EP1902160A1 - Ceramic heat insulating layer - Google Patents

Ceramic heat insulating layer

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Publication number
EP1902160A1
EP1902160A1 EP06764032A EP06764032A EP1902160A1 EP 1902160 A1 EP1902160 A1 EP 1902160A1 EP 06764032 A EP06764032 A EP 06764032A EP 06764032 A EP06764032 A EP 06764032A EP 1902160 A1 EP1902160 A1 EP 1902160A1
Authority
EP
European Patent Office
Prior art keywords
thermal barrier
barrier coating
component
intermetallic compound
adhesive layer
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
EP06764032A
Other languages
German (de)
French (fr)
Other versions
EP1902160B1 (en
Inventor
Mohamed Youssef Nazmy
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.)
General Electric Technology GmbH
Original Assignee
Alstom Technology AG
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Filing date
Publication date
Application filed by Alstom Technology AG filed Critical Alstom Technology AG
Publication of EP1902160A1 publication Critical patent/EP1902160A1/en
Application granted granted Critical
Publication of EP1902160B1 publication Critical patent/EP1902160B1/en
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • 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
    • 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
    • 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
    • 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
    • C23C28/36—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including layers graded in composition or 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • 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
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material

Definitions

  • the invention relates to the field of materials technology. It relates to a ceramic thermal barrier coating, which for coating thermally highly stressed components such. As blades of a gas turbine, is used.
  • thermal barrier coatings thermal barrier coatings
  • TBC thermal barrier coatings
  • Y 2 O 3 yttrium oxide
  • ZrO 2 zirconium oxide
  • adhesive layers of MCrAIY are often provided between the thermal barrier coating and the surface of the component, where M stands for metal, specifically for Ni, Fe, Co or combinations thereof.
  • Plasma spraying such as.
  • Air Plasma Spraying APS low-pressure plasma spraying (LPPS), vacuum plasma spraying (VPS) or flame spraying, such.
  • High Velocity Oxygen Fuel (HVOF) as well as Physical Vapor Deposition (PVD), e.g. B. by electron beam (Electron Beam Physical Vapor Deposition EP-PVD) known (see, for example, US 6,352,788 B2, US 6,544,665 B2).
  • APS-sprayed TBCs have e.g. B. a high degree of inhomogeneities and porosity, which advantageously reduces the heat transfer through the TBC.
  • B a high degree of inhomogeneities and porosity
  • One of these countermeasures is, for example, the spraying of thicker layers. This is disadvantageous 3 B04 / 002-0
  • TBC layer thicknesses are approx. 250-300 ⁇ m.
  • Al2O 3 (at least 0.1-3 mol%) in the microstructure of a TBC bring.
  • the Al 2 O 3 does not combine with the matrix of the ceramic layer, but forms deposits and thus prevents grain growth. However, this does not have a positive influence on the voltage gradient and thus on the reduction of the danger of the TBC breaking away.
  • the aim of the invention is to avoid the mentioned disadvantages of the prior art.
  • the invention is based on the object, for coating a component of a nickel-base superalloy, of an improved ceramic thermal barrier coating based on yttrium oxide
  • Y2O 3 stabilized zirconia
  • Z1O2 which is characterized by a long life and high oxidation resistance and ductility.
  • this object is achieved in that the thermal barrier coating on the basis of yttria (Y2O 3 ) stabilized zirconia (ZrO 2 ) in addition to production-related impurities still at least one high-temperature and oxidation-resistant intermetallic compound whose volume fraction as a function of the distance from the surface of Nickel-based superalloy decreases continuously or stepwise, preferably in exponential or linear form.
  • Y2O 3 yttria
  • ZrO 2 stabilized zirconia
  • Superalloy and optionally applied thereon applied metallic adhesive layer component is characterized in that a) ceramic powder of yttria (Y2O 3 ) stabilized zirconia (Zr ⁇ 2) and powder of at least one intermetallic compound are mixed together, b) this powder mixture then by means of known thermal Spray method is sprayed either directly on the surface of the component or in the presence of a metallic adhesive layer directly on the metallic adhesive layer, c) the process steps a) and b) are repeated several times, wherein the
  • Powder mixture in each case has a smaller volume fraction of intermetallic compound than in the preceding process steps and the powder mixture is sprayed in each case on the already sprayed in the previous process step layer, so that ultimately a thermal barrier coating with a on the
  • the advantage of the invention is that a gradual change in the composition of the thermal barrier coating as a function of the thickness of the thermal barrier coating produces a less steep gradient of stress. This leads to a higher strain tolerance of the TBC layer and thus on the one hand to an increased service life at thermal
  • intermetallic compounds NiAl, alloyed NiAl, YRh or ErIr are used as intermetallic compounds. These intermetallic compounds are resistant to oxidation and have sufficient ductility in a wide temperature range. In addition, they have little tendency for interdiffusion and have a high melting point. 5 B04 / 002-0
  • the volume fraction of the intermetallic compound in the layer at the surface of the component is about 80% by volume and at the free surface is about 5%.
  • Fig. 1 is a perspective view of a blade of a
  • FIG. 2 shows a section along the line M-II in FIG. 1 and
  • FIG. 3 shows a schematic profile of the volume fractions in the TBC in FIG
  • the invention is applicable to all components which are exposed to high temperatures and oxidative / corrosive environmental influences, such. As blades, heat accumulation segments or parts of the combustion chambers of gas turbines.
  • Fig. 1 shows in perspective view as an example of such components 1, a blade of a gas turbine.
  • the blade 1 6 B04 / 002-0
  • the blade 1 consists of a blade root 2, a platform 3 and an airfoil 4, in which cooling air channels are present, whose openings are designated in Fig. 1 with 5.
  • the blade 1 is anchored with its blade root 2 in circumferential grooves in the rotor of the gas turbine, not shown.
  • the blade 4 is subjected to hot combustion gases, so that the surface 7 of the airfoil 4 is exposed to both the hot combustion gases and attacks by oxidation, corrosion and erosion.
