EP2855733B1 - Procédé pour recouvrir un substrat à base de cobalt, de nickel et/ou de fer d'une couche résistant à la corrosion - Google Patents

Procédé pour recouvrir un substrat à base de cobalt, de nickel et/ou de fer d'une couche résistant à la corrosion Download PDF

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Publication number
EP2855733B1
EP2855733B1 EP13734317.4A EP13734317A EP2855733B1 EP 2855733 B1 EP2855733 B1 EP 2855733B1 EP 13734317 A EP13734317 A EP 13734317A EP 2855733 B1 EP2855733 B1 EP 2855733B1
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Prior art keywords
slurry
substrate
nickel
aluminum
coating
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EP13734317.4A
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German (de)
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EP2855733A1 (fr
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Mathias GALETZ
Michael Schütze
Xabier MONTERO
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DECHEMA -FORSCHUNGSINSTITUT
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DECHEMA -FORSCHUNGSINSTITUT
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    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/10—Coating starting from inorganic powder by application of heat or pressure and heat with intermediate formation of a liquid phase in the layer
    • C23C24/103—Coating with metallic material, i.e. metals or metal alloys, optionally comprising hard particles, e.g. oxides, carbides or nitrides
    • C23C24/106—Coating with metal alloys or metal elements only
    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/60—After-treatment
    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/02—Pretreatment of the material to be coated
    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/18—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions
    • C23C10/26—Solid state diffusion of only metal elements or silicon into metallic material surfaces using liquids, e.g. salt baths, liquid suspensions more than one element being diffused
    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
    • C23C18/08—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of metallic material
    • C23C18/10—Deposition of aluminium only
    • 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
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/08—Coating starting from inorganic powder by application of heat or pressure and heat
    • C23C24/082—Coating starting from inorganic powder by application of heat or pressure and heat without intermediate formation of a liquid in the layer
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying

