA
Publication of EP1567807A1 publication Critical patent/EP1567807A1/en
Application granted granted Critical
Publication of EP1567807B1 publication Critical patent/EP1567807B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • 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
    • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
    • C23C28/042—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material including a refractory ceramic layer, e.g. refractory metal oxides, ZrO2, rare earth oxides
    • 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

Definitions

  • the present invention relates to heating devices or intended to be heated during their use and comprising a self-cleaning coating.
  • Certain heating appliances such as for example iron soles or even cooking appliances, have qualities of ease of use and efficiency, depending inter alia on the state and nature of the surface of their coating. .
  • the iron soles could be improved by the care given to the sliding qualities of the ironing surface, combined with the qualities allowing easier spreading of the laundry.
  • One way to obtain these qualities is to use enameled soles with a smooth-looking enamel, possibly with extra thickness lines to spread the fabric during the movement of the iron.
  • Other metal soles treated mechanically and / or covered or not with a deposit to facilitate sliding can also be suitable for satisfactory use.
  • the soleplate may tarnish by carbonizing in a more or less diffuse manner on its ironing surface, and in a more or less incomplete manner, various organic particles captured by friction on the ironed fabrics.
  • Iron soleplates comprising a hard and resistant layer covered, as indicated by US Pat. No. 4,862,609, with a layer improving the surface properties. But this patent does not indicate a solution to combat fouling.
  • the walls of cooking appliances are also often covered with an enamelled layer of smooth appearance so that any splashes of grease or food do not adhere to the surface.
  • Self-cleaning enamelled surfaces are known, for example in ovens and cooking utensils as described for example in patent US4029603 or patent FR2400876. However, these coatings are not entirely satisfactory with regard to their self-cleaning properties.
  • the present invention relates to a heating appliance comprising a metal support at least part of which is covered with a self-cleaning coating, characterized in that the coating comprises:
  • an outer layer in contact with ambient air, comprising at least one oxidation catalyst chosen from the oxides of platinoids,
  • At least one internal layer located between the metal support and the external layer, comprising at least one oxidation catalyst chosen from the oxides of the transition elements from group Ib.
  • the present invention also relates to a method for covering the metal support of a heating appliance with a self-cleaning coating as above, characterized in that it comprises the following steps: - i) the surface of the support is heated metallic to be covered in an oven at around 400 ° C,
  • the surface of the metal support to be covered is placed under infrared at a temperature ranging from 400 ° C. to 600 ° C. for a few seconds, iii) a solution of an oxidation catalyst precursor chosen from oxides is sprayed transition elements of group Ib on the surface of the metal support to be covered to obtain the internal layer,
  • the surface of the metal support to be covered is placed, with the internal layer, under infrared at a temperature ranging from 400 ° C. to 600 ° C. for a few seconds,
  • an apparatus is obtained whose self-cleaning coating has a particularly excellent catalytic activity and whose adhesion to the metal support is very good.
  • the organic particles in contact with the outer layer of the coating are oxidized when the device is heated. Furthermore, the synergistic effect obtained by the particular association of an internal layer comprising a specific oxidation catalyst and an external layer comprising a specific oxidation catalyst different from that of the internal layer makes it possible to obtain a coating with particularly effective catalytic activity. Thus, the surface of the coating is regenerated very quickly. For example, when ironing with an iron, the organic particles captured by the soleplate are oxidized. They are somehow burned when the iron is hot, the possible solid residue loses all grip and comes off the soleplate. The sole stays clean. Likewise, in a cooking appliance such as an oven for example, the projections of grease present on the wall of the oven are oxidized hot, the solid residue is detached from the wall which is kept clean.
  • the adhesion of the coating to the metal support is particularly good.
  • This improved adhesion makes it possible to increase the resistance to friction of the coating, this property being particularly advantageous in the case of an iron soleplate for example.
  • heating appliance is meant within the meaning of the present application, any appliance, article or utensil, which during its operation reaches a temperature at least equal to 45 ° C, and preferably at least equal to 90 ° C.
  • the device can reach this temperature operating by means which are specific to it, such as for example a heating base integrated into the apparatus and provided with heating elements, or by external means.
  • Such devices are for example iron soles, cooking appliances, ovens, grills, cooking utensils.
  • the outer layer of the coating according to the invention comprises an oxidation catalyst chosen from the oxides of platinoids.
  • 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 .
  • the outer layer comprises an oxidation catalyst chosen from palladium oxides, platinum oxides and their mixtures.
  • oxidation catalysts are well known in themselves, as well as their processes for obtaining them, without it being necessary to describe in detail their methods of preparation respectively.
  • platinum as an oxidation catalyst, its catalytically active form can be obtained by calcination or decomposition of a chloro-platinic acid salt or any other precursor.
  • any oxidation catalyst retained according to the present invention must remain sufficiently stable at the operating temperature of the device, and this within the limits of the useful life of the device.
  • the surface of the outer layer is in direct contact with the ambient air and with organic dirt.
  • organic soiling is meant in the sense of the present application 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 of organic polymer such as polyamide or polyester, any organic residue of washing product and optionally of softening product, any organic substance such as splashes of fat or food.
  • the oxidation catalyst chosen from platinum oxides is distributed on and / or in the outer layer of the coating, where it is in contact with dirt, and depending on all or part of the outer layer, continuously or discontinuously.
  • the oxidation catalyst chosen from among the platinoids is distributed on the external surface of the sole, intended to be brought into contact with the laundry.
  • the coating can comprise, in addition to the oxidation catalyst chosen from platinoid oxides, any internal support layer which is catalytically inert with regard to oxidation.
  • This support which adheres to the metallic and catalytically inert support is preferably chosen from aluminum or silicon compounds, such as, for example, alumina in divided or particle form, enamel, polytetrafluoroethylene and their mixtures.
  • the catalytically inert support with regard to oxidation is an enamel with low porosity and / or roughness, on a 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 the penetration of steam or hot humidity.
  • the outer layer of the coating preferably has a thickness, measured according to the RBS method described in Example 1 of the present application, ranging from 10 nanometers to 500 nanometers, and more preferably ranging from 20 nanometers to 120 nanometers.
  • the oxidation catalyst of the outer layer being active at a coating temperature greater than or equal to 90 ° C., it cleans said coating when the latter is heated at least to such a temperature.
  • the internal layer comprises at least one oxidation catalyst chosen from the oxides of the transition elements of group Ib, preferably chosen from copper oxides, silver oxides and their mixtures.
  • oxidation catalysts are well known in themselves, as well as their processes for obtaining them, without it being necessary to describe in detail their methods of preparation respectively.
  • silver oxide as an oxidation catalyst, commercial nitrate of silver sold by the company Aldrich can be used as a precursor.
  • the catalytically active inner layer has a thickness, measured according to the RBS method described in Example 1 of the present application, ranging from 20 nanometers to 50 nanometers.
  • the oxidation catalyst present in the inner layer has a good affinity with the oxidation catalyst present in the outer layer.
  • the support is annealed and, during this step, the oxidation catalyst present in the inner layer can diffuse in the outer layer and the oxidation catalyst present in the outer layer can diffuse in the inner layer.
  • the outer layer comprises as an oxidation catalyst a palladium oxide and the inner layer comprises as the oxidation catalyst a silver oxide.
  • the silver oxide has diffused in the external layer and the external layer therefore comprises a mixture of palladium oxide and silver oxide. A particular synergistic effect has been observed at the level of the catalytic activity of the coating in such an embodiment of the invention.
  • the heating device is in the form of an iron soleplate comprising an ironing surface and the covering covers the ironing surface.
  • the heating appliance is a cooking appliance comprising walls capable of coming into contact with organic dirt and the coating covers these walls.
  • the catalyst acts at the operating temperature of the device and the coating is kept clean as the device is used.
  • a second operating mode during a so-called self-cleaning phase, before or after the use of the appliance, the latter is adjusted 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. The user can thus maintain his device regularly, without waiting for a harmful fouling.
  • the metal support of the device according to the invention can be based on any metal commonly used in the field of heating devices such as aluminum, steel or even titanium.
  • This metallic support may itself be covered with a protective layer such as for example an enameled layer before being covered with the coating of the present invention.
  • the device comprises an intermediate enamel layer situated between the metal support and the catalytically active internal layer of the coating.
  • the application of the internal and external catalytically active layers to the metallic support, covered or not by an enameled layer, is preferably done by pyrolysis, by heating the surface to be covered and then spraying on this hot surface with a solution containing a precursor of the oxidation catalyst.
  • precursor any chemical or physicochemical form of the oxidation catalyst, which is capable of resulting in, or of liberating the latter by any suitable treatment, for example pyrolysis.
  • the surface of the metal support to be covered is heated in an oven to approximately 400 ° C. and then placed very briefly, for example for a few seconds, under infrared, until reaching a surface temperature ranging from 400 ° C to 600 ° C.
  • This operation softens the surface of the support and makes it possible to increase the subsequent adhesion of the coating.
  • a solution of the precursor of the oxidation catalyst chosen from the transition elements of group Ib is sprayed onto the surface of the metal support. On contact with the surface, the precursor oxidizes and fixes on the support and the water evaporates. A layer of thickness ranging from 20 to 50 nm is deposited. The support cools very quickly.
  • a support is obtained covered with a coating whose self-cleaning properties are particularly good.
  • Figure 1 is a sectional view of an iron soleplate according to the invention
  • Figure 2 is a sectional view of an iron soleplate according to the invention comprising an enameled protective layer.
  • a heater 1 in the form of an iron soleplate comprising a metal support 2 covered with an inner layer 3 and an outer layer 4.
  • the soleplate comprises also 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 catalyst oxidation chosen from the oxides of the transition elements of group Ib and the outer layer 4 comprises an oxidation catalyst chosen from the oxides of platinoids.
  • an iron soleplate 1 comprising a metal support 2 covered with an intermediate layer 5, an inner layer 3 and an outer layer 4.
  • the sole also includes a heating base 6 provided with heating elements 7, bonded to the support 2.
  • the internal layer 3 comprises an oxidation catalyst chosen from the oxides of the transition elements of group Ib and the external layer 4 comprises a selected oxidation catalyst among the oxides of platinoids.
  • the protective layer 5 is made of enamel.
  • a clean soleplate of enameled aluminum iron is placed on an aluminum support of about 2 cm to conserve heat as well as possible. The whole is heated to 400 ° C in an oven. The sole, with the support, is placed for a few seconds under infrared until a surface temperature of between 400 ° C. and 600 ° C. is reached. Silver nitrate, sold by the company Aldrich, is dissolved in water at 4 g / 1 and is sprayed by means of a pneumatic gun on the sole. A layer of about 40 to 50 nm, measured according to the RBS method, is deposited.
  • the RBS (Rutherford Backscattering Spectroscopy) method is an analysis technique based on the elastic interaction between a 4 He 2+ ion beam and the component particles of the sample.
  • the high energy beam (2MeV) hits the sample, the backscattered ions are detected at a teta angle.
  • the spectrum thus acquired represents the intensity of the ions detected as a function of their energy and makes it possible to determine the thickness of the layer. This method is described in WK Chu and G. Langouche, MRS Bulletin, January 1993, p 32.
  • the soleplate is again heated in the oven at 400 ° C and then placed for a few seconds under infrared at a temperature between 400 ° C and 600 ° C.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Textile Engineering (AREA)
  • Catalysts (AREA)
  • Cookers (AREA)
  • Resistance Heating (AREA)
  • Irons (AREA)
  • Electric Ovens (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)

