US20170058383A1 - Rhenium-free nickel base superalloy of low density - Google Patents

Rhenium-free nickel base superalloy of low density Download PDF

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Publication number
US20170058383A1
US20170058383A1 US15/142,068 US201615142068A US2017058383A1 US 20170058383 A1 US20170058383 A1 US 20170058383A1 US 201615142068 A US201615142068 A US 201615142068A US 2017058383 A1 US2017058383 A1 US 2017058383A1
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United States
Prior art keywords
alloy
cobalt
titanium
rhenium
tantalum
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Abandoned
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US15/142,068
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English (en)
Inventor
Thomas Goehler
Ralf RETTIG
Robert F. Singer
Steffen NEUMEIER
Nils RITTER
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MTU Aero Engines AG
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MTU Aero Engines AG
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Assigned to MTU Aero Engines AG reassignment MTU Aero Engines AG ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: Ritter, Nils, Neumeier, Steffen, SINGER, ROBERT F., RETTIG, Ralf, GOEHLER, THOMAS
Publication of US20170058383A1 publication Critical patent/US20170058383A1/en
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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
    • C22C19/057—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being less 10%
    • 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
    • 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
    • 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

Definitions

  • the present invention relates to a nickel base alloy which is substantially free of rhenium but at the same time shows the creep resistance of a nickel base superalloy of the second generation and a density which is lower than that of comparable alloys.
  • nickel base superalloys are employed, for example, as blade materials because these materials exhibit a sufficient strength for high mechanical stress even at high operating temperatures.
  • turbine blades of stationary gas turbines or jet engines are exposed to exhaust gas temperatures of up to 1500° C. and at the same time are subject to high mechanical stress caused by centrifugal forces. Under these conditions it is important in particular for the creep resistance of the material employed to meet the corresponding requirements. To further increase the creep resistance it has also been practice for decades to manufacture monocrystalline turbine blades in order to improve the creep resistance by avoiding grain boundaries.
  • the currently employed nickel base superalloys of the so-called second and third usually contain the element rhenium at a concentration of from three to six percent because rhenium further improves the creep resistance.
  • EP 2 725 110 A1 discloses a nickel base superalloy which is substantially free of rhenium and exhibits a solidus temperature of higher than 1320° C., where at temperatures from 1050° C. to 1100° C. precipitates of a ⁇ ′-phase in a ⁇ -matrix are present in a proportion of from 40 to 50 vol. %, the ⁇ / ⁇ ′-mismatch at temperatures from 1050° C. to 1100° C. ranges from ⁇ 0,15% to ⁇ 0,25%, and the concentration of tungsten in the ⁇ -matrix is higher than that in the precipitated ⁇ ′-phases.
  • the alloy has the following composition: aluminum from 11 to 13 at.-%, cobalt from 4 to 14 at. ⁇ %, chromium from 6 to 12 at.-%, molybdenum from 0.1 to 2 at.-%, tantalum from 0.1 bis 3.5 at.-%, titanium from 0.1 bis 3.5 at.-%, tungsten from 0.1 to 3 at.-%, remainder nickel and unavoidable impurities.
  • the present invention provides a nickel base alloy exhibiting high creep resistance and being substantially free of rhenium, wherein the alloy comprises the following elements in % by weight based on the total weight of the alloy:
  • cobalt from 0 to 16.8, e.g., from 2.6 to 13.6, or from 2.9 to 13.3;
  • chromium from 3 to 11.8, e.g., from 4 to 11.8, from 5 to 11.8, from 6 to 11.8, from 6.3 to 7.3, or from 6.6 to 7;
  • molybendum from 3.1 to 11.3, e.g., from 3.3 to 11.3, from 3.4 to 11.3, from 3.6 to 11.3, from 3.7 to 4.7, or from 4 to 4.4;
  • tantalum from 0 to 3.9, e.g., from 0 to 0.5, or from 0 to 0.2.
  • this alloy may further comprise one or more (e.g. at least 2, at least 3, at least 4, at least 5, at least 6, at least 7, or at least 8) other elements, for example one or more of the following (in % by weight):
  • titanium e.g., up to 6, up to 5, up to 4, up to 3.6, from 2.8 to 3.6, or from 3.1 to 3.5
  • tungsten e.g., up to 11.3, from 7.4 to 8.4, or from 7.7 to 8.1
  • phosphorus e.g., up to 0.015
  • zirconium e.g., up to 0,015.
  • silicon e.g., up to 6.0, up to 5.0, up to 4.0, up to 3.0, or up to 2.0
  • manganese e.g., up to 0.05
  • boron e.g., up to 6.0, up to 5.0, or up to 4.0
  • hafnium e.g., up to 4.0, up to 3.0, up to 2.0, or up to 1.0
  • yttrium e.g., up to 0.002
  • niobium e.g., up to 8.0, up to 7.0, up to 6.0, up to 5.0, up to 4.0, up to 3.0, up to 2.0, or up to 1.0
  • niobium e.g., up to 8.0, up to 7.0, up to 6.0, up to 5.0, up to 4.0, up to 3.0, up to 2.0, or up to 1.0
  • germanium e.g., up to 8.0, up to 7.0, up to 6.0, up to 5.0, up to 4.0, up to 3.0, up to 2.0, or up to 1.0).
  • the alloy may comprise less than 5% by weight cobalt, e.g., less than 4% by weight cobalt.
  • the alloy may comprise more than 11% by weight cobalt, e.g., more than 12%, or more than 13% of cobalt.
  • the alloy may have a density of not higher than 8.5 g/cm 3 , e.g., not higher than 8.4 g/cm 3 and/or the alloy may have a solidus temperature of higher than 1320° C. and/or a residual eutecticum of not more than 4%, e.g, not more than 3%.
  • the present invention also provides an article that is made of the alloy of the present invention as set forth above (including the various aspects thereof).
  • the alloy may be monocrystalline or directionally solidified.
  • the article may be a component of a gas turbine or an aircraft engine such as, e.g., a turbine blade.
  • the present invention also provides a method of making a nickel base alloy as set forth above (including the various aspects thereof).
  • the method comprises melting together elements in proportions which result in the alloy of the present invention.
  • the present invention provides a nickel base superalloy which contains at least the elements Al, Cr and Mo (and often also Co) and which has been optimized with respect to the following:
