EP1507897A1 - Mcral layer - Google Patents

Mcral layer

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Publication number
EP1507897A1
EP1507897A1 EP03727493A EP03727493A EP1507897A1 EP 1507897 A1 EP1507897 A1 EP 1507897A1 EP 03727493 A EP03727493 A EP 03727493A EP 03727493 A EP03727493 A EP 03727493A EP 1507897 A1 EP1507897 A1 EP 1507897A1
Authority
EP
European Patent Office
Prior art keywords
layer
mcral
mcral layer
elements
group
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.)
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Application number
EP03727493A
Other languages
German (de)
French (fr)
Inventor
Willem J. Quadakkers
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
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Publication date
Application filed by Siemens AG filed Critical Siemens AG
Priority to EP03727493A priority Critical patent/EP1507897A1/en
Priority to EP10007167.9A priority patent/EP2251457B1/en
Publication of EP1507897A1 publication Critical patent/EP1507897A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • 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
    • 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
    • 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
    • Y10T428/12583—Component contains compound of adjacent metal
    • Y10T428/1259—Oxide
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
    • Y10T428/12611—Oxide-containing component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12944—Ni-base component

Definitions

  • the invention relates to an MCrAl layer for components exposed to high temperatures, in particular for a turbine blade, in particular for a gas turbine.
  • the MCrAl layers are usually applied to the metallic high-temperature component by means of vacuum or air plasma spraying.
  • the ß-NiAl layers are applied using an alitizing process.
  • these types of protective layers are used both as a pure oxidation and corrosion protection layer and in the form of adhesion promoter layers for ceramic thermal insulation layers, for example based on zirconium oxide.
  • the protective effect of the layer systems is based on an aluminum oxide layer which forms on these layers at the high operating temperatures.
  • the MCrAl and ⁇ -NiAl layers usually contain small amounts of oxygen-affine elements, in particular yttrium.
  • ⁇ -NiAl layers this is usually about 25-30% by weight, while the MCrAl layer contain about 8 - 14 wt% aluminum.
  • the MCrAl layers have the advantage compared to the ß-NiAl layers that they are less brittle and more corrosion-resistant in sulfur-containing process gases.
  • the problems with the adhesion of the TGO are mainly due to the fact that when the MCrAl-coated component cools, thermally induced voltages occur in and near the TGO, which are due to the differences in the thermal
  • the regular flaking of the TGO and the subsequent re-fertilization of an oxide layer leads to an accelerated consumption of the covering layer-forming element aluminum and thus to a shortening of the life of the MCrAl layer ,
  • the MCrAl layer is used as an adhesion promoter layer for ceramic thermal insulation layers, flaking off of the TGO will immediately cause flaking and thus catastrophic failure of the thermal insulation layer. So far, attempts have been made to achieve a layer structure with good interlocking with the ceramic by overplating the MCrAl layer with low aluminum contents of approximately 8 wt%. However, this means applying another layer.
  • US Pat. No. 5,741,556 shows a MCrAl layer with yttrium, in which nitrogen is used as the inert gas in the production of the layer.
  • U.S. Patent 5,981,091 shows an MCrAl layer which can contain hafnium, yttrium, carbon and nitrogen. In this thermal insulation layer system, however, a layer enriched with platinum is applied to the MCrAl layer.
  • US Pat. No. 4,774,149 discloses an MCrAl layer with hafnium, yttrium and a nitrogen content in the powder, which is, however, undesirable and should be reduced to a minimum.
  • US Pat. No. 5,780,171 discloses an MCrAl layer with hafnium and yttrium, nitrogen being used as the carrier gas in the production of the layer.
  • WO 99/23270 discloses an MCrAl layer to which lanthanum and hafnium are added.
  • GB 2 243 161 A discloses an MCrAl layer with additions of zirconium, silicon, tantalum, hafnium, yttrium, scandium or lanthanum.
  • U.S. Patent 5,141,821 discloses an MCrAl layer, with included particles of carbides, to maintain abrasion to improve the layer.
  • the MCrAl layer can also contain zirconium, hafnium and tantalum.
  • the invention is based on the finding that good adhesion of the TGO to the MCrAl layer is positively influenced by a microporosity of the TGO.
  • the pores present in the TGO should have a diameter of 10 to 500 nm.
  • the pore spacing is 30 to 600 nm, the pore spacing increasing with increasing pore size.
