EP1466037A1 - High-temperature protective coating - Google Patents

High-temperature protective coating

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Publication number
EP1466037A1
EP1466037A1 EP03700010A EP03700010A EP1466037A1 EP 1466037 A1 EP1466037 A1 EP 1466037A1 EP 03700010 A EP03700010 A EP 03700010A EP 03700010 A EP03700010 A EP 03700010A EP 1466037 A1 EP1466037 A1 EP 1466037A1
Authority
EP
European Patent Office
Prior art keywords
protective layer
temperature
temperature protective
layer according
coating
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP03700010A
Other languages
German (de)
French (fr)
Other versions
EP1466037B1 (en
Inventor
Dietrich Eckardt
Klaus Erich Schneider
Christoph Toennes
Hans-Peter Bossmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
General Electric Technology GmbH
Original Assignee
Alstom Technology AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Alstom Technology AG filed Critical Alstom Technology AG
Publication of EP1466037A1 publication Critical patent/EP1466037A1/en
Application granted granted Critical
Publication of EP1466037B1 publication Critical patent/EP1466037B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • 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 used above all where the base material of components made of heat-resistant steels and / or alloys that are used at temperatures above 600 S C is to be protected.
  • high-temperature protective layers are intended to slow down or completely prevent the effects of high-temperature corrosion, especially of sulfur, oil ash, oxygen, alkaline earths and vanadium.
  • Such high-temperature protective layers are designed so that they can be applied directly to the base material of the component to be protected.
  • High-temperature protective layers are of particular importance for components of gas turbines. They are mainly applied to rotor blades and guide vanes as well as to heat accumulation segments in gas turbines.
  • An austenitic material based on nickel, cobalt or iron is preferably used to manufacture these components.
  • nickel superalloys in particular are used as the base material.
  • the layers differ in the concentration of the "family elements" nickel, cobalt, chromium, aluminum and yttrium and in the addition of other elements.
  • the composition of the layer decisively determines the behavior at high temperature in an oxidizing or corrosive atmosphere, with temperature changes and with mechanical stress.
  • the composition of the layer determines the material and manufacturing costs.
  • Many known layers only show excellent properties in some aspects.Although widely used worldwide, the addition of cobalt has, according to our own investigations, negatively influenced both the corrosion resistance and the costs.
  • the invention is based on the object of creating a high-temperature protective layer which is inexpensive, oxidation-resistant, corrosion-resistant and resistant to temperature changes.
  • composition of this alloy according to the invention has (% by weight) 23 to 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. All weights refer to the total weight of the respective alloy. The rest of the alloy consists of nickel and unavoidable impurities. The Al content is preferably in a range from over 5 to 6% by weight.
  • the protective layer according to the invention is a NiCrAlY alloy. It shows a significant improvement in the resistance to oxidation and corrosion compared to the already known high-temperature protective layers.
  • the high-temperature protective layer according to the invention it can be ascertained that at high temperatures (depending on the version above 800 ° C.) it has aluminum-containing ⁇ and ⁇ ' phases with a volume fraction of at least 50%, which enables the formation of an aluminum oxide-containing protective layer, at low temperatures and at medium temperatures (depending on the version below 900 ° C.) has chromium-containing ⁇ -Cr phases (referred to as BCC in FIG. 1) of more than 5%, which enables the formation of a chromium oxide-containing protective layer.
  • BCC chromium-containing ⁇ -Cr phases
  • the adhesion of the aluminum oxide-containing cover layer at high temperature improves, which significantly increases the protection of the high-temperature protective layer and the component located underneath.
  • magnesium Calcium and calcium are primarily bound to the impurities that are naturally present in the production process, thereby increasing the corrosion resistance for temperatures below 850-950 ° C.
  • the quantity ratio of chromium to aluminum is limited to 3.6 to 6.5 in order to prevent the formation of brittle ß phases.
  • the quantity ratio of nickel to chromium is limited to 2.3 to 3.0 in order to prevent brittle ⁇ phases, which improves the resistance to temperature changes.