  • a nickel base alloy may have the following exemplary composition, in % by weight based on the total weight of the alloy: aluminum from 3.0 to 7.7, cobalt from 0 to 16.8, chromium from 3 to 11.8, molybdenum from 3.1 to 11.3, tantalum from 0 to 3.9, titanium from 0 to 6.0, tungsten from 0 to 11.3, carbon from 0 to 0.05, phosphorus from 0 to 0.015, copper from 0 to 0.05, zirconium from 0 to 0.015, silicon from 0 to 6.0, sulfur from 0 to 0.001, iron from 0 to 0.15, manganese from 0 to 0.05, boron from 0 to 6.0, hafnium from 0 to 4.0, yttrium from 0 to 0.002, niobium from 0 to 8.0, germanium from 0 to 8.0, remainder nickel and unavoidable impurities.
  • the alloy is substantially free of rhenium, i.e., it contains rhenium, if at all, only in trace amounts (e.g., not more than 0.001% by weight).
  • the alloy may further also be substantially free of tantalum.
  • a nickel base alloy of the present invention may have the following composition, in % by weight: aluminum from 4.1 to 7.7, cobalt from 0 to 16.8, chromium from 6 to 11.8, molybdenum from 3.6 to 11.3, tantalum from 0 to 3.9, titanium from 0 to 3.6, tungsten from 0 to 11.3, carbon from 0 to 0.05, phosphorus from 0 to 0.015, copper from 0 to 0.05, zirconium from 0 to 0.015, silicon from 0 to 0.01, sulfur from 0 to 0.001, iron from 0 to 0.15, manganese from 0 to 0.05, boron from 0 to 0.003, hafnium from 0 to 0.15, yttrium from 0 to 0.002, remainder nickel and unavoidable impurities.
  • the alloy of the present invention may have the following composition, in % by weight relative to the total weight of the alloy: aluminum from 4.4 to 5.7, cobalt from 2.6 to 13.6, chromium from 6.3 to 7.3, molybdenum from 3.7 to 4.7, tantalum from 0 to 0.5, titanium from 2.8 to 3.6, tungsten from 7.4 to 8.4, carbon from 0 to 0.05, phosphorus from 0 to 0.015, copper from 0 to 0.05, zirconium from 0 to 0.015, silicon from 0 to 0.01, sulfur from 0 to 0.001, iron from 0 to 0.15, manganese from 0 to 0.05, boron from 0 to 0.003, hafnium from 0 to 0.15, yttrium from 0 to 0.002, remainder nickel and unavoidable impurities.
  • the alloy of the present invention may have the following composition, in % by weight relative to the total weight of the alloy: aluminum from 5.0 to 5.4, cobalt from 2.9 to 13.3, chromium from 6.6 to 7, molybdenum from 4 to 4.4, tantalum from 0 to 0.2, titanium from 3.1 to 3.5, tungsten from 7.7 to 8.1, carbon from 0 to 0.05, phosphorus from 0 to 0.015, copper from 0 to 0.05, zirconium from 0 to 0.015, silicon from 0 to 0.01, sulfur from 0 to 0.001, iron from 0 to 0.15, manganese from 0 to 0.05, boron from 0 to 0.003, hafnium from 0 to 0.15, yttrium from 0 to 0.002, remainder nickel and unavoidable impurities.
  • the alloy comprises less than 5% by weight, e.g., less than 4% by weight, of cobalt. Since cobalt has a higher atomic weight than nickel, a relatively low cobalt concentration has a favorable effect on the total density of the nickel base alloy, and thus on the total weight of the target component made from the alloy.
  • the nickel base alloy of the present invention may comprise more than 11% by weight, e.g., more than 13% by weight, of cobalt.
  • a corresponding cobalt concentration has a positive effect on segregation during solidification and the stability of the microstructure with respect to undesired formation of TCP phases.
  • nickel base alloy of the present invention comprises at least 67 at.-%, for example at least 68 at.-% nickel.
  • the nickel base alloy of the present invention may further exhibit one or more (for example, all) of the following properties:
  • unavoidable impurities in the alloy as used herein and the appended claims means elements whose presence in the alloy is unintentional but cannot be avoided for technical reasons or can only be avoided with extreme difficulty.
  • the following elements may be present in the alloy of the present invention in the form of trace elements, in % by weight: Bi up to 0.00003, Se up to 0.0001, Tl up to 0.00005, Pb up to 0,0005, and Te up to 0.0001.
  • the alloy of the present invention can be used, for example, in the manufacture of components of gas turbines, preferably turbine blades, and the like, which components may be present in monocrystalline or directionally solidified form.
  • the attached FIGURE shows a Larson-Miller plot for illustrating the creep resistance of the alloy of the present invention compared to that of known alloys.
  • Alloy 1 An alloy according to the present invention whose composition can be taken from the following table was prepared (Alloy 1 ). Alloys 2 and 3 were chosen as comparative alloys, Alloy 3 corresponding in its chemical composition essentially to that of the rhenium containing material CMSX-4 and Alloy 2 being the rhenium-free nickel base superalloy disclosed in EP 2 725 110 A1. The components of the alloys are indicated in wt. % (remainder Ni and unavoidable impurities).
  • Alloy 1 according to the present invention was prepared in a Labor-Bridgman casting apparatus in three-bar geometry. Each of the bars had a diameter of 12 mm and a length of 180 mm and exhibited a typical dendritic microstructure with a dendrite distance of about 230 ⁇ m. The proportion of residual eutectic of 2.8% is very low (Alloy 2 and Alloy 3 showed a residual eutectic of 6.5% and 9.0% respectively). If suitably heat-treated (see below), Alloy 1 has a typical, completely cubic y′-phase morphology.
  • Alloy 1 according to the invention shows a creep resistance which is substantially the same as that of the rhenium-free Alloy 2 (L 2 ), the creep resistances of these alloys being similar to the creep resistance of Alloy 3 which corresponds to a nickel base superalloy of the second generation.
  • Alloy 1 particularly shows a lower density Analysis of the microstructure of Alloy 1 according to the invention after creep does not reveal any TCP phase formation.
  • the present invention can provide nickel base alloys which do not depend on the presence of the not readily available element rhenium but nevertheless can exhibit high temperature mechanical properties such as creep resistance similar to those of known rhenium-containing alloys and additionally have a lower density than known rhenium-containing and rhenium-free alloys.
  • Annealing of Alloy 1 may for example be carried out in two stages as follows:
  • Alloy 1 may be subjected to one or both of the following precipitation hardening treatments:
  • Annealing times of more than 2 hours at 1050° C. or higher temperatures result in an excessive aging of the microstructure.

