EP1637622A1 - Process for application of a protective coating - Google Patents

Process for application of a protective coating Download PDF

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Publication number
EP1637622A1
EP1637622A1 EP05018871A EP05018871A EP1637622A1 EP 1637622 A1 EP1637622 A1 EP 1637622A1 EP 05018871 A EP05018871 A EP 05018871A EP 05018871 A EP05018871 A EP 05018871A EP 1637622 A1 EP1637622 A1 EP 1637622A1
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EP
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Prior art keywords
layer
diffusion
diffusion layer
content
adhesive layer
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EP05018871A
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German (de)
French (fr)
Inventor
Sharad Dr. Chandra
Norbert Dr. Czech
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MAN Energy Solutions SE
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MAN Turbo AG
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/60—After-treatment
    • 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
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/02—Pretreatment of the material to be coated
    • 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
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/36—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including layers graded in composition or physical properties

Definitions

  • the invention relates to a method for applying a protective layer to a base metal having the features of the preamble of claim 1.
  • thermal barrier coatings serve to lower the material temperature of cooled components. This can extend their service life, reduce cooling air or operate the machine with higher inlet temperatures.
  • Thermal barrier coating systems always consist of a metal with the base material (base metal) by diffusion bonded metallic adhesive layer and an overlying ceramic layer with poor thermal conductivity, which is the actual barrier to heat flow and protects the base metal against high temperature corrosion and high temperature erosion.
  • thermal barrier coating zirconia As a ceramic material for the thermal barrier coating zirconia has prevailed, which is partially stabilized with about 7 wt .-% yttria (International abbreviation: "YPSZ" Yttria Partially Stabilized Zirconia).
  • the thermal barrier coatings are divided into two main classes according to the respective application method. In the layers sprayed thermally (usually with atmospheric plasma, APS), a porosity of between about 10 and 25% by volume is set depending on the desired layer thickness and stress distribution. The bond to the rough sprayed adhesive layer is made by mechanical clamping.
  • Thermal barrier coatings deposited by physical vapor deposition processes by electron beam have a columnar (columnar), strain-tolerant structure, while maintaining certain deposition conditions.
  • the layer is chemically bonded by the formation of an Al / Zr mixed oxide on a pure aluminum oxide layer (T G hermally rown O xide, TGO) which is subsequently formed from the adhesive layer during the application and operation.
  • T G hermally rown O xide
  • Adhesive layers are subject to the following complex requirements, namely low static and cyclic oxidation rates, the formation of a pure aluminum oxide layer as TGO (for layers produced by the EB-PVD process), sufficient resistance to high-temperature corrosion, low brittleness, Ductile transition temperature, high creep resistance, good adhesion, minimal long-term interdiffusion with the base material and economical application of the adhesive layer in reproducible quality.
  • the properties of the coating layers can be further improved by adding special refractory elements such as rhenium and tantalum or by alitating.
  • MCrAlY layers contain the intermetallic ⁇ -phase NiCoAl as an aluminum source. However, this phase also has a brittle effect, so that the practically realizable Al content in the MCrAlY layer is less than 12% by weight.
  • the invention has for its object to provide a method by which the oxidation resistance of simple MCrAlY layers as adhesive layers by increasing the Al content of the MCrAlY layer to improve without embrittlement occurs.
  • the structure of the aluminized MCrAlY layer consists of the inner, largely unchanged y / ⁇ mixed phase, a diffusion zone in which the A1 content increases to about 20% and an outer layer with a ⁇ -NiAl phase, which forms a fraction of has about 30% Al.
  • This outer layer represents the weak point of the layer system with regard to brittleness and crack sensitivity. It is removed according to the invention by the abrasive treatment down to the diffusion zone, whereby an Al content of 18 to less than 30% is set in the surface of the remaining layer. Removal of the outer layer may be accomplished by blasting with conventional media such as corundum, silicon carbide, reduced metal wires, and similar materials.
  • the oxidation resistance of this adhesive layer is improved.
  • the embrittlement on the surface of the aluminized layer caused by the alitization is avoided by the abrasive aftertreatment, or at least minimized.
  • the method according to the invention is applicable to all blades and, if appropriate, other turbine components subjected to hot gas, which are coated with thermal barrier coatings, in particular with thermal barrier coatings produced by the EB-PVD method.
  • the gas turbine blade 10 according to FIG. 2 is hollow and has cooling channels 11 in the interior.
  • the thermal barrier coating 2 consists of zirconium oxide, which is teilstablinstrument with about 7 wt .-%.
  • the adhesive layer 3 consists of a special alloy based on MCrAlY.
  • M stands for Ni or Co.
  • the adhesive layer is applied after the physical vapor deposition process using electron beam (EB-PVD method) or preferably by the low pressure plasma spray method (LPPS method).
  • Coating is accomplished by alitination, that is, a treatment in which a reactive Al-containing gas, which is typically an Al halide (AlX 2 ), causes inward diffusion of Al at higher temperature, associated with outward diffusion of Ni ,
  • a reactive Al-containing gas which is typically an Al halide (AlX 2 )
  • the outer make coat 4,2 is removed by blasting with hard particles, such as corundum, silicon carbide, metal wires or other known grinding or polishing down to the inner diffusion zone 4,1 of the diffusion layer 4.
  • hard particles such as corundum, silicon carbide, metal wires or other known grinding or polishing down to the inner diffusion zone 4,1 of the diffusion layer 4.
  • the abrasive treatment is driven so far that the surface of the remaining diffusion layer 4 has an Al content of more than 18% and less than 30%.
  • the blasted diffusion layer 4 is preferably subjected to fine flattening after the abrasive treatment.
  • the thermal barrier coating 2 is applied by a physical vapor deposition process by means of electron beams.

