EP2075349B1 - Titanaluminidlegierungen - Google Patents

Titanaluminidlegierungen Download PDF

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Publication number
EP2075349B1
EP2075349B1 EP08020431.6A EP08020431A EP2075349B1 EP 2075349 B1 EP2075349 B1 EP 2075349B1 EP 08020431 A EP08020431 A EP 08020431A EP 2075349 B1 EP2075349 B1 EP 2075349B1
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EP
European Patent Office
Prior art keywords
phase
alloy
lamellar structures
lamellae
composite lamellar
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.)
Not-in-force
Application number
EP08020431.6A
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German (de)
English (en)
French (fr)
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EP2075349A3 (de
EP2075349A2 (de
Inventor
Michael Oehring
Fritz Appel
Jonathan Paul
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.)
Helmholtz Zentrum Geesthacht Zentrum fuer Material und Kustenforschung GmbH
Original Assignee
Helmholtz Zentrum Geesthacht Zentrum fuer Material und Kustenforschung GmbH
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Application filed by Helmholtz Zentrum Geesthacht Zentrum fuer Material und Kustenforschung GmbH filed Critical Helmholtz Zentrum Geesthacht Zentrum fuer Material und Kustenforschung GmbH
Priority to EP11187502.7A priority Critical patent/EP2423341B1/de
Priority to EP09010152.8A priority patent/EP2145967B1/de
Publication of EP2075349A2 publication Critical patent/EP2075349A2/de
Publication of EP2075349A3 publication Critical patent/EP2075349A3/de
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Publication of EP2075349B1 publication Critical patent/EP2075349B1/de
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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 an alloy based on, in particular using melt or powder metallurgy produced titanium aluminides, preferably based on ⁇ (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, which are based on an intermetallic phase ⁇ (TiAl) with tetragonal structure and in addition to the majority phase ⁇ (TiAl) 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 based on ⁇ 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.
  • 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 .)
  • TAKEYAMA MASAO ET AL Phase equilibria among ⁇ , ⁇ 2, ⁇ and y phases in ternary Ti-AI-X systems at elevated temperatures
  • TITANIUM '95 SCI-ENCE AND TECHNOLOGY, PROCEEDINGS OF THE WORLD CONFERENCE ON TITANIUM, 8TH , Birmingham, UK, OCT. 22-26, 1995, INSTITUTE OF MATERIALS, LONDON, UK, Vol. 1, Jan. 1, 1995 (1995-01-01), pages 294-301, XP009178047 Titanium aluminides described with a composition of titanium-38, aluminum-6, niobium, which are produced by arc melting.
  • the samples are homogenized at 1350 ° C for two hours and then quenched in a water bath. Subsequently, the material is tempered at temperatures between 1100 ° Celsius and 1200 ° Celsius in an argon atmosphere and quenched after a certain holding time in ice water.
  • the object of the invention is to provide a titanium aluminide alloy having a fine grain morphology, in particular in the nanometer range. Furthermore, the object is to provide a component with a homogeneous alloy and a use of this alloy.
  • an intermetallic compound or alloy based on, in particular using melt or powder metallurgy produced, titanium aluminides, preferably based on ⁇ (TiAl), in the following composition: Ti - 38 atom % al - 5 to 10 atom % Nb .
  • the composite having B19-phase and ⁇ -phase composite lamellar structures in each lamella of the composite lamellar structures, wherein the volume ratio of the B19 phase and the ⁇ -phase are each in a lamella of the composite lamellar structures between 0.05 and 20, in particular between 0.1 and 10, wherein the B19 phase is formed by shear conversion of the ⁇ -phase, wherein the lamellae of the composite lamellar structures, the phase ⁇ 2 -Ti 3 Al in a proportion of up to 20 %, wherein the lamellae of the composite lamellar structures are surrounded by lamellae of the ⁇ (TiAl) type and wherein the lamellae of the composite lamellar structures have a volume fraction of more than 10% of the alloy, the alloy being developed thereby in that the composition optionally has (0.1 to 1 at.%) B (boron) and / or (0.1 to 1 at.%) C (carbon).
  • Such composite lamellar structures can be prepared in alloys by known manufacturing technologies, ie, casting, forming, and powder technologies.
  • the alloys are characterized by extremely high strength and creep resistance combined with high ductility and fracture toughness.
  • alloys are provided which are used as a lightweight material for high temperature applications, e.g. Turbine blades or engine and turbine components are suitable.
  • the alloys are produced using casting metallurgy, melt metallurgy or powder metallurgy techniques, or using these methods in combination with forming techniques.
  • the alloys are characterized by that they have a very fine microstructure and high strength and creep resistance, while having good ductility and fracture toughness, especially over alloys without the composite lamellar structures.
  • 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. Such a method is not yet known for titanium aluminide alloys in the scientific literature. In the case of the abovementioned alloys, shearing transformations also prevent brittle phases such as ⁇ , ⁇ 'and ⁇ ", which are extremely disadvantageous for the mechanical material properties.
  • 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 in a lamella between 0.75 and 1.25, in particular between 0.8 and 1.2, preferably between 0.9 and 1.1, is.
  • the alloys are further distinguished by the fact that the lamellae of the composite lamellar structures have a volume fraction of more than 20% of the total alloy.
  • the fine lamellar structure is retained in the composite structures, if the lamellae of the composite lamellar structures TiAl have the phase ⁇ 2 -Ti 3 Al 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 are suitable as high-temperature lightweight materials for components 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 product further heat treatment of the intermediate at temperatures above 900 ° C, preferably above 1000 ° C, especially 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 process being developed by cooling the heat-treated alloy 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.
  • alloys according to the invention described above, for the production of a component.
  • the alloys having the above-mentioned compositions are preferably produced by using conventional metallurgical casting methods or by powder-metallurgical techniques known per se, 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 picture of the Gedemandgleiter, which was taken with the aid of a transmission electron microscope is.
  • 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. 1 b 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 ⁇ -phases or embedded in the ⁇ -phase.
  • Fig. 1c a cast structure of the same alloy Ti-42 atom% 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 ⁇ phases (in the lower region). From the recording in Fig. 2a It can be seen that the composite lamellar structures contain the two crystallographically 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 in the Essentially from well deformable lamellae, which are embedded in the relatively brittle ⁇ -phase.
  • 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.
  • crack propagation is impeded on account of 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 made from TiAl alloys, vacuum arc melting, induction melting or plasma melting can also be used for the production.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Laminated Bodies (AREA)
  • Pressure Welding/Diffusion-Bonding (AREA)
EP08020431.6A 2007-12-13 2008-11-25 Titanaluminidlegierungen Not-in-force EP2075349B1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP11187502.7A EP2423341B1 (de) 2007-12-13 2008-11-25 Titanaluminidlegierungen
EP09010152.8A EP2145967B1 (de) 2007-12-13 2008-11-25 Titanaluminidlegierungen

