EP1584697A2 - 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
EP1584697A2
EP1584697A2 EP05290750A EP05290750A EP1584697A2 EP 1584697 A2 EP1584697 A2 EP 1584697A2 EP 05290750 A EP05290750 A EP 05290750A EP 05290750 A EP05290750 A EP 05290750A EP 1584697 A2 EP1584697 A2 EP 1584697A2
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EP
European Patent Office
Prior art keywords
aluminum
alloys
iron
ductility
molybdenum
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EP05290750A
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English (en)
French (fr)
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EP1584697B1 (de
EP1584697A3 (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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Publication of EP1584697A3 publication Critical patent/EP1584697A3/de
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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

  • the invention relates to an alloy consisting of aluminum aluminide titanium in which a minority fraction of the atoms of aluminum and titanium is replaced by other atoms.
  • TiAl intermetallic alloys find a advantageous use at high temperature in turbomachines aeronautical.
  • TiAl is characterized by its weak density which gives it a mechanical resistance to hot relative to the density higher than that of the conventional titanium alloys and even to that of some superalloys of nickel. This is due to a limit of elasticity which remains constant typically between 20 and 700 ° C. Nevertheless, the low ductility of this alloy is of a nature to compromise its use for rotating parts. So research is being done around the world for the development of transformation ranges that ductilize TiAl to allow the introduction of this material in aeronautical turbomachines. The work is parallel on the choice of shades most suited to such or such range of transformation.
  • the object of the present invention is to provide an alloy of TiAl type having 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 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 to 2% molybdenum, 0.2 to 0.5% silicon and 0 to 3% niobium.
  • the subject of the invention is also a method of treatment of an alloy as defined above, in which its constituent elements are put in solution by heating to a temperature of between 1200 ° C and 1350 ° C, cool to room temperature and annealing at a temperature between 800 ° C and 950 ° C.
  • the dissolution is carried out at 1250 ° C. about 4 hours and annealing at 900 ° C. about 4 hours.
  • alloy grades of the TiAl type (or more briefly "TiAl alloys") with high aluminum content 48% are more ductile and less resistant than shades with low aluminum content such as 44%.
  • contents greater than 48% the trend reverses quickly with reduced ductility then creep resistance and oxidation resistance are find improved.
  • the aluminum content must be locked 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 degree of precision in quantities of added elements. An ingot of several kilograms can thus present variations in levels in aluminum greater than 1% in different places, with consequence of the different properties, which may differ from user specifications.
  • aluminum is volatile during the merger, causing a loss of aluminum concentration which is dependent on the number of mergers. This is another reason why he is difficult to scrupulously respect the levels in nominal aluminum.
  • Iron has the effect of enlarging the window of aluminum for which the good compromise of properties is respected. In other words, the properties of ductility and mechanical strength remain constant over a wider aluminum content range, thus making the delicate manufacturing of alloys to obtain the desired properties.
  • TiAl alloys containing iron are distinguished by a another way. While almost all TiAl alloys in the poured state plastically deform only at temperatures above 800 ° C, the shades containing Iron 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 big number of elementary additives proved to be ineffective in the past to improve ductility at temperatures below 800 ° C. However, it has been found that the addition joint of iron and zirconium makes TiAl alloys even more ductile at 800 ° C. The advantage then removed is to be able to manufacture them by resorting to traditional shaping processes using temperatures compatible with common tools.
  • the only penalizing effect of iron that has been found is a decrease in creep resistance, which may lead to the addition of iron to small amounts (around 1%).
  • the use of silicon in the present invention can compensate for this effect by providing an extremely fast gain creep resistance, which limits its concentration at 0.5%. Indeed, higher silicon contents are discouraged because they cause the precipitation of silicides that are known to be detrimental to the ductility.
  • zirconium With regard to zirconium, it has been found that high level (5%) had the effect of delaying the transition fragile-ductile towards high temperatures and therefore counteract the beneficial effect of iron. Therefore, the zirconium content to be used must be significantly lower at 5 %. It is also preferable to limit the content of zirconium for density reasons. Finally, Macroscopic properties of TiAl can be affected by presence of zirconium due to steric effects which predominate over electronic effects. Works made by the inventors made it possible to verify that was not desirable to incorporate more than 2 to 3% of zirconium to maintain an acceptable compromise resistance-ductility.
  • the alloys according to the invention correspond to the poured state high hot ductility requirements allowing their implementation form by anisothermic 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 W, Mo, Fe and Cr which are known as ⁇ -generic elements, in that they stabilize the formation of the ⁇ phase.
  • 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.
  • 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 1% in the zirconium content (Table 2).
  • the ductility results reveal that the elongations do not exceed 1% at 20 ° C. Tungsten clearly appears to be responsible for this fragility at low temperature, 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 other 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. 200 MPa on most alloys of the previous three series in order to test them in the most close to use in aerospace 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 shades with high aluminum content, the ⁇ phase is smaller and is characterized by a dense precipitation 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 resistance to oxidation of alloys may, if necessary, be improved by introducing of a certain amount of niobium, an element known for his 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)
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 true EP1584697A2 (de) 2005-10-12
EP1584697A3 EP1584697A3 (de) 2009-07-15
EP1584697B1 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)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022200736A1 (fr) * 2021-03-25 2022-09-29 Safran Alliage de fonderie intermétallique tial
JPWO2022260026A1 (de) * 2021-06-09 2022-12-15

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US5207982A (en) 1990-05-04 1993-05-04 Asea Brown Boveri Ltd. High temperature alloy for machine components based on doped tial
US6165414A (en) 1997-12-26 2000-12-26 Ishikawajima-Harima Heavy Industries Co., Ltd. Titanium aluminide for precision casting and method of casting using titanium aluminide
US6174495B1 (en) 1998-03-25 2001-01-16 Ishikawajima-Harima Heavy Industries Co., Ltd. Titanium aluminide for precision casting

Family Cites Families (10)

* 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
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
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
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

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US5207982A (en) 1990-05-04 1993-05-04 Asea Brown Boveri Ltd. High temperature alloy for machine components based on doped tial
US6165414A (en) 1997-12-26 2000-12-26 Ishikawajima-Harima Heavy Industries Co., Ltd. Titanium aluminide for precision casting and method of casting using titanium aluminide
US6174495B1 (en) 1998-03-25 2001-01-16 Ishikawajima-Harima Heavy Industries Co., Ltd. Titanium aluminide for precision casting

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022200736A1 (fr) * 2021-03-25 2022-09-29 Safran Alliage de fonderie intermétallique tial
FR3121149A1 (fr) * 2021-03-25 2022-09-30 Safran Alliage de fonderie intermétallique TiAl
CN117043369A (zh) * 2021-03-25 2023-11-10 赛峰公司 TiAl金属间铸造合金
JPWO2022260026A1 (de) * 2021-06-09 2022-12-15

Also Published As

Publication number Publication date
EP1584697B1 (de) 2010-12-15
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

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