  • microporosity is based on the fact that the thermal stresses that occur during cooling can be reduced by strains that occur in the aluminum oxide layer in the micro-range. This is not possible in high-density TGOs, since even the slightest stretch leads to catastrophic crack growth and thus to TGO spalling.
  • Microporous TGOs are therefore more tolerant to stretching and more suitable for reducing thermally induced stresses than high-density TGOs.
  • the MCrAl layer used for example is a Ni-CoCrAl layer and has concentrations of the main alloy elements in accordance with the prior art: 10 to 82 wt% cobalt, 10 to 35 wt% chromium, 8 to 14 wt% aluminum, Rest of nickel with other optional alloy additives.
  • Such alloy additives are for this composition or other compositions, for example silicon (up to 2 wt%), rhenium (0.3 to 5 wt%) and tantalum (up to 8 wt%).
  • the MCrAl layer must also have the following additions of at least one element from each of groups I, II and III:
  • Group I at least one oxygen-affine element, i.e.
  • the concentration of the sum of these elements is in the range 0.02 to 1 wt%, preferably between 0.05 to 0.5 wt%.
  • Group II at least one element from the group of hafnium, zirconium and titanium, since these elements form thermodynamically very stable compounds with nitrogen and carbon (nitrides and carbides);
  • concentration of the sum of these elements is in the range 0.02 to 1 wt%, preferably 0.05 to 0.3 wt%.
  • Group III carbon and / or nitrogen, the concentration of the sum of carbon and nitrogen being 0.005 to 0.2 wt%, preferably 0.01 to 0.1 wt%.
  • the elements from group II are also very oxygen-affine elements, but at the same time they form very stable nitrides and carbides. Since the MCrAl layer contains both additions of elements of group I and group II, the elements of group I are preferably oxidized. The elements of group II are preferred with the in carbon and / or nitrogen present in the MCrAlY layer react and thus form fine precipitates of carbides and / or nitrides.
  • the Group II elements would preferably react with oxygen, since the relevant oxides of the elements have a higher thermodynamic stability than the respective carbides, nitrides or carbonitrides. The elements from group II would be consumed by this oxide formation and therefore the formation of carbides and nitrides would not take place.
  • the elements of group II become fine precipitates with a typical diameter of 10 to 900 nm in the form of carbides, nitrides with high temperature use or prior heat treatment with carbon and / or nitrogen and / or form carbonitrides.
  • a targeted pre-oxidation process i.e. Before the MCrAl adhesion promoter layer is coated with a ceramic thermal insulation layer, the fine precipitates which are close to the surface of the MCrAl layer are enclosed by the inwardly growing aluminum oxide layer. If the layer continues to grow, the enclosed carbides and / or nitrides or carbonitrides will oxidize because of the locally increasing oxygen partial pressure. This is associated with a change in volume and release of gases.
  • These two processes lead to the formation of very fine pores with a diameter of 10 to 800 nm and microcracks with a length of 10 to 600 nm in the aluminum oxide layer (TGO).

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Coating By Spraying Or Casting (AREA)

Abstract

MCrAl layers according to prior art often display chipping of the thermally grown aluminium oxide layer (TGO) as a result of thermally induced stresses, which significantly reduces the oxidation behaviour or the bonding behaviour of ceramic heat insulating layers. An inventive MCrAl layer is designed in such a way that the TGO created thereon is microporous and thus allows expansion. The microporosity of the TGO is ensured by adding elements into the MCrAl layer in a targeted manner.

Description

MCrAl-Schicht MCrAl layer
Die Erfindung betrifft eine MCrAl-Schicht für hochtemperatur- belastete Bauteile, insbesondere für eine Turbinenschaufel, insbesondere für eine Gasturbine.The invention relates to an MCrAl layer for components exposed to high temperatures, in particular for a turbine blade, in particular for a gas turbine.
Metallische Komponenten, die bei hohen Temperaturen eingesetzt werden, müssen in vielen Bereichen der Technik durch SchichtSysteme gegen den oxidierenden, korrosiven und/oder degradierenden Angriff der Betriebsatmosphäre geschützt werden. Für den Bereich Gasturbinen, d.h. Flugtriebwerke und industrielle stationäre Gasturbinen, ist es seit vielen Jahren Stand der Technik die Hochtemperaturkomponenten gegen die Degradation durch Aufbringen von Schichten vom Typ MCrAl (M= Fe, Co, Ni) oder ß-NiAl zu schützen.Metallic components that are used at high temperatures must be protected in many areas of technology by layer systems against the oxidizing, corrosive and / or degrading attack of the operating atmosphere. For the gas turbine sector, i.e. Aircraft engines and industrial stationary gas turbines, it has been the state of the art for many years to protect the high-temperature components against degradation by applying layers of the type MCrAl (M = Fe, Co, Ni) or ß-NiAl.