  • the firm and permanent adhesion of the protective layer and its cover layer with frequent changes in temperature is achieved by the percentage of yttrium specifically determined for the alloy.
  • composition chosen here shows no or only small proportions by volume of ⁇ -phase or ß-NiAI-phase (FIG. 1), so that significant advantages can be expected under thermal cycling.
  • the comparative alloy from FIG. 2 shows a similar composition for some elements, but due to the differences in other elements, a very different microstructure is shown, which, based on our experience, will not have sufficient resistance to thermal shock for turbines and also due to the beginning melting above 900 ° C cannot be used.
  • the production-related, inherent contamination of sulfur which can typically reach a concentration of less than 10 ppm, but in some cases up to 50ppm, leads to reduced resistance to oxidation and corrosion.
  • the trace elements Mg and Ca which absorb sulfur, are added during the production of the coating.
  • the alloy is applied directly to the base material of the component or to an intermediate layer consisting of a third composition.
  • the layer thicknesses vary between 0.03 mm and 1.5 mm.
  • Fig. 1 shows the phase balance (molar fraction ⁇ [%] vs. temperature [ 9 C]) according to the composition given here
  • Fig. 2 shows the phase balance (molar fraction ⁇ [%] vs. temperature [ Q C]) according to that in the US patent -A-4,973,445 specified composition.
  • the invention is explained in more detail using an exemplary embodiment which describes the production of a coated gas turbine component or another component of a thermal turbomachine.
  • 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 using a blasting process. The component is coated under vacuum, under protective gas or in air by means of thermal spray processes (LPPS, VPS, APS), high-speed spraying (HVOF), electrochemical processes, physical / chemical evaporation (PVD, CVD) or another known from the prior art coating process.
  • LPPS thermal spray processes
  • VPS high-speed spraying
  • PVD physical / chemical evaporation
  • CVD chemical evaporation
  • a NiCrAlY alloy is used for the coating, which according to the invention (% by weight) contains 23 to 27% by weight chromium, 4 to 7% by weight aluminum, 0.1 to 3% by weight silicon, 0.1 to 3% by weight. % Tantalum, 0.2 to 2% by weight yttrium, 0.001 to 0.01% by weight boron, 0.001 to 0.01% by weight magnesium and 0.001 to 0.01% by weight calcium.
  • the rest of the alloy consists of nickel and unavoidable impurities.
  • the Al content is preferably in a range from over 5 to 6% by weight. All weights refer to the total weight of the alloy used.
  • the alloy according to the invention has a significant improvement in the oxidation and corrosion resistance compared to the already known high-temperature protective layers.
  • the high-temperature protective layer according to the invention it can be established that it is at high temperatures (depending on the design above 800 ° C) has aluminum-containing ⁇ and ⁇ ' phases with a volume fraction of at least 50%, which enables the formation of an aluminum oxide-containing protective layer, at low and at medium temperatures (depending on the version below 900 ° C) chromium-containing ⁇ -Cr phases of more than 5%, which enables the formation of a protective layer containing chromium oxide.
  • the composition selected here shows no or only small proportions by volume of ⁇ -phase or ⁇ -NiAI phase or boride phases (referred to in FIG. 1 as M2B_ORTH), so that there are clear advantages under thermal cycling are to be expected.
  • the comparative alloy (Fig. 2) shows a similar composition for some elements, but due to the differences in other elements, a very different microstructure is shown which, based on our experience, will not have sufficient resistance to temperature changes for turbines and also due to the beginning melting above 900 ° C cannot be used.
  • silicon and boron are added to the base material that forms the high temperature protective layer. This significantly increases the protection of the high-temperature protective layer and the component located underneath.
  • the production-related, inherent contamination of sulfur which can typically reach a concentration of less than 10 ppm, but in some cases also 50 ppm, leads to reduced oxidation and corrosion resistance.
  • the Spu 'renetti Mg and Ca added in the preparation of the coating to absorb the sulfur and thereby increases in temperatures below 850 to 950 ° C the corrosion resistance.
  • the quantity ratio of chromium to aluminum is limited to 3.6 to 6.5 in order to prevent the formation of brittle ß phases.
