EP2342365B1 - Procédé de fabrication d'un alliage de beta-gamma ti-al - Google Patents

Procédé de fabrication d'un alliage de beta-gamma ti-al Download PDF

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Publication number
EP2342365B1
EP2342365B1 EP10765988A EP10765988A EP2342365B1 EP 2342365 B1 EP2342365 B1 EP 2342365B1 EP 10765988 A EP10765988 A EP 10765988A EP 10765988 A EP10765988 A EP 10765988A EP 2342365 B1 EP2342365 B1 EP 2342365B1
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EP
European Patent Office
Prior art keywords
base alloy
electrode
titanium
tial base
tial
Prior art date
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EP10765988A
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German (de)
English (en)
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EP2342365A1 (fr
Inventor
Matthias Achtermann
Willy FÜRWITT
Volker GÜTHER
Hans-Peter Nicolai
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.)
GfE Metalle und Materialien GmbH
TiTAL GmbH
Original Assignee
GfE Metalle und Materialien GmbH
TiTAL GmbH
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Publication of EP2342365A1 publication Critical patent/EP2342365A1/fr
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    • 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
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1295—Refining, melting, remelting, working up of titanium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
    • C22B9/16—Remelting metals
    • C22B9/20—Arc remelting
    • 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

Definitions

  • the invention relates to a process for the production of ⁇ -TiAl base alloys by means of vacuum arc melting (VAR), which solidify completely or at least partially primarily via the ⁇ -phase.
  • VAR vacuum arc melting
  • Such target alloys will hereinafter be referred to as ⁇ - ⁇ -TiAl base alloy.
  • the technical field of the present invention is the melt metallurgical production of ⁇ - ⁇ -TiAl alloys by means of vacuum arc melting (VAR).
  • VAR vacuum arc melting
  • the DE 195 81 384 T1 describes intermetallic TiAl compounds and processes for their preparation, wherein the alloy by heat treatment of an alloy having a Ti concentration of 42 to 48 atom%, an Al concentration of 44 to 47 atom%, a Nb concentration of 6 to 10 at.% And a Cr concentration of 1 to 3 at.% At a temperature in the range of 1300 to 1400 ° C.
  • the DE 196 31 583 A1 discloses a method for producing an alloy TiAl-Nb product in which an alloy electrode is first prepared from the alloy components. The formation of the alloy electrode is carried out by pressing and / or sintering the alloy components to the electrode. The latter is melted off by an induction coil.
  • a heat-resistant TiAl based alloy is known in which specific amounts of V and Cr are incorporated into a Ti-Al intermetallic compound for the purpose of improving heat resistance and ductility.
  • a new generation of ⁇ -TiAl high performance materials has a structural design different from conventional TiAl alloys.
  • ⁇ -stabilizing elements such as Cr, Cu, Hf, Mn, Mo, Nb, V, Ta and Zr is set a primary solidification path over the ⁇ -Ti phase. This results in very fine microstructure, in addition to lamellar ⁇ 2 / ⁇ colonies also contain globular ⁇ grains and globular ⁇ grains, sometimes including globular ⁇ 2 grains.
  • a temperature field of melting temperature (about 1570 ° C.) at the bottom of the electrode extends to near room temperature at the electrode suspension through the material. Not far from the melt front, the critical temperature interval between 1000 and 1200 ° C is reached.
