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EP1948836A1 - Alloy, protective layer for protecting a component from corrosion and/or oxidation at high temperatures and component - Google Patents

Alloy, protective layer for protecting a component from corrosion and/or oxidation at high temperatures and component

Info

Publication number
EP1948836A1
EP1948836A1 EP06807569A EP06807569A EP1948836A1 EP 1948836 A1 EP1948836 A1 EP 1948836A1 EP 06807569 A EP06807569 A EP 06807569A EP 06807569 A EP06807569 A EP 06807569A EP 1948836 A1 EP1948836 A1 EP 1948836A1
Authority
EP
European Patent Office
Prior art keywords
alloy
component
protective layer
rhenium
cobalt
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.)
Withdrawn
Application number
EP06807569A
Other languages
German (de)
French (fr)
Inventor
Werner Stamm
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Siemens AG
Original Assignee
Siemens AG
Siemens Corp
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, Siemens Corp filed Critical Siemens AG
Priority to EP06807569A priority Critical patent/EP1948836A1/en
Publication of EP1948836A1 publication Critical patent/EP1948836A1/en
Withdrawn legal-status Critical Current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
    • 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
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
    • 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
    • C23C28/34—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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00—Aeronautics or air transport
    • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft
    • 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.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12778—Alternative base metals from diverse categories

