EP1640465B1 - Alliage de Ni-Cr-Co-Mo pour un moteur à turbine à gaz - Google Patents

Alliage de Ni-Cr-Co-Mo pour un moteur à turbine à gaz Download PDF

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EP1640465B1
EP1640465B1 EP05018830A EP05018830A EP1640465B1 EP 1640465 B1 EP1640465 B1 EP 1640465B1 EP 05018830 A EP05018830 A EP 05018830A EP 05018830 A EP05018830 A EP 05018830A EP 1640465 B1 EP1640465 B1 EP 1640465B1
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alloy
alloys
chromium
nickel
gas turbine
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EP1640465A2 (fr
EP1640465A3 (fr
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Lee M. Pike Jr.
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Haynes International Inc
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C19/00—Alloys based on nickel or cobalt
    • C22C19/03—Alloys based on nickel or cobalt based on nickel
    • C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/056—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 10% but less than 20%

Definitions

  • This invention relates to wroughtable high strength alloys for use at elevated temperatures.
  • it is related to alloys which possess sufficient creep strength, thermal stability, and resistance to strain age cracking to allow for fabrication and service in gas turbine transition ducts and other gas turbine components.
  • Transition ducts are often welded components made of sheet or thin plate material and thus need to be weldable as well as wroughtable.
  • gamma-prime strengthened alloys are used in transition ducts due to their high-strength at elevated temperatures.
  • current commercially available wrought gamma-prime strengthened alloys either do not have the strength or stability to be used at the very high temperatures demanded by advanced gas turbine design concepts, or can present difficulties during fabrication.
  • one such fabrication difficulty is the susceptibility of many wrought gamma-prime strengthened alloys to strain age cracking. The problem of strain age cracking will be described in more detail later in this document.
  • Wrought gamma-prime strengthened alloys are often based on the nickel-chromium-cobalt system, although other base systems are also used. These alloys will typically have aluminum and titanium additions which are responsible for the formation of the gamma-prime phase, Ni 3 (Al,Ti). Other gamma-prime forming elements, such as niobium and/or tantalum, can also be employed.
  • An age-hardening heat treatment is used to develop the gamma-prime phase into the alloy microstructure. This heat treatment is normally given to the alloy when it is in the annealed condition. The presence of gamma-prime phase leads to a considerable strengthening of the alloy over a broad temperature range.
  • Other elemental additions may include molybdenum or tungsten for solid solution strengthening, carbon for carbide formation, and boron for improved high temperature ductility.
  • Strain age cracking is a problem which limits the weldability of many gamma-prime strengthened alloys. This phenomenon typically occurs when a welded part is subjected to a high temperature for the first time after the welding operation. Often this is during the post-weld annealing treatment given to most welded gamma-prime alloy fabrications. The cracking occurs as a result of the formation of the gamma-prime phase during the heat up to the annealing temperature. The formation of the strengthening gamma-prime phase in conjunction with the low ductility many of these alloys possess at intermediate temperatures, as well as the mechanical restraint typically imposed by the welding operation will often lead to cracking. The problem of strain age cracking can limit alloys to be used up to only a certain thickness since greater material thickness leads to greater mechanical restraint.
  • CHRT controlled heating rate tensile
  • the test sample is pulled to fracture at a constant engineering strain rate.
  • the test sample starts in the annealed (not age-hardened) condition, so that the gamma-prime phase is precipitating during the heat-up stage as would be the case in a welded component being subjected to a post-weld heat treatment.
  • the percent elongation to fracture in the test sample is taken as a measure of susceptibility to strain age cracking (lower elongation values suggesting greater susceptibility to strain age cracking).
  • the elongation in the CHRT is a function of test temperature and normally will exhibit a minimum at a particular temperature. The temperature at which this occurs is around 816°C (1500°F) for many wrought gamma-prime strengthened alloys.
  • High temperature strength has long been evaluated with the use of creep-rupture tests, where samples are isothermally subjected to a constant load until the sample fractures. The time to fracture, or rupture life, is then used as a measure of the alloy strength at that temperature.
  • Thermal stability is a measure of whether the alloy microstructure remains relatively unaffected during a thermal exposure. Many high-temperature alloys can form brittle intermetallic or carbide phases during thermal exposure. The presence of these phases can dramatically reduce the room-temperature ductility of the material. This loss of ductility can be effectively measured using a standard tensile test.
  • Rene-41 or R-41 alloy U.S. Patent No. 2,945,758
  • M-252 alloy U.S. Patent No. 2,747,993
  • the M-252 alloy has good creep strength and resistance to strain age cracking, but like R-41 alloy is limited by poor thermal stability.
