EP2185738B1 - Fabrication d'alliages a base d'aluminures de titane - Google Patents

Fabrication d'alliages a base d'aluminures de titane Download PDF

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Publication number
EP2185738B1
EP2185738B1 EP08749011A EP08749011A EP2185738B1 EP 2185738 B1 EP2185738 B1 EP 2185738B1 EP 08749011 A EP08749011 A EP 08749011A EP 08749011 A EP08749011 A EP 08749011A EP 2185738 B1 EP2185738 B1 EP 2185738B1
Authority
EP
European Patent Office
Prior art keywords
alloy
titanium
halogens
aluminide
halogen
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
EP08749011A
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German (de)
English (en)
Other versions
EP2185738A2 (fr
Inventor
Jonathan Paul
Fritz Appel
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 Hereon GmbH
Original Assignee
Helmholtz Zentrum Geesthacht Zentrum fuer Material und Kustenforschung GmbH
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Publication date
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Publication of EP2185738A2 publication Critical patent/EP2185738A2/fr
Application granted granted Critical
Publication of EP2185738B1 publication Critical patent/EP2185738B1/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
    • 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
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0408—Light metal alloys
    • C22C1/0416—Aluminium-based alloys
    • 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
    • C22C21/00—Alloys based on aluminium
    • C22C21/003—Alloys based on aluminium containing at least 2.6% of one or more of the elements: tin, lead, antimony, bismuth, cadmium, and titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • the invention relates to a method for producing an alloy based on titanium aluminides.
  • Alloys based on titanium aluminides prepared using melt and powder metallurgy techniques with a predetermined alloy composition of titanium and aluminum and optionally other constituents, e.g. Niobium, boron, chromium, molybdenum, manganese and vanadium etc. as well as carbon in different compositions are known in the art.
  • Titanium aluminide alloys have properties that are particularly favorable for use as a lightweight material, especially for high temperature applications. These lightweight materials based on titanium aluminides open due to their strength and creep properties at high temperatures Possibilities for the production of mechanically stressed components in the high temperature technology, eg as turbine blades in the aircraft industry, final stage blades, engine valves, etc. In addition, they offer because of their low density (about 3.8 - 4.3 g / cm 3 ) as a substitute for nickel base Superalloys, which typically have a density of 8.5 g / cm 3 .
  • titanium aluminide alloys The approach of titanium aluminide alloys is limited by its limited oxidation resistance to temperatures below about 750 ° C.
  • halogen effect is significantly improved by small amounts of halogens in the surface of the titanium aluminide materials, whereby the range of application of the materials is extended to temperatures above 1000 ° C.
  • DE-A-103 51 946 discloses a method of treating the surface of a titanium aluminide alloy-based member to improve its oxidation resistance. Further disclosed DE-C-196 27 605 a method of increasing corrosion resistance for titanium aluminide based alloys wherein halogens are transferred to the material surface via the ion implantation process.
  • intermetallic compounds of the Ti-Al system comprising essentially titanium and aluminum, wherein the intermetallic compound of the Ti-Al system has at least one surface layer which 0.005 at% to 1.0 at% of at least one halogen element selected from the group consisting of fluorine, chlorine, bromine and iodine.
  • US-A-5 520 879 a method for producing sintered titanium alloys, wherein titanium powder is subjected to a rubbing process in one method step.
  • EP-A-0 770 702 discloses a method for increasing the corrosion resistance of Ti-Al based alloys, wherein halogens or halogen containing compounds are transferred to the surface of the material.
  • the present invention seeks to provide titanium aluminide alloys having a high oxidation resistance, wherein when using the alloys or when using the alloys any damage to the alloy in the surface should have no effect on the oxidation resistance. Furthermore, the object is to provide a component of a corresponding titanium aluminide alloy. This is done according to the method of claim 1, to which the invention is limited.
  • metal droplets are obtained from a titanium aluminide molten metal, particularly using the gas atomization method, the metal droplets are enriched with halogens by the action of a halogen-containing gas, so that halogen-enriched titanium-aluminide metal droplets or halogen-enriched TiAl metal powder
  • the alloy is formed.
  • halogen-containing gas is used to enrich metal droplets with halogens, it is achieved that the entire material from the titanium aluminide alloy halogens are alloyed, whereby a fine or homogeneous distribution of the halogens throughout the material and in each sub-volume of the material or the alloy and not only on the surface of the material or the alloy is achieved.
