EP1082216B1 - Erzeugnis mit einer schutzschicht gegen korrosion sowie verfahren zur herstellung einer schutzschicht gegen korrosion - Google Patents
Erzeugnis mit einer schutzschicht gegen korrosion sowie verfahren zur herstellung einer schutzschicht gegen korrosion Download PDFInfo
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- EP1082216B1 EP1082216B1 EP99929016A EP99929016A EP1082216B1 EP 1082216 B1 EP1082216 B1 EP 1082216B1 EP 99929016 A EP99929016 A EP 99929016A EP 99929016 A EP99929016 A EP 99929016A EP 1082216 B1 EP1082216 B1 EP 1082216B1
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- mcraly alloy
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- protective layer
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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
- C23C28/30—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
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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
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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
- C23C28/023—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
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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
- C23C28/30—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
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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
- C23C28/30—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
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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
- C23C28/30—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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- 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
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- Y10T428/12944—Ni-base component
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- 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 for Protection of the base body against corrosion, especially if the product is exposed to a hot, aggressive gas.
- the protective layer has an alloy of the MCrAlY type, where M is one or more elements from the group Iron, cobalt or nickel stands for Cr for chrome, Al for aluminum and Y for yttrium and / or an element from the group including scandium and the rare earths.
- the invention relates also a gas turbine blade with a protective layer and a method for producing a protective layer to protect a product against corrosion.
- EP 0 486 489 B1 describes a corrosion-resistant protective coating for medium and high temperatures up to approx 1050 ° C for a gas turbine part made of a nickel base or Cobalt-based alloy specified.
- the protective coating shows in weight% 25 to 40% nickel, 28 - 30% chromium, 7 - 9% aluminum, 1 - 2% silicon and 0.3 to 1% at least one reactive Element of the rare earth, at least 5% cobalt as well 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, on.
- the Protective coating only the elements nickel, chrome, aluminum, Silicon, yttrium and additionally rhenium in one area from 1 to 15% and a remainder made of cobalt. Through the Adding the rhenium shows the corrosion properties improved.
- Protective layers are also used in US Pat. No. 4,585,481 Protection of a metallic super alloy alloy substrate against high temperature oxidation and corrosion.
- For the protective layers are used in MCrAlY alloys. 5 to 40% chromium, 8 to 35% aluminum, 0.1 to 2% of an oxygen-active element from group IIIB of the periodic table including the lanthanides and actinides as well Mixtures thereof, 0.1 to 7% silicon, 0.1 to 3% hafnium and a radical comprising nickel and / or cobalt.
- the corresponding protective layers made of MCrAlY alloy according to US Pat. No. 4,585,481 by means of a plasma spraying process upset.
- German laid-open specification DE 196 09 690 A1 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 down to a depth of 5 to 50 ⁇ m, uniformly over the entire surface layer, 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 oxide cover layers made of Al 2 O 3 .
- cover layers made of aluminum oxide with an interrupted structure there is less tendency to spallation (flaking).
- WO 81/01983 A1 describes a method for producing a metallic component, which has a ceramic thermal barrier coating contains, specified. This is based on a substrate a super alloy with a clean surface a thin one Layer of an McrAlY alloy applied, this layer polished, an aluminum oxide layer is applied thereon and on the aluminum oxide layer by means of a columnar ceramic layer Gas deposition (vapor deposition) produced.
- EP 0 846 788 A1 relates to a product, in particular a product Gas turbine component, with a substrate on which one Protective layer made of and of an MCrAlY type alloy a ceramic thermal barrier coating is arranged.
- the substrate is a nickel-based superalloy that has chrome.
- a outer layer of the substrate is enriched with chromium, which diffuses into the substrate through a diffusion process is.
- the chromium has diffused into the substrate and forms a matrix that contains chromium dissolved in the nickel the gamma phase. The chromium is diffused in after the so-called "chroming" process.
- EP 0 718 420 A1 describes a method for applying a Thermal insulation layer described on a component made of a super alloy.
- the thermal insulation layer is made of different Layers built up.
- the super alloy product immediately borders a layer of a platinum group metal on.
- This layer of the platinum group metal consists of an outer layer and an inner layer, the outer layer being the metal of the platinum group in the Gamma phase.
- On the outer part of the layer the metal of the platinum group is made of aluminum Coating arranged. There is a thin oxide layer on top and then a ceramic coating is placed on top of it.
- US-PS 4,321,310 and US-PS 4,321,311 are each Coating systems for a component of a turbine known in which a protective layer on the component an MCrAlY alloy is applied to which a Aluminum oxide layer as an adhesion promoter layer or Connection layer connects, and on the one ceramic Thermal insulation layer is applied.
