EP1029100A1 - Produit pourvu d'un systeme stratifie pour la protection contre un gaz chaud agressif - Google Patents

Produit pourvu d'un systeme stratifie pour la protection contre un gaz chaud agressif

Info

Publication number
EP1029100A1
EP1029100A1 EP98959748A EP98959748A EP1029100A1 EP 1029100 A1 EP1029100 A1 EP 1029100A1 EP 98959748 A EP98959748 A EP 98959748A EP 98959748 A EP98959748 A EP 98959748A EP 1029100 A1 EP1029100 A1 EP 1029100A1
Authority
EP
European Patent Office
Prior art keywords
product
lanthanum
hafnium
aluminum
yttrium
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
EP98959748A
Other languages
German (de)
English (en)
Other versions
EP1029100B1 (fr
Inventor
Wolfram Beele
Beate Heimberg
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 EP1029100A1 publication Critical patent/EP1029100A1/fr
Application granted granted Critical
Publication of EP1029100B1 publication Critical patent/EP1029100B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

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
    • C23C28/30—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
    • 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
    • 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

Definitions

  • the invention relates to a product with a metallic base orper and a layer system thereon to protect the base body against a hot aggressive gas, with an adhesive layer made of an alloy of the type MCrAlY.
  • an alloy of the type MCrAlY stands for one or more elements from the group iron, cobalt and nickel, Cr for chromium, Al for aluminum and Y for yttrium and / or an element of the rare earths.
  • EP 0 486 489 B1 describes a corrosion-resistant protective coating for medium and high temperatures up to approximately
  • the protective coating has 25 to 40% nickel, 28 to 32% chromium, 7 to 9% aluminum, 1 to 2% silicon and 0.3 to 1% of at least one reactive element of the rare earths, at least 5% cobalt and optionally 0 up 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 only has 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. 4,321,310 describes a gas turbine component which has a basic body made of a nickel-based superalloy MAR-M-200.
  • a layer of an MCrAlY alloy, in particular a NiCOCrAlY alloy with 18% chromium, 23% cobalt, 12.5% aluminum, 0.3% yttrium and a remainder made of nickel is applied to the base material.
  • This layer of the MCrAlY alloy has a polished Surface on which an aluminum oxide layer is applied.
  • a ceramic heat dam layer is applied to this aluminum oxide layer, which has a stalk-shaped structure.
  • 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.
  • the corresponding protective layers made of MCrAlY alloys are applied according to US Pat. No. 4,585,481 by means of a plasma spraying process.
  • US Pat. No. 4,339,509 also relates to the application of a protective layer to a superalloy for protection against oxidation and sulfidation.
  • the protective layer is again of the MCrAlY type with 10 to 35% chromium, 5 to 15% aluminum, 0.1 to 10% magnesium, up to 8% tantalum, up to 5% tungsten, up to 12% silicon, up to 10% hafnium and 5 up to 35% cobalt and a remainder made of nickel.
  • the alloy has 15 to 40% chromium, 3 to 13% aluminum, 0.1 to 10% magnesium, up to 5% tantalum, up to 2% tungsten, up to 12% silicon, up to 10% hafnium and a balance of cobalt.
  • the alloy can at least have a single element from the group of lanthanum, yttrium or other rare earths up to 15%.
  • the only specifically disclosed embodiment of the alloy of the protective layer has yttrium alone or yttrium with an addition of tungsten and tantalum. Alloys containing lanthanum have at least a further proportion of tantalum, magnesium or titanium in addition to a proportion of nickel, cobalt, chromium and aluminum.
  • WO 96/3582 AI specifies a thermal barrier layer for a turbine blade made of a superalloy which is exposed to a hot gas.
  • the product layer here has a ceramic protective layer which is attached to an adhesion promoter layer made of an aluminide or an alloy of the type
  • MCrAlY is connected.
  • the nickel-based alloy with a proportion of hafnium Mar-M247 and the cobalt-based alloy Mar-M509 with a proportion of zircon are specified as superalloys.
  • a MCrAlY alloy with a proportion of 10 to 35% chromium, 5 to 15% aluminum and 0.01 to 1% of one of the elements yttrium, hafnium or lanthanum is indicated on this.
  • Oxidation of aluminum in the adhesion promoter layer creates an aluminum oxide layer, which enables the ceramic protective layer to be bonded to the adhesion promoter layer.
  • Partially stabilized zirconium oxide is used as the ceramic protective layer, the stabilization being able to be carried out using calcium oxide, magnesium oxide, cerium oxide or yttrium oxide.
  • the object of the invention is to provide a product with a metallic base body and a layer system located thereon, which has an adhesive layer with an alloy for connecting a thermal insulation layer, in particular with a ternary oxide.
  • the object is achieved by a product in which the adhesive layer is an alloy (details below sometimes in percent by weight) with 3 to 50% chromium, 3 to 20% aluminum, 0 to 0.5% yttrium and / or a rare earth element, 0.1 to 10% lanthanum, 0 to 10% hafnium, 0 to 10 % Magnesium, 0 to 2% silicon and one or more elements from the group comprising iron, cobalt and nickel.
  • the adhesive layer is an alloy (details below sometimes in percent by weight) with 3 to 50% chromium, 3 to 20% aluminum, 0 to 0.5% yttrium and / or a rare earth element, 0.1 to 10% lanthanum, 0 to 10% hafnium, 0 to 10 % Magnesium, 0 to 2% silicon and one or more elements from the group comprising iron, cobalt and nickel.
