US3620855A - Superalloys incorporating precipitated topologically close-packed phases - Google Patents

Superalloys incorporating precipitated topologically close-packed phases Download PDF

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Publication number
US3620855A
US3620855A US861496A US3620855DA US3620855A US 3620855 A US3620855 A US 3620855A US 861496 A US861496 A US 861496A US 3620855D A US3620855D A US 3620855DA US 3620855 A US3620855 A US 3620855A
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United States
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percent
nickel
alloy
phase
molybdenum
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Expired - Lifetime
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US861496A
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English (en)
Inventor
David H Wagner
David N Duhl
Edward H Van Der Molen
Cornelius P Sullivan
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RTX Corp
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United Aircraft Corp
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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

Definitions

  • the present invention relates in general to certain nickelbase and cobalt-base superalloy components, particularly those having substantial utility in gas turbine engine application.
  • the superalloys in general consist of those alloys exhibiting very high strengths at the temperatures associated with gas turbine engine use. They typically comprise a solid solution strengthened nickel or cobalt-rich matrix phase in which a carbide phase has been precipitated to strengthen grain boundaries.
  • a precipitated phase such as the intermetallic compound represented by the fonnula Ni (Al, Ti), usually referred to as the -y' phase.
  • This phase may exist as a fine, uniformly distributed, solid state precipitate or as a globular, kidney-shaped structure resulting from a liquid-solid phase reaction.
  • the former type of the y precipitate because of its size and distribution, is generally the one most effective in the promotion of alloy strength.
  • the strength of the nickel-base superalloys has been basically a function of three distinct mechanisms: (1) solid solution strengthening; (2) carbide precipitation; and (3) 7' phase precipitation.
  • Solid solution strengthening is imparted by the addition to the alloy of refractory elements with very high melting points, such as tungsten, molybdenum, tantalum, columbium and chromium. These strengtheners are primarily found in the matrix phase of the processed alloys.
  • Carbide precipitation is promoted through the addition of carbidefonning elements and carbon to the alloy, and these may include those elements which also contribute to solid solution strengthening.
  • titanium, zirconium and hafnium promote carbide formation. Precipitation of the phase is effected through the addition of those elements needed to form this phase, principally aluminum and titanium, although limited quantities of other elements are often found in this phase on chemical analysis.
  • TCP topologically closepacked
  • sigma is a particularly well known precipitate of this general type and many of the commercially available superalloys are specifically formulated to avoid the formation of sigma.
  • rigid control standards are frequently written into the superalloy material's specifications to prevent the selection of a formulation yielding precipitation of these undesirable phases.
  • TCP phases results from the fact that they typically form as platelets or needles which provide the natural sites for mechanical weakness and, in addition, compete with the matrix phase for the solid solution strengthening elements.
  • a detailed discussion of the sigma phase may be found in an article by E. 0. Hall et al., The Institute for Metals, Vol. 11 (1961) p. 61.
  • the present invention relates in general to the superalloys in the nickel-base and cobalt-base alloy systems characterized by a fine dispersion of the topologically close-packed phases, such as sigma, in an equiaxed morphology, and to compositions and methods for providing such superalloys.
  • the TCP phases are intermediate phases of no precise composition.
  • the formation of such phases in the nickel-base superalloys is efi'ected by providing a sufficiency of those constituents particularly the transition elements including chromium, cobalt and molybdenum, which actively participate in the formation of the TCP phases.
  • depletion of the matrix phase in nickel will increase the propensity for TCP phase formation. This is conveniently accomplished by enriching the alloy in aluminum or titanium which causes more nickel to be tied up in the 7' phase thereby depleting the matrix phase in nickel.
  • silicon to the superalloys will enhance the formation of the TCP phases.
  • tungsten, tantalum, chromium and molybdenum are particularly effective in providing the precipitated TCP phases.
  • the nickel-base superalloys will generally contain, by weight, 10-25 percent chromium, 10-25 percent cobalt, 0-7 percent molybdenum, 1.5-7 percent titanium, 1.5-7 percent aluminum, 0.01-0.5 percent carbon and 0003-002 percent boron.
  • the particular quantities of the alloy constituents within the above ranges, together with the other ingredients present in the alloy, are selected to promote the precipitation of copious quantities of the TCP phases.
  • the allow composition be such that TCP phase precipitation is provided.
  • the metallurgical character of the alloy must also be such as to permit processing to provide precipitation not in the usual detrimental acicular form but in an equiaxed morphology.