- the two documents deal with this coating system underlying problem of connecting the thermal insulation layer to the MCrAlY protective layer via the aluminum oxide bonding layer.
- U.S. Patent 4,321,310 provided the surface of the Polish aluminum oxide bonding layer.
- According to the US PS 4,321,311 will be a new one for an improved connection Microstructure of the ceramic thermal barrier coating proposed.
- the object of the invention is to provide a product with a metallic Basic body and one attached to it Coating system consisting of a protective layer, one Connection layer and a heat insulation layer as well as a Process for producing such a coating system specify where a good connection of the thermal insulation layer is guaranteed.
- a protective layer made of an MCrAlY alloy is applied, with a thin bonding layer Aluminum oxide and a thermal insulation layer applied thereon is, wherein the protective layer is an inner layer of a first MCrAlY alloy and an outer layer of one second MCrAlY alloy, which is predominantly in the ⁇ phase is present, and the aluminum oxide predominantly in the ⁇ phase is present.
- an alloy of the MCrAlY type is understood to be an alloy that contains a proportion of chromium Aluminum and a reactive element such as yttrium and / or comprise at least one equivalent metal from the group Scandium and rare earth elements.
- Alloy component such as rhenium, silicon, Hafnium, tantalum, zircon, tungsten, magnesium or niobium.
- a proportion of rhenium can lead to an improvement corrosion resistance.
- the rest contains the MCrAlY alloy one or more elements of the group Iron, cobalt and nickel, which is symbolically abbreviated to M. is.
- Such an MCrAlY alloy is preferably used as Corrosion protection layer on metallic components, in particular with a base body made of a super alloy (Nickel or cobalt super alloy, possibly also iron super alloy), which is an elevated temperature and is exposed to a hot, aggressive gas.
- a super alloy Nickel or cobalt super alloy, possibly also iron super alloy
- the crucial one There is an advantage of the MCrAlY alloy specified here in that they are very good as an adhesive layer for safe and permanent connection of the thermal insulation layer. In order to a coating system is produced, which both is corrosion and oxidation inhibiting and use of the product at a high temperature, for example over 1,000 ° C.
- the outer layer which has a MCrAlY alloy, which is predominantly in the ⁇ phase takes place at an oxidation of the outer layer a growth of an aluminum oxide (thermally grown oxide) instead, which in the Areas of the ⁇ phase of the MCrAlY alloy in the ⁇ modification is present.
- an aluminum oxide thermalally grown oxide
- the aluminum oxide is therefore predominantly in the stable ⁇ -modification. This has the advantage that compared to one growing up first in the ⁇ phase Aluminum oxide, the aluminum oxide layer with greater density, lower oxidation speed and smoother structure grows up so that a longer adhesion of the aluminum oxide layer is guaranteed on the outer layer.
- the invention is based on the knowledge that on a MCrAlY layer surface partial in the initial state of the oxidation or completely a ⁇ phase of the aluminum oxide is formed there, where the MCrAlY alloy is in the ⁇ phase. That in the ⁇ -phase growing aluminum oxide has a low density, a high rate of oxidation and a pointed structure on, so that, although later a certain layer thickness sets the stable ⁇ -modification, a failure, i.e. chipping that can occur on the alumina layer. It is therefore particularly favorable if the MCrAlY alloy in the outer layer almost completely single-phase in the ⁇ phase is present.
- the second MCrAlY alloy preferably has the same chemical composition like the first MCrAlY alloy, depending on the properties of the individual alloy components also differences in a few percent by weight or a few tenths of a percent by weight of each, corresponding alloy components of the first MCrAlY alloy and the second MCrAlY alloy are present can. It is also possible that the second MCrAlY alloy additional or alternative alloying elements of the first MCrAlY alloy.
- the outer layer is preferably on average between 5 microns and 50 ⁇ m thick, especially less than 20 ⁇ m.
- the entire middle Layer thickness of the protective layer is preferably between 100 ⁇ m and 200 ⁇ m,
- the first MCrAlY alloy and / or the second MCrAlY alloy the following alloy components ( Figures in percent by weight) on: 15 to 35% chromium; 7 to 18 % Aluminum; 0.3 to 2% yttrium and / or at least one equivalent Element from the group comprising Scandium and the Rare earth elements and optionally 0 to 20% rhenium as well as other optional alloy elements such as hafnium, silicon, Tantalum, zircon, tungsten, magnesium and niobium.
- the amount rhenium is preferably between 1% and 20%, in particular between 5% to 11%.
