US3671223A - Anisotropic polyphase structure of multivariant eutectic composition - Google Patents

Anisotropic polyphase structure of multivariant eutectic composition Download PDF

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US3671223A
US3671223A US883713A US3671223DA US3671223A US 3671223 A US3671223 A US 3671223A US 883713 A US883713 A US 883713A US 3671223D A US3671223D A US 3671223DA US 3671223 A US3671223 A US 3671223A
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anisotropic
nickel
multivariant
eutectic
percent
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US883713A
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Earl R Thompson
Franklin D Lemkey
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Raytheon Technologies Corp
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United Aircraft Corp
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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B21/00—Unidirectional solidification of eutectic materials
    • C30B21/02—Unidirectional solidification of eutectic materials by normal casting or gradient freezing
    • 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
    • C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C30/00—Alloys containing less than 50% by weight of each constituent

Definitions

  • Quaternary or higher order alloy systems are unidirectionally solidified to provide anisotropic polyphase structures wherein one or more phases of a Whisker or lamellar morphology in substantial alignment is embedded in a matrix phase. Included in the systems described are the cobalt, nickel and iron alloys containing chromium, aluminum and/ or nickel.
  • the present invention relates in general to those compositions, including the alloys, selected from the quaternary or high order systems which display multivariant eutectic behavior and, more particularly, to such compositions as unidirectionally solidified into polyphase anisotropic structures.
  • a recognized disadvantage to the usual binary eutectic or pseudo-binary eutectic approach in the production of composite structures by directional solidification techniques has been the lack of versatility of these systems for many applications.
  • the volume fraction and chemistry of the respective phases are fixed by the uniqueness of the invariant equilibrium. Accordingly, since no significant variation in the volume fraction or chemistry of the phases is possible during equilibrium freezing, the total number of these alloys having all of the requisite characteristics or optimum properties for a specific, predetermined use is very limited, particularly when several ditferent physical or chemical criteria are demanded for that use.
  • the monovariant eutectic systems provide a considerable measure of latitude in the selection of 3,671,223 Patented June 20, 1972 compositions satisfying particular end objectives, particularly when compared to the invariant eutectic compositions.
  • the monovariant system there exists a unique capability of changing the chemistry and morphology of the phases, along the eutectic trough of their phase diagram, and it is possible to alter the volume fractions of their phases as well as their compositions.
  • This invention relates to aligned polyphase structures formed from the quaternary or high order compositions which respond to unidirectional solidification from a melt to form a dispersed fibrous or lamellar phase or phases embedded in substantial alignment in a matrix phase.
  • the structures contemplated are formed from the compositions which are multivariant thermodynamically and not as in the binary systems invariant at a fixed composition or as the monovariant eutectic systems variant monolinearly along a eutectic trough.
  • compositions formed as described herein consist of an aligned fibrous or lamellar, collectively referred to as fibrous, phase or phases embedded in a cobalt, nickel or iron solid solution matrix phase.
  • FIG. 1 is a photomicrograph of a quaternary cobaltbase alloy containing nickel, chromium and carbon, unidirectionally solidified at a rate of 10 cm./hr. to provide an aligned microstructure.
  • FIG. 2 is a phase diagram comprising a polythermal projection of a quaternary system illustrating freezing of an alloy by the reaction L- (1+5.
  • phase alignment is achieved is similar to that used for the invariant and monovariant eutectics, and is involved with the simultaneous freezing of two or more solid phases from the liquid.
  • preparation techniques described by Kraft, supra, and others, with the solidification parameters selected to provide macroscopically plane front growth, successful solidification rates generally being achieved within at least the range of 220 cm./hr.
  • FIG. 2 shows a polythermal projection of a simple, hypothetical quaternary system, ABCD, where A, B, C and D are the system components.
  • the binaries AC, BC and CD form the eutectics E E and Q, respectively, and the corresponding melting temperature are on the order E E E
  • the systems between A, B and D form a continuous series of solid solutions.
  • the faces of the tetrahedron show polythermal projections of the ternary systems ACD, ABC, and BCD. No reactions are shown on the ABD face of the tetrahedron since this is on isomorphous system.
  • the binary eutectics E E and E solidify upon directional casting to form anisotropic structures as taught by Kraft, supra, at a fixed composition and temperature.
  • the lines E E E l-3 and E E define monovariant eutectic troughs, and composi tions lying along these lines, excluding the end points, may be solidified by directional casting techniques to produce anisotropic polyph-ase structures, as taught in the copending application relating to monovariant eutectic systems.
  • the surface E 'E E (liquidus surface), excluding the end lines and end points, is, in the system described, the locus of those compositions covered herein.
  • An alloy on this surface, of composition begins to freeze forming solids a and ,3, simultaneously.
  • the composition of the liquid shifts along the line l l while the equilibrium compositions of the crystallizing solids shift along the lines 04 and 5 5 At l the last liquid freezes with a and 3 as the conjugate solids.