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102007060587A DE102007060587B4 (de) 2007-12-13 2007-12-13 Titanaluminidlegierungen

Related Child Applications (3)

Application Number Title Priority Date Filing Date
EP09010152.8A Division-Into EP2145967B1 (de) 2007-12-13 2008-11-25 Titanaluminidlegierungen
EP09010152.8A Division EP2145967B1 (de) 2007-12-13 2008-11-25 Titanaluminidlegierungen
EP11187502.7A Division-Into EP2423341B1 (de) 2007-12-13 2008-11-25 Titanaluminidlegierungen

Publications (3)

Publication Number Publication Date
EP2075349A2 EP2075349A2 (de) 2009-07-01
EP2075349A3 EP2075349A3 (de) 2009-09-09
EP2075349B1 true EP2075349B1 (de) 2016-03-09

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EP09010152.8A Not-in-force EP2145967B1 (de) 2007-12-13 2008-11-25 Titanaluminidlegierungen
EP08020431.6A Not-in-force EP2075349B1 (de) 2007-12-13 2008-11-25 Titanaluminidlegierungen
EP11187502.7A Not-in-force EP2423341B1 (de) 2007-12-13 2008-11-25 Titanaluminidlegierungen

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Country Status (10)

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US (3) US20090151822A1 (pt)
EP (3) EP2145967B1 (pt)
JP (1) JP5512964B2 (pt)
KR (1) KR20090063173A (pt)
CN (1) CN101457314B (pt)
BR (1) BRPI0806979A2 (pt)
CA (1) CA2645843A1 (pt)
DE (1) DE102007060587B4 (pt)
IL (1) IL195756A0 (pt)
RU (1) RU2466201C2 (pt)

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KR20090063173A (ko) 2009-06-17
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EP2423341B1 (de) 2013-07-10
US20100000635A1 (en) 2010-01-07
RU2008149177A (ru) 2010-06-20
JP5512964B2 (ja) 2014-06-04
EP2423341A1 (de) 2012-02-29
US20090151822A1 (en) 2009-06-18
US20140010701A1 (en) 2014-01-09
DE102007060587A1 (de) 2009-06-18
EP2075349A3 (de) 2009-09-09
EP2075349A2 (de) 2009-07-01
IL195756A0 (en) 2009-11-18
CN101457314B (zh) 2013-07-24
EP2145967A2 (de) 2010-01-20
EP2145967B1 (de) 2013-07-24
CA2645843A1 (en) 2009-06-13
RU2466201C2 (ru) 2012-11-10
CN101457314A (zh) 2009-06-17
BRPI0806979A2 (pt) 2010-04-20

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