Abstract

A heating device has metal walls which are at least partly covered with a self-cleaning coating having an outer layer in contact with ambient air, made of at least one oxidizing catalyst chosen from among the platinum oxides, and at least one inner layer (3) between the metallic support and the outer layer made of an oxidation catalyst chosen from the oxides of Group 1b transition elements. The catalyst in the outer layer is an oxide of palladium or platinum or a mixture of these. The catalyst in the inner layer is an oxide of copper, silver or a mixture of these. In particular, the outer layer is a palladium oxide and the inner layer a silver oxide, or the outer layer is a mixture of palladium oxide and silver oxide. The thickness of the outer layer, measured using the RBS method, is 10-500 nm, preferably 20-120 nm. The thickness of the inner layer, measured using the RBS method, is 20-50 nm. An additional intermediate layer (5) can be placed between the metallic support and the inner layer, forming a catalytically inert support made of aluminum, enamel, polytetrafluoroethylene or a mixture of these. The intermediate layer is made of enamel. The device is in the shape of a cooking device with walls which are prone to be in contact with organic dirt and the coating covers these walls. An Independent claim is included for coating the metallic support of a heating device with a self-cleaning coating as described above, by (i) heating the surface of the metallic support to 400degreesC, (ii) placing it in contact under infrared at 400-600degreesC for several seconds, (iii) spraying a solution of a catalytic precursor to form the inner layer, (iv) reheating the surface in an oven to ca. 400degreesC, (v) placing it again under infrared at 400-600degreesC for several seconds, spraying a solution of a catalytic precursor to form the outer layer, and (vii) reheat the metallic support with infrared for several minutes.