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

Abstract

The method involves applying a undercoating (3) of MCrAIY base on a base metal layer (1). Undercoating is applied with an alarmed heat insulation layer (2) made of zirconium oxide, where the heat insulation layer is partly stabilized by yttrium oxide. A diffusion layer (4) is subjected to an abrasive treatment, so that an outer structure layer (4.2) of the diffusion layer is removed by the abrasive treatment.

Description

Die Erfindung betrifft ein Verfahren zum Aufbringen einer Schutzschicht auf ein Basismetall mit den Merkmalen des Oberbegriffes des Anspruches 1.The invention relates to a method for applying a protective layer to a base metal having the features of the preamble of claim 1.

Die Oberflächen im Heißgasbereich werden in modernen Gasturbinen fast vollständig mit Beschichtungen versehen. Die dabei eingesetzten Wärmedämmschichten dienen zur Absenkung der Materialtemperatur gekühlter Bauteile. Hierdurch kann deren Lebensdauer verlängert, Kühlluft reduziert oder die Maschine mit höheren Eintrittstemperaturen betrieben werden. Wärmedämmschichtsysteme bestehen immer aus einer mit dem Grundwerkstoff (Basismetall) durch Diffusion verbundenen metallischen Haftschicht und einer darüber liegenden Keramikschicht mit schlechter Wärmeleitfähigkeit, die die eigentliche Barriere gegen den Wärmestrom darstellt und das Basismetall gegen Hochtemperaturkorrosion und Hochtemperaturerosion schützt.The surfaces in the hot gas area are almost completely provided with coatings in modern gas turbines. The thermal barrier coatings used serve to lower the material temperature of cooled components. This can extend their service life, reduce cooling air or operate the machine with higher inlet temperatures. Thermal barrier coating systems always consist of a metal with the base material (base metal) by diffusion bonded metallic adhesive layer and an overlying ceramic layer with poor thermal conductivity, which is the actual barrier to heat flow and protects the base metal against high temperature corrosion and high temperature erosion.

