EP0587341B1 - Revêtements composites résistant à la corrosion à haute température - Google Patents

Revêtements composites résistant à la corrosion à haute température Download PDF

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Publication number
EP0587341B1
EP0587341B1 EP93306699A EP93306699A EP0587341B1 EP 0587341 B1 EP0587341 B1 EP 0587341B1 EP 93306699 A EP93306699 A EP 93306699A EP 93306699 A EP93306699 A EP 93306699A EP 0587341 B1 EP0587341 B1 EP 0587341B1
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Prior art keywords
coating
platinum
mcraly
surface layer
aluminising
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EP93306699A
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German (de)
English (en)
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EP0587341A1 (fr
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Mehar Chand Meelu
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Rolls Royce PLC
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Rolls Royce PLC
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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
    • 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
    • C23C28/02—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 only including layers of metallic material
    • C23C28/021—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 only including layers of metallic material including at least one metal alloy layer
    • C23C28/022—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 only including layers of metallic material including at least one metal alloy layer with at least one MCrAlX 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
    • 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
    • C23C10/34—Embedding in a powder mixture, i.e. pack cementation
    • C23C10/58—Embedding in a powder mixture, i.e. pack cementation more than one element being diffused in more than one step
    • 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
    • C23C28/02—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 only including layers of metallic material
    • C23C28/028—Including graded layers in composition or in physical properties, e.g. density, porosity, grain size