  • the relatively poor ductility of the intermetallic material then leads in this zone to the fact that the stresses formed there discharge in the form of cracks, which in turn lead to the described chipping of unmelted pieces from the electrode.
  • the present invention seeks to provide a method for producing a ⁇ -phase solidified ⁇ -TiAl base alloy - hereinafter referred to as ⁇ - ⁇ -TiAl base alloy - specify that Avoiding the cracking problem leads to a reliable production of such a target alloy.
  • the successive remelting steps during the vacuum arc melting are thus subdivided into the melting of a primary alloy in the first remelting steps, wherein a base melted electrode is produced from a conventional ⁇ -TiAl primary alloy, and the melting of the target alloy in the form of the desired ⁇ - ⁇ -TiAl-based alloy in the last remelting step.
  • the primary alloy has a deficiency of titanium and / or a deficiency of ⁇ -stabilizing elements such as Nb, Mo, Cr, Mn, V, and Ta.
  • the alloy is a defined amount of titanium and / or ⁇ in the preparation of the pressed base melt electrode deprived of stabilizing elements, so that an aluminum content of the primary alloy preferably between 45 at .-% (particularly preferably 45.5 at .-%) and 50 at .-% sets.
  • the contents of aluminum and ⁇ -stabilizing elements are chosen so that the solidification path of the primary alloy is at least partially via the peritectic conversion. It is thus set a structure analogous to conventional TiAl alloys, which can be processed easily in the VAR oven.
  • the target alloy is readjusted by the addition of the materials originally removed from the press electrode.
  • these materials are welded as cladding to form a composite electrode firmly on the outer surface of the Abschmelzelektrode to safely exclude a solid state drop into the molten bath. It is also possible to accomplish this by a sheath insert of the deficient alloy content on the inside of the Umschmelzkokille the VAR furnace.
  • the VAR furnace 1 has a copper crucible 4 with a bottom plate 5.
  • a water jacket 6 with water inlet 7 and 8 water outlet is arranged.
  • the copper crucible 4 is also closed at the top of a vacuum bell 9, passes through the top of a lifting bar 10 vertically displaceable. At this lifting bar 10 sits the holder 11, on which the actual electrode 2 is suspended.
  • a DC voltage is applied between the copper crucible 4 and the lifting rod 10, due to which a high-current arc is ignited and maintained between the electrode 2 electrically connected to the lifting rod 10 and the copper crucible 4.
  • the electrode 2 is successively remelted to ingot 3 under homogenization of the alloy components.
  • the target composition of the ⁇ - ⁇ -TiAl alloy is Ti-43.5Al-4.0Nb-1.0Mo-0.1B (at.%) Or Ti-A128.6-Nb9.1-Mo2.3. B0.03 (m-%).
  • the composition of the primary alloy for the base melt electrode is determined by a reduction of the titanium content to Ti - 45.93Al - 4.22Nb - 1.06Mo - 0.11B (at .-%).
  • a ingot 3 of the primary alloy of 200 mm in diameter and 1.4 m in length is prepared from a press electrode 2 by 2-fold VAR melting as described above, without cracking problem.
  • As starting materials for the production of the pressing electrode 2 titanium sponge pure aluminum and master alloys are used.
  • the entire surface area of the ingot 3 becomes of the primary alloy Pure titanium sheet 15 with a thickness of 3 mm (mass 12 kg) wound and partially welded to the outer surface 16 of the ingot 3, as shown in Fig. 2 is shown.
  • the upper edge 17 of the titanium sheet 15 is completely welded over the circumference of the ingot 3 with this.