Als Keramikwerkstoff für die Wärmedämmschicht hat sich Zirkoniumoxid durchgesetzt, das mit etwa 7 Gew.-% Yttriumoxid teilstabilisiert ist (Internationale Kurzbezeichnung: "YPSZ" von Yttria Partially Stabilised Zirconia). Die Wärmedämmschichten werden nach dem jeweiligen Aufbringungsverfahren in zwei wesentliche Klassen eingeteilt. Bei den thermisch (meist mit atmosphärischem Plasma, APS) gespritzten Schichten wird abhängig von der gewünschten Schichtdicke und Spannungsverteilung eine Porosität zwischen etwa 10 und 25 Vol.-% eingestellt. Die Bindung zur rau gespritzten Haftschicht erfolgt durch mechanische Verklammerung.As a ceramic material for the thermal barrier coating zirconia has prevailed, which is partially stabilized with about 7 wt .-% yttria (International abbreviation: "YPSZ" Yttria Partially Stabilized Zirconia). The thermal barrier coatings are divided into two main classes according to the respective application method. In the layers sprayed thermally (usually with atmospheric plasma, APS), a porosity of between about 10 and 25% by volume is set depending on the desired layer thickness and stress distribution. The bond to the rough sprayed adhesive layer is made by mechanical clamping.

Wärmedämmschichten, die durch physikalische Dampfabscheideprozesse mittels Elektronenstrahl (EB-PVD-Verfahren) aufgedampft sind, weisen bei Einhaltung bestimmter Abscheidebedingungen eine säulenförmige (kolumnare), dehnungstolerante Struktur auf. Bei diesem Verfahren ist die Schicht chemisch durch Bildung eines Al/Zr-Mischoxides auf einer reinen Aluminiumoxidschicht(Thermally Grown Oxide, TGO) gebunden, die von der Haftschicht während der Aufbringung und anschließend im Betrieb gebildet wird. Dieses Verfahren stellt besondere Anforderungen an das Oxidwachstum auf der Haftschicht. Als Haftschichten können prinzipiell sowohl Diffusions- als auch Auflageschichten zum Einsatz kommen.Thermal barrier coatings deposited by physical vapor deposition processes by electron beam (EB-PVD process) have a columnar (columnar), strain-tolerant structure, while maintaining certain deposition conditions. In this method, the layer is chemically bonded by the formation of an Al / Zr mixed oxide on a pure aluminum oxide layer (T G hermally rown O xide, TGO) which is subsequently formed from the adhesive layer during the application and operation. This process places special demands on the oxide growth on the adhesive layer. In principle, both adhesion layers and application layers can be used as adhesion layers.

An die Haftschichten werden die folgenden komplexen Anforderungen gestellt, nämlich geringe statische und zyklische Oxidationsraten, die Bildung einer möglichst reinen Aluminiumoxidschicht als TGO (bei nach dem EB-PVD-Verfahren hergestellten Schichten), eine hinreichende Beständigkeit gegen Hochtemperaturkorrosion, eine niedrige Spröd-/, Duktil-Übergangstemperatur, eine hohe Kriechfestigkeit, eine gute Haftung, eine minimale Langzeit-Interdiffusion mit dem Grundwerkstoff und ein wirtschaftliches Aufbringen der Haftschicht in reproduzierbarer Qualität.Adhesive layers are subject to the following complex requirements, namely low static and cyclic oxidation rates, the formation of a pure aluminum oxide layer as TGO (for layers produced by the EB-PVD process), sufficient resistance to high-temperature corrosion, low brittleness, Ductile transition temperature, high creep resistance, good adhesion, minimal long-term interdiffusion with the base material and economical application of the adhesive layer in reproducible quality.