Definitions

  • the invention relates to a process for coating a cobalt-, nickel- and / or iron-containing substrate with a corrosion-resistant layer.
  • Substrates such as components and components used at high temperatures, e.g. Plant components in the chemical industry must be protected against corrosion. There is therefore a general need to produce cost-effective and effective coatings for such components and components.
  • the most commonly used technique to avoid hot gas corrosion and component oxidation is to apply aluminum-rich topcoats to the substrates, a process called aluminizing.
  • aluminizing a process called aluminum-rich topcoats.
  • the surfaces of components which are used at high temperatures and which are also exposed to strong corrosion attacks are equipped with conventional aluminide coatings, hardfacing layers or high-alloyed thermal spray coatings.
  • Aluminum preferably forms intermetallic compounds with nickel, cobalt and iron.
  • the phases with less Al content namely the aluminum-poorer phases NiAl or Co-Al or FeAl, are resistant to the extremely brittle phases such as Fe 14 Al 86 [Xiang et al.] Or Fe 2 Al 5 [Perez et al., Pipe et al.], NiAl 3 or Ni 2 Al 3 or Co 2 Al 5 , because they are less prone to cracking.
  • a protective oxide layer which also forms on the aluminum-poor intermetallic compounds, consists of slow-growing, well-adhering and very stable alumina.
  • coatings There are two types of coatings: On the one hand, surface coatings applied to the substrate surface and, on the other hand, diffusion coatings produced by diffusing elements such as aluminum, chromium or silicon into the edge zone of the substrate.
  • CVD Chemical Vapor Deposition
  • a second possibility is the application of aluminum-rich metal (Fe, Ni, Co) chromium-aluminum-yttrium (MCrAlY) overlays.
  • These layers are usually applied, for example, by means of build-up welding or thermal spraying. In use, these layers also form protective alumina on the surface. In addition, however, they contain other elements that contribute to the oxidation protection, such as chromium and yttrium. As a result, the aluminum content in these layers may be less than is necessary in diffusion layers. In this way, other alloys can be used be applied to corrosion-prone materials. However, the process is relatively expensive and expensive.
  • Slurry coatings are another alternative that is already being used as commercial coatings and that, for example, of Allen et al. US 3,248,251 or Mosser et al. in US 5,650,235 have been described.
  • intermetallic coatings are produced by reaction and interdiffusion between the substrate and a metal-containing powder applied to the component surface along with a binder, see e.g. See, for example, Joseph US 3,102,044 .
  • the layers produced are similar to those produced by packing methods and, in addition to the elements from the slurry, always contain the elements of the base material due to the high temperature during the interdiffusion step.
  • the slurry coatings are also diffused in a diffusion step above 800 ° C.
  • this diffusion step which is usually carried out in slurry coating in an inert atmosphere or in a vacuum
  • the elements of the base material and the coating diffuse into one another and form not only enriched mixed crystals but also intermetallic compounds.
  • the aluminum from the slurry reacts with nickel, cobalt or iron of the base material and forms the desired aluminides.
  • Previous methods are limited to nickel, cobalt base materials or austenitic steels, since the temperature treatment above 800 ° C must be carried out because otherwise form on the surface due to the high aluminum supply very aluminum-rich intermetallic brittle phases such as Fe 2 Al 5 or NiAl 3 . For this reason, a coating of ferritic steels with Slurry coatings previously not possible due to the temperature limits for these materials.
  • the previously known coatings often contain other elements and components in addition to aluminum in the slurry.
  • the best known commercial alloy powder in this field sold under the trade name Serma Loy J by Sermatech Int., USA, consists of 35% Al powder, 6% Si powder, 47% water, and 12% phosphate and chromate containing ties.
  • Serma Loy J sold under the trade name Serma Loy J by Sermatech Int., USA
  • an eutectic alloy system Al-Si is diffused as a component of the slurry.
  • All these coatings are therefore based on the fact that the aluminum atoms of the slurry during the heat treatment with certain elements from the substrate, which have a special affinity for aluminum, to intermetallic compounds. Particularly suitable for this are the substrate components nickel or cobalt, but also iron.
  • the US 2 927 043 A discloses a method of coating ferrous components: A slurry of aluminum particles with a flux is applied to the surface of a component, after which the component is heat treated for 5 to 10 minutes at a temperature that avoids stress in the base material of the component. During this process, the flux and the aluminum particles melt, forming a protective aluminum layer.
  • the CN 1 397 664 A discloses a member of magnesium coated with aluminum using surface annealing.
  • the invention is thus based on the object of representing a cost-effective method for corrosion protection of substrates (components) made of cobalt, nickel and / or iron-containing materials, in which the material and the resulting corrosion protection layers do not tend to form cracks.