Description

APPAREIL CHAUFFANT RECOUVERT D'UN REVETEMENT HEATING APPLIANCE COVERED WITH A COATING
AUTONETTOYANTSELF-CLEANING
La présente invention concerne des appareils chauffants ou destinés à être chauffés lors de leur utilisation et comprenant un revêtement autonettoyant.The present invention relates to heating devices or intended to be heated during their use and comprising a self-cleaning coating.
Certains appareils chauffants, comme par exemple les semelles de fer à repasser ou encore les appareils de cuisson, présentent des qualités de facilité d'usage et d'efficacité, dépendantes entre autres de l'état et de la nature de la surface de leur revêtement.Certain heating appliances, such as for example iron soles or even cooking appliances, have qualities of ease of use and efficiency, depending inter alia on the state and nature of the surface of their coating. .
Les semelles de fer à repasser ont pu être améliorées par le soin apporté aux qualités de glisse de la surface de repassage, combinées aux qualités permettant l'étalement plus facile du linge. Une façon d'obtenir ces qualités est de recourir à des semelles émaillées avec un émail d'aspect lisse, avec éventuellement des lignes de surépaisseur permettant d'étaler le tissu pendant le déplacement du fer. D'autres semelles métalliques traitées mécaniquement et/ou recouvertes ou non d'un dépôt pour faciliter la glisse peuvent également convenir à un usage satisfaisant. Cependant, à l'usage, la semelle peut se ternir en carbonisant de façon plus ou moins diffuse sur sa surface de repassage, et de façon plus ou moins incomplète, des particules organiques diverses captées par frottement sur les tissus repassés.The iron soles could be improved by the care given to the sliding qualities of the ironing surface, combined with the qualities allowing easier spreading of the laundry. One way to obtain these qualities is to use enameled soles with a smooth-looking enamel, possibly with extra thickness lines to spread the fabric during the movement of the iron. Other metal soles treated mechanically and / or covered or not with a deposit to facilitate sliding can also be suitable for satisfactory use. However, in use, the soleplate may tarnish by carbonizing in a more or less diffuse manner on its ironing surface, and in a more or less incomplete manner, various organic particles captured by friction on the ironed fabrics.
Mais lorsque la semelle est ternie, même de façon peu visible, elle perd partiellement ses qualités de glisse. Insensiblement, avec l'encrassage, le repassage devient plus difficile. Par ailleurs, l'utilisatrice appréhende de se servir d'un fer terni/redoutant qu'il puisse altérer son linge.But when the sole is tarnished, even in an inconspicuous way, it partially loses its sliding qualities. Imperceptibly, with soiling, ironing becomes more difficult. In addition, the user is apprehensive about using a tarnished / dreaded iron that he may alter his laundry.
On connaît des revêtements de semelle de fer à repasser, comportant une couche dure et résistante couverte, comme indiqué par le brevet US4862609, par une couche améliorant les propriétés en surface. Mais ce brevet n'indique pas de solution pour lutter contre l'encrassage.Iron soleplates are known, comprising a hard and resistant layer covered, as indicated by US Pat. No. 4,862,609, with a layer improving the surface properties. But this patent does not indicate a solution to combat fouling.
Les parois des appareils de cuisson sont également souvent recouvertes d'une couche émaillée d'aspect lisse pour que les éventuelles projections de graisse ou d'aliments n'adhèrent pas à la surface. On connaît des surfaces autonettoyantes émaillées, par exemple dans des fours et les ustensiles de cuisson tels que décrits par exemple dans le brevet US4029603 ou le brevet FR2400876. Toutefois, ces revêtements ne donnent pas entière satisfaction en ce qui concerne leurs propriétés autonettoyantes.The walls of cooking appliances are also often covered with an enamelled layer of smooth appearance so that any splashes of grease or food do not adhere to the surface. Self-cleaning enamelled surfaces are known, for example in ovens and cooking utensils as described for example in patent US4029603 or patent FR2400876. However, these coatings are not entirely satisfactory with regard to their self-cleaning properties.
Il existe donc le besoin d'un revêtement d'appareil chauffant comme les appareils de cuisson ou les semelles de fer à repasser, qui maintienne la surface recouverte nette de toute contamination par des particules organiques, et ne s'encrasse pas en usage normal, de façon à conserver ses qualités initiales.There is therefore a need for a coating of a heating appliance such as cooking appliances or iron soles, which keeps the covered surface clean of any contamination by organic particles, and does not get dirty in normal use, so as to retain its original qualities.
La présente invention concerne un appareil chauffant comprenant un support métallique dont au moins une partie est recouverte d'un revêtement autonettoyant, caractérisé en ce que le revêtement comprend :The present invention relates to a heating appliance comprising a metal support at least part of which is covered with a self-cleaning coating, characterized in that the coating comprises:
- a°) une couche externe, au contact de l'air ambiant, comprenant au moins un catalyseur d'oxydation choisi parmi les oxydes de platinoïdes,a) an outer layer, in contact with ambient air, comprising at least one oxidation catalyst chosen from the oxides of platinoids,
- b°) au moins une couche interne, située entre le support métallique et la couche externe, comprenant au moins un catalyseur d'oxydation choisi parmi les oxydes des éléments de transition du groupe Ib.b) at least one internal layer, located between the metal support and the external layer, comprising at least one oxidation catalyst chosen from the oxides of the transition elements from group Ib.
La présente invention a également pour objet un procédé pour recouvrir le support métallique d'un appareil chauffant d'un revêtement autonettoyant tel que ci-dessus, caractérisé en ce qu'il comprend les étapes suivantes : - i) on chauffe la surface du support métallique à recouvrir dans un four à environ 400°C,The present invention also relates to a method for covering the metal support of a heating appliance with a self-cleaning coating as above, characterized in that it comprises the following steps: - i) the surface of the support is heated metallic to be covered in an oven at around 400 ° C,
- ii) on place la surface du support métallique à recouvrir sous infrarouge à une température allant de 400°C à 600°C pendant quelques secondes, - iii) on pulvérise une solution d'un précurseur de catalyseur d'oxydation choisi parmi les oxydes des éléments de transition du groupe Ib sur la surface du support métallique à recouvrir pour obtenir la couche interne,ii) the surface of the metal support to be covered is placed under infrared at a temperature ranging from 400 ° C. to 600 ° C. for a few seconds, iii) a solution of an oxidation catalyst precursor chosen from oxides is sprayed transition elements of group Ib on the surface of the metal support to be covered to obtain the internal layer,
- iv) on chauffe à nouveau la surface du support métallique à recouvrir, avec la couche interne, dans un four à environ 400°C,iv) the surface of the metal support to be covered is heated again, with the internal layer, in an oven at approximately 400 ° C.,
- v) on place la surface du support métallique à recouvrir, avec la couche interne, sous infrarouge à une température allant de 400°C à 600°C pendant quelques secondes,v) the surface of the metal support to be covered is placed, with the internal layer, under infrared at a temperature ranging from 400 ° C. to 600 ° C. for a few seconds,
- vi) on pulvérise une solution d'un précurseur de catalyseur d'oxydation choisi parmi les oxydes de platinoïdes sur la couche interne pour obtenir la couche externe, - vii) on recuit la surface du support métallique recouverte des couches interne et externe sous infrarouge pendant quelques minutes.vi) spraying a solution of an oxidation catalyst precursor chosen from platinoid oxides on the internal layer to obtain the external layer, vii) the surface of the metal support covered with the inner and outer layers is annealed under infrared for a few minutes.
Grâce à l'invention, on obtient un appareil dont le revêtement autonettoyant présente une activité catalytique particulièrement excellente et dont l'adhérence au support métallique est très bonne.Thanks to the invention, an apparatus is obtained whose self-cleaning coating has a particularly excellent catalytic activity and whose adhesion to the metal support is very good.
Il a en effet été constaté que l'association d'un catalyseur d'oxydation choisi parmi les oxydes des éléments de transition du groupe Ib dans la couche interne avec un catalyseur d'oxydation choisi parmi les oxydes de platinoïdes dans la couche externe augmentait en fonctionnement l'activité autonettoyante du revêtement de façon synergique.It has in fact been observed that the association of an oxidation catalyst chosen from the oxides of the transition elements of group Ib in the inner layer with an oxidation catalyst chosen from the oxides of platinoids in the outer layer increases in functioning of the self-cleaning activity of the coating synergistically.