Für die besonderen Anforderungen in stationären Gasturbinen bieten metallische Auflageschichten aus einer Sonderlegierung auf MCrAlY-Basis (M = Ni, Co) die besten Möglichkeiten zur Erfüllung der chemischen und mechanischen Voraussetzungen. Die Eigenschaften der Auflageschichten können durch Zulegieren spezieller Refraktärelemente wie Rhenium und Tantal oder durch Alitieren weiter verbessert werden. MCrAlY-Schichten enthalten in einer NiCoCr ("y")-Matrix die intermetallische β-Phase NiCoAl als Aluminium-Vorrat. Diese Phase hat allerdings auch einen versprödenden Einfluss, so dass der praktisch realisierbare Al-Gehalt in der MCrAlY-Schicht bei weniger als 12 Gew.-% liegt. Zur weiteren Steigerung der Oxidationsbeständigkeit ist es bekannt (WO 96/34129), die MCrAlY-Schichten mit einer Al-Diffusionsschicht zu überziehen, um deren Al-Gehalt zu erhöhen. Wegen der Versprödungsgefahr beschränkte man dieses Verfahren allerdings bisher weitgehend auf aluminiumarme Ausgangsschichten.For the special requirements in stationary gas turbines, metallic overlay layers made from a special alloy based on MCrAlY (M = Ni, Co) offer the best possibilities for meeting the chemical and mechanical requirements. The properties of the coating layers can be further improved by adding special refractory elements such as rhenium and tantalum or by alitating. In a NiCoCr ("y") matrix, MCrAlY layers contain the intermetallic β-phase NiCoAl as an aluminum source. However, this phase also has a brittle effect, so that the practically realizable Al content in the MCrAlY layer is less than 12% by weight. To further increase the oxidation resistance, it is known (WO 96/34129) to coat the MCrAlY layers with an Al diffusion layer in order to increase their Al content. Because of the risk of embrittlement, however, this process has hitherto largely been limited to aluminum-poor starting layers.

Der Erfindung liegt die Aufgabe zugrunde, ein Verfahren anzugeben, mit dessen Hilfe die Oxidationsbeständigkeit einfacher MCrAlY-Schichten als Haftschichten durch eine Erhöhung des Al-Gehaltes der MCrAlY-Schicht zu verbessern, ohne dass eine Versprödung eintritt.The invention has for its object to provide a method by which the oxidation resistance of simple MCrAlY layers as adhesive layers by increasing the Al content of the MCrAlY layer to improve without embrittlement occurs.

Die Aufgabe wird bei einem gattungsgemäßen Verfahren erfindungsgemäß durch die kennzeichnenden Merkmale des Anspruches 1 gelöst. Vorteilhafte Ausgestaltungen der Erfindung sind Gegenstand der Unteransprüche.The object is achieved in a generic method according to the invention by the characterizing features of claim 1. Advantageous embodiments of the invention are the subject of the dependent claims.

Die Struktur der alitierten MCrAlY-Schicht besteht aus der inneren, weitgehend unveränderten y/β-Mischphase, einer Diffusionszone, in der der A1-Gehalt auf etwa 20 % ansteigt und einer äußeren Schicht mit einer β-NiAl-Phase, die einen Anteil von etwa 30 % Al aufweist. Diese äußere Schicht stellt die Schwachstelle des Schichtsystems hinsichtlich Sprödigkeit und Rissempfindlichkeit dar. Sie wird erfindungsgemäß durch die Abrasivbehandlung bis herab zur Diffusionszone entfernt, wodurch in der Oberfläche der verbleibenden Schicht ein Al-Gehalt von 18 bis unter 30 % eingestellt wird. Das Entfernen der äußeren Schicht kann durch Strahlen mit üblichen Medien wie Korund, Siliziumkarbid, verkleinerten Metalldrähten und ähnliche Materialien erfolgen.The structure of the aluminized MCrAlY layer consists of the inner, largely unchanged y / β mixed phase, a diffusion zone in which the A1 content increases to about 20% and an outer layer with a β-NiAl phase, which forms a fraction of has about 30% Al. This outer layer represents the weak point of the layer system with regard to brittleness and crack sensitivity. It is removed according to the invention by the abrasive treatment down to the diffusion zone, whereby an Al content of 18 to less than 30% is set in the surface of the remaining layer. Removal of the outer layer may be accomplished by blasting with conventional media such as corundum, silicon carbide, reduced metal wires, and similar materials.