  • the alloy of the adhesive layer corresponds to an MCrAlY alloy with an addition of 0.1% to 10% lanthanum and at least 0.01 to 0.5% yttrium and / or at least 0.1 to 10% hafnium. Due to the addition of lanthanum, the adhesive layer is not only suitable, common thermal insulation layers, in particular ceramic thermal insulation layers, with zirconium oxide, e.g. partially stabilized with yttrium oxide to bind to the body. It is also suitable for connecting ceramic thermal insulation layers with ternary oxides.
  • Such ternary oxides contain oxygen as the third element and preferably nickel, magnesium or cobalt as the first element and aluminum or chromium as the second element.
  • the first element of the ternary oxide is calcium or lanthanum and the second element is aluminum, zirconium or hafnium.
  • the adhesive layer enables the production of a chemically suitable interface composite.
  • This good adhesion to a thermal insulation layer made of a ternary oxide is achieved by lanthanum oxide formed due to oxidation of the adhesive layer and, if appropriate, additional hafnium oxide formed. Oxidation of the lanthanum-containing adhesive layer can result in a thermally grown intermediate layer of lanthanum-containing bonding oxides on the surface of the adhesive layer facing away from the base body, to which the thermal insulation layer bonds well.
  • An intermediate layer also referred to as an application layer, can have aluminum oxide (A1 2 0 3 ), chromium oxide (Cr 2 0 3 ) and / or hafnium oxide (Hf0 2 ) in addition to lanthanum oxide (La 2 0 3 ).
  • An intermediate Layer can be produced separately as a separate layer by coating processes.
  • a preferred alloy of the adhesive layer has 15 to 25% chromium, 10 to 20% aluminum, 0.01 to 0.3% yttrium, 0 to 33% cobalt and 0.1% to 2% lanthanum, 0.1 to 2% hafnium apart from production-related impurities, no magnesium and no silicon, and a remainder made of nickel.
  • the proportion of lanthanum can be 0.1 to 5%, the proportion of hafnium 0 to 2%, the proportion of magnesium 0.1 to 2% and the proportion of silicon 0 to 2%.
  • the alloy of the adhesive layer has 3 to 15% chromium, 3 to 10% aluminum, 0.5 to 10% lanthanum, 0 to 10% hafnium, 0 to 2% magnesium, 0.01 to 0, 3% yttrium, except for production-related impurities, no silicon, 0 to 33% cobalt and a remainder made of nickel. It is also possible here that a further rare earth element, scandium or an element of the lanthanides, such as cerium, is used instead of or in addition to yttrium. If necessary, an element of the actinides can also be added.
  • the alloy preferably has a combination of lanthanum, hafnium and yttrium in the ranges of lanthanum 0.5 to 10%, hafnium 0.5 to 10% and yttrium 0.1 to 0.5%.
  • the alloy has cobalt between 0 and 33%, chromium between 15 and 25%, aluminum 10 to 20%, hafnium 0.5 to 2%, yttrium 0.01 to
  • the proportion of lanthanum is between 0.5 and 5%, of magnesium between 0.1 to 2% and of silicon up to 2%.
  • the proportion of chromium is 3 to 15%, aluminum 3 to 10%, lanthanum 0.5 to 10%, hafnium 0.5 to 10%, yttrium 0.01 to 0.3%, of magnesium 0 to 2%, of cobalt to 33% and a remainder of nickel, essentially no silicon being contained.
  • the lanthanum content is over 5%, preferably between 5 and 10%.
  • the chromium content is between 3 and 15%, aluminum between 3 and 10%, hafnium between 2 and 10%, magnesium between 0 and 10%, yttrium between 0.01 and 0.5%, of silicon between 0 and 2% and a remainder made of cobalt, nickel or a mixture thereof.
  • the alloy of the adhesive layer preferably has the elements lanthanum, hafnium and yttrium and optionally other elements of the rare earths with a total weight fraction of more than 2%. Up to a total of these elements of less than 5%, at least two of the elements mentioned are present in the alloy at the same time.
  • the alloys, in which at least two of the components lanthanum, hafnium and yttrium are always present, as well as the alloy with a weight fraction of more than 5% lanthanum are, in addition to the application of a ternary oxide, also preferred for the application of conventional zirconium oxide-based thermal insulation systems.
  • the product is preferably a component of a gas turbine, in particular a rotor blade, a guide blade or a heat shield element.
  • the basic body preferably consists of a nickel-based or cobalt-based alloy.
  • FIG. 1 shows a perspective view of a gas turbine rotor blade
  • FIG. 2 shows a section through the basic body and layer of the gas turbine rotor blade according to FIG. 1.
  • the gas turbine blade 1 shown in FIG. 1 has a metallic base body 2 made of a nickel-based or cobalt-based superalloy.
  • an adhesive layer 7 made of an alloy comprising chromium, aluminum, yttrium, lanthanum, hafnium, magnesium, silicon and a remainder composed of one or more elements from the group comprising iron, cobalt and nickel is applied to the base body 2.
  • a thermal insulation layer 5 made of a ternary oxide is applied to this adhesive layer 7.
  • an attachment layer 8 of lanthanum-containing adhesive oxides is formed, in particular by oxidation of the adhesive layer 7.
  • the thermal insulation layer is well bonded to the metallic base body 2 via the adhesive layer 7.
  • the invention is characterized by an adhesive layer made of an alloy of the MCrAlY type with the addition of lanthanum, whereby in particular the application of a ternary oxide, particularly including lanthanum, is given.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Laminated Bodies (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)