Grâce à l'invention, les particules organiques en contact avec la couche externe du revêtement sont oxydées lorsque l'appareil est chauffé. Par ailleurs, l'effet de synergie obtenu par l'association particulière d'une couche interne comprenant un catalyseur d'oxydation spécifique et d'une couche externe comprenant un catalyseur d'oxydation spécifique différent de celui de la couche interne permet d'obtenir un revêtement présentant une activité catalytique particulièrement performante. Ainsi, la surface du revêtement est régénérée très rapidement. Par exemple, lors du repassage avec un fer à repasser, les particules organiques captées par la semelle sont oxydées. Elles sont en quelque sorte brûlées lorsque le fer à repasser est chaud, le résidu solide éventuel perd toute adhérence et se détache de la semelle. La semelle se maintient propre. De même, dans un appareil de cuisson tel qu'un four par exemple, les projections de graisses présentes sur la paroi du four sont oxydées à chaud, le résidu solide se détache de la paroi qui se maintient propre.Thanks to the invention, the organic particles in contact with the outer layer of the coating are oxidized when the device is heated. Furthermore, the synergistic effect obtained by the particular association of an internal layer comprising a specific oxidation catalyst and an external layer comprising a specific oxidation catalyst different from that of the internal layer makes it possible to obtain a coating with particularly effective catalytic activity. Thus, the surface of the coating is regenerated very quickly. For example, when ironing with an iron, the organic particles captured by the soleplate are oxidized. They are somehow burned when the iron is hot, the possible solid residue loses all grip and comes off the soleplate. The sole stays clean. Likewise, in a cooking appliance such as an oven for example, the projections of grease present on the wall of the oven are oxidized hot, the solid residue is detached from the wall which is kept clean.
De plus, grâce au procédé de l'invention et en particulier grâce à l'exposition aux infrarouges de la surface du support métallique à recouvrir, l'adhérence du revêtement au support métallique est particulièrement bonne. Cette adhérence améliorée permet d'augmenter la résistance aux frottements du revêtement, cette propriété étant particulièrement avantageuse dans le cas d'une semelle de fer à repasser par exemple.In addition, thanks to the process of the invention and in particular thanks to the infrared exposure of the surface of the metal support to be covered, the adhesion of the coating to the metal support is particularly good. This improved adhesion makes it possible to increase the resistance to friction of the coating, this property being particularly advantageous in the case of an iron soleplate for example.
Par " appareil chauffant ", on entend au sens de la présente demande, tout appareil, article ou ustensile, qui au cours de son fonctionnement atteint une température au moins égale à 45°C, et de préférence au moins égale à 90°C. L'appareil peut atteindre cette température de fonctionnement par des moyens qui lui sont propres, comme par exemple une base chauffante intégrée à l'appareil et munie d'éléments chauffants, ou par des moyens extérieurs. De tels appareils sont par exemple les semelles de fer à repasser, les appareils de cuisson, les fours, les grills, les ustensiles de cuisine.By "heating appliance" is meant within the meaning of the present application, any appliance, article or utensil, which during its operation reaches a temperature at least equal to 45 ° C, and preferably at least equal to 90 ° C. The device can reach this temperature operating by means which are specific to it, such as for example a heating base integrated into the apparatus and provided with heating elements, or by external means. Such devices are for example iron soles, cooking appliances, ovens, grills, cooking utensils.
La couche externe du revêtement selon l'invention comprend un catalyseur d'oxydation choisi parmi les oxydes de platinoïdes. Par " platinoïdes ", on entend, au sens de la présente demande, les éléments ayant des propriétés analogues à celles du platine, et en particulier, outre le platine, le ruthénium, le rhodium, le palladium, l'osmium et l'iridium. De préférence, la couche externe comprend un catalyseur d'oxydation choisi parmi les oxydes de palladium, les oxydes de platine et leurs mélanges.The outer layer of the coating according to the invention comprises an oxidation catalyst chosen from the oxides of platinoids. By “platinoids” 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 . Preferably, the outer layer comprises an oxidation catalyst chosen from palladium oxides, platinum oxides and their mixtures.
En pratique, de tels catalyseurs d'oxydation sont bien connus en eux-mêmes, ainsi que leurs procédés d'obtention, sans qu'il soit besoin d'en décrire par le détail leurs méthodes de préparation respectivement. Ainsi, à titre d'exemple, s'agissant du platine en tant que catalyseur d'oxydation, sa forme catalytiquement active peut être obtenue par calcination ou décomposition d'un sel acide chloro-platinique ou tout autre précurseur.In practice, such oxidation catalysts are well known in themselves, as well as their processes for obtaining them, without it being necessary to describe in detail their methods of preparation respectively. Thus, by way of example, with regard to platinum as an oxidation catalyst, its catalytically active form can be obtained by calcination or decomposition of a chloro-platinic acid salt or any other precursor.
Bien entendu tout catalyseur d'oxydation retenu selon la présente invention devra demeurer suffisamment stable à la température de fonctionnement de l'appareil, et ce dans les limites de la durée de vie utile de l'appareil.Of course, any oxidation catalyst retained according to the present invention must remain sufficiently stable at the operating temperature of the device, and this within the limits of the useful life of the device.
La surface de la couche externe est directement en contact avec l'air ambiant et avec les salissures organiques. Par "salissures organiques ", on entend au sens de la présente demande toute substance combustible ou oxydable au contact de l'air ambiant, complètement ou partiellement. A titre d'exemple, on peut citer tout résidu de fibres synthétiques, telles qu'utilisées dans les articles textiles, par exemple en polymère organique tel que polyamide ou polyester, tout résidu organique de produit de lavage et éventuellement de produit d'assouplissement, toute substance organique comme des projections de graisses ou d'aliments.The surface of the outer layer is in direct contact with the ambient air and with organic dirt. By "organic soiling" is meant in the sense of the present application any combustible or oxidizable substance in contact with the ambient air, completely or partially. By way of example, mention may be made of any residue of synthetic fibers, as used in textile articles, for example of organic polymer such as polyamide or polyester, any organic residue of washing product and optionally of softening product, any organic substance such as splashes of fat or food.
Le catalyseur d'oxydation choisi parmi les oxydes de platinoïdes est distribué sur et/ou dans la couche externe du revêtement, là où il est en contact avec les salissures, et selon tout ou partie de la couche externe, de manière continue ou discontinue.The oxidation catalyst chosen from platinum oxides is distributed on and / or in the outer layer of the coating, where it is in contact with dirt, and depending on all or part of the outer layer, continuously or discontinuously.
Dans le cas d'une semelle de fer à repasser qui comporte ou non des zones de relief, le catalyseur d'oxydation choisi parmi les platinoïdes est distribué sur la surface externe de la semelle, destinée à être mise en contact avec le linge.In the case of an iron soleplate which may or may not have relief zones, the oxidation catalyst chosen from among the platinoids is distributed on the external surface of the sole, intended to be brought into contact with the laundry.