Durch die Erhöhungdes Al-Gehaltes in der einfachen MCrAlY-Schicht aufgrund der Alitierung wird die Oxidationsbeständigkeit dieser als Haftschicht dienenden Schicht verbessert. Die durch die Alitierung hervorgerufene Versprödung an der Oberfläche der alitierten Schicht wird durch die abrasive Nachbehandlung vermieden, zumindest aber minimiert werden.By increasing the Al content in the simple MCrAlY layer due to alitization, the oxidation resistance of this adhesive layer is improved. The embrittlement on the surface of the aluminized layer caused by the alitization is avoided by the abrasive aftertreatment, or at least minimized.

Die Standzeit der insbesondere mittels Elektronenstrahl aufgedampften Wärmedämmschichten wird durch den höheren Aluminiumgehalt der alitierten Schicht erheblich verlängert. Bei vorzeitigem Versagen der Wärmedämmschicht, z. B. durch Fremdkörpereinschlag oder Erosion ist ein längerer "Notbetrieb" möglich. Andererseits wird durch das Entfernen der besonders spröden ß-NiAl-Phase das Risiko einer Risseinleitung minimiert.The service life of the vapor-deposited in particular by means of electron beam thermal insulation layers is considerably extended by the higher aluminum content of the alitierten layer. In case of premature failure of the thermal barrier coating, z. B. by foreign body impact or erosion a longer "emergency operation" is possible. On the other hand, the removal of the particularly brittle beta-NiAl phase minimizes the risk of crack initiation.

Die Alitierung der Haftschicht und der inneren Kühlkanäle des Bauteils kann simultan durchgeführt werden, so dass nur geringe Mehrkosten für das Abstrahlen entstehen.The Alitierung of the adhesive layer and the inner cooling channels of the component can be performed simultaneously, so that only small additional costs for the blasting arise.

Das erfindungsgemäße Verfahren ist auf alle Schaufeln und gegebenenfalls andere heißgasbeaufschlagte Turbinenbauteile anwendbar, die mit Wärmedämmschichten, insbesondere mit nach dem EB-PVD-Verfahren hergestellten Wärmedämmschichten beschichtet werden.The method according to the invention is applicable to all blades and, if appropriate, other turbine components subjected to hot gas, which are coated with thermal barrier coatings, in particular with thermal barrier coatings produced by the EB-PVD method.

Ein Ausführungsbeispiel der Erfindung ist in der Zeichnung dargestellt und wird nachfolgend näher erläutert. Es zeigen:

Fig. 1
schematisch und in nicht maßstabsgerechter Darstellung den Schnitt durch ein mit einer Beschichtung versehenes Basismetall und
Fig. 2
den Längsschnitt durch eine Gasturbinenschaufel.
An embodiment of the invention is illustrated in the drawing and will be explained in more detail below. Show it:
Fig. 1
schematically and not to scale the section through a provided with a coating base metal and
Fig. 2
the longitudinal section through a gas turbine blade.

Die Gasturbinenschaufel 10 gemäß Fig. 2 ist hohl ausgebildet und weist im Inneren Kühlkanäle 11 auf.
Eine Basismetallschicht 1, die der Grundwerkstoff für die Schaufel 10 der Gasturbine oder auch für ein anderes mit Heißgas in Berührung kommendes Bauteil einer Gasturbine sein kann, ist zum Schutz gegen Hochtemperaturkorrosion und Hochtemperaturerosion mit einer keramischen Wärmedämmschicht 2 versehen. Die Wärmedämmschicht 2 besteht aus Zirkonoxid, das mit etwa 7 Gew.-% teilstablisiert ist.The gas turbine blade 10 according to FIG. 2 is hollow and has cooling channels 11 in the interior.
A base metal layer 1, which may be the base material for the blade 10 of the gas turbine or for another hot gas contacting component of a gas turbine, is provided with a ceramic thermal barrier coating 2 for protection against high temperature corrosion and high temperature erosion. The thermal barrier coating 2 consists of zirconium oxide, which is teilstablisiert with about 7 wt .-%.

