EP2703507A1 - Ni-Basislegierung und Gasturbinenschaufel und Gasturbine damit - Google Patents

Ni-Basislegierung und Gasturbinenschaufel und Gasturbine damit Download PDF

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Publication number
EP2703507A1
EP2703507A1 EP13180298.5A EP13180298A EP2703507A1 EP 2703507 A1 EP2703507 A1 EP 2703507A1 EP 13180298 A EP13180298 A EP 13180298A EP 2703507 A1 EP2703507 A1 EP 2703507A1
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Prior art keywords
phase
base alloy
less
gas turbine
alloy
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EP13180298.5A
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English (en)
French (fr)
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EP2703507B1 (de
Inventor
Takashi Shibayama
Shinya Imano
Hironori Kamoshida
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Mitsubishi Power Ltd
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Hitachi Ltd
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/12—Blades
    • F01D5/14—Form or construction
    • F01D5/147—Construction, i.e. structural features, e.g. of weight-saving hollow blades
    • 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%
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01D—NON-POSITIVE DISPLACEMENT MACHINES OR ENGINES, e.g. STEAM TURBINES
    • F01D5/00—Blades; Blade-carrying members; Heating, heat-insulating, cooling or antivibration means on the blades or the members
    • F01D5/12—Blades
    • F01D5/28—Selecting particular materials; Particular measures relating thereto; Measures against erosion or corrosion

