EP2423341A1 - Titanium aluminide alloys - Google Patents

Titanium aluminide alloys Download PDF

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EP2423341A1
EP2423341A1 EP11187502A EP11187502A EP2423341A1 EP 2423341 A1 EP2423341 A1 EP 2423341A1 EP 11187502 A EP11187502 A EP 11187502A EP 11187502 A EP11187502 A EP 11187502A EP 2423341 A1 EP2423341 A1 EP 2423341A1
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Prior art keywords
phase
alloy
alloy according
lamella
alloys
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German (de)
French (fr)
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EP2423341B1 (en
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Fritz Appel
Jonathan Paul
Michael Oehring
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Helmholtz Zentrum Geesthacht Zentrum fuer Material und Kustenforschung GmbH
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Helmholtz Zentrum Geesthacht Zentrum fuer Material und Kustenforschung GmbH
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/045—Alloys based on refractory metals
    • C22C1/0458—Alloys based on titanium, zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C14/00—Alloys based on titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/047—Making non-ferrous alloys by powder metallurgy comprising intermetallic compounds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
    • C22F1/18—High-melting or refractory metals or alloys based thereon
    • C22F1/183—High-melting or refractory metals or alloys based thereon of titanium or alloys based thereon

Definitions

  • the invention relates to alloys based on titanium aluminides, in particular those produced using melt or powder metallurgical processes, preferably based on y (TiAl).
  • Titanium aluminide alloys are characterized by low density, high strength and good corrosion resistance. In the solid state, they have domains with hexagonal ( ⁇ ), biphasic structures ( ⁇ + ⁇ ) and cubic body-centered ⁇ -phase and / or ⁇ -phase.
  • alloys are interesting, based on an intermetallic phase ⁇ (TiAI) with tetragonal structure and in addition to the majority phase ⁇ (TiAI) and minority components of the intermetallic phase ⁇ 2 (Ti 3 Al) with hexagonal structure.
  • These ⁇ -titanium aluminide alloys are characterized by properties such as low density (3.85 - 4.2 g / cm 3 ), high elastic modulus, high strength and creep resistance up to 700 ° C, making them a lightweight material for high temperature applications make attractive. Examples of this are turbine blades in aircraft engines and in stationary gas turbines, valves in engines and hot gas fans.
  • ⁇ -titanium aluminide alloys are highly anisotropic due to their deformation and fracture behavior, but also because of the microstructural anisotropy of the preferred lamellar structure or duplex structure.
  • different powder metallurgy and forming methods and combinations of these production methods are used.
  • a titanium aluminide alloy which has a structurally and chemically homogeneous structure.
  • the majority phases ⁇ (TiAl) and ⁇ 2 (Ti 3 Al) are finely dispersed.
  • the disclosed titanium aluminide alloy with an aluminum content of 45 atom% is characterized by exceptionally good mechanical properties and high-temperature properties.
  • titanium aluminides have been softened mainly by additions of boron, which lead to the formation of titanium borides (cf. TT Cheng, in: Gamma Titanium Aluminides 1999, Eds. Y.-W. Kim, DM Dimiduk, MH Loretto, TMS, Warrendale PA, 1999, p. 389 , such as Y.-W. Kim, DM Dimiduk, in: Structural Intermetallics 2001, Eds. KJ Hemker, DM Dimiduk, H. Clemens, R. Darolia, H. Inui, JM Larsen, VK Sikka, M. Thomas, JD Whittenberger, TMS, Warrendale PA, 2001, p. 625 .)
  • the present invention seeks to provide a titanium aluminide alloy having a fine grain morphology, especially in the nanometer range. Furthermore, the object is to provide a component with a homogeneous alloy.
  • an intermetallic compound or alloy is proposed on the basis of titanium aluminides, preferably based on ⁇ (TiAl), prepared in particular using melt or powder metallurgical processes, in the following composition: Ti - 38 to 42 atom % ⁇ al - 5 to 10 atom % Nb . wherein the composition comprises composite lamellar structures having B19 phase and ⁇ phase in each lamella, wherein the ratio, in particular the volume ratio, of the B19 phase and the ⁇ phase in each case in a lamella between 0.05 and 20, in particular between 0.1 and 10, is.
  • Such composite lamellar structures can be used in alloys via known manufacturing technologies, i. by casting, forming and powder technologies.
  • the alloys are characterized by extremely high strength and creep resistance combined with high ductility and fracture toughness.
  • composition has composite lamellar structures with B19 phase and ⁇ -phase in each lamella, wherein the ratio, in particular the volume ratio of the B19 phase and ⁇ -phase in each case in a lamella between 0.05 and 20, in particular between 0.1 and 10.
  • an alloy has one of the following compositions: Ti - 38.5 to 42.5 At % ⁇ al - 5 to 10 At % Nb - 0.5 to 5 At % Cr , Ti - 39 to 43 At % ⁇ al - 5 to 10 At % Nb - 0.5 to 5 At % Zr , Ti - 41 to 44.5 At % ⁇ al - 5 to 10 At % Nb - 0.5 to 5 At % Not a word , Ti - 41 to 44.5 At % ⁇ al - 5 to 10 At % Nb - 0.5 to 5 At % Fe , Ti - 41 to 45 At % ⁇ al - 5 to 10 At % Nb - 0.1 to 1 At % La , Ti - 41 to 45 At % ⁇ al - 5 to 10 At % Nb - 0.1 to 1 At % sc , Ti - 41 to 45 At % ⁇ al - 5 to 10 At % Nb - 0.1 to 1 At
  • Each of said titanium aluminide alloys may optionally comprise the additions of boron and / or carbon, wherein in one embodiment the compositions of said alloys or intermetallic compounds are each optionally (0.1 to 1 at.%) B (boron) and / or ( 0.1 to 1 at.%) C (carbon). As a result, the already fine structure of the alloy is further softened.
  • alloys are provided which are suitable as a lightweight material for high temperature applications, such as turbine blades or engine and turbine components.
  • the alloys of the invention are prepared using casting metallurgy, melt metallurgy or powder metallurgy techniques, or using these methods in combination with forming techniques.
  • the alloys according to the invention are characterized in that they have a very fine microstructure and have high strength and creep resistance combined with good ductility and fracture toughness, in particular with respect to alloys without the composite lamellar structures according to the invention.
  • other additives for example, of refractory elements
  • the crystallographic lattices of these two phases are mechanically unstable to homogeneous shear processes, which can lead to lattice transformations. This property is mainly due to the anistropic bonding and the symmetry of the cubic body-centered lattice. The inclination of the ⁇ or B2 phase to the lattice transformation is thus pronounced.
  • various orthorhombic phases can be formed, including, in particular, phases B19 and B33.
  • the invention is based on the idea of utilizing these lattice transformations by shear conversion for additional refining of the microstructure of the titanium aluminide alloys of the present invention.
  • One such method is for titanium aluminide alloys also unknown in the scientific literature.
  • shearing transformations additionally avoid brittle phases such as ⁇ , ⁇ 'and ⁇ ", which are extremely disadvantageous for the mechanical material properties.
  • a significant advantage of the alloys according to the invention is that the microstructural refinement of the alloys without the addition of grain-fining elements or additives such as e.g. Boron (B) is reached and therefore the alloys contain no borides. Since the borides occurring in TiAl alloys are brittle, they lead to the embrittlement of TiAl alloys above a certain content and generally represent potential cracking nuclei in boron-containing alloys.
  • B Boron
  • the alloys are further characterized in that the corresponding composition has composite lamellar structures with the B19 phase and ⁇ phase in each lamella, the lamellae being surrounded by the TiAl ⁇ phase.
  • the ratio, in particular the volume ratio, of the B19 phase and ⁇ -phase in each case is between 0.05 and 20, in particular between 0.1 and 10.
  • the ratio, in particular the volume ratio, of the B19 phase and ⁇ phase is in each case in a lamella between 0.2 and 5, in particular between 0.25 and 4.
  • a particularly fine microstructure in the alloy composition is characterized in that the ratio, in particular the volume ratio, of the B19 phase and ⁇ -phase in each case is between 0.75 and 1.25, in particular between 0.8 and 1.2, preferably between 0.9 and 1.1.
  • lamellae of the composite lamellar structures are surrounded by lamellae of the ⁇ (TiAl) type, preferably on both sides of the lamella.
  • the alloys are further characterized in that the lamellae of the composite lamellar structures have a volume fraction of more than 10%, preferably more than 20%, of the entire alloy.
  • the fine lamellar structure is retained in the composite structures when the lamellae of the composite lamellar structures TiAl have the phase ⁇ 2 -Ti 3 A l in a proportion of up to 20%, in particular the (volume) ratio of the B19 phase and ⁇ phase in the lamellae remain unchanged and constant.
  • the alloys according to the invention are suitable as high-temperature lightweight materials for components which are exposed to temperatures of up to 800 ° C.
  • the object is achieved by a method for producing an alloy described above using melt or powder metallurgy techniques, wherein after the production of the alloy to an intermediate, further heat treatment of the intermediate at temperatures above 900 ° C, preferably above 1000 ° C, in particular at temperatures between 1000 ° C and 1200 ° C, for a predetermined period of time of more than 60 minutes, preferably more than 90 minutes, is carried out, and subsequently the heat-treated alloy with a predetermined cooling rate of more than 0.5 ° C per minute is cooled.
  • the heat-treated alloy is cooled at a predetermined cooling rate between 1 ° C per minute to 20 ° C per minute, preferably to 10 ° C per minute.
  • the object of the invention is achieved by a component which is produced from an alloy according to the invention, wherein in particular the alloy is produced by melt or powder metallurgical methods or techniques.
  • the alloys based on a ⁇ -TiAl intermetallic compound provide lightweight (high temperature) materials or components for use or for use in heat engines such as internal combustion engines, gas turbines, aircraft engines.
  • the alloys of the present invention having the above compositions are preferably produced by using conventional metallurgical casting techniques or by per se known powder metallurgy techniques, and can be processed, for example, by hot forging, hot pressing, and hot rolling.
  • the composite lamellar structures are shown below using an alloy with a composition Ti - 42 At% Al - 8.5 At% Nb.
  • Fig. 1a shows a photograph of the Gedemandgleiter, which has been recorded by means of a transmission electron microscope.
  • the overview in Fig. 1 shows that the composite lamellar structures in Fig. 1 with T, have a streaky contrast to the structures surrounding the structures of the ⁇ -phase.
  • Fig. 1b shows a recording of the alloy structure with a higher magnification, wherein it can be seen that the modulated composite lamellar structures (reference symbol T) are surrounded by the ⁇ phase or embedded in the ⁇ phase.
  • Fig. 1c a cast structure of the same alloy Ti-42 at% Al-8.5 atom% Nb is shown, in which also a composite lamellar structure (reference T) is formed, which is surrounded by the ⁇ -phase.
  • Fig. 2a shows in a high-resolution representation the atomic structure of the composite lamellar structures above the ⁇ -phase.
  • the composite lamellar structures consist of the ordered B19 phase and the disordered ⁇ phase, which adjoin the ⁇ phase (in the lower region). From the recording in Fig. 2a it can be seen that the composite lamellar structures are the two crystallographic different phases B19 and ⁇ / B2, which are arranged at intervals of a few nanometers.
  • the composite lamellar structures contain phases B19 and ⁇ , both of which are considered ductile.
  • the volume ratio of B19 phases and ⁇ phases in a composite lamellar structure is 0.8 to 1.2. Due to the ductile phases B19 and ⁇ , the structure consists essentially of easily deformable lamellae, which are embedded in the relatively brittle ⁇ -hare.
  • FIG. 2b The illustration of a B19 structure is shown with an enlarged view.
  • the corresponding diffractogram, from the in Fig. 2b shown section and is characteristic of the B19 structure is in Fig. 2c shown.
  • Fig. 3 is an electron micrograph of a crack C of the above alloy shown.
  • the image shows that the crack C is deflected at the modulated composite lamellar structures (T), and that the composite lamellar structures form ligaments that can bridge the crack edges.
  • T modulated composite lamellar structures
  • Such a behavior differs significantly from the crack propagation in the previously known Ti-Al alloys, in which a gap fracture occurs in the microscopic scale considered here. In the alloy crack propagation is hindered due to the formed composite lamellar structures.
  • the alloys may be formed by the technologies known for TiAl alloys, i. via melt metallurgy, forming technologies and powder metallurgy. For example, alloys are melted in an electric arc furnace and remelted several times and then subjected to a heat treatment.
  • the production methods known for primary cast blocks of TiAl alloys may also be used for the production of vacuum arc melting, induction melting or plasma melting.
  • hot isostatic pressing may be used as the densification process at temperatures of 900 ° C to 1300 ° C or heat treatments in the temperature range of 700 ° C to 1400 ° C or a combination of these treatments to close pores and to adjust a microstructure in the material.