  • Halogens are also in deeper layers than the previous known oxidation layers of titanium aluminide alloys, which are larger or lower, for example, in depths of more than 100, 200, 300, 400, 500 microns and more below the surface of the alloy or present throughout the alloy, whereby the oxidation resistance even after damage to the surface of a titanium aluminide alloy produced component is or is maintained, as well as in depth by the introduced, in particular homogeneously distributed or evenly distributed random halogens in the alloy or in the material, the oxidation resistance of the entire alloy is maintained.
  • Chlorine and / or fluorine are preferably introduced as halogens into the bulk material prepared from titanium aluminide. Moreover, the use of other halogens, e.g. of iodine and / or bromine possible.
  • hot isostatic pressing achieves an alloy with high isotropy and uniform compaction of the material.
  • the process of hot isostatic pressing takes place at very high pressures, e.g. 100 Mpa and under high temperatures, e.g. between 1000 ° C to 2000 ° C, instead.
  • the molten metal and / or the metal droplets are treated by means of a carrier gas, preferably by means of an inert gas, wherein in particular the carrier gas is mixed with the halogen-containing gas or is.
  • inert gases such as argon or helium or other inert gases have proven to be effective, whereby when mixed with a halogen-containing gas, the molten metal is treated specifically to enrich the metal droplets with halogens.
  • a titanium-aluminide metal powder is formed from the halogen-enriched metal droplets, from which the alloy is formed. This is usually done by hot isostatic pressing.
  • the molded alloy is made into a member having high oxidation resistance even if the surface of the component is damaged.
  • the components may be components for example from the automotive, aerospace, aircraft and industrial machine tools sector.
  • the metal powder has an intensive contact with ball milling and introduction of gases in the ball mill, a, in particular homogeneous, enrichment of powdered titanium aluminide is also achieved, whereby the halogens are distributed throughout the alloy produced or formed.
  • the Distribution of the halogens in the alloy is such that the (relative) content in any predetermined volume or partial volume or even in small partial volume of the finished alloy Halogens (per volume) is almost constant or kept constant.
  • the halogen-enriched atmosphere is provided as a gaseous and / or liquid atmosphere, whereby an intense exchange or intensive accumulation of the powder in the gaseous or in the liquid, halogen-containing atmosphere, such as in liquid carbon tetrachloride ( CCl 4 ).
  • the halogen-enriched atmosphere in particular gaseous atmosphere, with at least one inert gas, such as argon or helium provided.
  • a component is produced from the alloy with a constant (relative) proportion of halogens in each volume or partial volume or volume of the alloy.
  • a process for producing a titanium aluminide based alloy wherein powdered titanium aluminide, in particular titanium aluminide metal powder, is heated in a, preferably closed, container for a predetermined period of time, wherein in the container is a halogenated atmosphere or so that halogen-enriched titanium aluminide metal powder is formed during the heating period, and then the halogen-enriched titanium aluminide metal powder is alloyed by, preferably, hot isostatic pressing.
  • an alloy which has the same advantages as the above-described manufactured alloys in the same way.
  • titanium-aluminide alloys are also prepared in which halogens are added to the entire material, wherein the (relative) proportion of halogens (by volume) in the alloy over the entire volume or in a (small) sub-volume of
  • the proportion of halogens may vary with a typical fluctuation range of ⁇ 15%, preferably ⁇ 10%, more preferably ⁇ 5%, since the proportion of halogens in the alloy between 0.005 at% to 1.5 at%, preferably between 0.005 at% or 0.01 at% to 0.9 at%.
  • halogens in addition to fluorine and / or chlorine, in a Alloy are distributed, other halogens such as bromine and / or iodine can be used.
  • halogen-like compounds for example silicon-halogen-containing compounds or silicon-halogen mixtures, are used in the processes mentioned, which likewise have a positive influence on the oxidation resistance of the alloy.
  • a halogen-containing gas is understood as meaning a gas which, in addition to other gases, preferably inert gases, has both a halogen element and a mixture of a plurality of halogen elements.
  • the pulverulent titanium aluminide in particular titanium aluminide metal powder
  • a further method step in the gassing of the metal powder is characterized in that the atmosphere enriched with halogens with at least one inert gas, in particular after evacuation of the container is provided.
  • the container and / or the powdered titanium aluminide are heated to a temperature between 300 ° C to 1300 ° C, preferably between 500 ° C to 1000 ° C, whereby a good enrichment of the metal powder with halogens or halogen-like compounds is achieved.
