EP0760869A1 - Nickel-aluminium intermetallic basis alloy - Google Patents

Nickel-aluminium intermetallic basis alloy

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Publication number
EP0760869A1
EP0760869A1 EP95920844A EP95920844A EP0760869A1 EP 0760869 A1 EP0760869 A1 EP 0760869A1 EP 95920844 A EP95920844 A EP 95920844A EP 95920844 A EP95920844 A EP 95920844A EP 0760869 A1 EP0760869 A1 EP 0760869A1
Authority
EP
European Patent Office
Prior art keywords
chromium
tantalum
nial
alloy
alloy according
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
EP95920844A
Other languages
German (de)
French (fr)
Other versions
EP0760869B1 (en
Inventor
Gerhard Sauthoff
Benedikt Zeumer
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.)
HC Starck GmbH
Siemens AG
Original Assignee
HC Starck GmbH
Siemens AG
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Publication of EP0760869A1 publication Critical patent/EP0760869A1/en
Application granted granted Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ

Definitions

  • the invention relates to an intermetallic nickel aluminum base alloy which has the binary phase NiAl.
  • the invention further relates to the use of the intermetallic nickel-aluminum base alloy.
  • DE-AS 18 12 144 describes a process for producing a high-strength nickel-aluminum material with good resistance to oxidation.
  • nickel powder is mixed with aluminum powder and then pressed and cold-formed, so that a self-supporting and coherent shaped body with a fibrous or lamenarene
  • connection NissAl is also created. This solid solution as well as the compound Ni3Al could be verified with X-ray analysis. The extent to which other connections between nickel and aluminum can be achieved with the method cannot be found in the design specification.
  • the object of the invention is to improve the thermo-mechanical properties of a nickel-aluminum alloy. These include in particular the heat resistance, the oxidation resistance and the thermal shock resistance. Another object of the invention is to provide a use of such an improved nickel-aluminum alloy.
  • the object directed to a nickel-aluminum alloy is achieved by an intermetallic nickel-aluminum base alloy which predominantly has the binary phase NiAl and additionally chromium and tantalum, wherein the total proportion of chromium and tantalum is a maximum of 12 at.%.
  • the proportion of the binary phase NiAl is preferably between 70 to 95 at .-%, in particular between 85 and 90 at * t .-%.
  • the preferred content ranges for tantalum and chromium are 0.3 to 3.8 at .-% and 1.0 to 9.0 at .-%. Within these ranges, 0.3 to 0.9 at.% Tantalum and 1.0 to 3 at.% Chromium or 1.7 to 3.0 at.% Tan tal and 6.0 to 9 are preferred .0 at .-% chromium used.
  • the ratio of tantalum to chromium is preferably 1: 3 or less. With such a ratio, the concentration of substitution elements in the NiAl reaches a maximum.
  • the ratio of tantalum and chromium precipitations occur in the coarse, mul- tular Laves phase in the non-metallic nickel-aluminum base alloy on the grain boundaries of the binary phase NiAl, on which the elements Ni, Al, Cr and Ta can be involved.
  • there are excretions of finely divided Laves phase and ⁇ -chromium within the NiAl grains It is preferred that the structure of 5 to 11% by volume Laves phase, 3 to 10% by volume precipitates in NiAl and one
  • a structure has proven to be particularly advantageous which comprises approximately 11 vol.% Laves phase on the grain boundaries and approximately 10 vol.% Precipitates in the NiAl and NiAl as the remainder.
  • a further improvement in certain properties results if at least one element from the group iron, molybdenum, tungsten and hafnium is present in the alloy in an amount of up to 1 at.%, But not more than 3 at are included.
  • the alloy can also contain trace elements such as oxygen, nitrogen and sulfur, as well as production-related impurities.
  • the coarse or fine-particle multinary Laves phases and ⁇ -chromium are formed. These excretions are usually based on gussets points of different NiAl grains. Higher than the specified amounts of alloying elements tantalum or chromium can lead to an undesirable increase in the amount of precipitates. If the volume fractions of Laves phase increases too much, a cellular structure arises in which the Laves phase takes over the function of the matrix. Too large a proportion of Laves phase in the structure makes the intermetallic alloy brittle and difficult to process.
  • the object aimed at using the alloy is achieved according to the invention in that components of a gas turbine, in particular components exposed to high temperatures, such as gas turbine blades, are produced with the NiAl base alloy.
  • a component of a gas turbine, in particular a turbine blade, made from the base alloy is particularly suitable due to the high oxidation resistance for continuous use at high temperatures, for example above 1100 ° C., in particular at 1350 ° C.
  • an additional coating with protective layers can be dispensed with in such a component, depending on the requirements.
  • the intermetallic nickel-aluminum base alloy is generally also suitable as a material for the production of objects which must have high strength, high heat resistance, good toughness, good oxidation resistance and good thermal shock resistance.