  • the invention provides that an aluminum-containing slurry is applied to the substrate and the substrate is then subjected to the slurry a short-term temperature-reduced surface annealing.
  • the aluminum in the slurry can be in pure form or alloyed, for.
  • Under surface annealing should be understood as a heat treatment, which acts essentially on the edge zone of the substrate and therefore only there causes an increase in temperature, while the interior - the body - of the substrate remains substantially unaffected.
  • heat treatments are z. B. used for surface hardening of components.
  • Short-term means that the surface annealing takes less than 10 minutes.
  • Reduced temperature means that the temperature during surface layer annealing in the surface layer and in the slurry is between 550 ° C and 800 ° C.
  • the formation of the layer thus takes place not only by interdiffusion with the substrate during a heat treatment of the entire component in the new coating, but by a reaction between the components of the slurry and the nickel of a galvanic layer or the material during a Rander stiirmung and possibly only in the contact zone with the substrate under the nickel plating.
  • the invention allows the application of a corrosion protection for steels or nickel alloys which are exposed to a corrosion attack, z. B. in the high temperature range by oxidation, sulfidation or hot gas corrosion.
  • the invention is suitable for steels which offer a cost advantage over nickel and cobalt base materials as iron base materials for many applications in the chemical and energy industries.
  • the coatings are thus of particular interest for more temperature-sensitive ferritic / martensitic steels, but generally also for components made of austenitic steels, nickel or cobalt-based alloys, since the production costs are significantly lower than those of a complete heat treatment and the parts can be aluminized directly at low cost in air.
  • the substrate is heated to a temperature which is above the melting temperature of the aluminum in the slurry.
  • Melting temperature of the aluminum refers to the respective appearance of the aluminum (pure or alloyed) in the slurry.
  • the duration of the surface layer annealing can be shortened and the process carried out in air, if the slurry contains the aluminum as metal powder with 5-100 ⁇ m particle size, wherein the aluminum can be in pure form, alloyed or as a mixture thereof. Due to the optimized particle size, the aluminum melts in a controlled manner and still reacts easily with the substances in the substrate.
  • the surface of the substrate is cleaned prior to application of the slurry.
  • the cleaning can preferably be done by sand or shot peening.
  • the invention provides that the surface of the substrate before the application of the slurry can be precoated galvanically or by thermal spraying.
  • the edge annealing is carried out in vacuo, in an inert gas atmosphere or preferably in air.
  • the slurry contains an organic solvent and a binder system which is thermally decomposable.
  • the binder system is preferably a synthetic water-soluble or dispersible polymer which does not contain inorganic chromates, phosphates, molybdates or tungstates which are known to be harmful to the environment.
  • the binder system contains amphiphiles, low molecular weight phenols, aromatic acids, alkyl phosphates and / or high molecular weight polyelectrolytes.
  • the particles of the metal powder are optionally coated with a silicon-containing compound, for. B. with alkoxides, such as tetraethoxysilane as a silicon-containing precursor.
  • the substrate is heated to 400 ° C prior to edge annealing, where the aluminide phases forming the coating are formed.
  • the metallic powder preferably contains, in addition to the aluminum, at least one of the following elements in the specified maximum contents: Si (10% by mass), Ge (20% by mass), Cr (25% by mass), Ti (2% by mass), Ta, V or Mo (5 mass% each), B (2 mass%), Fe (10 mass%), Co (20 mass%), Ni (30 mass%).
  • the slurry contains tin (to 30 mass%), Si (to 10 mass%), Pt (to 10 mass%), Mg (to 20 mass%), Ca (to 20% by mass), one or more elements from the group (lanthanum, cerium, zirconium, hafnium, yttrium) ( ⁇ 1% by mass) or their oxides.
  • a proportion of tin in particular allows the use of the invention in metal dusting environments.
  • the additives Si, Pt, Mg and Ca and their oxides protect especially from hot gas corrosion.
  • the elements of the group (lanthanum, cerium, zirconium, hafnium, yttrium) and their oxides increase the adhesion of oxide layers that form during operation of the components on these.
  • the substrate is a steel or a nickel-base alloy or the nickel-plated surface of a component.
  • thermochemical diffusion treatment In the heat treatment process, a distinction is made between surface hardening and thermochemical diffusion treatment. In surface hardening, the chemical composition of the surface layer is not changed.
  • Surface hardening methods include induction hardening, flame hardening, hardening by means of conductive heating of the surface layer and hardening by means of high-energy heating.