Definitions

  • the invention relates to an alloy according to claim 1, a protective layer for protecting a component against corrosion and / or oxidation at high temperatures according to claim 16 and a component according to claim 17.
  • the invention relates in particular to a protective layer for ⁇ a component made of a superalloy based on nickel or cobalt base.
  • MCrAlY Protective coatings for metallic components to increase their corrosion- ⁇ onsbehav and / or oxidation resistance are known in the art in great number. Most of these protective layers are known under the collective name MCrAlY, where M stands for at least one of the elements from the group comprising iron, cobalt and nickel and wei ⁇ tere essential components are chromium, aluminum and yttrium.
  • US Pat. No. 6,280,857 B1 discloses a protective layer which discloses the elements cobalt, chromium and aluminum based on nickel as well as compelling admixtures of yttrium, rhenium and silicon.
  • a protective layer In addition to the sufficient chemical resistance of a protective layer under the attacks that are expected of flue gases at temperatures in the order of 1000 0 C, a protective layer must also have sufficient mechanical properties, not least in view of the mechanical interaction between the protective layer and the base material , to have. In particular, the protective layer must be sufficiently ductile in order to be able to follow any deformations of the base material and not to break, since in this way points of attack for oxidation and corrosion would be created.
  • the problem typically arises that increasing the proportions of elements such as aluminum and chromium, which can improve the resistance of a protective layer against oxidation and corrosion, leads to a deterioration of the ductility of the protective layer, so that mechanical failure, in particular the formation of cracks, is expected in a gas turbine usually occurring mechanical stress. Accordingly, it is an object of the present invention to provide an alloy and a protective layer which has good high-temperature resistance in corrosion and oxidation, has good long-term stability and, in addition, a mechanical stress to be expected particularly in a gas turbine at a high temperature well adjusted.
  • the object is achieved by an alloy according to claim 1 and a protective layer according to claim 16.
  • Another object of the invention is to provide a component which has increased protection against corrosion and oxidation.
  • the object is also achieved by a component according to claim 17, in particular by a component of a gas turbine or steam turbine, the protection at high temperatures of a protective layer of the type described above has to protect against corrosion and oxidation.
  • the invention is inter alia based on the finding that the protective layer is in the protective layer itself and in the over ⁇ transition region between the protective layer and the base material brittle precipitates.
  • This time and temperature in use strengthened forming brittle phases result in the operation to very pronounced longitudinal cracks in the protective layer and in the interface layer base material with ⁇ connect the replacement of the protective layer.
  • carbon which can diffuse from the base material into the protective layer or during a heat treatment into sound dif ⁇ in the furnace through the surface in the protective layer, in addition, the brittleness of the off ⁇ increases decisions. By oxidation of these phases, the driving force for cracking is enhanced.
  • FIG. 1 shows a layer system with a protective layer
  • FIG. 2 shows compositions of superalloys
  • FIG. 3 shows a gas turbine
  • FIG. 4 shows a perspective view of a combustion chamber
  • FIG. 5 shows a perspective view of a turbine blade.
  • a protective layer 7 for protecting a component 1 against corrosion and oxidation at a high temperature contains the following elements (wt%): 26% to 28% cobalt (Co) 20% to 22% chromium (Cr) 7 % to 9% aluminum (Al) 0.5% to 0.7% yttrium (Y) and / or at least one equivalent metal from the group comprising scandium (Sc) and the elements of the rare earths, balance nickel (NiCoCrAlY).
  • the alloy contains up to 2.0wt% silicon.
  • the alloy may have up to 1 wt% rhenium. In this case, the beneficial effect of the element rhenium can be exploited while preventing the formation of brittle phase.
  • the alloy may also include ruthenium.
  • the ruthenium with a maximum proportion of llwt% can replace the rhenium partially or completely.
  • the proportions of the individual elements are specially tuned with regard to their effects. When the proportions are dimensioned to be that no chromium-off decisions ⁇ form, advantageously there are no brittle phases during use of the protective layer, so that the runtime behavior improved and extended is. This is done not only by a low chromium content, but also, taking into account the influence of aluminum on the phase formation, by exact measurement of the content of aluminum.
  • the protective layer 7, with good corrosion resistance, has a particularly good resistance to oxidation and is also distinguished by particularly good ductility properties, so that it is particularly qualified for use in a gas turbine with a further increase in the inlet temperature.
  • embrittlement hardly occurs since the layer has hardly any chromium precipitates, in particular no chromium-rhenium precipitates, which become brittle in the course of use.
  • the aluminum content is advantageous to set to 8% by weight and not to form Al 2 O 3 during coating with the alloy. Therefore, the aluminum content can be kept low. It is also advantageous to set the proportion of yttrium or the at least one equivalent element from the group consisting of scandium and the elements of the rare earths to 0.6 wt%. Certain fluctuations result from large-scale industrial production, so that also yttrium contents of 0.4wt% to 0.5wt% or 0.7wt% to 0.8wt% are used and also show good properties.
  • the alloy contains no other elements than the elements nickel, chromium, cobalt, aluminum, yttrium (Sc, rare earths), silicon and rhenium.
  • the powders are applied for example by plasma spraying (APS, LPPS, VPS, ).
  • Other methods are also conceivable (PVD, CVD, cold gas spraying).
  • the thickness of the protective layer 7 on the component 1 is preferably dimensioned to a value of between about 100 ⁇ m and 300 ⁇ m.
  • the protective layer 7 is advantageously applied to a substrate 4 made of a nickel or cobalt-based superalloy.
  • composition is suitable as substrate 4 (data in wt%):
  • compositions of this type are known as casting alloys under the designations GTD222, IN939, IN6203 and Udimet 500.
  • the protective layer 7 is particularly suitable for protecting a component against corrosion and oxidation, while the component is acted upon by a flue gas at a material temperature of about 95O 0 C, in airplanes also by about HOO 0 C.
  • the protective layer 7 is thus particularly qualified for protecting a component of a gas turbine 100, in particular a guide blade 120, blade 130 or other component, which is acted upon by hot gas before or in the turbine of the gas turbine.
  • the protective layer 7 can be used as an overlay (protective layer is the outer layer or as a bondcoat (protective layer is an intermediate layer).
  • FIG. 1 shows a layer system 1 as a component.
  • the layer system 1 consists of a substrate 4.
  • the substrate 4 may be metallic and / or ceramic.
  • turbine components such as e.g. Turbine barrel 120 (FIG. 1) or vanes 130 (FIGS. 3, 5), combustor liners 155 (FIG. 4), as well as other housing parts
  • the substrate 4 consists of a nickel-, cobalt- or iron-based superalloy.
  • cobalt-based superalloys are used.
  • the protective layer 7 is present on the substrate 4, the protective layer 7 according to the invention is present.
  • this protective layer is applied by LPPS (low pres sure ⁇ plasma spraying). 7
  • This can be used as outer layer (not shown) or intermediate layer (FIG. 1). In the latter case, a ceramic thermal barrier coating 10 is present on the protective layer 7.
  • the protective layer 7 can be applied to newly manufactured components and refurbished components from the refurbishment.
  • Reprocessing means that components 1 are separated after their use, if appropriate, of layers (heat insulating layer) and corrosion and oxidation products are removed, for example by a sheurebehand ⁇ averaging (acid stripping). If necessary, cracks must still be repaired. Thereafter, such a component can be coated again because the substrate 4 is very expensive.
  • FIG. 3 shows by way of example a gas turbine 100 in a longitudinal partial section.
  • the gas turbine 100 has inside a rotatably mounted about a rotation axis 102 rotor 103, which is also referred to as a turbine runner. Along the rotor 103 successively follow an intake housing 104, a compressor 105, for example, a torus-like
  • Combustion chamber 110 in particular annular combustion chamber 106, with a plurality of coaxially arranged burners 107, a turbine 108 and the exhaust housing 109.
  • the annular combustion chamber 106 communicates with an example annular hot gas channel 111.
  • Each turbine stage 112 is formed of two blade rings. As seen in the direction of flow of a working medium 113, in the hot gas channel 111 of a row of guide vanes 115, a series 125 formed of rotor blades 120 follows.
  • the guide vanes 130 are fastened to an inner housing 138 of a stator 143, whereas the moving blades 120 of a row 125 are attached to the rotor 103 by means of a turbine disk 133, for example.
  • Coupled to the rotor 103 is a generator or work machine (not shown).
  • air 105 is sucked in and compressed by the compressor 105 through the intake housing 104.
  • the compressed air provided at the turbine-side end of the compressor 105 is guided to the burners 107 and mixed there with a fuel.
  • the mixture is then burned to form the working fluid 113 in the combustion chamber 110.
  • the working medium 113 flows along the hot-gas passage 111 past the guide vanes 130 and the rotor ⁇ blades 120.
  • the working medium 113 is expanded, transferring its momentum, so that the run show ⁇ feln 120 drive the rotor 103 and the latter attached to him work machine.
  • the components exposed to the hot working medium 113 are subject to thermal loads during operation of the gas turbine 100.
  • the guide vanes 130 and rotor blades 120 of the first turbine stage 112, viewed in the direction of flow of the working medium 113, are subjected to the greatest thermal stress in addition to the heat shield bricks lining the annular combustion chamber 106.
  • the substrates may likewise have a directional structure sen aufwei ⁇ she ie are monocrystalline (SX structure) or have only longitudinally oriented grains (DS structure).
  • the material used is iron, nickel or cobalt-based superalloys.
  • superalloys are used, as are known from EP 1 204 776, EP 1 306 454, EP 1 319 729, WO 99/67435 or WO 00/44949.
  • the blades 120, 130 have protective layers 7 according to the invention against corrosion and corrosion and / or a thermal barrier coating.
  • the thermal barrier coating consists, for example, ZrO 2, Y 2 O 3 -ZrO 2, ie it is not, partly full text or ⁇ dig stabilized by yttrium oxide and / or calcium and / or magnesium oxide.
  • Suitable coating processes such as electron beam evaporation (EB-PVD), produce stalk-shaped grains in the thermal barrier coating.
  • the vane 130 has a guide vane foot (not shown here) facing the inner housing 138 of the turbine 108 and a vane head opposite the vane foot.
  • the vane head faces the rotor 103 and fixed to a mounting ring 140 of the stator 143.
  • FIG. 4 shows a combustion chamber 110 of a gas turbine 100, which may have a layer system 1.
  • the combustion chamber 110 is designed, for example, as a so-called annular combustion chamber, in which a multiplicity of burners 102 arranged around the turbine shaft 103 in the circumferential direction open into a common combustion chamber space.
  • the combustion chamber 110 is configured in its entirety as an annular structure, which is positioned around the turbine shaft 103 around.
  • the combustion chamber 110 is designed for a comparatively high temperature of the working medium M of about 1000 ° C. to 1600 ° C.
  • the combustion chamber wall 153 is on its side facing the working medium M, with a facing side of heat shield elements 155 formed inner lining provided.
  • Each heat shield element 155 is the working medium side with a particularly hit ⁇ zebe operatingn protective layer or made of high-tempe ⁇ raturbe drivingm material and has the protective layer 7 according to Figure 1 on.
  • a cooling system is additionally provided for the heat shield elements 155 or for their holding elements.
  • the materials of the combustor wall and their coatings may be similar to the turbine blades 120, 130.
  • the combustion chamber 110 is designed in particular for detecting losses of the heat shield elements 155.
  • a number of temperature sensors 158 are positioned between the combustion chamber wall 153 and the heat shield elements 155.
  • FIG. 5 shows a perspective view of a blade 120, 130 which has a layer system 1 with the protective layer 7 according to the invention.
  • the blade 120, 130 extends along a longitudinal axis 121.
  • the blade 120, 130 has, along the longitudinal axis 121, a fastening area 400, an adjacent blade platform 403 and an airfoil area 406.
  • the protective layer 7 or a layer system 1 according to FIG. 1 is formed in particular in the airfoil region 406, the protective layer 7 or a layer system 1 according to FIG. 1 is formed.
  • a blade root 183 is formed, which serves for fastening the rotor blades 120, 130 to the shaft.
  • the blade root 183 is designed as a hammer head. Other configurations, for example as a Christmas tree or Schwalbenschwanzfuß are possible.
  • solid metallic materials are used in all regions 400, 403, 406 of the blades 120, 130.
  • the blade 120, 130 can be replaced by a casting process. ren, be made by a forging method, by a milling method or combinations thereof.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Ceramic Engineering (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)

Abstract

Known protective layers with a high Cr content form brittle phases which become even more brittle during use under the influence of carbon. The protective layer (7) according to the invention has the composition 26% to 28% cobalt, 20% to 22% chromium, 7% to 8% aluminium, 0.5% to 0.7% yttrium and/or at least one equivalent metal from the group comprising scandium and the rare-earth elements, optionally silicon and/or rhenium and the rest made up of nickel.

Description

Legierung, Schutzschicht zum Schutz eines Bauteils gegen Korrosion und/oder Oxidation bei hohen Temperaturen und Alloy, protective layer for protecting a component against corrosion and / or oxidation at high temperatures and

Bauteilcomponent

Die Erfindung betrifft eine Legierung gemäß Anspruch 1, eine Schutzschicht zum Schutz eines Bauteils gegen Korrosion und/oder Oxidation bei hohen Temperaturen gemäß Anspruch 16 und ein Bauteil gemäß Anspruch 17.The invention relates to an alloy according to claim 1, a protective layer for protecting a component against corrosion and / or oxidation at high temperatures according to claim 16 and a component according to claim 17.