Die MCrAl-Schichten werden üblicherweise mittels Vakuum- oder Luftplasmaspritzen auf die metallische Hochtemperaturkomponente aufgebracht . Die ß-NiAl-Schichten werden über Alitierverfahren aufge- bracht.The MCrAl layers are usually applied to the metallic high-temperature component by means of vacuum or air plasma spraying. The ß-NiAl layers are applied using an alitizing process.
Diese Arten von Schutzschichten werden, abhängig von der jeweiligen Komponente und den Betriebsbedingungen, sowohl als reine Oxidations- und Korrosionsschutzschicht als auch in Form von Haftvermittlerschichten für keramische Wärmedämm- schichten, beispielsweise auf Zirkonoxidbasis, eingesetzt.Depending on the respective component and the operating conditions, these types of protective layers are used both as a pure oxidation and corrosion protection layer and in the form of adhesion promoter layers for ceramic thermal insulation layers, for example based on zirconium oxide.
In beiden genannten Anwendungsf llen beruht die Schutzwirkung der Schichtsysteme auf einer Aluminiumoxidschicht, die sich bei den hohen Betriebstemperaturen auf diesen Schichten bil- det. Zum Erzielen einer geringen Wachstumsrate und einer guten Haftung der Aluminiumoxidschicht enthalten die MCrAl- und ß-NiAl -Schichten üblicherweise geringe Mengen Sauerstoff- affiner Elemente, insbesondere Yttrium.In both of the applications mentioned, the protective effect of the layer systems is based on an aluminum oxide layer which forms on these layers at the high operating temperatures. To achieve a low growth rate and good adhesion of the aluminum oxide layer, the MCrAl and β-NiAl layers usually contain small amounts of oxygen-affine elements, in particular yttrium.
Um die Aluminiumoxidbildung auch während eines Langzeitein- satzes zu gewährleisten, muss der Aluminiumgehalt in demIn order to ensure the formation of aluminum oxide even during long-term use, the aluminum content in the
Schichtsystem ausreichend hoch sein. Bei ß-NiAl-Schichten ist dies üblicherweise etwa 25 - 30wt%, während die MCrAl-Schich- ten etwa 8 - 14 wt% Aluminium enthalten. Die MCrAl-Schichten haben im Vergleich zu den ß-NiAl-Schichten den Vorteil, dass sie weniger spröde sind und außerdem korrosionsbeständiger in schwefelhaltigen Betriebsgasen sind.Layer system must be sufficiently high. In the case of β-NiAl layers, this is usually about 25-30% by weight, while the MCrAl layer contain about 8 - 14 wt% aluminum. The MCrAl layers have the advantage compared to the ß-NiAl layers that they are less brittle and more corrosion-resistant in sulfur-containing process gases.
Aufgrund von Laboruntersuchungen und Betriebserfahrungen hat sich gezeigt, dass die Langzeiteigenschaften und die Funktion zur Sicherheit der MCrAl-Schichten maßgeblich von der Haftung der thermisch gewachsenen Oxidschicht (TGO) auf Aluminium- oxidbasis, die sich auf den Oberflächen bei den hohen Betriebstemperaturen bildet, bestimmt wird. Dies gilt sowohl beim Einsatz der MCrAl-Schichten zwecks Oxidations- und Korrosionsschutz einer metallischen Komponente, jedoch auch insbesondere im Falle einer Anwendung als Haftvermittlerschicht für keramische Warmedammschichten.Laboratory studies and operating experience have shown that the long-term properties and the function for the safety of the MCrAl layers are largely determined by the adhesion of the thermally grown oxide layer (TGO) based on aluminum oxide, which forms on the surfaces at high operating temperatures , This applies both when using the MCrAl layers for the protection against oxidation and corrosion of a metallic component, but also particularly when used as an adhesion promoter layer for ceramic thermal insulation layers.
