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US20120183432A1 - Nickel-based superalloy and parts made from said superalloy - Google Patents

Nickel-based superalloy and parts made from said superalloy Download PDF

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Publication number
US20120183432A1
US20120183432A1 US13/391,454 US201013391454A US2012183432A1 US 20120183432 A1 US20120183432 A1 US 20120183432A1 US 201013391454 A US201013391454 A US 201013391454A US 2012183432 A1 US2012183432 A1 US 2012183432A1
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Prior art keywords
alloy
superalloy
gamma
expressed
composition
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US13/391,454
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English (en)
Inventor
Alexandre Devaux
Philippe Heritier
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Aubert and Duval SA
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Aubert and Duval SA
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Assigned to AUBERT & DUVAL reassignment AUBERT & DUVAL ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HERITIER, PHILIPPE, DEVAUX, ALEXANDRE
Publication of US20120183432A1 publication Critical patent/US20120183432A1/en
Abandoned legal-status Critical Current

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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
    • 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%
    • 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
    • C22C1/023—Alloys based on nickel
    • 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
    • C22F1/10—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of nickel or cobalt or alloys based thereon
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05C—INDEXING SCHEME RELATING TO MATERIALS, MATERIAL PROPERTIES OR MATERIAL CHARACTERISTICS FOR MACHINES, ENGINES OR PUMPS OTHER THAN NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES
    • F05C2201/00—Metals
    • F05C2201/04—Heavy metals
    • F05C2201/0433—Iron group; Ferrous alloys, e.g. steel
    • F05C2201/0466—Nickel