Die Erfindung bezieht sich insbesondere auf eine Schutz¬ schicht für ein Bauteil, das aus einer Superlegierung auf Nickel- oder Kobaltbasis besteht.The invention relates in particular to a protective layer for ¬ a component made of a superalloy based on nickel or cobalt base.

Schutzschichten für metallische Bauteile, die deren Korrosi¬ onsbeständigkeit und/oder Oxidationsbeständigkeit erhöhen sollen, sind im Stand der Technik in großer Zahl bekannt. Die meisten dieser Schutzschichten sind unter dem Sammelnamen MCrAlY bekannt, wobei M für mindestens eines der Elemente aus der Gruppe umfassend Eisen, Kobalt und Nickel steht und wei¬ tere wesentliche Bestandteile Chrom, Aluminium und Yttrium sind.Protective coatings for metallic components to increase their corrosion- ¬ onsbeständigkeit and / or oxidation resistance are known in the art in great number. Most of these protective layers are known under the collective name MCrAlY, where M stands for at least one of the elements from the group comprising iron, cobalt and nickel and wei ¬ tere essential components are chromium, aluminum and yttrium.

Typische Beschichtungen dieser Art sind aus den US-Patenten 4,005,989 und 4,034,142 bekannt.Typical coatings of this type are known from U.S. Patents 4,005,989 and 4,034,142.

Die US 6,280,857 Bl offenbart eine Schutzschicht, die die Elemente Kobalt, Chrom und Aluminium auf Nickelbasis sowie zwingende Beimengungen von Yttrium, Rhenium und Silizium offenbart.US Pat. No. 6,280,857 B1 discloses a protective layer which discloses the elements cobalt, chromium and aluminum based on nickel as well as compelling admixtures of yttrium, rhenium and silicon.

Die Bemühung um die Steigerung der Eintrittstemperaturen sowohl bei stationären Gasturbinen als auch bei Flugtriebwerken hat auf dem Fachgebiet der Gasturbinen eine große Bedeutung, da die Eintrittstemperaturen wichtige Bestimmungsgrößen für die mit Gasturbinen erzielbaren thermodyna- mischen Wirkungsgrade sind. Durch den Einsatz speziell ent¬ wickelter Legierungen als Grundwerkstoffe für thermisch hoch zu belastende Bauteile wie Leit- und Laufschaufeln, insbesondere durch den Einsatz einkristalliner Superlegie- rungen, sind Eintrittstemperaturen von deutlich über 10000C möglich. Inzwischen erlaubt der Stand der Technik Ein- trittstemperaturen von 95O0C und mehr bei stationären Gasturbinen sowie HOO0C und mehr in Gasturbinen von Flugtriebwerken .The effort to increase the inlet temperatures both in stationary gas turbines and in aircraft engines has in the field of gas turbines of great importance, since the inlet temperatures are important determinants of the achievable with gas turbines thermodynamic efficiencies. Through the use of specially developed ¬ Wrapped alloys as base materials for thermally High-load components such as guide vanes and rotor blades, in particular through the use of monocrystalline superalloys, inlet temperatures of well over 1000 0 C are possible. Meanwhile, the prior art allows entry temperatures of 95O 0 C and more in stationary gas turbines and HOO 0 C and more in gas turbines of aircraft engines.

Beispiele zum Aufbau einer Turbinenschaufel mit einem einkri- stallinen Substrat, die seinerseits komplex aufgebaut sein kann, gehen hervor aus der WO 91/01433 Al.Examples of the construction of a turbine blade with a monocrystalline substrate, which in turn can be complex, are shown in WO 91/01433 A1.

Während die physikalische Belastbarkeit der inzwischen entwickelten Grundwerkstoffe für die hoch belasteten Bauteile im Hinblick auf mögliche weitere Steigerungen der Eintrittstemperaturen weitgehend unproblematisch ist, muss zur Erzielung einer hinreichenden Beständigkeit gegen Oxidation und Korrosion auf Schutzschichten zurückgegriffen werden. Neben der hinreichenden chemischen Beständigkeit einer Schutzschicht unter den Angriffen, die von Rauchgasen bei Temperaturen in der Größenordnung von 10000C zu erwarten sind, muss eine Schutzschicht auch genügend gute mechanische Eigenschaften, nicht zuletzt im Hinblick auf die mechanische Wechselwirkung zwischen der Schutzschicht und dem Grundwerkstoff, haben. Insbesondere muss die Schutzschicht hinreichend duktil sein, um eventuellen Verformungen des Grundwerkstoffes folgen zu können und nicht zu reißen, da auf diese Weise Angriffspunkte für Oxidation und Korrosion geschaffen würden. Hierbei kommt typischerweise das Problem auf, dass eine Erhöhung der An- teile von Elementen wie Aluminium und Chrom, die die Beständigkeit einer Schutzschicht gegen Oxidation und Korrosion verbessern können, zu einer Verschlechterung der Duktilitat der Schutzschicht führt, so dass mit einem mechanischen Versagen, insbesondere der Bildung von Rissen, bei einer in einer Gasturbine üblicherweise auftretenden mechanischen Belastung zu rechnen ist. Dementsprechend liegt der Erfindung die Aufgabe zugrunde, eine Legierung und eine Schutzschicht anzugeben, die eine gute Hochtemperaturbeständigkeit in Korrosion und Oxidation aufweist, eine gute Langzeitstabilität aufweist und die außerdem einer mechanischen Beanspruchung, die insbesondere in einer Gasturbine bei einer hohen Temperatur zu erwarten ist, besonders gut angepasst ist.While the physical strength of the now developed base materials for the highly loaded components with regard to possible further increases in the inlet temperatures is largely unproblematic, must be used to achieve a sufficient resistance to oxidation and corrosion on protective layers. In addition to the sufficient chemical resistance of a protective layer under the attacks that are expected of flue gases at temperatures in the order of 1000 0 C, a protective layer must also have sufficient mechanical properties, not least in view of the mechanical interaction between the protective layer and the base material , to have. In particular, the protective layer must be sufficiently ductile in order to be able to follow any deformations of the base material and not to break, since in this way points of attack for oxidation and corrosion would be created. Here, the problem typically arises that increasing the proportions of elements such as aluminum and chromium, which can improve the resistance of a protective layer against oxidation and corrosion, leads to a deterioration of the ductility of the protective layer, so that mechanical failure, in particular the formation of cracks, is expected in a gas turbine usually occurring mechanical stress. Accordingly, it is an object of the present invention to provide an alloy and a protective layer which has good high-temperature resistance in corrosion and oxidation, has good long-term stability and, in addition, a mechanical stress to be expected particularly in a gas turbine at a high temperature well adjusted.

Die Aufgabe wird gelöst durch eine Legierung gemäß Anspruch 1 und eine Schutzschicht gemäß Anspruch 16.The object is achieved by an alloy according to claim 1 and a protective layer according to claim 16.

Eine weitere Aufgabe der Erfindung besteht darin, ein Bauteil aufzuzeigen, das einen erhöhten Schutz gegen Korrosion und Oxidation aufweist.Another object of the invention is to provide a component which has increased protection against corrosion and oxidation.