  • the process steps evacuation, gasification and heating can also be carried out several times in succession to achieve a higher concentration of halogens.
  • the powdered titanium aluminide in particular titanium-aluminide metal powder, subjected to negative pressure or a vacuum.
  • a component is provided which is made of an alloy which is produced by the method according to the invention or according to the method steps.
  • Titanium aluminide alloys are preferably prepared using casting metallurgy or powder metallurgy techniques, and titanium aluminide alloys are used to carry out the processes In powder form usually present to the metal powders with halogens. Titanium aluminide components are usually produced in accordance with the known forming processes and atomization processes.
  • the TiAl based intermetallic compounds may be alloys having a general composition of titanium and aluminum according to the desired and predetermined requirements in the alloy.
  • Titanium aluminide alloys produced by the processes presented can generally have, for example, between 30 atom% to 70 atom% aluminum, with additional substances or elements, which are mentioned below, corresponding to the desired requirements for the alloy or alloy the material is absorbed.
  • the alloys may have aluminum contents between 44 atom% to 49 atom% Al.
  • other ingredients such as e.g. Chromium (Cr), niobium (Nb), manganese (Mn), vanadium (V), tantalum (Ta), molybdenum (Mo), zirconium (Zr), tungsten (W), silicon (Si) and, if necessary, additions of carbon (C) and / or boron (B), these additives may have a proportion of 0.1 at% to 10 at%.
  • Alloys which are based on the intermetallic phase ⁇ (TiAl) of a tetragonal structure are also of interest for industrial practice.
  • These ⁇ -titanium aluminide alloys are characterized by properties such as a low density (3.85 to 4.3 g / cm 3 ), high elastic modulus and high strength and creep resistance up to 700 ° C.
  • a particularly high-strength titanium aluminide alloy is an alloy composition of titanium, aluminide and niobium, to which optional components of boron and / or carbon are added, the proportion of boron and / or carbon in the alloy being below a concentration of 0.5 atom%. is selected.
  • the titanium aluminide alloy has a composition of Ti-45 at% Al-x Nb with 5 at% ⁇ x ⁇ 10 at% and optionally up to 0.5 at% B (boron) and / or up to 0.5 atom % C (carbon).
  • the methods can also provide titanium aluminide alloys having a fine and homogeneous grain morphology, wherein the titanium aluminides have an alloy composition of Ti-z Al-y Nb of 44.5 at% ⁇ z ⁇ 47 at%, especially at 44.5 Atom% ⁇ z ⁇ 45.5 atomic%, and 5 atomic% ⁇ y ⁇ 10 atomic%, wherein this molybdenum (Mo) ranges between 0.1 atomic% to 3.0 atomic%.
  • the rest of the alloy is Ti (titanium).
  • the abovementioned alloy likewise contains boron, preferably with a boron content in the alloy in the range from 0.05 atom% to 0.8 atom%.
  • boron advantageously results in the formation of stable precipitates which contribute to the mechanical hardening of the alloy and stabilization of the microstructure of the alloy.
  • the alloy contains carbon, preferably with a carbon content in the range of 0.05 at% to 0.8 at%.
  • carbon preferably in combination with the above-described additive boron, leads to the formation of stable precipitates, which also contribute to the mechanical hardening of the alloy and to the stabilization of the structure.
  • an alloy based on titanium aluminides prepared by using melting and powder metallurgy techniques and having an alloy composition of Ti - Z Al - y Nb - x B having 44.5 at% ⁇ z ⁇ 47 at%, especially at 44.5 at % ⁇ z ⁇ 45.5 at%, 5 at% ⁇ y ⁇ 10 at% and 0.05 at% ⁇ x ⁇ 0.8 at%, wherein this molybdenum (Mo) ranges between 0.1 at% to 3 Atom atom%, a titanium aluminide alloy having a fine and homogeneous grain morphology is provided to form a stable ⁇ phase at high temperatures above 700 ° C.
  • Mo molybdenum
  • an alloy composition of Ti - z Al - y Nb - w C shows 44.5 at% ⁇ z ⁇ 47 at%, in particular at 44.5 at% ⁇ z ⁇ 45.5 at%, 5 at% ⁇ y ⁇ 10 atomic% and 0.05 atomic% ⁇ w ⁇ 0.8 atomic%, said molybdenum (Mo) im Range between 0.5 atom% to 3 atom%, a fine and homogeneous Gefömgemorphologie, with the formation of the ⁇ -phase, this ⁇ -phase to temperatures of 1320 ° C are stable.
  • a corresponding TiAl alloy as metal powder or in powder form for carrying out any of the above-mentioned processes in order to obtain a TiAl alloy by halogenation of the TiAl metal powder in a small partial volume at the surface and in the depth has a nearly constant relative proportion of halogens, whereby the oxidation resistance of the material or the entire alloy is improved.
  • silicons or combinations of halogens with halogens are further employed in the practice of the processes, thereby improving the oxidation resistance of the titanium aluminide alloys produced by enhancing the oxidation resistance enhancing elements at both the surface and the surface Material are consistently homogeneous or distributed statistically distributed.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Claims (4)

