EP1262569B1 - Superalliage monocristallin à base de nickel - Google Patents

Superalliage monocristallin à base de nickel Download PDF

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Publication number
EP1262569B1
EP1262569B1 EP02253782A EP02253782A EP1262569B1 EP 1262569 B1 EP1262569 B1 EP 1262569B1 EP 02253782 A EP02253782 A EP 02253782A EP 02253782 A EP02253782 A EP 02253782A EP 1262569 B1 EP1262569 B1 EP 1262569B1
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Prior art keywords
phase
strength
single crystal
alloy
based single
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Expired - Lifetime
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EP02253782A
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German (de)
English (en)
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EP1262569A8 (fr
EP1262569A1 (fr
Inventor
Yutaka c/o Nat.Inst. f. Materials Science Koizumi
Toshiharu c/o Nat.Inst. f. Mat. Science Kobayashi
Tadaharu c/o Nat.Inst. f. Mat. Science Yokokawa
Hiroshi c/o Nat.Inst. f. Material Science Harada
Yasuhiro Ishikawajima-Harima Heavy I. Co.Ltd Aoki
Mikiya Ishikawajima-Harima Heavy Ind.Co.Ltd Arai
Shoju Ishikawajima-Harima Heavy Ind.Co.Ltd Masaki
Ryoji Ishikawajima-Harima HeavyInd.Co.Ltd Kakiuchi
Kazuyoshi Ishikawajima-HarimaHeavyI.Co.Ltd Chikugo
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IHI Corp
National Institute for Materials Science
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IHI Corp
National Institute for Materials Science
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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%