  • welding point 18 are set distributed over the lateral surface 16.
  • the self-consumable electrode thus assembled is remelted as a composite electrode 19 in a final melting step in the VAR furnace 1 to a ingot 3 having a diameter of 280 mm and the composition of the target alloy.
  • the target composition, the feeds used and the composition of the primary alloy correspond to Embodiment 1.
  • an ingot 3 having a diameter of 140 mm and a length of 1.8 m is manufactured by simply VAR-melting press electrodes 2.
  • the mass of the ingot is 115 kg.
  • a sheet of pure titanium with the dimensions circumference 628 mm x height 880 mm x thickness 3 mm (mass 7.6 kg) in the inserted inner surface.
  • the composition of the primary alloy ingot forming the base melt electrode 2 and the titanium sheet thus provide the target composition.
  • the remelting takes place in the lined with the titanium sheet copper crucible 4 to an intermediate electrode such that the outer skin of the titanium sheet is not completely melted with and remains as a stable shell.
  • an intermediate electrode such that the outer skin of the titanium sheet is not completely melted with and remains as a stable shell.
  • cracking may occur, but due to the mechanical stabilization by the ductile outer shell, this does not lead to cracking Drop down of electrode material in the melt reservoir 14 lead.
  • the target composition, the feeds used and the composition of the primary alloy correspond to the embodiment 1, also the production of the composite electrode 19.
  • the last remelting takes place in a so-called VAR skull melter, ie a vacuum arc melting device with a water-cooled, tiltable copper crucible.
  • the target material's molten alloy material is poured into permanent molds made of stainless steel, which are attached to a rotating casting wheel.
  • the casting bodies produced by centrifugal casting are used as starting material for the production of components from the target alloy.
  • a ⁇ - ⁇ -TiAl alloy according to U.S. Patent 6,669,791 has a composition (target alloy) of Ti - 43.0Al - 6.0V (at .-%) and Ti - A129.7 - V7.8 (m%).
  • the composition of the primary alloy is determined by the complete reduction of the strongly ⁇ -stabilizing element vanadium to Ti - 45.75A1 (at .-%) or Ti - A132.2 (m -%).
  • the starting materials used are titanium sponge, aluminum and vanadium.
  • a base melt electrode 2 is conventionally produced as an ingot of the binary TiAl primary alloy with a diameter of 200 mm and a length of 1 m by double VAR melting (mass 126 kg).
  • FIG. 3 shows, along the entire surface 16 of the base melt electrode 2 along axialaxialparallel eight vanadium rods 20 with a diameter of 16.7 mm and a length of 1 m (total mass 10.7 kg) each offset by 45 ° to each other and thus uniformly over the circumference of Electrode 2 distributed welded.
  • the resulting composite electrode 19 'of the binary primary alloy and the welded vanadium rods 20 is remelted in the final third melting process to an ingot of target alloy with a diameter of 300 mm in the VAR furnace 1.
  • the target composition of the ⁇ -TiAl alloy corresponds to that of Embodiment 1 (Ti - 43.5A1 - 4.0Nb - 1.0Mo - 0.1 B at .-%).
  • the composition of the primary alloy is determined by a complete reduction of the molybdenum content and a partial reduction of the titanium content to Ti - 49.63A1 - 4.57Nb - 0.11 B (at .-%).
  • a base melt electrode 2 having a diameter of 200 mm and a length of 1 m is produced by double VAR melting.
  • the ingot mass is 126 kg.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Claims (10)