Definitions

  • the present invention relates to an Ni base alloy and a gas turbine blade utilizing the same and more particularly to the Ni base alloy having improved high-temperature strength while maintaining the weldablity and corrosion resistance and the gas turbine blade utilizing the same.
  • GTD-111 there is a nickel base alloy known generally as GTD-111 ( U.S. Pat. No. 6,416,596 ).
  • Casting material of GTD-111 includes nominal composition containing Cr of 14 mass%, Co of 10 mass%, Mo of 1.5 mass%, W of 3.8 mass%, Ta of 3 mass%, Al of 3 mass%, C of 0.10 mass%, Ti of 5 mass%, B of 0.02 mass%, Zr of 0.04 mass% and the remainder containing Ni.
  • This alloy is excellent in the weldability and corrosion resistance, although the strength at higher temperature region is low and it is difficult to apply it to a high-efficient gas turbine.
  • JP-A-2004-197131 discloses a nickel base alloy known as RM02B, which contains Cr of 12.0 to 16.0, Co of 4.0 to 9.0, Al of 3.4 to 4.6, Nb of 0.5 to 1.6, C of 0.05 to 0.16, B of 0.005 to 0.025 in mass %, Ti, Ta, Mo and W.
  • RM02B nickel base alloy
  • This alloy has the high-temperature creep strength, the corrosion resistance and the oxidation resistance in balance.
  • the alloy is highly strengthened by addition of precipitation strengthening elements and solid solution strengthening elements, whereas the solid solution temperature of y'-phase is high and there is a possibility that the weldability is not sufficient.
  • Ni base alloy containing Al of 2.5 to 3.5%, Co of 1.5 to 5.5%, Cr of 11.8 to 13.8%, Mo of 0.4 to 1.4%, Ta of 3.0 to 5.0%, Ti of 5.1 to 6.1%, W of 3.3 to 4.3%, B of 0.01 to 0.02%, C of 0.08 to 0.12% and remainder containing Ni and inevitable impurities.
  • the Ni base alloy having improved high-temperature strength while maintaining the weldability and corrosion resistance and a gas turbine blade utilizing the same.
  • Ni base alloy of the present invention contains Al of 2.5 to 3.5%, Co of 1.5 to 5.5%, Cr of 11.8 to 13.8%, Mo of 0.4 to 1.4%, Ta of 3.0 to 5.0%, Ti of 5.1 to 6.1%, W of 3.3 to 4.3%, B of 0.01 to 0.02% and C of 0.08 to 0.12% in mass %.
  • the Ni base alloy suppresses precipitation of harmful phase and improves high-temperature strength while maintaining the weldability and oxidation resistance.
  • an addition amount is substantially 0, although mixing of the following elements (Nb of 0 to 0.2% or less, Hf of 0 to 2.0% or less, Re of 0 to 0.5% or less, Zr of 0 to 0.05% or less, O of 0 to 0.005% or less, N of 0 to 0.005% or less, Si of 0 to 0.01 % or less, Mn of 0 to 0.02% or less, P of 0 to 0.01 % or less and S of 0 to 0.01 % or less) is recognized as inevitable impurities mixed upon manufacturing of alloy within the above range.
  • the Ni base alloy of the present invention is an alloy of ⁇ '-phase precipitation strengthening type, in which the y'-phase having Ni 3 Al which is intermetallic compound as representation is dispersedly precipitated in the ⁇ -phase which is the matrix phase finely and innumerably. Ti and Ta are also solidly dissolved in the y'-phase as alloy composition and Ni 3 Ti and Ni 3 GTa are formed.
  • composition ranges are all expressed by mass percentage (%).
  • the component range of Al is set to be 2.5 to 3.5%. It is preferable that the content thereof falls within the range of 2.7 to 3.3% in consideration of balance of the precipitation amount of y' and the solid solution temperature of the harmful phase and a component ratio to other elements.
  • Co is effective in strengthening solid solution of the ⁇ -phase and improving the corrosion resistance at high temperature.
  • the effects require the content of Co larger than or equal to 1.5%, although in the alloy of the present invention since the solid solution temperature of the y'-phase is increased with increased amount of Co, the weldability is reduced when Co is added excessively. Accordingly, the upper limit thereof is set to be 5.5% and the preferable component range is 3.0 to 4.0%.
  • Cr has the effect that Cr is solidly dissolved in the ⁇ -phase to improve the corrosion resistance at high temperature.
  • the content thereof is larger than or equal to 11.8%, the sufficient effect is attained, although the solid solution amount of Cr in the ⁇ -phase has an upper limit and when the upper limit is exceeded, there is a possibility that surplus Cr is stabilized as the harmful phase such as ⁇ -Cr. Since the harmful phase reduces the high-temperature strength, the content of Cr is set to be 11.8 to 13.8% in consideration of balance with phase fraction of the ⁇ -phase.
  • the preferable range of the content is 12.3 to 13.3%.
  • Mo is an element which is solidly dissolved in both of the ⁇ -phase and the ⁇ '-phase and contributes to the high-temperature strength. This effect is attained when the content thereof is larger than or equal to 0.4%, although when this element is added excessively, the oxidation resistance and the corrosion resistance are reduced remarkably and accordingly the upper limit is set to be 1.4%. When the balance of these properties is considered, the preferable range is 0.6 to 1.2%.
  • Ti is solidly dissolved in the y'-phase in the form of Ni 3 (A, Ti) and strengthens solid solution. Further, Ti is effective in improving the corrosion resistance at high temperature and accordingly the addition amount ofTi is set to be larger than or equal to 5.1 %. However, since the excessive addition reduces the oxidation resistance, the upper limit of the content of Ti is set to 6.1%. The preferable content range is set to 5.3 to 5.9% in order to balance the high-temperature strength, the corrosion resistance and the oxidation resistance.