Abstract

Alloy based on titanium aluminides has the composition: Ti - (38-42 at.%) Al - (5-10 at.%) Nb. The composition has composite lamellae structures with B19-phase and beta -phase in each lamella. The ratio, especially the volume ratio, of the B19-phase and the beta -phase in each lamella is 0.05-20, especially 0.1-10. Independent claims are also included for the following: (1) Method for the production of the alloy; and (2) Component made from the alloy.

Description

Die Erfindung betrifft Legierungen auf der Basis von, insbesondere unter Verwendung von schmelz- oder pulvermetallurgischen Verfahren hergestellten, Titanaluminiden, vorzugsweise auf Basis von y (TiAI).The invention relates to alloys based on titanium aluminides, in particular those produced using melt or powder metallurgical processes, preferably based on y (TiAl).

Titanaluminid-Legierungen zeichnen sich durch eine geringe Dichte, eine hohe Festigkeit und gute Korrosionsbeständigkeit aus. Im festen Zustand weisen sie Domänen mit hexagonaler (α), zweiphasige Strukturen (α + β) sowie kubisch raumzentrierte β-Phase und/oder γ-Phase auf.Titanium aluminide alloys are characterized by low density, high strength and good corrosion resistance. In the solid state, they have domains with hexagonal (α), biphasic structures (α + β) and cubic body-centered β-phase and / or γ-phase.

Für die industrielle Praxis sind insbesondere Legierungen interessant, die auf einer intermetallischen Phase γ (TiAI) mit tetragonaler Struktur beruhen und neben der Majoriätsphase γ (TiAI) auch Minoritätsanteile der intermetallischen Phase α2(Ti3Al) mit hexagonaler Struktur enthalten. Diese γ-Titanaluminid-Legierungen zeichnen sich durch Eigenschaften wie geringe Dichte (3,85 - 4,2 g/cm3), hohe elastische Module, hohe Festigkeit und Kriechfestigkeit bis zu 700°C aus, die sie als Leichtbau-Werkstoff für Hochtemperaturanwendungen attraktiv machen. Beispiele hierfür sind Turbinenschaufeln in Flugzeugtriebwerken und in stationären Gasturbinen, Ventile bei Motoren sowie Heißgasventilatoren.For industrial practice, in particular alloys are interesting, based on an intermetallic phase γ (TiAI) with tetragonal structure and in addition to the majority phase γ (TiAI) and minority components of the intermetallic phase α 2 (Ti 3 Al) with hexagonal structure. These γ-titanium aluminide alloys are characterized by properties such as low density (3.85 - 4.2 g / cm 3 ), high elastic modulus, high strength and creep resistance up to 700 ° C, making them a lightweight material for high temperature applications make attractive. Examples of this are turbine blades in aircraft engines and in stationary gas turbines, valves in engines and hot gas fans.

Im technisch wichtigen Bereich von Legierungen mit Aluminium-Gehalten zwischen 45 Atom % und 49 Atom % treten beim Erstarren aus der Schmelze und beim nachfolgenden Abkühlen eine Reihe von Phasenumwandlungen auf. Die Erstarrung kann entweder vollständig über den β-Mischkristall mit kubisch raumzentrierter Struktur (Hochtemperaturphase) oder in zwei peritektischen Reaktionen erfolgen, an denen der α-Mischkristall mit hexagonaler Struktur und die γ-Phase beteiligt sind.In the technically important range of alloys with aluminum contents between 45 atom% and 49 atom%, a number of phase transformations occur on solidification from the melt and subsequent cooling. The solidification can take place either completely via the β-mixed crystal with cubic body-centered structure (high-temperature phase) or in two peritectic reactions in which the α-mixed crystal with hexagonal structure and the γ-phase are involved.

