EP0370838A1 - Verfahren zum Schutz der Oberflächen von Metallteilen gegen Hochtemperaturkorrosion sowie dadurch behandeltes Teil - Google Patents

Verfahren zum Schutz der Oberflächen von Metallteilen gegen Hochtemperaturkorrosion sowie dadurch behandeltes Teil Download PDF

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Publication number
EP0370838A1
EP0370838A1 EP89402753A EP89402753A EP0370838A1 EP 0370838 A1 EP0370838 A1 EP 0370838A1 EP 89402753 A EP89402753 A EP 89402753A EP 89402753 A EP89402753 A EP 89402753A EP 0370838 A1 EP0370838 A1 EP 0370838A1
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EP
European Patent Office
Prior art keywords
deposit
nickel
metal
phase
platinum
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
EP89402753A
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English (en)
French (fr)
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EP0370838B1 (de
Inventor
Serge Alperine
Pierre Josso
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Office National dEtudes et de Recherches Aerospatiales ONERA
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Office National dEtudes et de Recherches Aerospatiales ONERA
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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
    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/02—Pretreatment of the material to be coated
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12875—Platinum group metal-base component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12931—Co-, Fe-, or Ni-base components, alternative to each other

Definitions

  • the invention relates to protection against corrosion at high temperature of metallic materials, and more particularly of materials based on nickel, cobalt and / or iron, including steels.
  • the invention relates more particularly to superalloys, in particular nickel-based, used for the manufacture of hot parts of a turbomachine, for example fixed or mobile turbine blades and distributors, which must have excellent resistance to oxidation and to corrosion at high temperature, in particular in the presence of molten sodium sulphate originating from the spray and sulfur impurities contained in the fuel.
  • a known protection method for this purpose consists in forming, by deposition and / or diffusion on the surface of the substrate to be protected, a layer containing a nickel, cobalt and / or iron aluminide, by a treatment comprising bringing into contact of the part to be treated with a filler material containing aluminum.
  • the filler material comprises a chromium-based alloy comprising aluminum in a proportion by weight of 5 to 25% and, optionally, silicon in a proportion by weight of 3 to 10%, and the parts to be treated are brought into contact with the finely divided filler material, under a hydrogenated atmosphere, at a temperature between 750 and 1200 ° C.
  • the aluminization treatment can be either the low activity aluminization already mentioned, or a variant thereof called high activity aluminization, or another type of treatment, for example a vapor phase aluminization such as that designated under the reference RT22 by the Chromalloy Company.
  • High activity aluminization differs from low activity aluminization described above in that the metal part of the filler material is composed by weight of 55 to 70% aluminum and 45 to 30% chromium, in that that the treatment temperature is between 650 and 750 ° C, and preferably equal to approximately 700 ° C, its duration being between 7 and 8 hours and preferably equal to approximately 7 hours 30.
  • This high activity deposit is followed by a post-diffusion treatment in a non-oxidizing atmosphere (argon or hydrogen), the duration and temperature of which vary depending on the substrate.
  • argon or hydrogen non-oxidizing atmosphere
  • platinum mine metal in the pre-deposit treatment is platinum itself, which significantly improves the protection provided by the aluminizing treatment.
  • platinum has the disadvantage of being very expensive.
  • the object of the invention is to obtain an aluminide coating modified by a pre-deposit containing a platinum-mine metal other than the platinum itself, and in particular palladium, by avoiding the occlusion of hydrogen or any other gas liable to cause the blistering phenomenon.
  • the subject of the invention is a part comprising a metallic substrate based on nickel, cobalt and / or iron and a protective coating composed of a deposit and a pre-deposit interposed between the substrate and the deposit, the pre-deposit containing at minus a platinum mine metal other than platinum itself and comprising one or more layers and the deposit containing a nickel and / or cobalt and / or iron aluminide modified by said platinum mine metal, characterized in that the pre-deposit also contains at least one barrier metal chosen from nickel, cobalt and chromium, the barrier metal being present in any layer containing said platinum mine metal and / or in at least one overlying layer.
  • Nickel, cobalt and chromium have the property of practically not dissolving gas even at high temperature and thus protect the metals from the platinum mine, in particular palladium, against such dissolution.
  • the thickness of the pre-deposit does not exceed approximately 100 ⁇ m and can be of the order of 10 ⁇ m.
  • At least one layer of the pre-deposit is formed essentially by an alloy of at least one metal of the platinum mine and at least one barrier metal.
  • the pre-deposit can then have a single layer.
  • a first layer of the pre-deposit is formed essentially of at least one metal of the platinum mine and a second layer, overlying the first, is formed essentially of at least one barrier metal.
  • first layer and second layer do not refer here to the absolute position of the layers in the pre-deposit, but simply serve to identify the two layers in relation to each other. In this case, the first and second layers may be adjacent and may constitute the only two layers of the pre-deposit.