  • the strength lies here with a 0.2% proof stress at room temperature of over 600 MPa.
  • the heat resistance lies at the 0.2% proof stress at over 200 MPa at 800 ° C and at over 90 MPa at 1000 ° C.
  • the toughness is at least 7 MPa / m and the oxidation resistance is of the order of magnitude
  • composition (in at.%) Of alloys sought is given in Table 1 below.
  • the structure of the structure ie the grain size, the distribution of precipitates and the size of the precipitate, varies greatly with the manufacturing process.
  • the distribution of the Laves phase particles is homogenized by thermodynamic treatments, extrusion (SP) or by using the powder metallurgical production route (PM).
  • SP thermodynamic treatments
  • PM powder metallurgical production route
  • the mechanical properties of the alloys are also heavily dependent on the selected manufacturing process. The following production routes for these alloys were followed:
  • Powder metallurgy by inert gas atomization and subsequent hot isostatic pressing at 1250 ° C.
  • the creep resistance (in MPa) of the alloys tested in the compression test (secondary stationary creep resistance than Funk ⁇ tion of the strain rate [1 / s] at 1000 ° C and 1100 ° C *) is shown in Table 3 below.
  • the creep strengths of this alloy are higher than the creep strengths of comparable intermetallic phases, for example higher than the creep strength of binary NiAl or NiAlCr alloys.
  • Table 4a gives a comparison of the 0.2% proof stress (in MPa) in the compression test of a conventional superalloy, a binary NiAl alloy and a NiAl-Ta-Cr alloy.
  • the superiority of the alloy according to the invention proves at temperatures above 1000 ° C.
  • the NiAl-Ta-Cr alloy Compared to conventional superalloys, the NiAl-Ta-Cr alloy has the advantage that it also has sufficient strength above 1050 ° C to 1150 ° C. There is no sudden drop in strength in this alloy due to the dissolution of the solidified phase.
  • Table 5 shows a comparison of the values of K ⁇ values of various ceramics known from industry data and of the powder-metallurgical processed NiAl-Ta-Cr alloy produced.
  • the alloy has a good oxidation resistance of the order of magnitude 5 * 10- ⁇ g 2 c " ⁇ s, which is therefore equal to or better than the oxidation resistance of binary NiAl.
  • no protective layers for example, are formed at high temperatures ceramic material, this eliminates the problem of the connection between ceramic and metallic components.
  • Adequate thermal shock resistance is given. At 1350 ° C, 500 temperature cycles of the alloy are achieved without damaging the material.

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

Abstract

A nickel-aluminium intermetallic basis alloy has a structure mainly made of the binary phase NiAl and further contains the elements chromium and tantalum. The total proportion of the elements chromium and tantalum amounts to maximum 12 % by atoms. The preferable content ranges lie from 0.3 to 3.8 % by atoms tantalum and from 1.0 to 9.0 % by atoms chromium. The nickel-aluminium intermetallic basis alloy is characterised in particular by a high oxidation resistance at high temperatures, such as 1350 °C. It is therefore suitable for producing pieces exposed to a high and continuous thermal stress, such as gas turbine blades. This high oxidation resistance allows additional anti-oxidation layers to be dispensed with.

Description

Beschreibungdescription
Intermetallische Nickel-Aluminium-BasislegierungIntermetallic nickel-aluminum base alloy
Die Erfindung betrifft eine intermetallische Nickel-Alumini¬ um-Basislegierung, die die binäre Phase NiAl aufweist. Wei¬ terhin betrifft die Erfindung eine Verwendung der intermetal¬ lischen Nickel-Aluminium-Basislegierung.The invention relates to an intermetallic nickel aluminum base alloy which has the binary phase NiAl. The invention further relates to the use of the intermetallic nickel-aluminum base alloy.
In der DE-AS 18 12 144 ist ein Verfahren zur Herstellung ei¬ nes hochfesten Nickel-Aluminium-Werkstoffs mit guter Oxidati¬ onsbeständigkeit beschrieben. Bei dem Verfahren wird Nickel¬ pulver mit Aluminiumpulver gemischt und anschließend gepreßt und kalt verformt, so daß ein selbsttragender und zuεammen- hängender Formkörper mit einer faserigen oder lamenarenDE-AS 18 12 144 describes a process for producing a high-strength nickel-aluminum material with good resistance to oxidation. In the process, nickel powder is mixed with aluminum powder and then pressed and cold-formed, so that a self-supporting and coherent shaped body with a fibrous or lamenarene
Struktur entsteht. Der Anteil des Nitkels liegt bei minde¬ stens 80 % und der des Aluminiums bei maximal 20 %. Der zu¬ sammenhängende Formkörper wird anschließend nacheinander bei jeweils erhöhten Temperaturen warmverformt. Neben einer fe- sten Lösung des Aluminiums in dem Nickel entsteht zusätzlich hierbei vor allem die Verbindung NißAl. Diese feste Lösung sowie die Verbindung Ni3Al konnten mit Röntgenstrahlenanalyse nachgewiesen werden. Inwieweit andere Verbindungen zwischen Nickel und Aluminium mit dem Verfahren erreichbar sind, ist der Auslegungsschrift nicht zu entnehmen.Structure arises. The proportion of nitrous oxide is at least 80% and that of aluminum is at most 20%. The connected molded body is then successively thermoformed at elevated temperatures. In addition to a solid solution of the aluminum in the nickel, the connection NissAl is also created. This solid solution as well as the compound Ni3Al could be verified with X-ray analysis. The extent to which other connections between nickel and aluminum can be achieved with the method cannot be found in the design specification.