  1. Procédé de fabrication d'un alliage à base d'aluminures de titane, dans lequel une poudre contenant du titane et une poudre contenant de l'aluminium ou un aluminure de titane en poudre, en particulier une poudre métallique d'aluminure de titane, sont broyées à l'aide d'un broyeur, de préférence sont broyées à l'aide d'un broyeur à billes, une atmosphère enrichie en halogènes étant ou ayant été mise à disposition pendant l'opération de broyage dans le broyeur, de préférence un broyeur à billes, de façon qu'il se forme pendant l'opération de broyage une poudre métallique d'aluminure de titane enrichie en halogènes, puis l'aluminure de titane en poudre enrichi en halogènes est façonné par compression, de préférence par compression isostatique à chaud, pour donner un alliage, la proportion des halogènes dans l'alliage étant comprise entre 0,005 et 1,5 % en atomes.
  2. Procédé selon la revendication 1, caractérisé en ce que l'atmosphère enrichie en halogènes est mise à disposition sous forme d'une atmosphère gazeuse et/ou liquide.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que l'atmosphère enrichie en halogènes est mise à disposition avec au moins un gaz inerte.
  4. Procédé selon l'une des revendications 1 à 3, caractérisé en ce qu'on fabrique un composant à partir de l'alliage.
EP08749011A 2007-07-10 2008-04-21 Fabrication d'alliages a base d'aluminures de titane Not-in-force EP2185738B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102007032406A DE102007032406B3 (de) 2007-07-10 2007-07-10 Herstellung von Legierungen auf Basis von Titanaluminiden
PCT/EP2008/003173 WO2009006954A2 (fr) 2007-07-10 2008-04-21 Fabrication d'alliages à base d'aluminures de titane