Die Aufgabe wird ebenso gelöst durch ein Bauteil gemäß Anspruch 17, insbesondere durch ein Bauteil einer Gasturbine oder Dampfturbine, das zum Schutz gegen Korrosion und Oxida- tion bei hohen Temperaturen einer Schutzschicht der vorbeschriebenen Art aufweist.The object is also achieved by a component according to claim 17, in particular by a component of a gas turbine or steam turbine, the protection at high temperatures of a protective layer of the type described above has to protect against corrosion and oxidation.

In den Unteransprüchen sind weitere vorteilhafte Maßnahmen aufgelistet . Die in den Unteransprüchen aufgelisteten Maßnahmen können in vorteilhafter Art und Weise beliebig miteinander kombiniert werden .In the subclaims further advantageous measures are listed. The measures listed in the dependent claims can be combined in any advantageous manner with each other.

Der Erfindung liegt u. a. die Erkenntnis zugrunde, dass die Schutzschicht in der Schutzschicht selber und in dem Über¬ gangsbereich zwischen Schutzschicht und Grundwerkstoff spröde Ausscheidungen zeigt. Diese mit der Zeit und Temperatur im Einsatz sich verstärkt ausbildenden Sprödphasen führen im Betrieb zu stark ausgeprägten Längsrissen in der Schutzschicht als auch im Interface Schicht-Grundwerkstoff mit anschließen¬ der Ablösung der Schutzschicht. Durch die Wechselwirkung mit Kohlenstoff, der aus dem Grundwerkstoff in die Schutzschicht hinein diffundieren kann oder während einer Wärmebehandlung im Ofen durch die Oberfläche in die Schutzschicht hinein dif¬ fundiert, erhöht sich zusätzlich die Sprödigkeit der Aus¬ scheidungen. Durch eine Oxidation dieser Phasen wird die Triebkraft zur Rissbildung noch verstärkt.The invention is inter alia based on the finding that the protective layer is in the protective layer itself and in the over ¬ transition region between the protective layer and the base material brittle precipitates. This time and temperature in use strengthened forming brittle phases result in the operation to very pronounced longitudinal cracks in the protective layer and in the interface layer base material with ¬ connect the replacement of the protective layer. By interaction with carbon, which can diffuse from the base material into the protective layer or during a heat treatment into sound dif ¬ in the furnace through the surface in the protective layer, in addition, the brittleness of the off ¬ increases decisions. By oxidation of these phases, the driving force for cracking is enhanced.

Wichtig ist dabei auch der Einfluss von Kobalt, das die ther¬ mischen und mechanischen Eigenschaften bestimmt.It is important the influence of cobalt, which mix the ther ¬ and determines mechanical properties.

Die Erfindung wird im Folgenden näher erläutert.The invention will be explained in more detail below.

Es zeigenShow it

Figur 1 ein Schichtsystem mit einer Schutzschicht, Figur 2 Zusammensetzungen von Superlegierungen, Figur 3 eine Gasturbine, Figur 4 eine perspektivische Ansicht einer Brennkammer und Figur 5 eine perspektivische Ansicht einer Turbinenschaufel.1 shows a layer system with a protective layer, FIG. 2 shows compositions of superalloys, FIG. 3 shows a gas turbine, FIG. 4 shows a perspective view of a combustion chamber and FIG. 5 shows a perspective view of a turbine blade.

Erfindungsgemäß enthält eine Schutzschicht 7 (Fig. 1) zum Schutz eines Bauteils 1 gegen Korrosion und Oxidation bei einer hohen Temperatur folgende Elemente (in wt%) : 26% bis 28% Kobalt (Co) 20% bis 22% Chrom (Cr) 7% bis 9% Aluminium (Al) 0,5% bis 0,7% Yttrium (Y) und/oder zumindest ein äquivalentes Metall aus der Gruppe umfassend Scandium (Sc) und die Elemente der Seltenen Erden, Rest Nickel (NiCoCrAlY) . Optional enthält die Legierung bis 2.0wt% Silizium. Weiterhin kann die Legierung bis llwt% Rhenium aufweisen. Dabei kann die vorteilhafte Wirkung des Elementes Rhenium unter Verhinderung der Sprödphasenbildung ausgenutzt werden. Optional kann die Legierung auch Ruthenium aufweisen. Das Ruthenium mit einem maximalen Anteil von llwt% kann das Rhenium teilweise oder vollständig ersetzen. Vorzugsweise wird nur Rhenium verwendet. Festzustellen ist, dass die Anteile der einzelnen Elemente besonders abgestimmt sind im Hinblick auf ihre Wirkungen. Wenn die Anteile so bemessen sind, dass sich keine Chrom-Aus¬ scheidungen bilden, entstehen vorteilhafterweise keine Spröd- phasen während des Einsatzes der Schutzschicht, so dass das Laufzeitverhalten verbessert und verlängert ist. Dies geschieht nicht nur durch einen geringen Chromgehalt, sondern auch, unter Berücksichtigung des Einflusses von Aluminium auf die Phasenbildung, durch genaue Bemessung des Ge- halts an Aluminium.According to the invention, a protective layer 7 (FIG. 1) for protecting a component 1 against corrosion and oxidation at a high temperature contains the following elements (wt%): 26% to 28% cobalt (Co) 20% to 22% chromium (Cr) 7 % to 9% aluminum (Al) 0.5% to 0.7% yttrium (Y) and / or at least one equivalent metal from the group comprising scandium (Sc) and the elements of the rare earths, balance nickel (NiCoCrAlY). Optionally, the alloy contains up to 2.0wt% silicon. Furthermore, the alloy may have up to 1 wt% rhenium. In this case, the beneficial effect of the element rhenium can be exploited while preventing the formation of brittle phase. Optionally, the alloy may also include ruthenium. The ruthenium with a maximum proportion of llwt% can replace the rhenium partially or completely. Preferably, only rhenium is used. It should be noted that the proportions of the individual elements are specially tuned with regard to their effects. When the proportions are dimensioned to be that no chromium-off decisions ¬ form, advantageously there are no brittle phases during use of the protective layer, so that the runtime behavior improved and extended is. This is done not only by a low chromium content, but also, taking into account the influence of aluminum on the phase formation, by exact measurement of the content of aluminum.

Die Auswahl von 26wt% bis 28wt% Kobalt verbessert überraschend deutlich und überproportional die thermischen und mechanischen Eigenschaften der Schutzschicht 7.The selection of 26wt% to 28wt% cobalt surprisingly significantly and disproportionately improves the thermal and mechanical properties of the protective layer 7.

Die Schutzschicht 7 weist bei guter Korrosionsbeständigkeit eine besonders gute Beständigkeit gegen Oxidation auf und zeichnet sich auch durch besonders gute Duktilitätseigen- schaften aus, so dass sie besonders qualifiziert ist für die Anwendung in einer Gasturbine bei einer weiteren Steigerung der Eintrittstemperatur. Während des Betriebs kommt es kaum zu einer Versprödung, da die Schicht kaum Chrom-Ausscheidungen, insbesondere keine Chrom-Rhenium-Ausscheidungen, aufweist, die im Laufe des Einsatzes verspröden.The protective layer 7, with good corrosion resistance, has a particularly good resistance to oxidation and is also distinguished by particularly good ductility properties, so that it is particularly qualified for use in a gas turbine with a further increase in the inlet temperature. During operation, embrittlement hardly occurs since the layer has hardly any chromium precipitates, in particular no chromium-rhenium precipitates, which become brittle in the course of use.