  • the Pratt & Whitney developed alloy known commercially as WASPALOY alloy (apparently having no U.S. patent coverage) is another gamma-prime strengthened alloy intended for use in turbine engines and available in sheet form. However, this alloy has marginal creep strength above 1500°F, marginal thermal stability, and has fairly poor resistance to strain age cracking.
  • the alloy commercially known as 263 alloy ( U.S. Patent 3,222,165 ) was developed in the late 1950's and introduced in 1960 by Rolls-Royce Limited. This alloy has excellent thermal stability and resistance to strain age cracking, but has very poor creep strength at temperatures greater than 816°C (1500°F).
  • the PK-33 alloy ( U.S. Patent No. 3,248,213 ) was developed by the International Nickel Company and introduced in 1961.
  • US 3207599 also discloses a creep resistant nickel based alloy having good strain age ductility and weldability but contains silicon and manganese. As suggested by these examples, no currently commercially available alloys are available which possess the unique combination of three key properties: good creep strength and good thermal stability in the 871°C-927°C (1600 to 1700°F) temperature range as well as good resistance to strain age cracking.
  • the principal objective of this invention is to provide new wrought age-hardenable nickel-chromium-cobalt based alloys which are suitable for use in high temperature gas turbine transition ducts and other gas turbine components possessing a combination of three specific key properties, namely resistance to strain age cracking, good thermal stability, and good creep-rupture strength.
  • the wrought age-hardenable nickel-chromium-cobalt based alloys described here have sufficient creep strength, thermal stability, and resistance to strain age cracking to allow for service in sheet or plate form in gas turbine transition ducts as well as in other product forms and other demanding gas turbine applications.
  • This combination of critical properties is achieved through control of several critical elements each with certain functions.
  • the presence of gamma-prime forming elements such as aluminum, titanium, and niobium contribute significantly to the high creep-rupture strength through the formation of the gamma-prime phase during the age-hardening process.
  • the combined amount of aluminum, titanium, and niobium must be carefully controlled to allow for good resistance to strain age cracking.
  • Molybdenum and possibly tungsten are added to provide additional creep-rupture strength through solid solution strengthening. Again, however, the total combined molybdenum and tungsten concentration must be carefully controlled, in this case to ensure sufficient thermal stability of the alloy.
  • gamma-prime strengthened alloys Based on the projected requirements for the next generation of gas turbine transition ducts, gamma-prime strengthened alloys have significant potential. Three of the more critical properties are creep strength, weldability (i.e. strain age cracking resistance), and thermal stability. However, producing a gamma-prime strengthened alloy which excels in all three of these properties is not straightforward and no commercially available alloy was found which possessed all three properties to a sufficient degree.
  • the experimental alloys have been labeled A through Z.
  • the commercial alloys were HAYNES R-41 alloy, HAYNES WASPALOY alloy, HAYNES 263 alloy, M-252 alloy, and NIMONIC PK-33 alloy.
  • the alloys (including both the experimental and the commercial alloys) had a Cr content which ranged from 17.5 to 21.3 wt.%, as well as a cobalt content ranging from 8.3 to 19.6 wt.%.
  • the aluminum content ranged from 0.49 to 1.89 wt.%, the titanium content from 1.53 to 3.12 wt.%, and the niobium content ranged from nil to 0.79 wt.%.
  • the molybdenum content ranged from 3.2 to 10.5 wt.% and the tungsten ranged from nil up to 8.3 wt.%.
  • Intentional minor element additions carbon and boron ranged from 0.034 to 0.163 wt.% and from nil to 0.008 wt.%, respectively.
  • Iron ranged from nil to 3.6 wt.%.
  • the cold rolled sheets were annealed at temperatures between 1121-1190°C (2050 and 2175°F) as necessary to produce a fully recrystallized, equiaxed grain structure with an ASTM grain size between 4 and 5. Finally, the sheet material was given an age-hardening heat treatment of 802°C (1475°F) for 8 hours to produce the gamma-prime phase.
  • the commercial alloys HAYNES R-41 alloy, HAYNES WASPALOY alloy, HAYNES 263 alloy, and NIMONIC PK-33 alloy were obtained in sheet form in the mill annealed condition. Since no commercially available M-252 alloy sheet could be found, a 22 kg (50 lb). heat was produced for evaluation using the same method as described above for the experimental alloys. All five of the commercial alloys were given post-anneal age-hardening heat treatments according accepted standards. These heat treatments are reported in Table 2.
  • the critical property in this test is the tensile ductility, as measured by a measurement of the elongation to failure. Alloys with a greater ductility in this test are expected to have greater resistance to strain age cracking. The objective of the present study was to have a ductility of 4.5% or greater. Of the experimental alloys, only alloy W failed to meet this requirement.
  • the tensile ductility (measured as the percent elongation to failure) is plotted as a function of the compositional variable A1 + 0.56Ti + 0.29Nb (where the elemental compositions are in wt.%).