  • the invention provides for the use of such a method, but it does not depend on the curing of the surface layer, so that the method in connection with the present invention is also referred to as surface layer annealing.
  • a substrate 1 here a tube
  • a slurry 2 of aluminum particles on its outer surface.
  • the tube is pulled through a coil system 3, inducing electrical currents in the surface of the tube which heat the surface, whereby the slurry 2 converts to an aluminide layer 4 by the reaction excited thereby.
  • a substrate 1 here a plate
  • a slurry 2 of aluminum particles on its surface.
  • One or more burner flames 5 are passed over the surface of the plate, whereby it is heated and the slurry 2 is converted to an aluminide layer 4.
  • the surface of the component to be coated is cleaned and freed from dirt and grease.
  • the surface can be coated before the coating z. B. blasted with glass beads or sand.
  • a slurry is applied to the cleaned surface.
  • the binder is preferably an organic polymer, but also silicone-containing binders or additives are conceivable.
  • the metal powder in the slurry consists essentially of aluminum or an aluminum alloy. In addition, other alloying elements in elemental or oxidic form may be mixed or alloyed with the aluminum powder.
  • the surface can then optionally be galvanically provided with a nickel layer.
  • the slurry is applied to the substrate or to the nickel layer and then dried.
  • the substrate with the slurry is subjected to an edge-layer annealing in air, in which the reaction between iron / nickel / cobalt and aluminum to aluminides takes place.
  • the new coating is more environmentally friendly than conventional coatings, since neither environmentally harmful halides are needed in the production, such.
  • chromates or phosphates are still included, as for most conventional slurry coatings, z. From Meelu et. al. in US 6,126,758 respectively. US 5547770 described, needed. In the realization of the new process should even be expressly dispensed with these ingredients.
  • the coatings have a homogeneous composition and that the film formation and the connection to the substrate are achieved by an exothermic aluminide formation, which takes place in the temperature range of the melting point of the aluminum alloy.
  • an exothermic aluminide formation which takes place in the temperature range of the melting point of the aluminum alloy.
  • a heat treatment between 550 ° C and 700 ° C can be generated in this way a layer.
  • the minimum necessary temperature for a thin layer is just below or above the melting point of the aluminum powder in the slurry, d. H. the aluminum alloy used.
  • a significant advantage of the innovation is that even a short-term, a few minutes lasting surface treatment of the surface layer is sufficient to achieve a coating, in contrast to conventional methods that often require long process times in heat treatment furnaces. Nevertheless, in the layers obtained by the new process, there is sufficient excess aluminum to allow for limited reaction with the substrate, thus ensuring firm bonding of the layer.
  • the highlight is the rapid heating in the range between 400 ° C and 700 ° C, whereby a relatively short and local heat treatment, limited to the surface layer, sufficient.
  • the metal powder fraction is mixed with binder and solvent, preferably water.
  • binder is preferably an organic polymer, but also silicone-containing binders or additives are conceivable.
  • the powder in the slurry consists essentially of aluminum or an aluminum alloy. In addition, further alloying elements in elemental or oxidic form may be mixed or alloyed with the aluminum powder or may also be deposited during the galvanic coating step.
  • the coated samples were first held at 300 ° C for four hours to burn out the binder.
  • reaction step was carried out for coating in laboratory air.
  • Example 1 Coating on austenitic iron-based alloy by means of a gas burner
  • Fig. 3 The transverse section of an AISI 347 sample can be seen after a flame treatment, as in Fig. 2 shown.
  • a short flame reaction time of only five minutes was used to convert the dried and debinded slurry in an area adjoining the substrate into an aluminide diffusion layer 4 by a butane flame as a heat source.
  • the layer thickness of the aluminide diffusion layer 4 was already about 25-30 ⁇ m after 5 minutes.
  • Example 2 Coating on ferritic iron-based alloy by means of an induction process
  • the surface of the component (substrate 1) made of a ferritic P 91 alloy was heated for only two minutes with an induction heating source according to Fig. 1 heated. Since in this case the wall thickness of the component was small (2 mm), the back of the component was also heated to such an extent that a slurry applied there also reacted. As a result, inner surfaces can even be coated by means of the heating according to the invention in the case of thin-walled components.
  • the thickness of the aluminide diffusion layer 4 on the substrate P91 in this case is about 60 ⁇ m on the outside (see Fig. 4a ) and about 40-50 ⁇ m on the side facing away from the induction coil (see Fig. 4b ). Again, each remained a residual layer 6 of unconverted slurry.
  • Microstructure transformations and changes are suppressed due to the moderate process temperatures ( ⁇ 700 ° C) and times (less than 2 minutes in both examples).