Definitions

  • the present invention relates to so-called "MCrAlY” overlay coating systems modified to enhance resistance of superalloy gas turbine components to high temperature oxidation and corrosion attack.
  • MrAlY is a shorthand way of referring to well known temperature and oxidation/corrosion resistant alloy systems comprising in general one or more of nickel, cobalt and iron as the major "M” constituent, together with chromium and aluminium in quite large amounts, plus (usually) a minor amount of yttrium or other rare earth element.
  • M nickel, cobalt and iron
  • chromium and aluminium in quite large amounts, plus (usually) a minor amount of yttrium or other rare earth element.
  • weight percentage terms such alloys may be broadly defined as having the following compositions:
  • one well known alloy used as the basis of the present work, has a nominal composition in weight percent of:
  • MCrAlY coatings do act as a barrier between the base material and any outer aluminide coating to limit migration of base material elements, particularly aluminium and chromium, during service.
  • MCrAlY coatings by the argon shrouded plasma spray process as mentioned above, proprietary to Union Carbide Coatings Service Corporation, of Indianapolis, U.S.A.
  • the coatings can be aluminised, but must, of course, be heat treated to inter-diffuse them with the base material.
  • the required extra Al to maintain the concentration of aluminides in the surface layers of the coating could be supplied from the MCrAlY inner portion of the coating.
  • the Al content is insufficient for the migration mechanism to be able to continue to supply the deficient surface layers with Al for a lengthy period.
  • MCrAlY coatings with such relatively low aluminium contents are preferred because higher Al contents tend to make the coating brittle in service after the necessary diffusion heat treatment has been carried out.
  • low temperature in the present context meaning about 550 - 750 °C. This, of course, should be accomplished without any detrimental effect on the high temperature protection afforded by the coatings.
  • Chromising improves low temperature oxidation/ corrosion resistance of coating systems because Cr oxidises to form chromia, Cr2O3, which forms a protective oxide film at the coating surface.
  • Cr oxidises to form chromia, Cr2O3, which forms a protective oxide film at the coating surface.
  • chromising is ineffective to improve high temperature oxidation/corrosion resistance of coating systems. This is because Cr2O3 dissociates into Cr and gaseous CrO3 at temperatures above about 750°C.
  • the present invention includes a process for providing an M-based superalloy base material, where M is at least one of iron, cobalt and nickel, with a graded multiplex protective coating system containing aluminides in and near its surface, the process comprising the steps of:
  • the platinum layer has a thickness of 5 to 15 ⁇ m when applied, and the subsequent diffusing heat treatment is conveniently that normally utilised to restore the properties of the base material after the aluminising step.
  • the subsequent diffusing heat treatment is conveniently that normally utilised to restore the properties of the base material after the aluminising step.
  • this is one hour diffusion treatment at 1120°C, gas fan quench, and age 24 hours at 845°C.
  • the thickness of the platinum layer as deposited is very important to the final structure of the above coating.
  • a deposited platinum layer having a thickness of 10 to 15 ⁇ m gives a structure comprising an MCrAlY coating having a single surface layer containing platinum modified aluminide. This is achieved because during heat treatment the platinum and the underlying aluminides inter-diffuse completely.
  • the deposited platinum layer should have a thickness of 5 to 10 ⁇ m. This can be achieved because during heat treatment the platinum and the underlying aluminides do not inter-diffuse completely.
  • the present invention also includes an alternative process for providing an M-based superalloy base material, where M is at least one of iron, cobalt and nickel, with a graded multiplex protective coating system containing aluminides with enhanced aluminium content in and near its surface, the process comprising the steps of:
  • the platinum layer has a thickness of 5 to 10 ⁇ m when applied.
  • the time of aluminising is very important to the final structure of the above coating.
  • the platinised coating should be aluminised only for a relatively short time of about 4 to 6 hours at the aluminising temperature. This will allow the aluminium to diffuse into the platinised coating only about as far as the platinum has already diffused.
  • the platinised coating should be aluminised for a relatively long time of about 6 to 12 hours at the aluminising temperature. This will allow the aluminium to diffuse into the platinised coating further than the platinum has already diffused.
  • the chromising step in the above processes is performed essentially to obtain a large gradient of concentration of Cr in and near the surface of the MCrAlY coating. This increases its low temperature sulphidation resistance.
  • the overlay coating was first applied to IN738 alloy bars by the previously mentioned argon shrouded plasma spray technique. Extra elements were then introduced into the outer layer of the coating using various methods as described below:
  • the vapour aluminising process took place in an argon-filled retort vessel, with the parts to be aluminised being suspended in close proximity over packs of aluminising powder which liberate aluminium halide gas when heated. Aluminium from the gas is deposited onto the parts and diffuses into it due to the elevated temperature.
  • RT69 trade name
  • Chromalloy U.K. Limited of Bramble Way, Clover Nook Industrial Estate, Somercoates, Derby DE55 4RH, England, or its parent company, Chromalloy Research and Technology, Blaisdell, Orangeburg, NY 10962, U.S.A.
  • Platinum plating was accomplished by an electroplating process, again available from Chromalloy at the sites mentioned above under the trade name RT22.
  • Vapour chromising is performed in a similar way to vapour aluminising and is also available from Chromalloy under the trade name CN70.
  • Coating (4) had been processed in the same way as coating (5), except for the application of the thicker 16 ⁇ m (micron) platinum plate.
  • Coating (6) had been chromised and aluminised, but not platinised.
  • Coatings (3) and (2) had been aluminised and platinised, but not chromised.
  • Figure 5 shows a typical microstructure of coating (5) at x200 magnification before sulphidation testing, with the various layers indicated.
  • Figure 6 shows the result of an electron probe microanalysis of this coating, in which the concentration in weight percentage terms of various elements in the coating is graphically plotted against the depth of the coating in ⁇ m (microns).
  • the Cr content of the coating is up to about 40wt.% in the chromised layer, up to about 20 wt.% in the platinum aluminide layer and about 25wt.% retained in the body of the MCrAlY coating.
  • the highest aluminium content is only about 20 wt.% and is less than this near the surface of the coating in the platinum modified layer.
  • the results of the electron probe microanalysis as plotted are subject to variation due to experimental error and to local variations in element concentrations in the small scale microstructure.
  • the method of platinising an MCrAlY coating before aluminising it, in order to gain higher Al concentrations in the platinum modified aluminide surface layer of the finished coating will also plainly be advantageous when utilised without the prior chromising step.