Ferner ist bekannt, dass Aluminium in γ-Titanaluminid-Legierungen eine Erhöhung der Duktilität und der Oxidationsbeständigkeit bewirkt. Außerdem führt das Element Niob (Nb) zu einer Steigerung der Festigkeit, Kriechfestigkeit, Oxidationsbeständigkeit, aber auch der Duktilität. Mit dem in der γ-Phase praktisch nicht löslichen Element Bor kann eine Kornfeinung sowohl im Gusszustand als auch nach dem Umformen mit anschließender Wärmebehandlung im α― Gebiet erreicht werden. Ein erhöhter Anteil an β-Phase im Gefüge infolge von niedrigen Aluminium-Gehalten und hohen Konzentrationen von β-stabilisierenden Elementen kann zu grober Dispersion dieser Phase führen und eine Verschlechterung der mechanischen Eigenschaften bewirken.It is also known that aluminum in γ-titanium aluminide alloys causes an increase in ductility and oxidation resistance. In addition, the element niobium (Nb) leads to an increase in strength, creep resistance, oxidation resistance, but also the ductility. With the element boron, which is practically insoluble in the γ-phase, grain refining can be achieved both in the cast state and after the forming with subsequent heat treatment in the α-region. An increased proportion of β-phase in the microstructure due to low aluminum contents and high concentrations of β-stabilizing elements can lead to coarse dispersion of this phase and cause a deterioration of the mechanical properties.

Die mechanischen Eigenschaften von γ-Titanaluminid-Legierungen sind aufgrund ihres Verformungs- und Bruchverhaltens, aber auch wegen der Gefügeanisotropie der bevorzugt eingestellten lamellaren Gefüge bzw. Duplex-Gefüge stark anisotrop. Zu einer gezielten Einstellung von Gefüge und Textur bei der Herstellung von Bauteilen aus Titanaluminiden werden Gießverfahren, unterschiedliche pulvermetallurgische und Umform-Verfahren sowie Kombinationen dieser Herstellungsverfahren angewandt.The mechanical properties of γ-titanium aluminide alloys are highly anisotropic due to their deformation and fracture behavior, but also because of the microstructural anisotropy of the preferred lamellar structure or duplex structure. For a specific adjustment of structure and texture in the production of components made of titanium aluminides casting methods, different powder metallurgy and forming methods and combinations of these production methods are used.

Darüber hinaus ist aus EP 1 015 650 B1 eine Titanaluminid-Legierung bekannt, die ein strukturell und chemisch homogenes Gefüge aufweist. Hierbei sind die Majoritätsphasen γ (TiAl) und α2 (Ti3AI) fein dispers verteilt. Die offenbarte Titanaluminid-Legierung mit einem Aluminium-Gehalt von 45 Atom % zeichnet sich durch außergewöhnlich gute mechanische Eigenschaften und Hochtemperatureigenschaften aus.In addition, is off EP 1 015 650 B1 a titanium aluminide alloy is known, which has a structurally and chemically homogeneous structure. In this case, the majority phases γ (TiAl) and α 2 (Ti 3 Al) are finely dispersed. The disclosed titanium aluminide alloy with an aluminum content of 45 atom% is characterized by exceptionally good mechanical properties and high-temperature properties.

Titanaluminide auf der Basis von γ (TiAI) zeichnen sich im Allgemeinen durch relativ hohe Festigkeiten, hohe elastische Moduln, gute Oxidations- und Kriechbeständigkeit bei gleichzeitig geringer Dichte aus. Aufgrund dieser Eigenschaften sollen TiAI-Legierungen als Hochtemperatur-Werkstoffe eingesetzt werden. Derartige Anwendungen werden durch die sehr geringe plastische Verformbarkeit und die niedrige Bruchzähigkeit stark beeinträchtigt. Hierbei verhalten sich Festigkeit und Verformbarkeit, wie bei vielen anderen Werkstoffen, zueinander invers. Dadurch sind gerade die technisch interessanten hochfesten Legierungen oft besonders spröde. Zur Behebung dieser sehr nachteiligen Eigenschaften wurden umfangreiche Untersuchungen zur Optimierung der Gefüge durchgeführt. Die bisher entwickelten Gefügetypen können grob in a) gleichachsige Gamma-Gefüge, b) Duplexgefüge und c) lamellare Gefüge eingeteilt werden. Der derzeit erreichte Entwicklungsstand ist beispielsweise ausführlich dargestellt in:

  • Y.-W. Kim, D.M. Dimiduk, in: Structural Intermetallics 1997, Eds. M.V. Nathal, R. Darolia, CT. Liu, P.L. Martin, D.B. Miracle, R. Wagner, M. Yamaguchi, TMS, Warrendale PA, 1996, S. 531 .
  • M. Yamaguchi, H. Inui, K. Ito, Acta mater. 48 (2000), S. 307 .
Titanium aluminides based on γ (TiAl) are generally characterized by relatively high strengths, high elastic moduli, good oxidation and creep resistance with low density at the same time. Due to these properties, TiAl alloys are to be used as high-temperature materials. Such applications are severely impaired by the very low plastic deformability and the low fracture toughness. Here, strength and deformability, as with many other materials, behave inversely to each other. As a result, especially the technically interesting high-strength alloys are often particularly brittle. To remedy these very disadvantageous properties, extensive investigations were carried out to optimize the microstructure. The previously developed microstructure types can roughly be divided into a) equiaxed gamma microstructure, b) duplex microstructure and c) lamellar microstructure. For example, the current state of development is described in detail in:
  • Y.-W. Kim, DM Dimiduk, in: Structural Intermetallics 1997, Eds. MV Nathal, R. Darolia, CT. Liu, PL Martin, DB Miracle, R. Wagner, M. Yamaguchi, TMS, Warrendale PA, 1996, p. 531 ,
  • M. Yamaguchi, H. Inui, K. Ito, Acta mater. 48 (2000), p. 307 ,

Bisher wurden die Gefüge von Titanaluminiden vor allem durch Borzusätze gefeint, die zur Bildung von Titanboriden führen (vgl. T.T. Cheng, in: Gamma Titanium Aluminides 1999, Eds. Y.-W. Kim, D.M. Dimiduk, M.H. Loretto, TMS, Warrendale PA, 1999, S. 389 , sowie Y.-W. Kim, D.M. Dimiduk, in: Structural Intermetallics 2001, Eds. K.J. Hemker, D.M. Dimiduk, H. Clemens, R. Darolia, H. Inui, J.M. Larsen, V.K. Sikka, M. Thomas, J.D. Whittenberger, TMS, Warrendale PA, 2001, S. 625 .)So far, the structure of titanium aluminides have been softened mainly by additions of boron, which lead to the formation of titanium borides (cf. TT Cheng, in: Gamma Titanium Aluminides 1999, Eds. Y.-W. Kim, DM Dimiduk, MH Loretto, TMS, Warrendale PA, 1999, p. 389 , such as Y.-W. Kim, DM Dimiduk, in: Structural Intermetallics 2001, Eds. KJ Hemker, DM Dimiduk, H. Clemens, R. Darolia, H. Inui, JM Larsen, VK Sikka, M. Thomas, JD Whittenberger, TMS, Warrendale PA, 2001, p. 625 .)