  • the invention also relates to a method for protecting the surface of a metallic substrate based on nickel, cobalt and / or iron, comprising a pre-deposition treatment followed by a deposition treatment, the deposition treatment comprising the deposition and / or the diffusion of aluminum on the surface of the pretreated substrate and the pre-deposit treatment comprising one or more successive phases during which are provided with material which is deposited and / or which is diffused on the surface of the substrate, the composition of the filler material being able to be different from one phase to another and said filler material containing , during at least one phase, at least one metal from the platinum mine other than the platinum itself, characterized in that the filler material contains, during any phase for which it contains said metal from the mine platinum and / or at least one subsequent pre-treatment phase, at least one barrier metal chosen from nickel, cobalt and chromium.
  • Such a deposition treatment is, for example, a high activity or low activity aluminization as defined above.
  • At least one phase of the pre-deposition treatment may comprise a deposition operation of filler material at low temperature followed by a diffusion operation at high temperature under vacuum, this diffusion operation being carried out, preferably, at a temperature of about 850 ° C under an air pressure at most equal to 10 ⁇ 5 torr.
  • At least one phase of the pre-deposition treatment comprises the deposition and / or diffusion of an alloy of at least one metal of the platinum mine and at least one barrier metal .
  • the pre-deposit treatment can then comprise a single material supply phase.
  • the filler material in a first phase of the pre-deposition treatment, is formed essentially of at least one metal of the platinum mine, and in a second phase after the first, the material of intake is basically formed at least one barrier metal.
  • first phase and second phase call for the same remark made above with regard to the terms “first layer” and “second layer”.
  • the first and second phases can then follow each other directly and constitute, for example, the only two phases of supply of material from the pre-deposition treatment.
  • the invention applies more particularly to a nickel-based substrate, the aluminide being essentially a nickel aluminide and the barrier metal preferably also being essentially nickel.
  • the metal of the platinum mine it is preferably essentially palladium.
  • this advantageously comprises approximately 80% of palladium and 20% of nickel by weight and can be deposited, for example by electrolytic means.
  • the first can be deposited by an autocatalytic chemical process and the second by triode sputtering.
  • a pre-deposit of pure palladium 8 ⁇ m thick was sputtered on a substrate made of IN100 superalloy. triode.
  • the sample was then subjected to a 2 hour heat treatment to diffuse the pre-deposit at 850 ° C, under a total air pressure at most equal to 10 ⁇ 5 torr.
  • a nickel aluminide coating of high activity type as defined above was then produced on this sample by activated case hardening in a pack.
  • the surface of the sample was covered with a very large number of blisters ( Figure 1).
  • Such a coating surface condition makes the material unusable for turbomachine components.
  • the sample was then subjected to a high temperature corrosion test consisting of thermal cycling in an air oven between temperatures of about 850 ° C and 200 ° C, with one hour increments at 850 ° C and with periodic contamination of the sample with sodium sulfate at a rate of 0.5 mg / cm2 every 50 cycles.
  • This test is representative of the stresses on the components of the hot parts of the turbomachinery under so-called hot corrosion conditions.
  • the resistance of the coating to hot corrosion has been found to be very low.
  • the degraded state of the sample is critical (Figure 2) and there is significant pitting corrosion.
  • the mass gain is very high ( Figure 3, curve A).
  • the behavior of this sample is comparable to that of a sample having undergone a conventional high activity aluminization in the absence of any pre-deposit, as can be seen in FIG. 3 where curve B relates to this last sample.
  • Example 2 The procedure was as in Example 1, replacing the high activity aluminization with a standard low activity type aluminization. The same result was obtained (see FIG. 3, curve E), FIGS. 6 and 7 showing the sample respectively before and after the corrosion test.
  • Example 1 differs from Example 1 only in the pre-filing processing.
  • the latter here comprises two phases of material input.
  • the first phase approximately 8 ⁇ m of pure palladium was deposited by autocatalytic chemistry.
  • the sample was then subjected to a 2 hour diffusion heat treatment at 850 ° C under a total air pressure at most equal to 10 ⁇ 5 torr.
  • a deposit of approximately 3 ⁇ m of pure nickel was applied by triode sputtering.
  • the sample then underwent a second diffusion heat treatment identical to the first.
  • FIG. 8 shows that the sample obtained is free from all blisters and has an integrity condition.
  • Example 4 The procedure was as in Example 4, but omitting the diffusion heat treatment between the deposition of palladium and the deposition of nickel. Here again, the surface of the sample was free of any blistering and its surface condition was integrity.
  • Example 5 The procedure was as in Example 5, replacing the nickel deposit by a deposit of approximately 3 ⁇ m of cobalt by electrolytic means under the conditions below: Composition of the bath: - hydrated cobalt sulfate: 175 g / l - cobalt chloride: 80 g / l - boric acid: 20 g / l Current density between 2 and 4 A / dm2 Temperature: 45 ° C.
  • Example 7 The procedure was as in Example 7, replacing the low activity aluminide coating with a standard high activity aluminide coating.
  • Example 9 The procedure was as in Example 9, replacing the low activity aluminide coating with a standard high activity type aluminide coating.
  • the pre-deposit can be carried out in particular by chemical, electrolytic, thermochemical, physical or by spraying.
  • the aluminization can be carried out in particular by diffusion or by chemical, electrolytic, thermochemical or physical way.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Physical Vapour Deposition (AREA)
EP89402753A 1988-10-26 1989-10-05 Verfahren zum Schutz der Oberflächen von Metallteilen gegen Hochtemperaturkorrosion sowie dadurch behandeltes Teil Expired - Lifetime EP0370838B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8813991A FR2638174B1 (fr) 1988-10-26 1988-10-26 Procede de protection de surface de pieces metalliques contre la corrosion a temperature elevee, et piece traitee par ce procede
FR8813991 1988-10-26