  • the blade 4 is therefore provided on its outer surface 7 with a metallic adhesive layer 6 (not visible in FIG. 1) on which a ceramic thermal barrier coating 8 is sprayed.
  • the turbine blade may preferably consist of a single-crystal alloy, for example with the following chemical composition (in% by weight): 7.7-8.3 Cr, 5.0-5.25 Co, 2.0-2.1 Mo, 7.8-8.3 W, 5.8-6.1 Ta, 4.9-5.1 Al, 1.3-1.4 Ti, 0.11-0.15 Si, 0.11-0.15 Hf, 200-750 ppm C, 50-400 ppm B, balance nickel and manufacturing impurities.
  • These base materials are provided on their outer surface 7 with a metallic adhesive layer 6, preferably of the type MCrAIY, where M is metal (Ni, Co, Fe or combinations thereof).
  • M metal
  • NiCrAlY was used for the adhesive layer 6.
  • the Al-rich adhesive layers of this type form an Al 2 O 3 -Zdertik 9, which forms by thermal oxidation of the adhesive layer 6.
  • the TBC 8 consists of yttria (Y 2 O 3) stabilized zirconia (ZrO 2), with about 7% yttria is present.
  • the thermal barrier coating 8 is sprayed by means of known thermal spraying, for example by means of APS.
  • the ceramic powder is first mixed with powder of an intermetallic compound 12, in the present embodiment of nickel aluminide NiAl, and then this powder mixture is thermally sprayed onto the adhesive layer 6.
  • the volume fraction of the intermetallic compound 12 is very high, here 80 vol .-%.
  • FIG. 3 where the schematic profile of the volume fractions of intermetallic compounds 12 or of zirconium oxide (ZrO 2 ) stabilized with yttrium oxide (Y 2 O 3 ) in the thermal barrier coating 8 depends on the distance from the adhesive layer 6, ie from the Thickness of the thermal barrier coating 8 is shown.
  • the volume fraction of intermetallic compound 12 decreases continuously here exponentially. In other embodiments, it may also be linear or stepwise decreasing.
  • the ceramic thermal barrier coatings produced by APS consist of individual grains and have a relatively large porosity. In Fig. 2, these grains are with the 8 B04 / 002-0
  • the intermetallic compound 12, here NiAl preferably deposits in these pores 11.
  • the intermetallic compounds such as nickel aluminide, are resistant to oxidation and have sufficient ductility in a wide temperature range. In addition, they have little tendency for interdiffusion and have a high melting point. Due to the gradual change in the composition of the thermal barrier coating as a function of the thickness of the thermal barrier coating, a less steep stress gradient is advantageously generated in the layer. This leads to a higher elongation tolerance of the thermal barrier coating and thus on the one hand to increased life under thermal stress (no chipping) and on the other hand to the possibility to apply thicker thermal barrier coatings and thus use the coated components at higher temperatures.
  • layer thicknesses of approximately 250-300 ⁇ m could be sprayed by means of APS in the case of conventional yttria-stabilized zirconium oxide thermal barrier coatings, layer thicknesses of up to approximately 2 mm can easily be achieved in the present invention.
  • the invention is not limited to the embodiment described.
  • the following intermetallic compounds are also suitable for achieving the advantages according to the invention: YRh, ErIr and alloyed NiAl, since these intermetallic compounds are resistant to oxidation, have good ductility in all temperature ranges, and a low tendency for interdiffusion and high melting points to have. Due to the gradual grading of the volume fraction of intermetallic compound, a less steep voltage gradient is achieved, so that the thermal barrier coating is substantially more strain-tolerant and thus has a longer life under thermal stress. 9 B04 / 002-0
  • the inventive thermal barrier coatings can also be applied to other thermally highly loaded gas turbine components, such as heat shields or combustion chamber liner, wherein the base material of the component z.
  • B. Hastalloy or Haynes 230 may be and the adhesive layer z.
  • B. may be a NiCoCrAlY layer.
  • thermal spraying of the TBC according to the present invention also other spraying methods are suitable as APS, z. Eg EB-PVD.
  • the thermal barrier coatings produced are stalk-shaped.

Abstract

The invention relates to a ceramic heat insulating layer (8) for coating the surface (7) of a component (1), preferably a gas turbine component, which is composed of a nickel-base superalloy and a metallic adhesive layer (6) that is optionally applied thereto. The heat insulating layer (8) contains zirconium oxide (ZrO<SUB>2</SUB>) stabilized by means of yttria (Y<SUB>2</SUB>O<SUB>3</SUB>), production-related impurities, and at least one high temperature-resistant and oxidation-resistant intermetallic compound, e.g. NiAl, YRh, Erlr, whose volume fraction decreases continuously or gradually as the distance from the surface (7) of the component (1)/the adhesive layer (6) increases. The advantage of the invention lies in the fact that a less steep tensile gradient is obtained due to the gradual change of the composition of the heat insulating layer (8), resulting in greater elasticity tolerance of the heat insulating layer (8) and thus an increased service life under thermal stress (no flaking) while making it possible to apply thicker heat insulating layers (8) and therefore use the coated components (1) at higher temperatures.

Description

Keramische Wärmedämmschicht Ceramic thermal barrier coating
Technisches GebietTechnical area
Die Erfindung bezieht sich auf das Gebiet der Werkstofftechnik. Sie betrifft eine keramische Wärmedämmschicht, welche zum Beschichten thermisch hochbelasteter Bauteile, wie z. B. Laufschaufeln einer Gasturbine, eingesetzt wird.The invention relates to the field of materials technology. It relates to a ceramic thermal barrier coating, which for coating thermally highly stressed components such. As blades of a gas turbine, is used.