  • compositions solidifying according to the multivariant eutectic reaction are those defined by the liquidus surface (quaternary systems) or liquidus volume (higher order systems), exclusive in the case of the quaternary systems, of boundary compositions.
  • the ability to form an anisotropic biphase structure employing the teachings herein was demonstrated in the cobalt-chromium-nickel-carbon quaternary.
  • An alloy of the nominal composition, by weight, 41 percent chromium, 10 percent nickel, 2.4 percent carbon, balance cobalt was unidirectionally solidified at approximately 10 cm./hr. Growth occurred by macroscopically plane front solidification to provide an aligned microstructure, as evidenced by FIG. 1.
  • the structure comprises a matrix phase consisting essentially of cobalt, chromium nickel and carbon in solid solution and a reinforcing phase comprising on M C type of carbide, when M consists of chromium, cobalt and nickel.
  • An iron-base alloy of the nominal composition by weight, 43 percent iron, 35 percent chromium, 20 percent nickel and 2 percent carbon, as directionally solidified at 8 cm./hr. provided an aligned microstructure with the aligned phase comprising the carbide Cr yC embedded in a solid solution matrix of iron, nickel and chromium.
  • phase alignment according to the multivariant eutectic reaction has been demonstrated in the nickel-base alloy systems including an alloy of the composition, by weight, 36 percent chromium, 110 percent cobalt, 1.5 percent carbon, balance essentially nickel.
  • Fiber-strengthened composite structures may be particularly attractive for gas turbine engine use when the melting points of the respective phases are high and the reinforcing phases are strong. With the present invention considerable compositional latitude is provided to afford not only reasonable high temperature strengths but also a balance of other alloy criteria such as oxidation, sulfidation, erosion and thermal shock resistance. And, of course, since the mechanisms involved in the generation of these composites is one of equilibrium freezing, there is provided, in general, good metallurgical and chemical stability over the temperature ranges contemplated in practical use.
  • a unidirectionally solidified anisotropic body formed of the quaternary or higher order material systems of multivariant eutectic composition segregated into a matrix phase and at least one dispersed phase, said dispersed phases being fibrous with the individual fibers thereof oriented in substantial alignment over a substantial por tion of the body and embedded in the matrix phase.
  • a unidirectionally solidified anisotropic body formed of the quaternary or higher order alloys of multivariant eutectic composition segregated into a matrix phase consisting essentially of a nickel-cobalt or iron-base alloy and a dispersed phase, the dispersed phase consisting of a plurality of high strength carbide fibers oriented in substantial alignment over a substantial portion of the body and integrally embedded in the matrix phase.
  • a unidirectionally solidified anisotropic composite formed of the quaternary or higher order alloys of multivariant eutectic composition which comprises a matrix phase consisting of an alloy of cobalt, nickel or iron, and a dispersed phase embedded therein in the form of high strength fibers oriented in substantial alignment over a major portion of the composite, the dispersed phase consisting essentially of a carbide of the M7C type, where M is either chromium or a mixture of elements including chromium.
  • a unidirectionally solidified article formed of the quaternary or higher order alloys of multivariant eutectic composition having anisotropic properties comprising a fiber-strengthened composite consisting of a nickel alloy matrix and analigned fibrous phase consisting of a mixed carbide of the M C type where M includes chromium and nickel.
  • a unidirectionally solidified article formed of the quaternary or higher order alloys of multivariant eutectic composition halving anisotropic properties comprising a fiber-strengthened composite consisting of an iron alloy matrix and an aligned fibrous phase consisting of a mixed carbide of the M C type where M includes chromium and iron.
  • a unidirectionally solidified casting of a nominal composition consisting essentially of, by weight, about 41 percent chromium, about, 2.4 percent carbon, remainder cobalt together with at least one of the following, about '10 percent nickel, about 1.5 percent aluminum, the casting being characterized by pronounced alignment of a dispersed phase comprising a carbide of the M7C3 type, where M is predominantly chromium.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
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  • Crystallography & Structural Chemistry (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
US883713A 1969-12-10 1969-12-10 Anisotropic polyphase structure of multivariant eutectic composition Expired - Lifetime US3671223A (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3767479A (en) * 1972-02-14 1973-10-23 Gen Electric Multicomponent eutectics for high temperature applications
US3793008A (en) * 1972-03-01 1974-02-19 Gen Electric Monocarbide fiber-reinforced iron-base superalloy composite eutectic castings and method
US3844845A (en) * 1973-11-15 1974-10-29 Gen Electric Directional composites by solid-state up-transformation
US3847679A (en) * 1973-11-15 1974-11-12 Gen Electric Directional eutectoid composites by solid-state up-transformation
US3915761A (en) * 1971-09-15 1975-10-28 United Technologies Corp Unidirectionally solidified alloy articles
US3920489A (en) * 1970-03-02 1975-11-18 Gen Electric Method of making superalloy bodies
US4054469A (en) * 1976-06-01 1977-10-18 General Electric Company Directionally solidified eutectic γ+β nickel-base superalloys
US4288259A (en) * 1978-12-04 1981-09-08 United Technologies Corporation Tantalum modified gamma prime-alpha eutectic alloy
US4543235A (en) * 1982-09-22 1985-09-24 United Technologies Corporation Eutectic superalloy compositions and articles
US4859416A (en) * 1986-03-17 1989-08-22 Stuart Adelman Superalloy compositions and articles
US5858558A (en) * 1996-10-30 1999-01-12 General Electric Company Nickel-base sigma-gamma in-situ intermetallic matrix composite
US20090136381A1 (en) * 2007-11-23 2009-05-28 Rolls-Royce Plc Ternary nickel eutectic alloy