Le revêtement peut comprendre, outre le catalyseur d'oxydation choisi parmi les oxydes de platinoïdes, toute sous couche support interne catalytiquement inerte en ce qui concerne l'oxydation. Ce support adhérent au support métallique et catalytiquement inerte est de préférence choisi parmi les composés d'aluminium ou de silicium, comme par exemple de l'alumine sous forme divisée ou de particules, l'émail, le polytetrafluoroéthylène et leurs mélanges. Dans une forme préférée de réalisation de l'invention, le support catalytiquement inerte en ce qui concerne l'oxydation est un émail à faible porosité et/ou rugosité, à l'échelle micrométrique et/ou nanométrique. L'émail est par exemple un émail vitrifié. L'émail doit de préférence être dur, avoir une bonne glisse et résister à la pénétration de vapeur ou humidité chaudes. La couche externe du revêtement a de préférence une épaisseur, mesurée selon la méthode RBS décrite dans l'Exemple 1 de la présente demande, allant de 10 nanomètres à 500 nanomètres, et de préférence encore allant de 20 nanomètres à 120 nanomètres.The coating can comprise, in addition to the oxidation catalyst chosen from platinoid oxides, any internal support layer which is catalytically inert with regard to oxidation. This support which adheres to the metallic and catalytically inert support is preferably chosen from aluminum or silicon compounds, such as, for example, alumina in divided or particle form, enamel, polytetrafluoroethylene and their mixtures. In a preferred embodiment of the invention, the catalytically inert support with regard to oxidation is an enamel with low porosity and / or roughness, on a 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 the penetration of steam or hot humidity. The outer layer of the coating preferably has a thickness, measured according to the RBS method described in Example 1 of the present application, ranging from 10 nanometers to 500 nanometers, and more preferably ranging from 20 nanometers to 120 nanometers.
Le catalyseur d'oxydation de la couche externe étant actif à une température du revêtement supérieure ou égale à 90°C, il nettoie ledit revêtement lorsque ce dernier est chauffé au moins à une telle température.The oxidation catalyst of the outer layer being active at a coating temperature greater than or equal to 90 ° C., it cleans said coating when the latter is heated at least to such a temperature.
La couche interne comprend au moins un catalyseur d'oxydation choisi parmi les oxydes des éléments de transition du groupe Ib, de préférence choisi parmi les oxydes de cuivre, les oxydes d'argent et leurs mélanges. En pratique, de tels catalyseurs d'oxydation sont bien connus en eux-mêmes, ainsi que leurs procédés d'obtention, sans qu'il soit besoin d'en décrire par le détail leurs méthodes de préparation respectivement. A titre d'exemple, s'agissant de l'oxyde d'argent en tant que catalyseur d'oxydation, on peut utiliser comme précurseur du nitrate d'argent commercial vendu par la société Aldrich.The internal layer comprises at least one oxidation catalyst chosen from the oxides of the transition elements of group Ib, preferably chosen from copper oxides, silver oxides and their mixtures. In practice, such oxidation catalysts are well known in themselves, as well as their processes for obtaining them, without it being necessary to describe in detail their methods of preparation respectively. By way of example, with regard to silver oxide as an oxidation catalyst, commercial nitrate of silver sold by the company Aldrich can be used as a precursor.
De préférence, la couche interne catalytiquement active a une épaisseur, mesurée selon la méthode RBS décrite dans l'Exemple 1 de la présente demande, allant de 20 nanomètres à 50 nanomètres.Preferably, the catalytically active inner layer has a thickness, measured according to the RBS method described in Example 1 of the present application, ranging from 20 nanometers to 50 nanometers.
De préférence, le catalyseur d'oxydation présent dans la couche interne a une bonne affinité avec le catalyseur d'oxydation présent dans la couche externe. En effet, après application sur le support des couches interne et externe, le support est recuit et, lors de cette étape, le catalyseur d'oxydation présent dans la couche interne peut diffuser dans la couche externe et le catalyseur d'oxydation présent dans la couche externe peut diffuser dans la couche interne. Dans une forme préférée de réalisation de l'invention, la couche externe comprend comme catalyseur d'oxydation un oxyde de palladium et la couche interne comprend comme catalyseur d'oxydation un oxyde d'argent. Dans une forme encore préférée de réalisation de l'invention, l'oxyde d'argent a diffusé dans la couche externe et la couche externe comprend donc un mélange d'oxyde de palladium et d'oxyde d'argent. Il a été observé un effet de synergie particulier au niveau de l'activité catalytique du revêtement dans une telle forme de réalisation de l'invention.Preferably, the oxidation catalyst present in the inner layer has a good affinity with the oxidation catalyst present in the outer layer. Indeed, after application to the support of the internal and external layers, the support is annealed and, during this step, the oxidation catalyst present in the inner layer can diffuse in the outer layer and the oxidation catalyst present in the outer layer can diffuse in the inner layer. In a preferred embodiment of the invention, the outer layer comprises as an oxidation catalyst a palladium oxide and the inner layer comprises as the oxidation catalyst a silver oxide. In a still preferred embodiment of the invention, the silver oxide has diffused in the external layer and the external layer therefore comprises a mixture of palladium oxide and silver oxide. A particular synergistic effect has been observed at the level of the catalytic activity of the coating in such an embodiment of the invention.
Dans une forme préférée de réalisation de l'invention, l'appareil chauffant est sous la forme d'une semelle de fer à repasser comprenant une surface de repassage et le revêtement recouvre la surface de repassage.In a preferred embodiment of the invention, the heating device is in the form of an iron soleplate comprising an ironing surface and the covering covers the ironing surface.
Dans une autre forme préférée de réalisation de l'invention, l'appareil chauffant est un appareil de cuisson comprenant des parois susceptibles de venir au contact de salissures organiques et le revêtement recouvre ces parois.In another preferred embodiment of the invention, the heating appliance is a cooking appliance comprising walls capable of coming into contact with organic dirt and the coating covers these walls.
Dans un premier mode de fonctionnement, le catalyseur agit à la température de fonctionnement de l'appareil et le revêtement se maintient propre au fur et à mesure de l'utilisation de l'appareil.In a first mode of operation, the catalyst acts at the operating temperature of the device and the coating is kept clean as the device is used.
Dans un deuxième mode de fonctionnement, lors d'une phase dite d'autonettoyage, préalable ou postérieure à l'utilisation de l'appareil, ce dernier est réglé à une température élevée, égale ou supérieure aux températures de fonctionnement les plus hautes, il est alors laissé en attente pendant un temps prédéterminé, pendant lequel le catalyseur d'oxydation produit son effet. L'utilisateur peut ainsi entretenir son appareil régulièrement, sans attendre un encrassage néfaste.In a second operating mode, during a so-called self-cleaning phase, before or after the use of the appliance, the latter is adjusted 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. The user can thus maintain his device regularly, without waiting for a harmful fouling.
Le support métallique de l'appareil selon l'invention peut être à base de tout métal couramment employé dans le domaine des appareils chauffants comme l'aluminium, l'acier ou encore le titane. Ce support métallique peut lui-même être recouvert d'une couche protectrice comme par exemple une couche émaillée avant d'être recouvert par le revêtement de la présente invention. Ainsi, dans une forme préférée de réalisation de l'invention, l'appareil comprend une couche intermédiaire en émail située entre le support métallique et la couche interne catalytiquement active du revêtement.The metal support of the device according to the invention can be based on any metal commonly used in the field of heating devices such as aluminum, steel or even titanium. This metallic support may itself be covered with a protective layer such as for example an enameled layer before being covered with the coating of the present invention. Thus, in a preferred embodiment of the invention, the device comprises an intermediate enamel layer situated between the metal support and the catalytically active internal layer of the coating.
L'application des couches catalytiquement actives interne et externe sur le support métallique, recouvert ou non par une couche émaillée, se fait de préférence par pyrolyse, par chauffage de la surface à recouvrir puis pulvérisation sur cette surface chaude d'une solution contenant un précurseur du catalyseur d'oxydation.The application of the internal and external catalytically active layers to the metallic support, covered or not by an enameled layer, is preferably done by pyrolysis, by heating the surface to be covered and then spraying on this hot surface with a solution containing a precursor of the oxidation catalyst.
Par " précurseur ", on entend toute forme chimique ou physico- chimique, du catalyseur d'oxydation, qui est susceptible d'aboutir à, ou de libérer ce dernier par tout traitement approprié, par exemple pyrolyse.By "precursor" is meant any chemical or physicochemical form of the oxidation catalyst, which is capable of resulting in, or of liberating the latter by any suitable treatment, for example pyrolysis.