- the connection 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 in the ⁇ -phase, preferably almost exclusively of aluminum oxide in the ⁇ -phase, the bonding 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 connection layer which has almost exclusively aluminum oxide from the start of oxidation in the ⁇ phase is particularly advantageous, since this results in a uniform, homogeneous, low growth of the connection layer.
- the thermal insulation layer applied to the connection layer preferably has a columnar microstructure, where the axis direction of the in the columnar microstructure existing crystallites essentially perpendicular to the surface of the basic body is.
- the thermal barrier coating preferably has a thickness of between 150 and 300 ⁇ m, preferably about 200 ⁇ m.
- the columnar, stem-shaped crystallites preferably have an average diameter of less than 5 ⁇ m, in particular less than 2.5 ⁇ m.
- the thermal barrier coating preferably has a ceramic, which in particular with yttrium oxide is partially stabilized zirconium oxide.
- the product can also comprise other thermal insulation layers tertiary oxides, spinels or mullites are used.
- the product is preferably a component of a gas turbine, in particular a gas turbine blade, a moving blade or a vane.
- a protective layer of the above Kind as well as one over a connection layer
- Alumina-bonded thermal barrier coating is preferred Gas turbine blades of the first two rows of guide vanes and the first row of blades immediately downstream of one Combustion chamber of a gas turbine coated.
- the outer layer of the protective layer is preferably remelted the inner layer is produced in the area of its surface, i.e. an area of the inner layer is remelted.
- This remelting is preferably done by electron beams or ion beams carried out, which rapidly melt without a significant change in chemical Composition of the MCrAlY alloy in the outer layer and cause the inner layer.
- By melting the free, i.e. untreated surface of the MCrAlY alloy of the inner layer by electron beams, ion beams or the like it is possible in the upper fringes of some Micrometers an essentially pure, temperature-stable ⁇ phase to generate, which forms the outer layer.
- This ⁇ phase causes, as already stated above, that immediately during the formation of an oxide layer on the Surface of the outer layer is a stable, dense and thin ⁇ -aluminum oxide layer, the connection layer, forms.
- the oxide formed by oxidation mainly aluminum oxide, is called thermally grown oxide (thermally grown oxide, TGO).
- TGO thermally grown oxide
- the formation of this oxide, the connection layer can both before applying the thermal barrier coating as well as during and after the application of the thermal barrier coating respectively.
- the thermal barrier coating is preferred here applied by vapor deposition.
- TGO thermal grown Oxides
- the outer layer from a liquid Phase, in particular galvanically, on a previously apply the inner layer made of a MCrAlY alloy.
- the inner layer can be suitably and If necessary, also by separating from a liquid phase to be applied to the base body.
- the second MCrAlY alloy of the outer layer has the Composition of a ⁇ phase.
- the first MCrAlY alloy can be sprayed on conventionally.
- the on a process of making a protective layer directed a metallic base body of a product The object is achieved in that an inner layer is applied with a first MCrAlY alloy and this inner layer in the area of its free surface like this is remelted that an outer layer is formed in which the MCrAlY alloy is essentially in the ⁇ phase.
- a protective layer on the metallic base body (Adhesive layer) tied to protect against corrosion is made of an inner layer attached to the base body a first adhesive alloy and one bonded to the inner layer Has an outer layer with a second adhesive alloy, the second adhesive alloy predominantly, preferably almost completely, in the ⁇ phase and to the Outer layer a thin bonding layer with aluminum oxide predominantly connected to the ⁇ phase and attached to it a thermal insulation layer is connected.
- the first adhesive alloy and the second adhesive alloy are preferably each one (same) Alloy of the type MCrAlY, modified depending on the requirement by adding one alloy element or several alloy elements, especially rhenium.
- the base body preferably consists of a nickel-based or cobalt-based superalloy, possibly also an iron-based superalloy.
- the product especially the gas turbine blade, with the protective layer, the connection layer and the Thermal insulation layer explained in more detail.
- the product 1 shown in Figure 1, a gas turbine blade 1, has a metallic base body 2 a nickel-based or cobalt-based superalloy.
- the base body 2 serves as an adhesive layer Protective layer 3, 4 from an inner layer 3, the immediate is connected to the base body 2, and one to the Inner layer 3 attached outer layer 4 applied.
- the Inner layer 3 has a first alloy of the MCrAlY type and the outer layer a second alloy also of the type MCrAlY, the second alloy being essentially, preferably almost completely, in the ⁇ phase.
- this protective layer 3, 4 serving as an adhesive layer is a Thermal insulation layer 6 tied, which preferably consists of a stem-shaped ceramics, for example partially stabilized with yttrium oxide Zirconium oxide exists.