  • a line is drawn on the figure corresponding to a tensile ductility of 4.5%. All alloys plotted above this line (symbol: filled circles) were considered to have passed the controlled heating rate tensile test, while alloys plotted below the line (symbol: x-marks) were considered to have failed.
  • a dashed vertical line is drawn at a value of 2.9 wt.% for the compositional variable, Al + 0.56Ti + 0.29Nb.
  • a line is drawn on the figure corresponding to a tensile ductility of 20%. All alloys plotted above this line (symbol: filled circles) were considered to have passed the thermal stability test, while alloys plotted below the line (symbol: x-marks) were considered to have failed.
  • a dashed vertical line is drawn at a value of 9.5 wt.% for the compositional variable, Mo + 0.52W. All alloys with a value greater than 9.5 were found to fail the thermal stability test.
  • the third key property for the target application is creep strength.
  • the creep-rupture strength of the alloys was measured at 927°C (1700°F) with a load of 7 ksi. A rupture life of greater than 300 hours was the established goal.
  • the results for the experimental and commercial alloys are shown in Table 5. All of the experimental alloys were found to pass the goal, with the exception of alloys V, Y, and Z. The commercial alloys all passed with the exception of 263 alloy and WASPALOY alloy. Of the total of five alloys which failed the creep-rupture goal, three of them (alloys V and Z, as well as WASPALOY alloy) did not satisfy one or both of Eqs. (1) and (2) and were thermally unstable. Thermal instability can be a negative influence on creep strength.
  • alloy Y and 263 alloy both had a relatively low total content of the solid solution strengthening elements molybdenum and tungsten. Additionally, the 263 alloy had a low total content of the gamma-prime forming elements aluminum, titanium, and niobium.
  • the Eqs. (1) and (2) were modified respectfully as (where the elemental compositions are in wt.%): 2.2 ⁇ Al + 0.56 ⁇ Ti + 0.29 ⁇ Nb ⁇ 2.9 and 6.5 ⁇ Mo + 0.52 ⁇ W ⁇ 9.5
  • the acceptable alloys contained in weight percent 17.5 to 21.3 chromium, 8.3 to 14.2 cobalt, 4.3 to 9.3 molybdenum, up to 7.0 tungsten, 1.29 to 1.63 aluminum, 1.59 to 2.28 titanium, up to 0.79 niobium, 0.034 to 0.097 carbon, 0.002 to 0.007 boron and up to 2.6 iron.
  • alloys containing these elements within the following ranges and meeting Eqs.
  • the alloy may also contain tantalum, up to 1.5 wt. %, and one or more of magnesium, calcium, hafnium, zirconium, yttrium, cerium and lanthanum. Each of these seven elements may be present up to 0.05 wt. %.
  • the acceptable alloys had a range of values for Al + 0.56 Ti + 0.29 Nb of from 2.35 to 2.84 and a range for Mo + 0.52 W of from 7.1 to 9.3.
  • TABLE 5 Alloy Rupture Life (hours) A 304 B 560 C 481 D 375 E 346 F 522 G 584 H 764 I 410 J 767 K 560 L 522 M 581 N 401 O 403 P 664 Q 419 R 328 S 641 T 506 U 384 V 284 W 463 X 339 Y 271 Z 283 R-41 alloy 618 WASPALOY 243 263 alloy 139 M-252 alloy 392 PK-33 alloy 412
  • chromium Cr
  • the chromium level should be between 17 to 22 wt.%.
  • Co Co
  • Cobalt is a common element in many wrought gamma-prime strengthened alloys. Cobalt decreases the solubility of aluminum and titanium in nickel at lower temperatures allowing for a greater gamma-prime content for a given level of aluminum and titanium. It was found that Co levels of 8 to 15 wt.% are acceptable for the alloys of this invention.
  • Al aluminum
  • Ti titanium
  • Nb niobium
  • Mo molybdenum
  • W tungsten
  • Carbon (C) is a necessary component and contributes to creep-strength of the alloys of this invention through formation of carbides. Carbides are also necessary for proper grain size control. Carbon should be present in the amount of 0.01 to 0.2 wt.%.
  • Iron is not required, but typically will be present.
  • the presence of Fe allows economic use of revert materials, most of which contain residual amounts of Fe.
  • An acceptable, Fe-free alloy might be possible using new furnace linings and high purity charge materials.
  • the presented data indicate that levels up to at least 3.0 wt.% are acceptable.
  • Boron (B) is normally added to wrought gamma-prime strengthened alloys in small amounts to improve elevated temperature ductility. Too much boron may lead to weldability problems. The range is up to 0.015 wt.%.
  • Tantalum (Ta) is a gamma-prime forming element in this class of alloys. It is expected that tantalum could be partially substituted for aluminum, titanium, or niobium at levels up to 1.5 wt.%.
  • Silicon (Si) can be present as an impurity.
  • Copper (Cu) can be present as an impurity originating either from the use of revert materials or during the melting and processing of the alloy itself. It is expected that Cu could be present in amounts up to at least 0.5 wt.%.
  • magnesium (Mg) and calcium (Ca) is often employed during primary melting of nickel base alloys. It is expected that levels of these elements up to 0.05 wt.% could be present in alloys of this invention.
  • nickel based alloys to provide increased environmental resistance.
  • These elements include, but are not necessarily limited to lanthanum (La), cerium (Ce), yttrium (Y), zirconium (Zr), and hafnium (Hf). It is expected that amounts of each of these elements up to 0.5 wt.%, especially up to 0.05 wt.% could be present in alloys of this invention.
  • the alloys should exhibit comparable properties in other wrought forms (such as plates, bars, tubes, pipes, forgings, and wires) and in cast, spray-formed, or powder metallurgy forms, namely, powder, compacted powder and sintered compacted powder. Consequently, the present invention encompasses all forms of the alloy composition.

