WO2012143386A1 - Composant métallique et procédé de modification de surface d'un composant revêtu - Google Patents

Composant métallique et procédé de modification de surface d'un composant revêtu Download PDF

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Publication number
WO2012143386A1
WO2012143386A1 PCT/EP2012/057066 EP2012057066W WO2012143386A1 WO 2012143386 A1 WO2012143386 A1 WO 2012143386A1 EP 2012057066 W EP2012057066 W EP 2012057066W WO 2012143386 A1 WO2012143386 A1 WO 2012143386A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
metallic
intermediate layer
component
transition metal
Prior art date
Application number
PCT/EP2012/057066
Other languages
German (de)
English (en)
Inventor
Kathrin Urban
Lars Schrubke
Willi Grigat
Arthur Krause
Harald Deppe
Friedrich Meyer
David FRIEDHOF
Lars TIEDEMANN
Original Assignee
Paul Hettich Gmbh & Co. Kg
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 Paul Hettich Gmbh & Co. Kg filed Critical Paul Hettich Gmbh & Co. Kg
Priority to EP12716368.1A priority Critical patent/EP2699360A1/fr
Publication of WO2012143386A1 publication Critical patent/WO2012143386A1/fr

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/50Multilayers
    • B05D7/52Two layers
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
    • B05D7/14Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
    • B05D7/16Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies using synthetic lacquers or varnishes
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0209Multistage baking
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B05SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05DPROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D3/00Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
    • B05D3/02Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
    • B05D3/0254After-treatment