  1. Procédé de fabrication d'un alliage de base γ-TiAl se solidifiant par la phase ß (alliage de base ß-γ-TiAl) par une fusion par arc sous vide,
    caractérisé par les étapes de procédé suivantes :
    - fusion d'une électrode fusible de base (2) constituée d'un alliage primaire γ-TiAl traditionnel comprenant une teneur déficitaire en titane et/ou au moins en un élément de stabilisation β par rapport à l'alliage de base ß-γ-TiAl à fabriquer dans au moins une première étape de fusion par arc sous vide,
    - mise à l'équilibre avec une quantité de titane et/ou d'élément de stabilisation ß correspondant à la teneur déficitaire en titane et/ou en élément stabilisant ß dans une distribution homogène dans la longueur et le pourtour, et
    - alliage complémentaire de la quantité de titane et/ou d'élément de stabilisation ß correspondant à la teneur déficitaire en titane et/ou en élément de stabilisation ß dans l'électrode fusible de base pour la formation de l'alliage de base ß-γ-TiAl de base dans une dernière étape de fusion par arc sous vide.
  2. Procédé de fabrication d'un alliage de base ß-γ-TiAl selon la revendication 1 caractérisé en ce que l'électrode fusible de base (2) constituée de l'alliage primaire γ-TiAl traditionnel présente une teneur en aluminium de 45 % en atomes à 50 % en atomes.
  3. Procédé de fabrication d'un alliage de base ß-γ-TiAl selon les revendications 1 ou 2 caractérisé en ce que l'électrode fusible de base (2) présente un déficit en titane et/ou au moins en un élément jouant un rôle de stabilisation ß dans l'alliage TiAl faisant partie du groupe constitué par le B, le Cr, le Cu, le Hf, le Mn, le Mo, le Nb, le Si, le Ta, le V et le Zr.
  4. Procédé de fabrication d'un alliage de base ß-γ-TiAl selon l'une des revendications précitées caractérisé en ce que l'électrode fusible de base (2) est fabriquée par une ou plusieurs opérations de fusion d'un des constituants de l'alliage de l'électrode fusible de base (2) en une électrode de pression présentant une distribution homogène.
  5. Procédé de fabrication d'un alliage de base ß-γ-TiAl selon l'une des revendications précitées caractérisé en ce que, pour équilibrer la teneur déficitaire en titane et/ou en élément de stabilisation ß pour l'électrode fusible de base, une électrode composite (19, 19') est fabriquée qui est constituée de l'électrode fusible de base (2) et, sur son pourtour et sur sa longueur, d'une couche (15) d'épaisseur régulière appropriée de titane et/ou d'élément de stabilisation ß.
  6. Procédé de fabrication d'un alliage de base ß-γ-TiAl selon la revendication 5 caractérisé en ce que la couche est constituée d'un manchon dans une plaque de titane (15) s'étendant sur la longueur de l'électrode fusible de base (2).
  7. Procédé de fabrication d'un alliage de base ß-γ-TiAl selon la revendication 6 caractérisé en ce que le manchon constitué de la plaque de titane (15) est fixé à l'électrode de soudure de base au moyen de points de soudure (18) uniformément distribués sur la surface du manchon (16) et/ou au moyen d'un cordon de soudure sur le rebord (17) supérieur de l'électrode de soudure (2) sur son pourtour entier.
  8. Procédé de fabrication d'un alliage de base ß-γ-TiAl selon la revendication 6 caractérisé en ce que le manchon constitué de la plaque de titane (15) est formé par un revêtement du manchon sur la face interne de la coquille de fusion (4) du four de fusion par arc sous vide (1), où, dans une étape intermédiaire de fusion, le manchon constitué de la plaque de titane (15) est collé par fusion sur l'électrode fusible de base (2) en formant une électrode intermédiaire et ensuite l'électrode intermédiaire est fondue une nouvelle fois dans une dernière étape de fusion par arc sous vide pour la formation de l'alliage de base homogène ß-γ-TiAl.
  9. Procédé de fabrication d'un alliage de base ß-γ-TiAl selon l'une des revendications de 1 à 4 caractérisé en ce que, pour équilibrer la teneur déficitaire en titane et/ou en élément de stabilisation ß, une quantité appropriée de titane et/ou d'élément de stabilisation ß, une électrode composite (19') est fabriquée en plus de l'électrode fusible de base, qui est constituée de l'électrode fusible de base (2) et de plusieurs tiges (20) d'épaisseur appropriée en titane et/ou en élément de stabilisation ß, disposées parallèlement à son axe longitudinal de manière uniforme sur le pourtour de l'électrode fusible de base.
  10. Procédé de fabrication d'un alliage de base ß-γ-TiAl selon l'une des revendications précitées, caractérisé en ce que la dernière étape de fusion par arc sous vide pour la formation de l'alliage de base ß-γ-TiAl homogène est effectuée dans un dispositif de fusion par arc sous vide sur skull, après quoi le produit liquide fondu constitué par l'alliage de base ß-γ-TiAl est coulé en pièces par fonderie de précision ou par fonderie en coquille de l'alliage de base ß-γ-TiAl.
EP10765988A 2009-10-24 2010-09-28 Procédé de fabrication d'un alliage de beta-gamma ti-al Active EP2342365B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009050603A DE102009050603B3 (de) 2009-10-24 2009-10-24 Verfahren zur Herstellung einer β-γ-TiAl-Basislegierung
PCT/EP2010/064306 WO2011047937A1 (fr) 2009-10-24 2010-09-28 PROCÉDÉ DE FABRICATION D'UN ALLIAGE À BASE DE ß-γ-TIAL