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Claims (9)

  1. Alliage au nickel-chrome-cobalt présentant une composition constituée, en pourcentage massique, de : 17 à 22 chrome 8 à 15 cobalt 4,0 à 9,5 molybdène jusqu'à 7,0 tungstène 1,28 à 1,65 aluminium 1,50 à 2,30 titane jusqu'à 0,80 niobium 0,01 à 0,2 carbone jusqu'à 0,015 bore
    et contenant également du fer en quantité jusqu'à 3,0 fer
    et contenant également au moins l'un parmi jusqu'à 1,5 tantale jusqu'à 0,5 cuivre
    et contenant également au moins un élément parmi jusqu'à 0,5 magnésium jusqu'à 0,5 calcium jusqu'à 0,5 hafnium jusqu'à 0,5 zirconium jusqu'à 0,5 yttrium jusqu'à 0,5 cérium jusqu'à 0,5 lanthane
    le solde étant constitué de nickel et d'impuretés, l'alliage satisfaisant en outre les relations de composition qui suivent, définies avec les quantités des éléments exprimées en pourcentage massique: 2 , 2 < Al + 0 , 56 ⁢ Ti + 0 , 29 ⁢ Nb < 2 , 9
    Figure imgb0013
     6 , 5 < Mo + 0 , 52 W < 9 , 5
    Figure imgb0014
  2. Alliage au nickel-chrome-cobalt selon la revendication 1, dans lequel l'alliage est sous une forme corroyée choisie dans le groupe comprenant tôles, plaques, barres, fils, tubes, conduites et produits forgés.
  3. Alliage au nickel-chrome-cobalt selon la revendication 1, dans lequel l'alliage est sous une forme coulée.
  4. Alliage au nickel-chrome-cobalt selon la revendication 1, dans lequel l'alliage a été formé par pulvérisation.
  5. Alliage au nickel-chrome-cobalt selon la revendication 1, dans lequel l'alliage est sous la forme d'une poudre métallurgique.
  6. Alliage au nickel-chrome-cobalt selon l'une quelconque des revendications précédentes, présentant une composition constituée, en pourcentage massique, de : 17,5 à 21,3 chrome 8,3 à 14,2 cobalt 4,3 à 9,3 molybdène jusqu'a 7,0 tungstène 1,29 à 1,63 aluminium 1,59 à 2,28 titane jusqu'à 0,79 niobium 0,034 à 0,097 carbone 0,002 à 0,007 bore jusqu'à 2,6 fer
    le solde étant constitué de nickel et d'impuretés, l'alliage satisfaisant en outre les relations de composition qui suivent, définies avec les quantités des éléments exprimées en pourcentage massique: 2 , 35 < Al + 0.56 Ti + 0 , 29 Nb < 2 , 84
    Figure imgb0015
     7 , 2 < Mo + 0 , 52 W < 9 , 3
    Figure imgb0016
  7. Alliage au nickel-chrome-cobalt selon la revendication 1 ou 6, dans lequel l'alliage est façonné en un composant d'un moteur à turbine à gaz.
  8. Moteur à turbine à gaz du type possédant plusieurs composants métalliques, dans lequel l'un au moins des composants métalliques est en un alliage selon la revendication 1 ou 6.
  9. Moteur à turbine à gaz perfectionné selon la revendication 9, dans lequel le composant métallique au moins présent est un conduit de transition.
EP05018830A 2004-09-03 2005-08-30 Alliage de Ni-Cr-Co-Mo pour un moteur à turbine à gaz Active EP1640465B1 (fr)

