EP1466037B1 - High-temperature protective coating - Google Patents

High-temperature protective coating Download PDF

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Publication number
EP1466037B1
EP1466037B1 EP03700010A EP03700010A EP1466037B1 EP 1466037 B1 EP1466037 B1 EP 1466037B1 EP 03700010 A EP03700010 A EP 03700010A EP 03700010 A EP03700010 A EP 03700010A EP 1466037 B1 EP1466037 B1 EP 1466037B1
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EP
European Patent Office
Prior art keywords
protection layer
temperature protection
temperature
coating
layer
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Expired - Lifetime
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EP03700010A
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German (de)
French (fr)
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EP1466037A1 (en
Inventor
Dietrich Eckardt
Klaus Erich Schneider
Christoph Toennes
Hans-Peter Bossmann
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General Electric Technology GmbH
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Alstom Technology 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
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/073—Metallic material containing MCrAl or MCrAlY alloys, where M is nickel, cobalt or iron, with or without non-metal elements
    • 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
    • Y10T428/12937—Co- or Ni-base component next to Fe-base 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
    • 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
    • Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension

Definitions

  • the invention relates to a high-temperature protective layer according to the independent Claim.
  • Such high-temperature protective layers are mainly used where the base material of components made of heat-resistant steels and / or alloys which is used at temperatures above 600 oC.
  • Such high temperature protective layers Due to these high-temperature protective layers, the effect of high-temperature corrosion especially of sulfur, oil pockets, oxygen, alkaline earths and vanadium slowed down or completely stopped.
  • Such high temperature protective layers are designed to be directly on the base material of the protective component can be applied.
  • high temperature protective coatings are of particular importance Importance. They are mainly used on runners and vanes as well Applied thermal heat segments of gas turbines.
  • these components is preferably an austenitic material used on the basis of nickel, cobalt or iron.
  • nickel superalloys are used as base material Application.
  • Most of the coatings for high temperature applications come from the Families of NiCrAlY, CoCrAlY or NiCoCrAlY.
  • the layers are different through the concentration of "family elements" nickel, cobalt, chrome, aluminum and Yttrium and by adding more elements.
  • the composition of the layer determined Significantly, the behavior at high temperature in oxidizing or corrosive Atmosphere, with temperature changes and under mechanical load. moreover the composition of the layer determines the material and manufacturing costs.
  • Many known layers show excellent properties only in some aspects. Although widely used worldwide, by adding cobalt according to their own Investigations have negatively affected both corrosion resistance and cost.
  • the invention is based on the above-mentioned prior art the The object of the invention is to provide a high-temperature protective layer which is cost-effective, resistant to oxidation, corrosion and temperature change resistant.
  • the inventive composition of this alloy has (wt .-%) 23 bis 27% chromium, 4 to 7% aluminum, 0.1 to 3% silicon, 0.1 to 3% tantalum, 0.2 to 2% Yttrium, 0.001 to 0.01% boron, 0.001 to 0.01% magnesium and 0.001 to 0.01% calcium on. All weights are based on the total weight of the respective Alloy. The remainder of the alloy is nickel and unavoidable Impurities.
  • the Al content is in a range of more than 5 to 6 Wt .-%.
  • the protective layer according to the invention is a NiCrAlY alloy. It shows a significant improvement in oxidation and corrosion resistance compared to the already known high-temperature protective layers.
  • the high-temperature protective layer according to the invention it should be noted that they at high temperatures (depending on the design above 800 ° C) aluminum-containing ⁇ and ⁇ '-phases having a volume fraction of at least 50%, which the Formation of an aluminum oxide-containing protective layer allows, at low and at medium temperatures (depending on the design below 900 ° C) chromium-containing ⁇ -Cr phases (referred to in Fig. 1 as BCC) of more than 5%, which the training a chromium oxide-containing protective layer allows.
  • BCC chromium-containing ⁇ -Cr phases
  • the adhesion of the alumina-containing cover layer improves High temperature, which is the protection of the high-temperature protective layer and the underneath located significantly increased component.
  • magnesium and calcium are especially the naturally occurring impurities in the production bound and thus for temperatures below 850-950 ° C the Increased corrosion resistance.
  • the amount ratio of chromium to aluminum is limited to 3.6 to 6.5 to prevent the formation of brittle ⁇ -phases.
  • the ratio of nickel to chromium is limited to 2.3 to 3.0 in order to obtain brittle ⁇ phases to prevent what improves the thermal shock resistance.