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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)
US15/142,068 2015-05-05 2016-04-29 Rhenium-free nickel base superalloy of low density Abandoned US20170058383A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP15166317.6 2015-05-05
EP15166317.6A EP3091095B1 (de) 2015-05-05 2015-05-05 Rheniumfreie nickelbasis-superlegierung mit niedriger dichte

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EP (1) EP3091095B1 (de)
ES (1) ES2682362T3 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111235434A (zh) * 2020-03-02 2020-06-05 北京钢研高纳科技股份有限公司 一种高温使用的镍基变形高温合金轮盘锻件的制备方法
WO2020129282A1 (ja) * 2018-12-17 2020-06-25 日立金属株式会社 Ｎｉ基超耐熱合金
US11859267B2 (en) 2016-10-12 2024-01-02 Oxford University Innovation Limited Nickel-based alloy

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112760525B (zh) * 2019-11-01 2022-06-03 利宝地工程有限公司 高γ′镍基超级合金、其用途及制造涡轮发动机构件的方法

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11859267B2 (en) 2016-10-12 2024-01-02 Oxford University Innovation Limited Nickel-based alloy
WO2020129282A1 (ja) * 2018-12-17 2020-06-25 日立金属株式会社 Ｎｉ基超耐熱合金
CN111235434A (zh) * 2020-03-02 2020-06-05 北京钢研高纳科技股份有限公司 一种高温使用的镍基变形高温合金轮盘锻件的制备方法

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EP3091095A1 (de) 2016-11-09
ES2682362T3 (es) 2018-09-20
EP3091095B1 (de) 2018-07-11

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