Publications (2)

Publication Number Publication Date
EP0370838A1 true EP0370838A1 (de) 1990-05-30
EP0370838B1 EP0370838B1 (de) 1994-07-20

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EP89402753A Expired - Lifetime EP0370838B1 (de) 1988-10-26 1989-10-05 Verfahren zum Schutz der Oberflächen von Metallteilen gegen Hochtemperaturkorrosion sowie dadurch behandeltes Teil

Country Status (5)

Country Link
US (1) US4962005A (de)
EP (1) EP0370838B1 (de)
JP (1) JP2700931B2 (de)
DE (1) DE68916914T2 (de)
FR (1) FR2638174B1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2768750A1 (fr) * 1997-09-25 1999-03-26 Snecma Procede pour ameliorer la resistance a l'oxydation et a la corrosion d'une piece en superalliage et piece en superalliage obtenue par ce procede

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US5139824A (en) * 1990-08-28 1992-08-18 Liburdi Engineering Limited Method of coating complex substrates
US5334263A (en) * 1991-12-05 1994-08-02 General Electric Company Substrate stabilization of diffusion aluminide coated nickel-based superalloys
EP0567755B1 (de) * 1992-04-29 1996-09-04 WALBAR INC. (a Delaware Corporation) Verbessertes Verfahren zur Diffusionsbeschichtung und Produkte
US5500252A (en) * 1992-09-05 1996-03-19 Rolls-Royce Plc High temperature corrosion resistant composite coatings
WO1995002900A1 (en) * 1993-07-15 1995-01-26 Astarix, Inc. Aluminum-palladium alloy for initiation of electroless plating
FR2721105B1 (fr) * 1994-06-09 1996-08-14 Onera (Off Nat Aerospatiale) Capteur capacitif a électrodes concentriques et son procédé de fabrication.
US5658614A (en) * 1994-10-28 1997-08-19 Howmet Research Corporation Platinum aluminide CVD coating method
US5897966A (en) * 1996-02-26 1999-04-27 General Electric Company High temperature alloy article with a discrete protective coating and method for making
GB9612811D0 (en) * 1996-06-19 1996-08-21 Rolls Royce Plc A thermal barrier coating for a superalloy article and a method of application thereof
EP0821076B1 (de) * 1996-07-23 2001-11-28 ROLLS-ROYCE plc Verfahren zur Aluminisierung einer Superlegierung
US6022632A (en) * 1996-10-18 2000-02-08 United Technologies Low activity localized aluminide coating
FR2757181B1 (fr) * 1996-12-12 1999-02-12 Snecma Procede de realisation d'un revetement protecteur a haute efficacite contre la corrosion a haute temperature pour superalliages, revetement protecteur obtenu par ce procede et pieces protegees par ce revetement
US5817371A (en) * 1996-12-23 1998-10-06 General Electric Company Thermal barrier coating system having an air plasma sprayed bond coat incorporating a metal diffusion, and method therefor
US5958204A (en) * 1997-09-26 1999-09-28 Allison Enaine Company, Inc. Enhancement of coating uniformity by alumina doping
EP1033417A1 (de) * 1999-03-04 2000-09-06 Siemens Aktiengesellschaft Verfahren und Einrichtung zur Beschichtung eines Erzeugnisses, insbesondere eines Hochtemperaturbauteils einer Gasturbine