  • the solid and the consistent adhesion of the protective layer and its topcoat in frequent Temperature change is due to the specified for the alloy share Yttrium reached.
  • composition chosen here shows no or only small proportions by volume of ⁇ -phase or ⁇ -NiAl phase (FIG. 1), so that under thermal cycling clearly advantages are to be expected.
  • the comparative alloy of Fig. 2 shows a similar one Composition of some elements, but due to the differences of others Elements show a very different microstructure based on In our experience, no adequate thermal shock resistance for turbine and can not be used by the incipient melting over 900 ° C. is.
  • the production-related, inherent contamination of sulfur which is typically in concentrations of less than 10 ppm, in some cases up to 50 ppm can lead to reduced oxidation and corrosion resistance.
  • the trace elements Mg and Ca added, which absorb sulfur.
  • the alloy is applied directly to the base material of the component or to an intermediate layer, consisting of a third composition, applied.
  • the layer thicknesses vary depending on the coating method between 0.03 mm to 1.5 mm.
  • the gas turbine component to be coated is made of an austenitic material, in particular a nickel superalloy.
  • the coating of the component takes place under Vacuum, under inert gas or in air by means of thermal spraying (LPPS, VPS, APS), high speed spraying (HVOF), electrochemical processes, physical / chemical vaporization (PVD, CVD) or another from the Prior art known coating method.
  • a NiCrAlY alloy is used according to the invention (Wt .-%) 23 to 27 wt .-% chromium, 4 to 7 wt .-% aluminum, 0.1 to 3 wt .-% silicon, 0.1 to 3% by weight of tantalum, 0.2 to 2% by weight of yttrium, 0.001 to 0.01% by weight of boron, 0.001 to 0.01% by weight of magnesium and 0.001 to 0.01% by weight of calcium.
  • the remaining portion of the alloy consists of nickel and unavoidable impurities.
  • the Al content is in a range of over 5 to 6 wt .-%. All weights refer to the total weight of the alloy used.
  • the alloy according to the invention has a marked improvement in the oxidation and corrosion resistance over the already known high-temperature protective layers on.
  • inventive high-temperature protective layer is determine that they are at high temperatures (depending on the design above 800 ° C) aluminum-containing ⁇ and ⁇ '-phases with a volume fraction of at least 50%, which allows the formation of an aluminum oxide-containing protective layer, at low and medium temperatures (depending on the version below of 900 ° C) chromium-containing ⁇ -Cr phases of more than 5%, which the training a chromium oxide-containing protective layer allows.
  • the composition selected here shows no or only small volume fractions of ⁇ -phase or ⁇ -NiAl phase or boride phases (in Fig. 1 as M2B_ORTH), so that under thermal cycling significant benefits are expected.
  • the comparative alloy ( Figure 2) shows a similar one Composition of some elements, but due to the differences of others Elements show a very different microstructure based on In our experience, no adequate thermal shock resistance for turbine and can not be used by the incipient melting over 900 ° C. is.
  • the base material that forms the high-temperature protective layer silicon and boron added. This increases the protection of the high-temperature protective layer and the underlying device essential.
  • the production-related, inherent contamination of sulfur which is typically in a concentration of less than 10 ppm, in some cases 50 ppm can lead to reduced oxidation and corrosion resistance.
  • the trace elements Mg and Ca are added, which absorb sulfur and thereby in for temperatures below from 850 to 950 ° C increases the corrosion resistance.
  • the ratio of chromium to aluminum is limited to 3.6 to 6.5 to the Prevent training of brittle ⁇ -phases.
  • the ratio of nickel to Chromium is limited to 2.3 to 3.0, to prevent brittle ⁇ -phases, what the thermal shock resistance improved.
  • the firm and consistent adhesion of the protective layer and its topcoat Frequent temperature change is determined by the specific for the alloy Proportion of yttrium reached.
  • the material forming the alloy is in powder form for the thermal spraying processes before and preferably has a particle size of 5 to 90 microns.
  • the alloy is prepared as a target or as a suspension.
  • the alloy is applied directly to the base material of the component or to an intermediate layer, consisting of a third composition, applied.
  • the layer thicknesses vary depending on the coating method between 0.03 mm to 1.5 mm.
  • the device is subjected to a heat treatment. This takes place at a temperature of 1000 to 1200 ° C for about 10 minutes up to 24 hours.

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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)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Inorganic Insulating Materials (AREA)
  • Surface Treatment Of Glass Fibres Or Filaments (AREA)
  • Physical Vapour Deposition (AREA)
  • Spark Plugs (AREA)
  • Laminated Bodies (AREA)
  • Insulated Conductors (AREA)
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  • Ceramic Products (AREA)
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Abstract

A high-temperature protection layer contains (% by weight) 23 to 27% Cr, 4 to 7% Al, 0.1 to 3% Si, 0.1 to 3% Ta, 0.2 to 2% Y, 0.001 to 0.01% B, 0.001 to 0.01% Mg and 0.001 to 0.01% Ca, remainder Ni and inevitable impurities. Optionally, the Al content is in a range from over 5 up to 6% by weight.