Definitions

  • the invention relates to a metallic component according to the preamble of claim 1 and to a method for surface modification of a coated component and the use of a component.
  • a coating can be highly scratch resistant but have low adhesion to the substrate.
  • the low adhesion is often found, for example, in PTFE coatings, which flake off large areas of scratches or mechanical shocks.
  • EP 0 937 012 therefore proposes the application of compounds from the group of polydimethylsiloxanes for the protection of stainless steel surfaces in domestic appliances.
  • the excess organic components of the coating are removed and It comes to the formation of an organic material layer on the stainless steel surface.
  • the coating thus produced has a non-stick effect.
  • WO 2010/063776 A1 discloses a double-layer structure with an upper covering layer with a high silicon content and an intermediate layer underneath, which already contains transition metals, such as e.g. Have chrome. In the course of the depth profile, the chromium content within the intermediate layer rises continuously starting from the cover layer towards the metallic substrate.
  • the surface described in WO 2010/063776 A1 has basically proven itself in terms of cleanability and scratch resistance. However, if the scratch resistance of the coating is overcome in the case of improper cleaning or heavy point load and deep scratches are introduced into the coating material, constituents of the coating burst to a small extent.
  • the present invention solves this object by a component having the features of claim 1 and by a method having the features of claim 12.
  • a metallic component in particular for use in household appliances, has a metallic main body. On the metallic one
  • Body is at least partially applied a multi-layered sintered coating containing a silicon-based inorganic-organic hybrid polymer, wherein the coating at least
  • a) has a cured topcoat
  • the intermediate layer has a mass concentration of a first transition metal of more than 10%, wherein the first transition metal is not the main component of the metallic see basic body.
  • the functionality of the intermediate layer can be additionally improved by a further transition metal with a mass concentration of more than 9%.
  • a first transition metal is preferably a transition metal in question, which is also part of the metallic body.
  • the composition of the coating is approximated to the alloy character of the metallic base body, whereby advantageously a better adhesion or penetration of the phase boundary surfaces can take place.
  • Chromium can be used with particular preference as the first transition metal. This also has a passivating effect and allows secondary corrosion protection if the top layer is damaged. For a particularly high scratch resistance of the coating, it is advantageous if the cover layer has a mass concentration of silicon of more than 30%, preferably more than 50%.
  • a method for surface modification of a coated component in particular for improving its usefulness in household appliances, comprises the following steps:
  • a residual inorganic-organic hybrid polymer concentration is maintained in the altered coating composition and the concentration of at least one transition metal in the altered coating composition is increased.
  • Advantageous embodiments of the method are the subject of the dependent claims. It is advantageous for an energy-efficient operation of the process if the thermal treatment takes place with less than fifty heating cycles, preferably less than five heating cycles.
  • a heating in a heating cycle up to 500 ° C, within at least 20 minutes, preferably within at least 65 min.
  • a new heating cycle begins as soon as the coated component has cooled by 400 ° C, preferably by 300-200 ° C after the previous heating cycle.
  • An inventive component or a component which has been produced by a method according to the invention can universally in household appliances, in particular as a pull-out guide in ovens, in refrigerators, in freezers, in microwave ovens, in Dampfgarierin, in dryers, in food warmers, in Gerschirrchiprn, in Laboratory equipment, in medical devices and in washing machines or as a furniture fitting.
  • a metallic component having a coating comprising an inorganic-organic hybrid polymer has at least one cover layer and an adhesion-promoting intermediate layer, wherein the coating after carrying out a cross hatch test in accordance with DIN ISO 2409, there are no detached segments.
  • the component according to the invention can also be used in food-sensitive areas.
  • the inorganic-organic hybrid polymer-containing coating also increases the corrosion resistance during transport of the components, in particular the resistance to external climatic influences such as rain, snow, salt water, seawater spray and fog increases.
  • external climatic influences such as rain, snow, salt water, seawater spray and fog increases.
  • containers are protected against external influences, condensate can nevertheless form inside.
  • the current temperature and the moisture that is brought into the container during loading affect the current relative humidity in the container.
  • the trapped air in the container, the cargo, its packaging or the dunnage are sources of moisture. Due to its better adhesive properties on the metallic base body, a corresponding coating is also suitable as corrosion protection, in particular during sea transport of the coated components. Furthermore, a use of the coated components in seawater climate is possible.
  • the components can be used in the form of Pbe- blows in kitchen and / or laboratory furniture used for the storage of cleaning agents or chemicals.
  • made of metal furniture can be provided with a surface according to the invention. Furniture made of metal or sheet metal is frequently used in the medical sector, in the office, in kitchens, in laundries, in vehicles, on ships, in aircraft and in workshops.
  • the component according to the invention is particularly well suited for the production of a pullout guide, in particular, the rails of the pullout guide can be coated accordingly.
  • FIG. 1 shows a perspective view of a device according to the invention.
  • Fig. 2 is a schematic representation of the concentration profile of individual elements of the coating in the depth profile of the component according to the invention
  • a pull-out guide for high-temperature applications, in particular for ovens, comprising a guide rail 1 and a running rail 2 movable relative to the guide rail, between which a middle rail 3 (see FIG. 1) is mounted.
  • pullout guides are known, which have only a guide and a running rail.
  • pull-out guides are also used which have a guide rail, a running rail and more than one middle rail.
  • rolling elements in particular made of ceramic, are provided.
  • a plurality of raceways 6 are provided for the spherical rolling elements 4 on the guide rail 1, the middle rail 3 and the running rail 2.
  • the rolling elements are spaced apart in the rolling element cage, so as not to touch each other during rolling, whereby the smooth running would be hindered.
  • FIG. 2 shows an exemplary structure of a coating A1 of a component according to the invention, which was applied in this embodiment to the pullout guide described in FIG.
  • the values result from the spectroscopic determination of the profile depth by means of glow discharge or glow discharge.
  • the spectrometer carries the type designation GDA 550/750.
  • the detection was carried out as PMT detection, with a 2.5 mm anode as RF measurement in a universal measuring chamber.