  • the quantity ratio of nickel to chromium is limited to 2.3 to 3.0 to prevent brittle ⁇ phases, which improves the resistance to temperature changes.
  • the firm and permanent adhesion of the protective layer and its cover layer with frequent changes in temperature is achieved by the percentage of yttrium specifically determined for the alloy.
  • the material forming the alloy is in powder form for the thermal spraying processes and preferably has a grain size of 5 to 90 ⁇ m.
  • the alloy is produced 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. Depending on the coating process, the layer thicknesses vary between 0.03 mm and 1.5 mm.
  • the component is subjected to a heat treatment. This takes place at a temperature of 1000 to 1200 ° C. for about 10 minutes to 24 hours.

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

Hochtemperatur-Schutzschicht High-temperature protective layer
Technisches GebietTechnical field
Die Erfindung bezieht sich auf eine HoQhtemperatur-Schutzschicht gemäss dem unabhängigen Patentanspruch.The invention relates to a high temperature protective layer according to the independent claim.
Stand der TechnikState of the art
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 SC verwendet werden.Such high-temperature protective layers are used above all where the base material of components made of heat-resistant steels and / or alloys that are used at temperatures above 600 S C is to be protected.
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.These high-temperature protective layers are intended to slow down or completely prevent the effects of high-temperature corrosion, especially of sulfur, oil ash, oxygen, alkaline earths and vanadium. Such high-temperature protective layers are designed so that they can be applied directly to the base material of the component to be protected.
Bei Bauelementen von Gasturbinen sind Hochtemperatur-Schutzschichten von besonderer Bedeutung. Sie werden vor allem auf Lauf- und Leitschaufeln sowie auf Wärmestausegmenten von Gasturbinen aufgetragen. 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.High-temperature protective layers are of particular importance for components of gas turbines. They are mainly applied to rotor blades and guide vanes as well as to heat accumulation segments in gas turbines. An austenitic material based on nickel, cobalt or iron is preferably used to manufacture these components. In the manufacture of gas turbine components, nickel superalloys in particular are used as the base material.
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.Until now, it has been customary to provide components intended for gas turbines with protective layers formed by alloys, the essential components of which are nickel, chromium, aluminum and yttrium. Such high-temperature protective layers have a matrix in which an aluminum-containing phase is embedded.
Die meisten der Beschichtungen für Hochtemperaturanwendungen stammen aus den Familien der NiCrAIY, CoCrAIY 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 be- einflusst.Most of the coatings for high-temperature applications come from the families of NiCrAIY, CoCrAIY or NiCoCrAlY. The layers differ in the concentration of the "family elements" nickel, cobalt, chromium, aluminum and yttrium and in the addition of other elements. The composition of the layer decisively determines the behavior at high temperature in an oxidizing or corrosive atmosphere, with temperature changes and with mechanical stress. In addition, the composition of the layer determines the material and manufacturing costs.Many known layers only show excellent properties in some aspects.Although widely used worldwide, the addition of cobalt has, according to our own investigations, negatively influenced both the corrosion resistance and the costs.
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 NiCrAIY" bekannt geworden. Die thermodynamische Modellierung für den Temperaturbereich 800°C bis 1050°C des Phasenbestandes dieser Legierungen hat gezeigt, dass die spezifizierten Zu¬ sammensetzungen zu MikroStrukturen mit unerwünschten Phasen bzw. thermisch aktivierten Phasenübergängen führen, namentlich σ- und/oder ß-NiAl in nachteilig gro- ssen Volumenanteilen. Darstellung der ErfindungFrom documents 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 and -US- A-4,743,514 are numerous alloys of the family "cobalt-free NiCrAlY" become known. the thermodynamic modeling for the temperature range 800 ° C to 1050 ° C of the phase content of these alloys has been shown that the specified sammensetzungen to ¬ to microstructures with undesirable phases or cause thermally activated phase transitions, namely σ and / or ß-NiAl in disadvantageously large volume fractions. Presentation of the invention
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.Based on the prior art mentioned at the outset, the invention is based on the object of creating a high-temperature protective layer which is inexpensive, oxidation-resistant, corrosion-resistant and resistant to temperature changes.