Description

Die Erfindung bezieht sich auf eine Hochtemperatur-Schutzschicht gemäss dem unabhängigen Patentanspruch.The invention relates to a high-temperature protective layer according to the independent Claim.

Solche Hochtemperatur-Schutzschichten kommen vor allem dort zur Anwendung, wo das Grundmaterial von Bauelementen aus warmfesten Stählen und/oder Legierungen zu schützen ist, die bei Temperaturen über 600 ºC verwendet werden.Such high-temperature protective layers are mainly used where the base material of components made of heat-resistant steels and / or alloys which is used at temperatures above 600 ºC.

Durch diese Hochtemperatur-Schutzschichten soll die Wirkung von Hochtemperaturkorrosionen vor allem von Schwefel, Ölaschen, Sauerstoff, Erdalkalien und Vanadium verlangsamt bzw. vollständig unterbunden werden. Solche Hochtemperatur-Schutzschichten sind so ausgebildet, dass sie direkt auf das Grundmaterial des zu schützenden Bauelementes aufgetragen werden können.Due to these high-temperature protective layers, the effect of high-temperature corrosion especially of sulfur, oil pockets, oxygen, alkaline earths and vanadium slowed down or completely stopped. Such high temperature protective layers are designed to be directly on the base material of the protective component can be applied.

Bei Bauelementen von Gasturbinen sind Hochtemperatur-Schutzschichten von besonderer Bedeutung. Sie werden vor allem auf Lauf- und Leitschaufeln sowie auf Wärmestausegmenten von Gasturbinen aufgetragen. For gas turbine components, high temperature protective coatings are of particular importance Importance. They are mainly used on runners and vanes as well Applied thermal heat segments of gas turbines.

Für die Fertigung dieser Bauelemente wird vorzugsweise ein austenitisches Material auf der Basis von Nickel, Kobalt oder Eisen verwendet. Bei der Herstellung von Gasturbinenbauteilen kommen vor allem Nickel-Superlegierungen als Grundmaterial zur Anwendung.For the production of these components is preferably an austenitic material used on the basis of nickel, cobalt or iron. In the manufacture of gas turbine components In particular, nickel superalloys are used as base material Application.

Bis jetzt ist es üblich, Bauelemente, die für Gasturbinen bestimmt sind, mit Schutzschichten zu versehen, die durch Legierungen gebildet werden, deren wesentliche Bestandteile Nickel, Chrom, Aluminium und Yttrium sind. Solche Hochtemperatur-Schutzschichten weisen eine Matrix auf, in die eine aluminiumhaltige Phase eingelagert ist.So far, it is common to design components intended for gas turbines with protective coatings provided by alloys whose essential Components are nickel, chromium, aluminum and yttrium. Such high temperature protective layers have a matrix in which an aluminum-containing phase embedded is.

Die meisten der Beschichtungen für Hochtemperaturanwendungen stammen aus den Familien der NiCrAlY, CoCrAlY oder NiCoCrAlY. Die Schichten unterscheiden sich durch die Konzentration der "Familenelemente" Nickel, Kobalt, Chrom, Aluminium und Yttrium und durch Zugabe weiterer Elemente. Die Zusammensetzung der Schicht bestimmt massgeblich das Verhalten bei Hochtemperatur in oxidierender bzw. korrodierender Atmosphäre, bei Temperaturwechsel und bei mechanischer Belastung. Zudem bestimmt die Zusammensetzung der Schicht die Material- und Herstellungskosten. Viele bekannte Schichten zeigen nur bei Teilaspekten hervorragende Eigenschaften. Obwohl weltweit vielfach benutzt, werden durch Zugabe von Kobalt gemäss eigenen Untersuchungen sowohl die Korrosionsbeständigkeit als auch die Kosten negativ beeinflusst.Most of the coatings for high temperature applications come from the Families of NiCrAlY, CoCrAlY or NiCoCrAlY. The layers are different through the concentration of "family elements" nickel, cobalt, chrome, aluminum and Yttrium and by adding more elements. The composition of the layer determined Significantly, the behavior at high temperature in oxidizing or corrosive Atmosphere, with temperature changes and under mechanical load. moreover the composition of the layer determines the material and manufacturing costs. Many known layers show excellent properties only in some aspects. Although widely used worldwide, by adding cobalt according to their own Investigations have negatively affected both corrosion resistance and cost.