  • the spectrometer was tested with certified reference materials. and calibrated according to ISO14707 and ISO / DIS16962.2 (ISO / TC 201 / SC 8).
  • the measurement conditions were RF excitation at 700 V and 2.5 hPa with a 2.5 mm anode.
  • the coating has a cover layer and an intermediate layer which have been applied to a metallic base body.
  • the cover layer particularly preferably has a layer thickness of between 0.1 and 2 ⁇ m, in particular between 0.1 and 0.7 ⁇ m, and has the following preferred mass concentration ranges for the following elements:
  • the cover layer may preferably contain iron (Fe), manganese (Mn), nickel (Ni), copper (Cu), manganese (Mn), aluminum (Al), nitrogen (N), sulfur (S), phosphorus (P). and / or hydrogen (H) in each case 0.1 to 5%.
  • the intermediate layer particularly preferably has a layer thickness of between 3 and 20 ⁇ m, in particular between 4 and 1 ⁇ m, and has the following elements in the following preferred mass concentration ranges:
  • the cover layer may preferably contain iron (Fe), manganese (Mn), nickel (Ni), copper (Cu), manganese (Mn), aluminum (Al), nitrogen (N), sulfur (S), phosphorus (P). and / or hydrogen (H) up to 12% each.
  • the cover layer may preferably contain iron (Fe), manganese (Mn), nickel (Ni), copper (Cu), manganese (Mn), aluminum (Al), nitrogen (N), sulfur (S), phosphorus (P). and / or hydrogen (H) up to 12% each.
  • the coating A1 of FIG. 2 in this case has a covering layer in the range from 0 to 0.4 ⁇ m.
  • the outer layer has the following composition at 0, 1014 m (data in mass concentration): Fe 0.57
  • the intermediate layer is followed by an intermediate layer in the range between 0.4-9.5 ⁇ m.
  • the intermediate layer has the following composition at 6.4283 pm (data in mass concentration): Fe 0.57
  • the metallic base body joins the intermediate layer.
  • the metallic base body has the following composition at 13.40 pm (data in mass concentration): Fe 83.82
  • the material of the metallic base body is an alloy steel of the class of chrome steels.
  • This cross-hatch test was carried out in accordance with DIN ISO 2409.
  • the coating is scratched crosswise and thereby divided into checkerboard-like individual segments. Then an adhesive tape is glued on and pulled off again. Based on the number of torn off segments, the adhesive strength of the coating is then determined.
  • the cross hatch test of the coating A1 did not give rise to detachment of segments of the coating by the torn off adhesive tape. It has surprisingly been found in extensive material experiments that an improved connection of a coating overall and in particular the cover layer is possible, provided that at least 20% of the depth profile of the intermediate layer has a mass concentration of a first transition metal of more than 10%, wherein the first transition metal is not the main component of the metallic body.
  • the adhesion-promoting properties of the intermediate layer can advantageously be further enhanced if 50%, preferably at least 90%, of the depth profile of the intermediate layer has a mass concentration of the first transition metal of more than 16% and preferably more than 19%.
  • a further advantageous contribution to the adhesion-promoting properties of the intermediate layer can additionally be effected by a second transition metal.
  • the first and second transition metal is not the main constituent of the metallic base body. In the case of stainless steel, the main constituent of the body would be iron.
  • the first transition metal is preferably chromium, the second transition metal is preferably copper or manganese.
  • the integrity of the layer is advantageously retained even if the component coated in this way is exposed to a welding flame of 1000-1500 ° C. for a short time, ie for about 30 seconds.
  • the coating can be at least partially applied and used on metallic components, which are welded to an uncoated surface with another metallic surface. If the welding flame comes into contact with a coated area of the fitting, the coating will not be destroyed.
  • the following table shows various test series which were undertaken as proof of the usability of the coated drawer slide with the coating A1, in particular in the area of the ovens, preferably with pyrolysis function (up to 500 ° C.).
  • the coating was individually soiled with three different components, which were then heated under oven conditions.
  • the components are substances from the food industry, which have proven to be particularly problematic in terms of cleanability. Specifically, this concerns plum jam, mayonnaise and virgin olive oil. In this case, the cleanability proved to be sufficient to ablate these baked-on soiling with household detergents without damaging the surface of the coating again.
  • the pyrolysis capability was tested. This is important to confirm the usefulness of the drawer runner in ovens with pyrolysis function.
  • the coating quality at a temperature load of 500 ° C at 2h remain unchanged.
  • a corrosion test according to ISO 9227 was carried out in a corresponding test chamber. Even after the maximum test time of 240 hours no base material corrosion was observed. Only at the cut edges of the rails of the pullout guide was red and black rust observed. The immigration resistance is further evidence of the improved adhesion of the coating to the metallic body.
  • the coated drawer slide with the coating A1 was scratched down to the substrate similar to a cross-hatch test and then stored for several weeks in a moist, warm environment. No corrosive infiltration of the cut in the area of the introduced scratches or grooves could be detected.
  • metallic components with an inorganic-organic hybrid polymer coating at 500 ° C for a long period of time are resilient, so that for such components, the use in the high temperature range and under corrosive conditions (high humidity, high salinity, scratched surface) is possible ,
  • the applied coating has a hardness that is comparable to a glassy coating, it is also tear-resistant, mechanically strong and protects the blank from corrosion. In addition, it conceals temper colors of steel-containing materials, for example as a metallic finish.
  • pigments such as, for example, carbon black, can additionally be added.
  • the layer thickness of a coating according to the invention may preferably be between 4 and 200 ⁇ m.
  • the layer thickness is particularly preferably 7-60 ⁇ m.
  • preferably more than 80% of the layer thickness is accounted for by the intermediate layer and preferably less than 10%, particularly preferably less than 5%, of the layer thickness on the cover layer.
  • the intermediate layer of the coating is more flexible than the rather hard top layer, so that the coating has an increased mechanical impact resistance over other coatings which do not have such a high proportion of an intermediate layer.
  • the running quality and noise quality of the coated drawer slide with coating A1 after 15 pyrolysis cycles (500 ° C.) at a test load of 10-16 kg were continuously assigned to running qualities 2 or 3, the curves of run quality and sound quality in FIG. 4 overlap.
  • the measurement results showed consistently good running quality (classification 1 - 7, where 1 corresponds to the highest running quality and 7 to the lowest running quality).
  • the measurement results also show a consistently low-noise mobility (classification 1 -7, where 1 is defined as no noise and 7 as the highest possible noise level.)
  • the forces which were used to pull out the coated pullout guide should preferably be in the range below 10 N, more preferably in the range below 4 N. This is the case with the coated pullout guide after evaluation of the measurement results from FIG.