Der Erfindung liegt die Aufgabe zugrunde, die thermo-mechani¬ schen Eigenschaften einer Nickel-Aluminium-Legierung zu ver¬ bessern. Hierzu zählen insbesondere die Warmfestigkeit, der Oxidationswiderstand und die Thermoschockbeständigkeit. Eine weitere Aufgabe der Erfindung besteht darin, eine Verwendung einer so verbesserten Nickel-Aluminium-Legierung anzugeben.The object of the invention is to improve the thermo-mechanical properties of a nickel-aluminum alloy. These include in particular the heat resistance, the oxidation resistance and the thermal shock resistance. Another object of the invention is to provide a use of such an improved nickel-aluminum alloy.
Erfindungsgemäß wird die auf eine Nickel-Aluminium-Legierung gerichtete Aufgabe durch eine intermetallische Nickel-Alumi¬ nium-Basislegierung gelöst, welche überwiegend die binäre Phase NiAl sowie zusätzlich Chrom und Tantal aufweist, wobei der gesamte Anteil an Chrom und Tantal maximal 12 at.-% be¬ trägt. Der Anteil der binären Phase NiAl liegt vorzugsweise zwischen 70 bis 95 at.-%, insbesondere zwischen 85 und 90 a*t.-%. Die bevorzugten Gehaltsbereiche für Tantal bzw. Chrom liegen bei 0,3 bis 3,8 at.-% bzw. 1,0 bis 9,0 at.-%. Innerhalb dieser Bereiche werden bevorzugt 0,3 bis 0,9 at.-% Tantal und 1,0 bis 3 at.-% Chrom bzw. 1,7 bis 3,0 at.-% Tan¬ tal und 6,0 bis 9,0 at.-% Chrom verwendet.According to the invention, the object directed to a nickel-aluminum alloy is achieved by an intermetallic nickel-aluminum base alloy which predominantly has the binary phase NiAl and additionally chromium and tantalum, wherein the total proportion of chromium and tantalum is a maximum of 12 at.%. The proportion of the binary phase NiAl is preferably between 70 to 95 at .-%, in particular between 85 and 90 at * t .-%. The preferred content ranges for tantalum and chromium are 0.3 to 3.8 at .-% and 1.0 to 9.0 at .-%. Within these ranges, 0.3 to 0.9 at.% Tantalum and 1.0 to 3 at.% Chromium or 1.7 to 3.0 at.% Tan tal and 6.0 to 9 are preferred .0 at .-% chromium used.
Das Verhältnis von Tantal zu Chrom beträgt dabei vorzugsweise 1 : 3 oder kleiner. Bei einem derartigen Verhältnis erreicht die Konzentration von Substituierungsele enten im NiAl ein Maximum. Durch Zugabe von Tantal und Chrom treten in der in¬ termetallischen Nickel-Aluminium-Basislegierung auf den -Korn- grenzen der binären Phase NiAl Ausscϊieidungen in grober mul- tinärer Laves-Phase auf, an der die 'Elemente Ni, AI, Cr und Ta beteiligt sein können. Zudem sind innerhalb der NiAl-Kör- ner Ausscheidungen feinteiliger Laves-Phase und α-Chrom. Da¬ bei wird bevorzugt, daß das Gefüge aus 5 bis 11 Vol.-% Laves- Phase, 3 bis 10 Vol.-% Ausscheidungen im NiAl sowie einemThe ratio of tantalum to chromium is preferably 1: 3 or less. With such a ratio, the concentration of substitution elements in the NiAl reaches a maximum. Through the addition of tantalum and chromium, precipitations occur in the coarse, mul- tular Laves phase in the non-metallic nickel-aluminum base alloy on the grain boundaries of the binary phase NiAl, on which the elements Ni, Al, Cr and Ta can be involved. In addition, there are excretions of finely divided Laves phase and α-chromium within the NiAl grains. It is preferred that the structure of 5 to 11% by volume Laves phase, 3 to 10% by volume precipitates in NiAl and one
Rest aus NiAl besteht. Besonders vorteilhaft hat sich ein Ge¬ füge erwiesen, das etwa 11 Vol.-% Laves-Phase auf den Korn¬ grenzen und etwa 10 Vol.-% Ausscheidungen im NiAl sowie NiAl als Rest umfaßt.Rest consists of NiAl. A structure has proven to be particularly advantageous which comprises approximately 11 vol.% Laves phase on the grain boundaries and approximately 10 vol.% Precipitates in the NiAl and NiAl as the remainder.