Aus den Dokumenten JP-A-53-085736, US-A-3,620,693, US-A-4,477,538, US-A-4,537,744, US-A-3,754,903, US-A-4,013,424, US-A-4,022,587 und US-A-4,743,514 sind zahlreiche Legierungen der Familie "kobald-freier NiCrAlY" bekannt geworden. Die thermodynamische Modellierung für den Temperaturbereich 800°C bis 1050°C des Phasenbestandes dieser Legierungen hat gezeigt, dass die spezifizierten Zusammensetzungen zu Mikrostrukturen mit unerwünschten Phasen bzw. thermisch aktivierten Phasenübergängen führen, namentlich σ- und/oder β-NiAl in nachteilig grossen Volumenanteilen. From documents JP-A-53-085736, US-A-3,620,693, US-A-4,477,538, US-A-4,537,744, U.S. Patent Nos. 3,754,903, 4,013,424, 4,022,587 and 4,743,514 numerous alloys of the family "Kobald-free NiCrAlY" have become known. The thermodynamic modeling for the temperature range 800 ° C to 1050 ° C The phase balance of these alloys has shown that the specified compositions to microstructures with undesirable phases or thermally activated Phase transitions lead, in particular σ- and / or β-NiAl in disadvantageously large Volume fractions.

Der Erfindung liegt ausgehend von dem eingangs genannten Stand der Technik die Aufgabe zugrunde, eine Hochtemperatur-Schutzschicht zu schaffen, die kostengünstig, oxidationsbeständig, korrosionsbeständig und temperaturwechselbeständig ist.The invention is based on the above-mentioned prior art the The object of the invention is to provide a high-temperature protective layer which is cost-effective, resistant to oxidation, corrosion and temperature change resistant.

Diese Aufgabe wird erfindungsgemäss durch die Merkmale des Patentanspruches 1 gelöst.This object is achieved according to the invention by the features of claim 1 solved.

Die erfindungsgemässe Zusammensetzung dieser Legierung weist (Gew.-%) 23 bis 27% Chrom, 4 bis 7% Aluminium, 0.1 bis 3% Silizium, 0.1 bis 3% Tantal, 0.2 bis 2% Yttrium, 0.001 bis 0.01% Bor, 0.001 bis 0.01% Magnesium und 0.001 bis 0.01% Kalzium auf. Alle Gewichtsangaben beziehen sich auf das Gesamtgewicht der jeweiligen Legierung. Der übrige Anteil der Legierung besteht aus Nickel und unvermeidbaren Verunreinigungen. Vorzugsweise liegt der Al-Gehalt in einem Bereich von über 5 bis 6 Gew.-%.The inventive composition of this alloy has (wt .-%) 23 bis 27% chromium, 4 to 7% aluminum, 0.1 to 3% silicon, 0.1 to 3% tantalum, 0.2 to 2% Yttrium, 0.001 to 0.01% boron, 0.001 to 0.01% magnesium and 0.001 to 0.01% calcium on. All weights are based on the total weight of the respective Alloy. The remainder of the alloy is nickel and unavoidable Impurities. Preferably, the Al content is in a range of more than 5 to 6 Wt .-%.

Bei der erfindungsgemässen Schutzschicht handelt es sich um eine NiCrAIY-Legierung. Sie weist eine deutliche Verbesserung der Oxidation- und Korrosionsbeständigkeit gegenüber den bereits bekannten Hochtemperatur-Schutzschichten auf. Bei der erfindungsgemässen Hochtemperatur-Schutzschicht ist festzustellen, dass sie bei hohen Temperaturen (je nach Ausführung oberhalb von 800°C) aluminiumhaltige γ und γ'-Phasen mit einem Volumenanteil von mindestens 50% aufweist, welche die Ausbildung einer aluminiumoxidhaltigen Schutzschicht ermöglicht, bei niedrigen und bei mittleren Temperaturen (je nach Ausführung unterhalb von 900°C) chromhaltige α-Cr-Phasen (in Fig. 1 als BCC bezeichnet) von mehr als 5% aufweist, welche die Ausbildung einer chromoxidhaltigen Schutzschicht ermöglicht.The protective layer according to the invention is a NiCrAlY alloy. It shows a significant improvement in oxidation and corrosion resistance compared to the already known high-temperature protective layers. In the high-temperature protective layer according to the invention, it should be noted that they at high temperatures (depending on the design above 800 ° C) aluminum-containing γ and γ'-phases having a volume fraction of at least 50%, which the Formation of an aluminum oxide-containing protective layer allows, at low and at medium temperatures (depending on the design below 900 ° C) chromium-containing α-Cr phases (referred to in Fig. 1 as BCC) of more than 5%, which the training a chromium oxide-containing protective layer allows.