Vorteilhaft ist es, den Aluminiumanteil auf 8wt% festzulegen und kein AI2O3 beim Beschichten mit der Legierung zu bilden. Daher kann der Aluminiumanteil gering gehalten werden. Ebenso vorteilhaft ist es, den Anteil von Yttrium oder dem zumindest einen äquivalenten Element aus der Gruppe umfassend Scandium und den Elementen der Seltenen Erden auf 0,6wt% festzulegen. Gewisse Schwankungen ergeben sich aufgrund groß- industrieller Herstellung, so dass auch Yttriumgehalte von 0,4wt% bis 0,5wt% bzw. 0,7wt% bis 0,8wt% verwendet werden und ebenfalls gute Eigenschaften zeigen.It is advantageous to set the aluminum content to 8% by weight and not to form Al 2 O 3 during coating with the alloy. Therefore, the aluminum content can be kept low. It is also advantageous to set the proportion of yttrium or the at least one equivalent element from the group consisting of scandium and the elements of the rare earths to 0.6 wt%. Certain fluctuations result from large-scale industrial production, so that also yttrium contents of 0.4wt% to 0.5wt% or 0.7wt% to 0.8wt% are used and also show good properties.

Besonders günstig ist es dabei jeweils den Chromgehalt auf etwa 21wt%, den Aluminiumgehalt auf etwa 8wt% und den Kobaltgehalt auf etwa 27wt% festzulegen. Vorzugsweise enthält die Legierung gegenüber den Elementen Nickel, Chrom, Kobalt, Aluminium, Yttrium (Sc, Seltene Erden), Silizium und Rhenium keine weiteren Elemente.It is particularly favorable in each case to set the chromium content to about 21% by weight, the aluminum content to about 8% by weight and the cobalt content to about 27% by weight. Preferably, the alloy contains no other elements than the elements nickel, chromium, cobalt, aluminum, yttrium (Sc, rare earths), silicon and rhenium.

Besonders gute Ausführungsbeispiele sind:Particularly good embodiments are:

1) Ni - 27Co - 21Cr - 8Al - 0.6Y1) Ni - 27Co - 21Cr - 8Al - 0.6Y

2) Ni - 27Co - 21Cr - 8Al - 0.6Y - 1.5Si 3) Ni - 27Co - 21Cr - 8Al - 0.6Y - 1.5Si - Re2) Ni - 27Co - 21Cr - 8Al - 0.6Y - 1.5Si 3) Ni - 27Co - 21Cr - 8Al - 0.6Y - 1.5Si - Re

Eine ebenso wichtige Rolle spielen die Spurenelemente im zu verspritzenden Pulver, die Ausscheidungen bilden und damit Versprödungen darstellen.An equally important role is played by the trace elements in the powder to be sprayed, which form precipitates and thus embrittle them.

Die Pulver werden beispielsweise durch Plasmaspritzen aufgebracht (APS, LPPS, VPS, ...) . Andere Verfahren sind ebenso denkbar (PVD, CVD, Kaltgasspritzen) .The powders are applied for example by plasma spraying (APS, LPPS, VPS, ...). Other methods are also conceivable (PVD, CVD, cold gas spraying).

Die Dicke der Schutzschicht 7 auf dem Bauteil 1 wird vorzugsweise auf einen Wert zwischen etwa lOOμm und 300μm bemessen .The thickness of the protective layer 7 on the component 1 is preferably dimensioned to a value of between about 100 μm and 300 μm.

Bei diesem Bauteil ist die Schutzschicht 7 vorteilhafter- weise aufgetragen auf ein Substrat 4 aus einer Superlegie- rung auf Nickel- oder Kobaltbasis.In this component, the protective layer 7 is advantageously applied to a substrate 4 made of a nickel or cobalt-based superalloy.

Als Substrat 4 kommt insbesondere folgende Zusammensetzung in Frage (Angaben in wt%) :In particular, the following composition is suitable as substrate 4 (data in wt%):

0, 1% bis 0, 15% Kohlenstoff0, 1% to 0, 15% carbon

18% bis 22% Chrom18% to 22% chrome

18% bis 19% Kobalt18% to 19% cobalt

0% bis 2% Wolfram0% to 2% tungsten

0% bis 4% Molybdän0% to 4% molybdenum

0% bis 1,5% Tantal0% to 1.5% tantalum

0% bis 1% Niob0% to 1% niobium

1% bis 3% Aluminium1% to 3% aluminum

2% bis 4% Titan 0% bis 0,75% Hafnium wahlweise geringe Anteile von Bor und/oder Zirkon, Rest Nickel .2% to 4% titanium 0% to 0.75% hafnium optionally small amounts of boron and / or zirconium, remainder nickel.

Zusammensetzungen dieser Art sind als Gusslegierungen unter den Bezeichnungen GTD222, IN939, IN6203 und Udimet 500 bekannt .Compositions of this type are known as casting alloys under the designations GTD222, IN939, IN6203 and Udimet 500.

Weitere vorteilhafte Alternativen für das Substrat 4 des Bauteils werden in Figur 2 aufgelistet.Further advantageous alternatives for the substrate 4 of the component are listed in FIG.

Die Schutzschicht 7 eignet sich besonders zum Schutz eines Bauteils gegen Korrosion und Oxidation, während das Bauteil bei einer Materialtemperatur um etwa 95O0C, bei Flugturbinen auch um etwa HOO0C, mit einem Rauchgas beaufschlagt wird.The protective layer 7 is particularly suitable for protecting a component against corrosion and oxidation, while the component is acted upon by a flue gas at a material temperature of about 95O 0 C, in airplanes also by about HOO 0 C.

Die Schutzschicht 7 gemäß der Erfindung ist damit besonders qualifiziert zum Schutz eines Bauteils einer Gasturbine 100, insbesondere einer Leitschaufel 120, Laufschaufel 130 oder anderen Komponente, die mit heißem Gas vor oder in der Turbine der Gasturbine beaufschlagt wird. Die Schutzschicht 7 kann als overlay (Schutzschicht ist die äußere Schicht oder als Bondcoat (Schutzschicht ist eine Zwischenschicht) verwendet werden.The protective layer 7 according to the invention is thus particularly qualified for protecting a component of a gas turbine 100, in particular a guide blade 120, blade 130 or other component, which is acted upon by hot gas before or in the turbine of the gas turbine. The protective layer 7 can be used as an overlay (protective layer is the outer layer or as a bondcoat (protective layer is an intermediate layer).

Figur 1 zeigt als ein Bauteil ein Schichtsystem 1. Das Schichtsystem 1 besteht aus einem Substrat 4. Das Substrat 4 kann metallisch und/oder keramisch sein. Insbesondere bei Turbinenbauteilen, wie z.B. Turbinenlauf- 120 (Fig. 1) oder -leitschaufeln 130 (Fig. 3, 5), Brennkammeraus- kleidungen 155 (Fig. 4) sowie anderen Gehäuseteilen einerFIG. 1 shows a layer system 1 as a component. The layer system 1 consists of a substrate 4. The substrate 4 may be metallic and / or ceramic. In particular with turbine components, such as e.g. Turbine barrel 120 (FIG. 1) or vanes 130 (FIGS. 3, 5), combustor liners 155 (FIG. 4), as well as other housing parts

Dampf- oder Gasturbine 100 (Fig. 3), besteht das Substrat 4 aus einer nickel-, kobalt- oder eisenbasierten Superlegie- rung.Steam turbine or gas turbine 100 (FIG. 3), the substrate 4 consists of a nickel-, cobalt- or iron-based superalloy.