Eine weitere Verbesserung bestimmter Eigenschaften ergibt sich, wenn zusätzlich mindestens ein Element aus der Gruppe Eisen, Molybdän, Wolfram und Hafnium in einer Menge von je¬ weils bis 1 at.-%, insgesamt jedoch nicht mehr als 3 at.-% in der Legierung enthalten sind. Die Legierung kann darüber hin¬ aus Spurenelemente wie Sauerstoff, Stickstoff und Schwefel sowie herstellungsbedingte Verunreinigungen aufweisen.A further improvement in certain properties results if at least one element from the group iron, molybdenum, tungsten and hafnium is present in the alloy in an amount of up to 1 at.%, But not more than 3 at are included. The alloy can also contain trace elements such as oxygen, nitrogen and sulfur, as well as production-related impurities.
Durch Zusatz von Tantal und Chrom in den vorstehend jeweils angegebenen Gehaltsbereichen werden die bereits erwähnten groben bzw. feinteiligen multinären Laves-Phasen und α-Chrom gebildet. Diese Ausscheidungen sind in der Regel auf Zwickel- punkten verschiedener NiAl-Körnern zu finden. Höhere als die angegebenen Mengen an Legierungselementen Tantal bzw. Chrom können dazu führen, daß die Menge der Ausscheidungen in uner¬ wünschter Weise zunimmmt. Bei einer zu starken Zunahme der Volumenanteile an Laves-Phase entsteht eine zellulare Struk¬ tur, in der die Laves-Phase die Funktion der Matrix über¬ nimmt. Ein zu großer Anteil an Laves-Phase im Gefüge macht die intermetallische Legierung spröde und schlechter verar¬ beitbar.By adding tantalum and chromium in the above-mentioned content ranges, the coarse or fine-particle multinary Laves phases and α-chromium are formed. These excretions are usually based on gussets points of different NiAl grains. Higher than the specified amounts of alloying elements tantalum or chromium can lead to an undesirable increase in the amount of precipitates. If the volume fractions of Laves phase increases too much, a cellular structure arises in which the Laves phase takes over the function of the matrix. Too large a proportion of Laves phase in the structure makes the intermetallic alloy brittle and difficult to process.
Durch Zusatz eines oder mehrerer Elemente aus der Gruppe Ei¬ sen, Molybdän, Wolfram, Niob und Hafnium von jeweils bis 1 at.-%, insgesamt jedoch nicht mehr als 3 at.-%, kann eine Festigkeitssteigerung bei Kurzzeitbelastung erreicht werden. Allerdings wird die Kriechfestigkeit.'1verringert. Durch Zusatz von Hafnium wird nach erster Korrosi n eine verbesserte Haf¬ tung der Oxidschicht bewirkt.By adding one or more elements from the group of iron, molybdenum, tungsten, niobium and hafnium, each of up to 1 atom%, but not more than 3 atom% in total, an increase in strength under short-term stress can be achieved. However, the creep resistance. '1 decreased. The addition of hafnium results in improved adhesion of the oxide layer after the first corrosion.
Die auf eine Verwendung der Legierung gerichtete Aufgabe wird erfindungsgemäß dadurch gelöst, daß mit der NiAl-Basislegie- rung Bauteile einer Gasturbine, insbesondere hochtemperatur- belastete Bauteile wie Gasturbinenschaufeln, hergestellt wer¬ den. Ein aus der Basislegierung hergestelltes Bauteil einer Gasturbine, insbesondere eine Turbinenschaufel, ist aufgrund des hohen Oxidationswiderstandes für den Dauereinsatz bei ho¬ hen Temperaturen beispielsweise von über 1100° C, insbeson¬ dere bei 1350° C, besonders geeignet. Je nach Anforderung kann bei einem solchen Bauteil im Gegensatz zu Superlegierun- gen von einer zusätzlichen Beschichtung mit Schutzschichten abgesehen werden. Eine so hergestellte Turbinenschaufel be¬ stehend aus einer einheitlichen Legierung ohne zusätzlich darauf anzubringende Schichten ist wesentlich einfacher her¬ stellbar und gegenüber den aus mehereren Schichten bestehen¬ den Turbinenschaufeln um die Problematik der Verbindung zwi- sehen den einzelnen Schichten befreit. Die intermetallische Nickel-Aluminium-Basislegierung eignet sich allgemein auch als Werkstoff für die Herstellung von Ge¬ genständen, die eine hohe Festigkeit, eine hohe Warmfestig¬ keit, eine gute Zähigkeit, einen guten Oxidationswiderstand und eine gute Thermoschockbeständigkeit besitzen müssen. Die Festigkeit liegt hierbei mit einer 0,2 %-Dehngrenze bei Raum¬ temperatur von über 600 MPa. Die Warmfestigkeit liegt bei der 0,2 %-Dehngrenze bei über 200 MPa bei 800° C und bei über 90 MPa bei 1000° C. Die Zähigkeit beträgt mindestens 7 MPa /m und