Zur weiteren Feinung und Konsolidierung des Gefüges werden die Legierungen meist mehreren Hochtemperaturumformungen durch Extrudieren bzw. Schmieden unterzogen. Hierzu wird ergänzend auf die folgenden Veröffentlichungen verwiesen:

  • Gamma Titanium Aluminides, Eds. Y.-W. Kim, R. Wagner, M. Yamaguchi, TMS, Warrendale PA, 1995 .
  • Structural Intermetallics 1997, Eds. M.V. Nathal, R. Darolia, CT. Liu, P.L. Martin, D.B. Miracle, R. Wagner, M. Yamaguchi, TMS, Warrendale PA, 1997 .
  • Gamma Titanium Aluminides 1999, Eds. Y-W. Kim, D.M. Dimiduk, M.H. Loretto, TMS, Warrendale PA, 1999 .
  • Structural Intermetallics 2001, Eds. K.J. Hemker, D.M. Dimiduk, H. Clemens, R. Darolia, H. Inui, J.M. Larsen, V.K. Sikka, M. Thomas, J.D. Whittenberger, TMS, Warrendale PA, 2001 .
For further refining and consolidation of the structure, the alloys are usually subjected to several high-temperature transformations by extrusion or forging. Reference is additionally made to the following publications:
  • Gamma Titanium Aluminides, Eds. Y.-W. Kim, R. Wagner, M. Yamaguchi, TMS, Warrendale PA, 1995 ,
  • Structural Intermetallics 1997, Eds. MV Nathal, R. Darolia, CT. Liu, PL Martin, DB Miracle, R. Wagner, M. Yamaguchi, TMS, Warrendale PA, 1997 ,
  • Gamma Titanium Aluminides 1999, Eds. YW. Kim, DM Dimiduk, MH Loretto, TMS, Warrendale PA, 1999 ,
  • Structural Intermetallics 2001, Eds. KJ Hemker, DM Dimiduk, H. Clemens, R. Darolia, H. Inui, JM Larsen, VK Sikka, M. Thomas, JD Whittenberger, TMS, Warrendale PA, 2001 ,

Ausgehend von diesem Stand der Technik liegt der vorliegenden Erfindung die Aufgabe zugrunde, eine Titanaluminid-Legierung mit einer feinen Gefügemorphologie, insbesondere im Nanometerbereich, bereitzustellen. Des Weiteren besteht die Aufgabe darin, ein Bauteil mit einer homogenen Legierung bereitzustellen.Based on this prior art, the present invention seeks to provide a titanium aluminide alloy having a fine grain morphology, especially in the nanometer range. Furthermore, the object is to provide a component with a homogeneous alloy.

Beispielsweise wird eine intermetallische Verbindung bzw. Legierung vorgeschlagen auf der Basis von, insbesondere unter Verwendung von schmelz- oder pulvermetallurgischen Verfahren hergestellten, Titanaluminiden, vorzugsweise auf Basis von γ (TiAI), in der folgenden Zusammensetzung: Ti - 38 bis 42 Atom % ⁢ Al - 5 bis 10 Atom % Nb ,

Figure imgb0001

wobei die Zusammensetzung Komposit-Lamellen-Strukturen mit B19-Phase und β-Phase in jeder Lamelle aufweist, wobei das Verhältnis, insbesondere das Volumenverhältnis, der B19-Phase und der β-Phase jeweils in einer Lamelle zwischen 0.05 und 20, insbesondere zwischen 0.1 und 10, beträgt.For example, an intermetallic compound or alloy is proposed on the basis of titanium aluminides, preferably based on γ (TiAl), prepared in particular using melt or powder metallurgical processes, in the following composition: Ti - 38 to 42 atom % ⁢ al - 5 to 10 atom % Nb .
Figure imgb0001
wherein the composition comprises composite lamellar structures having B19 phase and β phase in each lamella, wherein the ratio, in particular the volume ratio, of the B19 phase and the β phase in each case in a lamella between 0.05 and 20, in particular between 0.1 and 10, is.

Es hat sich gezeigt, dass bei einer derartigen intermetallischen Verbindung Komposit-Lamellen-Strukturen mit Strukturen im Nanometermaßstab erzeugt werden bzw. vorhanden sind, wobei die lamellenartigen Gebilde bzw. modulierte Lamellen aus den kristallographisch unterschiedlichen, alternierend ausgebildeten B19-Phase und β-Phase aufgebaut sind. Hierbei sind die erzeugten Komposit-Lamellen-Strukturen größtenteils von γ-TiAl umgeben.It has been found that in such an intermetallic compound composite lamellar structures are generated with structures on the nanometer scale or are present, wherein the lamellar Structure or modulated lamellae of the crystallographically different, alternately formed B19 phase and β-phase are constructed. Here, the composite lamellar structures produced are largely surrounded by γ-TiAl.

Derartige Komposit-Lamellen-Strukturen können in Legierungen über bekannte Herstellungstechnologien, d.h. durch Gießen, Umformen und Pulvertechnologien, hergestellt werden. Die Legierungen zeichnen sich durch extrem hohe Festigkeit und Kriechbeständigkeit bei gleichzeitig hoher Duktilität und Bruchzähigkeit aus.Such composite lamellar structures can be used in alloys via known manufacturing technologies, i. by casting, forming and powder technologies. The alloys are characterized by extremely high strength and creep resistance combined with high ductility and fracture toughness.

Gelöst wird diese Aufgabe durch eine Legierung auf der Basis von, insbesondere unter Verwendung von schmelz- oder pulvermetallurgischen Verfahren hergestellten, Titanaluminiden, vorzugsweise auf Basis von γ (TiAI), wobei TiAI-Legierungen mit weiteren Zusätzen Volumenanteile der β-Phase enthalten, die dadurch weitergebildet wird, dass die Zusammensetzung Komposit-Lamellen-Strukturen mit B19-Phase und β-Phase in jeder Lamelle aufweist, wobei das Verhältnis, insbesondere das Volumenverhältnis, der B19-Phase und β-Phase jeweils in einer Lamelle zwischen 0.05 und 20, insbesondere zwischen 0.1 und 10, beträgt.This object is achieved by an alloy based on, in particular using melt or powder metallurgy produced titanium aluminides, preferably based on γ (TiAl), TiAl alloys containing further additives containing volume fractions of the β-phase, thereby is further developed that the composition has composite lamellar structures with B19 phase and β-phase in each lamella, wherein the ratio, in particular the volume ratio of the B19 phase and β-phase in each case in a lamella between 0.05 and 20, in particular between 0.1 and 10.

Hierbei weist eine Legierung eine der folgenden Zusammensetzungen auf: Ti - 38.5 bis 42.5 At % ⁢ Al - 5 bis 10 At % Nb - 0.5 bis 5 At % Cr .

Figure imgb0002
Ti - 39 bis 43 At % ⁢ Al - 5 bis 10 At % Nb - 0.5 bis 5 At % Zr .
Figure imgb0003
 Ti - 41 bis 44.5 At % ⁢ Al - 5 bis 10 At % Nb - 0.5 bis 5 At % Mo .
Figure imgb0004
 Ti - 41 bis 44.5 At % ⁢ Al - 5 bis 10 At % Nb - 0.5 bis 5 At % Fe .
Figure imgb0005
 Ti - 41 bis 45 At % ⁢ Al - 5 bis 10 At % Nb - 0.1 bis 1 At % La .
Figure imgb0006
 Ti - 41 bis 45 At % ⁢ Al - 5 bis 10 At % Nb - 0.1 bis 1 At % Sc .
Figure imgb0007
 Ti - 41 bis 45 At % ⁢ Al - 5 bis 10 At % Nb - 0.1 bis 1 At % Y .
Figure imgb0008
 Ti - 42 bis 46 At % ⁢ Al - 5 bis 10 At % Nb - 0.5 bis 5 At % Mn .
Figure imgb0009
 Ti - 41 bis 45 At % ⁢ Al - 5 bis 10 At % Nb - 0.5 bis 5 At % Ta .
Figure imgb0010
 Ti - 41 bis 45 At % ⁢ Al - 5 bis 10 At % Nb - 0.5 bis 5 At % V .
Figure imgb0011
 Ti - 41 bis 46 At % ⁢ Al - 5 bis 10 At % Nb - 0.5 bis 5 At % W .
Figure imgb0012
 Here, an alloy has one of the following compositions: Ti - 38.5 to 42.5 At % ⁢ al - 5 to 10 At % Nb - 0.5 to 5 At % Cr ,
Figure imgb0002
 Ti - 39 to 43 At % ⁢ al - 5 to 10 At % Nb - 0.5 to 5 At % Zr ,
Figure imgb0003
 Ti - 41 to 44.5 At % ⁢ al - 5 to 10 At % Nb - 0.5 to 5 At % Not a word ,
Figure imgb0004
 Ti - 41 to 44.5 At % ⁢ al - 5 to 10 At % Nb - 0.5 to 5 At % Fe ,
Figure imgb0005
 Ti - 41 to 45 At % ⁢ al - 5 to 10 At % Nb - 0.1 to 1 At % La ,
Figure imgb0006
 Ti - 41 to 45 At % ⁢ al - 5 to 10 At % Nb - 0.1 to 1 At % sc ,
Figure imgb0007
 Ti - 41 to 45 At % ⁢ al - 5 to 10 At % Nb - 0.1 to 1 At % Y ,
Figure imgb0008
 Ti - 42 to 46 At % ⁢ al - 5 to 10 At % Nb - 0.5 to 5 At % Mn ,
Figure imgb0009
 Ti - 41 to 45 At % ⁢ al - 5 to 10 At % Nb - 0.5 to 5 At % Ta ,
Figure imgb0010
 Ti - 41 to 45 At % ⁢ al - 5 to 10 At % Nb - 0.5 to 5 At % V ,
Figure imgb0011
 Ti - 41 to 46 At % ⁢ al - 5 to 10 At % Nb - 0.5 to 5 At % W ,
Figure imgb0012