Abstract

L'invention concerne un produit (1) comportant un corps de base (2) métallique sur lequel se trouve un système stratifié (3) servant à la protection dudit corps de base (2) contre un gaz (4) chaud agressif. Le système stratifié (3) comporte une couche adhésive (7), constituée d'un alliage MCrAlY auquel sont ajoutés 0,1 % à 10 % de lanthane et 0 à 10 % d'hafnium.
EP98959748A 1997-11-03 1998-10-21 Produit pourvu d'un systeme stratifie pour la protection contre un gaz chaud agressif Expired - Lifetime EP1029100B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19748506 1997-11-03
DE19748506 1997-11-03
PCT/DE1998/003092 WO1999023270A1 (fr) 1997-11-03 1998-10-21 Produit pourvu d'un systeme stratifie pour la protection contre un gaz chaud agressif

Publications (2)

Publication Number Publication Date
EP1029100A1 true EP1029100A1 (fr) 2000-08-23
EP1029100B1 EP1029100B1 (fr) 2001-09-19

Family

ID=7847452

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98959748A Expired - Lifetime EP1029100B1 (fr) 1997-11-03 1998-10-21 Produit pourvu d'un systeme stratifie pour la protection contre un gaz chaud agressif

Country Status (5)

Country Link
US (1) US6416882B1 (fr)
EP (1) EP1029100B1 (fr)
JP (1) JP2001521987A (fr)
DE (1) DE59801544D1 (fr)
WO (1) WO1999023270A1 (fr)

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Also Published As

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EP1029100B1 (fr) 2001-09-19
WO1999023270A1 (fr) 1999-05-14
DE59801544D1 (de) 2001-10-25
JP2001521987A (ja) 2001-11-13
US6416882B1 (en) 2002-07-09

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