  • the preferred thermomechanical processing utilized with the nickel-base alloys involves the following steps: (1) heat treating the alloy to solution the precipitates; (2) aging the alloy to precipitate the 7' phase to a minimum of about 25 volume percent in a homogeneous distribution having an effective interparticle spacing not exceeding about 5 microns at a temperature sufficiently high to prevent substantial precipitation of the TCP phases; (3) warm working the alloy to effect an area reduction of at least 15 percent while maintaining essentially the same volume percent and distribution of the y phase established in the aging process, usually at about the aging temperature; and (4) heat treating the alloy to cause precipitation of the TCP phases in a thermally and mechanically stable array of microcrystalline imperfections.
  • precipitation of these phases should preferably occur within a range of temperatures where the phase is stable without any of the TCP phases in precipitate form. Basically, this is achieved by providing a formulation wherein the 'y' solvus temperature of the alloy is above and, preferably, considerably above the precipitation temperature of the TCP phases.
  • the precipitation mechanism must be such in the nickel-base superalloy systems that precipitation of the phase must occur, if not prior to, more expeditiously than the TCP phase precipitation since the phase morphology and distribution is the controlling factor in providing the desired TCP phase morphology after processing.
  • a high y solvus temperature may be effected by providing a high aluminum plus titanium content in the alloy, typically about 9 percent. It is usually advisable to maintain the aluminum to titanium ratio at or near unity.
  • the alloys were vacuum induction melted and cast as electrodes which were subsequently consumable arc melted under vacuum into two l-inch-diameter bars.
  • the bars were solution annealed at 2,150 F. for four hours and fast air-cooled.
  • Bar A was then heattreated at l,975 F. for four hours to precipitate the 7' phase, and it was swaged to a 60 percent area reduction at 1,975", F. using a reduction of six percent per pass with a l-minute reheat between passes.
  • Bar B was given a precipitation heat treatment at 1,875" F. but no deformation, and it was used as the standard.
  • Bar A was given final heat treatments of 4 and 24 hours at temperatures of 1,875 F-1,200 F.
  • the hardness of the warm-worked material was significantly higher than that of conventional nickel base superalloys. Hardness values in the R 50s were obtained after aging at temperatures below 1,700 F. For comparison the hardness of fully heattreated Udimet 700 is about R, 39. Furthermore the yield strength of the warm-worked material in compression was significantly higher than the conventional superalloys. At room temperature the ductility of the hardest warm-worked specimen is above that of tool steel although the yield strength was 100,000 p.s.i. lower. However, at 1,000 F. where the strength of the tool steel was sharply reduced, the strength of the warm-worked alloys with the/TCP phases lost very little strength.
  • compositions providing copious quantities of TCP precipitates and amenable to processing by thermomechanical means to provide the equiaxed TCP morphology are the following:
  • the nickelbase superalloy formulations particularly susceptible to strengthening and hardening improvements utilizing TCP phase precipitation generally contain about, by weight, 10-25 percent chromium for oxidation resistance, 10-25 percent 1 cobalt, O7 percent molybdenum, 1.5-7 percent titanium,
  • cobalt-base superalloys In the cobalt-base superalloy systems, generally higher chromium contents are usable. Thus, cobalt-base superalloys containing 20-30 percent chromium, 5-20 percent nickel, 10-20 percent tungsten or molybdenum, 0-15 percent tantalum, 0.25-1 percent silicon, and 0.05-1 percent carbon precipitating copious quantities of the TCP phases, are suited to the present strengthening mechanism.
  • the above formulations in addition to the strengthening or hardening effect provided by the equiaxed sigma, are of fundamental interest to the gas turbine engine industry. Because TCP phase precipitation is usually associated with generally higher aluminum and ,titanium contents than conventional superalloys, low alloy densities are provided.
  • An alloy article characterized by high strength and hardness at high temperatures which consists essentially of an alloy selected from the group consisting of the nickel-base and cobalt-base superalloys having uniformly dispersed therein a substantial quantity of a topologically close-packed phase in a substantially equiaxed morphology.
  • a nickel-base superalloy article characterized by high strength and hardness at high temperature which consists essentially of a nickel-base alloy matrix of high melting point, a 7' phase uniformly dispersed therein, and a dispersed topologically close-packed phase in a substantially equiaxed morphology.
  • alloy microstructure is characterized by a polygonal substructure consisting of dislocations aligned as subcell boundaries to provide a regular array of defects.
  • An article according to claim 2 wherein the allow contains, by weight, l0-25 percent chromium, 10-25 percent cobalt, 0-7 percent molybdenum, 1.5-7 percent titanium, 1.5-7 percent aluminum, 0.01-0.5 percent carbon, and 0.003-0.02 percent boron.
  • talum, 0-l percent silicon, and 0.054 percent carbon have a dispersed topologically close-packed phase precipitated

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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)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Heat Treatment Of Nonferrous Metals Or Alloys (AREA)
US861496A 1969-09-26 1969-09-26 Superalloys incorporating precipitated topologically close-packed phases Expired - Lifetime US3620855A (en)