Diese Aufgabe wird erfindungsgemäss durch die Merkmale des Patentanspruches 1 gelöst.According to the invention, this object is achieved by the features of patent claim 1.
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 AI-Gehalt in einem Bereich von über 5 bis 6 Gew.-%.The composition of this alloy according to the invention has (% by weight) 23 to 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. All weights refer to the total weight of the respective alloy. The rest of the alloy consists of nickel and unavoidable impurities. The Al content is preferably in a range from over 5 to 6% by weight.
Bei der erfindungsgemässen Schutzschicht handelt es sich um eine NiCrAlY- 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 the resistance to oxidation and corrosion compared to the already known high-temperature protective layers. In the high-temperature protective layer according to the invention, it can be ascertained that at high temperatures (depending on the version above 800 ° C.) it has aluminum-containing γ and γ ' phases with a volume fraction of at least 50%, which enables the formation of an aluminum oxide-containing protective layer, at low temperatures and at medium temperatures (depending on the version below 900 ° C.) has chromium-containing α-Cr phases (referred to as BCC in FIG. 1) of more than 5%, which enables the formation of a chromium oxide-containing protective layer.
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 ß-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.If silicon and boron are added to the alloy that forms the high-temperature protective layer, the adhesion of the aluminum oxide-containing cover layer at high temperature improves, which significantly increases the protection of the high-temperature protective layer and the component located underneath. With an addition of magnesium Calcium and calcium are primarily bound to the impurities that are naturally present in the production process, thereby increasing the corrosion resistance for temperatures below 850-950 ° C. The quantity ratio of chromium to aluminum is limited to 3.6 to 6.5 in order to prevent the formation of brittle ß phases. The quantity ratio of nickel to chromium is limited to 2.3 to 3.0 in order to prevent brittle σ phases, which improves the resistance to temperature changes. The firm and permanent adhesion of the protective layer and its cover layer with frequent changes in temperature is achieved by the percentage of yttrium specifically determined for the alloy.
Die hier gewählte Zusammensetzung zeigt keine bzw. nur geringe Volumenanteile von σ-Phase bzw. ß-NiAI-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 ß-NiAI-phase (FIG. 1), so that significant advantages can be expected under thermal cycling. The comparative alloy from FIG. 2 shows a similar composition for some elements, but due to the differences in other elements, a very different microstructure is shown, which, based on our experience, will not have sufficient resistance to thermal shock for turbines and also due to the beginning melting above 900 ° C cannot be used.
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. Erfindungs- gemäss werden bei der Herstellung der Beschichtung die Spurenelemente Mg und Ca zugegeben, die Schwefel absorbieren.The production-related, inherent contamination of sulfur, which can typically reach a concentration of less than 10 ppm, but in some cases up to 50ppm, leads to reduced resistance to oxidation and corrosion. According to the invention, the trace elements Mg and Ca, which absorb sulfur, are added during the production of the coating.
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. Depending on the coating process, the layer thicknesses vary between 0.03 mm and 1.5 mm.
KURZE BESCHREIBUNG DER ZEICHNUNGENBRIEF DESCRIPTION OF THE DRAWINGS
Die Erfindung wird an Hand der beiliegenden Zeichnungen erläutert, in denen Fig. 1 das Phasengleichgewicht (Molanteil Φ [%] vs. Temperatur [9 C]) gemäss der hier angegebenen Zusammensetzung zeigt, Fig. 2 das Phasengleichgewicht (Molanteil Φ [%] vs. Temperatur [Q C]) gemäss der im Patent US-A-4,973,445 angegebenen Zusammensetzung darstellt.The invention is explained with reference to the accompanying drawings, in which Fig. 1 shows the phase balance (molar fraction Φ [%] vs. temperature [ 9 C]) according to the composition given here, Fig. 2 shows the phase balance (molar fraction Φ [%] vs. temperature [ Q C]) according to that in the US patent -A-4,973,445 specified composition.