Stand der TechnikState of the art
Um die Effizienz von Gasturbinen zu erhöhen werden diese bei sehr hohen Betriebstemperaturen gefahren. Die den heissen Gasen ausgesetzten Bauteile, z. B. Leit- und Laufschaufeln oder Brennkammerelemente, werden daher bekanntermassen auf ihrer Oberfläche mit Wärmedämmschichten (Thermal Barrier Coatings, TBC) versehen, um höhere Betriebstemperaturen zu erreichen bzw. die Lebensdauer der Bauteile zu verlängern. Diese Wärmedämmschichten bestehen üblicherweise aus einem keramischen Material, meist aus mit Yttriumoxid (Y2O3) stabilisiertem Zirkonoxid (Zrθ2), das 2 B04/002-0 auf die Oberfläche der oftmals aus Nickelbasis-Superlegierungen bestehenden Bauteile aufgebracht wird. Um die Haftung der keramischen Schicht auf dem Bauteil zu verbessern, werden zwischen der Wärmedämmschicht und der Oberfläche des Bauteiles oftmals Haftschichten aus MCrAIY vorgesehen, wobei M für Metall, und zwar für Ni, Fe, Co oder Kombinationen daraus, steht.In order to increase the efficiency of gas turbines, they are operated at very high operating temperatures. The hot gases exposed components, eg. As guide and blades or combustion chamber elements are therefore known to be provided on its surface with thermal barrier coatings (thermal barrier coatings, TBC) to achieve higher operating temperatures and to extend the life of the components. These thermal barrier coatings usually consist of a ceramic material, usually of yttrium oxide (Y 2 O 3 ) stabilized zirconium oxide (ZrO 2), the 2 B04 / 002-0 is applied to the surface of components often made of nickel-based superalloys. In order to improve the adhesion of the ceramic layer on the component, adhesive layers of MCrAIY are often provided between the thermal barrier coating and the surface of the component, where M stands for metal, specifically for Ni, Fe, Co or combinations thereof.
Es ist bekannter Stand der Technik, die TBC thermisch aufzuspritzen. Als mögliche Verfahren zum Aufbringen dieser Schichten sind Plasmaspritzen, wie z. B. Plasmaspritzen in Luft (Air Plasma Spraying APS), Niederdruck- Plasmaspritzen (Low Pressure Plasma Spraying LPPS), Vakuum- Plasmaspritzen (Vacuum Plasma Spraying VPS) oder Flammenspritzen, wie z. B. Hochgeschwindigkeitsflammenspritzen (High Velocity Oxygen Fuel HVOF), sowie physikalische Dampfabscheidung (Physical Vapour Deposition PVD), z. B. mittels Elektronenstrahl (Electron Beam Physical Vapour Deposition EP-PVD) bekannt (siehe z. B. US 6,352,788 B2, US 6,544,665 B2).It is well known in the art to thermally spray on the TBC. As a possible method for applying these layers are plasma spraying, such as. As plasma spraying in air (Air Plasma Spraying APS), low-pressure plasma spraying (LPPS), vacuum plasma spraying (VPS) or flame spraying, such. High Velocity Oxygen Fuel (HVOF), as well as Physical Vapor Deposition (PVD), e.g. B. by electron beam (Electron Beam Physical Vapor Deposition EP-PVD) known (see, for example, US 6,352,788 B2, US 6,544,665 B2).
Mit Hilfe des EP-PVD-Verfahren werden säulenartige Schichten erzeugt, die eine dehnungstolerante Kornstruktur aufweisen, die fähig ist sich bei unterschiedlicher Beanspruchung auszudehnen oder zusammenzuziehen, so dass keine Spannungen erzeugt werden, welche beispielsweise zum Abplatzen der Schichten führen würden. Nachteilig sind bei diesem Verfahren aber die hohen Kosten.With the aid of the EP-PVD method, columnar layers are produced which have an expansion-tolerant grain structure that is capable of expanding or contracting under different stresses, so that no stresses are generated which would, for example, cause the layers to flake off. The disadvantage of this method but the high cost.
Im Gegensatz dazu haben APS-gespritze TBC z. B. einen hohen Grad an Inhomogenitäten und Porosität, was vorteilhaft den Wärmetransfer durch die TBC reduziert. Während des Betriebes einer Gasturbine erhöht aber sich durch Strukturveränderungen, z. B. Kornwachstum, die thermische Leitfähigkeit, so dass Gegenmassnahmen getroffen werden müssen um einen ausreichenden Wärmeschutz zu erreichen. Eine dieser Gegenmassnahmen ist beispielsweise das Spritzen dickerer Schichten. Dies ist nachteilig 3 B04/002-0In contrast, APS-sprayed TBCs have e.g. B. a high degree of inhomogeneities and porosity, which advantageously reduces the heat transfer through the TBC. During operation of a gas turbine but increased by structural changes, eg. As grain growth, the thermal conductivity, so that countermeasures must be taken to achieve adequate thermal protection. One of these countermeasures is, for example, the spraying of thicker layers. This is disadvantageous 3 B04 / 002-0
einerseits sehr teuer, andererseits praktisch oftmals nicht machbar. Übliche TBC-Schichtdicken sind ca. 250-300 μm.on the one hand very expensive, on the other hand practically impossible in many cases. Typical TBC layer thicknesses are approx. 250-300 μm.
Gemäss US 6,544,665 B2 wird deshalb vorgeschlagen, z. B. AI2O3 (mindestens 0.1-3 Mol-%) in die Mikrostruktur einer TBC einzubringen. Das AI2O3 verbindet sich nicht mit der Matrix der keramischen Schicht, sondern bildet Ablagerungen und verhindert damit das Kornwachstum. Einen positiven Einfluss auf den Spannungsgradienten und damit auf die Senkung der Abplatzgefahr der TBC hat dies aber nicht.According to US 6,544,665 B2 is therefore proposed, for. B. Al2O 3 (at least 0.1-3 mol%) in the microstructure of a TBC bring. The Al 2 O 3 does not combine with the matrix of the ceramic layer, but forms deposits and thus prevents grain growth. However, this does not have a positive influence on the voltage gradient and thus on the reduction of the danger of the TBC breaking away.