Dans une forme de réalisation du procédé selon l'invention, la surface du support métallique à recouvrir est chauffée dans un four à environ 400°C puis placée très brièvement, par exemple pendant quelques secondes, sous infrarouge, jusqu'à atteindre une température superficielle pouvant aller de 400°C à 600°C. Cette opération ramollit la surface du support et permet d'augmenter l'adhérence ultérieure du revêtement. Une solution du précurseur du catalyseur d'oxydation choisi parmi les éléments de transition du groupe Ib est pulvérisée sur la surface du support métallique. Au contact de la surface, le précurseur s'oxyde et se fixe sur le support et l'eau s'évapore. Une couche d'épaisseur allant de 20 à 50 nm est déposée. Le support refroidit très rapidement. Il est chauffé à nouveau au four à 400°C puis sous infrarouge à une température pouvant aller de 400°C à 600°C pendant quelques secondes. Une solution du précurseur du catalyseur d'oxydation choisi parmi les platinoïdes est pulvérisée par dessus la couche interne. Une couche d'épaisseur allant de 20 à 50 nm est déposée. Le support ainsi recouvert est ensuite recuit sous infrarouge pendant quelques minutes, par exemple pendant cinq minutes.In one embodiment of the method according to the invention, the surface of the metal support to be covered is heated in an oven to approximately 400 ° C. and then placed very briefly, for example for a few seconds, under infrared, until reaching a surface temperature ranging from 400 ° C to 600 ° C. This operation softens the surface of the support and makes it possible to increase the subsequent adhesion of the coating. A solution of the precursor of the oxidation catalyst chosen from the transition elements of group Ib is sprayed onto the surface of the metal support. On contact with the surface, the precursor oxidizes and fixes on the support and the water evaporates. A layer of thickness ranging from 20 to 50 nm is deposited. The support cools very quickly. It is heated again in the oven to 400 ° C and then under infrared at a temperature which can range from 400 ° C to 600 ° C for a few seconds. A solution of the precursor of the oxidation catalyst chosen from the platinoids is sprayed on top of the internal layer. A layer of thickness ranging from 20 to 50 nm is deposited. The support thus covered is then annealed under infrared for a few minutes, for example for five minutes.
On obtient un support recouvert d'un revêtement dont les propriétés autonettoyantes sont particulièrement bonnes.A support is obtained covered with a coating whose self-cleaning properties are particularly good.
L'invention sera mieux comprise à la lecture des exemples ci après et des dessins annexés.The invention will be better understood on reading the examples below and the accompanying drawings.
La figure 1 est une vue en coupe d'une semelle de fer à repasser selon l'invention, La figure 2 est une vue en coupe d'une semelle de fer à repasser selon l'invention comprenant une couche protectrice émaillée.Figure 1 is a sectional view of an iron soleplate according to the invention, Figure 2 is a sectional view of an iron soleplate according to the invention comprising an enameled protective layer.
En se référant à la figure 1 , est représenté en coupe un appareil chauffant 1 sous la forme d'une semelle de fer à repasser comprenant un support métallique 2 recouvert d'une couche interne 3 et d'une couche externe 4. La semelle comprend également une base chauffante 6 munie d'éléments chauffants 7. Le support 2 et la base 6 sont assemblées par des moyens mécaniques ou par collage. La couche interne 3 comprend un catalyseur d'oxydation choisi parmi les oxydes des éléments de transition du groupe Ib et la couche externe 4 comprend un catalyseur d'oxydation choisi parmi les oxydes de platinoïdes.Referring to Figure 1, there is shown in section a heater 1 in the form of an iron soleplate comprising a metal support 2 covered with an inner layer 3 and an outer layer 4. The soleplate comprises also 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 catalyst oxidation chosen from the oxides of the transition elements of group Ib and the outer layer 4 comprises an oxidation catalyst chosen from the oxides of platinoids.
En se référant à la figure 2, est représentée en coupe une semelle de fer à repasser 1 comprenant un support métallique 2 recouvert d'une couche intermédiaire 5, d'une couche interne 3 et d'une couche externe 4. La semelle comprend également une base chauffante 6 munie d'éléments chauffants 7, collée sur le support 2. La couche interne 3 comprend un catalyseur d'oxydation choisi parmi les oxydes des éléments de transition du groupe Ib et la couche externe 4 comprend un catalyseur d'oxydation choisi parmi les oxydes de platinoïdes. La couche protectrice 5 est en émail.Referring to Figure 2, is shown in section an iron soleplate 1 comprising a metal support 2 covered with an intermediate layer 5, an inner layer 3 and an outer layer 4. The sole also includes a heating base 6 provided with heating elements 7, bonded to the support 2. The internal layer 3 comprises an oxidation catalyst chosen from the oxides of the transition elements of group Ib and the external layer 4 comprises a selected oxidation catalyst among the oxides of platinoids. The protective layer 5 is made of enamel.
Exemple IExample I
Une semelle propre de fer à repasser en aluminium émaillé est placée sur un support en aluminium d'environ 2 cm pour conserver au mieux la chaleur. L'ensemble est chauffé à 400°C dans un four. La semelle, avec le support, est placée pendant quelques secondes sous infrarouge jusqu'à atteindre une température superficielle comprise entre 400°C et 600°C. Du nitrate d'argent, vendu par la société Aldrich, est mis en solution dans l'eau à 4 g/1 et est pulvérisé au moyen d'un pistolet pneumatique sur la semelle. Une couche d'environ 40 à 50 nm, mesurée selon la méthode RBS, est déposée. La méthode RBS (Rutherford Backscattering Spectroscopy) est une technique d'analyse basée sur l'interaction élastique entre un faisceau d'ion 4He2+ et les particules composantes de l'échantillon. Le faisceau de haute énergie (2MeV) frappe l'échantillon, les ions rétrodiffusés sont détectés sous un angle téta. Le spectre ainsi acquis représente l'intensité des ions détectés en fonction de leur énergie et permet de déterminer l'épaisseur de la couche. Cette méthode est décrite dans W.K. Chu and G. Langouche, MRS Bulletin, January 1993, p 32.A clean soleplate of enameled aluminum iron is placed on an aluminum support of about 2 cm to conserve heat as well as possible. The whole is heated to 400 ° C in an oven. The sole, with the support, is placed for a few seconds under infrared until a surface temperature of between 400 ° C. and 600 ° C. is reached. Silver nitrate, sold by the company Aldrich, is dissolved in water at 4 g / 1 and is sprayed by means of a pneumatic gun on the sole. A layer of about 40 to 50 nm, measured according to the RBS method, is deposited. The RBS (Rutherford Backscattering Spectroscopy) method is an analysis technique based on the elastic interaction between a 4 He 2+ ion beam and the component particles of the sample. The high energy beam (2MeV) hits the sample, the backscattered ions are detected at a teta angle. The spectrum thus acquired represents the intensity of the ions detected as a function of their energy and makes it possible to determine the thickness of the layer. This method is described in WK Chu and G. Langouche, MRS Bulletin, January 1993, p 32.
Après l'application de cette couche interne, la semelle est de nouveau chauffée au four à 400°C puis placée pendant quelques secondes sous infrarouge à une température comprise entre 400°C et 600°C. Une solution aqueuse de nitrate de palladium stabilisée par de l'acide nitrique, vendue par la société Metalor, est pulvérisée au moyen d'un pistolet pneumatique sur la semelle. Une couche d'environ 40 à 50 nm, mesurée selon la méthode RBS décrite ci-dessus, est déposée.After the application of this internal layer, the soleplate is again heated in the oven at 400 ° C and then placed for a few seconds under infrared at a temperature between 400 ° C and 600 ° C. An aqueous solution of palladium nitrate stabilized by nitric acid, sold by the company Metalor, is sprayed using a gun pneumatic on the sole. A layer of about 40 to 50 nm, measured according to the RBS method described above, is deposited.
Après l'application de cette couche externe, l'ensemble est recuit sous infrarouge à 500°C pendant trois minutes. On obtient une semelle de fer à repasser dont le revêtement autonettoyant adhère particulièrement bien à la semelle et possède une très bonne activité catalytique et conserve ses qualités de glisse. After the application of this external layer, the whole is annealed under infrared at 500 ° C for three minutes. An iron soleplate is obtained, the self-cleaning coating of which adheres particularly well to the soleplate and has very good catalytic activity and retains its sliding qualities.