  • Ta is solidly dissolved in the y'-phase which is the precipitation strengthening phase in the form of Ni 3 (Al, Ti, Ta) and contributes to the high-temperature strength.
  • the composition range thereof is set to 3.0 to 5.0%.
  • the total amount of Al, Ti and Ta which contribute to formation of the y'-phase greatly is increased excessively, the solid solution temperature of the y'-phase and the harmful phase is increased remarkably.
  • W is solidly dissolved in the ⁇ -phase which is the matrix phase and the y'-phase which is the precipitation phase and enhances the creep strength by solid solution strengthening.
  • the content larger than or equal to 3.3% is required, although since the specific gravity of W is large, the mass of alloy is increased. Further, when W is added excessively, the corrosion resistance at high temperature is reduced and the strength and toughness by precipitation of ⁇ -W which is harmful phase are reduced. Accordingly, the upper limit is set to 4.3%.
  • the preferable range is set to 3.6 to 4.0% in consideration of the high-temperature strength, the corrosion resistance and the phase stability.
  • B is segregated in the crystal grain boundary to improve the grain boundary strength and part of B forms boride such as (Cr, Ni, Ti, Mo) 3 B 2 to be precipitated in the grain boundary of the alloy.
  • boride such as (Cr, Ni, Ti, Mo) 3 B 2 to be precipitated in the grain boundary of the alloy.
  • the addition amount of B larger than or equal to 0.01 % is required, although the boride generated has the melting point lower than that of the alloy, so that the temperature of the melting point of the alloy is reduced to narrow the temperature range of solution treatment. Accordingly, the upper limit is set to 0.02% and when balance of the strength and the temperature range of solution treatment is considered, the preferable range is 0.012 to 0.018%.
  • C is segregated in the crystal grain boundary to improve the grain boundary strength and part of C forms carbide such as TiC and TaC to be precipitated massively.
  • the addition amount of C larger than or equal to 0.08% is required.
  • C is added over 0.12%, excessive carbide is formed to reduce not only the high-temperature strength and ductility but also the corrosion resistance.
  • carbide is pinned between dendrites and porosities which are defects in casting are produced.
  • the preferable component range is 0.9 to 0.11%.
  • the following component elements are inevitable impurities.
  • Nb is solidly dissolved in the y'-phase in the form of Ni 3 Nb similarly to Ti and strengthens the solid solution.
  • the solid solution temperature of the harmful phase such as ⁇ -phase is increased remarkably and ⁇ -phase which is embrittlement phase is also precipitated. Accordingly, Nb is not added and the content of Nb is set to be substantially 0%.
  • the mixed amount is suppressed to be smaller than or equal to 0.2%.
  • Hf does not almost contribute to improvement of strength but improves the corrosion resistance and the oxidation resistance at high temperature by improving adhesion properties of protective scales such as Cr 2 O 3 and Al 2 O 3 formed on the surface of alloy and when the addition amount of Hf is increased, the adhesion properties of protective scales are improved.
  • protective scales such as Cr 2 O 3 and Al 2 O 3 formed on the surface of alloy
  • the addition amount of Hf exceeds 2.0%, a lot of eutectic of Ni 3 (Hf, Ti) is formed to reduce the melting point of the Ni base alloy remarkably and make the solution treatment difficult.
  • the upper limit thereof is required to be 2.0%. It is preferable that the upper limit is set to be smaller than or equal to 0.1 % and Hf is not substantially added.
  • Re can be replaced by part of W if necessary and is an element which is solidly dissolved in the ⁇ -phase to strengthen the solid solution and is effective in improvement of the corrosion resistance.
  • Re is expensive and has the large specific gravity, so that the specific gravity of the alloy is increased. Accordingly, the upper limit is required to be 0.5% and it is preferable that it is smaller than or equal to 0.1 %.
  • the upper limit is set to 0.05% and it is preferable that the upper limit is set to be smaller than or equal to 0.01% and Zr is not substantially added.
  • O and N are impurities and both of them are often mixed from alloy material.
  • O is mixed even from a melting pot and exists in the alloy as oxide Al 2 O 3 and nitrides TiN and AlN massively.
  • these elements exist in an ingot, they are starting points of crack in creep deformation, so that creep rupture life is reduced and they are starting points of fatigue crack generation, so that fatigue life is reduced. It is preferable that the content of these elements is smaller, although when actual ingot is formed, these elements cannot be reduced to 0 and accordingly the upper limit of both elements is set to be 0.005% as the range in which properties are not deteriorated greatly.
  • Si is brought from the alloy material.
  • this element is not an effective element particularly, it is preferable that this element is not contained and when it is contained, the content thereof is suppressed to be smaller than or equal to 0.01 %.
  • Mn is also brought from the alloy material.
  • this element is not an effective element particularly, it is preferable that this element is not contained and when it is contained, the content thereof is suppressed to be smaller than or equal to 0.02%.