Definitions

  • the present invention relates to a Ni-based single crystal super alloy, and more particularly, to a technology employed for improving the creep characteristics of Ni-based single crystal super alloy.
  • Ni-based single crystal super alloys after performing solution treatment at a prescribed tempetature, aging treatment is performed to obtain an Ni-based single crystal super alloy.
  • This alloy is referred to as a so-called precipitation hardened alloy, and has a from in which the precipitation phase in the form of a ⁇ ' phase is precipitated in a matrix in the form of a ⁇ phase.
  • CMSX-2 (Canon-Muskegon, US Patent No. 4,582,548) is a first-generation alloy
  • CMSX-4 Canon-Muskegon, US Patent No. 4,643,782
  • Rene'N6 General Electric, US Patent No. 5,455,120
  • CMSX-10K (Canon-Muskegon, US Patent No. 5,366,695) are third-generation alloys
  • 3B General Electric, US Patent No. 5,151,249 is a fourth-generation alloy.
  • CMSX-2 which is a first-generation alloy
  • CMSX-4 which is a second-generation alloy
  • their creep strength is inferior to third-generation alloys.
  • the third-generation alloys of Rene'N6 and CMSX-10 are alloys designed to have improved creep strength at high temperatures in comparison with second-generation alloys, since the composite ratio of Re (5 wt% or more) exceeds the amount of Re that dissolves into the matrix ( ⁇ phase), the excess Re compounds with other elemems and as a result, a so-called TCP (topologically close packed) phase precipitates at high temperatures causing the problem of decreased creep strength.
  • Japanese patent application publication no. 2000239771 discloses a Ni based super alloy, its production and gas turbine parts.
  • the Ni based super alloy is intended to have high temperature corrosion resistance.
  • FR2780983 provides a nickel based single crystal super alloy containing various alloying materials, intended to provide creep resistance at high temperature.
  • the object of present invention is to provide a Ni-based single crystal super alloy that makes it possible to improve strength by preventing precipitation of the TCP phase at high temperatures.
  • the present invention provides an Ni-based single crystal super alloy having a composition consisting of 5.0-7.0 wt% Al, 4.0-8.0 wt% Ta, 2.9-4.5 wt% Mo, 4.0-8.0 wt% W, 3.0-6.0 wt% Re, 0.01-0.50 wt% Hf, 2.0-5.0 wt% Cr, 0.1-5.9 wt% Co and 1.0-4.0 wt% Ru in terms of its weight ratio, with the remainder consisting of Ni and unavoidable impurities; and characterized in that, when the lattice constant of the matrix is taken to be a1 and the lattice constant of the precipitation phase is taken to be a2, a2 ⁇ 0.999a1.
  • the present invention further provides an Ni-based single crystal super alloy having a composition consisting of 5.0-7.0 wt% Al, 4.0-6.0 wt% Ta, 1.0-4.5 wt% Mo, 4.0-8.0 wt% W, 3.0-6.0 wt% Re, 0.01-0.50 wt% Hf, 2.0-5.0 wt% Cr, 0.1-5.9 wt% Co, and 1.0-4.0 wt% Ru in terms of weight ratio, with the remainder consisting of Ni and unavoidable impurities; and characterized in that, when the lattice constant of the matrix is taken to be a1 and the lattice constant of the precipitation phase is taken to be a2, a2 ⁇ 0.999a1.
  • the present invention further provides an Ni-based single crystal super alloy having a composition consisting of 5.0-7.0 wt% Al, 4.0-6.0 wt% Ta, 2.9-4.5 wt% Mo, 4.0-8.0 wt% W, 3.0-6.0 wt% Re, 0.01-0.50 wt% Hf, 2.0-5.0 wt% Cr, 0.1-5.9 wt% Co and 1.0-4.0 wt% Ru in terms of weight ratio, with the remainder consisting of Ni and unavoidable impurities; and characterized in that, when the lattice constant of the matrix is taken to be a1 and the lattice constant of the precipitation phase is taken to be a2, a2 ⁇ 0.999a1.
  • the lattice constant of the matrix ( ⁇ phase) and the lattice constant of the precipitation phase ( ⁇ ' phase) can be made to have optimum values. Consequently, strength at high temperatures can be enhanced.
  • the Ni-based single crystal supper alloy ot the present invention preferably has a composition of 5.9 wt% Al, 5.9 wt% Ta, 2.9 wt% Mo, 5.9 wt% W, 4.9 wt% Re, 0.10 wt% Hf, 2.9 wt% Cr, 5.9 wt% Co and 2.0 wt% Ru in terms of weight ratio, with the remainder consisting of Ni and unavoidable impurities, in the Ni-based single crystal super alloys previously described.
  • the creep endurance tempetature at 137 MPa and 1000 hours can be made to be 1356 K (1083°C).
  • the relationship between a1 and a2 is such that a2 ⁇ 0.999a1 when the lattice constant of the matrix is taken to be a1 and the lattice constant of the precipitation phase is taken to be a2, and since the lattice constant a2 of the precipitation phase is -0.1% or less of the lattice constant a1 of the matrix, the precipitation phase that precipitates in the matrix precipitates so as to extend continuously in the direction perpendicular to the direction of the load.
  • strength at high temperatures can be enhanced without dislocation defects moving within the alloy structure under stress.
  • the Ni-based single crystal super alloy of the present invention is an alloy comprised of Al, Ta, Mo, W, Re, Hf, Cr, Co, Ru, Ni (remainder) and unavoidable impurities.