Claims

REVENDICATIONS
1) Appareil chauffant (1) comprenant un support métallique (2) dont au moins une partie est recouverte d'un revêtement autonettoyant, caractérisé en ce que le revêtement comprend : a°) une couche externe (4), au contact de l'air ambiant, comprenant au moins un catalyseur d'oxydation choisi parmi les oxydes de platinoïdes, b°) au moins une couche interne (3), située entre le support métallique (2) et la couche externe (4), comprenant au moins un catalyseur d'oxydation choisi parmi les oxydes des éléments de transition du groupe Ib.1) Heating appliance (1) comprising a metal support (2) at least part of which is covered with a self-cleaning coating, characterized in that the coating comprises: a °) an external layer (4), in contact with the ambient air, comprising at least one oxidation catalyst chosen from platinoid oxides, b °) at least one internal layer (3), located between the metal support (2) and the external layer (4), comprising at least one oxidation catalyst chosen from the oxides of the transition elements of group Ib.
2) Appareil selon la revendication 1 , caractérisé en ce que le catalyseur d'oxydation de la couche externe (4) est choisi parmi les oxydes de palladium, les oxydes de platine et leurs mélanges.2) Apparatus according to claim 1, characterized in that the oxidation catalyst of the outer layer (4) is chosen from palladium oxides, platinum oxides and their mixtures.
3) Appareil selon la revendication 1 ou 2, caractérisé en ce que le catalyseur d'oxydation de la couche interne (3) est choisi parmi les oxydes de cuivre, les oxydes d'argent et leurs mélanges.3) Apparatus according to claim 1 or 2, characterized in that the oxidation catalyst of the inner layer (3) is chosen from copper oxides, silver oxides and their mixtures.
4) Appareil selon l'une quelconque des revendications précédentes, caractérisé en ce que la couche externe (4) comprend comme catalyseur d'oxydation un oxyde de palladium et la couche interne (3) comprend comme catalyseur d'oxydation un oxyde d'argent.4) Apparatus according to any one of the preceding claims, characterized in that the outer layer (4) comprises as an oxidation catalyst a palladium oxide and the inner layer (3) comprises as the oxidation catalyst a silver oxide .
5) Appareil selon la revendication 4, caractérisé en ce que la couche externe comprend un mélange d'oxyde de palladium et d'oxyde d'argent. 6) Appareil selon l'une quelconque des revendications précédentes, caractérisé en ce que l'épaisseur de la couche externe (4), mesurée selon la méthode RBS, va de 10 à 500 nanomètres, et de préférence encore va de 20 nanomètres à 120 nanomètres.5) Apparatus according to claim 4, characterized in that the outer layer comprises a mixture of palladium oxide and silver oxide. 6) Apparatus according to any one of the preceding claims, characterized in that the thickness of the outer layer (4), measured according to the RBS method, ranges from 10 to 500 nanometers, and more preferably ranges from 20 nanometers to 120 nanometers.
7) Appareil selon l'une quelconque des revendications précédentes, caractérisé en ce que l'épaisseur de la couche interne (3), mesurée selon la méthode RBS, va de 20 nanomètres à 50 nanomètres.7) Apparatus according to any one of the preceding claims, characterized in that the thickness of the internal layer (3), measured according to the RBS method, ranges from 20 nanometers to 50 nanometers.
8) Appareil selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il comprend en outre une couche intermédiaire (5) située entre le support métallique (2) et la couche interne (3) du revêtement constituant un support catalytiquement inerte en ce qui concerne l'oxydation choisi parmi les alliages d'aluminium, l'émail, le polytetrafluoroéthylène et leurs mélanges.8) Apparatus according to any one of the preceding claims, characterized in that it further comprises an intermediate layer (5) located between the metal support (2) and the internal layer (3) of the coating constituting a catalytically inert support in regarding oxidation chosen from aluminum alloys, enamel, polytetrafluoroethylene and their mixtures.
9) Appareil selon la revendication 8, caractérisé en ce que la couche intermédiaire (5) située entre le support métallique (2) et la couche interne (3) du revêtement est en émail.9) Apparatus according to claim 8, characterized in that the intermediate layer (5) located between the metal support (2) and the inner layer (3) of the coating is enamel.
10)Appareil selon l'une quelconque des revendications précédentes, caractérisé en ce qu'il est sous la forme d'une semelle de fer à repasser comprenant une surface de repassage et que le revêtement recouvre la surface de repassage. 11)Appareil selon l'une quelconque des revendications 1 à 10, caractérisé en ce qu'il est sous la forme d'un appareil de cuisson comprenant des parois susceptibles de venir au contact de salissures organiques et le revêtement recouvre ces parois.10) Apparatus according to any one of the preceding claims, characterized in that it is in the form of an iron soleplate comprising an ironing surface and that the coating covers the ironing surface. 11) Apparatus according to any one of claims 1 to 10, characterized in that it is in the form of a cooking appliance comprising walls capable of coming into contact with organic dirt and the coating covers these walls.
12) Procédé pour recouvrir le support métallique (2) d'un appareil chauffant (1) d'un revêtement autonettoyant selon l'une des revendications 1 à 10, caractérisé en ce qu'il comprend les étapes suivantes :12) Method for covering the metal support (2) of a heating appliance (1) with a self-cleaning coating according to one of claims 1 to 10, characterized in that it comprises the following steps:
- i) on chauffe la surface du support métallique à recouvrir dans un four à environ 400°C,i) the surface of the metal support to be covered is heated in an oven to around 400 ° C.,
- ii) on place la surface du support métallique à recouvrir sous infrarouge à une température allant de 400°C à 600°C pendant quelques secondes,ii) the surface of the metal support to be covered is placed under infrared at a temperature ranging from 400 ° C. to 600 ° C. for a few seconds,
- iii) on pulvérise une solution d'un précurseur de catalyseur d'oxydation choisi parmi les oxydes des éléments de transition du groupe Ib sur la surface du support métallique à recouvrir pour obtenir la couche interne (3),iii) a solution of an oxidation catalyst precursor chosen from the oxides of group Ib transition elements is sprayed onto the surface of the metal support to be covered in order to obtain the internal layer (3),
- iv) on chauffe à nouveau la surface du support métallique à recouvrir, avec la couche interne, dans un four à environ 400°C,iv) the surface of the metal support to be covered is heated again, with the internal layer, in an oven at approximately 400 ° C.,
- v) on place la surface du support métallique à recouvrir, avec la couche interne, sous infrarouge à une température allant de 400°C à 600°C pendant quelques secondes,v) the surface of the metal support to be covered is placed, with the internal layer, under infrared at a temperature ranging from 400 ° C. to 600 ° C. for a few seconds,
- vi) on pulvérise une solution d'un précurseur de catalyseur d'oxydation choisi parmi les oxydes de platinoïdes sur la couche interne pour obtenir la couche externe (4),vi) spraying a solution of an oxidation catalyst precursor chosen from platinoid oxides on the internal layer to obtain the external layer (4),
- vii) on recuit la surface du support métallique recouverte des couches interne et externe sous infrarouge pendant quelques minutes. vii) the surface of the metal support covered with the inner and outer layers is annealed under infrared for a few minutes.
EP03786028A 2002-12-05 2003-11-20 Heating device coated with a self-cleaning coating Expired - Lifetime EP1567807B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
FR0215360 2002-12-05
FR0215360A FR2848290B1 (en) 2002-12-05 2002-12-05 HEATING APPARATUS COVERED WITH SELF-CLEANING COATING
PCT/FR2003/003429 WO2004061371A1 (en) 2002-12-05 2003-11-20 Heating device coated with a self-cleaning coating

