EP1082216A2 - Produit pourvu d'une couche de protection anticorrosion, et procede de realisation d'une couche de protection anticorrosion - Google Patents

Produit pourvu d'une couche de protection anticorrosion, et procede de realisation d'une couche de protection anticorrosion

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Publication number
EP1082216A2
EP1082216A2 EP99929016A EP99929016A EP1082216A2 EP 1082216 A2 EP1082216 A2 EP 1082216A2 EP 99929016 A EP99929016 A EP 99929016A EP 99929016 A EP99929016 A EP 99929016A EP 1082216 A2 EP1082216 A2 EP 1082216A2
Authority
EP
European Patent Office
Prior art keywords
layer
alloy
phase
mcraly
base body
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
EP99929016A
Other languages
German (de)
English (en)
Other versions
EP1082216B1 (fr
Inventor
Werner Stamm
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Original Assignee
Siemens AG
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 Siemens AG filed Critical Siemens AG
Publication of EP1082216A2 publication Critical patent/EP1082216A2/fr
Application granted granted Critical
Publication of EP1082216B1 publication Critical patent/EP1082216B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • C23C28/3215—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer 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
    • 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
    • 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
    • C23C28/023—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 only coatings of 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
    • 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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/325—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with layers graded in composition or in physical properties
    • 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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide 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
    • 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
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/12—Blades
    • F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion
    • F01D5/288—Protective coatings for blades
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2230/00—Manufacture
    • F05D2230/90—Coating; Surface treatment
    • 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.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12611—Oxide-containing 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.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12611—Oxide-containing component
    • Y10T428/12618—Plural oxides
    • 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.]
    • Y10T428/12736—Al-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
    • 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
    • Y10T428/12944—Ni-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
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension

Definitions

  • the invention relates to a product with a metallic base body and a protective layer thereon to protect the base body against corrosion, in particular when the product is exposed to a hot, aggressive gas.
  • the protective layer has an alloy of the type MCrAlY, in which M stands for one or more elements from the group iron, cobalt or nickel, Cr for chromium, Al for aluminum and Y for yttrium and / or an element from the group comprising scandium and the rare earths.
  • the invention further relates to a gas turbine blade with a protective layer and a method for producing a protective layer for protecting a product against corrosion.
  • EP 0 486 489 B1 describes a corrosion-resistant protective coating for medium and high temperatures up to approximately
  • the protective coating has, in% by weight, 25 to 40% nickel, 28-30% chromium, 7-9% aluminum, 1-2% silicon and 0.3 to 1% of at least one reactive element of the rare earths, at least 5% Cobalt and optionally 0 to 15% of at least one of the elements from the group consisting of rhenium, platinum, palladium, zircon, manganese, tungsten, titanium, molybdenum, niobium, iron, hafnium, tantalum.
  • the protective coating has only the elements nickel, chromium, aluminum, silicon, yttrium and additionally rhenium in a range from 1 to 15% and a remainder made of cobalt.
  • the addition of rhenium significantly improves the corrosion properties.
  • US Pat. No. 4,585,481 also specifies protective layers for protecting a metallic substrate made of a superalloy against high-temperature oxidation and corrosion.
  • MCrAlY alloys are used for the protective layers. 5 to 40% chromium, 8 to 35% aluminum, 0.1 to 2% of an oxygen-active element from group IIIB of the periodic system including the lanthanides and actinides and mixtures thereof, 0.1 to 7% silicon, 1 to 3% hafnium and a radical comprising nickel and / or cobalt are specified.
  • the corresponding protective layers made of MCrAlY alloy are applied according to US Pat. No. 4,585,481 by means of a plasma spraying process.
  • the German published patent application DE 196 09 69 AI specifies a turbine blade with a corrosion-resistant MCrAlY protective layer, in which the surface layer of the MCrAlY protective layer consists of a single-phase alloy over a large area, uniformly over the entire surface layer, down to a depth of 5 to 50 ⁇ m, the single-phase alloy being produced by remelting with a pulsed electron beam.
  • the single-phase structure is achieved, which leads to the formation of uniform, uninterrupted ones Oxide top layers from A1 2 0 3 leads.
  • Opposite outer layers' of aluminum oxide with a broken structure is given a lower tendency to spallation (spalling).
  • spallation spalling
  • WO 81/01983 AI specifies a method for producing a metallic component which contains a ceramic thermal barrier coating.
  • a thin layer of an McrAlY alloy is applied to a substrate made of a superalloy with a clean surface, this layer is polished, an aluminum oxide layer is applied to it and a columnar ceramic layer is produced on the aluminum oxide layer by means of gas deposition (vapor deposition).
  • EP 0 846 788 A1 relates to a product, in particular a gas turbine component, with a substrate on which a protective layer made of an alloy of the MCrAlY type and a ceramic thermal insulation layer is arranged thereon.
  • the substrate is a nickel-based super alloy that has chromium.
  • An outer layer of the substrate is enriched with chromium, which is diffused into the substrate by a diffusion process.
  • the chromium has diffused into the substrate and forms a matrix which has chromium dissolved in the nickel in the gamma phase.
  • the chromium is diffused in according to the so-called "chromation" process.
  • EP 0 718 420 AI describes a method for applying a thermal insulation layer to a component made of a superalloy.
  • the thermal insulation layer is made up of different layers.
  • a layer of a metal directly adjoins the superalloy product
  • This layer of the platinum group metal consists of an outer layer and an inner layer, the outer layer comprising the platinum group metal in the gamma phase.
  • An aluminum-containing coating is arranged on the outer part of the platinum group metal layer.
  • the object of the invention is to provide a product with a metallic base body and a protective layer thereon for protection against corrosion. Further objects of the invention consist in specifying a gas turbine blade with an adhesive layer with an alloy for binding a thermal insulation layer and a method for producing a protective layer for protection against corrosion.
  • the object aimed at a product with a metallic base body is achieved in that a protective layer for protection against corrosion is attached to the metallic base body, de an inner layer made of a first MCrAlY alloy attached to the base body and an outer layer attached to the inner layer with a second MCrAlY alloy, the second MCrAlY alloy being predominantly in the ⁇ phase.
  • a protective layer for protection against corrosion is attached to the metallic base body, de an inner layer made of a first MCrAlY alloy attached to the base body and an outer layer attached to the inner layer with a second MCrAlY alloy, the second MCrAlY alloy being predominantly in the ⁇ phase.
  • Alloy of the MCrAlY type is understood to mean an alloy which comprises a proportion of chromium, aluminum and a reactive element such as yttrium and / or at least one equivalent metal from the group comprising scandium and the elements of the rare earths.
  • further elements can be alloy constituents, such as, for example, rhenium, silicon, hafnium, tantalum, zirconium, tungsten, magnesium or niobium.
  • a proportion of rhenium in particular can lead to an improvement in the ability to corrode.
  • the rest contains the
  • MCrAlY alloy one or more elements from the group iron, cobalt and nickel, which is symbolically abbreviated to M.
  • Such an alloy is preferably used as a corrosion protection layer on metallic components, in particular with a base body made of a super alloy (nickel or cobalt super alloy, optionally also iron super alloy), which is exposed to an elevated temperature and a hot, aggressive gas.
  • the MCrAlY alloy specified here is also preferably suitable as an adhesive layer for the application of a thermal insulation layer, i.e. for the production of a coating system which is both corrosion and oxidation-inhibiting and enables the use of the product at a high temperature, for example above 1,000 ° C.
  • an aluminum oxide thermalally grown oxide
  • grows through the outer layer which has an MCrAlY alloy that is predominantly in the ⁇ phase, and which in the areas of the ⁇ phase of the MCrAlY Alloy in the ⁇ -modification.
  • the aluminum oxide is predominantly in the stable ⁇ -modification.
  • the invention is based on the finding that partial on an MCrAlY layer surface in the initial state of the oxidation or entirely a ⁇ phase of the aluminum oxide is formed where the MCrAlY alloy is present in the ß phase.
  • the aluminum oxide growing up in the ⁇ phase has a low density, a high rate of oxidation and a pointed structure, so that although the stable ⁇ -modification occurs later from a certain layer thickness, failure, ie chipping, of the aluminum oxide layer occurs can. It is therefore particularly favorable if the MCrAlY alloy is almost completely single-phase in the ⁇ -phase in the outer layer.
  • the second MCrAlY alloy preferably has the same chemical composition as the first MCrAlY alloy, whereby, depending on the properties of the individual alloy components, there are also differences in a few percent by weight or a few tenths by weight of the corresponding alloy components of the first MCrAlY Alloy and the second MCrAlY alloy can be present. It is also possible for the second MCrAlY alloy to have additional or alternative alloy elements to the first MCrAlY alloy.
