EP0962542A1 - Wärmebehandlungsfähige, stabile und einkristalline Superlegierung auf Nickelbasis und Artikel - Google Patents

Wärmebehandlungsfähige, stabile und einkristalline Superlegierung auf Nickelbasis und Artikel Download PDF

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Publication number
EP0962542A1
EP0962542A1 EP98303479A EP98303479A EP0962542A1 EP 0962542 A1 EP0962542 A1 EP 0962542A1 EP 98303479 A EP98303479 A EP 98303479A EP 98303479 A EP98303479 A EP 98303479A EP 0962542 A1 EP0962542 A1 EP 0962542A1
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EP
European Patent Office
Prior art keywords
cobalt
composition
rhenium
single crystal
alloy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Application number
EP98303479A
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English (en)
French (fr)
Inventor
David N. Duhl
Alan D. Cetel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Raytheon Technologies Corp
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United Technologies Corp
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Publication date
Application filed by United Technologies Corp filed Critical United Technologies Corp
Priority to EP98303479A priority Critical patent/EP0962542A1/de
Publication of EP0962542A1 publication Critical patent/EP0962542A1/de
Withdrawn legal-status Critical Current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
    • C22C19/057—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
    • 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 compositions which have utility as single crystal gas turbine engine components.
  • the broad composition contains 5%-12% chromium, 2%-8% aluminum, 0%-6% titanium, 0%-9.5% tantalum, 0%-12% tungsten, 0%-3% molybdenum; 0%-3% columbium; 0%-3.5% hafnium; 0%-7% rhenium; and balance essentially nickel.
  • the composition contains the following preferred levels of additions: 7%-12% chromium; 3%-7% aluminium; 1%-5% titanium; 1%-8% tantalum; 0%-12% tungsten; 0%-0.8% molybdenum; 0%-3% columbium; 0%-2.5% hafnium; and 0%-7% rhenium.
  • the composition is free from intentional additions of carbon, boron, zirconium and vanadium.
  • the composition contains an intentional addition of cobalt sufficient to render it stable and immune to the formation of deleterious phases.
  • the composition with the addition of cobalt also has enhanced heat treatability; the temperature range between the gamma prime solvus temperature and incipient melting temperature is increased over that which would be possessed by a cobalt-free alloy.
  • the present invention is concerned with nickel base single crystal articles which find application in aircraft gas turbine engines. More specifically, the invention relates to nickel base single crystal articles containing from about 5% to about 12% chromium, from about 2% to about 8% aluminum, up to about 6% titanium, with the sum of the aluminum and titanium exceeding about 4%, up to about 9.5% tantalum, up to about 12% tungsten, up to about 3% molybdenum, up to about 3% columbium, up to about 3.5% hafnium, up to about 7% rhenium, with the sum of the molybdenum, columbium, hafnium, rhenium, tantalum and tungsten contents exceeding 5%, with the composition being free from intentional additions of carbon, boron, zirconium and vanadium, and with the composition containing an intentional addition of cobalt sufficient to render it stable (unless otherwise indicated, all percentage values are in weight percents).
  • the composition contains additions which are within at least one of the following ranges: 5%-12% chromium, 3%-7% aluminum, 1%-5% titanium, 1%-8% tantalum, 0%-12% tungsten, 0%-0.8% molybdenum, 0%-3% columbium, 0%-2.5% hafnium and 0%-7% rhenium.
  • the titanium content is greater than 0.9 wt%.
  • the sum of the aluminum and titanium contents exceeds about 5% and the sum of the molybdenum, columbium, hafnium, rhenium, tantalum and tungsten exceeds about 10%.
  • the ratio of the titanium to aluminum is preferably less than about 1:1.
  • Chromium and aluminum contents in the amounts presented above ensure that the alloy forms a protective alumina layer upon exposure to elevated temperatures. This type of oxidation behavior is necessary for long component life. With less than about 5% chromium, the required aluminum layer will not form reliably while chromium contents in excess of about 12% tend to reduce the overall strength of the alloy.
  • the aluminum and titanium act together to form the gamma prime strengthening phase (Ni 3 (Al, Ti)).
  • the required alloy strength will be obtained when the sum of the aluminum and titanium exceeds 4%, and preferably about 5%.
  • the ratio of the titanium to aluminum is controlled, preferably to be less than about 1:1; again, this helps to ensure that the desired alumina oxide protective layer is formed.
  • the elements tantalum, tungsten, molybdenum, columbium, hafnium and rhenium are referred to as refractory elements and are present in the alloy for the purpose of strengthening.
  • the elements tungsten, molybdenum and rhenium partition mainly to the gamma matrix phase while the elements tantalum and columbium partition to the gamma prime strengthening phase.
  • a mixture of refractory elements is desirable for satisfactory alloy performance and the sum of these elements should exceed 5% and preferably 10%.
  • Those alloys which contain the lesser amounts of these strengthening elements will generally be useful in vane or other nonrotating applications while those compositions containing the higher amounts of these strengthening elements will find application in blades and other similar more highly stressed engine components.
  • compositions find application in single crystal components which are cast components free from internal grain boundaries.