Die Probleme mit der Haftung der TGO beruhen vorwiegend auf der Tatsache, dass beim Abkühlen der MCrAl beschichteten Komponente in und in der Nähe der TGO thermisch induzierte Span- nungen auftreten, die auf die Unterschiede im thermischenThe problems with the adhesion of the TGO are mainly due to the fact that when the MCrAl-coated component cools, thermally induced voltages occur in and near the TGO, which are due to the differences in the thermal
Ausdehnungskoeffizienten zwischen der MCrAl-Schicht und der TGO auf Aluminiumoxidbasis zurückzuführen sind. Wenn während des Langzeiteinsatzes wachstumsbedingte Risse in der Nähe der Grenzfläche zwischen TGO und MCrAl-Schicht entstehen, führen die thermisch induzierten Spannungen zum Abplatzen der TGO.Expansion coefficients between the MCrAl layer and the TGO based on aluminum oxide. If growth-related cracks occur in the vicinity of the interface between the TGO and MCrAl layer during long-term use, the thermally induced stresses cause the TGO to flake off.
Beim Einsatz des MCrAl-Werkstoffs als reine Oxidations- und Korrosionsschicht einer metallischen Komponente, führt das regelmäßige Abplatzen der TGO und die darauf folgende Neubil- düng einer Oxidschicht zu einem beschleunigten Verbrauch des deckschichtbildenden Elements Aluminium und somit zu einer Verkürzung der Lebensdauer der MCrAl-Schicht.When using the MCrAl material as a pure oxidation and corrosion layer of a metallic component, the regular flaking of the TGO and the subsequent re-fertilization of an oxide layer leads to an accelerated consumption of the covering layer-forming element aluminum and thus to a shortening of the life of the MCrAl layer ,
Beim Einsatz der MCrAl-Schicht als Haftvermittlerschicht für keramische Warmedammschichten wird ein Abplatzen der TGO unmittelbar ein Abplatzen und damit ein katastrophales Versagen der Wärmedämmschicht bewirken. Bisher wurde versucht, durch ein Überplatinieren der MCrAl- Schicht mit niedrigen Aluminiumgehalten von etwa 8wt% eine SchichtStruktur mit guter Verzahnung zur Keramik zu errei- chen. Dies bedeutet jedoch das Aufbringen einer weiteren Schicht .If the MCrAl layer is used as an adhesion promoter layer for ceramic thermal insulation layers, flaking off of the TGO will immediately cause flaking and thus catastrophic failure of the thermal insulation layer. So far, attempts have been made to achieve a layer structure with good interlocking with the ceramic by overplating the MCrAl layer with low aluminum contents of approximately 8 wt%. However, this means applying another layer.
Die US-PS 5,741,556 zeigt eine MCrAl-Schicht mit Yttrium, bei der Stickstoff als Inertgas bei der Herstellung der Schicht verwendet wird.US Pat. No. 5,741,556 shows a MCrAl layer with yttrium, in which nitrogen is used as the inert gas in the production of the layer.
Die US-PS 5,981,091 zeigt eine MCrAl-Schicht, die Hafnium, Yttrium, Kohlenstoff und Stickstoff enthalten kann. Bei diesem Wärmedämmschichtsystem wird jedoch eine mit Platin ange- reicherte Schicht auf die MCrAl-Schicht aufgebracht.U.S. Patent 5,981,091 shows an MCrAl layer which can contain hafnium, yttrium, carbon and nitrogen. In this thermal insulation layer system, however, a layer enriched with platinum is applied to the MCrAl layer.
Die US-PS 4,774,149 offenbart eine MCrAl-Schicht mit Hafnium, Yttrium und einem Stickstoffgehalt im Pulver, der jedoch unerwünscht ist und auf ein Minimum reduziert werden soll .US Pat. No. 4,774,149 discloses an MCrAl layer with hafnium, yttrium and a nitrogen content in the powder, which is, however, undesirable and should be reduced to a minimum.
Die US-PS 5,780,171 offenbart eine MCrAl-Schicht mit Hafnium und Yttrium, wobei beim Herstellen der Schicht Stickstoff als Trägergas verwendet wird.US Pat. No. 5,780,171 discloses an MCrAl layer with hafnium and yttrium, nitrogen being used as the carrier gas in the production of the layer.
Die US-PS 5,652,028 offenbart eine MCrAl-Schicht der Zusammensetzung NiCoCrAl .US Pat. No. 5,652,028 discloses an MCrAl layer of the composition NiCoCrAl.
Die WO 99/23270 offenbart eine MCrAl-Schicht der Lanthan und Hafnium zugesetzt ist.WO 99/23270 discloses an MCrAl layer to which lanthanum and hafnium are added.