Darstellung der ErfindungPresentation of the invention
Ziel der Erfindung ist es, die genannten Nachteile des Standes der Technik zu vermeiden. Der Erfindung liegt die Aufgabe zu Grunde, zur Beschichtung einer Komponente aus einer Nickelbasis-Superlegierung eine verbesserte keramische Wärmedämmschicht auf der Grundlage von mit YttriumoxidThe aim of the invention is to avoid the mentioned disadvantages of the prior art. The invention is based on the object, for coating a component of a nickel-base superalloy, of an improved ceramic thermal barrier coating based on yttrium oxide
(Y2O3) stabilisiertem Zirkonoxid (Z1O2) zu entwickeln, welche sich durch eine hohe Lebensdauer und hohe Oxidationsbeständigkeit und Duktilität auszeichnet.(Y2O 3 ) stabilized zirconia (Z1O2), which is characterized by a long life and high oxidation resistance and ductility.
Erfindungsgemäss wird diese Aufgabe dadurch gelöst, dass die Wärmedämmschicht auf der Grundlage von mit Yttriumoxid (Y2O3) stabilisiertem Zirkonoxid (ZrO2) neben herstellungsbedingten Verunreinigungen noch mindestens eine hochtemperatur- und oxidationsbeständige intermetallische Verbindung aufweist, deren Volumenanteil in Abhängigkeit vom Abstand von der Oberfläche der Nickel- Basis-Superlegierung kontinuierlich oder stufenweise, vorzugsweise in exponentieller oder linearer Form, abnimmt.According to the invention, this object is achieved in that the thermal barrier coating on the basis of yttria (Y2O 3 ) stabilized zirconia (ZrO 2 ) in addition to production-related impurities still at least one high-temperature and oxidation-resistant intermetallic compound whose volume fraction as a function of the distance from the surface of Nickel-based superalloy decreases continuously or stepwise, preferably in exponential or linear form.
Das erfindungsgemässe Verfahren zum Aufbringen der beschriebenen Wärmedämmschicht auf die Oberfläche einer aus einer Nickel-Basis- 4 B04/002-0The inventive method for applying the described thermal barrier coating on the surface of a nickel-based 4 B04 / 002-0
Superlegierung und einer wahlweise darauf aufgebrachten metallischen Haftschicht bestehenden Komponente ist dadurch gekennzeichnet, dass a) keramisches Pulver aus mit Yttriumoxid (Y2O3) stabilisiertem Zirkonoxid (Zrθ2) und Pulver aus mindestens einer intermetallischen Verbindung miteinander gemischt werden, b) diese Pulvermischung anschliessend mittels bekannter thermischer Spritzverfahren entweder direkt auf die Oberfläche der Komponente oder beim Vorhandensein einer metallischen Haftschicht direkt auf die metallische Haftschicht aufgespritzt wird, c) die Verfahrensschritte a) und b) mehrfach wiederholt werden, wobei dieSuperalloy and optionally applied thereon applied metallic adhesive layer component is characterized in that a) ceramic powder of yttria (Y2O 3 ) stabilized zirconia (Zrθ2) and powder of at least one intermetallic compound are mixed together, b) this powder mixture then by means of known thermal Spray method is sprayed either directly on the surface of the component or in the presence of a metallic adhesive layer directly on the metallic adhesive layer, c) the process steps a) and b) are repeated several times, wherein the
Pulvermischung jeweils einen geringeren Volumenanteil an intermetallischer Verbindung aufweist als in den vorangegangenen Verfahrensschritten und die Pulvermischung jeweils auf die bereits im vorausgegangenen Verfahrensschritt aufgespritzte Schicht aufgespritzt wird, so dass letztlich eine Wärmedämmschicht mit einem über diePowder mixture in each case has a smaller volume fraction of intermetallic compound than in the preceding process steps and the powder mixture is sprayed in each case on the already sprayed in the previous process step layer, so that ultimately a thermal barrier coating with a on the
Schichtdicke abnehmenden Volumenanteil an intermetallischen Verbindungen gebildet wird.Layer thickness decreasing volume fraction of intermetallic compounds is formed.
Der Vorteil der Erfindung besteht darin, dass durch die allmähliche Veränderung der Zusammensetzung der Wärmedämmschicht in Abhängigkeit von der Dicke der Wärmedämmschicht ein weniger steiler Spannungsgradient erzeugt wird. Dies führt zu einer höheren Dehnungstoleranz der TBC-Schicht und damit einerseits zu einer erhöhten Lebensdauer bei thermischerThe advantage of the invention is that a gradual change in the composition of the thermal barrier coating as a function of the thickness of the thermal barrier coating produces a less steep gradient of stress. This leads to a higher strain tolerance of the TBC layer and thus on the one hand to an increased service life at thermal
Beanspruchung (kein Abplatzen) und anderseits zur Möglichkeit, dickere Wärmedämmschichten aufzubringen und somit die beschichteten Bauteile bei höheren Temperaturen einzusetzen.Stress (no chipping) and on the other hand the possibility to apply thicker thermal barrier coatings and thus use the coated components at higher temperatures.
Es ist zweckmässig, wenn als intermetallische Verbindungen NiAI, legierte NiAI, YRh oder ErIr verwendet werden. Diese intermetallischen Verbindungen sind oxidationsbeständig und besitzen in einem grossen Temperaturbereich eine ausreichende Duktilität. Ausserdem haben sie nur eine geringe Tendenz zur Interdiffusion und besitzen einen hohen Schmelzpunkt. 5 B04/002-0It is expedient if NiAl, alloyed NiAl, YRh or ErIr are used as intermetallic compounds. These intermetallic compounds are resistant to oxidation and have sufficient ductility in a wide temperature range. In addition, they have little tendency for interdiffusion and have a high melting point. 5 B04 / 002-0
Vorteilhaft ist, wenn der Volumenanteil der intermetallischen Verbindung in der Schicht an der Oberfläche der Komponente ca. 80 Vol.-% und an der freien Oberfläche ca. 5 % beträgt.It is advantageous if the volume fraction of the intermetallic compound in the layer at the surface of the component is about 80% by volume and at the free surface is about 5%.
