EP1584697B1 - Titan-Aluminium-Legierung mit ausgezeichneter Dehnbarkeit bei hohen Temperaturen - Google Patents

Titan-Aluminium-Legierung mit ausgezeichneter Dehnbarkeit bei hohen Temperaturen Download PDF

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Publication number
EP1584697B1
EP1584697B1 EP05290750A EP05290750A EP1584697B1 EP 1584697 B1 EP1584697 B1 EP 1584697B1 EP 05290750 A EP05290750 A EP 05290750A EP 05290750 A EP05290750 A EP 05290750A EP 1584697 B1 EP1584697 B1 EP 1584697B1
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Prior art keywords
iron
alloys
alloy
ductility
titanium
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Expired - Lifetime
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EP05290750A
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English (en)
French (fr)
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EP1584697A3 (de
EP1584697A2 (de
Inventor
Marc Thomas
Agnès Bachelier-Locq
Shigehisa Naka
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Office National dEtudes et de Recherches Aerospatiales ONERA
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Office National dEtudes et de Recherches Aerospatiales ONERA
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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
    • 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

  • TiAl-type intermetallic alloys find advantageous use at high temperatures in aeronautical turbomachines.
  • TiAl is characterized by its low density which gives it a higher heat resistance to the density than conventional titanium alloys and even some nickel superalloys. This is due to a yield strength which remains constant typically between 20 and 700 ° C. However, the low ductility of this alloy is likely to compromise its use for rotating parts.
  • Research is currently being conducted around the world for the development of transformation ranges that use TiAl to allow the introduction of this material into aerospace turbomachines. The work deals in parallel with the choice of the most suitable shades for this or that transformation range.
  • the object of the present invention is to provide a TiAl-type alloy having a high ductility when hot, while retaining the usual mechanical properties for these alloys.
  • the invention aims in particular at an alloy of the kind defined in the introduction, and provides that it contains in atoms 44 to 49% of aluminum, 0.5 to 3% of zirconium, 0.5 to 2% of iron, 0.5 2% molybdenum, 0.2 to 0.5% silicon, 0 to 3% niobium, the balance to 100% titanium and unavoidable impurities.
  • the subject of the invention is also a process for the heat treatment of an alloy as defined above, in which its constituent elements are dissolved by heating at a temperature of between 1200 ° C. and 1350 ° C. for approximately 4 hours. cooled to room temperature and annealed at a temperature between 800 ° C and 950 ° C for about 4 hours.
  • the dissolution is carried out at about 1250 ° C for about 4 hours and annealing at about 900 ° C for about 4 hours.
  • alloy grades of TiAl type (or more succinctly TiAl alloys) with a high aluminum content such as 48% are more ductile and less resistant than low aluminum grades such as 44%.
  • contents greater than 48% the tendency is reversed rapidly with a reduced ductility while creep resistance and oxidation resistance are improved.
  • the aluminum content must be enclosed in a window of very narrow composition (47-48%) to ensure a good compromise of properties.
  • this high sensitivity of the aluminum content of TiAl alloys is a serious handicap for their development which requires a very high precision in the amounts of added elements.
  • An ingot weighing several kilograms can thus have variations in aluminum contents of greater than 1% in different places, with the consequence of different properties, which can deviate from the specifications of the users.
  • aluminum is volatile during melting, causing a loss of aluminum concentration that is dependent on the number of fusions. This is another reason why it is difficult to scrupulously respect the nominal aluminum contents.
  • the iron has the effect of enlarging the window of aluminum content for which the good compromise of properties is respected.
  • the ductility and mechanical strength properties remain constant over a wider range of aluminum content, making it less difficult to manufacture the alloys to achieve the desired properties.
  • TiAl alloys containing iron are singularized in another way. While virtually all cast TiAl alloys deform plastically only at temperatures above 800 ° C, iron-containing grades can deform plastically at lower temperatures. The brittle-ductile transition temperature is indeed very brutal for all TiAl alloys which can therefore be classified according to this characteristic. A large number of elemental additives have proven ineffective in the past to improve ductility at temperatures below 800 ° C. However, it has been found that the addition of iron and zirconium makes the TiAl alloys even more ductile at 800 ° C. The advantage that is then removed is to be able to manufacture them using traditional shaping methods using temperatures compatible with common tools.
  • the only penalizing effect of iron that has been observed is a decrease in creep resistance, which can lead to limiting the addition of iron to small quantities (around 1%).
  • the use of silicon in the present invention can compensate for this effect by providing an extremely fast gain on creep resistance, which makes it possible to limit its concentration to 0.5%. Indeed, higher silicon contents are disadvantageous because they cause the precipitation of silicides which are known to be detrimental to ductility.
  • zirconium it has been found that a high content (5%) has the effect of repelling the brittle-ductile transition towards high temperatures and thus counteracting the beneficial effect of iron. Therefore, the zirconium content to be used should be well below 5%. It is also preferable to limit the zirconium content for density reasons. Finally, the macroscopic properties of TiAl can be affected in the presence of zirconium because of steric effects which predominate over the electronic effects. The work done by the inventors made it possible to verify that it was undesirable to incorporate more than 2 to 3% of zirconium in order to maintain an acceptable compromise between strength and ductility.