  • the elements of carbon, boron, zirconium are added for the primary purpose of strengthening the grain boundaries while in single crystal components which contain no such grain boundaries; substantial benefits are obtained by the substantial exclusion of these elements. Exclusion of these elements also increases the incipient melting temperature, thereby making it easier to solution heat treat. This subject is discussed at some length in U. S. Patent No. 4,116,723. Vanadium has been added to certain superalloys for the purpose of gamma prime formation and minimizes the gamma prime being present as a low melting eutectic, but causes a substantial detriment in the hot corrosion behavior of the alloys and consequently is excluded from the present composition.
  • Nickel base superalloys are compositionally complex and are used in service under extreme conditions of temperature and stress. Certain superalloys have been observed to be microstructurally unstable under service conditions; the term instability relates to the formation of extraneous phases as a result of long term exposure to service conditions. These phases are often referred to as the topologically close-packed phases or TCP phases and include the phases, among others, referred to as sigma and mu. These phases are undesirable since they are generally brittle and of low strength, and their formation may deplete the alloy of the refractory elements that give it strength. Consequently, their formation in a highly stressed part in service can lead to premature catastrophic failure. Extensive prior art investigations have related the formation of these phases to the parameter referred to as N v or the electron vacancy number. A preferred method (used in the prior art) for calculating the N v number for a superalloy matrix is given below:
  • Fig. 1 shows the relationship between the electron vacancy number and a refractory parameter for several rhenium-free experimentally tested alloys.
  • Fig. 1 also shows several lines which define the stable and unstable alloy regions for alloys containing various cobalt levels. From Fig. 1, it can be seen that for a particular value of the refractory parameter, additions of cobalt up to about 10% or even 15% substantially increase the threshold electron vacancy number at which instability occurs. This observation is contrary to the prior art which had generally treated the N v number as being the sole parameter controlling alloy stability. Prior art indicated that additions of cobalt would increase the instability of the alloy.
  • alloys containing 5% cobalt are stable for N v ⁇ 2.74 - ((W + 2Mo) X 0.057) to a maximum of about 2.5 and alloys containing 10% cobalt are stable for N v ⁇ 2.82 - ((W + 2Mo) X 0.058) to a maximum of about 2.5.
  • a feature of this invention is the discovery of stable single crystal alloy compositions in the regions where: 2.39 - ((W + 2Mo) X 0.043) ⁇ N v ⁇ 2.82 - ((W + 2Mo) X 0.058) for alloys with 10% cobalt; and 2.39 - ((W + 2Mo) X 0.043) ⁇ N v ⁇ 2.74 - ((W + 2Mo) X 0.057) for alloys with 5% cobalt.
  • cobalt also plays a significant role in determining alloy stability. As taught by the present invention, sufficient additions of cobalt may be made to an unstable alloy to to render the alloy stable. Prior art would indicate that raising the level of cobalt in an unstable alloy, thus increasing the electron vacancy number (N v ) would further decrease alloy stability. As shown in Fig. 2, increases in alloy stability are acquired through judicious additions of cobalt.
  • alloy compositions which are shown as points in Fig. 2 are given in Table II. Compare, for example, alloy 250 and alloy 483, alloys which have substantially the same refractory element content. Alloy 250 is unstable, yet alloy 483 with 5% more cobalt than alloy 250 is stable enough, though its electron vacancy number is 1.0 higher than that of alloy 250. Thus, it is possible to control alloy stability and thus render unstable alloys suitable for long time service under severe conditions through judicious applications of cobalt.
  • alloys containing 5% cobalt are stable for N v ⁇ 2.23-0.027 (W+2Mo+2Re) .
  • a feature of this invention is the discovery of stable rhenium containing single crystal alloys in the region of 2.23-0.027 (W+2Mo+2Re) ⁇ N v ⁇ 2.56-0.027 (W+2Mo+2Re) for alloys with 10% cobalt (and for N v up to about 2.5).
  • each of the pairs of alloys set forth in Table III differs significantly only in the addition of 5% or 10% cobalt, yet in each of these cases, the cobalt addition makes a substantial change in the solution heat treatment range.
  • the change in the ranges from 10°F to 35°F (6°C to 19°C and in two cases, makes possible the heat treatment of alloys which could previously not be heat treated without incipient melting.
  • Some indication as to the significance of this improved heat treatment capability is shown in Table IV.
  • the alloys 255 and 454 are outside of the scope of the present invention by virtue of their high tantalum content. Nonetheless, a comparison of their properties is instructive. Alloy 255 differs from alloy 454 in that it lacks the cobalt content of alloy 454.
  • the incipient melting temperature and gamma prime solvus of alloy 255 are both about 2380°F (1304.4°C). Heat treatment at 2380°F (1304.4°C) of alloy 255 results in substantial incipient melting.
  • the rupture life of alloy 255 at 1800°F/36 ksi (982°C/25.3 kg/mm 2 ) after heat treatment at 2380°F (1304.4°C) is about 40 hours, and the time to 1% creep is about 15 hours. Decreasing the heat treatment temperature of alloy 255 to 2370°F (1299°C) effectively eliminates incipient melting, but produces only partial heat treatment since not all of the coarse, as-cast, gamma prime phase is dissolved into the gamma solid solution.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)
EP98303479A 1998-05-01 1998-05-01 Wärmebehandlungsfähige, stabile und einkristalline Superlegierung auf Nickelbasis und Artikel Withdrawn EP0962542A1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP98303479A EP0962542A1 (de) 1998-05-01 1998-05-01 Wärmebehandlungsfähige, stabile und einkristalline Superlegierung auf Nickelbasis und Artikel

