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EP2145967B1 - Alliages d'aluminure de titane - Google Patents

Alliages d'aluminure de titane Download PDF

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Publication number
EP2145967B1
EP2145967B1 EP09010152.8A EP09010152A EP2145967B1 EP 2145967 B1 EP2145967 B1 EP 2145967B1 EP 09010152 A EP09010152 A EP 09010152A EP 2145967 B1 EP2145967 B1 EP 2145967B1
Authority
EP
European Patent Office
Prior art keywords
phase
alloy
lamellas
lamellar structures
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
EP09010152.8A
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German (de)
English (en)
Other versions
EP2145967A2 (fr
EP2145967A3 (fr
Inventor
Fritz Appel
Jonathan Paul
Michael Oehring
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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Priority to EP11187502.7A priority Critical patent/EP2423341B1/fr
Publication of EP2145967A2 publication Critical patent/EP2145967A2/fr
Publication of EP2145967A3 publication Critical patent/EP2145967A3/fr
Application granted granted Critical
Publication of EP2145967B1 publication Critical patent/EP2145967B1/fr
Not-in-force legal-status Critical Current
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Classifications

    • 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 based on ⁇ (TiAl), in particular using melt or powder metallurgical processes.
  • 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 which are based on an intermetallic phase ⁇ (TiAl) with a tetragonal structure and, in addition to the majority phase ⁇ (TiAl), are also of interest, are of particular interest.
  • 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 .)
  • DE 10 2004 056 582 A1 discloses alloys based on titanium aluminides, wherein the alloy compositions consist of Ti (44.5 to 47 at%) Al (5 to 10 at%) Nb and optionally 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. These ⁇ -phases are present up to a temperature of less than 1320 ° C.
  • the present invention has the object, a titanium aluminide alloy with to provide a fine microstructure morphology, especially in the nanometer range. Furthermore, the object is to provide a component with a homogeneous alloy.
  • 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.
  • the heat-treated alloy becomes a predetermined one Cooling rate cooled to 10 ° C per minute.
  • Said titanium aluminide alloy may optionally comprise the additions of boron and / or carbon, wherein in one embodiment the composition of said alloys or of the intermetallic compounds is in each case 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.
  • the residues of titanium and unavoidable impurities exist in the case of the stated alloy composition.
  • alloys are provided which are suitable as a lightweight material for high temperature applications, such as turbine blades or engine and turbine components are.
  • 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.
  • additives for example 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 these lattice transformations by shear conversion for additional fine tuning of the microstructure of the titanium aluminide alloys of the invention use. 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 volume ratio of the B19 phase and ⁇ -phase in each case in a lamella between 0.2 and 5, in particular between 0.25 and 4.
  • the volume ratio of the B19 phase and ⁇ -phase in a lamella between (1/3) and 3, in particular between 0.5 and 2.
  • a particularly fine microstructure in the alloy composition is characterized in that 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.
  • 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 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 of the invention is achieved by the component according to claim 10.
  • 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 invention having the above composition are preferably produced by using conventional metallurgical casting methods or by powder metallurgy techniques known per se, and can be produced, 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. 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 ⁇ phase (in the lower region). From the recording in Fig. 2a is 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)

Claims (11)