Wird der Legierung, die die Hochtemperatur-Schutzschicht bildet, Silizium und Bor zugegeben, so verbessert sich die Haftung der aluminiumoxidhaltigen Deckschicht bei Hochtemperatur, welche den Schutz der Hochtemperatur-Schutzschicht und des darunter befindlichen Bauelementes wesentlich erhöht. Mit einem Zusatz von Magnesium und Kalzium werden vor allem die bei der Herstellung natürlich vorhandenen Verunreinigungen gebunden und dadurch für Temperaturen unterhalb von 850-950°C die Korrosionsbeständigkeit erhöht. Das Mengenverhältnis von Chrom zu Aluminium ist auf 3.6 bis 6.5 begrenzt, um die Ausbildung spröder β-Phasen zu verhindern. Das Mengenverhältnis von Nickel zu Chrom ist auf 2.3 bis 3.0 begrenzt, um spröde σ-Phasen zu verhindern, was die Temperaturwechselbeständigkeit verbessert. Die feste und die beständige Haftung der Schutzschicht und ihrer Deckschicht bei häufigen Temperaturwechsel wird durch den speziell für die Legierung festgelegten Anteil an Yttrium erreicht.Is added to the alloy forming the high temperature protective layer, silicon and boron, Thus, the adhesion of the alumina-containing cover layer improves High temperature, which is the protection of the high-temperature protective layer and the underneath located significantly increased component. With an addition of magnesium and calcium are especially the naturally occurring impurities in the production bound and thus for temperatures below 850-950 ° C the Increased corrosion resistance. The amount ratio of chromium to aluminum is limited to 3.6 to 6.5 to prevent the formation of brittle β-phases. The The ratio of nickel to chromium is limited to 2.3 to 3.0 in order to obtain brittle σ phases to prevent what improves the thermal shock resistance. The solid and the consistent adhesion of the protective layer and its topcoat in frequent Temperature change is due to the specified for the alloy share Yttrium reached.

Die hier gewählte Zusammensetzung zeigt keine bzw. nur geringe Volumenanteile von σ-Phase bzw. β-NiAl-Phase (Fig. 1), so dass unter Temperaturwechselbeanspruchung deutlich Vorteile zu erwarten sind. Die Vergleichslegierung aus Fig. 2 zeigt eine ähnliche Zusammensetzung bei einigen Elementen, aber aufgrund der Unterschiede anderer Elemente zeigt sich doch eine sehr verschiedene Mikrostruktur, die basierend auf unserer Erfahrung keine ausreichende Temperaturwechselbeständigkeit für Turbine haben wird und zudem durch das beginnende Aufschmelzen über 900 °C nicht einsetzbar ist.The composition chosen here shows no or only small proportions by volume of σ-phase or β-NiAl phase (FIG. 1), so that under thermal cycling clearly advantages are to be expected. The comparative alloy of Fig. 2 shows a similar one Composition of some elements, but due to the differences of others Elements show a very different microstructure based on In our experience, no adequate thermal shock resistance for turbine and can not be used by the incipient melting over 900 ° C. is.

Die produktionsbedingte, inhärente Verunreinigung von Schwefel, die typischerweise im Konzentration kleiner 10 ppm, in einzelnen Fällen aber auch bis zu 50ppm erreichen kann, führt zu reduzierter Oxidation- und Korrosionsbeständigkeit. Erfindungsgemäss werden bei der Herstellung der Beschichtung die Spurenelemente Mg und Ca zugegeben, die Schwefel absorbieren.The production-related, inherent contamination of sulfur, which is typically in concentrations of less than 10 ppm, in some cases up to 50 ppm can lead to reduced oxidation and corrosion resistance. According to the invention In the production of the coating, the trace elements Mg and Ca added, which absorb sulfur.

Die Legierung wird direkt auf das Grundmaterial des Bauelementes oder auf eine Zwischenlage, bestehend aus einer dritten Zusammensetzung, aufgetragen. Die Schichtdicken variieren je nach Beschichtungsverfahren zwischen 0.03 mm bis 1.5 mm.The alloy is applied directly to the base material of the component or to an intermediate layer, consisting of a third composition, applied. The layer thicknesses vary depending on the coating method between 0.03 mm to 1.5 mm.