  • the forces which are used for retracting the coated pullout guide should preferably be in the range below 1 1 N. This is also the case with the coated pullout guide after evaluation of the measurement results from FIG.
  • the rails 1 to 3 of the pullout guide are made of stamped and bent sheet steel for use in ovens and provided with a coating.
  • the production of the components of the pullout guide, in particular the rails 1 to 3 takes place by the following steps:
  • the metallic body of the pullout guide are made by punching and bending.
  • the main body can be machined.
  • an inorganic-organic hybrid polymer layer is applied to the surface of the base body.
  • the surface of the base body is pretreated. This pretreatment takes place only by degreasing by means of a basic cleaning agent, preferably at pH 8-10.5.
  • a roughening as it is often described in the prior art, can advantageously be omitted when applying the inorganic-organic hybrid polymer, since such a strong connection of the coating to the base body is achieved by the subsequent thermal treatment, that this additional process step is unnecessary ,
  • the coated bodies are then heated to a temperature of preferably at least 400 ° C and annealed for a predetermined period of time before being cooled back to room temperature.
  • the application of the inorganic-organic hybrid polymer layer takes place in the sol-gel process, preferably in the form of a polysiloxane coating which still has organic end groups after the coating.
  • alkoxy compounds of silicon be converted by hydrolysis with partial substitution of the alkoxy functions by hydroxy groups into reactive silanols present in the sol as colloidal particles. These particles are deposited on the application of the sol on a surface, preferably of metal, at this. Heating further enhances the interaction of silanol molecules with the surface, leading to the formation of covalent bonds. When heated, it also leads to the transformation of the sol in the gel state to form polysiloxanes. In this case, alcohols and water are formed in a condensation reaction. For example, in alkoxy compounds of silicon and other metals and semimetals, various interactions occur between the organic and inorganic components of the hybrid polymers. These are due to covalent or ionic-covalent bonds.
  • the coating sols of the inorganic-organic hybrid polymers can be applied in liquid form to a metallic component in a sol-gel process and flow and harden under mild reaction conditions.
  • TMOS tetramethoxysilane
  • the addition is in the range between 0-10 ° C, since TMOS is very flammable, toxic and corrosive.
  • TMOS tetramethoxysilane
  • the hydrolysis of the organic compound is concentrated aqueous HCl (about 1-3% by volume over the volume of TMOS) over 30 minutes with constant stirring.
  • the HCl can be cooled down to a temperature of about 0 ° C in advance.
  • the stirring is maintained for a few minutes, for example, 5-10 minutes.
  • the solvent may be protic or aprotic polar, for example isopropanol.
  • a coating based on 3-glycidyloxypropyltrimethoxysilane may also be converted to a flowable coating substance by hydrolysis under basic or acidic conditions, and then converted into an inorganic silicon dioxide layer by subsequent curing at 700-800 ° C. as a result of condensation.
  • the application of the liquid sol to the surface of the metallic component can be done by spraying, dipping, brushing or the like.
  • the coating composition in addition to the silicon-based compounds in the coating solution, other constituents, in particular also metal and particularly preferably transition metal compounds, such as, for example, copper species, may be present in the coating composition.
  • metal and particularly preferably transition metal compounds such as, for example, copper species
  • the concentration of at least one first transition metal, here in particular chromium, in the coating is further increased according to the invention by thermal treatment after the thermal compaction and cooling of the coated component.
  • This increase in transition metals in the intermediate layer of the coating gives the intermediate layer a stronger metallic character and makes it possible for the coating to be more strongly bonded or adhered to the metallic base body than if this thermal treatment were omitted.
  • the conditions of the thermal treatment with regard to the time and the temperature and the interval sequence are to be selected such that the organic constituents of the inorganic-organic hybrid polymer are not completely oxidized and the functionality thereof is retained.
  • the diffusion of chromium, manganese, but also of nickel compounds in the intermediate layer is greater than the diffusion of iron compounds in this layer, if it is the metallic base body is a stainless steel alloy.
  • the diffusion of the metal compounds through a temperature gradient during thermal treatment can advantageously be influenced with regard to the penetration depth and concentration distribution in the layer.
  • the transition metal may already be incorporated as part of the inorganic-organic hybrid polymer layer and accumulate in the center of the coating as a result of diffusion and distribution effects.
  • the thermal treatment after the actual coating of the component as described by the method according to the invention is advantageously carried out by one or more heating cycles up to 500 ° C.
  • a heating cycle is shown in more detail. This is done at the beginning of the heating cycle within 25 min, a heating by 200 ° C to 350 ° C. Later in the heating cycle, a slower rise in temperature of 150 ° C occurs within 50 minutes.
  • Fig. 6-I and II shows a cross-cut test on a pullout guide with the coating A1 described above. Already on the basis of the grid pattern with the defined groove structure, it can be seen that this coating has a low tendency to flake off.
  • Figures 6-I and II show a cross-hatch test on a comparative pull-out guide with a coating containing an inorganic-organic hybrid polymer which has not been additionally thermally treated.
  • a coating of the coating already takes place during the introduction of the grooves, and a part of the coating material remains on the adhesive tape.
  • the surface can be visually designed according to the customer's wishes. A leveling of the surface by application of the coating A leads to a better cleanability of the surface and to an attractive appearance.
  • the coatings described are preferably applied to a metallic component whose metallic base body made of steel of the material number 1 .4301 is a 18/10 chromium-nickel steel, steel of the material number 1 .4016, a ferritic 17 percent chromium steel or steel of the material number 1 .4310 a chromium nickel-alloyed steel.
  • the coating offers particular advantages in high-temperature application areas, in particular in ovens. However, it also offers advantages for components in areas with a high risk of corrosion. This includes, for example, the products of white goods, such. As refrigerators, refrigerators and freezers, steam cooking appliances, food and table warmer, combi steamers and washing machines. Also furniture fittings are exposed during transport, especially in overseas transport, higher risk of corrosion, for example, by humid climate and / or seawater. In these areas, coated hardware has a longer life compared to uncoated hardware.
  • the coating is preferably diffusion-stable after thermal treatment, i. a change in the material composition at