Die GB 2 243 161 A offenbart eine MCrAl-Schicht mit Zusätzen von Zirkonium, Silizium, Tantal, Hafnium, Yttrium, Scandium oder Lanthan.GB 2 243 161 A discloses an MCrAl layer with additions of zirconium, silicon, tantalum, hafnium, yttrium, scandium or lanthanum.
Die US-PS 5,141,821 offenbart eine MCrAl-Schicht, mit eingeschlossenen Partikeln von Karbiden, um das Abrasiwerhalten der Schicht zu verbessern. Die MCrAl-Schicht kann weiterhin Zirkonium, Hafnium und Tantal enthalten.U.S. Patent 5,141,821 discloses an MCrAl layer, with included particles of carbides, to maintain abrasion to improve the layer. The MCrAl layer can also contain zirconium, hafnium and tantalum.
Es ist daher Aufgabe der Erfindung eine MCrAl-Schicht aufzuzeigen, bei der ein Abplatzen der Aluminiumoxidschicht nicht stattfindet oder nur noch in geringem Maße.It is therefore an object of the invention to show an MCrAl layer in which the aluminum oxide layer does not flake off or only to a small extent.
Die Aufgabe wird durch eine MCrAl-Schicht gemäss den Patentansprüchen 1 und 2 gelost .The task is solved by an MCrAl layer according to patent claims 1 and 2.
In den Unteransprüchen sind weitere vorteilhafte Ausgestaltungen einer MCrAl-Schicht aufgelistet.Further advantageous configurations of an MCrAl layer are listed in the subclaims.
Der Erfindung liegt die Erkenntnis zugrunde, dass eine gute Haftung der TGO auf der MCrAl-Schicht positiv durch eine Mikroporosität der TGO beeinflusst wird.The invention is based on the finding that good adhesion of the TGO to the MCrAl layer is positively influenced by a microporosity of the TGO.
Dabei sollten die in der TGO vorliegenden Poren einen Durchmesser von 10 bis 500 nm aufweisen. Die Porenabstände betragen dabei 30 bis 600 nm, wobei der Porenabstand mit zunehmen- der Porengröße zunimmt.The pores present in the TGO should have a diameter of 10 to 500 nm. The pore spacing is 30 to 600 nm, the pore spacing increasing with increasing pore size.
Die positive Wirkung der Mikroporosität beruht auf der Tatsache, dass die beim Abkühlen auftretenden thermischen Spannungen durch Dehnungen, die in der Aluminiumoxidschicht im Mikrobereich auftreten, abgebaut werden können. In hochdich- ten TGO's ist dies nicht möglich, da bereits geringste Dehnungen zum katastrophalen Risswachstum und somit zum Abplatzen der TGO führen.The positive effect of microporosity is based on the fact that the thermal stresses that occur during cooling can be reduced by strains that occur in the aluminum oxide layer in the micro-range. This is not possible in high-density TGOs, since even the slightest stretch leads to catastrophic crack growth and thus to TGO spalling.
Mikroporöse TGO's sind somit dehnungstoleranter und besser geeignet zum Abbau von thermisch induzierten Spannungen als hochdichte TGO's.Microporous TGOs are therefore more tolerant to stretching and more suitable for reducing thermally induced stresses than high-density TGOs.
Die beispielsweise verwendete MCrAl-Schicht ist eine Ni- CoCrAl-Schicht und weist Konzentrationen der Hauptlegierungs- elemente entsprechend dem Stand der Technik auf : 10 bis 82 wt% Kobalt, 10 bis 35 wt% Chrom, 8 bis 14 wt% Aluminium, Rest Nickel mit weiteren optionalen Legierungszusätzen. Solche Legierungszusätze sind für diese Zusammensetzung oder auch andere Zusammensetzungen z.B. Silizium (bis 2 wt%) , Rhenium (0,3 bis 5 wt%) und Tantal (bis 8 wt%) .The MCrAl layer used for example is a Ni-CoCrAl layer and has concentrations of the main alloy elements in accordance with the prior art: 10 to 82 wt% cobalt, 10 to 35 wt% chromium, 8 to 14 wt% aluminum, Rest of nickel with other optional alloy additives. Such alloy additives are for this composition or other compositions, for example silicon (up to 2 wt%), rhenium (0.3 to 5 wt%) and tantalum (up to 8 wt%).