Es sind nur die für die Erfindung wesentlichen Elemente dargestellt.Only the elements essential to the invention are shown.
Wege zur Ausführung der ErfindungWays of Carrying Out the Invention
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.The invention is explained in more detail using an exemplary embodiment which describes the production of a coated gas turbine component or another component of a thermal turbomachine. 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 using a blasting process. The component is coated under vacuum, under protective gas or in air by means of thermal spray processes (LPPS, VPS, APS), high-speed spraying (HVOF), electrochemical processes, physical / chemical evaporation (PVD, CVD) or another known from the prior art coating process.
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 AI-Gehalt in einem Bereich von über 5 bis 6 Gew.-%. Alle Gewichtsangaben beziehen sich auf das Gesamtgewicht der verwendeten Legierung.A NiCrAlY alloy is used for the coating, which according to the invention (% by weight) contains 23 to 27% by weight chromium, 4 to 7% by weight aluminum, 0.1 to 3% by weight silicon, 0.1 to 3% by weight. % Tantalum, 0.2 to 2% by weight yttrium, 0.001 to 0.01% by weight boron, 0.001 to 0.01% by weight magnesium and 0.001 to 0.01% by weight calcium. The rest of the alloy consists of nickel and unavoidable impurities. The Al content is preferably in a range from over 5 to 6% by weight. 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 significant improvement in the oxidation and corrosion resistance compared to the already known high-temperature protective layers. In the high-temperature protective layer according to the invention, it can be established that it is at high temperatures (depending on the design above 800 ° C) has aluminum-containing γ and γ ' phases with a volume fraction of at least 50%, which enables the formation of an aluminum oxide-containing protective layer, at low and at medium temperatures (depending on the version below 900 ° C) chromium-containing α-Cr phases of more than 5%, which enables the formation of a protective layer containing chromium oxide.
Wie aus der Fig. 1 ersichtlich, zeigt die hier gewählte Zusammensetzung keine bzw. nur geringe Volumenanteile von σ-Phase bzw. ß-NiAI-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 proportions by volume of σ-phase or β-NiAI phase or boride phases (referred to in FIG. 1 as M2B_ORTH), so that there are clear advantages under thermal cycling are to be expected. The comparative alloy (Fig. 2) shows a similar composition for some elements, but due to the differences in other elements, a very different microstructure is shown which, based on our experience, will not have sufficient resistance to temperature changes for turbines and also due to the beginning melting above 900 ° C cannot be used.
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.In order to improve the adhesion of the cover layer containing aluminum oxide at high temperature, silicon and boron are added to the base material that forms the high temperature protective layer. This significantly increases the protection of the high-temperature protective layer and the component located underneath.
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. Erfin- dungsgemäss werden bei der Herstellung der Beschichtung die Spu'renelemente 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 can typically reach a concentration of less than 10 ppm, but in some cases also 50 ppm, leads to reduced oxidation and corrosion resistance. According to the invention, the Spu 'renelemente Mg and Ca added in the preparation of the coating to absorb the sulfur and thereby increases in temperatures below 850 to 950 ° C the corrosion resistance.
Das Mengenverhältnis von Chrom zu Aluminium ist auf 3.6 bis 6.5 begrenzt, um die Ausbildung spröder ß-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.The quantity ratio of chromium to aluminum is limited to 3.6 to 6.5 in order to prevent the formation of brittle ß phases. The quantity ratio of nickel to chromium is limited to 2.3 to 3.0 to prevent brittle σ phases, which improves the resistance to temperature changes. The firm and permanent adhesion of the protective layer and its cover layer with frequent changes in temperature is achieved by the percentage of yttrium specifically determined for the alloy.
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 QC für etwa 10 Minuten bis 24 h Stunden. The material forming the alloy is in powder form for the thermal spraying processes and preferably has a grain size of 5 to 90 μm. In the other processes mentioned above, the alloy is produced 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. Depending on the coating process, the layer thicknesses vary between 0.03 mm and 1.5 mm. After the alloy has been applied, the component is subjected to a heat treatment. This takes place at a temperature of 1000 to 1200 ° C. for about 10 minutes to 24 hours.