Abstract

L'invention concerne un composant métallique notamment destiné à être employé dans des appareils ménagers, le composant métallique présentant sur un corps de base métallique, au moins par endroits, un revêtement fritté conçu en plusieurs couches, contenant un polymère hybride inorganique-organique à base de silicium. Le composant métallique est conçu de telle manière que le revêtement présente a) au moins une couche de recouvrement durcie et b) une couche intermédiaire pour l'adhérence entre la couche de recouvrement durcie et la surface métallique, au moins 20 % du profil de profondeur de la couche intermédiaire présentant une concentration massique d'un premier métal de transition de plus de 10 %, le premier métal de transition n'étant pas le constituant principal du corps de base métallique.
PCT/EP2012/057066 2011-04-21 2012-04-18 Composant métallique et procédé de modification de surface d'un composant revêtu WO2012143386A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP12716368.1A EP2699360A1 (fr) 2011-04-21 2012-04-18 Composant métallique et procédé de modification de surface d'un composant revêtu

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102011002247 2011-04-21
DE102011002247.3 2011-04-21

Publications (1)

Publication Number Publication Date
WO2012143386A1 true WO2012143386A1 (fr) 2012-10-26

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EP (1) EP2699360A1 (fr)
DE (1) DE102012103380A1 (fr)
WO (1) WO2012143386A1 (fr)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0937012A1 (fr) 1997-07-05 1999-08-25 Miele & Cie. GmbH & Co. Revetement anti-adherence resistant aux temperatures elevees et aux rayures
WO2010063776A1 (fr) 2008-12-02 2010-06-10 Paul Hettich Gmbh & Co. Kg Procédé de fabrication de composants pour des applications haute température et composant métallique

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0937012A1 (fr) 1997-07-05 1999-08-25 Miele & Cie. GmbH & Co. Revetement anti-adherence resistant aux temperatures elevees et aux rayures
WO2010063776A1 (fr) 2008-12-02 2010-06-10 Paul Hettich Gmbh & Co. Kg Procédé de fabrication de composants pour des applications haute température et composant métallique

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Publication number Publication date
EP2699360A1 (fr) 2014-02-26
DE102012103380A1 (de) 2012-10-25

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