Um eine Mikroporosität in TGO's in bevorzugter Weise zu erreichen, muss die MCrAl-Schicht außerdem zwingend folgende Zusätze zumindest eines Elements aus jeweils einer der Gruppen I, II und III aufweisen: Gruppe I: mindestens ein Sauerstoffäffines Element, d.h. Elemente die thermodynamisch sehr stabile Oxide bilden, aus der Gruppe Yttrium, Cer, Scandium, Lanthan oder andere Lanthan- tide . Die Konzentration der Summe dieser Elemente liegt im Bereich 0,02 bis 1 wt%, bevorzugt zwischen 0,05 bis 0,5 wt%.In order to achieve a microporosity in TGO's in a preferred manner, the MCrAl layer must also have the following additions of at least one element from each of groups I, II and III: Group I: at least one oxygen-affine element, i.e. Elements that form thermodynamically very stable oxides from the group of yttrium, cerium, scandium, lanthanum or other lanthanides. The concentration of the sum of these elements is in the range 0.02 to 1 wt%, preferably between 0.05 to 0.5 wt%.
Gruppe II: mindestens ein Element der Gruppe Hafnium, Zirkonium und Titan, da diese Elemente thermodynamisch sehr stabile Verbindungen mit Stickstoff und Kohlenstoff bilden (Nitride und Karbide) ; Die Konzentration der Summe dieser Elemente liegt im Bereich 0,02 bis 1 wt%, bevorzugt 0,05 bis 0,3 wt%.Group II: at least one element from the group of hafnium, zirconium and titanium, since these elements form thermodynamically very stable compounds with nitrogen and carbon (nitrides and carbides); The concentration of the sum of these elements is in the range 0.02 to 1 wt%, preferably 0.05 to 0.3 wt%.
Gruppe III: Kohlenstoff und/oder Stickstoff, wobei die Konzentration der Summe an Kohlenstoff und Stickstoff 0,005 bis 0,2 wt%, bevorzugt 0,01 bis 0,1 wt% beträgt.Group III: carbon and / or nitrogen, the concentration of the sum of carbon and nitrogen being 0.005 to 0.2 wt%, preferably 0.01 to 0.1 wt%.
Durch diese zwingend erforderliche Kombination von Elementen für dieses Ausführungsbeispiel aus den drei oben genannten Gruppen wird folgendes erreicht: durch den Zusatz eines oder mehrerer Elemente aus Gruppe I wird die Haftung der Alumini- umoxidschicht auf der MCrAl-Schicht entsprechend dem Stand der Technik stark verbessert .This mandatory combination of elements for this exemplary embodiment from the three groups mentioned above achieves the following: by adding one or more elements from group I, the adhesion of the aluminum oxide layer to the MCrAl layer is greatly improved in accordance with the prior art.
Die Elemente aus der Gruppe II sind ebenfalls sehr Sauerstoffäffine Elemente, jedoch bilden sie gleichzeitig sehr stabile Nitride und Carbide. Da die MCrAl-Schicht sowohl Zu- sätze von Elementen der Gruppe I als auch der Gruppe II enthält, so werden die Elemente der Gruppe I bevorzugt oxidie- ren. Die Elemente der Gruppe II werden bevorzugt mit dem in der MCrAlY-Schicht vorhandenen Kohlenstoff und/oder Stickstoff reagieren und somit feine Ausscheidungen von Karbiden und/oder Nitriden bilden.The elements from group II are also very oxygen-affine elements, but at the same time they form very stable nitrides and carbides. Since the MCrAl layer contains both additions of elements of group I and group II, the elements of group I are preferably oxidized. The elements of group II are preferred with the in carbon and / or nitrogen present in the MCrAlY layer react and thus form fine precipitates of carbides and / or nitrides.
Würden die Elemente der Gruppe I nicht zugesetzt werden, so würden die Elemente der Gruppe II bevorzugt mit Sauerstoff reagieren, da die betreffenden Oxide der Elemente eine höhere thermodynamische Stabilität aufweisen als die jeweiligen Karbide, Nitride oder Karbonitride. Die Elemente aus Gruppe II würden durch diese Oxidbildung verbraucht und somit würde die Bildung von Karbiden und Nitriden nicht stattfinden.If the Group I elements were not added, the Group II elements would preferably react with oxygen, since the relevant oxides of the elements have a higher thermodynamic stability than the respective carbides, nitrides or carbonitrides. The elements from group II would be consumed by this oxide formation and therefore the formation of carbides and nitrides would not take place.