Jede der genannten Titanaluminid-Legierungen kann optional die Zusätze von Bor und/oder Kohlenstoff aufweisen, wobei in einer Ausgestaltung die Zusammensetzungen der genannten Legierungen bzw. der intermetallischen Verbindungen jeweils wahlweise (0.1 bis 1 At. %) B (Bor) und/oder (0.1 bis 1 At. %) C (Kohlenstoff) aufweisen. Hierdurch wird das ohnehin schon feine Gefüge der Legierung weiter gefeint.Each of said titanium aluminide alloys may optionally comprise the additions of boron and / or carbon, wherein in one embodiment the compositions of said alloys or intermetallic compounds are each optionally (0.1 to 1 at.%) B (boron) and / or ( 0.1 to 1 at.%) C (carbon). As a result, the already fine structure of the alloy is further softened.

Im Rahmen der Erfindung bestehen bei den angegebenen Legierungszusammensetzungen jeweils die Reste aus Titan und unvermeidbaren Verunreinigungen.In the context of the invention, the residues of titanium and unavoidable impurities exist in the case of the stated alloy compositions.

Damit werden gemäß der Erfindung Legierungen bereitgestellt, die als Leichtbau-Werkstoff für Hochtemperaturanwendungen, wie z.B. Turbinenschaufeln oder Motoren- und Turbinenkomponenten, geeignet sind.Thus, according to the invention, alloys are provided which are suitable as a lightweight material for high temperature applications, such as turbine blades or engine and turbine components.

Die erfindungsgemäßen Legierungen werden unter Verwendung von gießmetallurgischen, schmelzmetallurgischen oder pulvermetallurgischen Verfahren bzw. Techniken oder unter Verwendung dieser Verfahren in Kombination mit Umformtechniken hergestellt.The alloys of the invention are prepared using casting metallurgy, melt metallurgy or powder metallurgy techniques, or using these methods in combination with forming techniques.

Die erfindungsgemäßen Legierungen zeichnen sich dadurch aus, dass sie eine sehr feine Mikrostruktur haben und eine hohe Festigkeit und Kriechbeständigkeit bei gleichzeitig guter Duktilität und Bruchzähigkeit aufweisen, insbesondere gegenüber Legierungen ohne die erfindungsgemäßen Komposit―Lamellen―Strukturen.The alloys according to the invention are characterized in that they have a very fine microstructure and have high strength and creep resistance combined with good ductility and fracture toughness, in particular with respect to alloys without the composite lamellar structures according to the invention.

Es ist bekannt, dass Titanaluminid-Legierungen mit Aluminium-gehalten von 38 - 45 At.% und weiteren Zusätzen beispielsweise von Refraktärelementen relativ große Volumenanteile der β-Phase enthalten, die auch in geordneter Form als B2-Phase vorliegen kann. Die kristallografischen Gitter dieser beiden Phasen sind gegenüber homogenen Scherprozessen mechanisch instabil, was zu Gitterumwandlungen führen kann. Diese Eigenschaft ist im Wesentlichen auf die anistropen Bindungsverhältnisse und die Symmetrie des kubisch raumzentrierten Gitters zurückzuführen. Die Neigung der β― bzw. B2-Phase zur Gittertransformation ist damit stark ausgeprägt. Durch eine Scherumwandlung des kubisch-raumzentrierten Gitters der β― bzw. B2-Phase können verschiedene orthorhombische Phasen gebildet werden, wozu insbesondere die Phasen B19 und B33 gehören.It is known that titanium aluminide alloys with an aluminum content of 38-45 at.% And other additives, for example, of refractory elements, contain relatively large volume fractions of the β-phase, which may also be present in ordered form as the B2 phase. The crystallographic lattices of these two phases are mechanically unstable to homogeneous shear processes, which can lead to lattice transformations. This property is mainly due to the anistropic bonding and the symmetry of the cubic body-centered lattice. The inclination of the β or B2 phase to the lattice transformation is thus pronounced. By shearing the cubic body centered lattice of the β or B2 phase, various orthorhombic phases can be formed, including, in particular, phases B19 and B33.

Die Erfindung beruht auf dem Gedanken, diese Gittertransformationen durch Scherumwandlung für eine zusätzliche Feinung der Mikrostruktur der erfindungsgemäßen Titanaluminid-Legierungen zu nutzen. Ein derartiges Verfahren ist für Titanaluminid-Legierungen auch in der wissenschaftlichen Literatur bisher nicht bekannt. Bei den oben aufgeführten erfindungsgemäßen Legierungen werden durch die Scherumwandlungen zudem spröde Phasen wie ω, ω' und ω" vermieden, die für die mechanischen Werkstoffeigenschaften äußerst nachteilig sind.The invention is based on the idea of utilizing these lattice transformations by shear conversion for additional refining of the microstructure of the titanium aluminide alloys of the present invention. One such method is for titanium aluminide alloys also unknown in the scientific literature. In the case of the abovementioned alloys according to the invention, shearing transformations additionally avoid brittle phases such as ω, ω 'and ω ", which are extremely disadvantageous for the mechanical material properties.

Ein wesentlicher Vorteil der erfindungsgemäßen Legierungen besteht darin, dass die Gefügefeinung der Legierungen ohne den Zusatz von Korn-feinenden bzw. Gefüge-feinenden Elementen oder Zusätzen wie z.B. Bor (B) erreicht wird und die Legierungen demnach keine Boride enthalten. Da die in TiAl-Legierungen auftretenden Boride spröde sind, führen sie ab einem bestimmten Gehalt zur Versprödung von TiAl-Legierungen und stellen generell in Borhaltigen Legierungen potenzielle Risskeime dar.A significant advantage of the alloys according to the invention is that the microstructural refinement of the alloys without the addition of grain-fining elements or additives such as e.g. Boron (B) is reached and therefore the alloys contain no borides. Since the borides occurring in TiAl alloys are brittle, they lead to the embrittlement of TiAl alloys above a certain content and generally represent potential cracking nuclei in boron-containing alloys.

Die Legierungen zeichnen sich weiter dadurch aus, dass die entsprechende Zusammensetzung Komposit-Lamellen-Strukturen mit der B19-Phase und β-Phase in jeder Lamelle aufweist, wobei die Lamellen von der TiAl―γ―Phase umgeben sind.The alloys are further characterized in that the corresponding composition has composite lamellar structures with the B19 phase and β phase in each lamella, the lamellae being surrounded by the TiAl γ phase.