Claims (14)

  1. Procédé destiné à revêtir un substrat contenant du cobalt, du nickel et/ou du fer avec une couche résistant à la corrosion, caractérisé en ce que l'on applique une suspension visqueuse contenant de l'aluminium sur ledit substrat pour ensuite soumettre le substrat, pourvu de ladite suspension visqueuse, durant 10 min à un recuit de la zone marginale pendant lequel la température dans la zone marginale et dans la suspension visqueuse est comprise entre 550 °C et 800 °C.
  2. Procédé selon la revendication 1, caractérisé en ce que, lors du recuit de la zone marginale, le substrat est chauffé à une température supérieure à la température de fusion de l'aluminium dans la suspension visqueuse.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que la suspension, visqueuse contient ledit aluminium sous forme de poudre métallique ayant une taille des particules de 5 à 100 µm.
  4. Procédé selon l'une des revendications précédentes, caractérisé en ce que la surface du substrat est nettoyée avant l'application de la suspension visqueuse.
  5. Procédé selon l'une des revendications précédentes, caractérisé en ce que la surface du substrat subit un pré-revêtement par électrodéposition ou par projection thermique avant l'application de la suspension visqueuse.
  6. Procédé selon l'une des revendications précédentes, caractérisé en ce que le recuit de la zone marginale est réalisé sous vide, sous une atmosphère de gaz inerte ou en présence d'air.
  7. Procédé selon l'une des revendications précédentes, caractérisé en ce que la suspension visqueuse contient un solvant organique ainsi qu'un système liant lequel est susceptible de subir une décomposition thermique.
  8. Procédé selon la revendication 7, caractérisé en ce que ledit système liant est un polymère synthétique, hydrosoluble ou dispensable, ne contenant pas de chromate, phosphates, molybdates ni tungstates inorganiques.
  9. Procédé selon la revendication 7 ou 8, caractérisé en ce que le système liant contient des phénols amphiphiles à poids moléculaire faiblie, des acides aromatiques, des alkylphosphates tensioactifs et/ou du polyélectrolyte à poids moléculaire relevé.
  10. Procédé selon l'une des revendications précédentes, caractérisé en ce que les particules de ladite poudre métallique sont revêtues d'un composé contenant du silicium, par exemple d'alcoxydes tels que le tétraethoxysilane, servant de précurseur contenant du silicium.
  11. Procédé selon l'une des revendications précédentes, caractérisé en ce que le substrat est chauffé, préalablement au recuit de la zone marginale lors duquel intervient la formation des phases d'aluminiure formant le revêtement, jusqu'à 400 °C.
  12. Procédé selon l'une des revendications précédentes, caractérisé en ce que la poudre métallique contient au moins un des éléments suivants selon les teneurs maximales indiquées : Si (10 % en poids), Ge (20 % en poids), Cr (25 % en poids), Ti (2 % en poids), Ta, V ou Mo (chacun 5 % en poids), B (2 % en poids), Fe (10 % en poids), Co (20 % en poids), Ni (30 % en poids) .
  13. Procédé selon l'une des revendications précédentes, caractérisé en ce que le substrat ou la suspension visqueuse contient de l'étain (jusqu'à 30 % en poids), du Si (jusqu'à 10 % en poids), du Pt (jusqu'à 10 % en poids), du Mg (jusqu'à) 20 % en poids), du Ca (jusqu'à 20 % en poids) et, en outre, un ou plusieurs éléments choisis dans le groupe (lanthane, cérium, zirconium, hafnium, yttrium) ou leurs oxydes (< 1 % en poids).
  14. Procédé selon l'une des revendications précédentes, caractérisé en ce que le substrat est un acier ou un alliage à base de nickel ou que le substrat correspond à la surface nickelée d'une pièce.
EP13734317.4A 2012-05-30 2013-05-29 Procédé pour recouvrir un substrat à base de cobalt, de nickel et/ou de fer d'une couche résistant à la corrosion Not-in-force EP2855733B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012010602A DE102012010602A1 (de) 2012-05-30 2012-05-30 Verfahren zum Beschichten eines kobalt-, nickel- und/oder eisenhaltigenSubstrats mit einer korrosionsbeständigen Schicht
PCT/DE2013/000295 WO2013178216A1 (fr) 2012-05-30 2013-05-29 Procédé pour recouvrir un substrat à base de cobalt, de nickel et/ou de fer d'une couche résistant à la corrosion