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US86149669A 1969-09-26 1969-09-26

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US (1) US3620855A (fr)
JP (1) JPS5117491B1 (fr)
BE (1) BE756652A (fr)
CA (1) CA930204A (fr)
CH (1) CH557881A (fr)
DE (1) DE2043053A1 (fr)
FR (1) FR2062624A5 (fr)
GB (1) GB1318267A (fr)
NL (1) NL7014191A (fr)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3816920A (en) * 1972-11-30 1974-06-18 Gillette Co Novel cutting edges and processes for making them
US3973952A (en) * 1973-06-11 1976-08-10 The International Nickel Company, Inc. Heat resistant alloy casting
US4574015A (en) * 1983-12-27 1986-03-04 United Technologies Corporation Nickle base superalloy articles and method for making
US4579602A (en) * 1983-12-27 1986-04-01 United Technologies Corporation Forging process for superalloys
US4769087A (en) * 1986-06-02 1988-09-06 United Technologies Corporation Nickel base superalloy articles and method for making
US4908069A (en) * 1987-10-19 1990-03-13 Sps Technologies, Inc. Alloys containing gamma prime phase and process for forming same
US5169463A (en) * 1987-10-19 1992-12-08 Sps Technologies, Inc. Alloys containing gamma prime phase and particles and process for forming same
US5527403A (en) * 1993-11-10 1996-06-18 United Technologies Corporation Method for producing crack-resistant high strength superalloy articles
US20080289730A1 (en) * 2005-12-05 2008-11-27 Japan Science And Technology Agency Material having a high elastic deformation and process for producing the same
CN109921014A (zh) * 2017-12-13 2019-06-21 荆门市格林美新材料有限公司 具有亚晶结构的镍基锂离子电池正极材料及其制备方法
CN114990408A (zh) * 2022-04-26 2022-09-02 沈阳航空航天大学 综合力学性能优异的NiCoCrFeAlTi中熵合金及其制备方法

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2593830B1 (fr) * 1986-02-06 1988-04-08 Snecma Superalliage a matrice a base de nickel notamment elabore en metallurgie des poudres et disque de turbomachine constitue en cet alliage
GB0024031D0 (en) 2000-09-29 2000-11-15 Rolls Royce Plc A nickel base superalloy

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3147155A (en) * 1961-08-02 1964-09-01 Int Nickel Co Hot-working process

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3147155A (en) * 1961-08-02 1964-09-01 Int Nickel Co Hot-working process

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3816920A (en) * 1972-11-30 1974-06-18 Gillette Co Novel cutting edges and processes for making them
US3973952A (en) * 1973-06-11 1976-08-10 The International Nickel Company, Inc. Heat resistant alloy casting
US4574015A (en) * 1983-12-27 1986-03-04 United Technologies Corporation Nickle base superalloy articles and method for making
US4579602A (en) * 1983-12-27 1986-04-01 United Technologies Corporation Forging process for superalloys
US4769087A (en) * 1986-06-02 1988-09-06 United Technologies Corporation Nickel base superalloy articles and method for making
US4908069A (en) * 1987-10-19 1990-03-13 Sps Technologies, Inc. Alloys containing gamma prime phase and process for forming same
US5169463A (en) * 1987-10-19 1992-12-08 Sps Technologies, Inc. Alloys containing gamma prime phase and particles and process for forming same
US5527403A (en) * 1993-11-10 1996-06-18 United Technologies Corporation Method for producing crack-resistant high strength superalloy articles
US20080289730A1 (en) * 2005-12-05 2008-11-27 Japan Science And Technology Agency Material having a high elastic deformation and process for producing the same
CN109921014A (zh) * 2017-12-13 2019-06-21 荆门市格林美新材料有限公司 具有亚晶结构的镍基锂离子电池正极材料及其制备方法
CN109921014B (zh) * 2017-12-13 2021-10-01 荆门市格林美新材料有限公司 具有亚晶结构的镍基锂离子电池正极材料及其制备方法
CN114990408A (zh) * 2022-04-26 2022-09-02 沈阳航空航天大学 综合力学性能优异的NiCoCrFeAlTi中熵合金及其制备方法
CN114990408B (zh) * 2022-04-26 2023-02-10 沈阳航空航天大学 综合力学性能优异的NiCoCrFeAlTi中熵合金及其制备方法

Also Published As

Publication number Publication date
NL7014191A (fr) 1971-03-30
CA930204A (en) 1973-07-17
GB1318267A (en) 1973-05-23
BE756652A (fr) 1971-03-01
DE2043053A1 (de) 1971-04-22
CH557881A (de) 1975-01-15
FR2062624A5 (fr) 1971-06-25
JPS5117491B1 (fr) 1976-06-02

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