Da die MCrAl-Schicht die genannten Zusätze aus allen drei Gruppen enthält, werden die Elemente der Gruppe II bei Hochtemperatureinsatz oder vorheriger Wärmebehandlung mit dem von Kohlenstoff und/oder Stickstoff feine Ausscheidungen mit einem typischen Durchmesser von 10 bis 900 nm in Form von Karbiden, Nitriden und/oder Karbonitriden bilden. Bei einem gezielten Voroxidationsprozess, d.h. vor einer Be- Schichtung der MCrAl-Haftvermittlerschicht mit einer keramischen Wärmedämmschicht, werden die feinen Ausscheidungen, die sich in Oberflächennähe der MCrAl-Schicht befinden von der nach innen wachsenden Aluminiumoxidschicht eingeschlossen. Bei weiterem Wachstum der Schicht werden die eingeschlossenen Karbide und/oder Nitride oder Karbonitride wegen des lokal ansteigenden Sauerstoffpartialdrucks oxidieren. Dies ist mit einer Volumenveränderung und Freisetzung von Gasen verknüpft . Diese beiden Prozesse führen zur Bildung sehr feiner Poren mit einem Durchmesser von 10 bis 800nm und Mi- krorissen der Länge 10 bis 600nm in der Aluminiumoxidschicht (TGO) .Since the MCrAl layer contains the additives mentioned from all three groups, the elements of group II become fine precipitates with a typical diameter of 10 to 900 nm in the form of carbides, nitrides with high temperature use or prior heat treatment with carbon and / or nitrogen and / or form carbonitrides. With a targeted pre-oxidation process, i.e. Before the MCrAl adhesion promoter layer is coated with a ceramic thermal insulation layer, the fine precipitates which are close to the surface of the MCrAl layer are enclosed by the inwardly growing aluminum oxide layer. If the layer continues to grow, the enclosed carbides and / or nitrides or carbonitrides will oxidize because of the locally increasing oxygen partial pressure. This is associated with a change in volume and release of gases. These two processes lead to the formation of very fine pores with a diameter of 10 to 800 nm and microcracks with a length of 10 to 600 nm in the aluminum oxide layer (TGO).
Auf diese Art und Weise erhält man auf der Oberfläche der MCrAl-Schicht die Ausbildung einer gewünschten dehnungstole- ranten Aluminiumoxidschicht mit einer Mikroporosität. In this way, a desired stretch-tolerant aluminum oxide layer with a microporosity is obtained on the surface of the MCrAl layer.

Claims

Patentansprüche claims
1. MCrAl-Schicht, insbesondere für eine Turbinenschaufel, wobei M für ein Element der Elemente Fe, Co, Ni steht und wobei eine Aluminiumoxidschicht auf der MCrAl-Schicht angeordnet ist, d a d u r c h g e k e n n z e i c h n e t, dass die Aluminiumoxidschicht mikroporös ausgebildet ist.1. MCrAl layer, in particular for a turbine blade, where M stands for an element of the elements Fe, Co, Ni and wherein an aluminum oxide layer is arranged on the MCrAl layer, so that the aluminum oxide layer is microporous.
2. MCrAl-Schicht, wobei M für ein Element der Elemente Fe, Co, Ni steht, insbesondere für eine Turbinenschaufel, d a d u r c h g e k e n n z e i c h n e t, dass die MCrAl-Schicht jeweils zumindest ein Element aus folgenden drei Gruppen I, II und III aufweist:2. MCrAl layer, where M stands for an element of the elements Fe, Co, Ni, in particular for a turbine blade, so that the MCrAl layer in each case has at least one element from the following three groups I, II and III:
Gruppe I: Yttrium, Cer, Scandium, Lanthan oder andere Lanthantide, wobei die Summe der Konzentration im Bereich 0,02 bis 1 wt% liegt,Group I: yttrium, cerium, scandium, lanthanum or other lanthantides, the sum of the concentration being in the range 0.02 to 1 wt%,
Gruppe II : Hafnium, Zirkonium, Titan, wobei die Summe der Konzentration im Bereich 0,02 bis 1 wt% liegt,Group II: hafnium, zirconium, titanium, the sum of the concentration being in the range 0.02 to 1 wt%,
Gruppe III: Kohlenstoff oder Stickstoff, wobei die Summe der Konzentration im Bereich 0,005 bis 0,2 wt% liegt.Group III: carbon or nitrogen, the sum of the concentration being in the range 0.005 to 0.2 wt%.