Die Erfindung wird an Hand der beiliegenden Zeichnungen erläutert, in denen

Fig. 1
das Phasengleichgewicht (Molanteil Φ [%] vs. Temperatur [º C]) gemäss der hier angegebenen Zusammensetzung zeigt,
Fig. 2
das Phasengleichgewicht (Molanteil Φ [%] vs. Temperatur [º C]) gemäss der im Patent US-A-4,973,445 angegebenen Zusammensetzung darstellt.
The invention will be explained with reference to the accompanying drawings, in which
Fig. 1
the phase equilibrium (mole fraction Φ [%] vs. temperature [° C]) according to the composition given here shows
Fig. 2
represents the phase equilibrium (mole fraction Φ [%] vs. temperature [° C]) according to the composition given in US Pat. No. 4,973,445.

Es sind nur die für die Erfindung wesentlichen Elemente dargestellt.Only the elements essential to the invention are shown.

Anhand eines Ausführungsbeispiels, das die Herstellung eines beschichteten Gasturbinenbauteils oder eines anderen Bauelements einer thermischen Turbomaschine beschreibt, wird die Erfindung näher erläutert. Das zu beschichtende Gasturbinenbauteil ist aus einem austenitischen Material, insbesondere einer Nickel-Superlegierung gefertigt. Vor der Beschichtung wird das Bauteil zunächst chemisch gereinigt und dann mit einem Strahlprozess aufgerauht. Die Beschichtung des Bauelementes erfolgt unter Vakuum, unter Schutzgas oder in Luft mittels thermischen Spritzverfahren (LPPS, VPS, APS), Hochgeschwindigkeitsspritzen (HVOF), elektrochemischen Verfahren, physikalischen/chemischer Verdampfung (PVD, CVD) oder einem anderen aus dem Stand der Technik bekannten Beschichtungsverfahren.With reference to an embodiment, the preparation of a coated gas turbine component or another component of a thermal turbomachine, the invention will be explained in more detail. The gas turbine component to be coated is made of an austenitic material, in particular a nickel superalloy. Before coating, the component is first chemically cleaned and then roughened with a blasting process. The coating of the component takes place under Vacuum, under inert gas or in air by means of thermal spraying (LPPS, VPS, APS), high speed spraying (HVOF), electrochemical processes, physical / chemical vaporization (PVD, CVD) or another from the Prior art known coating method.

Für die Beschichtung wird eine NiCrAlY-Legierung verwendet, die erfindungsgemäss (Gew.-%) 23 bis 27 Gew.-% Chrom, 4 bis 7 Gew.-% Aluminium, 0.1 bis 3 Gew.-% Silizium, 0.1 bis 3 Gew.-% Tantal, 0.2 bis 2 Gew.-% Yttrium, 0.001 bis 0.01 Gew-% Bor, 0.001 bis 0.01 Gew-% Magnesium und 0.001 bis 0.01 Gew-% Kalzium aufweist. Der übrige Anteil der Legierung besteht aus Nickel und unvermeidbaren Verunreinigungen. Vorzugsweise liegt der Al-Gehalt in einem Bereich von über 5 bis 6 Gew.-%. Alle Gewichtsangaben beziehen sich auf das Gesamtgewicht der verwendeten Legierung.For the coating, a NiCrAlY alloy is used according to the invention (Wt .-%) 23 to 27 wt .-% chromium, 4 to 7 wt .-% aluminum, 0.1 to 3 wt .-% silicon, 0.1 to 3% by weight of tantalum, 0.2 to 2% by weight of yttrium, 0.001 to 0.01% by weight of boron, 0.001 to 0.01% by weight of magnesium and 0.001 to 0.01% by weight of calcium. Of the The remaining portion of the alloy consists of nickel and unavoidable impurities. Preferably, the Al content is in a range of over 5 to 6 wt .-%. All weights refer to the total weight of the alloy used.

Die erfindungsgemässe Legierung weist eine deutliche Verbesserung der Oxidation- und Korrosionsbeständigkeit gegenüber den bereits bekannten Hochtemperatur-Schutzschichten auf. Bei der erfindungsgemässen Hochtemperatur-Schutzschicht ist festzustellen, dass sie bei hohen Temperaturen (je nach Ausführung oberhalb von 800 °C) aluminiumhaltige γ und γ'-Phasen mit einem Volumenanteil von mindestens 50% aufweist, welche die Ausbildung einer aluminiumoxidhaltigen Schutzschicht ermöglicht, bei niedrigen und bei mittleren Temperaturen (je nach Ausführung unterhalb von 900°C) chromhaltige α-Cr-Phasen von mehr als 5% aufweist, welche die Ausbildung einer chromoxidhaltigen Schutzschicht ermöglicht.The alloy according to the invention has a marked improvement in the oxidation and corrosion resistance over the already known high-temperature protective layers on. In the inventive high-temperature protective layer is determine that they are at high temperatures (depending on the design above 800 ° C) aluminum-containing γ and γ'-phases with a volume fraction of at least 50%, which allows the formation of an aluminum oxide-containing protective layer, at low and medium temperatures (depending on the version below of 900 ° C) chromium-containing α-Cr phases of more than 5%, which the training a chromium oxide-containing protective layer allows.