Kurze Beschreibung der ZeichnungShort description of the drawing
In der Zeichnung ist ein Ausführungsbeispiel der Erfindung dargestellt.In the drawing, an embodiment of the invention is shown.
Es zeigen.Show it.
Fig. 1 eine perspektivische Darstellung einer Laufschaufel einerFig. 1 is a perspective view of a blade of a
Gasturbine;A gas turbine;
Fig. 2 einen Schnitt entlang der Linie M-Il in Fig. 1 und Fig. 3 einen schematischen Verlauf der Volumenanteile in der TBC in2 shows a section along the line M-II in FIG. 1 and FIG. 3 shows a schematic profile of the volume fractions in the TBC in FIG
Abhängigkeit vom Abstand vom Grundsubstrat.Dependence on the distance from the basic substrate.
Es sind nur die für die Erfindung wesentlichen Merkmale dargestellt. Gleiche Elemente haben in unterschiedlichen Figuren gleiche Bezugszeichen.Only the essential features of the invention are shown. Identical elements have the same reference numerals in different figures.
Wege zur Ausführung der ErfindungWays to carry out the invention
Nachfolgend wird die Erfindung anhand eines Ausführungsbeispieles näher erläutert.The invention will be explained in more detail with reference to an embodiment.
Die Erfindung ist anwendbar für alle Komponenten, welche hohen Temperaturen und oxidativen/korrosiven Umwelteinflüssen ausgesetzt sind, wie z. B. Schaufeln, Wärmestausegmente oder Teile der Brennkammern von Gasturbinen.The invention is applicable to all components which are exposed to high temperatures and oxidative / corrosive environmental influences, such. As blades, heat accumulation segments or parts of the combustion chambers of gas turbines.
Fig. 1 zeigt in perspektivischer Darstellung als ein Beispiel derartiger Komponenten 1 eine Laufschaufel einer Gasturbine. Die Laufschaufel 1 6 B04/002-0Fig. 1 shows in perspective view as an example of such components 1, a blade of a gas turbine. The blade 1 6 B04 / 002-0
besteht aus einem Schaufelfuss 2, einer Plattform 3 und einem Schaufelblatt 4, in welchem Kühlluftkanäle vorhanden sind, deren Öffnungen in Fig. 1 mit 5 bezeichnet sind. Die Laufschaufel 1 wird mit ihrem Schaufelfuss 2 in Umfangsnuten im nicht dargestellten Rotor der Gasturbine verankert. Während des Betriebes der Turbine wird das Schaufelblatt 4 mit heissen Verbrennungsgasen beaufschlagt, so dass die Oberfläche 7 des Schaufelblattes 4 sowohl den heissen Verbrennungsgasen als auch Angriffen durch Oxidation, Korrosion und Erosion ausgesetzt ist. Zum Schutz vor Oxidation/Korrosion sowie zu hoher thermischer Belastung ist das Schaufelblatt 4 daher auf seiner äusseren Oberfläche 7 mit einer metallischen Haftschicht 6 (in Fig. 1 nicht sichtbar) versehen, auf der eine keramische Wärmedämmschicht 8 aufgespritzt ist.consists of a blade root 2, a platform 3 and an airfoil 4, in which cooling air channels are present, whose openings are designated in Fig. 1 with 5. The blade 1 is anchored with its blade root 2 in circumferential grooves in the rotor of the gas turbine, not shown. During operation of the turbine, the blade 4 is subjected to hot combustion gases, so that the surface 7 of the airfoil 4 is exposed to both the hot combustion gases and attacks by oxidation, corrosion and erosion. For protection against oxidation / corrosion and high thermal stress, the blade 4 is therefore provided on its outer surface 7 with a metallic adhesive layer 6 (not visible in FIG. 1) on which a ceramic thermal barrier coating 8 is sprayed.
In der Schnittdarstellung gemäss Fig. 2 ist das Beschichtungssystem gut zu erkennen. Der Grundwerkstoff der Laufschaufel 1 der Gasturbine besteht beispielsweise aus einer gerichtet erstarrten Nickel-Basissuperlegierung CM 247 mit folgender chemischer Zusammensetzung (Angaben in Gew.-%): = 0.07 C, 8.1 Cr, 9.2 Cr, 0.5 Mo, 9.5 W, 3.2 Ta, 5.6 AI, 0.7 Ti, 0.015 B, 0.015 Zr, 1.4 Hf, Rest Ni.In the sectional view according to FIG. 2, the coating system is clearly visible. The base material of the rotor blade 1 of the gas turbine, for example, consists of a directionally solidified nickel base superalloy CM 247 with the following chemical composition (in wt .-%): = 0.07 C, 8.1 Cr, 9.2 Cr, 0.5 Mo, 9.5 W, 3.2 Ta, 5.6 Al, 0.7 Ti, 0.015 B, 0.015 Zr, 1.4 Hf, balance Ni.
In einem anderen Ausführungsbeispiel kann die Turbinenschaufel vorzugsweise aus einer Einkristalllegierung, beispielsweise mit folgender chemischer Zusammensetzung bestehen (Angaben in Gew.-%): 7.7-8.3 Cr, 5.0-5.25 Co, 2.0-2.1 Mo, 7.8-8.3 W, 5.8-6.1 Ta, 4.9-5.1 AI, 1.3-1.4 Ti, 0.11- 0.15 Si, 0.11-0.15 Hf, 200-750 ppm C, 50-400 ppm B, Rest Nickel und herstellungsbedingte Verunreinigungen.In another embodiment, the turbine blade may preferably consist of a single-crystal alloy, for example with the following chemical composition (in% by weight): 7.7-8.3 Cr, 5.0-5.25 Co, 2.0-2.1 Mo, 7.8-8.3 W, 5.8-6.1 Ta, 4.9-5.1 Al, 1.3-1.4 Ti, 0.11-0.15 Si, 0.11-0.15 Hf, 200-750 ppm C, 50-400 ppm B, balance nickel and manufacturing impurities.