Publications (2)

Publication Number Publication Date
EP2185738A2 EP2185738A2 (fr) 2010-05-19
EP2185738B1 true EP2185738B1 (fr) 2012-02-22

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP08749011A Not-in-force EP2185738B1 (fr) 2007-07-10 2008-04-21 Fabrication d'alliages a base d'aluminures de titane

Country Status (8)

Country Link
US (1) US20100119402A1 (fr)
EP (1) EP2185738B1 (fr)
JP (1) JP2010532822A (fr)
CN (1) CN101796205B (fr)
AT (1) ATE546556T1 (fr)
DE (1) DE102007032406B3 (fr)
ES (1) ES2378254T3 (fr)
WO (1) WO2009006954A2 (fr)

Families Citing this family (10)

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Publication number Priority date Publication date Assignee Title
CN102513537B (zh) * 2011-12-06 2013-07-17 中国航空工业集团公司北京航空材料研究院 一种氩气雾化粉末TiAl合金板材的制备方法
US9650309B2 (en) 2012-04-12 2017-05-16 Iowa State University Research Foundation, Inc. Stability of gas atomized reactive powders through multiple step in-situ passivation
US9833837B2 (en) * 2013-06-20 2017-12-05 Iowa State University Research Foundation, Inc. Passivation and alloying element retention in gas atomized powders
CN105274392B (zh) * 2015-10-26 2017-07-28 鲁东大学 一种汽车涡轮增压器涡轮叶片的制备方法
CN106835227B (zh) * 2016-12-05 2018-11-13 浙江工业大学 一种基于卤素效应和陶瓷涂层提高钛基合金抗高温氧化性能的方法
CN106906504B (zh) * 2016-12-31 2019-01-18 浙江工业大学 一种基于卤素效应和SiO2-水玻璃复合陶瓷涂层提高钛基合金抗高温氧化性能的方法
CN106906505B (zh) * 2016-12-31 2019-01-08 浙江工业大学 一种基于卤素效应和预处理得到陶瓷涂层提高钛基合金抗高温氧化性能的方法
WO2019140048A1 (fr) * 2018-01-12 2019-07-18 Arconic Inc. Procédés pour la production de matériaux en aluminiure de titane
EP3943208A4 (fr) 2019-03-18 2022-11-09 IHI Corporation Matériau en alliage d'aluminure de titane pour forgeage à chaud, et procédé de forgeage de matériau en alliage d'aluminure de titane
CN110605401B (zh) * 2019-10-09 2021-03-16 中南大学 一种钛铝合金粉末的制备方法

Citations (2)

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WO1995002252A1 (fr) * 1993-07-08 1995-01-19 Ugimag S.A. Procede de preparation de poudres magnetiques de type terres rares-cobalt contenant du fluor et aimants permanents densifies correspondants
US5411603A (en) * 1993-01-22 1995-05-02 Ugimag Sa Method of protecting magnetic powders and densified permanent magnets of the Fe Nd B type from oxidation and atmospheric corrosion

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US4915908A (en) * 1984-10-19 1990-04-10 Martin Marietta Corporation Metal-second phase composites by direct addition
EP0484931B1 (fr) * 1990-11-09 1998-01-14 Kabushiki Kaisha Toyota Chuo Kenkyusho Alliage de titane préparé par frittage de poudres et procédé pour leur fabrication
US5451366A (en) * 1992-07-17 1995-09-19 Sumitomo Light Metal Industries, Ltd. Product of a halogen containing Ti-Al system intermetallic compound having a superior oxidation and wear resistance
EP0770702A1 (fr) * 1995-10-23 1997-05-02 DECHEMA Deutsche Gesellschaft für Chemisches Apparatewesen, Chemische Technik und Biotechnologie e.V. Procédé pour augmenter la résistance à la corrosion des alliages à base de TiAl
DE19627605C1 (de) * 1996-07-09 1997-07-10 Dechema Verfahren zur Erhöhung der Korrosionsbeständigkeit von Werkstoffen auf der Basis TiAl über die Implantation von Halogenionen in die Werkstoffoberfläche
DE10351946A1 (de) * 2003-03-21 2004-10-07 Dechema Gesellschaft Für Chemische Technik Und Biotechnologie E.V. Verfahren zur Behandlung der Oberfläche eines aus einer AL-Legierung, insbesondere TiAL-Legierung bestehenden Bauteiles sowie die Verwendung organischer Halogenkohlenstoffverbindungen oder in einer organischen Matrik eingebundener Halogenide

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
US5411603A (en) * 1993-01-22 1995-05-02 Ugimag Sa Method of protecting magnetic powders and densified permanent magnets of the Fe Nd B type from oxidation and atmospheric corrosion
WO1995002252A1 (fr) * 1993-07-08 1995-01-19 Ugimag S.A. Procede de preparation de poudres magnetiques de type terres rares-cobalt contenant du fluor et aimants permanents densifies correspondants

Also Published As

Publication number Publication date
US20100119402A1 (en) 2010-05-13
CN101796205B (zh) 2012-07-25
CN101796205A (zh) 2010-08-04
WO2009006954A2 (fr) 2009-01-15
DE102007032406B3 (de) 2008-10-23
ATE546556T1 (de) 2012-03-15
WO2009006954A3 (fr) 2010-04-15
ES2378254T3 (es) 2012-04-10
JP2010532822A (ja) 2010-10-14
EP2185738A2 (fr) 2010-05-19

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