  • the above Ni-based single crystal super alloy is an alloy having a composition consisting of 5.0-7.0 wt% Al, 4.0-8.0 wt% Ta, 2.9-4.5 wt% Mo, 4.0-8.0 wt% W, 3.0-6.0 wt% Re, 0.01-0.5 wt% Hf, 2.0-5.0 wt% Cr, 0.1-5.9 wt% Co and 1.0-4.0 wt% Ru, with the remainder consisting of Ni and unavoidable impurities.
  • the above Ni-based single crystal super alloy is an alloy having a composition consisting of 5.0-7.0 wt% Al, 4.0-6.0 wt% Ta, 1.0-4.5 wt% Mo, 4.0-8.0 wt% W, 3.0-6.0 wt% Re, 0.01-0.5 wt% Hf, 2.0-5.0 wt% Cr, 0.1-5.9 wt% Co and 1.0-4.0 wt% Ru, with the remainder consisting of Ni and unavoidable impurities.
  • the above Ni-based single crystal super alloy is an alloy having a composition consisting of 5.0-7.0 wt% Al, 4.0-6.0 wt% Ta, 2.9-4.5 wt% Mo, 4.0-8.0 wt% W, 3.0-6.0 wt% Re, 0.01-0.5 wt% Hf, 2.0-5.0 wt% Cr, 0.1-5.9 wt% Co and 1.0-4.0 wt% Ru, with the remainder consisting of Ni and unavoidable impurities.
  • All of the above alloys have an austenite phase in the form ⁇ phase (matrix) and an intermediate regular phase in the form of a ⁇ ' phase (precipitation phase) that is dispersed and precipitated in the matrix.
  • the ⁇ ' phase is mainly composed of an intermetallic compound represented by Ni 3 Al, and the strength of the Ni-based single crystal super alloy at high temperatures is improved by this ⁇ ' phase.
  • the composite ratio of Cr is preferably within the range of 2.0 wt% or more to 5.0 wt% or less, and more preferably 2.9 wt%. If the composite ratio of Cr is less than 2.0 wt%, the desired high-temperature corrosion resistance cannot be secured, thereby making this undesirable. If the composite ratio of Cr exceeds 5.0 wt%, in addition to precipitation of the ⁇ ' phase being inhibited, harmful phases such as a ⁇ phase or ⁇ phase form that cause a decrease in strength at high temperatures, thereby making this undesirable.
  • Mo In addition to improving strength at high temperatures by dissolving into the matrix in the form of the y phase in the presence of W and Ta, Mo also improves strength at high temperatures due to precipitation hardening.
  • the composite ratio of Mo is preferably within the range of 1.0 wt% or more to 4.5 wt% or less, more preferably within the range of 2.9 wt% or more to 4.5 wt% or less, and most preferably 2.9 wt%. If the composite ratio of Mo is less than 1.0 wt%, strength at high temperatures cannot be maintained at the desired level, thereby making this undesirable. If the composite ratio of Mo exceeds 4.5 wt%, strength at high temperatures decreases, and corrosion resistance at high temperatures also decreases, thereby making this undesirable.
  • W improves strength at high temperatures due to the actions of solution hardening and precipitation hardening in the presence of Mo and Ta as previously mentioned.
  • the composite ratio of W is preferably within the range of 4.0 wt% or more to 8.0 wt% or less, and most preferably 5.9 wt%. If the composite ratio of W is less than 4.0 wt%, strength at high temperatures cannot be maintained at the desired level, thereby making this undesirable. If the composite ratio of W exceeds 8.0 wt%, high-temperature corrosion resistance decreases, thereby making this undesirable.
  • Ta improves high-temperature strength due to the actions of solution hardening and precipitation hardening in the presence of Mo and W as previously mentioned, and also improves high-temperature strength as a result of a portion of the Ta undergoing precipitation hardening relative to the ⁇ ' phase.
  • the composite ratio of Ta is preferably within the range of 4.0 wt% or more to 8.0 wt% or less, more preferably within the range of 4.0 wt% or more to 6.0 wt% or less, and most preferably 5.9 wt%. If the composite ratio of Ta is less than 4.0 wt%, strength at high temperatures cannot be maintained at the desired level, thereby making this undesirable. If the composite ratio of Ta exceeds 8.0 wt%, the ⁇ phase and ⁇ phase fonn that cause a decrease in strength at high temperatures, thereby making this undesirable.
  • Al improves high-temperature strength by compounding with Ni to form an intermetallic compound represented by Ni 3 Al, which composes the ⁇ ' phase that finely and uniformly disperses and precipitates in the matrix, at a ratio of 60-70% in terms of volume percent.
  • the composite ratio of Al is preferably within the range of 5.0 wt% or more to 7.0 wt% or less, and most preferably 5.9 wt%. If the composite ratio of Al is less than 5.0 wt%, the precipitated amount of the ⁇ ' phase becomes insufficient, and strength at high temperatures cannot be maintained at the desired level, thereby making this undesirable.
  • the composite ratio of Al exceeds 7.0 wt%, a large amount of a coarse ⁇ phase referred to as the eutectic ⁇ ' phase is formed, and this eutectic ⁇ ' phase prevents solution treatment and makes it impossible to maintain strength at high temperatures at a high level, thereby making this undesirable.