  • the alloys according to the invention are cast to the requirements of high ductility when hot for their shaping by anisothermal forging.
  • the alloys described in the examples below were manufactured using vacuum arc melting.
  • the ingots were then subjected to isostatic compaction at 1250 ° C for the closure of porosities and shrinkage.
  • the comparative characterization of the alloys took place after compaction and heat treatment.
  • the heat treatment comprises a solution of 4 hours at 1250 ° C followed by a cooling of the oven and a stress relieving annealing of 4 hours at 900 ° C. This treatment aims to generate two types of structures according to the aluminum concentration.
  • the alloys according to the invention comprise on the one hand an addition of zirconium, and on the other hand additions of elements Mo and Fe which are known as ⁇ - gene elements, in that they stabilize the formation of the ⁇ phase.
  • Other elements, W and Cr, also known as ⁇ -genes have been tested, but have not been retained in the alloy compositions of the invention.
  • the hot ductility is determined by the tensile properties at 800 ° C. Since these alloys must retain sufficient cold ductility to allow the machining and handling of parts, tensile properties at 20 ° C have also been determined.
  • the invention is illustrated hereinafter by the description of tests relating to various alloys, for each of which are successively indicated an identification number, the composition in atoms and the composition in mass.
  • a first series of tests is intended to test the combination of hardening elements (W, Mo) and a ductilizing element (Zr). Alloys containing either 2% W or 1% W + 1% Mo are prepared with, for each of these combinations, two values of Al + Mo, the aluminum content being thus chosen slightly lower in the presence of molybdenum because of the more low power ⁇ -gene molybdenum compared to that of tungsten.
  • the second series of shades is characterized by the following compositions: 1031 Ti-45Al-2W-2Cr-1ZR (Ti-29,1Al-8,8W-2,5Cr-2,2Zr) 1032 Ti-47Al-2W-2Cr-1ZR (Ti-30,7Al-8,9W-2,5Cr-2,2Zr) 1033 Ti-46Al-1FE-1W-1ZR (Ti-30,5Al-1,4Fe-4,6W-2,3Zr) 1034 Ti-48Al-1FE-1W-1ZR (Ti-32,6Al-1,4Fe-4,6W-2,3Zr)
  • the aim of this series is to test the combination of a single hardening element (W) and several ductilizing elements (Cr, Fe, Zr), which led to a reduction of the zirconium content to 1% (Table 2).
  • the ductility results reveal that the elongations do not exceed 1% at 20 ° C. Tungsten clearly appears to be responsible for this low temperature fragility, which confirms the results of the first series.
  • a 1% reduction in the hardening element content (W) is reflected in a softening manner. It should be noted that the two grades containing iron are characterized by the same ductility at 20 ° C despite the difference in aluminum content, a behavior that contrasts with other pairs of grades.
  • the single figure represents, for the alloys of the two previous series, the elastic limit and elongation at break at 20 ° C as a function of the aluminum content.
  • the points corresponding to each property are located approximately on a straight line.
  • ductility and the yield strength there is an inverse relationship between ductility and the yield strength.
  • the increase in ductility and the decrease in the yield strength as observed on the richer aluminum compositions are related to two microstructural changes.
  • the richer aluminum grade firstly has a higher monolithic ⁇ volume fraction (and correspondingly a lower lamellar fraction); however, it is known that duplex structures are more ductile and less resistant than fully lamellar structures. In addition, this shade is less rich in ⁇ phase.
  • the Ti-48Al-1Fe-1W-1Zr grade is predominantly composed of monolithic ⁇ -phase and the low volume fraction of lamellae no longer makes it possible to fractionate the grain size, which explains the level of ductility slightly reduced at ambient temperature than for other additions.
  • the incorporation of iron produces a particular effect since it makes it possible to reach a certain level of ductility for the standard heat treatment, in this case 0.8% for the alloy Ti-46Al-1Fe-1W- 1Zr, which is not the case for others shades rich in titanium.
  • the Ti-46Al-1Fe-1W-1Zr grade is characterized by the presence of a high amount of ⁇ - phase while the Ti-48Al-1Fe-1W-1Zr grade has a majority of monolithic ⁇ -phase. and a phase minority ⁇ .
  • the third series of shades is characterized by additions of iron, zirconium and molybdenum. Two shades correspond to a substitution of Mo to W with respect to the preferred shades above. The other two grades are characterized by the absence of molybdenum: 1144 Ti-46Al-1FE-1ZR-0,2Si (Ti-32A1-1,4Fe-2,4Zr-0,2Si) 1145 Ti-47Al-1FE-1ZR-0,2Si (Ti-32,9Al-1,4Fe-2,4Zr-0,2Si) 1147 Ti-46Al-1FE-1Mo-1ZR-0,2Si (Ti-31,6Al-1,4Fe-2.5Mo-2,3Zr-0,2Si) 1146 Ti-47Al-1FE-1Mo-1ZR-0,2Si (Ti-32,5Al-1,4Fe-2.5Mo-2,3Zr-0,2Si)
  • Creep tests were also carried out at 750 ° C. under 200 MPa on most alloys of the three previous series in order to test them under the conditions closest to use in aeronautical turbomachines.
  • the creep results of the first series reflect more strongly the strong influence of aluminum content and indirectly the microstructure on creep resistance than the effect of substitution of Mo to W (Table 4). Indeed, the comparison of the TiAl + 2W + 2Zr grades with different aluminum contents (1017 and 1029) reveals the high sensitivity of the creep resistance to aluminum. There is almost an order of magnitude between the secondary creep rates to the advantage of the aluminum rich shade. For low aluminum grades, the residual ⁇ phase is quite coarse. On the other hand, for the grades with a high aluminum content, the ⁇ phase is smaller and is characterized by precipitation. dense in the lamellae. These precipitates act as obstacles to deformation and explain the unexpected improvement in creep.
  • the alloys used in aeronautical turbomachines must also have good resistance to oxidation.
  • the oxidation resistance of the preferred alloys may, if necessary, be improved by the introduction of a certain amount of niobium, an element known for its favorable action on this property.