Wie aus der Fig. 1 ersichtlich, zeigt die hier gewählte Zusammensetzung keine bzw. nur geringe Volumenanteile von σ-Phase bzw. β-NiAl-Phase oder Borid-Phasen (in Fig. 1 als M2B_ORTH bezeichnet), so dass unter Temperaturwechselbeanspruchung deutliche Vorteile zu erwarten sind. Die Vergleichslegierung (Fig. 2) zeigt eine ähnliche Zusammensetzung bei einigen Elementen, aber aufgrund der Unterschiede anderer Elemente zeigt sich doch eine sehr verschiedene Mikrostruktur, die basierend auf unserer Erfahrung keine ausreichende Temperaturwechselbeständigkeit für Turbine haben wird und zudem durch das beginnende Aufschmelzen über 900 °C nicht einsetzbar ist.As can be seen from FIG. 1, the composition selected here shows no or only small volume fractions of σ-phase or β-NiAl phase or boride phases (in Fig. 1 as M2B_ORTH), so that under thermal cycling significant benefits are expected. The comparative alloy (Figure 2) shows a similar one Composition of some elements, but due to the differences of others Elements show a very different microstructure based on In our experience, no adequate thermal shock resistance for turbine and can not be used by the incipient melting over 900 ° C. is.

Um die Haftung der aluminiumoxidhaltigen Deckschicht bei Hochtemperatur zu verbessern, wird dem Basiswerkstoff, der die Hochtemperatur-Schutzschicht bildet, Silizium und Bor zulegiert. Dadurch erhöht sich der Schutz der Hochtemperatur-Schutzschicht und des darunter befindlichen Bauelementes wesentlich.To improve the adhesion of the alumina-containing topcoat at high temperature, becomes the base material that forms the high-temperature protective layer, silicon and boron added. This increases the protection of the high-temperature protective layer and the underlying device essential.

Die produktionsbedingte, inhärente Verunreinigung von Schwefel, die typischerweise in einer Konzentration von kleiner als 10 ppm, in einzelnen Fällen aber auch 50ppm erreichen kann, führt zu reduzierter Oxidation- und Korrosionsbeständigkeit. Erfindungsgemäss werden bei der Herstellung der Beschichtung die Spurenelemente Mg und Ca zugegeben, die Schwefel absorbieren und dadurch im für Temperaturen unterhalb von 850 bis 950 °C die Korrosionsbeständigkeit erhöht.The production-related, inherent contamination of sulfur, which is typically in a concentration of less than 10 ppm, in some cases 50 ppm can lead to reduced oxidation and corrosion resistance. According to the invention In the production of the coating, the trace elements Mg and Ca are added, which absorb sulfur and thereby in for temperatures below from 850 to 950 ° C increases the corrosion resistance.

Das Mengenverhältnis von Chrom zu Aluminium ist auf 3.6 bis 6.5 begrenzt, um die Ausbildung spröder β-Phasen zu verhindern. Das Mengenverhältnis von Nickel zu Chrom ist auf 2.3 bis 3.0 begrenzt, um spröde σ-Phasen zu verhindern, was die Temperaturwechselbeständigkeit verbessert. The ratio of chromium to aluminum is limited to 3.6 to 6.5 to the Prevent training of brittle β-phases. The ratio of nickel to Chromium is limited to 2.3 to 3.0, to prevent brittle σ-phases, what the thermal shock resistance improved.

Die feste und die beständige Haftung der Schutzschicht und ihrer Deckschicht bei häufigen Temperaturwechsel wird durch den speziell für die Legierung festgelegten Anteil an Yttrium erreicht.The firm and consistent adhesion of the protective layer and its topcoat Frequent temperature change is determined by the specific for the alloy Proportion of yttrium reached.

Das die Legierung bildende Material liegt für die thermischen Spritzprozesse in Pulverform vor und weist vorzugsweise eine Korngrösse von 5 bis 90 µm auf. Bei den anderen o.a. Verfahren wird die Legierung als Target bzw. als Suspension hergestellt. Die Legierung wird direkt auf das Grundmaterial des Bauelementes oder auf eine Zwischenlage, bestehend aus einer dritten Zusammensetzung, aufgetragen. Die Schichtdicken variieren je nach Beschichtungsverfahren zwischen 0.03 mm bis 1.5 mm. Nach dem Aufbringen der Legierung wird das Bauelement einer Wärmebehandlung unterzogen. Diese erfolgt bei einer Temperatur von 1000 bis 1200 ºC für etwa 10 Minuten bis 24 h Stunden.The material forming the alloy is in powder form for the thermal spraying processes before and preferably has a particle size of 5 to 90 microns. By the others O.A. Method, the alloy is prepared as a target or as a suspension. The alloy is applied directly to the base material of the component or to an intermediate layer, consisting of a third composition, applied. The layer thicknesses vary depending on the coating method between 0.03 mm to 1.5 mm. To the application of the alloy, the device is subjected to a heat treatment. This takes place at a temperature of 1000 to 1200 ° C for about 10 minutes up to 24 hours.