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
EP98303479A EP0962542A1 (de) 1998-05-01 1998-05-01 Wärmebehandlungsfähige, stabile und einkristalline Superlegierung auf Nickelbasis und Artikel

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1184473A2 (de) * 2000-08-30 2002-03-06 Kabushiki Kaisha Toshiba Monokristalline Nickel-Basis-Legierungen und Verfahren zur Herstellung und daraus hergestellte Hochtemperaturbauteile einer Gasturbine
US6468367B1 (en) * 1999-12-27 2002-10-22 General Electric Company Superalloy weld composition and repaired turbine engine component
US6565680B1 (en) * 1999-12-27 2003-05-20 General Electric Company Superalloy weld composition and repaired turbine engine component
EP1586669A1 (de) * 2004-04-07 2005-10-19 United Technologies Corporation Oxidationsbeständige Superlegierung und Gegenstand
WO2005111530A2 (en) * 2004-04-30 2005-11-24 Aerojet-General Corporation Single phase tungsten alloy for shaped charge liner
US8858876B2 (en) 2012-10-31 2014-10-14 General Electric Company Nickel-based superalloy and articles
EP3091095A1 (de) 2015-05-05 2016-11-09 MTU Aero Engines GmbH Rheniumfreie nickelbasis-superlegierung mit niedriger dichte