Definitions

  • the invention relates to the field of nickel-based superalloys, notably intended for making parts for land or aeronautical turbines, for example discs of turbines.
  • Improvement in the performances of turbines requires more and more performing alloys at high temperatures. They should notably be capable of supporting operating temperatures of the order of 700° C.
  • alloys were developed allowing an application via a conventional route.
  • This is notably the nickel-based superalloy known under the name of UDIMET 720, as notably described in documents U.S. Pat. No. 3,667,938 and U.S. Pat. No. 4,083,734.
  • This superalloy typically has the composition, described in weight percentages:
  • the 718 PLUS alloy has a high Nb content (comprised between 4 and 8%), which is detrimental to its chemical homogeneity during production.
  • Nb is an element which leads to substantial segregations at the end of the solidification. These segregations may lead to the formation of production defects (white spots). Only narrow and specific remelting rate windows during the production of the ingot allow reduction of these defects.
  • the production of 718 PLUS therefore involves a method which is complex and difficult to control. High Nb contents in superalloys are also known to be rather detrimental to the propagation of cracks at high temperatures.
  • the object of the invention is to propose an alloy having a low cost for obtaining it, i.e. with a less substantial cost in alloy elements than that of alloys of the UDIMET 720 type, and for which the forgeability would be increased relatively to alloys of the UDIMET 720 type, and this while having high mechanical properties at high temperatures (700° C.), i.e. higher than those of 718 PLUS.
  • the aim is to propose an alloy for which the composition would allow a compromise to be obtained between high hot mechanical properties and an acceptable cost for obtaining it for the aforementioned applications.
  • This alloy should also be able to be obtained under not too restrictive production and forging conditions in order to make their obtaining more reliable.
  • the object of the invention is a nickel-based superalloy of the following composition, the contents of the various elements being expressed as weight percentages:
  • composition satisfies the following equations wherein the contents are expressed as atomic percentages:
  • composition satisfies the following equation wherein the contents are expressed as atomic percentages:
  • it contains in weight percentages between 3 and 12% of Fe.
  • composition is expressed in weight percentages:
  • composition of the alloy is expressed in weight percentages:
  • these superalloys comprise a gamma′ phase fraction comprised between 30 and 44%, preferably between 32 and 42% and the solvus of the gamma′ phase of the superalloy is below 1,145° C.
  • the composition of the alloy satisfies the following equation, wherein the contents of the elements are calculated in the gamma matrix at 700° C. and are expressed as atomic percentages:
  • the Cr content (expressed as an atomic percentage) is in the gamma matrix at 700° C., greater than 24 at %.
  • the Mo+W content (expressed as an atomic percentage) is ⁇ 2.8 at % in the gamma matrix.
  • the object of the invention is also a part in a nickel superalloy, characterized in that its composition is of the previous type. This may be a component of an aeronautical or land turbine.
  • the invention is based on an accurate equilibration of the composition of the alloy in order to obtain both mechanical properties, ease in forging and preferably a material cost of the alloy as moderate as possible, making the alloy suitable for economical production via the standard ingot route of parts which may operate under high mechanical and thermal stresses, notably in land and aeronautical turbines.
  • FIG. 1 shows the respective forgeabilities (represented by striction) measured on remelted and homogenized ingots at temperatures from 1,000 to 1,180° C., of alloys according to the invention and of a reference alloy of the UDIMET 720 type, the substitution of which is aimed by the invention.
  • the alloy according to the invention has good forgeabilities by limited contents of elements generating the gamma′ phase, and notably of Nb, in order to also avoid segregation problems during the production.
  • An alloy according to the invention is for example forgeable in the domain of the supersolvus of the alloy by which it is possible to ensure better homogeneity of the metal and to significantly reduce the costs related to the forging process.
  • a superalloy according to the invention in addition to reducing the costs associated with the raw materials, allows reduction of the costs relating to the production processes and to the thermo-mechanical treatment processes (forging and closed die-forging) of a part made in this superalloy.
  • the alloys obtained according to this invention are globally obtained at a relatively low cost, in any case at a lower cost than those of the alloys of the UDIMET 720 type, and this while having a high mechanical properties at high temperatures i.e. greater than those of alloys of the 718 PLUS type.
  • the inventors were able to notice that by adding Fe as a partial substitution for the Co content (relatively to alloys of the UDIMET 720 or TMW-4 type) it was also possible to significantly reduce the cost of the alloy.
  • the inventors were able to notice that an optimum Co content was comprised between 7 and 11%, better 7 to 10%, in order to reach a significant increase in the mechanical properties such as creep resistance while maintaining a low cost in raw materials, preferably by adding 3 to 9% of Fe, better 3.6 to 7%, into the composition. Beyond 11% Co, the inventors were able to notice that the performances of the alloy were not significantly improved.