Claims (10)

  1. High-temperature protection layer for a component, characterized in that it contains (% by weight) 23 to 27% Cr, 4 to 7% Al, 0.1 to 3% Si, 0.1 to 3% Ta, 0.2 to 2% Y, 0.001 to 0.01% B, 0.001 to 0.01% Mg and 0.001 to 0.01% Ca, remainder Ni and inevitable impurities.
  2. The high-temperature protection layer as claimed in Claim 1, characterized in that the protection layer contains (% by weight) over 5% up to 6% Al.
  3. The high-temperature protection layer as claimed in Claim 1 or 2, characterized in that the quantitative ratio of Cr to Al is in a range from 3.6 to 6.5.
  4. The high-temperature protection layer as claimed in Claim 1 or 2, characterized in that the quantitative ratio of Ni to Cr is in a range from 2.3 to 3.0.
  5. The high-temperature protection layer as claimed in one of Claims 1 to 4, characterized in that the sum of the proportions by volume of the two phases γ (gamma) and γ' (gamma prime) in the temperature range from 800°C to 1050°C amounts to more than 50%.
  6. The high-temperature protection layer as claimed in one of Claims 1 to 5, characterized in that the proportion by volume of the α-Cr phases in the temperature range from 800°C to 900°C is more than 5%.
  7. The high-temperature protection layer as claimed in one of Claims 1 to 6, characterized in that the coating is produced under a vacuum, under shielding gas or in air by means of thermal spraying processes (LPPS, VPS, APS), high-velocity spraying (HVOF), electrochemical deposition, physical/chemical vapour deposition (PVD, CVD) or another coating process which is known from the prior art.
  8. The high-temperature protection layer as claimed in one of Claims 1 to 7, characterized in that it is a coating for components of thermal turbomachines.
  9. The high-temperature protection layer as claimed in one of Claims 1 to 8, characterized in that the layer thickness of between 0.03 mm and 1.5 mm is applied direct to the base material of the component or to an intermediate layer.
  10. The high-temperature protection layer as claimed in one of Claims 1 to 9, characterized in that the coating is used as a bonding layer beneath a thermal barrier coating.
EP03700010A 2002-01-18 2003-01-16 High-temperature protective coating Expired - Lifetime EP1466037B1 (en)

Applications Claiming Priority (3)

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DE10202012 2002-01-18
DE10202012 2002-01-18
PCT/CH2003/000023 WO2003060194A1 (en) 2002-01-18 2003-01-16 High-temperature protective coating

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JP (1) JP4217626B2 (en)
CN (1) CN100350075C (en)
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AU (1) AU2003200835A1 (en)
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EP2022870B1 (en) 2007-06-25 2014-07-23 Sulzer Metaplas GmbH Layer system for creating a surface layer on a surface of a substrate, vaporisation source for manufacturing a layer system
WO2009109199A1 (en) * 2008-03-04 2009-09-11 Siemens Aktiengesellschaft Alloy, high-temperature corrosion protection layer and layer system
DE102010021691A1 (en) * 2010-05-27 2011-12-01 Leibniz-Institut Für Neue Materialien Gemeinnützige Gmbh Layer composite with a one-dimensional composite structure
EP2474413A1 (en) * 2011-01-06 2012-07-11 Siemens Aktiengesellschaft Alloy, protective coating and component
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AU2003200835A1 (en) 2003-07-30
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US20050042474A1 (en) 2005-02-24
CA2473565C (en) 2010-12-07
JP2005514525A (en) 2005-05-19
EP1466037A1 (en) 2004-10-13
US7052782B2 (en) 2006-05-30
CN100350075C (en) 2007-11-21
RU2004125154A (en) 2005-07-20
CA2473565A1 (en) 2003-07-24
WO2003060194A1 (en) 2003-07-24
ATE299536T1 (en) 2005-07-15
ES2244914T3 (en) 2005-12-16
DE50300758D1 (en) 2005-08-18
RU2301284C2 (en) 2007-06-20
JP4217626B2 (en) 2009-02-04
BR0306989B1 (en) 2012-03-06

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