Vorzugsweise werden kobaltbasierte Superlegierungen verwen- det.Preferably, cobalt-based superalloys are used.

Auf dem Substrat 4 ist die erfindungsgemäße Schutzschicht 7 vorhanden. Vorzugsweise wird diese Schutzschicht 7 durch LPPS (low pres¬ sure plasma spraying) aufgebracht.On the substrate 4, the protective layer 7 according to the invention is present. Preferably, this protective layer is applied by LPPS (low pres sure ¬ plasma spraying). 7

Diese kann als äußere Schicht (nicht dargestellt) oder Zwischenschicht (Fig. 1) verwendet werden. Im letzteren Fall ist auf der Schutzschicht 7 eine keramische Wärmedämmschicht 10 vorhanden.This can be used as outer layer (not shown) or intermediate layer (FIG. 1). In the latter case, a ceramic thermal barrier coating 10 is present on the protective layer 7.

Die Schutzschicht 7 kann auf neu hergestellte Bauteile und wieder aufgearbeitete Bauteile aus dem Refurbishment aufgebracht werden. Wiederaufarbeitung (Refurbishment) bedeutet, dass Bauteile 1 nach ihrem Einsatz gegebenenfalls von Schichten (Wärmedämmschicht) getrennt werden und Korrosions- und Oxidationspro- dukte entfernt werden, beispielsweise durch eine Säurebehand¬ lung (Säurestrippen) . Gegebenenfalls müssen noch Risse repa- riert werden. Danach kann ein solches Bauteil wieder beschichtet werden, da das Substrat 4 sehr teuer ist.The protective layer 7 can be applied to newly manufactured components and refurbished components from the refurbishment. Reprocessing (Refurbishment) means that components 1 are separated after their use, if appropriate, of layers (heat insulating layer) and corrosion and oxidation products are removed, for example by a Säurebehand ¬ averaging (acid stripping). If necessary, cracks must still be repaired. Thereafter, such a component can be coated again because the substrate 4 is very expensive.

Die Figur 3 zeigt beispielhaft eine Gasturbine 100 in einem Längsteilschnitt.FIG. 3 shows by way of example a gas turbine 100 in a longitudinal partial section.

Die Gasturbine 100 weist im Inneren einen um eine Rotationsachse 102 drehgelagerten Rotor 103 auf, der auch als Turbinenläufer bezeichnet wird. Entlang des Rotors 103 folgen aufeinander ein Ansauggehäuse 104, ein Verdichter 105, eine beispielsweise torusartigeThe gas turbine 100 has inside a rotatably mounted about a rotation axis 102 rotor 103, which is also referred to as a turbine runner. Along the rotor 103 successively follow an intake housing 104, a compressor 105, for example, a torus-like

Brennkammer 110, insbesondere Ringbrennkammer 106, mit mehreren koaxial angeordneten Brennern 107, eine Turbine 108 und das Abgasgehäuse 109. Die Ringbrennkammer 106 kommuniziert mit einem beispielsweise ringförmigen Heißgaskanal 111. Dort bilden beispielsweise vier hintereinander geschaltete Turbinenstufen 112 die Turbine 108.Combustion chamber 110, in particular annular combustion chamber 106, with a plurality of coaxially arranged burners 107, a turbine 108 and the exhaust housing 109. The annular combustion chamber 106 communicates with an example annular hot gas channel 111. There, for example, four successively connected turbine stages 112 form the turbine 108th

Jede Turbinenstufe 112 ist aus zwei Schaufelringen gebildet. In Strömungsrichtung eines Arbeitsmediums 113 gesehen folgt im Heißgaskanal 111 einer Leitschaufelreihe 115 eine aus Laufschaufeln 120 gebildete Reihe 125. Die Leitschaufeln 130 sind dabei an einem Innengehäuse 138 eines Stators 143 befestigt, wohingegen die Laufschaufeln 120 einer Reihe 125 bspw. mittels einer Turbinenscheibe 133 am Rotor 103 angebracht sind. An dem Rotor 103 angekoppelt ist ein Generator oder eine Arbeitsmaschine (nicht dargestellt) .Each turbine stage 112 is formed of two blade rings. As seen in the direction of flow of a working medium 113, in the hot gas channel 111 of a row of guide vanes 115, a series 125 formed of rotor blades 120 follows. The guide vanes 130 are fastened to an inner housing 138 of a stator 143, whereas the moving blades 120 of a row 125 are attached to the rotor 103 by means of a turbine disk 133, for example. Coupled to the rotor 103 is a generator or work machine (not shown).

Während des Betriebes der Gasturbine 100 wird vom Verdichter 105 durch das Ansauggehäuse 104 Luft 135 angesaugt und verdichtet. Die am turbinenseitigen Ende des Verdichters 105 be- reitgestellte verdichtete Luft wird zu den Brennern 107 geführt und dort mit einem Brennmittel vermischt. Das Gemisch wird dann unter Bildung des Arbeitsmediums 113 in der Brennkammer 110 verbrannt. Von dort aus strömt das Arbeitsmedium 113 entlang des Heiß- gaskanals 111 vorbei an den Leitschaufeln 130 und den Lauf¬ schaufeln 120. An den Laufschaufeln 120 entspannt sich das Arbeitsmedium 113 impulsübertragend, so dass die Laufschau¬ feln 120 den Rotor 103 antreiben und dieser die an ihn angekoppelte Arbeitsmaschine.During operation of the gas turbine 100, air 105 is sucked in and compressed by the compressor 105 through the intake housing 104. The compressed air provided at the turbine-side end of the compressor 105 is guided to the burners 107 and mixed there with a fuel. The mixture is then burned to form the working fluid 113 in the combustion chamber 110. From there, the working medium 113 flows along the hot-gas passage 111 past the guide vanes 130 and the rotor ¬ blades 120. At the rotor blades 120, the working medium 113 is expanded, transferring its momentum, so that the run show ¬ feln 120 drive the rotor 103 and the latter attached to him work machine.

Die dem heißen Arbeitsmedium 113 ausgesetzten Bauteile unterliegen während des Betriebes der Gasturbine 100 thermischen Belastungen. Die Leitschaufeln 130 und Laufschaufeln 120 der in Strömungsrichtung des Arbeitsmediums 113 gesehen ersten Turbinenstufe 112 werden neben den die Ringbrennkammer 106 auskleidenden Hitzeschildsteinen am meisten thermisch belastet .The components exposed to the hot working medium 113 are subject to thermal loads during operation of the gas turbine 100. The guide vanes 130 and rotor blades 120 of the first turbine stage 112, viewed in the direction of flow of the working medium 113, are subjected to the greatest thermal stress in addition to the heat shield bricks lining the annular combustion chamber 106.