  • Hf is an element that segregates at the grain boundary and improves high-temperature strength by strengthening the grain boundary as a result of being segregated at the grain boundary between the ⁇ phase and ⁇ ' phase.
  • the composite ratio of Hf is preferably within the range of 0.01 wt% or more to 0.50 wt% or less, and most preferably 0.10wt%. If the composite ratio of Hf is less than 0.01 wt%, the precipitated amount of the ⁇ ' phase becomes insufficient and strength at high temperatures cannot be maintained at the desired level, thereby making this undesirable. If the composite ratio of Hf exceeds 0.50 wt%, local melting is induced which results in the risk of decreased strength at high temperatures, thereby making this undesirable.
  • Co improves strength at high temperatures by increasing the solution limit at high temperatures relative to the matrix such as Al and Ta, and dispersing and precipitating a fine ⁇ ' phase by heat treatment.
  • the composite ratio of Co is within the range of 0.1 wt% and 5.9 wt%. If the composite ratio of Co is less than 0.1 wt%, the precipitated amount of the ⁇ ' phase becomes insufficient and the strength at high temperatures cannot be maintained, thereby making this undesirable. If the composite ratio of Co excecds 5.9 wt%, the balance with other elements such as Al, Ta, Mo, W, Hf and Cr is disturbed resulting in the precipitation of harmful phases that cause a decrease in strength at high temperatures, thereby making this undesirable.
  • the composite ratio of Re is preferably within the range of 3.0 wt% or more to 6.0 wt% or less, and most preferably 4.9 wt%. If the composite ratio of Re is less than 3.0 wt%, solution strengthening of the ⁇ phase becomes insufficient and strength at high temperatures cannot be maintained at the desired level, thereby making this undesirable. If the composite ratio of Re exceeds 6.0 wt%, the TCP phase precipitates at high temperatures and strength at high temperatures cannot be maintained at a high level, thereby making this undesirable.
  • the composite ratio of Ru is preferably within the range of 1.0 wt% or more to 4.0 wt% or less, and most preferably 2.0 wt%. If the composite ratio of Ru is less than 1.0 wt%, the TCP phase precipitates at high temperatures and strength at high temperatures cannot be maintained at a high level, thereby making this undesirable. If the composite ratio of Ru exceeds 4.0 wt%, the cost increases which is also undesirable.
  • lattice constant a2 of the crystals of the precipitation phase is 00.1% or less lattice constant a1 of the crystals of the matrix.
  • lattice constant a2 of the crystals of the precipitation phase should be -0.5% or more of lattice constant a1 of the crystals of the matrix.
  • lattice constant a1 of the crystals of the matrix since both of the lattice constants are in the above relationship, since the precipitation phase precipitates so as to extend continuously in the direction perpendicular to the direction of the load when the precipitation phase precipitates in the matrix due to heat treatment, creep strength can be enhanced without movement of dislocation defects in the alloy structure in the presence of stress.
  • the composition of the composite elements that compose the Ni-based single crystal super alloy is suitably adjusted.
  • solution treatment and aging treatment were performed on the alloy ingots followed by observation of the state of the alloy structure with a scanning electron microscope (SEM).
  • Solution treatment consisted of holding for 1 hour at 1573K (1300°C) followed by heating to 1613K (1340°C) and holding for 5 hours.
  • aging treatment consisted of consecutively performing primary aging treatment consisting of holding for 4 hours at 1150°C and secondary aging treatment consisting of holding for 20 hours at 870°C.
  • the sample of the present embodiment was determined to have high strength even under high temperature conditions of 1273K (1000°C).
  • the sample of the present embodiment was determined to have a high withstand temperature (1356K (1083°C)) equal to or greater than Comparative Examples 1 through 5.
  • this alloy has a higher heat resistance temperature than Ni-based single crystal super alloys of the prior art, and was determined to have high strength even at high temperatures.
  • the fatigue strength were compared for the alloys of the Comparative Example 2 shown in Table 1 (CMSX-4) and the sample of the present embodiment shown in Table 2 (TMS-138).
  • HCF high cycle fatigue strength
  • LCF low cycle fatigue strength
  • the max stress at high temperature of 1373K (1100°C) were measured by controlling a load, and the number of fatigue fracture cycle (Nf) were determined as 10 6 and 10 7 .
  • the alternative peseudostress at high temperature of 1073K (800°C) were measured by controlling the distortion, and the number of fatigue fracture cycle (Nf) were determined as 10 3 and 10 4 .
  • the alloy of the present invention (TMS-138) was determined to have a high fatigue strength in addition to the Creep strength at high temperature compared to the conventional Ni-based single crystal super alloy.