Diese Grundwerkstoffe (Substrate) sind auf ihrer äusseren Oberfläche 7 mit einer metallischen Haftschicht 6, vorzugsweise des Typs MCrAIY versehen, wobei M für Metall steht (Ni, Co, Fe oder deren Kombinationen). Im vorliegenden Falle wurde NiCrAIY für die Haftschicht 6 verwendet. Die AI- reichen Haftschichten dieses Typs bilden eine AI2O3-Zunderschicht 9, die sich durch thermische Oxidation der Haftschicht 6 bildet. Diese AI2O3-Schicht 9 7 B04/002-0These base materials (substrates) are provided on their outer surface 7 with a metallic adhesive layer 6, preferably of the type MCrAIY, where M is metal (Ni, Co, Fe or combinations thereof). In the present case, NiCrAlY was used for the adhesive layer 6. The Al-rich adhesive layers of this type form an Al 2 O 3 -Zderschicht 9, which forms by thermal oxidation of the adhesive layer 6. This Al 2 O 3 layer 9 7 B04 / 002-0
bindet chemisch die keramische Wärmedämmschicht an die Haftschicht 6 und das Substrat (Nickel-Basissuperlegierung).chemically bonds the ceramic thermal barrier coating to the adhesive layer 6 and the substrate (nickel-base superalloy).
Die TBC 8 besteht aus mit Yttriumoxid (Y2O3) stabilisiertem Zirkonoxid (Zrθ2), wobei etwa 7 % Yttriumoxid vorhanden ist. Die Wärmedämmschicht 8 wird mittels bekannter thermischer Spritzverfahren beispielsweise mittels APS aufgespritzt. Erfindungsgemäss wird dazu das keramische Pulver zunächst mit Pulver aus einer intermetallischen Verbindung 12, im vorliegenden Ausführungsbeispiel aus Nickelaluminid NiAI, gemischt und anschliessend diese Pulvermischung auf die Haftschicht 6 thermisch aufgespritzt. Im ersten Verfahrensschritt ist der Volumenanteil der intermetallischen Verbindung 12 sehr hoch, hier 80 Vol.-%. Die beiden Verfahrensschritte werden nun mehrfach wiederholt werden, wobei die Pulvermischung jeweils einen geringeren Volumenanteil an der intermetallischen Verbindung NiAI aufweist als in den vorangegangenen Verfahrensschritten und die Pulvermischung jeweils auf die bereits im vorangegangenen Verfahrensschritt aufgespritzte Schicht aufgespritzt wird, so dass letztlich eine Wärmedämmschicht 8 mit einem über die Schichtdicke abnehmenden Volumenanteil an intermetallischer Verbindung 12 gebildet wird. Letztlich sind an der Oberfläche der fertig beschichteten Komponente 1 nur noch ca. 5 Vol.-% NiAI vorhanden.The TBC 8 consists of yttria (Y 2 O 3) stabilized zirconia (ZrO 2), with about 7% yttria is present. The thermal barrier coating 8 is sprayed by means of known thermal spraying, for example by means of APS. According to the invention, the ceramic powder is first mixed with powder of an intermetallic compound 12, in the present embodiment of nickel aluminide NiAl, and then this powder mixture is thermally sprayed onto the adhesive layer 6. In the first process step, the volume fraction of the intermetallic compound 12 is very high, here 80 vol .-%. The two process steps will now be repeated several times, wherein the powder mixture in each case has a smaller volume fraction of the intermetallic compound NiAI than in the preceding process steps and the powder mixture is sprayed onto the sprayed already in the previous process step layer, so that ultimately a thermal barrier coating 8 with a via the layer thickness decreasing volume fraction of intermetallic compound 12 is formed. Ultimately, only about 5 vol .-% NiAI are present on the surface of the finished coated component 1.
Dies ist in Fig. 3 dargestellt, wo der schematische Verlauf der Volumenanteile an intermetallischer Verbindungen 12 bzw. an mit Yttriumoxid (Y2O3) stabilisiertem Zirkonoxid (Zrθ2) in der Wärmedämmschicht 8 in Abhängigkeit vom Abstand von der Haftschicht 6, d.h. von der Dicke der Wärmedämmschicht 8 gezeigt wird. Der Volumenanteil an intermetallischer Verbindung 12 nimmt hier kontinuierlich exponentiell ab. In anderen Ausführungsbeispielen kann er auch linear oder stufenweise abnehmend sein.This is illustrated in FIG. 3, where the schematic profile of the volume fractions of intermetallic compounds 12 or of zirconium oxide (ZrO 2 ) stabilized with yttrium oxide (Y 2 O 3 ) in the thermal barrier coating 8 depends on the distance from the adhesive layer 6, ie from the Thickness of the thermal barrier coating 8 is shown. The volume fraction of intermetallic compound 12 decreases continuously here exponentially. In other embodiments, it may also be linear or stepwise decreasing.