- connection layer 5 is preferably made from a thermally grown oxide, in particular Alumina.
- This thermally grown oxide is already there at the beginning of the oxidation in the stable ⁇ phase before the immediate formation of the ⁇ phase at the beginning of the oxidation is caused by the ⁇ phase in the outer layer 4.
- a thermally grown oxide which is predominantly Growing up in the ⁇ phase shows that in the stable ⁇ phase growing oxide a significantly smaller layer thickness on.
- the thermal insulation layer 6 On the outer surface 8 of the thermal insulation layer 6 flows in one use of the gas turbine blade 1 in one illustrated gas turbine passing a hot aggressive gas 9, which by the protective layer 3, 4 of the connection layer 5 and the thermal insulation layer 6 layer system effective from the metallic base body 2 physically and is chemically kept away.
- a hot aggressive gas 9 which by the protective layer 3, 4 of the connection layer 5 and the thermal insulation layer 6 layer system effective from the metallic base body 2 physically and is chemically kept away.
- This is particularly beneficial in the case of a gas turbine blade 1 and in the case of a gas turbine guide blade, which the directly from a not shown Combustion chamber outflowing hot gas of up to over 1300 ° C is exposed.
Description
- FIG 1
- eine perspektivische Darstellung einer Gasturbinenlaufschaufel und
- FIG 2
- einen Ausschnitt eines Schnittes senkrecht zur Oberfläche der Gasturbinenlaufschaufel.
Claims (12)
- Erzeugnis (1), insbesondere eine Komponente einer Gasturbine, mit einem metallischen Grundkörper (2), auf den eine Schutzschicht (3,4) aus einer MCrAlY-Legierung aufgebracht ist, auf die eine dünne Anbindungsschicht (5) mit Aluminiumoxid und darauf eine Wärmedämmschicht (6) aufgebracht ist, wobei M für Fe, Ni, Co oder eine Mischung daraus sowie Y für Yttrium und/oder zumindest ein äquivalentes Element aus der Gruppe umfassend Scandium und die Elemente der Seltenen Erden stehen, dadurch gekennzeichnet, daß die Schutzschicht (3,4) eine Innenschicht (3) aus einer ersten MCrAlY-Legierung und eine Außenschicht (4) aus einer zweiten MCrAlY-Legierung aufweist, die überwiegend in der γ-Phase vorliegt, und daß das Aluminiumoxid überwiegend in der α-Phase vorliegt.
- Erzeugnis nach Anspruch 1,
dadurch gekennzeichnet, daß die zweite MCrAlY-Legierung die gleiche chemische Zusammensetzung wie die erste MCrAlY-Legierung aufweist. - Erzeugnis nach Anspruch 1 oder 2,
dadurch gekennzeichnet, daß die Außenschicht (4) zwischen 5 µm und 50 µm, insbesondere zwischen 5 um und 20 µm dick ist. - Erzeugnis nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß die erste MCrAlY-Legierung und/oder die zweite MCrAlY-Legierung als Legierungskomponenten enthalten / enthält (Angaben in Gewichtsprozent):15 bis 35 % Chrom;7 bis 18 % Aluminium;0,3 bis 2 % Yttrium und/oder zumindest eine äquivalentes Element Metall aus der Gruppe umfassend Scandium, die Elemente der Seltenen Erden; sowie0 bis 20 % Rhenium.