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US10/934,920 US20060051234A1 (en) 2004-09-03 2004-09-03 Ni-Cr-Co alloy for advanced gas turbine engines

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EP (1) EP1640465B1 (fr)
JP (1) JP4861651B2 (fr)
KR (1) KR100788527B1 (fr)
CN (2) CN1743483A (fr)
AT (1) ATE447048T1 (fr)
AU (1) AU2005205736B2 (fr)
CA (1) CA2517056A1 (fr)
DE (1) DE602005017338D1 (fr)
DK (1) DK1640465T3 (fr)
ES (1) ES2335503T3 (fr)
GB (1) GB2417729B (fr)
MX (1) MXPA05009401A (fr)
PL (1) PL1640465T3 (fr)
RU (1) RU2377336C2 (fr)
TW (1) TWI359870B (fr)

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CN114196854B (zh) * 2020-09-02 2022-07-15 宝武特种冶金有限公司 一种高强度难变形镍基高温合金及其制备方法
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EP1640465A2 (fr) 2006-03-29
AU2005205736A1 (en) 2006-03-23
ES2335503T3 (es) 2010-03-29
PL1640465T3 (pl) 2010-06-30
RU2377336C2 (ru) 2009-12-27
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JP2006070360A (ja) 2006-03-16
KR100788527B1 (ko) 2007-12-24
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CN102586652A (zh) 2012-07-18
GB2417729B (en) 2008-01-16
ATE447048T1 (de) 2009-11-15
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GB0517657D0 (en) 2005-10-05
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CN102586652B (zh) 2016-05-11
CN1743483A (zh) 2006-03-08

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