Publications (2)

Publication Number Publication Date
EP1567807A1 true EP1567807A1 (en) 2005-08-31
EP1567807B1 EP1567807B1 (en) 2007-10-31

Family

ID=32320016

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03786028A Expired - Lifetime EP1567807B1 (en) 2002-12-05 2003-11-20 Heating device coated with a self-cleaning coating

Country Status (16)

Country Link
US (1) US7339142B2 (en)
EP (1) EP1567807B1 (en)
JP (1) JP4358749B2 (en)
CN (1) CN1316202C (en)
AT (1) ATE377176T1 (en)
AU (1) AU2003295034B2 (en)
BR (1) BR0317056B1 (en)
CA (1) CA2508750C (en)
DE (1) DE60317233T2 (en)
ES (1) ES2295676T3 (en)
FR (1) FR2848290B1 (en)
HK (1) HK1081638A1 (en)
MX (1) MXPA05005918A (en)
PT (1) PT1567807E (en)
RU (1) RU2323287C2 (en)
WO (1) WO2004061371A1 (en)

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EP1911874A1 (en) * 2006-10-09 2008-04-16 Koninklijke Philips Electronics N.V. Soleplate for an iron
US7854222B2 (en) * 2008-06-26 2010-12-21 General Electric Company Pyrocatalytic coatings for heating devices
EP2228485A1 (en) * 2009-03-12 2010-09-15 Koninklijke Philips Electronics N.V. Domestic appliance comprising an antimicrobial agent
CN102575413B (en) * 2009-10-09 2015-09-16 Bsh家用电器有限公司 Especially for the flatiron substrate of steam iron
US10449685B2 (en) 2010-04-29 2019-10-22 Whirlpool Corporation Food processor with adjustable blade assembly
US8720325B2 (en) 2010-04-29 2014-05-13 Whirlpool Corporation Food processor with a lockable adjustable blade assembly
FR2968016B1 (en) * 2010-11-29 2013-05-03 Seb Sa HEATING APPARATUS COVERED WITH SELF-CLEANING COATING
EP2954114B1 (en) 2013-02-06 2019-03-13 Koninklijke Philips N.V. A treatment plate for a garment treatment appliance
US9841195B2 (en) 2013-02-28 2017-12-12 Haier Us Appliance Solutions, Inc. Non-stick, pyrolytic coatings for heating devices
CN104174413B (en) * 2014-09-10 2016-04-06 山东大学 A kind of infrared light Catalysts and its preparation method and application
US10085599B2 (en) 2014-12-19 2018-10-02 Whirlpool Corporation Multi-cook and food processing prep product
USD819389S1 (en) * 2015-05-29 2018-06-05 Seb Electric fryer
RU2764846C1 (en) * 2018-06-14 2022-01-21 Филип Моррис Продактс С.А. Aerosol generating device with pyrocatalytic material
CN109208262B (en) * 2018-10-29 2023-06-20 珠海格力电器股份有限公司 Steam generating device of washing machine, washing machine and cleaning method
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JPS6052871B2 (en) * 1980-03-14 1985-11-21 松下電器産業株式会社 Method of manufacturing self-purifying coating layer
EP0227111B1 (en) 1985-12-24 1991-01-16 Braun Aktiengesellschaft Iron sole plate
CN1083036C (en) * 1996-09-24 2002-04-17 皇家菲利浦电子有限公司 Iron and soleplate for iron

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Also Published As

Publication number Publication date
DE60317233D1 (en) 2007-12-13
US20060151474A1 (en) 2006-07-13
FR2848290A1 (en) 2004-06-11
FR2848290B1 (en) 2005-01-07
JP2006513747A (en) 2006-04-27
HK1081638A1 (en) 2006-05-19
BR0317056A (en) 2005-10-25
ATE377176T1 (en) 2007-11-15
CN1717565A (en) 2006-01-04
RU2005121142A (en) 2006-01-20
WO2004061371A1 (en) 2004-07-22
JP4358749B2 (en) 2009-11-04
BR0317056B1 (en) 2014-03-04
ES2295676T3 (en) 2008-04-16
RU2323287C2 (en) 2008-04-27
AU2003295034A1 (en) 2004-07-29
US7339142B2 (en) 2008-03-04
EP1567807B1 (en) 2007-10-31
DE60317233T2 (en) 2008-08-07
CN1316202C (en) 2007-05-16
CA2508750A1 (en) 2004-07-22
MXPA05005918A (en) 2005-08-26
AU2003295034B2 (en) 2008-12-11
PT1567807E (en) 2008-01-25
CA2508750C (en) 2011-02-22

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