Es ist bekannt, dass die durch APS erzeugten keramischen Wärmedämmschichten aus einzelnen Körner bestehen und eine relativ grosse Porosität aufweisen. In Fig. 2 sind diese Körner mit dem 8 B04/002-0It is known that the ceramic thermal barrier coatings produced by APS consist of individual grains and have a relatively large porosity. In Fig. 2, these grains are with the 8 B04 / 002-0
Bezugszeichen 10 und die Poren mit dem Bezugszeichen 11 bezeichnet. Bei der erfindungsgemässen Wärmedämmschicht 8 lagert sich die intermetallische Verbindung 12, hier NiAI, bevorzugt in diesen Poren 11 ab. Die intermetallischen Verbindungen, wie beispielsweise Nickelaluminid, sind oxidationsbeständig und besitzen in einem grossen Temperaturbereich eine ausreichende Duktilität. Ausserdem haben sie nur eine geringe Tendenz zur Interdiffusion und besitzen einen hohen Schmelzpunkt. Durch die allmähliche Veränderung der Zusammensetzung der Wärmedämmschicht in Abhängigkeit von der Dicke der Wärmedämmschicht wird mit Vorteil ein weniger steiler Spannungsgradient in der Schicht erzeugt. Dies führt zu einer höheren Dehnungstoleranz der Wärmedämmschicht und damit einerseits zu einer erhöhten Lebensdauer bei thermischer Beanspruchung (kein Abplatzen) und anderseits zur Möglichkeit, dickere Wärmedämmschichten aufzubringen und somit die beschichteten Bauteile bei höheren Temperaturen einzusetzen.Reference numeral 10 and the pores denoted by the reference numeral 11. In the case of the thermal barrier coating 8 according to the invention, the intermetallic compound 12, here NiAl, preferably deposits in these pores 11. The intermetallic compounds, such as nickel aluminide, are resistant to oxidation and have sufficient ductility in a wide temperature range. In addition, they have little tendency for interdiffusion and have a high melting point. Due to the gradual change in the composition of the thermal barrier coating as a function of the thickness of the thermal barrier coating, a less steep stress gradient is advantageously generated in the layer. This leads to a higher elongation tolerance of the thermal barrier coating and thus on the one hand to increased life under thermal stress (no chipping) and on the other hand to the possibility to apply thicker thermal barrier coatings and thus use the coated components at higher temperatures.
Während bei konventionellen mit Yttriumoxid stabilisierten Zirkonoxid- Wärmedämmschichten Schichtdicken von ca. 250-300 μm mittels APS gespritzt werden konnten, sind bei der vorliegenden Erfindung Schichtdicken bis ca. 2 mm problemlos machbar.While layer thicknesses of approximately 250-300 μm could be sprayed by means of APS in the case of conventional yttria-stabilized zirconium oxide thermal barrier coatings, layer thicknesses of up to approximately 2 mm can easily be achieved in the present invention.
Selbstverständlich ist die Erfindung nicht auf das beschriebene Ausführungsbeispiel beschränkt. Neben dem bereits erwähnten NiAI sind auch die folgenden intermetallischen Verbindungen geeignet, die erfindungsgemässen Vorteile zu erreichen: YRh, ErIr und legiertes NiAI, da diese intermetallischen Verbindungen oxidationsbeständig sind, in allen Temperaturbereichen eine gute Duktilität aufweisen, sowie eine geringe Tendenz zur Interdiffusion und hohe Schmelzpunkte haben. Infolge der allmählichen Abstufung des Volumenanteils an intermetallischer Verbindung wird ein weniger steiler Spannungsgradient erreicht, so dass die Wärmedämmschicht wesentlich dehnungstoleranter ist und damit eine längere Lebensdauer bei thermischer Beanspruchung aufweist. 9 B04/002-0Of course, the invention is not limited to the embodiment described. In addition to the NiAl already mentioned, the following intermetallic compounds are also suitable for achieving the advantages according to the invention: YRh, ErIr and alloyed NiAl, since these intermetallic compounds are resistant to oxidation, have good ductility in all temperature ranges, and a low tendency for interdiffusion and high melting points to have. Due to the gradual grading of the volume fraction of intermetallic compound, a less steep voltage gradient is achieved, so that the thermal barrier coating is substantially more strain-tolerant and thus has a longer life under thermal stress. 9 B04 / 002-0
Die erfindungsgemässen Wärmedämmschichten können auch auf andere thermisch hochbelastete Gasturbinenkomponenten, wie beispielsweise Wärmeschutzschilder oder Brennkammerliner, aufgebracht werden, wobei der Grundwerkstoff der Komponente z. B. Hastalloy oder Haynes 230 sein kann und die Haftschicht z. B. eine NiCoCrAlY-Schicht sein kann.The inventive thermal barrier coatings can also be applied to other thermally highly loaded gas turbine components, such as heat shields or combustion chamber liner, wherein the base material of the component z. B. Hastalloy or Haynes 230 may be and the adhesive layer z. B. may be a NiCoCrAlY layer.
Schliesslich sind zum thermischen Spritzen der TBC gemäss vorliegender Erfindung auch andere Spritzverfahren als APS geeignet, z. B. EB-PVD. Die damit erzeugten Wärmedämmschichten sind stängelförmig.Finally, for thermal spraying of the TBC according to the present invention, also other spraying methods are suitable as APS, z. Eg EB-PVD. The thermal barrier coatings produced are stalk-shaped.
Selbstverständlich ist es auch möglich, die TBC direkt auf die Oberfläche der Komponente zu spritzen, d.h. ohne eine zusätzliche Haftschicht.Of course, it is also possible to inject the TBC directly onto the surface of the component, i. without an additional adhesive layer.
BezugszeichenlisteLIST OF REFERENCE NUMBERS
1 Komponente, z. B. Laufschaufel1 component, eg. B. Blade
2 Schaufelfuss2 scoop feet
3 Plattform3 platform
4 Schaufelblatt4 airfoil
5 Öffnungen der Kühlluftkanäle5 openings of the cooling air ducts
6 Haftschicht6 adhesive layer
7 Oberfläche der Komponente7 Surface of the component
8 Wärmedämmschicht, TBC8 thermal barrier coating, TBC
9 AI2O3-Sd-IiCl-It9 Al 2 O 3 -Si-IiCl-It
10 Korn10 grains
11 Pore11 pore
12 Intermetallische Verbindung 12 Intermetallic compound

Claims

10 B04/002-0Patentansprüche 10 B04 / 002-0Patent claims
1. Keramische Wärmedämmschicht (8) zur Beschichtung der Oberfläche (7) einer aus einer Nickel-Basis-Superlegierung und einer wahlweise darauf aufgebrachten metallischen Haftschicht (6) bestehenden Komponente (1 ), wobei die Wärmedämmschicht (8) vorwiegend aus mit Yttriumoxid (Y2O3) stabilisiertem Zirkonoxid (Z1O2) und herstellungsbedingten Verunreinigungen besteht, dadurch gekennzeichnet, dass die Wärmedämmschicht (8) mindestens eine hochtemperatur- und oxidationsbeständige intermetallische Verbindung aufweist, deren Volumenanteil mit zunehmenden Abstand von der Oberfläche (7) derA ceramic thermal barrier coating (8) for coating the surface (7) of a component (1) consisting of a nickel-base superalloy and an optional metallic adhesive layer (6), the thermal barrier coating (8) consisting predominantly of yttria (Y 2 O 3 ) stabilized zirconium oxide (Z1O2) and production-related impurities, characterized in that the thermal barrier coating (8) comprises at least one high-temperature and oxidation-resistant intermetallic compound, the volume fraction with increasing distance from the surface (7) of
Komponente (1 )/der Haftschicht (6) kontinuierlich oder stufenweise abnimmt.Component (1) / the adhesive layer (6) continuously or gradually decreases.