Claims

Patentansprüche claims
1. Hochtemperatur-Schutzschicht für ein Bauelement, dadurch gekennzeichnet, dass diese (Gew.-%) 23 bis 27% Cr, 4 bis 7% AI, 0.1 bis 3% Si, 0.1 bis 3% Ta, 0.2 bis 2% Y, 0.001 bis 0.01 % B, 0.001 bis 0.01% Mg und 0.001 bis 0.01% Ca, Rest Ni und unvermeidbare Verunreinigungen enthält.1. High-temperature protective layer for a component, characterized in that this (% 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, balance Ni and unavoidable impurities.
2. Hochtemperatur-Schutzschicht nach Anspruch 1 , dadurch gekennzeichnet, dass die Schutzschicht (Gew.-%) über 5% bis 6% AI enthält.2. High-temperature protective layer according to claim 1, characterized in that the protective layer (wt .-%) contains over 5% to 6% AI.
3. Hochtemperatur-Schutzschicht nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Mengenverhältnis von Cr zu AI in einem Bereich von 3.6 bis 6.5 ist.3. High-temperature protective layer according to 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. Hochtemperatur-Schutzschicht nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Mengenverhältnis von Ni zu Cr in einem Bereich von 2.3 bis 3.0 ist.4. High-temperature protective layer according to 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. Hochtemperatur-Schutzschicht nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass die Summe der Volumenanteile der beiden Phasen γ (gamma) und γ' (gamma pri- me) im Temperaturbereich von 800°C bis 1050°C mehr als 50% beträgt.5. High-temperature protective layer according to one of claims 1 to 4, characterized in that the sum of the volume fractions of the two phases γ (gamma) and γ ' (gamma prime) in the temperature range from 800 ° C to 1050 ° C more than 50 % is.
6. Hochtemperatur-Schutzschicht nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass der Volumenanteil der α-Cr-Phasen im Temperaturbereich von 800°C bis 900°C mehr als 5% beträgt. 6. High-temperature protective layer according to one of claims 1 to 5, characterized in that the volume fraction of the α-Cr phases in the temperature range from 800 ° C to 900 ° C is more than 5%.
7. Hochtemperatur-Schutzschicht nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die Beschichtung unter Vakuum, unter Schutzgas oder in Luft mittels thermischen Spritzverfahren (LPPS, VPS, APS), Hochgeschwindigkeitsspritzen (HVOF), elektrochemischen Abscheidung, physikalischer/chemischer Verdampfung (PVD, CVD) oder einem anderem, aus dem Stand der Technik bekannten Beschichtungsverfah- ren hergestellt wird.7. High-temperature protective layer according to one of claims 1 to 6, characterized in that the coating under vacuum, under protective gas or in air by means of thermal spray processes (LPPS, VPS, APS), high-speed spraying (HVOF), electrochemical deposition, physical / chemical evaporation (PVD, CVD) or another coating method known from the prior art.
8. Hochtemperatur-Schutzschicht nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass diese eine Beschichtung von Bauelementen von thermischen Turbomaschinen ist.8. High-temperature protective layer according to one of claims 1 to 7, characterized in that it is a coating of components of thermal turbomachinery.
9. Hochtemperatur-Schutzschicht nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Schichtdicke zwischen 0.03 mm und 1.5 mm direkt auf dem Grundwerkstoff des Bauteils oder auf eine Zwischenlage aufgebracht ist.9. High-temperature protective layer according to one of claims 1 to 8, characterized in that the layer thickness between 0.03 mm and 1.5 mm is applied directly to the base material of the component or to an intermediate layer.
10. Hochtemperatur-Schutzschicht nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die Beschichtung unterhalb einer Wärmedämmschicht als Haftvermittlerschicht eingesetzt ist. 10. High-temperature protective layer according to one of claims 1 to 9, characterized in that the coating is used below a heat insulation layer as an adhesion promoter layer.
EP03700010A 2002-01-18 2003-01-16 High-temperature protective coating Expired - Lifetime EP1466037B1 (en)

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