der Oxidationswiderstand liegt in der Größenordnung vonThe object aimed at using the alloy is achieved according to the invention in that components of a gas turbine, in particular components exposed to high temperatures, such as gas turbine blades, are produced with the NiAl base alloy. A component of a gas turbine, in particular a turbine blade, made from the base alloy is particularly suitable due to the high oxidation resistance for continuous use at high temperatures, for example above 1100 ° C., in particular at 1350 ° C. In contrast to superalloys, an additional coating with protective layers can be dispensed with in such a component, depending on the requirements. A turbine blade made in this way, consisting of a uniform alloy without additional layers to be applied thereon, is much easier to manufacture and, compared to the turbine blades consisting of several layers, is freed from the problem of the connection between the individual layers. The intermetallic nickel-aluminum base alloy is generally also suitable as a material for the production of objects which must have high strength, high heat resistance, good toughness, good oxidation resistance and good thermal shock resistance. The strength lies here with a 0.2% proof stress at room temperature of over 600 MPa. The heat resistance lies at the 0.2% proof stress at over 200 MPa at 800 ° C and at over 90 MPa at 1000 ° C. The toughness is at least 7 MPa / m and the oxidation resistance is of the order of magnitude
10 -14 g2c -4«10 -14 g 2 c -4 «
Anhand der folgenden Beispiele wird die intermetallische Nik- kel-Aluminium-Basislegierung näher erläutert.The following examples are used to explain the intermetallic nickel-aluminum base alloy.
Die Zusammensetzung (in at.-%) von uYitersuchten Legierungen ist in der folgenden Tabelle 1 angegeben.The composition (in at.%) Of alloys sought is given in Table 1 below.
Tabelle 1Table 1
Die Ausbildung des Gefüges, d.h. die Korngröße, die Ausschei- dungsverteilung und die Ausscheidungsgröße variiert stark mit dem Herstellungsprozeß. Durch thermodynamische Behandlungen, Strangpressen (SP) oder Ausnutzung der pulvermetallurgischen Herstellungsroute (PM) wird die Verteilung der Laves-Phasen- Partikel homogenisiert. Auch die mechanischen Eigenschaften der Legierungen sind stark vom ausgewählten Herstellungsprozeß abhängig. Es wurden folgende Herstellungsrouten für diese Legierungen verfolgt:The structure of the structure, ie the grain size, the distribution of precipitates and the size of the precipitate, varies greatly with the manufacturing process. The distribution of the Laves phase particles is homogenized by thermodynamic treatments, extrusion (SP) or by using the powder metallurgical production route (PM). The mechanical properties of the alloys are also heavily dependent on the selected manufacturing process. The following production routes for these alloys were followed:
- gerichtete Erstarrung als Möglichkeit, fehlerarme Gefüge durch Gießtechnologie zu erzeugen. Die Prozeßparameter ent¬ sprechen denen der Superlegierungen (vgl. U. Paul, VDI- Fortschrittsbericht Nr. 264, VDI-Verlag) ,- Directional solidification as an opportunity to create low-defect structures using casting technology. The process parameters correspond to those of the superalloys (cf. U. Paul, VDI Progress Report No. 264, VDI-Verlag),
- Pulvermetallurgie: durch Inertgasverdüsung und anschließen¬ des heißisostatisches Pressen bei 1250° C,Powder metallurgy: by inert gas atomization and subsequent hot isostatic pressing at 1250 ° C.,
- Strangpressen zur Gefügehomogenisierung und Einstellung de¬ finierter Korndurchmessergrößen bei 1250° C,Extrusion for structural homogenization and setting of defined grain diameter sizes at 1250 ° C,
- Heißpressen bei einem mehrachsigen' Spannungszustand und 1100° C.- Hot pressing with a multi-axis' stress condition and 1100 ° C.
Gerichtet erstarrte Proben besitzen eindeutig höhere Festig- keit, während beispielsweise stranggepreßtes Material eine verringerte oder sehr geringe Festigkeit besitzt. In der fol¬ genden Tabelle 2 wird die 0,2 %-Dehngrenze im Stauchversuch für die verschiedenen Legierungen sowie für NiAl dargestellt.Directionally solidified samples have clearly higher strength, while, for example, extruded material has a reduced or very low strength. The following table 2 shows the 0.2% proof stress in the upsetting test for the various alloys and for NiAl.