Claims (18)

  1. Procédé pour fournir à un matériau de base de superalliage à base de M, où M est au moins un parmi le fer, le cobalt et le nickel, un système de revêtement de protection multiple stratifié comprenant des aluminures dans et à proximité de sa surface, le procédé comprenant les étapes de :
    appliquer un matériau de revêtement en alliage du type MCrAlY à la surface du matériau de base, la teneur en aluminium du matériau de revêtement étant de d'ordre de 4 à 20% en poids; et
    aluminer le revêtement pour produire un revêtement ayant une couche de surface contenant des aluminures du constituant M du revêtement ;
    le procédé étant caractérisé par les étapes de procédé additionnelles suivantes :
    après application du revêtement du type MCrAlY et avant l'étape d'aluminisation, chromiser optionnellement le revêtement du type MCrAlY pour produire un revêtement avec une couche supérieure chromisée ayant du chrome ajouté en solution solide dans le constituant M du revêtement, la teneur totale en chrome dans la couche de surface du revêtement du type MCrAlY après chromisation n'étant pas supérieure à environ 40% ;
    après l'étape d'aluminisation, déposer une couche de platine sur la surface du revêtement aluminé, et
    traiter thermiquement le revêtement résultant pour le platiner par diffusion de la couche de platine dans la couche sous-jacente contenant l'aluminure, pour produire ainsi un revêtement de MCrAlY ayant une couche de surface d'aluminure modifiée au platine.
  2. Procédé selon la revendication 1, dans lequel l'épaisseur du platine tel qu'appliqué et le traitement thermique ultérieur sont tels que pendant le traitement thermique, le platine et les aluminures sous-jacentes interdiffusent complètement pour donner une structure de revêtement comprenant un revêtement de MCrAlY ayant une seule couche de surface contenant de l'aluminure modifiée au platine.
  3. Procédé selon la revendication 2, dans lequel la couche de platine a une épaisseur de 10 à 15 µm lorsqu'appliquée.
  4. Procédé selon la revendication 1, dans lequel l'épaisseur du platine tel qu'appliqué et le traitement thermique ultérieur sont tels que pendant le traitement thermique le platine et les aluminures sous-jacentes n'interdiffusent pas complètement donnant ainsi une structure de revêtement comprenant un revêtement de MCrAlY ayant une couche de surface double sous la forme d'une couche supérieure contenant de l'aluminure modifiée au platine et une couche de sous-surface contenant des aluminures essentiellement sans modification au platine.
  5. Procédé selon la revendication 4, dans lequel la couche de platine a une épaisseur de 5 à 10 µm lorsqu'appliquée.
  6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel le traitement thermique de diffusion du platine est celui normalement utilisé pour restaurer les propriétés du matériau de base après l'étape d'aluminisation.
  7. Procédé pour fournir à un matériau de base de superalliage à base de M, où M est au moins un parmi le fer, le cobalt et le nickel, un système de revêtement de protection multiple stratifié contenant des aluminures avec une teneur en aluminium augmentée dans et à proximité de sa surface, le procédé comprenant les étapes de :
    appliquer un matériau de revêtement en alliage du type MCrAlY à la surface du matériau de base, la teneur en aluminium du matériau de revêtement étant de d'ordre de 4 à 20% en poids ; et
    aluminer le revêtement pour produire un revêtement ayant une couche de surface contenant des aluminures du constituant M du revêtement ; le procédé étant caractérisé par les étapes de procédé additionnelles suivantes :
    effectuer après application du matériau de revêtement du type MCrAlY et avant aluminisation :
    chromiser optionnellement le revêtement du type MCrAlY pour produire un revêtement avec une couche supérieure chromisée ayant du chrome ajouté en solution solide dans le constituant M du revêtement, la teneur totale en chrome dans la couche de surface du revêtement du type MCrAlY après chromisation n'étant pas supérieure à environ 40%;
    déposer une couche de platine sur la surface du revêtement résultant de l'étape de procédé précédente utilisée, et