Zur Verbesserung der Haftung der Wärmedämmschicht 2 auf dem Grundwerkwerkstoff der Basismetallschicht 1 wird zunächst auf den Grundwerkstoff eine als Haftschicht 3 dienende Auflageschicht aufgebracht. Die Haftschicht 3 besteht aus einer Sonderlegierung auf MCrAlY-Basis. Der Buchstabe M steht hier für Ni oder Co. Das Aufbringen der Haftschicht erfolgt nach dem physikalischen Dampfabscheideprozess unter Verwendung von Elektronenstrahlen (EB-PVD-Verfahren), oder vorzugsweise durch das Niederdruckplasmaspritz-Verfahren (LPPS-Verfahren).To improve the adhesion of the thermal barrier coating 2 on the base material of the base metal layer 1 is first applied to the base material serving as an adhesive layer 3 support layer. The adhesive layer 3 consists of a special alloy based on MCrAlY. Here, the letter M stands for Ni or Co. The adhesive layer is applied after the physical vapor deposition process using electron beam (EB-PVD method) or preferably by the low pressure plasma spray method (LPPS method).

Zur Erhöhung des Al-Gehaltes in der Haftschicht 3 wird diese mit einer Al-Diffusionsschicht 4 überzogen. Das Überziehen erfolgt durch Alitierung, das heißt durch eine Behandlung, bei der ein reaktives Al-haltiges Gas, das in der Regel ein Al-Halogenid (A1X2) ist, bei höherer Temperatur eine Einwärtsdiffusion von Al, verbunden mit einer Auswärtsdiffusion von Ni bewirkt.To increase the Al content in the adhesive layer 3, it is coated with an Al diffusion layer 4. Coating is accomplished by alitination, that is, a treatment in which a reactive Al-containing gas, which is typically an Al halide (AlX 2 ), causes inward diffusion of Al at higher temperature, associated with outward diffusion of Ni ,

Gleichzeitig kann durch eine entsprechende Führung des reaktiven Al-haltigen Gases (AlX2) eine Innenbeschichtung der Kühlkanäle 11 der Gasturbinenschaufel 10 vorgenommen werden.At the same time, by an appropriate guidance of the reactive Al-containing gas (AlX 2 ), an inner coating of the cooling channels 11 of the gas turbine blade 10 can be made.

Durch das Alitieren entsteht auf der weitgehend unveränderten Haftschicht 3 innerhalb der Diffusionsschicht 4 eine innere Diffusionszone 4,1 und darüber eine äußere Aufbauschicht 4,2 aus einer spröden β-NiAl-Phase.By Alitieren arises on the largely unchanged adhesive layer 3 within the diffusion layer 4, an inner Diffusion zone 4.1 and above an outer build-up layer 4.2 from a brittle β-NiAl phase.

Die äußere Aufbauschicht 4,2 wird durch Strahlen mit harten Partikeln, wie Korund, Siliziumkarbid, Metalldrähten oder anderen bekannten Schleif- oder Poliermitteln bis herab auf die innere Diffusionszone 4,1 der Diffusionsschicht 4 entfernt.The outer make coat 4,2 is removed by blasting with hard particles, such as corundum, silicon carbide, metal wires or other known grinding or polishing down to the inner diffusion zone 4,1 of the diffusion layer 4.

Die abrasive Behandlung wird soweit getrieben, dass die Oberfläche der verbliebenen Diffusionsschicht 4 einen Al-Gehalt von über 18% und unter 30% aufweist.The abrasive treatment is driven so far that the surface of the remaining diffusion layer 4 has an Al content of more than 18% and less than 30%.