2. Wärmedämmschicht (8) nach Anspruch 1 , dadurch gekennzeichnet, dass die intermetallische Verbindung NiAI und/oder legiertes NiAI ist.2. Thermal barrier coating (8) according to claim 1, characterized in that the intermetallic compound NiAl and / or alloyed NiAI.
3. Wärmedämmschicht (8) nach Anspruch 1 , dadurch gekennzeichnet, dass die intermetallische Verbindung YRh.3. thermal barrier coating (8) according to claim 1, characterized in that the intermetallic compound YRh.
4. Wärmedämmschicht (8) nach Anspruch 1 , dadurch gekennzeichnet, dass die intermetallische Verbindung ErIr ist.4. Thermal barrier coating (8) according to claim 1, characterized in that the intermetallic compound is ErIr.
5. Wärmedämmschicht (8) nach Anspruch 1 , dadurch gekennzeichnet, dass der Volumenanteil der intermetallischen Verbindung mit zunehmenden Abstand von der Oberfläche (7) der Komponente (1 )/der Haftschicht (6) exponentiell abnimmt. 11 B04/002-05. thermal barrier coating (8) according to claim 1, characterized in that the volume fraction of the intermetallic compound with increasing distance from the surface (7) of the component (1) / the adhesive layer (6) decreases exponentially. 11 B04 / 002-0
6. Wärmedämmschicht (8) nach Anspruch 1 , dadurch gekennzeichnet, dass der Volumenanteil der intermetallischen Verbindung mit zunehmenden Abstand von der Oberfläche (7) der Komponente (1 )/der Haftschicht (6) linear abnimmt.6. thermal barrier coating (8) according to claim 1, characterized in that the volume fraction of the intermetallic compound with increasing distance from the surface (7) of the component (1) / the adhesive layer (6) linearly decreases.
7. Wärmedämmschicht (8) nach Anspruch 1 , dadurch gekennzeichnet, dass der Volumenanteil der intermetallischen Verbindung in der Schicht an der Oberfläche (7) der Komponente (1 ) ca. 80 Vol.% und an der freien Oberfläche ca. 5 % beträgt.7. thermal barrier coating (8) according to claim 1, characterized in that the volume fraction of the intermetallic compound in the layer on the surface (7) of the component (1) is about 80 vol.% And at the free surface is about 5%.
8. Gasturbinenkomponente, dadurch gekennzeichnet, dass diese mit einer Wärmedämmschicht (8) nach einem der Ansprüche 1-7 beschichtet ist.8. gas turbine component, characterized in that it is coated with a thermal barrier coating (8) according to any one of claims 1-7.
9. Verfahren zum Aufbringen einer Wärmedämmschicht (8) auf die Oberfläche (7) einer aus einer Nickel-Basis-Superlegierung und einer wahlweise darauf aufgebrachten metallischen Haftschicht (6) bestehenden Komponente, dadurch gekennzeichnet, dass d) keramisches Pulver aus mit Yttriumoxid (Y2O3) stabilisiertem Zirkonoxid (Zrθ2) und Pulver aus mindestens einer intermetallischen Verbindung miteinander gemischt werden, e) diese Pulvermischung anschliessend mittels bekannter thermischer Spritzverfahren entweder direkt auf die Oberfläche (7) der Komponente (1 ) oder beim Vorhandensein einer metallischen Haftschicht (6) direkt auf die metallische Haftschicht (6) aufgespritzt wird, f) die Verfahrensschritte a) und b) mehrfach wiederholt werden, wobei die Pulvermischung jeweils einen geringeren Volumenanteil an intermetallischer Verbindung aufweist als in den vorangegangenen Verfahrensschritten und die Pulvermischung jeweils auf die bereits im vorausgegangenen Verfahrensschritt aufgespritzte Schicht aufgespritzt wird, so dass letztlich eine Wärmedämmschicht (8) mit einem über die Schichtdicke abnehmenden Volumenanteil an intermetallischen Verbindungen gebildet wird. 9. A method for applying a thermal barrier coating (8) on the surface (7) made of a nickel-based superalloy and an optionally applied thereto metallic adhesive layer (6) component, characterized in that d) ceramic powder with yttrium oxide (Y 2 O 3 ) stabilized zirconium oxide (ZrO 2) and powder of at least one intermetallic compound are mixed together, e) this powder mixture is then applied by known thermal spraying either directly to the surface (7) of the component (1) or in the presence of a metallic adhesive layer (6 f) the process steps a) and b) are repeated several times, the powder mixture each having a smaller volume fraction of intermetallic compound than in the preceding process steps and the powder mixture in each case to those already in the preceding Aufspri process step In this way, a heat-insulating layer (8) is formed with a volume fraction of intermetallic compounds which decreases over the layer thickness.
EP06764032A 2005-07-12 2006-07-04 Ceramic heat insulating layer Not-in-force EP1902160B1 (en)

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US7666516B2 (en) 2010-02-23
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US20080241560A1 (en) 2008-10-02
DE502006003197D1 (en) 2009-04-30
ATE426052T1 (en) 2009-04-15

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