  • An alloy according to this composition gives the possibility of reaching mechanical properties close to those of the most performing alloys such as the aforementioned ones (UDIMET 720 and TMW-4) while keeping a low cost for obtaining them since, for example, it is possible to easily reach a cost of raw materials of less than 24 /kg (a cost close to that of 718 PLUS, see the examples hereafter).
  • the costs of the raw materials making up the liquid metal from which the ingot will be cast and forged for each element the following costs per kg are considered:
  • the targeted ratio of the sum of the Ti, Nb and Ta contents and of the Al content gives the possibility of ensuring hardening via a solid solution of the gamma′ phase while avoiding the risk of occurrence of a needled phase in the alloy which may alter its ductility.
  • a minimum gamma′ phase fraction (preferably 30%, better 32%) is desired in order to obtain a very good strength during creep and traction at 700° C.
  • the fraction and the solvus of the gamma′ phase should however be preferably less than 44% (better 42%) and at 1,145° C. respectively so that the alloy retains good forgeability, and also so that the alloy may be partly forged in the supersolvus domain, i.e. at a temperature comprised between the gamma′ solvus and the melting onset temperature.
  • the proportions of the phases present in the alloy were determined by the inventors and according to the composition, by resorting to phase diagrams obtained by thermodynamic calculations (by means of the THERMOCALC software package currently used by metallurgists).
  • the parameter Md which is usually used as an indicator of the stability of superalloys, should be less than 0.901 in order to impart optimum stability to the alloy according to the invention.
  • the composition may therefore be adjusted so as to reach an Md ⁇ 0.901 without being detrimental to the other mechanical properties of the alloy. Beyond 0.901, the alloy risks being unstable, i.e. giving rise during extended use to the precipitation of detrimental phases, such as the sigma and mu phases which embrittle the alloy.
  • Md 0.717 Ni at %+0.858 Fe at %+1.142 Cr at %+0.777 Co at %+1.55 Mo at %+1.655 W at %+1.9 Al at %+2.271 Ti at %+2.117 Nb at %+2.224 Ta at % ⁇ 0.901, the contents (at %) of the various elements being calculated in the gamma matrix at 700° C. (an equation resulting from thermodynamic calculations made with models customarily known to metallurgists working in the field of nickel-based superalloys).
  • the cobalt content was limited to contents of less than 11%, better less than 10%, for economical reasons, insofar that this element is one of the most expensive of those entering the composition of the alloy (see equation (1) where this element has the second strongest weighting after Ta).
  • a minimum content of 7% is desired in order to retain very good creep strength.
  • Substitution of the nickel or cobalt with iron has the advantage of significantly reducing the cost of the alloy. Addition of iron however promotes precipitation of the sigma phase harmful for ductility and notch sensitivity.
  • the iron content of the alloy should therefore be adjusted so as to obtain a significant cost reduction while guaranteeing a highly stable alloy at a high temperature (equations (2), (7)).
  • the iron content in the general case is comprised between trace amounts and 12%, but is preferably comprised between 3 and 12%, better between 3 and 9%, better between 3.6 and 7%.
  • weight contents of these elements are from 1.3 to 2.8%, better 1.8 to 2.8% for Al, 2.5 to 4.5%, better 2.8 to 4.2% for Ti, 0.5 to 2.5%, better 0.5 to 2% for the sum Ta+Nb.
  • the precipitation of the gamma′ phase in the nickel-based alloys is essentially a matter of the presence of aluminum in a sufficient concentration
  • the elements, Ti, Nb and Ta may promote the occurrence of this phase if they are present in the alloy with a sufficient concentration: the elements aluminum, titanium, niobium and tantalum are elements said to be gamma′-genes .
  • the stability domain of the gamma′ phase (the gamma′ solvus of which the alloy is representative) and the gamma′ phase fraction therefore depend on the sum of the atomic concentrations (at %) of aluminum, titanium, niobium and tantalum.
  • a ⁇ ′ phase fraction comprised between 30% and 44%, better between 32% and 42%, and a gamma′ phase solvus of less than 1,145° C.
  • An adequate gamma′ phase fraction in the alloys of the invention is obtained with a sum of the Al, Ti, Nb and Ta contents greater than or equal to 8 at % and less than or equal to 11 at %.
  • a minimum gamma′ phase fraction is desired in order to obtain very good creep and tensile strength at 700° C.
  • the fraction and the solvus of the gamma′ phase should however preferably be less than 40% and 1,145° C.
  • the alloy retains good forgeability, and may also be partly forged in the supersolvus domain, i.e. at a temperature comprised between the gamma′ solvus and the melting onset temperature.
  • a ⁇ ′ phase fraction and a solvus temperature exceeding the upper limits mentioned earlier would make the application of the alloy more difficult via the conventional ingot route, which would risk attenuating one of the advantages of the invention.
  • the aluminum, titanium, niobium and tantalum contents are such that the ratio between the sum of the titanium, niobium and tantalum contents and the aluminum content is greater than or equal to 0.7 and less than or equal to 1.3.