Um den dort herrschenden Temperaturen standzuhalten, werden diese mittels eines Kühlmittels gekühlt. Ebenso können die Substrate eine gerichtete Struktur aufwei¬ sen, d.h. sie sind einkristallin (SX-Struktur) oder weisen nur längsgerichtete Körner auf (DS-Struktur) . Als Material werden eisen-, nickel- oder kobaltbasierte Su- perlegierungen verwendet . Beispielsweise werden Superlegierungen verwendet, wie sie aus der EP 1 204 776, EP 1 306 454, EP 1 319 729, WO 99/67435 oder WO 00/44949 bekannt sind. Diese Schriften bezüglich der Zusammensetzung der Superlegierungen und deren Vorteile sind Teil der Offenbarung.In order to withstand the temperatures prevailing there, they are cooled by means of a coolant. The substrates may likewise have a directional structure sen aufwei ¬ she ie are monocrystalline (SX structure) or have only longitudinally oriented grains (DS structure). The material used is iron, nickel or cobalt-based superalloys. For example, superalloys are used, as are known from EP 1 204 776, EP 1 306 454, EP 1 319 729, WO 99/67435 or WO 00/44949. These writings concerning the Composition of superalloys and their advantages are part of the disclosure.

Die Schaufeln 120, 130 weisen erfindungsgemäße Schutzschich- ten 7 gegen Korrosion und Korrosion und/oder eine Wärmedämmschicht auf. Die Wärmedämmschicht besteht beispielsweise ZrO2, Y2O3-ZrO2, d.h. sie ist nicht, teilweise oder vollstän¬ dig stabilisiert durch Yttriumoxid und/oder Kalziumoxid und/oder Magnesiumoxid. Durch geeignete Beschichtungsverfahren wie z.B. Elektronen- strahlverdampfen (EB-PVD) werden stängelförmige Körner in der Wärmedämmschicht erzeugt.The blades 120, 130 have protective layers 7 according to the invention against corrosion and corrosion and / or a thermal barrier coating. The thermal barrier coating consists, for example, ZrO 2, Y 2 O 3 -ZrO 2, ie it is not, partly full text or ¬ dig stabilized by yttrium oxide and / or calcium and / or magnesium oxide. Suitable coating processes, such as electron beam evaporation (EB-PVD), produce stalk-shaped grains in the thermal barrier coating.

Die Leitschaufel 130 weist einen dem Innengehäuse 138 der Turbine 108 zugewandten Leitschaufelfuß (hier nicht dargestellt) und einen dem Leitschaufelfuß gegenüberliegenden Leitschaufelkopf auf. Der Leitschaufelkopf ist dem Rotor 103 zugewandt und an einem Befestigungsring 140 des Stators 143 festgelegt .The vane 130 has a guide vane foot (not shown here) facing the inner housing 138 of the turbine 108 and a vane head opposite the vane foot. The vane head faces the rotor 103 and fixed to a mounting ring 140 of the stator 143.

Die Figur 4 zeigt eine Brennkammer 110 einer Gasturbine 100, die ein Schichtsystem 1 aufweisen kann.FIG. 4 shows a combustion chamber 110 of a gas turbine 100, which may have a layer system 1.

Die Brennkammer 110 ist beispielsweise als so genannte Ring- brennkammer ausgestaltet, bei der eine Vielzahl von in Um- fangsrichtung um die Turbinenwelle 103 herum angeordneten Brennern 102 in einen gemeinsamen Brennkammerraum münden. Dazu ist die Brennkammer 110 in ihrer Gesamtheit als ringförmige Struktur ausgestaltet, die um die Turbinenwelle 103 herum positioniert ist.The combustion chamber 110 is designed, for example, as a so-called annular combustion chamber, in which a multiplicity of burners 102 arranged around the turbine shaft 103 in the circumferential direction open into a common combustion chamber space. For this purpose, the combustion chamber 110 is configured in its entirety as an annular structure, which is positioned around the turbine shaft 103 around.

Zur Erzielung eines vergleichsweise hohen Wirkungsgrades ist die Brennkammer 110 für eine vergleichsweise hohe Temperatur des Arbeitsmediums M von etwa 10000C bis 16000C ausgelegt. Um auch bei diesen, für die Materialien ungünstigen Betriebsparametern eine vergleichsweise lange Betriebsdauer zu ermög¬ lichen, ist die Brennkammerwand 153 auf ihrer dem Arbeitsmedium M zugewandten Seite mit einer aus Hitzeschildelementen 155 gebildeten Innenauskleidung versehen. Jedes Hitzeschildelement 155 ist arbeitsmediumsseitig mit einer besonders hit¬ zebeständigen Schutzschicht ausgestattet oder aus hochtempe¬ raturbeständigem Material gefertigt und weist die Schutz- schicht 7 gemäß Figur 1 auf.To achieve a comparatively high efficiency, the combustion chamber 110 is designed for a comparatively high temperature of the working medium M of about 1000 ° C. to 1600 ° C. To even under these unfavorable for the materials operating parameters, a relatively long service life to union made ¬, the combustion chamber wall 153 is on its side facing the working medium M, with a facing side of heat shield elements 155 formed inner lining provided. Each heat shield element 155 is the working medium side with a particularly hit ¬ zebeständigen protective layer or made of high-tempe ¬ raturbeständigem material and has the protective layer 7 according to Figure 1 on.

Aufgrund der hohen Temperaturen im Inneren der Brennkammer 110 ist zudem für die Hitzeschildelemente 155 bzw. für deren Halteelemente ein Kühlsystem vorgesehen.Due to the high temperatures in the interior of the combustion chamber 110, a cooling system is additionally provided for the heat shield elements 155 or for their holding elements.

Die Materialien der Brennkammerwand und deren Beschichtungen können ähnlich der Turbinenschaufeln 120, 130 sein.The materials of the combustor wall and their coatings may be similar to the turbine blades 120, 130.

Die Brennkammer 110 ist insbesondere für eine Detektion von Verlusten der Hitzeschildelemente 155 ausgelegt. Dazu sind zwischen der Brennkammerwand 153 und den Hitzeschildelementen 155 eine Anzahl von Temperatursensoren 158 positioniert.The combustion chamber 110 is designed in particular for detecting losses of the heat shield elements 155. For this purpose, a number of temperature sensors 158 are positioned between the combustion chamber wall 153 and the heat shield elements 155.

Figur 5 zeigt in perspektivischer Ansicht eine Schaufel 120, 130, die ein Schichtsystem 1 mit der erfindungsgemäßen Schutzschicht 7 aufweist.FIG. 5 shows a perspective view of a blade 120, 130 which has a layer system 1 with the protective layer 7 according to the invention.