SG98436A1 (en) * 1999-12-21 2003-09-19 United Technologies Corp Method of forming an active-element containing aluminide as stand alone coating and as bond coat and coated article
US6560870B2 (en) * 2001-05-08 2003-05-13 General Electric Company Method for applying diffusion aluminide coating on a selective area of a turbine engine component
FR2881439B1 (fr) * 2005-02-01 2007-12-07 Onera (Off Nat Aerospatiale) Revetement protecteur pour superalliage monocristallin
FR2888145B1 (fr) 2005-07-07 2008-08-29 Onera (Off Nat Aerospatiale) Procede de fabrication et d'assemblage par brasure de billes en superalliage et objets fabriques avec de tels assemblages
US8124246B2 (en) * 2008-11-19 2012-02-28 Honeywell International Inc. Coated components and methods of fabricating coated components and coated turbine disks
GB201707986D0 (en) * 2017-05-18 2017-07-05 Rolls Royce Plc Coating for a nickel-base superalloy

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FR2072284A5 (de) * 1969-12-05 1971-09-24 Deutsche Edelstahlwerke Ag
US3979273A (en) * 1975-05-27 1976-09-07 United Technologies Corporation Method of forming aluminide coatings on nickel-, cobalt-, and iron-base alloys
EP0183852A1 (de) * 1984-05-24 1986-06-11 Electroplating Engineers of Japan Limited Hochreines palladium-nickellegierung-plattierungsbad, verfahren dazu, und mit dieser legierung beschichtete gegenstände sowie mit gold- oder goldlegierung beschichtete gegenstände

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US3979273A (en) * 1975-05-27 1976-09-07 United Technologies Corporation Method of forming aluminide coatings on nickel-, cobalt-, and iron-base alloys
EP0183852A1 (de) * 1984-05-24 1986-06-11 Electroplating Engineers of Japan Limited Hochreines palladium-nickellegierung-plattierungsbad, verfahren dazu, und mit dieser legierung beschichtete gegenstände sowie mit gold- oder goldlegierung beschichtete gegenstände

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2768750A1 (fr) * 1997-09-25 1999-03-26 Snecma Procede pour ameliorer la resistance a l'oxydation et a la corrosion d'une piece en superalliage et piece en superalliage obtenue par ce procede
EP0905281A1 (de) * 1997-09-25 1999-03-31 Societe Nationale D'etude Et De Construction De Moteurs D'aviation "Snecma" Verfahren zur Verbesserung der Oxidations- und Korrosionsbeständigkeit eines Gegenstand aus Superlegierung und Gegenstand aus Superlegierung so hergestellt
US6228513B1 (en) 1997-09-25 2001-05-08 Societe Nationale d'Etude et de Construction de Moteurs d'Aviation “SNECMA” Method of improving oxidation and corrosion resistance of a superalloy article, and a superalloy article obtained by the method

Also Published As

Publication number Publication date
JPH02277784A (ja) 1990-11-14
FR2638174A1 (fr) 1990-04-27
FR2638174B1 (fr) 1991-01-18
DE68916914D1 (de) 1994-08-25
JP2700931B2 (ja) 1998-01-21
EP0370838B1 (de) 1994-07-20
US4962005A (en) 1990-10-09
DE68916914T2 (de) 1994-12-15

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