  • the outer layer is preferably on average between 5 ⁇ m and 50 ⁇ m thick, in particular less than 20 ⁇ m.
  • the total average layer thickness of the protective layer is preferably between 100 ⁇ m and 200 ⁇ m,
  • the first MCrAlY alloy and / or the second MCrAlY alloy preferably has the following alloy components (details n percent by weight): 15 to 35% chromium; 7 to 18% aluminum; 0.3 to 2% yttrium and / or at least one aquivalent element from the group comprising scandium and the following alloy components (details n percent by weight): 15 to 35% chromium; 7 to 18% aluminum; 0.3 to 2% yttrium and / or at least one aquivalent element from the group comprising scandium and the following alloy components (details n percent by weight): 15 to 35% chromium; 7 to 18% aluminum; 0.3 to 2% yttrium and / or at least one aquivalent element from the group comprising scandium and the following alloy components (details n percent by weight): 15 to 35% chromium; 7 to 18% aluminum; 0.3 to 2% yttrium and / or at least one a
  • Rare earth elements and optional 0 to 20% rhenium as well as other optional alloy elements such as hafnium, silicon, tantalum, zircon, tungsten, magnesium and niobium.
  • the proportion of rhenium is preferably between 1% and 20%, especially between 5% and 11%.
  • the application layer preferably has a thickness between 0.3 ⁇ m and 0.6 ⁇ m at the beginning of an oxidation process. Due to a high proportion of aluminum oxide dm in the ⁇ phase, preferably almost exclusively of aluminum oxide in the ⁇ phase, the coating layer grows with an oxidation of the MCrAlY alloy in the outer layer with a significantly lower growth rate than with a high proportion of aluminum oxide in the ⁇ phase.
  • a coating layer which has almost exclusively aluminum oxide in the ⁇ phase from the start of oxidation is particularly advantageous, since this results in uniform, low growth of the coating layer.
  • a thermal insulation layer is preferably bonded to the application layer.
  • the thermal barrier layer preferably has a columnar microstructure, the axis direction of the crystals present in the columnar microstructure being substantially perpendicular to the surface of the basic structure. pers is.
  • the thermal insulation layer preferably has a thickness of between 150 and 300 ⁇ m, preferably about 200 ⁇ m.
  • the columnar, stem-shaped kstallite preferably have an average diameter of less than 5 ⁇ m, in particular less than 2.5 ⁇ m.
  • the thermal insulation layer preferably has a ceramic, which is in particular partially stabilized zirconium oxide with yttrium oxide. Depending on the requirements of the product, other thermal insulation layers including tertiary oxides, spinels or mullite can also be used.
  • the product is preferably a component of a gas turbine, in particular a gas turbine blade, a moving blade or a guide blade.
  • Gas turbine blades of the first two rows of guide vanes and of the first rows of rotor blades are preferably coated immediately downstream of a combustion chamber of a gas turbine with a protective layer of the type mentioned above and a thermal insulation layer bonded via an aluminum oxide layer.
  • the outer layer of the protective layer is made by remelting the inner layer in the area of its surface, i.e. an area of the inner layer is remelted.
  • This remelting is preferably carried out by electron beams or ion beams, which rapidly remelt without any significant change in the chemical
  • composition of the MCrAlY alloy of the outer layer and the inner layer By melting the free, ie untreated surface of the MCrAlY alloy of the inner layer by means of electron beams, ion beams or the like, it is possible to produce an essentially pure, temperature-stable ⁇ phase in the upper edge regions of a few micrometers, which forms the outer layer.
  • this ⁇ phase has the effect that a stable, dense and thin ⁇ -aluminum oxide layer, the attachment layer, now forms on the surface of the outer layer during the formation of an oxide layer.
  • the oxide formed by oxidation mainly aluminum oxide, is known as thermally grown oxide (TGO).
  • the formation of this oxide, the application layer can take place both before application of the thermal insulation layer and during and after the application of the thermal insulation layer.
  • the thermal insulation layer is preferably applied here by vapor deposition. Due to the low growth rate and homogeneous structure of the thermally grown oxide (TGO), the stresses in the area of the thermally grown oxide, the application layer, are reduced when the product is used at a high temperature in an oxidizing and corrosive environment, in particular when currents flow through em hot aggressive gas, reduced. This increases the service life of thermal insulation layers which are bonded to the base body via the lining layer and the protective layer, since the lining layer flakes off at a later point in time due to the low growth of the thermally grown oxide.
  • TGO thermally grown oxide
  • the outer layer from a liquid phase, in particular galvanically, to an inner layer made of a MCrAlY alloy that has already been applied beforehand.
  • the inner layer can also be applied to the base body in a suitable manner, if appropriate also by deposition from a liquid phase.
  • the second MCrAlY alloy of the outer layer has the
  • the first MCrAlY alloy can be sprayed on conventionally.
  • the object directed to a method for producing a protective layer on a metallic base body of a product is achieved according to the invention in that an inner layer is applied with a first MCrAlY alloy and this inner layer is remelted in the area of its free surface so that an outer layer is formed, m which the MCrAlY alloy is essentially in the ⁇ phase.
  • a second MCrAlY alloy can be deposited from a liquid phase, in particular galvanically, the second MCrAlY alloy forming the outer layer and being essentially in the ⁇ phase.
  • a protective layer for protection against corrosion is attached to the metallic base body, which has an inner layer made of a first adhesive alloy and one attached to the base body the inner layer has an outer layer bonded with a second Haf alloy, the second adhesive alloy being predominantly, preferably almost completely, in the ⁇ phase and a thin layer of aluminum oxide bonded predominantly with the ⁇ phase and one being attached to the outer layer Thermal insulation layer is connected.
  • the first adhesive alloy and the second adhesive alloy are each preferably a (same) alloy of the MCrAlY type, modified depending on the requirement by adding one alloy element or several alloy elements, in particular rhenium.
  • the basic body preferably consists of a nickel-based or cobalt-based superalloy, optionally also an iron-based superalloy.
  • 1 shows a perspective view of a gas turbine rotor blade and 2 shows a section of a section perpendicular to the surface of the gas turbine blade.
  • the product 1 shown in FIG. 1, a gas turbine blade 1, has a metallic base body 2 made of a nickel-based or cobalt-based superalloy.
  • a protective layer 3, 4 serving as an adhesive layer and consisting of an inner layer 3 which is directly connected to the basic body 2 and an outer layer 4 connected to the inner layer 3 is applied to the basic body 2.
  • the inner layer 3 has a first alloy of the MCrAlY type and the outer layer has a second alloy also of the MCrAlY type, the second alloy being present essentially, preferably almost completely, in the ⁇ phase.
  • An application layer 5 is arranged between the protective layer 3, 4 and the thermal insulation layer 6.
  • This application layer 5 preferably consists of a thermally grown oxide, in particular aluminum oxide.
  • This thermally grown oxide is already present in the stable ⁇ -phase at the beginning of the oxidation, the formation of the ⁇ -phase being caused by the ⁇ -phase in the outer layer 4 at the beginning of the oxidation.
  • the oxide growing up in the stable ⁇ phase has a significantly smaller layer thickness.