  • P is an impurity. It is preferable that the content thereof is as small as possible and it is necessary to suppress the content thereof to be smaller than or equal to 0.01%.
  • S is also an impurity. It is preferable that the content thereof is as small as possible similarly to P and it is necessary to suppress the content thereof to be smaller than or equal to 0.01 %.
  • Fig. 1 illustrates a gas turbine blade cast by the Ni base alloy containing the above composition elements (Al, Co, Cr, Mo, Ti, Ta, W, B and C).
  • the left of Fig. 1 is a perspective view of a first-stage blade and the right of Fig. 1 is a perspective view of a second-stage blade.
  • the first-stage blade which is heated to highest temperature is formed of directional solidification alloy or single crystal alloy and the heating temperature is reduced as the blades go to second-stage and third-stage, so that the blade is formed of conventional casting alloy.
  • the length of profile is longer as the profile approaches the lower temperature side.
  • Fig. 2 illustrates a gas turbine in which first to fourth blades cast by the Ni base alloy are incorporated.
  • Table 1 shows chemical composition of the alloys (Al to A28) of the present invention and existing alloys (GTD-111: B1 to B5 and RM02B: C1 to C5) as comparison.
  • the unit of numerical values is all mass percentage (%).
  • components (mass %) Ni Al Co Cr Mo Nb Ta Ti W B C
  • A1 66.285 3 3.5 12.8 0.9 0 4 5.6 3.8 0.015 0.1 A2 66.095 2.9 3.4 12.9 0.7 0 4.3 5.7 3.9 0.015 0.09 A3 66.185 3 3.5 12.8 0.9 0 4 5.7 3.8 0.015 0.1 A4 66.236 3 3.55 12.9 0.95 0 3.9 5.65 3.7 0.014 0.1 A5 66.485 3 3.5 12.8 0.9 0 3.8 5.6 3.8 0.015 0.1 A6 66.585 3 3.1 12.8 1.2 0 4 5.6 3.6 0.015 0.1 A7 66.285 3.1 3.45 12.8 0.9 0 4 5.55 3.8
  • Table 2 and Figs. 3 , 4 , 5 , 6 , 7 and 8 show numerical values and graphs of calculation results of the phase equilibrium state in the composition of Table 1.
  • Table 2 is a list of results. Evaluation of high-temperature strength uses the phase fraction of the y'-phase as an index.
  • Figs. 3 and 4 show the precipitation amounts of the y'-phase at 800°C and 1000°C, respectively.
  • Fig. 5 shows the solvus of the y'-phase.
  • Fig. 6 shows the solvus of the ⁇ -phase and harmful phase such as ⁇ -Cr and ⁇ -W.
  • Fig. 7 shows amounts of Cr in the ⁇ -phase at 800°C.
  • the precipitation amounts of the ⁇ '-phase of the alloys (A to A) of the present invention are increased at both temperatures of 800°C and 1000°C as compared with GTD-111 (B to B) of existing alloys. Since the precipitation amounts of the y'-phase in the Ni base alloy contribute to the precipitation strengthening, the strength by the precipitation strengthening is greatly improved in the alloys of the present invention. This reason is that the addition amounts of Ta and Ti are increased.
  • the solvus in the y'-phase is equivalent or a little low and the amount of Cr in the ⁇ -phase is substantially equivalent. The lower the solvus in the y'-phase is, the easier the welding is and the solution treatment temperature after welding can be also set to be low.
  • the solvus is also increased as the y'-phase is increased by great addition of Ti, although in the alloys of the present invention, the addition amount of Co is reduced, so that increase of the solvus is suppressed and the weldability is ensured.
  • the amount of Cr in the ⁇ -phase contributes to the corrosion resistance and the effect thereof is decided by the content of Cr.
  • the content of Cr in the ⁇ -phase is substantially equal to GTD-111 and the corrosion resistance is maintained.
  • the main harmful phase precipitated at high temperature is the ⁇ -phase in GTD-111 and ⁇ -Cr in the alloys of the present invention which are different in kind, although the solvus thereof is reduced slightly and precipitation of the harmful phase is suppressed.
  • the precipitation amount of the ⁇ '-phase at 1000°C is substantially equal but is slightly increased at 800°C.
  • the alloys of the present invention do not have much Al amount but Ta and Ti are increased greatly to be solidly dissolved in the y'-phase, so that the high-temperature strength is increased.
  • the Cr amount in the ⁇ -phase is substantially equal but the solvus in the y'-phase of RM02B is higher clearly.
  • RM02B There are two kinds of harmful phases of RM02B containing mainly the ⁇ -phase and ⁇ -W and the solvus of ⁇ -W is higher. Since the kind and the temperature of the precipitated harmful phase depend on composition of alloys greatly, the solvus is reduced by about 50°C by adjustment of Cr amount and W amount in the alloys of the present invention.
  • the alloy is characterized as shown in Fig. 8 in that the strength is suppressed to obtain excellent weldability or the strength is high but the weldablity is a little low.
  • the alloy of the present invention improves the high-temperature strength while having the same weldability and corrosion resistance as GTD-111.
  • the precipitation amount in the y'-phase at high temperature is equal to or larger than that of RM02B and the corrosion resistance is substantially equal and the weldability is improved.
  • the solvus of harmful phase is reduced greatly and precipitation of harmful phase is suppressed.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
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  • Turbine Rotor Nozzle Sealing (AREA)
EP13180298.5A 2012-08-30 2013-08-13 Ni-Basislegierung und Gasturbinenschaufel und Gasturbine damit Active EP2703507B1 (de)

