EP2423341B1 - Titanaluminidlegierungen - Google Patents

Titanaluminidlegierungen Download PDF

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Publication number
EP2423341B1
EP2423341B1 EP11187502.7A EP11187502A EP2423341B1 EP 2423341 B1 EP2423341 B1 EP 2423341B1 EP 11187502 A EP11187502 A EP 11187502A EP 2423341 B1 EP2423341 B1 EP 2423341B1
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EP
European Patent Office
Prior art keywords
alloy
phase
alloys
lamella
ratio
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
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EP11187502.7A
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German (de)
English (en)
French (fr)
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EP2423341A1 (de
Inventor
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 .)
  • JP-A-06 116691 discloses a method of heat treating titanium aluminide alloys to improve the hardness of the alloys.
  • the titanium alloys consist of Ti, 40-50% Al and 3 to 10% of at least one element Nb, Mo and Cr, wherein the alloys may also contain several of the latter elements.
  • DE-A-10 2004 056 582 relates to alloys based on titanium aluminides, the alloy compositions consisting of Ti (44.5 to 47) Al (5-10) Nb and Walweise boron and / or carbon.
  • the described alloys also contain molybdenum in the range of between 0.1 atom% to 3.0 atom%.
  • the alloys are characterized by the fact that they have stable ⁇ phases through the addition of molybdenum over a wide temperature range.
  • EP-A-1 889 939 discloses a method for increasing the massive transformation of titanium aluminide alloys with an ⁇ -phase, wherein up to 0.5 at% is introduced into the alloy.
  • the alloy may have up to 43 at% of aluminum, 0 to 9 at% of niobium, 0 to 10 at% of tantalum, and 0.01 to 0.15 at% of yttrium
  • 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.
  • 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.
  • 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 can be used as a lightweight material for high temperature applications, e.g. Turbine blades or engine and turbine components are suitable.
  • 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.
  • further additives for example of refractory elements
  • contain relatively large volume fractions of the ⁇ -phase which may also be present in ordered form as 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 ⁇ 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. Such a method is not yet known for titanium aluminide alloys 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 texture refinement of the alloys without the addition of grain-fining elements or additives such as. 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.
  • 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 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, 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 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 from melting 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 Duration of more than 60 minutes, preferably more than 90 minutes, is performed, and then the heat-treated alloy is cooled at a predetermined cooling rate of more than 0.5 ° C per minute.
  • 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.
  • alloys according to the invention with the above-mentioned compositions are preferably prepared by using conventional metallurgical casting methods or by per se known powder metallurgy techniques are produced and can be processed for example by hot forging, hot pressing or hot extrusion 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. 1 c 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 ⁇ phase (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 consists essentially of easily 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. 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.

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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)
EP11187502.7A 2007-12-13 2008-11-25 Titanaluminidlegierungen Not-in-force EP2423341B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE102007060587A DE102007060587B4 (de) 2007-12-13 2007-12-13 Titanaluminidlegierungen
EP08020431.6A EP2075349B1 (de) 2007-12-13 2008-11-25 Titanaluminidlegierungen
EP09010152.8A EP2145967B1 (de) 2007-12-13 2008-11-25 Titanaluminidlegierungen

Related Parent Applications (3)

Application Number Title Priority Date Filing Date
EP08020431.6A Division-Into EP2075349B1 (de) 2007-12-13 2008-11-25 Titanaluminidlegierungen
EP08020431.6 Division 2008-11-25
EP09010152.8 Division 2009-08-06

Publications (2)

Publication Number Publication Date
EP2423341A1 EP2423341A1 (de) 2012-02-29
EP2423341B1 true EP2423341B1 (de) 2013-07-10

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EP11187502.7A Not-in-force EP2423341B1 (de) 2007-12-13 2008-11-25 Titanaluminidlegierungen
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

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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

Country Status (10)

Country Link
US (3) US20090151822A1 (ru)
EP (3) EP2423341B1 (ru)
JP (1) JP5512964B2 (ru)
KR (1) KR20090063173A (ru)
CN (1) CN101457314B (ru)
BR (1) BRPI0806979A2 (ru)
CA (1) CA2645843A1 (ru)
DE (1) DE102007060587B4 (ru)
IL (1) IL195756A0 (ru)
RU (1) RU2466201C2 (ru)

Cited By (1)

* Cited by examiner, † Cited by third party
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US10544485B2 (en) 2016-05-23 2020-01-28 MTU Aero Engines AG Additive manufacturing of high-temperature components from TiAl

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CN107699738A (zh) * 2017-09-29 2018-02-16 成都露思特新材料科技有限公司 一种细晶TiAl合金及其制备方法、航空发动机、汽车
WO2019103539A1 (ko) * 2017-11-24 2019-05-31 한국기계연구원 고온 특성이 우수한 3d 프린팅용 타이타늄-알루미늄계 합금 및 이의 제조방법
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CN101457314A (zh) 2009-06-17
US20140010701A1 (en) 2014-01-09
EP2145967A3 (de) 2010-04-21
EP2075349B1 (de) 2016-03-09
EP2075349A3 (de) 2009-09-09
DE102007060587B4 (de) 2013-01-31
RU2008149177A (ru) 2010-06-20
JP5512964B2 (ja) 2014-06-04
KR20090063173A (ko) 2009-06-17
BRPI0806979A2 (pt) 2010-04-20
EP2145967A2 (de) 2010-01-20
EP2145967B1 (de) 2013-07-24
US20090151822A1 (en) 2009-06-18
CN101457314B (zh) 2013-07-24
EP2423341A1 (de) 2012-02-29
DE102007060587A1 (de) 2009-06-18
JP2009144247A (ja) 2009-07-02
IL195756A0 (en) 2009-11-18
EP2075349A2 (de) 2009-07-01
RU2466201C2 (ru) 2012-11-10
CA2645843A1 (en) 2009-06-13

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