Die Schaufel 120, 130 erstreckt sich entlang einer Längsachse 121. Die Schaufel 120, 130 weist entlang der Längsachse 121 auf- einander folgend einen Befestigungsbereich 400, eine daran angrenzende Schaufelplattform 403 sowie einen Schaufelblattbereich 406 auf. Insbesondere im Schaufelblattbereich 406 ist die Schutzschicht 7 oder ein Schichtsystem 1 gemäß Figur 1 ausgebildet . Im Befestigungsbereich 400 ist ein Schaufelfuß 183 gebildet, der zur Befestigung der Laufschaufeln 120, 130 an der Welle dient. Der Schaufelfuß 183 ist als Hammerkopf ausgestaltet. Andere Ausgestaltungen, beispielsweise als Tannenbaum- oder Schwalbenschwanzfuß sind möglich. Bei herkömmlichen Schaufeln 120, 130 werden in allen Bereichen 400, 403, 406 der Laufschaufel 120, 130 massive metallische Werkstoffe verwendet. Die Laufschaufel 120, 130 kann hierbei durch ein Gussverfah- ren, durch ein Schmiedeverfahren, durch ein Fräsverfahren oder Kombinationen daraus gefertigt sein. The blade 120, 130 extends along a longitudinal axis 121. The blade 120, 130 has, along the longitudinal axis 121, a fastening area 400, an adjacent blade platform 403 and an airfoil area 406. In particular in the airfoil region 406, the protective layer 7 or a layer system 1 according to FIG. 1 is formed. In the attachment region 400, a blade root 183 is formed, which serves for fastening the rotor blades 120, 130 to the shaft. The blade root 183 is designed as a hammer head. Other configurations, for example as a Christmas tree or Schwalbenschwanzfuß are possible. In conventional vanes 120, 130, solid metallic materials are used in all regions 400, 403, 406 of the blades 120, 130. The blade 120, 130 can be replaced by a casting process. ren, be made by a forging method, by a milling method or combinations thereof.

Claims

Patentansprüche claims 1. Legierung enthaltend folgende Elemente (in wt%) : 26% bis 28% Kobalt (Co)1. Alloy containing the following elements (in wt%): 26% to 28% cobalt (Co) 20% bis 22% Chrom (Cr)20% to 22% chromium (Cr) 8% bis 9% Aluminium (Al)8% to 9% aluminum (Al) 0,4% bis 0,8% Yttrium (Y) und/oder zumindest ein äquivalentes Metall aus der Gruppe umfassend Scandium (Sc] und die Elemente der Seltenen Erden optional0.4% to 0.8% yttrium (Y) and / or at least one equivalent metal from the group comprising scandium (Sc) and the rare earth elements optional 0% bis 2% Silizium (Si),0% to 2% silicon (Si), 0% bis 11% Rhenium (Re) und/oder Ruhtenium,0% to 11% rhenium (Re) and / or Ruhtenium, Rest Nickel (Ni) .Remainder nickel (Ni). 2. Legierung nach Anspruch 1, enthaltend 27wt% Kobalt.2. An alloy according to claim 1, containing 27wt% cobalt. 3. Legierung nach Anspruch 1 oder 2, enthaltend 21wt% Chrom.3. Alloy according to claim 1 or 2, containing 21wt% chromium. 4. Legierung nach Anspruch 1, 2 oder 3, enthaltend 0,6wt% Yttrium und/oder ein äquivalentes Metall aus der Gruppe umfassend Scandium und die Elemente der Seltenen Erden.4. The alloy of claim 1, 2 or 3, containing 0.6wt% of yttrium and / or an equivalent metal selected from the group consisting of scandium and the rare earth elements. 5. Legierung nach Anspruch 1, 2, 3 oder 4, enthaltend Silizium.5. The alloy of claim 1, 2, 3 or 4, containing silicon. 6. Legierung nach Anspruch 1 oder 5, enthaltend 1.0wt% bis 2.0wt% Silizium, insbesondere 1.5wt% Silizium. 6. The alloy of claim 1 or 5, containing 1.0wt% to 2.0wt% silicon, in particular 1.5wt% silicon. 7. Legierung nach Anspruch 1, 2, 3 oder 4, nicht enthaltend Silizium.7. An alloy according to claim 1, 2, 3 or 4, not containing silicon. 8. Legierung nach Anspruch 1, 2, 3, 4, 5, 6 oder 7, nicht enthaltend Rhenium.8. The alloy of claim 1, 2, 3, 4, 5, 6 or 7, not containing rhenium. 9. Legierung nach einem der Ansprüche 1 bis 7, enthaltend Rhenium.An alloy according to any one of claims 1 to 7, containing rhenium. 10. Legierung nach Anspruch 1 oder 9, enthaltend 9wt% - llwt% Rhenium, insbesondere 10wt% Rhenium.10. An alloy according to claim 1 or 9, containing 9wt% - wt% rhenium, in particular 10wt% rhenium. 11. Legierung nach Anspruch 1 oder 9, enthaltend lwt% - 3wt% Rhenium, insbesondere 1.5wt% Rhenium.11. An alloy according to claim 1 or 9, containing lwt% - 3wt% rhenium, in particular 1.5wt% rhenium. 12. Legierung nach einem der Ansprüche 1 bis 11, bestehend aus Nickel, Kobalt, Chrom, Aluminium, Yttrium und optional aus Silizium und/oder Rhenium.12. An alloy according to any one of claims 1 to 11, consisting of nickel, cobalt, chromium, aluminum, yttrium and optionally of silicon and / or rhenium. 13. Legierung nach Anspruch 1, enthaltend 0.5wt% bis 0.7wt% Yttrium.13. The alloy of claim 1, containing 0.5wt% to 0.7wt% yttrium. 14. Legierung nach Anspruch 1, 8 oder 9, enthaltend Ruthenium. 14. An alloy according to claim 1, 8 or 9, containing ruthenium. 15. Legierung nach Anspruch 1, 8 oder 9, nicht enthaltend Ruthenium.An alloy according to claim 1, 8 or 9, not containing ruthenium. 16. Schutzschicht zum Schutz eines Bauteils (1, 120, 130, 138, 155) gegen Korrosion und/oder Oxidation, insbesondere bei hohen Temperaturen, die die Zusammensetzung der Legierung gemäß einem oder mehreren der Ansprüche 1 bis 15 aufweist.16. A protective layer for protecting a component (1, 120, 130, 138, 155) against corrosion and / or oxidation, in particular at high temperatures, which has the composition of the alloy according to one or more of claims 1 to 15. 17. Bauteil, insbesondere ein Bauteil (1, 120, 130, 138, 155) einer Gasturbine (100), das zum Schutz gegen Korrosion und Oxidation bei hohen17. Component, in particular a component (1, 120, 130, 138, 155) of a gas turbine (100), which protects against corrosion and oxidation at high Temperaturen eine Schutzschicht (7) nach Anspruch 16 auf¬ weist .Temperatures a protective layer (7) according to claim 16 has ¬ . 18. Bauteil nach Anspruch 17, bei dem auf der Schutzschicht (7) eine keramische Wärmedämmschicht (10) aufgebracht ist.18. Component according to claim 17, wherein on the protective layer (7) a ceramic thermal barrier coating (10) is applied. 19. Bauteil nach Anspruch 17 oder 18, bei dem ein Substrat (4) des Bauteils (1, 120, 130, 138, 155) aus einer nickelbasierten Legierung besteht.19. Component according to claim 17 or 18, wherein a substrate (4) of the component (1, 120, 130, 138, 155) consists of a nickel-based alloy. 20. Bauteil nach Anspruch 17 oder 18, bei dem ein Substrat (4) des Bauteils (1, 120, 130, 13Ϊ 155) aus einer kobaltbasierten Legierung besteht. 20. Component according to claim 17 or 18, wherein a substrate (4) of the component (1, 120, 130, 13Ϊ 155) consists of a cobalt-based alloy.
EP06807569A 2005-11-04 2006-10-26 Alloy, protective layer for protecting a component from corrosion and/or oxidation at high temperatures and component Withdrawn EP1948836A1 (en)

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