Insbesondere beträgt das Verhältnis, insbesondere das Volumenverhältnis, der B19-Phase und β-Phase jeweils in einer Lamelle zwischen 0.05 und 20, insbesondere zwischen 0.1 und 10. Weiterhin beträgt das Verhältnis, insbesondere das Volumenverhältnis, der B19-Phase und β-Phase jeweils in einer Lamelle zwischen 0.2 und 5, insbesondere zwischen 0.25 und 4. Vorzugsweise beträgt das Verhältnis, insbesondere das Volumenverhältnis, der B19-Phase und β-Phase jeweils in einer Lamelle zwischen (1/3) und 3, insbesondere zwischen 0.5 und 2. Außerdem zeichnet sich eine besonders feine Gefügestruktur in der Legierungszusammensetzung dadurch aus, dass das Verhältnis, insbesondere das Volumenverhältnis, der B19-Phase und β-Phase jeweils in einer Lamelle zwischen 0.75 und 1.25, insbesondere zwischen 0.8 und 1.2, vorzugsweise zwischen 0.9 und 1.1, beträgt.In particular, the ratio, in particular the volume ratio, of the B19 phase and β-phase in each case is between 0.05 and 20, in particular between 0.1 and 10. Furthermore, the ratio, in particular the volume ratio, of the B19 phase and β phase is in each case in a lamella between 0.2 and 5, in particular between 0.25 and 4. Preferably, the ratio, in particular the volume ratio, of the B19 phase and β-phase in each case in a lamella between (1/3) and 3, in particular between 0.5 and 2. In addition, a particularly fine microstructure in the alloy composition is characterized in that the ratio, in particular the volume ratio, of the B19 phase and β-phase in each case is between 0.75 and 1.25, in particular between 0.8 and 1.2, preferably between 0.9 and 1.1.

Überdies ist es in einer Weiterbildung der erfindungsgemäßen Legierungen möglich, dass Lamellen der Komposit-Lamellen-Strukturen von Lamellen des γ (TiAl)-Typs, vorzugsweise beidseits der Lamelle, umgeben sind.Moreover, it is possible in a development of the alloys according to the invention that lamellae of the composite lamellar structures are surrounded by lamellae of the γ (TiAl) type, preferably on both sides of the lamella.

Die Legierungen zeichnen sich ferner dadurch aus, dass die Lamellen der Komposit-Lamellen-Strukturen ein Volumenanteil von mehr als 10%, vorzugsweise mehr als 20%, der gesamten Legierung haben.The alloys are further characterized in that the lamellae of the composite lamellar structures have a volume fraction of more than 10%, preferably more than 20%, of the entire alloy.

Zudem bleibt die feine lamellenartige Struktur in den Komposit-Strukuren erhalten, wenn die Lamellen der Komposit-Lamellen-Strukturen TiAl die Phase α2―Ti3Al mit einem Anteil von bis zu 20% aufweisen, wobei insbesondere das (Volumen-)Verhältnis von der B19―Phase und β-Phase in den Lamellen unverändert und konstant bleibt.In addition, the fine lamellar structure is retained in the composite structures when the lamellae of the composite lamellar structures TiAl have the phase α 2 -Ti 3 A l in a proportion of up to 20%, in particular the (volume) ratio of the B19 phase and β phase in the lamellae remain unchanged and constant.

Die erfindungsgemäßen Legierungen eignen sich als Hochtemperatur-Leichtbauwerkstoffe für Bauteile, die Temperaturen von bis zu 800 °C ausgesetzt sind.The alloys according to the invention are suitable as high-temperature lightweight materials for components which are exposed to temperatures of up to 800 ° C.

Darüber hinaus wird die Aufgabe gelöst durch ein Verfahren zum Herstellen einer voranstehend beschriebenen Legierung unter Verwendung von schmelz- oder pulvermetallurgischen Techniken, wobei nach der Herstellung der Legierung zu einem Zwischenprodukt eine weitere Wärmebehandlung des Zwischenprodukts bei Temperaturen oberhalb von 900°C, vorzugsweise über 1000°C, insbesondere bei Temperaturen zwischen 1000°C und 1200°C, für eine vorbestimmte Zeitdauer von mehr als 60 Minuten, vorzugsweise mehr als 90 Minuten, durchgeführt wird, und nachfolgend die wärmebehandelte Legierung mit einer vorbestimmten Kühlrate von mehr als 0.5°C pro Minute abgekühlt wird.In addition, the object is achieved by a method for producing an alloy described above using melt or powder metallurgy techniques, wherein after the production of the alloy to an intermediate, further heat treatment of the intermediate at temperatures above 900 ° C, preferably above 1000 ° C, in particular at temperatures between 1000 ° C and 1200 ° C, for a predetermined period of time of more than 60 minutes, preferably more than 90 minutes, is carried out, and subsequently the heat-treated alloy with a predetermined cooling rate of more than 0.5 ° C per minute is cooled.

Insbesondere wird die wärmebehandelte Legierung mit einer vorbestimmten Kühlrate zwischen 1°C pro Minute bis 20°C pro Minute, vorzugsweise bis 10°C pro Minute, abgekühlt.More specifically, the heat-treated alloy is cooled at a predetermined cooling rate between 1 ° C per minute to 20 ° C per minute, preferably to 10 ° C per minute.

Weiterhin wird die Aufgabe der Erfindung durch ein Bauteil gelöst, das aus einer erfindungsgemäßen Legierung hergestellt ist, wobei insbesondere die Legierung durch schmelz- oder pulvermetallurgische Verfahren oder Techniken hergestellt ist. Durch die Legierungen auf der Basis einer intermetallischen Verbindung vom Typ γ-TiAl werden leichte (Hochtemperatur-)Werkstoffe oder Bauteile für den Einsatz oder zur Verwendung in Wärmekraftmaschinen, wie Verbrennungsmotoren, Gasturbinen, Flugtriebwerken bereitgestellt.Furthermore, the object of the invention is achieved by a component which is produced from an alloy according to the invention, wherein in particular the alloy is produced by melt or powder metallurgical methods or techniques. The alloys based on a γ-TiAl intermetallic compound provide lightweight (high temperature) materials or components for use or for use in heat engines such as internal combustion engines, gas turbines, aircraft engines.

Überdies besteht eine weitere Lösung der Aufgabe in einer Verwendung einer erfindungsgemäßen, voranstehend beschriebenen Legierung zur Herstellung eines Bauteils. Zur Vermeidung von Wiederholungen wird auf die obigen Ausführungen ausdrücklich verwiesen.Moreover, a further solution of the problem is a use of an alloy according to the invention, described above, for the production of a component. To avoid repetition, reference is expressly made to the above statements.

Die erfindungsgemäßen Legierungen mit den oben aufgeführten Zusammensetzungen werden vorzugsweise durch Verwendung herkömmlicher metallurgischer Gießmethoden oder durch an sich bekannte pulvermetallurgische Techniken erzeugt und können beispielsweise durch Warmschmieden, Warmpressen bzw. Warmstrangpressen und Warmwalzen bearbeitet werden.The alloys of the present invention having the above compositions are preferably produced by using conventional metallurgical casting techniques or by per se known powder metallurgy techniques, and can be processed, for example, by hot forging, hot pressing, and hot rolling.

Nachfolgend werden anhand einer Legierung mit einer Zusammensetzung Ti - 42 Atom % Al ― 8.5 Atom % Nb die Komposit-Lamellen-Strukturen gezeigt.The composite lamellar structures are shown below using an alloy with a composition Ti - 42 At% Al - 8.5 At% Nb.

Fig. 1a zeigt eine Aufnahme der Gefügelegierung, die mit Hilfe eines Transmissions-Elektronenmikroskops aufgenommen worden ist. Die Übersichtsaufnahme in Fig. 1 zeigt, dass die Komposit-Lamellen―Strukturen, die in Fig. 1 mit T bezeichnet sind, einen streifigen Kontrast zu den die Strukturen umgebenden Gefüge der γ―Phase haben. Fig. 1a shows a photograph of the Gefreiegierung, which has been recorded by means of a transmission electron microscope. The overview in Fig. 1 shows that the composite lamellar structures in Fig. 1 with T, have a streaky contrast to the structures surrounding the structures of the γ-phase.

Fig. 1b zeigt eine Aufnahme des Legierungsgefüges mit einer höheren Vergrößerung, wobei ersichtlich ist, dass die modulierten Komposit-Lamellen-Strukturen (Bezugszeichen T) von der γ―Phase umgeben sind bzw. in die γ―Phase eingebettet sind. Fig. 1b shows a recording of the alloy structure with a higher magnification, wherein it can be seen that the modulated composite lamellar structures (reference symbol T) are surrounded by the γ phase or embedded in the γ phase.

Die in Fig. 1a und 1b gezeigten Gefüge wurden durch Extrudieren erhalten bzw. eingestellt.In the Fig. 1a and 1b The microstructures shown were obtained or adjusted by extrusion.