- Erzeugnis nach Anspruch 4,
dadurch gekennzeichnet, daß der Anteil an Rhenium zwischen 1 % und 20%, insbesondere 5 % bis 11%, beträgt. - Erzeugnis nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, daß die Anbindungsschicht (5) zu Beginn eines Oxidationsprozesses zwischen 0,3 µm und 0,6 µm dick ist. - Erzeugnis nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, daß die Wärmedämmschicht (6) eine kolumnare Mikrostruktur aufweist, wobei die Achsenrichtung der Kristallite im Wesentlichen senkrecht auf der Oberfläche des Grundkörpers (1) steht. - Erzeugnis nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, daß die Wärmedämmschicht (6) eine Keramik aufweist, insbesondere Zirkonoxid (ZrO2), welches teilstabilisiert mit Yttriumoxid (Y2O3) ist. - Erzeugnis nach einem der vorhergehenden Ansprüche,
dadurch gekennzeichnet, daß die Außenschicht (4) durch Umschmelzen der Innenschicht (3) im Bereich ihrer freien Oberfläche, insbesondere durch Elektronenstrahlen oder Ionenstrahlen, hergestellt ist. - Erzeugnis (1) nach einem der Ansprüche 1 bis 11,
dadurch gekennzeichnet, daß die Außenschicht (4) aus einer flüssigen Phase, insbesondere galvanisch, abgeschieden ist. - Verfahren zur Herstellung eines Beschichtungssystems umfassend eine Schutzschicht (3,4), eine Anbindungsschicht (5) und eine Wärmedämmschicht (6) auf einem metallischen Grundkörper (2) eines Erzeugnisses (1),
dadurch gekennzeichnet, daß auf den Grundkörper (2) als Schutzschicht (3,4) eine Innenschicht (3) mit einer MCrAlY-Legierung aufgebracht und die Innenschicht (3) im Bereich ihrer freien Oberfläche so umgeschmolzen wird, daß eine Außenschicht (4) gebildet ist, in der die MCrAlY-Legierung im wesentlichen in der γ-Phase vorliegt, daß auf der Außenschicht (4) die Anbindungsschicht (5) mit Aluminiumoxid überwiegend in der α-Phase ausgebildet wird, und dass auf die Anbindungsschicht (5) die Wärmedämmschicht (6) aufgebracht wird. - Verfahren zur Herstellung eines Beschichtungssystems umfassend eine Schutzschicht (3,4), eine Anbindungsschicht (5) und eine Wärmedämmschicht (6) auf einem metallischen Grundkörper (2) eines Erzeugnisses (1),
dadurch gekennzeichnet, daß auf den Grundkörper (2) als Schutzschicht (3,4) eine Innenschicht (3) mit einer ersten MCrAlY-Legierung aufgebracht wird und auf die Innenschicht (3) aus einer flüssigen Phase, insbesondere galvanisch, eine zweite MCrAlY-Legierung abgeschieden wird, die eine Außenschicht (4) bildet und im wesentlichen in der γ-Phase vorliegt, daß auf der Außenschicht (4) die Anbindungsschicht (5) mit Aluminiumoxid überwiegend in der α-Phase ausgebildet wird, und dass auf die Anbindungsschicht (5) die Wärmedämmschicht (6) aufgebracht wird.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19819026 | 1998-04-29 | ||
DE19819026 | 1998-04-29 | ||
PCT/DE1999/001217 WO1999055527A2 (de) | 1998-04-29 | 1999-04-22 | Erzeugnis mit einer schutzschicht gegen korrosion sowie verfahren zur herstellung einer schutzschicht gegen korrosion |
Publications (2)
Publication Number | Publication Date |
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EP1082216A2 EP1082216A2 (de) | 2001-03-14 |
EP1082216B1 true EP1082216B1 (de) | 2001-11-21 |
Family
ID=7866085
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
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EP99929016A Expired - Lifetime EP1082216B1 (de) | 1998-04-29 | 1999-04-22 | Erzeugnis mit einer schutzschicht gegen korrosion sowie verfahren zur herstellung einer schutzschicht gegen korrosion |
Country Status (5)
Country | Link |
---|---|
US (2) | US6610419B1 (de) |
EP (1) | EP1082216B1 (de) |
JP (1) | JP2002513081A (de) |
DE (1) | DE59900691D1 (de) |
WO (1) | WO1999055527A2 (de) |
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- 1999-04-22 WO PCT/DE1999/001217 patent/WO1999055527A2/de active IP Right Grant
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6924046B2 (en) | 2001-10-24 | 2005-08-02 | Siemens Aktiengesellschaft | Rhenium-containing protective layer for protecting a component against corrosion and oxidation at high temperatures |
EP2098615A1 (de) | 2002-07-09 | 2009-09-09 | Siemens Aktiengesellschaft | Hochoxidationsbeständige Komponente |
EP2098614A1 (de) | 2002-07-09 | 2009-09-09 | Siemens Aktiengesellschaft | Hoch oxidationsbeständiges Bauteil |
US7695827B2 (en) | 2004-12-30 | 2010-04-13 | Siemens Aktiengesellschaft | Component with a protective layer |
EP1837485A1 (de) | 2006-03-24 | 2007-09-26 | Forschungszentrum Jülich Gmbh | Component mit einer Schutzschicht |
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 |
Also Published As
Publication number | Publication date |
---|---|
JP2002513081A (ja) | 2002-05-08 |
US20040005477A1 (en) | 2004-01-08 |
DE59900691D1 (de) | 2002-02-21 |
WO1999055527A3 (de) | 1999-12-16 |
WO1999055527A2 (de) | 1999-11-04 |
EP1082216A2 (de) | 2001-03-14 |
US6610419B1 (en) | 2003-08-26 |
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