3. MCrAl-Schicht nach Anspruch 2, d a d u r c h g e k e n n z e i c h n e t, dass die Summe der Konzentrationen der Elemente aus Gruppe I im3. MCrAl layer according to claim 2, d a d u r c h g e k e n n z e i c h n e t that the sum of the concentrations of the elements from group I in
Bereich 0,05 bis 0,5 wt% liegt.Range is 0.05 to 0.5 wt%.
4. MCrAl-Schicht nach Anspruch 2, d a d u r c h g e k e n n z e i c h n e t, dass die Summe der Konzentration der Elemente aus Gruppe II im Bereich 0,05 bis 0,3 wt% liegt.4. MCrAl layer according to claim 2, characterized in that the sum of the concentration of the elements from group II in Range is 0.05 to 0.3 wt%.
5. MCrAl-Schicht nach Anspruch 2, d a d u r c h g e k e n n z e i c h n e t, dass die Summe der Konzentration der Elemente aus Gruppe III im Bereich 0,01 bis 0,1 wt% liegt.5. MCrAl layer according to claim 2, so that the sum of the concentration of the elements from group III is in the range from 0.01 to 0.1% by weight.
6. MCrAl-Schicht nach Anspruch 1 oder 2, d a d u r c h g e k e n n z e i c h n e t, dass die MCrAl-Schicht eine NiCoCrAl-Schicht ist.6. MCrAl layer according to claim 1 or 2, d a d u r c h g e k e n n z e i c h n e t that the MCrAl layer is a NiCoCrAl layer.
7. MCrAl-Schicht nach Anspruch 1 oder 2, d a d u r c h g e k e n n z e i c h n e t, dass die MCrAl-Schicht folgende Zusammensetzung aufweist: 10 bis 82 wt% Kobalt,7. MCrAl layer according to claim 1 or 2, d a d u r c h g e k e n n z e i c h n e t that the MCrAl layer has the following composition: 10 to 82 wt% cobalt,
10 bis 35 wt% Chrom, 8 bis 14 wt% Aluminium, optional weitere Legierungszusätze und Rest Nickel .10 to 35 wt% chromium, 8 to 14 wt% aluminum, optionally further alloy additives and the rest nickel.
8. MCrAl-Schicht nach Anspruch 1 oder 7, d a d u r c h g e k e n n z e i c h n e t, dass die MCrAl-Schicht weitere Legierungszusätze aufweist und dass als weiterer Legierungszusatz bis 2 wt% Silizium vorhanden ist.8. MCrAl layer according to claim 1 or 7, so that the MCrAl layer has further alloy additions and that up to 2 wt% silicon is present as a further alloy addition.
9. MCrAl-Schicht nach Anspruch 1 oder 7, d a d u r c h g e k e n n z e i c h n e t, dass die MCrAl-Schicht weitere Legierungszusätze aufweist und dass die MCrAl-Schicht als weiteren Legierungszusatz 0,3 bis 5 wt% Rhenium aufweist.9. MCrAl layer according to claim 1 or 7, so that the MCrAl layer has further alloy additives and that the MCrAl layer has 0.3 to 5 wt% rhenium as a further alloy additive.
10. MCrAl-Schicht nach Anspruch 1 oder 7, d a d u r c h g e k e n n z e i c h n e t, dass die MCrAl-Schicht weitere Legierungszusätze aufweist und dass als weiterer Legierungszusatz in der MCrAl-Schicht bis 8 wt% Tantal vorhanden ist.10. MCrAl layer according to claim 1 or 7, characterized in that the MCrAl layer has further alloy additives and that as a further alloy additive in the MCrAl layer up to 8 wt% Tantalum is present.
11. MCrAl-Schicht nach Anspruch 1 oder 2, d a d u r c h g e k e n n z e i c h n e t, dass die Mikroporosität durch eine Wärmebehandlung und/oder11. MCrAl layer according to claim 1 or 2, d a d u r c h g e k e n n z e i c h n e t that the microporosity by a heat treatment and / or
Oxidation in einer sich bildenden Aluminiumoxidschicht erzeugt ist.Oxidation is generated in an aluminum oxide layer that forms.
12. MCrAl-Schicht nach Anspruch 1 oder 2, d a d u r c h g e k e n z e i c h n e t, dass auf der MCrAl-Schicht eine keramischen Wärmedämmschicht angeordnet ist . 12. MCrAl layer according to claim 1 or 2, so that a ceramic thermal barrier layer is arranged on the MCrAl layer.
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