In Fig. 1c ist ein Gussgefüge der gleichen Legierung Ti-42 Atom % Al―8,5 Atom % Nb gezeigt, in der ebenfalls eine Komposit-Lamellen-Struktur (Bezugszeichen T) ausgebildet ist, die von der γ― Phase umgeben ist.In Fig. 1c a cast structure of the same alloy Ti-42 at% Al-8.5 atom% Nb is shown, in which also a composite lamellar structure (reference T) is formed, which is surrounded by the γ-phase.

Fig. 2a zeigt in einer hochauflösenden Darstellung die atomare Struktur der Komposit-Lamellen-Strukturen oberhalb der γ―Phase. Die Komposit―Lamellen―Strukturen bestehen aus der geordneten B19-Phase und der ungeordneten β―Phase, die an die γ―Phase angrenzen (im unteren Bereich). Aus der Aufnahme in Fig. 2a ist ersichtlich, dass die Komposit―Lamellen―Strukturen die beiden kristallographisch unterschiedlichen Phasen B19 und β/B2 enthalten, die in Abständen von wenigen Nanometern angeordnet sind. Die Komposit―Lamellen―Strukturen enthalten die Phasen B19 und β, die beide als duktil gelten. Das Volumenverhältnis der B19-Phasen und der β―Phasen in einer Komposit―Lamellen―Struktur beträgt 0,8 bis 1,2. Aufgrund der duktilen Phasen B19 und β besteht das Gefüge im Wesentlichen aus gut verformbaren Lamellen, die in die hierzu relativ spröden γ―hase eingebettet sind. Fig. 2a shows in a high-resolution representation the atomic structure of the composite lamellar structures above the γ-phase. The composite lamellar structures consist of the ordered B19 phase and the disordered β phase, which adjoin the γ phase (in the lower region). From the recording in Fig. 2a it can be seen that the composite lamellar structures are the two crystallographic different phases B19 and β / B2, which are arranged at intervals of a few nanometers. The composite lamellar structures contain phases B19 and β, both of which are considered ductile. The volume ratio of B19 phases and β phases in a composite lamellar structure is 0.8 to 1.2. Due to the ductile phases B19 and β, the structure consists essentially of easily deformable lamellae, which are embedded in the relatively brittle γ-hare.

In Fig. 2b ist die Abbildung einer B19 Struktur mit vergrößerter Darstellung gezeigt. Das entsprechende Diffraktogramm, das aus dem in Fig. 2b gezeigten Ausschnitt berechnet wurde und für die B19 Struktur charakteristisch ist, ist in Fig. 2c dargestellt.In Fig. 2b The illustration of a B19 structure is shown with an enlarged view. The corresponding diffractogram, from the in Fig. 2b shown section and is characteristic of the B19 structure is in Fig. 2c shown.

In Fig. 3 ist eine elektronenmikroskopische Aufnahme eines Risses C der oben genannten Legierung dargestellt. Hierbei geht aus der Aufnahme hervor, dass der Riss C an den modulierten Komposit-Lamellen―Strukturen (T) abgelenkt wird, und dass die Komposit-Lamellen―Strukturen Ligamente ausbilden, die die Rissufer überbrücken können. Ein derartiges Verhalten unterscheidet sich deutlich von der Rissausbreitung in den bisher bekannten Ti―Al― Legierungen, bei denen in dem hier betrachteten mikroskopischen Maßstab ein Spaltbruch auftritt. Bei der Legierung wird aufgrund der ausgebildeten Komposit―Lamellen―Strukturen eine Rissausbreitung behindert.In Fig. 3 is an electron micrograph of a crack C of the above alloy shown. Here, the image shows that the crack C is deflected at the modulated composite lamellar structures (T), and that the composite lamellar structures form ligaments that can bridge the crack edges. Such a behavior differs significantly from the crack propagation in the previously known Ti-Al alloys, in which a gap fracture occurs in the microscopic scale considered here. In the alloy crack propagation is hindered due to the formed composite lamellar structures.

Die für technische Anwendungen wichtige Bruchzähigkeit von Gefügen wurde mit Hilfe von gekerbten Chevron-Proben im Biegetest bei unterschiedlichen Temperaturen bestimmt. Die aufgenommene Registerkurve eines solchen Tests ist in Fig. 4 dargestellt. In der Kurve sind die durch die Pfeile markierten Zacken ersichtlich, die darauf hinweisen, dass während der Belastung der Probe zeitweise Rissausbreitung auftritt, die jedoch immer wieder gestoppt wird. Ein solches Verhalten ist typisch für Legierungen, die aus einer spröden Phase (γ―Phase) bestehen, in die die relativ duktilen Phasen B19 und β eingebettet sind.The fracture toughness of structures which is important for technical applications was determined by means of notched chevron samples in the bending test at different temperatures. The recorded register curve of such a test is in Fig. 4 shown. In the curve, the points marked by the arrows are visible, the point out that during the loading of the sample temporary crack propagation occurs, which however is stopped again and again. Such behavior is typical of alloys consisting of a brittle phase (γ-phase) in which the relatively ductile phases B19 and β are embedded.

Die Legierungen können durch die für TiAl―Legierungen bekannten Technologien, d.h. über Schmelzmetallurgie, Umformtechnologien und Pulvermetallurgie hergestellt werden. Beispielsweise werden Legierungen in einem Lichtbogenofen geschmolzen und mehrfach umgeschmolzen und anschließend einer Wärmebehandlung unterzogen. Darüber hinaus können zur Herstellung auch die für Primärgussblöcke aus TiAl―Legierungen bekannten Herstellverfahren Vakuum-Lichtenbogen-Schmelzen, Induktionsschmelzen oder Plasma-Schmelzen verwendet werden. Gegebenenfalls können nach dem Erstarren von Guss-Primärgussmaterial heiß-istostatisches Pressen als Verdichtungsverfahren bei Temperaturen von 900°C bis 1.300°C oder Wärmebehandlungen im Temperaturbereich von 700°C bis 1.400°C oder eine Kombination dieser Behandlungen angewendet werden, um Poren zu schließen und eine Mikrostruktur im Material einzustellen.The alloys may be formed by the technologies known for TiAl alloys, i. via melt metallurgy, forming technologies and powder metallurgy. For example, alloys are melted in an electric arc furnace and remelted several times and then subjected to a heat treatment. In addition, the production methods known for primary cast blocks of TiAl alloys may also be used for the production of vacuum arc melting, induction melting or plasma melting. Optionally, after the solidification of cast primary material, hot isostatic pressing may be used as the densification process at temperatures of 900 ° C to 1300 ° C or heat treatments in the temperature range of 700 ° C to 1400 ° C or a combination of these treatments to close pores and to adjust a microstructure in the material.

Claims (13)