  • hardening in a solid solution in the gamma′ phase provided by Ti, Nb and Ta is all the higher since the ratio (Ti at %+Nb at %+Ta at %)/Al at % is high.
  • a ratio greater than or equal to 1 will be preferred for guaranteeing better hardening.
  • too high Ti, Nb or Ta contents promote precipitation of needled phases of the eta type (Ni 3 Ti) or delta type (Ni 3 (Nb,Ta)) but which are not desired within the scope of the invention: these phases if they are present in too large amounts may alter the hot ductility of the alloy by precipitating as needles at the grain boundaries.
  • the ratio (Ti at %+Nb at %+Ta at %)/Al at % should therefore not exceed 1.3 and preferably 1.15 in order to prevent precipitation of these detrimental phases.
  • the Nb and Ta contents on the other hand are less than the titanium content so that the density of the alloy remains acceptable (less than 8.35), in particular for aeronautical applications.
  • niobium is preferably present in a larger proportion than tantalum insofar that tantalum has a higher cost and a higher atomic mass than niobium. Equations (1), (4) and (5) take these conditions into account.
  • the Mo content should be comprised between 2 and 5% and the W content between 1 and 4%. Optimally, the MO content is comprised between 2 and 4% and the W content comprised between 1.5 and 3.5%.
  • Molybdenum and tungsten provide strong hardening of the gamma matrix by a solid solution effect.
  • the Mo and W contents should be adjusted with care in order to obtain optimum hardening without causing precipitation of brittle intermetallic compounds of the sigma or mu type. These phases, when they develop in an excessive amount, cause a substantial reduction in the ductility and the mechanical strength of the alloys. It was also observed that excessive Mo and W contents strongly alter the forgeability of the alloy and considerably reduce the forgeability domain, i.e. the temperature domain where the alloy tolerates substantial deformations for hot shaping. These elements further have high atomic masses, and their presence is expressed by a notable increase in the specific gravity of the alloy, which is not desirable for aeronautical applications notably. Equations (2), (7) and (8) take these conditions into account.
  • Chromium is indispensable for resistance to oxidation and corrosion of the alloy and thus plays an essential role for the resistance of the alloy to environmental effects at high temperature.
  • the chromium content (14 to 17% by weight) of the alloys of the invention was determined so as to introduce a minimum concentration of 24 at % of Cr in the gamma phase at 700° C., by taking into account the fact that a too high chromium content promotes precipitation of detrimental phases such as the sigma phase and therefore deteriorates hot stability. Equations (2), (3) and (7) take these conditions into account.
  • the B content is comprised between 0.0030 and 0.030%.
  • the Zr content is comprised between 0.01 and 0.06%.
  • the C content is comprised between trace amounts and 0.1%, optimally between trace amounts and 0.07%.
  • minor elements such as carbon, boron and zirconium form segregations at the grain boundaries, for example as borides or carbides. They contribute to increasing the strength and the ductility of the alloys by trapping detrimental elements such as sulfur and by modifying the chemical composition at the grain boundaries. Their absence would be detrimental. However, excessive contents cause reduction in the melting temperature and strongly alter forgeability. They therefore have to be maintained within the limits which have been stated.
  • Examples 1 to 4 were elaborated by VIM (vacuum induction melting) in order to produce 10 kg ingots.
  • Examples 5 to 10 were elaborated by VIM and then by VAR (vacuum arc remelting) in order to produce 200 kg ingots.
  • Reference Example 1 corresponds to a conventional 718 PLUS alloy.
  • Reference Example 4 is outside the invention because of a too high Nb content which theoretically corresponds to the Nb content beyond which the delta phase may occur.
  • Example 6 The optimum composition was obtained for Example 6. By comparison with this Example 6:
  • Table 2 shows additional characteristics of the tested alloys, with their main mechanical properties: tensile strength Rm, yield strength Rp 0.2 , elongation at break A, creep lifetime at 700° C. under a stress of 600 MPa.
  • the mechanical properties are given in values relative to those of Reference Example 1 which is of the usual 718 PLUS type.
  • the tensile strength and the creep lifetime of the alloys of the invention are all clearly greater than that of the 718 PLUS alloy (Example 1), while the cost of the alloy is comparable or lower.
  • the gain in tensile strength, in yield strength and in resistance to creep is less than for Example 8, but the cost of this alloy is much less than that of 718 PLUS.
  • Examples 2 and 4 which are not part of the invention, show a reduction in the hot ductility relatively to the one obtained with 718 PLUS, which is expressed by a lesser elongation at break.
  • the alloys of the invention have a cost of raw materials which is less than or equal to 718 PLUS, and therefore they are much less expensive than UDIMET 720, for which the cost of raw materials, calculated according to the same criteria, would amount to 26.6 /kg.
  • FIG. 1 shows that the alloys of the invention have a better striction coefficient and therefore excellent forgeability in the stage of an ingot homogenized between 1,100 and 1,180° C., and that these alloys unlike UDIMET 720 tolerate forging at a temperature above the solvus of the gamma′ phase.
  • the refining of the grain may be carried out during the first transformation stages in the absence of gamma′ phase.