  1. Procédé de fabrication d'un alliage à base d'aluminures de titane, fabriqué en particulier par utilisation de procédés de la métallurgie de fusion ou de la métallurgie des poudres, à base de γ (TiAl) ayant la composition suivante :
    Ti - 4,1 à 44,5 % en atomes d'Al - 5 à 10 % en atomes de Nb - 0,5 à 5 % en atomes de Mo, en option 0,1 à 1 % en atomes de B et/ou 0,1 à 1 % en atomes de C,
    dans lequel, après la fabrication de l'alliage pour obtenir un produit intermédiaire, on met en oeuvre un traitement thermique supplémentaire du produit intermédiaire à des températures comprises entre 1000 et 1200°C pendant une durée prédéfinie supérieure à 60 minutes, de préférence supérieure à 90 minutes, puis l'alliage ayant subi le traitement thermique est refroidi à une vitesse de refroidissement prédéfinie comprise entre 1 °C par minute et 20°C par minute,
    où l'alliage, après le traitement thermique supplémentaire, contient des proportions volumiques de la phase β, comprend des structures en lamelles composites ayant une phase B19 et une phase β dans chaque lamelle des structures de lamelles composites, et le rapport en volume de la phase B19 à la phase β est, dans chaque lamelle, compris entre 0,05 et 20, en particulier entre 0,1 et 10, la phase B19 étant formée par conversion en cisaillement de la phase β, les lamelles des structures de lamelles composites présentant la phase α2-Ti3Al selon une proportion allant jusqu'à 20 %, les lamelles des structures de lamelles composites étant entourées de lamelles du type γ(TiAl), et les lamelles des structures de lamelles composites représentant une proportion volumique de l'alliage supérieure à 10 %.
  2. Procédé selon la revendication 1, caractérisé en ce que l'alliage ayant subi le traitement thermique est refroidi à une vitesse de refroidissement prédéfinie de 10°C par minute.
  3. Alliage à base d'aluminures de titane, fabriqué en particulier par utilisation de procédés de la métallurgie de fusion ou de la métallurgie des poudres, à base de γ(TiAl), ayant la composition suivante :
    Ti - 41 à 44,5 % en atomes d'Al - 5 à 10 % en atomes de Nb - 0,5 à 5 % en atomes de Mo, en option 0,1 à 1 % en atomes de B et/ou 0,1 à 1 % en atomes de C,
    qui contient des proportions volumiques de la phase β, la composition comportant des structures de lamelles composites ayant une phase B19 et une phase β dans chaque lamelle des structures de lamelles composites, le rapport en volume de la phase B19 à la phase β étant dans chaque lamelle compris entre 0,05 et 20, en particulier entre 0,1 et 10, la phase B19 étant formée par conversion en cisaillement de la phase β, les lamelles des structures de lamelles composites comportant la phase α2-Ti3Al selon une proportion allant jusqu'à 20 %, les lamelles des structures des lamelles composites étant entourées de lamelles du type γ(TiAl), et les lamelles des structures des lamelles composites représentant une proportion volumique supérieure à 10 % de l'alliage, fabriqué par un procédé selon la revendication 1 ou 2.
  4. Alliage selon la revendication 3, caractérisé en ce que le rapport en volume de la phase B19 et de la phase β est dans chaque lamelle compris entre 0,2 et 5, en particulier entre 0,25 et 4.
  5. Alliage selon la revendication 3 ou 4, caractérisé en ce que le rapport en volume de la phase B19 à la phase β est dans chaque lamelle compris entre (1/3) et 3, en particulier entre 0,5 et 2.
  6. Alliage selon l'une des revendications 3 à 5, caractérisé en ce que le rapport en volume de la phase B19 à la phase β est dans chaque lamelle compris entre 0,75 et 1,25, en particulier entre 0,8 et 1,2, de préférence entre 0,9 et 1,1.
  7. Alliage selon l'une des revendications 3 à 6, caractérisé en ce que la composition comprend en option (0,1 à 1 % en atomes) de B (bore) et/ou (0,1 à 1 % en atomes) de C (carbone).
  8. Alliage selon l'une des revendications 3 à 7, caractérisé en ce que les lamelles des structures de lamelles composites sont entourées, sur les deux côtés de chaque lamelle, par des lamelles du type γ(TiAl).
  9. Alliage selon l'une des revendications 3 à 8, caractérisé en ce que les lamelles des structures de lamelles composites correspondent à une proportion volumique de l'alliage supérieure à 20 %.
  10. Composant qui est fabriqué à partir d'un alliage selon l'une des revendications 3 à 9, l'alliage étant fabriqué par des procédés ou des techniques de la métallurgie de fusion ou de la métallurgie des poudres.
  11. Utilisation d'un alliage selon l'une des revendications 3 à 9 pour la fabrication d'un composant.
EP09010152.8A 2007-12-13 2008-11-25 Alliages d'aluminure de titane Not-in-force EP2145967B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11187502.7A EP2423341B1 (fr) 2007-12-13 2008-11-25 Alliages d'aluminure de titane

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007060587A DE102007060587B4 (de) 2007-12-13 2007-12-13 Titanaluminidlegierungen
EP08020431.6A EP2075349B1 (fr) 2007-12-13 2008-11-25 Alliages d'aluminure de titane

Related Parent Applications (3)

Application Number Title Priority Date Filing Date
EP08020431.6 Division 2008-11-25
EP08020431.6A Division EP2075349B1 (fr) 2007-12-13 2008-11-25 Alliages d'aluminure de titane
EP08020431.6A Division-Into EP2075349B1 (fr) 2007-12-13 2008-11-25 Alliages d'aluminure de titane

Related Child Applications (1)