Publications (2)

Publication Number Publication Date
EP2342365A1 EP2342365A1 (fr) 2011-07-13
EP2342365B1 true EP2342365B1 (fr) 2013-03-06

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US (1) US8668760B2 (fr)
EP (1) EP2342365B1 (fr)
JP (1) JP5492982B2 (fr)
CN (1) CN102449176B (fr)
DE (1) DE102009050603B3 (fr)
ES (1) ES2406904T3 (fr)
RU (1) RU2490350C2 (fr)
WO (1) WO2011047937A1 (fr)

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CN102312111B (zh) * 2011-09-07 2013-02-06 上海交通大学 采用真空自耗电弧炉熔炼TiAl合金的方法
WO2013172745A1 (fr) * 2012-05-16 2013-11-21 Gkn Aerospace Sweden Ab Procédé d'application d'un alliage de titane sur un substrat
JP5857917B2 (ja) * 2012-08-28 2016-02-10 新日鐵住金株式会社 Ｎｉ基超合金の鋳塊の製造方法
CN103014386B (zh) * 2012-12-10 2014-07-09 西安诺博尔稀贵金属材料有限公司 一种铌钨钼锆合金铸锭的制备方法
CN103276229A (zh) * 2013-06-06 2013-09-04 广西大学 一种减少高温结构材料Ti-40Al-10Fe合金熔炼过程中铝烧损的熔炼方法
EP2851445B1 (fr) * 2013-09-20 2019-09-04 MTU Aero Engines GmbH Alliage TiAl résistant au fluage
WO2015058611A1 (fr) * 2013-10-23 2015-04-30 Byd Company Limited Appareil de formage de métal
CN104532061A (zh) * 2014-12-26 2015-04-22 北京科技大学 一种抗高温氧化钛铝合金及制备方法
DE102015103422B3 (de) * 2015-03-09 2016-07-14 LEISTRITZ Turbinentechnik GmbH Verfahren zur Herstellung eines hochbelastbaren Bauteils aus einer Alpha+Gamma-Titanaluminid-Legierung für Kolbenmaschinen und Gasturbinen, insbesondere Flugtriebwerke
CN104976888B (zh) * 2015-06-08 2017-03-08 重庆钢铁(集团)有限责任公司 一种真空自耗冶炼炉
DE102015115683A1 (de) * 2015-09-17 2017-03-23 LEISTRITZ Turbinentechnik GmbH Verfahren zur Herstellung einer Vorform aus einer Alpha+Gamma-Titanaluminid-Legierung zur Herstellung eines hochbelastbaren Bauteils für Kolbenmaschinen und Gasturbinen, insbesondere Flugtriebwerke
RU2621500C1 (ru) * 2015-12-21 2017-06-06 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский технологический университет "МИСиС" Интерметаллический сплав на основе TiAl
CN107385370B (zh) * 2017-06-23 2019-04-05 太原理工大学 Ti-44Al-4Nb-4V-0﹒3Mo合金细晶化热处理方法
KR102095463B1 (ko) 2018-05-24 2020-03-31 안동대학교 산학협력단 우수한 고온 성형성을 가지는 TiAl계 합금 및 이를 이용한 TiAl계 합금 부재의 제조방법
CN110814481B (zh) * 2019-10-30 2021-07-13 西部超导材料科技股份有限公司 一种钛合金用辅助电极的对焊方法
CN113234960A (zh) * 2021-05-08 2021-08-10 陕西工业职业技术学院 一种合金的制备方法
CN113351838B (zh) * 2021-05-17 2022-11-04 西部超导材料科技股份有限公司 一种用于钛合金铸锭制备的气体冷却装置、控制系统及控制方法

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CN102449176B (zh) 2014-04-16
US20110219912A1 (en) 2011-09-15
EP2342365A1 (fr) 2011-07-13
RU2011143579A (ru) 2013-05-10
JP5492982B2 (ja) 2014-05-14
DE102009050603B3 (de) 2011-04-14
CN102449176A (zh) 2012-05-09
ES2406904T3 (es) 2013-06-10
WO2011047937A1 (fr) 2011-04-28
RU2490350C2 (ru) 2013-08-20
US8668760B2 (en) 2014-03-11
JP2012527533A (ja) 2012-11-08

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