Applications Claiming Priority (1)

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JP2012189418A JP2014047371A (ja) 2012-08-30 2012-08-30 Ｎｉ基合金と、それを用いたガスタービン動翼兼ガスタービン

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EP2703507A1 true EP2703507A1 (de) 2014-03-05
EP2703507B1 EP2703507B1 (de) 2016-01-20

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0387976A2 (de) * 1989-03-15 1990-09-19 Institute Of Metal Research Academia Sinica Superlegierungen und Verfahren zur Verbesserung der Eigenschaften von Superlegierungen
EP0637476A1 (de) * 1993-08-06 1995-02-08 Hitachi, Ltd. Gasturbinenschaufel, Verfahren zur Herstellung sowie Gasturbine mit dieser Schaufel
EP1207212A2 (de) * 2000-11-18 2002-05-22 Rolls-Royce Plc Nickel - Legierung
US6416596B1 (en) 1974-07-17 2002-07-09 The General Electric Company Cast nickel-base alloy
JP2004197131A (ja) 2002-12-17 2004-07-15 Hitachi Ltd ニッケル基耐熱合金及びガスタービン翼
EP2169087A2 (de) * 2008-09-30 2010-03-31 Hitachi Ltd. Nickelbasierte Superlegierung und Gasturbinenschaufel damit
EP2298946A2 (de) * 2009-09-15 2011-03-23 Hitachi Ltd. Hochfeste Knett-Superlegierung auf Nickelbasis und Verfahren zur Herstellung

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5489346A (en) 1994-05-03 1996-02-06 Sps Technologies, Inc. Hot corrosion resistant single crystal nickel-based superalloys
EP1211335B1 (de) * 2000-11-30 2007-05-09 ONERA (Office National d'Etudes et de Recherches Aérospatiales) Superlegierung auf Nickelbasis mit sehr hoher Beständigkeit gegen Heisskorrosion für Einkristallturbinenschaufeln von industriellen Turbinen
JP5427642B2 (ja) * 2010-02-24 2014-02-26 株式会社日立製作所 ニッケル基合金及びそれを用いたランド用ガスタービン部品
EP2554697B1 (de) * 2010-03-29 2017-09-27 Mitsubishi Hitachi Power Systems, Ltd. Legierung auf ni-basis sowie gasturbinen-rotorblatt und statorblatt damit

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6416596B1 (en) 1974-07-17 2002-07-09 The General Electric Company Cast nickel-base alloy
EP0387976A2 (de) * 1989-03-15 1990-09-19 Institute Of Metal Research Academia Sinica Superlegierungen und Verfahren zur Verbesserung der Eigenschaften von Superlegierungen
EP0637476A1 (de) * 1993-08-06 1995-02-08 Hitachi, Ltd. Gasturbinenschaufel, Verfahren zur Herstellung sowie Gasturbine mit dieser Schaufel
EP1207212A2 (de) * 2000-11-18 2002-05-22 Rolls-Royce Plc Nickel - Legierung
JP2004197131A (ja) 2002-12-17 2004-07-15 Hitachi Ltd ニッケル基耐熱合金及びガスタービン翼
EP2169087A2 (de) * 2008-09-30 2010-03-31 Hitachi Ltd. Nickelbasierte Superlegierung und Gasturbinenschaufel damit
EP2298946A2 (de) * 2009-09-15 2011-03-23 Hitachi Ltd. Hochfeste Knett-Superlegierung auf Nickelbasis und Verfahren zur Herstellung

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JP2014047371A (ja) 2014-03-17
US20140064982A1 (en) 2014-03-06
EP2703507B1 (de) 2016-01-20

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