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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)
  • Turbine Rotor Nozzle Sealing (AREA)
  • Powder Metallurgy (AREA)
  • Laminated Bodies (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Furnace Charging Or Discharging (AREA)
  • Heat Treatment Of Steel (AREA)

Claims (7)

  1. Legierung gebildet aus Titan-Aluminid, bei dem ein minoritärer Bruchteil von Aluminium- und Titanatomen ersetzt ist durch andere Atome, dadurch gekennzeichnet, dass sie an Atomen 44 bis 49% Aluminium, 0,5 bis 3% Zirkonium, 0,5 bis 2% Eisen, 0,5 bis 2% Molybdän, 0,2 bis 0,5% Silizium, 0 bis 3% Niob, die Ergänzung zu 100% Titan und unvermeidbare Verunreinigungen aufweist.
  2. Legierung nach Anspruch 1, die an Atomen 45 bis 48% Aluminium, ungefähr 1% Zirkonium, ungefähr 1% Eisen, ungefähr 1% Molybdän und ungefähr 0,2% Silizium enthält.
  3. Legierung nach Anspruch 2, die an Atomen ungefähr 46% Aluminium enthält.
  4. Legierung nach Anspruch 2, die an Atomen ungefähr 47% Aluminium enthält.
  5. Legierung nach einem der vorhergehenden Ansprüche, die ausschließlich gebildet ist aus Aluminium, Titan, Zirkonium, Eisen, Molybdän, Silizium und gegebenenfalls Niob, unter dem Vorhandensein von möglichen Verunreinigungen.
  6. Verfahren zur thermischen Behandlung einer Legierung nach einem der vorhergehenden Ansprüche, bei dem die sie bildenden Elemente in Lösung gesetzt werden durch Erwärmen auf eine Temperatur zwischen 1.200°C und 1.350°C während ungefähr vier Stunden, auf Umgebungstemperatur abgekühlt und erneut bei einer Temperatur zwischen 800°C und 950°C während ungefähr vier Stunden ausgeglüht wird.
  7. Verfahren nach Anspruch 6, bei dem das In-Lösung-Setzen bei ungefähr 1.250°C während ungefähr vier Stunden und das Ausglühen bei ungefähr 900°C während ungefähr vier Stunden durchgeführt wird.
EP05290750A 2004-04-07 2005-04-05 Titan-Aluminium-Legierung mit ausgezeichneter Dehnbarkeit bei hohen Temperaturen Expired - Lifetime EP1584697B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR0403658A FR2868791B1 (fr) 2004-04-07 2004-04-07 Alliage titane-aluminium ductile a chaud
FR0403658 2004-04-07