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3920489A (en) * 1970-03-02 1975-11-18 Gen Electric Method of making superalloy bodies
US3915761A (en) * 1971-09-15 1975-10-28 United Technologies Corp Unidirectionally solidified alloy articles
US3767479A (en) * 1972-02-14 1973-10-23 Gen Electric Multicomponent eutectics for high temperature applications
US3793008A (en) * 1972-03-01 1974-02-19 Gen Electric Monocarbide fiber-reinforced iron-base superalloy composite eutectic castings and method
US3844845A (en) * 1973-11-15 1974-10-29 Gen Electric Directional composites by solid-state up-transformation
US3847679A (en) * 1973-11-15 1974-11-12 Gen Electric Directional eutectoid composites by solid-state up-transformation
US4054469A (en) * 1976-06-01 1977-10-18 General Electric Company Directionally solidified eutectic γ+β nickel-base superalloys
US4288259A (en) * 1978-12-04 1981-09-08 United Technologies Corporation Tantalum modified gamma prime-alpha eutectic alloy
US4543235A (en) * 1982-09-22 1985-09-24 United Technologies Corporation Eutectic superalloy compositions and articles
US4859416A (en) * 1986-03-17 1989-08-22 Stuart Adelman Superalloy compositions and articles
US5858558A (en) * 1996-10-30 1999-01-12 General Electric Company Nickel-base sigma-gamma in-situ intermetallic matrix composite
US20090136381A1 (en) * 2007-11-23 2009-05-28 Rolls-Royce Plc Ternary nickel eutectic alloy
US8858874B2 (en) 2007-11-23 2014-10-14 Rolls-Royce Plc Ternary nickel eutectic alloy

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DE2060206A1 (de) 1971-06-16
DE2060206B2 (de) 1973-12-20
GB1297657A (de) 1972-11-29
FR2072682A5 (de) 1971-09-24
DE2060206C3 (de) 1974-07-18

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