Die gestrahlte Diffusionsschicht 4 wird nach der abrasiven Behandlung vorzugsweise einer Feinglättung unterworfen.The blasted diffusion layer 4 is preferably subjected to fine flattening after the abrasive treatment.

Im Anschluss an die oben geschilderten Verfahrensschritte wird die Wärmedämmschicht 2 durch einen physikalischen Dampfabscheideprozess mittels Elektronenstrahlen aufgebracht.Following the above-described process steps, the thermal barrier coating 2 is applied by a physical vapor deposition process by means of electron beams.

Claims (4)

Verfahren zum Aufbringen einer gegen Hochtemperaturkorrosion und Hochtemperaturerosion beständigen Schutzschicht auf eine Basismetallschicht (1), wobei auf die Basismetallschicht (1) eine Haftschicht (3) auf MCrAlY-Basis aufgebracht wird, die Haftschicht (3) durch Alitieren mit einer Al-Diffusionschicht (4) überzogen wird, auf die Diffusionschicht (4) eine keramische Wärmedämmschicht (2) aus Zirkonoxid, das durch Yttriumoxid teilstabilisiert ist, aufgebracht wird, dadurch gekennzeichnet, dass die Diffusionsschicht (4) einer Abrasivbehandlung unterworfen wird, so dass durch die Abrasivbehandlung die äußere Aufbauschicht (4,2) der durch Alitierung erzeugten Diffusionsschicht (4) entfernt wird.A method for applying a protective layer resistant to high-temperature corrosion and high-temperature erosion to a base metal layer (1), wherein an MCrAlY-based adhesive layer (3) is applied to the base metal layer (1), the adhesive layer (3) being alitized with an Al diffusion layer (4 ) is coated on the diffusion layer (4) a ceramic thermal barrier coating (2) of zirconia, which is partially stabilized by yttria, is applied, characterized in that the diffusion layer (4) is subjected to an abrasive treatment, so that by the abrasive treatment, the outer build-up layer (4,2) of the diffusion layer (4) produced by alitization. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass durch das Alitieren eine Diffusionsschicht (4) mit der eigentlichen Diffusionszone (4,1) mit einem Al-Gehalt von etwa 20 % und eine äußere Aufbauschicht (4,2) mit einem Al-Gehalt von etwa 30% erzeugt wird und dass durch die Abrasivbehandlung die äußere Aufbauschicht (4,2) der Diffusionsschicht(4), die oberhalb der eigentlichen Diffusionszone (4,1) liegt, soweit entfernt wird, dass der Gehalt an A1 in der Oberfläche der verbliebenen Diffusionsschicht (4) mindestens 18% und maximal 30% beträgt.A method according to claim 1, characterized in that by Alitieren a diffusion layer (4) with the actual diffusion zone (4.1) with an Al content of about 20% and an outer build-up layer (4.2) with an Al content of about 30% is generated and that by the abrasive treatment, the outer build-up layer (4,2) of the diffusion layer (4), which is above the actual diffusion zone (4,1) is removed so far that the content of A1 in the surface of the remaining Diffusion layer (4) is at least 18% and a maximum of 30%. Verfahren nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass die abrasiv behandelte Diffusionsschicht (4) einer Feinglättung unterworfen wird.A method according to claim 1 or 2, characterized in that the abrasive-treated diffusion layer (4) is subjected to a fine smoothing. Verfahren nach Ansprüchen 1 bis 3, dadurch gekennzeichnet, dass das Alitieren der Haftschicht (3) in einem Verfahrensschritt simultan mit einer Innenbeschichtung der Kühlkanäle eines hohlen Bauteils vorgenommen wird.A method according to claims 1 to 3, characterized in that the Alitieren the adhesive layer (3) is carried out in a process step simultaneously with an inner coating of the cooling channels of a hollow component.
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