    traiter thermiquement le revêtement résultant pour le platiner par diffusion de la couche de platine dans la couche de MCrAlY sous-jacente pour produire un revêtement de MCrAlY ayant une couche de surface contenant des aluminures modifiées au platine du constituant M du revêtement, où, lorsque le revêtement platiné est aluminé, l'aluminium est diffusé dans la surface du revêtement platiné.
  8. Procédé selon la revendication 1 ou la revendication 7, dans lequel la teneur totale en chrome dans la couche de surface du revêtement du type MCrAlY après chromisation est de l'ordre de 35 à 40%.
  9. Procédé selon la revendication 1 ou la revendication 7, dans lequel la couche de platine à une épaisseur de 5 à 15 µm lorsqu'appliquée.
  10. Procédé selon la revendication 7, dans lequel l'épaisseur du platine lorsqu'appliqué, le traitement thermique de platinage et l'étape d'aluminisation ultérieure sont tels que pendant l'aluminisation, l'aluminium diffuse dans le revêtement platiné seulement environ aussi loin que le platine a déjà diffusé donnant ainsi une structure de revêtement comprenant un revêtement de MCrAlY ayant une seule couche de surface contenant de l'aluminure modifiée au platine.
  11. Procédé selon la revendication 7, dans lequel l'épaisseur du platine lorsqu' appliqué, le traitement thermique de platinage et l'étape ultérieure d'aluminisation sont tels que pendant l'aluminisation, l'aluminium diffuse dans la couche platinée plus loin que le platine a déjà diffusé donnant ainsi une structure de revêtement comprenant un revêtement de MCrAlY ayant une couche de surface double sous la forme d'une couche supérieure contenant de l'aluminure modifiée au platine et une couche de sous-surface contenant des aluminures sensiblement sans modification au platine.
  12. Procédé selon la revendication 10, dans lequel la couche de platine a une épaisseur de 5 à 10 µm lorsqu'appliquée et l'étape d'aluminisation comprend une aluminisation sous vide à 1 090°C pendant environ 4 à 6 heures.
  13. Procédé selon la revendication 11, dans lequel la couche de platine à une épaisseur de 5 à 10 µm lorsqu'appliquée et l'étape d'aluminisation comprend une aluminisation sous vide à 1 090°C pendant 6 à 12 heures environ.
  14. Procédé selon l'une quelconque des revendications précédentes, dans lequel le traitement thermique de platinage comprend un chauffage à 1050°C pendant deux heures.
  15. Objet revêtu comprenant un revêtement de base de superalliage à base M et un système de revêtement au MCrAlY de protection multiple, où M est au moins un parmi le fer, le cobalt et le nickel, le revêtement ayant une couche de surface contenant des aluminures de platine et du constituant M du revêtement,
    caractérisé en ce que la couche de surface comprend du chrome ajouté en solution solide dans le constituant M du revêtement, la teneur totale en chrome dans la couche de surface du revêtement n'étant pas supérieure à environ 40%.
  16. Objet revêtu comprenant un matériau de base de superalliage à base de M et un système de revêtement au MCrAlY de protection multiple, où M est au moins un parmi le fer, le cobalt et le nickel, le revêtement ayant une couche de surface contenant des aluminures de platine et du constituant M du revêtement, caractérisé en ce que la couche de surface est une couche de surface double sous la forme d'une couche supérieure contenant de l'aluminium modifié au platine et une couche de sous-surface contenant des aluminures essentiellement sans modification au platine.
  17. Objet revêtu selon la revendication 16, dans lequel la couche de surface a du chrome ajouté en solution solide dans le constituant M du revêtement, la teneur totale en chrome dans la couche de surface du revêtement n'étant pas supérieure à environ 40%.
  18. Objet revêtu selon la revendication 15 ou la revendication 17, dans lequel la teneur totale en chrome dans la couche de surface du revêtement est de l'ordre de 35 à 40%.
EP93306699A 1992-09-05 1993-08-24 Revêtements composites résistant à la corrosion à haute température Expired - Lifetime EP0587341B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB9218858 1992-09-05
GB929218858A GB9218858D0 (en) 1992-09-05 1992-09-05 High temperature corrosion resistant composite coatings