Tabelle 2:Table 2:
Der Kriechwiderstand (in MPa) der untersuchten Legierungen im Druckversuch (sekundäre stationäre Kriechfestigkeit als Funk¬ tion der Dehngeschwindigkeit [in 1/s] bei 1000° C und 1100*° C) ist in Tabelle 3 dargestellt. The creep resistance (in MPa) of the alloys tested in the compression test (secondary stationary creep resistance than Funk¬ tion of the strain rate [1 / s] at 1000 ° C and 1100 ° C *) is shown in Table 3 below.
Tabelle 3:Table 3:
Die Kriechfestigkeiten dieser Legierung sind höher als die Kriechfestigkeiten vergleichbarer intermetallischer Phasen, beispielsweise höher als die Kriechfestigkeit von binärem NiAl bzw. NiAlCr-Legierungen.The creep strengths of this alloy are higher than the creep strengths of comparable intermetallic phases, for example higher than the creep strength of binary NiAl or NiAlCr alloys.
Tabelle 4a gibt einen Vergleich der 0,2 %-Dehngrenze (in MPa) im Druckversuch einer konventionellen Superlegierung, einer binären NiAl-Legierung und einer NiAl-Ta-Cr-Legierung an.Table 4a gives a comparison of the 0.2% proof stress (in MPa) in the compression test of a conventional superalloy, a binary NiAl alloy and a NiAl-Ta-Cr alloy.
Tabelle 4a:Table 4a:
In bezug auf die 0,2 %-Dehngrenze erweist sich die Überlegen¬ heit der erfindungsgemäßen Legierung bei Temperaturen ober¬ halb 1000° C. With regard to the 0.2% proof stress, the superiority of the alloy according to the invention proves at temperatures above 1000 ° C.
Einen Vergleich des stationären Kriechwiderstands bei έ = 10"7 1/s (in MPa) im Druckversuch einer Superlegierung, einer binären NiAl-Legierung und der entwickelten NiAl-Ta-Cr- Legierung vermittelt die folgende Tabelle 4b:The following Table 4b provides a comparison of the steady-state creep resistance at έ = 10 " 7 1 / s (in MPa) in the compression test of a superalloy, a binary NiAl alloy and the developed NiAl-Ta-Cr alloy:
Tabelle 4b:Table 4b:
Temperatur : NiAl-Ta-Cr NiAl-Ta-CrTemperature: NiAl-Ta-Cr NiAl-Ta-Cr
Ni50Al50 2823 / 2922 PM75 / SP75 Ni 50 Al 50 2823/2922 PM75 / SP75
1000 ° C 13 79 /89 23 /191000 ° C 13 79/89 23/19
1100° C n .b . 3-3 /33 10/ 61100 ° C n.a. 3-3 / 33 10/6
1200° C n .b . f /211200 ° C n.a. f / 21
Hierin bedeutet die Abkürzung n.b. daß der entsprechende Wert nicht bestimmt wurde.The abbreviation n.b. that the corresponding value has not been determined.
Gegenüber konventionellen Superlegierungen besitzt die NiAl- Ta-Cr-Legierung den Vorteil, daß sie auch oberhalb von 1050° C bis 1150° C eine ausreichende Festigkeit besitzt. Es gibt in dieser Legierung keinen plötzlichen Festigkeitsab¬ fall, der auf ein Auflösen der verfestigten Phase zurückzu¬ führen ist.Compared to conventional superalloys, the NiAl-Ta-Cr alloy has the advantage that it also has sufficient strength above 1050 ° C to 1150 ° C. There is no sudden drop in strength in this alloy due to the dissolution of the solidified phase.
Tabelle 5 zeigt einen Vergleich der aus Industrieangaben be¬ kannten Werte von K ^-Werten verschiedener Keramiken sowie der hergestellten pulvermetallurgischen prozessierten NiAl- Ta-Cr-Legierung .Table 5 shows a comparison of the values of K ^ values of various ceramics known from industry data and of the powder-metallurgical processed NiAl-Ta-Cr alloy produced.
Tabelle 5 :Table 5:
NiAl NiAl-Ta-Cr NiAl-Ta-Cr NiAl -Ta-Cr Sie Guß Guß PM SPNiAl NiAl-Ta-Cr NiAl-Ta-Cr NiAl -Ta-Cr you cast cast PM SP
Kτ /MPa 4-5 * 4 , 5 8 8-11 4 , 6K τ / MPa 4-5 * 4, 5 8 8-11 4, 6
* Reuß, Disertation, RWTH Aachen Die Zähigkeit der intermetallischen NiAl-Basislegierung ist deutlich besser als die gemessenen Daten für binäres NiAl und SiC.* Reuss, dissertation, RWTH Aachen The toughness of the intermetallic NiAl base alloy is significantly better than the measured data for binary NiAl and SiC.