Abstract

L'invention concerne un produit (1), en particulier une aube de turbine à gaz (1), comportant un corps de base métallique (2) auquel est liée une couche de protection (3, 4) anticorrosion. La couche de protection (3, 4) comprend une couche intérieure (3), qui est constituée d'un premier alliage MCrAlY, et une couche extérieure (4) avec un second alliage MCrAlY. Ce second alliage est principalement présent en phase η. L'invention concerne en outre un procédé permettant de produire une telle couche de protection (3, 4), la couche extérieure (4) étant obtenue par refusion d'une zone de la couche intérieure (3) ou par dépôt d'un alliage MCrAlY à partir d'une phase liquide.
EP99929016A 1998-04-29 1999-04-22 Produit pourvu d'une couche de protection anticorrosion, et procede de realisation d'une couche de protection anticorrosion Expired - Lifetime EP1082216B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19819026 1998-04-29
DE19819026 1998-04-29
PCT/DE1999/001217 WO1999055527A2 (fr) 1998-04-29 1999-04-22 Produit pourvu d'une couche de protection anticorrosion, et procede de realisation d'une couche de protection anticorrosion

Publications (2)

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EP1082216A2 true EP1082216A2 (fr) 2001-03-14
EP1082216B1 EP1082216B1 (fr) 2001-11-21

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US (2) US6610419B1 (fr)
EP (1) EP1082216B1 (fr)
JP (1) JP2002513081A (fr)
DE (1) DE59900691D1 (fr)
WO (1) WO1999055527A2 (fr)

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WO1999055527A3 (fr) 1999-12-16
JP2002513081A (ja) 2002-05-08
US6610419B1 (en) 2003-08-26
US20040005477A1 (en) 2004-01-08
EP1082216B1 (fr) 2001-11-21
DE59900691D1 (de) 2002-02-21
WO1999055527A2 (fr) 1999-11-04

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