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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)
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US13/391,454 2009-08-20 2010-08-20 Nickel-based superalloy and parts made from said superalloy Abandoned US20120183432A1 (en)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
FR0955714 2009-08-20
FR0955714A FR2949234B1 (fr) 2009-08-20 2009-08-20 Superalliage base nickel et pieces realisees en ce suparalliage
FR1053607A FR2949235B1 (fr) 2009-08-20 2010-05-07 Superalliage base nickel et pieces realisees en ce superalliage
FR1053607 2010-05-07
PCT/FR2010/051748 WO2011020976A1 (fr) 2009-08-20 2010-08-20 Superalliage base nickel et pièces réalisées en ce superalliage

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US16/266,764 Active US11193187B2 (en) 2009-08-20 2019-02-04 Nickel-based superalloy and parts made from said superalloy
US17/512,439 Active US12024758B2 (en) 2009-08-20 2021-10-27 Nickel-based superalloy and parts made from said superalloy

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EP (1) EP2467505B1 (fr)
JP (2) JP5684261B2 (fr)
CN (1) CN102625856B (fr)
BR (1) BR112012003536B1 (fr)
CA (1) CA2771739C (fr)
DK (1) DK2467505T3 (fr)
ES (1) ES2426143T3 (fr)
FR (2) FR2949234B1 (fr)
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EP2826877A2 (fr) 2013-07-12 2015-01-21 Daido Steel Co.,Ltd. Superalliage à base de Nickel à forgeage à chaud présentant une excellente résistance aux températures élevées
EP3208354A1 (fr) * 2016-02-18 2017-08-23 Daido Steel Co.,Ltd. Superalliage à base de ni pour forgeage à chaud
US9828657B2 (en) 2014-09-29 2017-11-28 Hitachi Metals, Ltd. Ni-base super alloy
US10119182B2 (en) 2016-02-18 2018-11-06 Daido Steel Co., Ltd. Ni-based superalloy for hot forging
US20220154311A1 (en) * 2019-03-29 2022-05-19 Hitachi Metals, Ltd. Ni-BASED SUPERALLOY AND METHOD FOR MANUFACTURING Ni-BASED SUPERALLOY

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CN107419136B (zh) * 2016-05-24 2019-12-03 钢铁研究总院 一种服役温度达700℃以上的镍基变形高温合金及其制备方法
CN106435279B (zh) * 2016-10-24 2018-06-15 四川六合锻造股份有限公司 一种高强度抗氧化高温合金及其热处理工艺和应用
CA3053741A1 (fr) * 2017-02-15 2018-08-23 Nippon Steel Corporation Alliage resistant a la chaleur a base de ni et son procede de fabrication
US10109383B1 (en) * 2017-08-15 2018-10-23 General Electric Company Target assembly and nuclide production system
US12000025B2 (en) 2018-04-25 2024-06-04 Satyajeet Sharma Powder composition for additive manufacturing
FR3085967B1 (fr) * 2018-09-13 2020-08-21 Aubert & Duval Sa Superalliages a base de nickel
FR3130294B1 (fr) * 2021-12-15 2025-05-16 Safran Alliage à base de nickel
CN115354194A (zh) * 2022-09-06 2022-11-18 中国科学院金属研究所 一种增材修复用镍基高温合金材料及其应用
CN115896585B (zh) * 2022-12-28 2024-04-02 大连理工大学 一种密度低于8.0g/cm3的变形高强高温高熵合金及其制备方法
CN117286371B (zh) * 2023-09-05 2025-10-31 钢铁研究总院有限公司 一种镍基耐热合金及其制备方法和应用
FR3160706A1 (fr) 2024-03-29 2025-10-03 Aubert & Duval Superalliage base nickel spécifique, lingots et pièces réalisés en ce superalliage

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US20220049326A1 (en) 2022-02-17
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CN102625856B (zh) 2014-12-31
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US20190169715A1 (en) 2019-06-06
BR112012003536B1 (pt) 2021-05-11
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FR2949235B1 (fr) 2011-09-09
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EP2467505B1 (fr) 2013-06-19
FR2949234A1 (fr) 2011-02-25
US12024758B2 (en) 2024-07-02
SI2467505T1 (sl) 2013-10-30
CN102625856A (zh) 2012-08-01
DK2467505T3 (da) 2013-09-30
PT2467505E (pt) 2013-09-24
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BR112012003536A2 (pt) 2020-11-03
FR2949235A1 (fr) 2011-02-25

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