Die Legierung besitzt einen guten Oxidationswiderstand der Größenordnung 5 • lO--^ g2c"^s, welcher somit gleich oder besser als der Oxidationswiderstand von binärem NiAl ist. Im Gegensatz zur Superlegierung sind somit bei hohen Temperatu¬ ren keine Schutzschichten, beispielsweise aus keramischem Ma- terial, nötig. Hierdurch entfällt die Problematik der Verbin¬ dung zwischen keramischen und metallischen Komponenten.The alloy has a good oxidation resistance of the order of magnitude 5 * 10-^ g 2 c " ^ s, which is therefore equal to or better than the oxidation resistance of binary NiAl. In contrast to the superalloy, no protective layers, for example, are formed at high temperatures ceramic material, this eliminates the problem of the connection between ceramic and metallic components.
Eine ausreichende Thermoschockbeständigkeit ist gegeben. Bei 1350° C werden von der Legierung 500 Temperaturzyklen ohne eine Schädigung des Werkstoffes erreicht. Adequate thermal shock resistance is given. At 1350 ° C, 500 temperature cycles of the alloy are achieved without damaging the material.

Claims

Patentansprüche Claims
1. Intermetallische Nickel-Aluminium-Basislegierung, deren Gefüge überwiegend aus der binären Phase NiAl besteht und Chrom und Tantal aufweist, wobei die beiden Elemente Chrom und Tantal bis zu einem Gehalt von maximal 12 at.-% enthalten sind.1. Intermetallic nickel-aluminum base alloy, the structure of which consists predominantly of the binary phase NiAl and has chromium and tantalum, the two elements chromium and tantalum being present up to a maximum content of 12 at.
2. Legierung nach Anspruch 1, d a d u r c h g e k e n n z e i c h n e t , daß die binä¬ re Phase NiAl 70 at.-% bis 95 at.-%, insbesondere 85 at.-% bis 90 ät.-%, an dem Gefüge ausmacht.2. Alloy according to claim 1, so that the binary phase NiAl makes up 70 at.% To 95 at.%, In particular 85 at.% To 90 at.%, Of the structure.
3. Legierung nach Anspruch 1 oder 2, d a d u r c h g e k e n n z e i c h n e t , daß sie3. Alloy according to claim 1 or 2, d a d u r c h g e k e n n z e i c h n t that they
0,3 at.-% bis 3,0 at.-% Tantal und 1,0 at.- % bis 9,0 at.-% Chrom enthält.Contains 0.3 at.% To 3.0 at.% Tantalum and 1.0 at.% To 9.0 at.% Chromium.
4. Legierung nach Anspruch 3, d a d u r c h g e k e n n z e i c h n e t , daß sie 0,3 at.-% bis 0,9 at.-% Tantal und 1,0 at.- % bis 3,0 at Chrom enthält.4. An alloy according to claim 3, which also contains 0.3 at.% To 0.9 at.% Tantalum and 1.0 at.% To 3.0 at chromium.
5. Legierung nach Anspruch 3, d a d u r c h g e k e n n z e i c h n e t , daß sie5. Alloy according to claim 3, d a d u r c h g e k e n n z e i c h n e t that they
0,7 at.-% bis 3,0 at.-% Tantal und 6,0 at.- % bis 9,0 at.-% Chrom enthält.Contains 0.7 at.% To 3.0 at.% Tantalum and 6.0 at.% To 9.0 at.% Chromium.
6. Legierung nach einem der vorhergehenden Ansprüche, d a d u r c h g e k e n n z e i c h n e t , daß sie Tan¬ tal und Chrom im Verhältnis von 1 : 3 oder kleiner enthält.6. Alloy according to one of the preceding claims, d a d u r c h g e k e n n z e i c h n e t that it contains tan tal and chromium in a ratio of 1: 3 or less.
7. Legierung nach einem der vorhergehenden Ansprüche, d a d u r c h g e k e n n z e i c h n e t , daß auf zu- mindest einigen NiAl-Korngrenzen Ausscheidungen grober Laves- Phase und innerhalb zumindest einiger Nickel-Aluminium-Körner Ausscheidungen feinteiliger Laves-Phase und α-Chrom vorhan¬ den sind.7. Alloy according to one of the preceding claims, characterized in that on at least some NiAl grain boundaries precipitates of coarse Laves phase and within at least some nickel-aluminum grains Excretions of finely divided Laves phase and α-chromium are present.
8. Legierung nach Anspruch 7, d a d u r c h g e k e n n z e i c h n e t , daß ihr Ge¬ füge aus 5 bis 11 Vol.-% Ausscheidungen grober Laves-Phase, 3 bis 10 Vol.-% Ausscheidungen feinteiliger Laves-Phase und α- Chrom im NiAl enthält.8. Alloy according to claim 7, d a d u r c h g e k e n n z e i c h n e t that her structure contains from 5 to 11 vol .-% precipitates of coarse Laves phase, 3 to 10 vol .-% precipitates of finely divided Laves phase and α-chromium in NiAl.