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023217326A1 (fr) * 2022-05-13 2023-11-16 Dechema-Forschungsinstitut Stiftung Bürgerlichen Rechts Procédé de revêtement par diffusion avec une barbotine contenant du cr-si

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018213441A1 (fr) * 2017-05-18 2018-11-22 Magna International Inc. Revêtement pour acier, acier revêtu et procédé associé
WO2020023863A1 (fr) * 2018-07-27 2020-01-30 Magna International Inc. Procédé d'assemblage à faible coût d'aluminium coulé sous pression élevée

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2927043A (en) * 1957-02-20 1960-03-01 Solar Aircraft Co Aluminum coating processes and compositions
US3102044A (en) 1960-09-12 1963-08-27 United Aircraft Corp Applying protective coating from powdered material utilizing high temperature and low pressure
US3248251A (en) 1963-06-28 1966-04-26 Teleflex Inc Inorganic coating and bonding composition
US3257230A (en) 1964-03-24 1966-06-21 Chromalloy American Corp Diffusion coating for metals
US3544348A (en) 1968-10-25 1970-12-01 United Aircraft Corp Overhaul process for aluminide coated gas turbine engine components
US4228203A (en) * 1978-01-27 1980-10-14 Toyo Kogyo Co., Ltd. Method of forming aluminum coating layer on ferrous base alloy workpiece
JPH02282465A (ja) * 1989-04-24 1990-11-20 Mazda Motor Corp 摺動部材の製造方法
GB9210683D0 (en) 1992-05-19 1992-07-08 Rolls Royce Plc Multiplex aluminide-silicide coating
US5795659A (en) 1992-09-05 1998-08-18 International Inc. Aluminide-silicide coatings coated products
US5650235A (en) 1994-02-28 1997-07-22 Sermatech International, Inc. Platinum enriched, silicon-modified corrosion resistant aluminide coating
US6485780B1 (en) * 1999-08-23 2002-11-26 General Electric Company Method for applying coatings on substrates
US6395406B1 (en) * 2000-04-24 2002-05-28 General Electric Company Methods for preparing and applying coatings on metal-based substrates, and related compositions and articles
US6428630B1 (en) * 2000-05-18 2002-08-06 Sermatech International, Inc. Method for coating and protecting a substrate
CN1236105C (zh) * 2002-06-24 2006-01-11 西安交通大学 感应加热镁合金表面合金化改性方法
US7270852B2 (en) * 2003-08-04 2007-09-18 General Electric Company Aluminizing slurry compositions free of hexavalent chromium, and related methods and articles
US7390534B2 (en) * 2003-10-31 2008-06-24 General Electric Company Diffusion coating process
US7597934B2 (en) * 2006-02-21 2009-10-06 General Electric Company Corrosion coating for turbine blade environmental protection
JP5403881B2 (ja) * 2007-07-10 2014-01-29 ゼネラル・エレクトリック・カンパニイ ジェットエンジンブレードのサーペンタイン冷却通路のアルミナイジング法
WO2010134917A1 (fr) * 2009-05-21 2010-11-25 General Electric Company Articles résistant à la corrosion
SG173932A1 (en) * 2010-02-25 2011-09-29 United Technologies Corp Repair of a coating on a turbine component

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023217326A1 (fr) * 2022-05-13 2023-11-16 Dechema-Forschungsinstitut Stiftung Bürgerlichen Rechts Procédé de revêtement par diffusion avec une barbotine contenant du cr-si

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US20150203952A1 (en) 2015-07-23
DE112013002721A5 (de) 2015-02-26
DE102012010602A1 (de) 2013-12-05
EP2855733A1 (fr) 2015-04-08
WO2013178216A1 (fr) 2013-12-05

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