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0052911A1 (de) * 1980-11-24 1982-06-02 Cannon-Muskegon Corporation Einkristall-Legierung (einzelnes Korn)
US4371404A (en) * 1980-01-23 1983-02-01 United Technologies Corporation Single crystal nickel superalloy
US4402772A (en) * 1981-09-14 1983-09-06 United Technologies Corporation Superalloy single crystal articles
US4492672A (en) * 1982-04-19 1985-01-08 The United States Of America As Represented By The Secretary Of The Navy Enhanced microstructural stability of nickel alloys
EP0240451A2 (de) * 1986-04-03 1987-10-07 United Technologies Corporation Einkristalline Körper mit geringer Anisotropie
US4878965A (en) * 1987-10-05 1989-11-07 United Technologies Corporation Oxidation resistant superalloy single crystals

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4371404A (en) * 1980-01-23 1983-02-01 United Technologies Corporation Single crystal nickel superalloy
EP0052911A1 (de) * 1980-11-24 1982-06-02 Cannon-Muskegon Corporation Einkristall-Legierung (einzelnes Korn)
US4402772A (en) * 1981-09-14 1983-09-06 United Technologies Corporation Superalloy single crystal articles
US4492672A (en) * 1982-04-19 1985-01-08 The United States Of America As Represented By The Secretary Of The Navy Enhanced microstructural stability of nickel alloys
EP0240451A2 (de) * 1986-04-03 1987-10-07 United Technologies Corporation Einkristalline Körper mit geringer Anisotropie
US4878965A (en) * 1987-10-05 1989-11-07 United Technologies Corporation Oxidation resistant superalloy single crystals

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6468367B1 (en) * 1999-12-27 2002-10-22 General Electric Company Superalloy weld composition and repaired turbine engine component
US6565680B1 (en) * 1999-12-27 2003-05-20 General Electric Company Superalloy weld composition and repaired turbine engine component
EP1184473A2 (de) * 2000-08-30 2002-03-06 Kabushiki Kaisha Toshiba Monokristalline Nickel-Basis-Legierungen und Verfahren zur Herstellung und daraus hergestellte Hochtemperaturbauteile einer Gasturbine
EP1184473A3 (de) * 2000-08-30 2002-05-22 Kabushiki Kaisha Toshiba Monokristalline Nickel-Basis-Legierungen und Verfahren zur Herstellung und daraus hergestellte Hochtemperaturbauteile einer Gasturbine
US6673308B2 (en) 2000-08-30 2004-01-06 Kabushiki Kaisha Toshiba Nickel-base single-crystal superalloys, method of manufacturing same and gas turbine high temperature parts made thereof
EP1586669A1 (de) * 2004-04-07 2005-10-19 United Technologies Corporation Oxidationsbeständige Superlegierung und Gegenstand
GB2429463A (en) * 2004-04-30 2007-02-28 Aerojet General Co Single phase tungsten alloy for shaped charge liner
WO2005111530A3 (en) * 2004-04-30 2006-03-23 Aerojet General Co Single phase tungsten alloy for shaped charge liner
WO2005111530A2 (en) * 2004-04-30 2005-11-24 Aerojet-General Corporation Single phase tungsten alloy for shaped charge liner
US7360488B2 (en) * 2004-04-30 2008-04-22 Aerojet - General Corporation Single phase tungsten alloy
GB2429463B (en) * 2004-04-30 2008-11-19 Aerojet General Co Single phase tungsten alloy for shaped charge liner
US7921778B2 (en) * 2004-04-30 2011-04-12 Aerojet - General Corporation Single phase tungsten alloy for shaped charge liner
DE112005000960B4 (de) 2004-04-30 2022-03-03 Aerojet Rocketdyne, Inc. Einphasige Wolframlegierung für eine Hohlladungseinlage
US8858876B2 (en) 2012-10-31 2014-10-14 General Electric Company Nickel-based superalloy and articles
US10280486B2 (en) 2012-10-31 2019-05-07 General Electric Company Nickel-based superalloy and articles
EP3091095A1 (de) 2015-05-05 2016-11-09 MTU Aero Engines GmbH Rheniumfreie nickelbasis-superlegierung mit niedriger dichte

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