9. Legierung nach Anspruch 8, d a d u r c h g e k e n n z e i c h n e t , daß ihr Ge¬ füge etwa 11 Vol.-% Laves-Phase auf den Korngrenzen und etwa 10 Vol.-% Ausscheidungen im binären NiAl aufweist.9. Alloy according to claim 8, so that the structure has about 11 vol.% Laves phase on the grain boundaries and about 10 vol.% Precipitates in the binary NiAl.
10. Legierung nach einem der vorhergehenden Ansprüche, d a d u r c h g e k e n n z e i c h n e t , daß sie zu¬ mindest ein Element aus der Gruppe Eisen, Molybdän, Wolfram, Niob und Hafnium in einer Menge von jeweils bis 1 at.-%, insgesamt jedoch nicht mehr als 3 at.-% enthält.10. Alloy according to one of the preceding claims, characterized in that it contains at least one element from the group consisting of iron, molybdenum, tungsten, niobium and hafnium in an amount of up to 1 at.% Each, but in total not more than 3 at. -% contains.
11. Verwendung einer intermetallischen Nickel-Aluminium-Ba¬ sislegierung, die überwiegend die binäre Phase NiAl sowie die Elemente Tantal und Chrom aufweist, wobei der gesamte Anteil an Tantal und Chrom bis maximal 12 at.-% beträgt, als Werk- stoff für die Herstellung von Gasturbinenbauteilen, wie Gasturbinenlaufschaufeln und Gasturbinenleitschaufeln.11. Use of an intermetallic nickel-aluminum base alloy, which predominantly has the binary phase NiAl and the elements tantalum and chromium, the total proportion of tantalum and chromium being up to a maximum of 12 at.%, As the material for the Manufacture of gas turbine components such as gas turbine blades and gas turbine guide vanes.
12. Verwendung einer Legierung der Zusammensetzung nach einem der Ansprüche 1 bis 10 als Werkstoff für die Herstellung von Gegenständen, mit einer hohen Festigkeit (0,2 %-Dehngrenze bei Raumtemperatur von über 600 MP) , eine hohe Warmfestigkeit (0,2 %-Dehngrenze von über 200 MP bei 800° C und über 90 MP bei 1000° C) , eine gute Zähigkeit (Kκ mindestens 7 MP/m) , ei¬ nen guten Oxidationswiderstand (ca. 5 • 10"^-^ g2c~^s) und ei- ne gute Thermoschockbeständigkeit aufweist. 12. Use of an alloy of the composition according to any one of claims 1 to 10 as a material for the production of objects with a high strength (0.2% proof stress at room temperature of over 600 MP), a high heat resistance (0.2% - Yield strength of over 200 MP at 800 ° C and over 90 MP at 1000 ° C), good toughness (K κ at least 7 MP / m), good oxidation resistance (approx. 5 • 10 " ^ - ^ g 2 c ~ ^ s) and has good thermal shock resistance.
EP95920844A 1994-05-21 1995-05-19 Nickel-aluminium intermetallic basis alloy Expired - Lifetime EP0760869B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4417936A DE4417936C1 (en) 1994-05-21 1994-05-21 Nickel aluminum alloy
DE4417936 1994-05-21
PCT/EP1995/001921 WO1995032314A1 (en) 1994-05-21 1995-05-19 Nickel-aluminium intermetallic basis alloy

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SE521471C2 (en) 2001-03-27 2003-11-04 Koncentra Holding Ab Piston ring and coating on a piston ring comprising a composite material of a ceramic and an intermetallic compound
CN100422369C (en) * 2006-12-13 2008-10-01 北京航空航天大学 Ti-modified NiAl-Cr(Mo) polyphase eutectic intermetallic compound
BR102013019686B1 (en) 2013-08-01 2020-11-03 Mahle Metal Leve S/A piston ring and its manufacturing process
CN104073688B (en) * 2014-06-19 2016-08-17 湖南科技大学 A kind of NiAl-2.5Ta-7.5Cr alloy is as the application of self-lubricating abrasion-proof material under caustic corrosion operating mode
CN104294328B (en) * 2014-10-23 2017-02-01 上海应用技术学院 Nickel-molybdenum-aluminum-rare earth coating and preparation method thereof
DE102017109156A1 (en) 2016-04-28 2017-11-02 Hochschule Flensburg High-temperature resistant material and its production
CN115595486B (en) * 2022-10-14 2024-03-22 中国科学院金属研究所 Wear-resistant cutting coating for blade tips of high-temperature turbine blades and preparation method and application thereof

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DE1812144C3 (en) * 1967-12-06 1974-04-18 Cabot Corp., Boston, Mass. (V.St.A.) Process for the production of a high-strength nickel-aluminum material
US5116691A (en) * 1991-03-04 1992-05-26 General Electric Company Ductility microalloyed NiAl intermetallic compounds

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