Legierung auf der Basis von, insbesondere unter Verwendung von schmelz- oder pulvermetallurgischen Verfahren hergestellten, Titanaluminiden, vorzugsweise auf Basis von γ (TiAl), wobei TiAl-Legierungen mit weiteren Zusätzen Volumenanteile der β―Phase enthalten, dadurch gekennzeichnet, dass die Zusammensetzung Komposit-Lamellen-Strukturen mit B19-Phase und β―Phase in jeder Lamelle aufweist, wobei das Verhältnis, insbesondere das Volumenverhältnis, der B19-Phase und β Phase jeweils in einer Lamelle zwischen 0.05 und 20, insbesondere zwischen 0.1 und 10, beträgt.Alloy based on titanium aluminides, in particular produced by means of fusion or powder metallurgical processes, preferably based on γ (TiAl), TiAl alloys with further additives containing volume fractions of the β-phase, characterized in that the composition is composite Having lamellar structures with B19 phase and β-phase in each lamella, wherein the ratio, in particular the volume ratio of the B19 phase and β phase in each case in a lamella between 0.05 and 20, in particular between 0.1 and 10, is. Legierung nach Anspruch 1, dadurch gekennzeichnet, dass eine Legierung eine der folgenden Zusammensetzungen aufweist: Ti - (38.5 bis 42.5 At %) Al - (5 bis 10 At %) Nb - (0.5 bis 5 At %) Cr
oder Ti - (39 bis 43 At %) Al - (5 bis 10 At %) Nb - (0.5 bis 5 At %) Zr
oder Ti - (41 bis 44.5 At %) Al - (5 bis 10 At %) Nb - (0.5 bis 5 At %) Mo
oder Ti - (41 bis 44.5 At %) Al - (5 bis 10 At %) Nb - (0.5 bis 5 At %) Fe
oder Ti - (41 bis 45 At %) Al - (5 bis 10 At %) Nb - (0.1 bis 1 At %) La
oder Ti - (41 bis 45 At %) Al - (5 bis 10 At %) Nb - (0.1 bis 1 At %) Sc
oder Ti - (41 bis 45 At %) Al - (5 bis 10 At %) Nb - (0.1 bis 1 At %) Y
oder Ti - (42 bis 46 At %) Al - (5 bis 10 At %) Nb - (0.5 bis 5 At %) Mn
oder Ti - (41 bis 45 At %) Al - (5 bis 10 At %) Nb - (0.5 bis 5 At %) Ta
oder Ti - (41 bis 45 At %) Al - (5 bis 10 At %) Nb - (0.5 bis 5 At %) V
oder Ti - (41 bis 46 At %) Al - (5 bis 10 At %) Nb - (0.5 bis 5 At %) W. An alloy according to claim 1, characterized in that an alloy has one of the following compositions: Ti - (38.5 to 42.5 at%) Al - (5 to 10 at%) Nb - (0.5 to 5 at%) Cr
or Ti - (39 to 43 at%) Al - (5 to 10 at%) Nb - (0.5 to 5 at%) Zr
or Ti - (41 to 44.5 At%) Al - (5 to 10 At%) Nb - (0.5 to 5 At%) Mo
or Ti - (41 to 44.5 At%) Al - (5 to 10 At%) Nb - (0.5 to 5 At%) Fe
or Ti - (41 to 45 At%) Al - (5 to 10 At%) Nb - (0.1 to 1 At%) La
or Ti - (41 to 45 At%) Al - (5 to 10 At%) Nb - (0.1 to 1 At%) Sc
or Ti - (41 to 45 At%) Al - (5 to 10 At%) Nb - (0.1 to 1 At%) Y
or Ti - (42 to 46 At%) Al - (5 to 10 At%) Nb - (0.5 to 5 At%) Mn
or Ti - (41 to 45 At%) Al - (5 to 10 At%) Nb - (0.5 to 5 At%) Ta
or Ti - (41 to 45 At%) Al - (5 to 10 At%) Nb - (0.5 to 5 At%) V
or Ti - (41 to 46 at%) Al - (5 to 10 at%) Nb - (0.5 to 5 at%) W. Legierung nach Anspruch 1 oder 2, dadurch gekennzeichnet, dass das Verhältnis, insbesondere das Volumenverhältnis, der B19―Phase und β―Phase jeweils in einer Lamelle zwischen 0.2 und 5, insbesondere zwischen 0.25 und 4, beträgt.Alloy according to claim 1 or 2, characterized in that the ratio, in particular the volume ratio of the B19 phase and β-phase in each case in a lamella between 0.2 and 5, in particular between 0.25 and 4, is. Legierung nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, dass das Verhältnis, insbesondere das Volumenverhältnis, der B19-Phase und β―Phase jeweils in einer Lamelle zwischen (1/3) und 3, insbesondere zwischen 0.5 und 2, beträgt.Alloy according to one of claims 1 to 3, characterized in that the ratio, in particular the volume ratio of the B19 phase and β-phase in each case in a lamella between (1/3) and 3, in particular between 0.5 and 2, is. Legierung nach einem der Ansprüche 1 bis 4, dadurch gekennzeichnet, dass das Verhältnis, insbesondere das Volumenverhältnis, der B19-Phase und β―Phase jeweils in einer Lamelle zwischen 0.75 und 1.25, insbesondere zwischen 0.8 und 1.2, vorzugsweise zwischen 0.9 und 1.1, beträgt.Alloy according to one of claims 1 to 4, characterized in that the ratio, in particular the volume ratio of the B19 phase and β-phase in each case in a lamella between 0.75 and 1.25, in particular between 0.8 and 1.2, preferably between 0.9 and 1.1 , Legierung nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, dass die Zusammensetzung wahlweise (0.1 bis 1 At. %) B (Bor) und/oder (0.1 bis 1 At. %) C (Kohlenstoff) aufweist.An alloy according to any one of claims 1 to 5, characterized in that the composition optionally comprises (0.1 to 1 at.%) B (boron) and / or (0.1 to 1 at.%) C (carbon). Legierung nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass Lamellen der Komposit-Lamellen-Strukturen von Lamellen des γ (TiAl)-Typs, vorzugsweise beidseits der Lamelle, umgeben sind.Alloy according to one of Claims 1 to 6, characterized in that lamellae of the composite lamellar structures are surrounded by lamellae of the γ (TiAl) type, preferably on both sides of the lamella. Legierung nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass Lamellen der Komposit-Lamellen-Strukturen ein Volumenanteil von mehr als 10%, vorzugsweise mehr als 20%, der Legierung haben.Alloy according to one of claims 1 to 7, characterized in that lamellae of the composite lamellar structures have a volume fraction of more than 10%, preferably more than 20%, of the alloy. Legierung nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die Lamellen der Komposit-Lamellen-Strukturen die Phase α2―Ti3Al mit einem Anteil von bis zu 20% aufweisen.Alloy according to one of claims 1 to 8, characterized in that the lamellae of the composite lamellar structures have the phase α 2 -Ti 3 Al in a proportion of up to 20%. Verfahren zum Herstellen einer Legierung nach einem der Ansprüche 1 bis 9 unter Verwendung von schmelz- oder pulvermetallurgischen Techniken, wobei nach der Herstellung der Legierung zu einem Zwischenprodukt eine weitere Wärmebehandlung des Zwischenprodukts bei Temperaturen oberhalb von 900°C, vorzugsweise über 1000°C, insbesondere bei Temperaturen zwischen 1000°C und 1200°C, für eine vorbestimmte Zeitdauer von mehr als 60 Minuten, vorzugsweise mehr als 90 Minuten, durchgeführt wird, und nachfolgend die wärmebehandelte Legierung mit einer vorbestimmten Kühlrate von mehr als 0.5°C pro Minute abgekühlt wird.A process for producing an alloy according to any one of claims 1 to 9 using melt or powder metallurgy techniques, wherein after the alloy has been made into an intermediate, further heat treatment of the intermediate at temperatures above 900 ° C, preferably above 1000 ° C, in particular at temperatures between 1000 ° C and 1200 ° C, for a predetermined period of time greater than 60 minutes, preferably greater than 90 minutes, and subsequently cooling the heat-treated alloy at a predetermined cooling rate greater than 0.5 ° C per minute. Verfahren nach Anspruch 10, dadurch gekennzeichnet, dass die wärmebehandelte Legierung mit einer vorbestimmten Kühlrate zwischen 1°C pro Minute bis 20°C pro Minute, vorzugsweise bis 10°C pro Minute, abgekühlt wird.A method according to claim 10, characterized in that the heat-treated alloy is cooled at a predetermined cooling rate between 1 ° C per minute to 20 ° C per minute, preferably to 10 ° C per minute. Bauteil, das aus einer Legierung nach einem der Ansprüche 1 bis 9 hergestellt ist, wobei insbesondere die Legierung durch schmelz- oder pulvermetallurgische Verfahren oder Techniken hergestellt ist.A component made of an alloy according to any one of claims 1 to 9, wherein in particular the alloy is made by melt or powder metallurgy techniques or techniques. Verwendung einer Legierung nach einem der Ansprüche 1 bis 9 zur Herstellung eines Bauteils.Use of an alloy according to any one of claims 1 to 9 for the manufacture of a component.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012222745A1 (en) 2012-12-11 2014-06-12 MTU Aero Engines AG Turbine blade, useful in fluid-flow machine e.g. stationary gas turbine or aircraft engine, comprises monocrystalline of titanium aluminide material in blade portion, and blade root made of polycrystalline material
CN106148739A (en) * 2016-06-29 2016-11-23 西安西工大超晶科技发展有限责任公司 A kind of preparation method containing niobium Ti3Al alloy cast ingot
CN106148739B (en) * 2016-06-29 2018-02-06 西安西工大超晶科技发展有限责任公司 A kind of preparation method of the alloy cast ingots of Ti3Al containing niobium

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