Application Number Title Priority Date Filing Date
EP11187502.7 Division-Into 2011-11-02

Publications (3)

Publication Number Publication Date
EP2145967A2 EP2145967A2 (fr) 2010-01-20
EP2145967A3 EP2145967A3 (fr) 2010-04-21
EP2145967B1 true EP2145967B1 (fr) 2013-07-24

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Family Applications (3)

Application Number Title Priority Date Filing Date
EP09010152.8A Not-in-force EP2145967B1 (fr) 2007-12-13 2008-11-25 Alliages d'aluminure de titane
EP08020431.6A Not-in-force EP2075349B1 (fr) 2007-12-13 2008-11-25 Alliages d'aluminure de titane
EP11187502.7A Not-in-force EP2423341B1 (fr) 2007-12-13 2008-11-25 Alliages d'aluminure de titane

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EP08020431.6A Not-in-force EP2075349B1 (fr) 2007-12-13 2008-11-25 Alliages d'aluminure de titane
EP11187502.7A Not-in-force EP2423341B1 (fr) 2007-12-13 2008-11-25 Alliages d'aluminure de titane

Country Status (10)

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

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DE102009050603B3 (de) * 2009-10-24 2011-04-14 Gfe Metalle Und Materialien Gmbh Verfahren zur Herstellung einer β-γ-TiAl-Basislegierung
WO2012041276A2 (fr) 2010-09-22 2012-04-05 Mtu Aero Engines Gmbh Alliage tial résistant à la chaleur
DE102011110740B4 (de) * 2011-08-11 2017-01-19 MTU Aero Engines AG Verfahren zur Herstellung geschmiedeter TiAl-Bauteile
EP2620517A1 (fr) 2012-01-25 2013-07-31 MTU Aero Engines GmbH Alliage TiAl thermostable
US20130248061A1 (en) * 2012-03-23 2013-09-26 General Electric Company Methods for processing titanium aluminide intermetallic compositions
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US10597756B2 (en) 2012-03-24 2020-03-24 General Electric Company Titanium aluminide intermetallic compositions
KR101261885B1 (ko) * 2012-07-25 2013-05-06 한국기계연구원 베타-감마상을 포함하는 층상 구조의 타이타늄-알루미늄계 합금
RU2502824C1 (ru) * 2012-11-13 2013-12-27 Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Национальный исследовательский технологический университет "МИСиС" Способ термообработки отливок из сплавов на основе гамма алюминида титана
DE102012222745A1 (de) 2012-12-11 2014-06-12 MTU Aero Engines AG Einkristalline Turbinenschaufel aus Titanaluminid
WO2014115921A1 (fr) * 2013-01-23 2014-07-31 한국기계연구원 Alliage de titane-aluminium présentant une résistance aux hautes températures et une résistance à l'oxydation améliorées
WO2014149122A2 (fr) * 2013-03-15 2014-09-25 United Technologies Corporation Procédé permettant de fabriquer un composant de turbine en aluminure de titane gamma
CN103484701B (zh) * 2013-09-10 2015-06-24 西北工业大学 一种铸造钛合金晶粒细化的方法
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JP6439287B2 (ja) * 2014-06-18 2018-12-19 株式会社デンソー 運転支援装置、運転支援方法、画像補正装置、画像補正方法
RU2592657C2 (ru) * 2014-12-29 2016-07-27 Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") Жаропрочный сплав на основе титана и изделие, выполненное из него
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IL195756A0 (en) 2009-11-18
CN101457314B (zh) 2013-07-24
EP2423341B1 (fr) 2013-07-10
US20140010701A1 (en) 2014-01-09
CN101457314A (zh) 2009-06-17
US20100000635A1 (en) 2010-01-07
EP2145967A2 (fr) 2010-01-20
EP2075349A2 (fr) 2009-07-01
EP2145967A3 (fr) 2010-04-21
DE102007060587A1 (de) 2009-06-18
EP2075349B1 (fr) 2016-03-09
RU2008149177A (ru) 2010-06-20
BRPI0806979A2 (pt) 2010-04-20
KR20090063173A (ko) 2009-06-17
JP2009144247A (ja) 2009-07-02
DE102007060587B4 (de) 2013-01-31
CA2645843A1 (fr) 2009-06-13
RU2466201C2 (ru) 2012-11-10
US20090151822A1 (en) 2009-06-18
EP2075349A3 (fr) 2009-09-09
EP2423341A1 (fr) 2012-02-29

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