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EP0587341A1 EP0587341A1 (fr) 1994-03-16
EP0587341B1 true EP0587341B1 (fr) 1996-03-20

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JP (1) JPH06220607A (fr)
DE (1) DE69301883T2 (fr)
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DE102005060243A1 (de) * 2005-12-14 2007-06-21 Man Turbo Ag Verfahren zum Beschichten einer Schaufel und Schaufel einer Gasturbine
US8545183B2 (en) 2007-09-06 2013-10-01 Siemens Aktiengesellschaft Seal coating between rotor blade and rotor disk slot in gas turbine engine
DE102012015586A1 (de) * 2012-08-08 2014-05-15 MTU Aero Engines AG Duplex Phasen CrAl-Beschichtung für verbesserten Korrosions-/Oxidations-Schutz
US9222163B2 (en) 2009-05-26 2015-12-29 Siemens Aktiengesellschaft Layered coating system with a MCrAlX layer and a chromium rich layer and a method to produce it
DE102021127344A1 (de) 2021-10-21 2023-04-27 MTU Aero Engines AG Verfahren zum Beschichten eines Bauteils eines Flugtriebwerks mit einer Verschleißschutzschicht und Bauteil für ein Flugtriebwerk mit wenigstens einer Verschleißschutzschicht

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JP2003073841A (ja) * 2001-08-28 2003-03-12 Kyocera Corp 配線基板およびその製造方法
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GB2421032A (en) * 2004-12-11 2006-06-14 Siemens Ind Turbomachinery Ltd A method of protecting a component against hot corrosion
US20070116875A1 (en) 2005-11-22 2007-05-24 United Technologies Corporation Strip process for superalloys
US20070138019A1 (en) * 2005-12-21 2007-06-21 United Technologies Corporation Platinum modified NiCoCrAlY bondcoat for thermal barrier coating
US8968528B2 (en) 2008-04-14 2015-03-03 United Technologies Corporation Platinum-modified cathodic arc coating
EP2537959B1 (fr) 2011-06-22 2013-12-25 MTU Aero Engines GmbH Revêtement multicouches anti-usure et procédé de fabrication
US10266926B2 (en) 2013-04-23 2019-04-23 General Electric Company Cast nickel-base alloys including iron
DE102013207457B4 (de) 2013-04-24 2017-05-18 MTU Aero Engines AG Verfahren zur Herstellung einer Hochtemperaturschutzbeschichtung
EP3080329B1 (fr) 2013-12-10 2023-04-05 Raytheon Technologies Corporation Revêtement de chromisation sur arc cathodique
US10202855B2 (en) 2016-06-02 2019-02-12 General Electric Company Airfoil with improved coating system
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DE102005060243A1 (de) * 2005-12-14 2007-06-21 Man Turbo Ag Verfahren zum Beschichten einer Schaufel und Schaufel einer Gasturbine
US8545183B2 (en) 2007-09-06 2013-10-01 Siemens Aktiengesellschaft Seal coating between rotor blade and rotor disk slot in gas turbine engine
US9222163B2 (en) 2009-05-26 2015-12-29 Siemens Aktiengesellschaft Layered coating system with a MCrAlX layer and a chromium rich layer and a method to produce it
DE102012015586A1 (de) * 2012-08-08 2014-05-15 MTU Aero Engines AG Duplex Phasen CrAl-Beschichtung für verbesserten Korrosions-/Oxidations-Schutz
EP2695965A3 (fr) * 2012-08-08 2017-03-29 MTU Aero Engines GmbH Revêtement CrAl à phases duplex pour une meilleure protection contre la corrosion/l'oxydation
US9689270B2 (en) 2012-08-08 2017-06-27 MTU Aero Engines AG Duplex-phase CrAl coating for improved corrosion/oxidation protection
DE102021127344A1 (de) 2021-10-21 2023-04-27 MTU Aero Engines AG Verfahren zum Beschichten eines Bauteils eines Flugtriebwerks mit einer Verschleißschutzschicht und Bauteil für ein Flugtriebwerk mit wenigstens einer Verschleißschutzschicht

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EP0587341A1 (fr) 1994-03-16
JPH06220607A (ja) 1994-08-09
DE69301883D1 (de) 1996-04-25
DE69301883T2 (de) 1996-08-08
GB9218858D0 (en) 1992-10-21

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