Publications (3)

Publication Number Publication Date
EP1584697A2 EP1584697A2 (de) 2005-10-12
EP1584697A3 EP1584697A3 (de) 2009-07-15
EP1584697B1 true EP1584697B1 (de) 2010-12-15

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EP (1) EP1584697B1 (de)
AT (1) ATE491819T1 (de)
DE (1) DE602005025273D1 (de)
FR (1) FR2868791B1 (de)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR3121149B1 (fr) * 2021-03-25 2023-04-21 Safran Alliage de fonderie intermétallique TiAl
JP7732507B2 (ja) * 2021-06-09 2025-09-02 株式会社Ihi ＴｉＡｌ合金、ＴｉＡｌ合金粉末、ＴｉＡｌ合金部品及びその製造方法

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3203794A (en) * 1957-04-15 1965-08-31 Crucible Steel Co America Titanium-high aluminum alloys
JP2569710B2 (ja) * 1988-04-04 1997-01-08 三菱マテリアル株式会社 常温靱性を有するＴｉ−Ａ▲ｌ▼系金属間化合物型鋳造合金
US4983357A (en) 1988-08-16 1991-01-08 Nkk Corporation Heat-resistant TiAl alloy excellent in room-temperature fracture toughness, high-temperature oxidation resistance and high-temperature strength
JPH03257130A (ja) * 1990-03-05 1991-11-15 Daido Steel Co Ltd Ｔｉ―Ａｌ系耐熱材料
JPH03285051A (ja) * 1990-03-30 1991-12-16 Sumitomo Light Metal Ind Ltd チタニウムアルミナイドの鍛造方法
DE59106459D1 (de) * 1990-05-04 1995-10-19 Asea Brown Boveri Hochtemperaturlegierung für Maschinenbauteile auf der Basis von dotiertem Titanaluminid.
JPH0441682A (ja) * 1990-06-08 1992-02-12 Sumitomo Light Metal Ind Ltd チタニウムアルミナイド製内燃機関用吸、排気バルブ
JP3283546B2 (ja) * 1991-07-26 2002-05-20 大同特殊鋼株式会社 Ｔｉ Ａｌ，Ｔｉ３Ａｌ 金属間化合物製部材用耐酸化性肉盛材およびＴｉ Ａｌ，Ｔｉ３Ａｌ 金属間化合物製バルブ
JPH06192776A (ja) * 1992-12-28 1994-07-12 Sumitomo Metal Ind Ltd 常温延性に優れるＴｉＡｌ基合金部品とその製造方法
GB9714391D0 (en) * 1997-07-05 1997-09-10 Univ Birmingham Titanium aluminide alloys
JPH11193431A (ja) 1997-12-26 1999-07-21 Ishikawajima Harima Heavy Ind Co Ltd 精密鋳造用チタンアルミナイド及びその製造方法
JPH11269584A (ja) 1998-03-25 1999-10-05 Ishikawajima Harima Heavy Ind Co Ltd 精密鋳造用チタンアルミナイド
JP3915324B2 (ja) * 1999-06-08 2007-05-16 石川島播磨重工業株式会社 チタンアルミナイド合金材料及びその鋳造品
DE10024343A1 (de) * 2000-05-17 2001-11-22 Gfe Met & Mat Gmbh Bauteil auf Basis von gamma-TiAl-Legierungen mit Bereichen mit gradiertem Gefüge

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Publication number Publication date
DE602005025273D1 (de) 2011-01-27
FR2868791B1 (fr) 2006-07-14
ATE491819T1 (de) 2011-01-15
FR2868791A1 (fr) 2005-10-14
EP1584697A3 (de) 2009-07-15
EP1584697A2 (de) 2005-10-12

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