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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)
  • Crystals, And After-Treatments Of Crystals (AREA)

Claims (4)

  1. Superalliage monocristallin à base de Ni possédant une composition constituée de 5,0-7,0% en poids de Al, 4,0-8,0% en poids de Ta, 2,9-4,5% en poids de Mo, 4,0-8,0% en poids de W, 3,0-6,0% en poids de Re, 0,01-0,50% en poids de Hf, 2,0-5,0% en poids de Cr, 0,1-5,9% en poids de Co et 1,0-4,0% en poids de Ru en termes de son rapport en poids, le reste étant constitué de Ni et d'impuretés inévitables; et caractérisé en ce que, lorsque la constante de réseau de la matrice est appelée a1 et la constante de réseau de la phase de précipitation est appelée a2, a2 ≤ 0,999a1.
  2. Superalliage monocristallin à base de Ni possédant une composition constituée de 5,0-7,0% en poids de Al, 4,0-6,0% en poids de Ta, 1,0-4,5% en poids de Mo, 4,0-8,0% en poids de W, 3,0-6,0% en poids de Re, 0,01-0,50% en poids de Hf, 2,0-5,0% en poids de Cr, 0,1-5,9% en poids de Co et 1,0-4,0% en poids de Ru en termes de rapport en poids, le reste étant constitué de Ni et d'impuretés inévitables; et caractérisé en ce que, lorsque la constante de réseau de la matrice est appelée a1 et la constante de réseau de la phase de précipitation est appelée a2, a2 ≤ 0,999a1.
  3. Superalliage monocristallin à base de Ni suivant la revendication 2, dans lequel la composition est constituée de 5,0-7,0% en poids de Al, 4,0-6,0% en poids de Ta, 2,9-4,5% en poids de Mo, 4,0-8,0% en poids de W, 3,0-6,0% en poids de Re, 0,01-0,50% en poids de Hf, 2,0-5,0% en poids de Cr, 0,1-5,9% en poids de Co et 1,0-4,0% en poids de Ru en termes de rapport en poids, le reste étant constitué de Ni et d'impuretés inévitables.
  4. Superalliage monocristallin à base de Ni suivant l'une quelconque des revendications 1 à 3, qui possède une composition constituée de 5,9% en poids de Al, 5,9% en poids de Ta, 2,9% en poids de Mo, 5,9% en poids de W, 4,9% en poids de Re, 0,10% en poids de Hf, 2,9% en poids de Cr, 5,9% en poids de Co et 2,0% en poids de Ru en termes de rapport en poids, le reste étant constitué de Ni et d'impuretés inévitables.
EP02253782A 2001-05-30 2002-05-29 Superalliage monocristallin à base de nickel Expired - Lifetime EP1262569B1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2001161919 2001-05-30
JP2001161919 2001-05-30
JP2002143572A JP3840555B2 (ja) 2001-05-30 2002-05-17 Ｎｉ基単結晶超合金
JP2002143572 2002-05-17

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EP1262569A1 EP1262569A1 (fr) 2002-12-04
EP1262569A8 EP1262569A8 (fr) 2003-05-21
EP1262569B1 true EP1262569B1 (fr) 2005-04-06

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US (1) US20030075247A1 (fr)
EP (1) EP1262569B1 (fr)
JP (1) JP3840555B2 (fr)
CA (1) CA2387828C (fr)
DE (1) DE60203562T2 (fr)

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JP3840555B2 (ja) 2006-11-01
EP1262569A8 (fr) 2003-05-21
CA2387828C (fr) 2009-09-15
JP2003049231A (ja) 2003-02-21
EP1262569A1 (fr) 2002-12-04
DE60203562D1 (de) 2005-05-12
US20030075247A1 (en) 2003-04-24
CA2387828A1 (fr) 2002-11-30
DE60203562T2 (de) 2006-02-09

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