EP1715068B1 - Auf nickel basierende superwärmebeständige legierung und gasturbinenbauteil damit - Google Patents

Auf nickel basierende superwärmebeständige legierung und gasturbinenbauteil damit Download PDF

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Publication number
EP1715068B1
EP1715068B1 EP04807451A EP04807451A EP1715068B1 EP 1715068 B1 EP1715068 B1 EP 1715068B1 EP 04807451 A EP04807451 A EP 04807451A EP 04807451 A EP04807451 A EP 04807451A EP 1715068 B1 EP1715068 B1 EP 1715068B1
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Prior art keywords
alloy
resistance
corrosion
gas turbine
present
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English (en)
French (fr)
Japanese (ja)
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EP1715068A4 (de
EP1715068A1 (de
Inventor
Masahiro Sato
Tsuyoshi Takenaka
Seiya Nitta
Toshiharu Ind. Admint. Inst. National KOBAYASHI
Yutaka Ind. Adm. Institution National KOIZUMI
Hiroshi Ind. Adm. Institution National HARADA
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Kawasaki Heavy Industries Ltd
National Institute for Materials Science
Kawasaki Motors Ltd
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Kawasaki Heavy Industries Ltd
National Institute for Materials Science
Kawasaki Jukogyo KK
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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

  • the present invention relates to a Ni-base superalloy having an excellent resistance to corrosion at high temperatures, an excellent resistance to oxidation at high temperatures, and high-temperature strength, and gas turbine component using the same, in order to deal with low-quality fuel.
  • Ni-base superalloy is widely used as industrial gas turbine components, for example, turbine blade materials such as Rene80 and IN792 having an excellent resistance to corrosion, Mar-M247 having an excellent resistance to oxidation and a high strength are known. Further, CMSX-11 having both a good resistance to corrosion and a high strength realized by single crystal casting of the high chromium content alloy is also known.
  • Ni-base superalloys cannot share the properties of the high resistance to corrosion (Rene80, etc.) and the high resistance to oxidation and high strength (Mar-M247, etc.), so that there is a failure that they cannot be applied to improve the efficiency of a gas turbine dealing with low-quality fuel such as heavy oil.
  • an alloy (CMSX-11, etc.) having a resistance to corrosion and a strength realized by single crystal casting of the high chromium content alloy does not have a sufficient resistance to oxidation, and moreover there is a problem with single-crystal material that the casting yield of components in complicated shapes is lowered.
  • a high corrosion resistant and high strength alloy containing, by weight % (wt%), Cr: 6 to 12%, Al (aluminum): 4.5 to 6.5%, W(tungsten): 2 to 12%, Ta(tantalum): 2.5 to 10%, Mo(molybdenum) : up to 5.8%, Co (cobalt) : 0.1 to 3%, Nb(niobium) : 0.2 to 3%, Re (rhenium) : 0.1 to 4%, and Hf (hafnium) : up to 0.3%, having a P value (calculated by weight % by Formula (1) indicated below) of 2350 to 3280, and the balance of Ni and inevitable impurities is known.
  • Ni series supper-alloy suitable for single-crystal solidification containing, by weight %, Co: 4.75 to 5.25%, Cr: 15.5 to 16.5%, Mo: 0.8 to 1.2%, W: 3.75 to 4.25%, Al: 3.75 to 4.25%, Ti: 1.75 to 2.25%, Ta: 4.75 to 5.25%, C: 0.006 to 0.04%, B: up to 0.01%, Zr: up to 0.01%, Hf: up to 1%, Nb: up to 1%, and Ni and impurity components added so as to reach 100% in total is known.
  • this Ni series super-alloy contains Cr too much, so that the resistance to oxidation is insufficient.
  • Ni-based single crystal supper-alloy containing, by weight %, Cr: 8 to 14%, Co: 3 to 7%, Al: 4 to 8%, Ti: up to 5%, W: 6 to 10%, Ta: 4 to 8%, Mo: 0.5 to 4%, Hf: up to 1.4%, Zr: up to 0.01%, C: up to 0.07%, B: up to 0.015%, and the balance of Ni and inevitable impurities, wherein 5% ⁇ Al + Ti, 4 ⁇ Al/Ti, and W + Ta + Mo ⁇ 18% is known.
  • the Ni-based single crystal super-alloy is deficient in Ti due to the restriction of 4 ⁇ Al / Ti, so that the resistance to corrosion is insufficient.
  • Ni-based super-alloy containing, by weight %, Cr: 7 to 12%, Co: 5 to 15%, Mo: 0.5 to 5%, W: 3 to 12%, Ta: 2 to 6%, Ti: 2 to 5%, Al: 3 to 5%, Nb: up to 2%, Hf: up to 2%, C: 0.03 to 0.25%, and B: 0.002 to 0.05% and composed of residual components of Ni and accompanying impurities is known.
  • this Ni-based super-alloy is improved in the balance between the resistance to oxidation and the resistance to corrosion by an increase in the ratio of Al to Ti, the relation to the element added to increase the strength is not taken into account.
  • Ni-based alloy containing, by weight %, Cr: 2 to 25%, Al: 1 to 7%, W: 2 to 15%, Ti: 0.5 to 5%, Nb: up to 3%, Mo: up to 6%, Ta: 1 to 12%, Re: up to 4%, Co: 7.5 to 25%, Fe (iron) : up to 0.5%, C: up to 0.2%, B: 0.002 to 0.035%, Hf: up to 2.0%, Zr: 0.02%, and Ni: 40% or more is known.
  • this Ni-based alloy the relationship between the balance of elements and the material properties is not taken into account.
  • Japanese Patent Publication No. 2843476 Japanese Patent Publication No. 3246376
  • Japanese Patent Laid-Open Publication No. 2002-235135 Japanese Patent Laid-Open Publication No. 7-300639
  • Japanese Patent Laid-Open Publication No. 5-59473 Japanese Patent Laid-Open Publication No. 9-170402 may be cited.
  • WO 01/64964 A1 discloses a nickel base superalloy suitable for the production of a large, crack-free nickel-base superalloy gas turbine bucket suitable for use in a large land-based utility gas turbine engine, comprising, by weight percents: Chromium 7.0 to 12.0; Carbon 0.06 to 0.10; Cobalt 5.0 to 15; Titanium 3.0 to 5.0; Aluminium 3.0 to 5.0; Tungsten 3.0 to 12.0; Molybdenum 1.0 to 5.0; Boron 0.0080 to 0.01; Rhenium 0 to 10.0; Tantalum 2.0 to 6.0; Columbium 0 to 2.0; Vanadium 0 to 3.0; Hafnium 0 to 2.0; and remainder nickel and incidental impurities.
  • the present invention is intended to provide, as a component material of an industrial gas turbine, a Ni-base superalloy having an excellent resistance to hot corrosion with low-quality fuel and an excellent resistance to oxidation at high temperatures and a high-temperature strength to improve the thermal efficiency, also having a high yield at the precision casting process, and gas turbine component using the same.
  • the first Ni-base superalloy of the present invention consists of: by weight %, Co: 9 to 11%, Cr: 9 to 12%, Mo: up to 1%, W: 6 to 9%, Al: 4 to 5%, Ti: 4 to 5%, Nb: up to 1%, Ta: up to 3%, Hf: 0.5 to 2.5%, Re: up to 3%, C: 0.05 to 0.15%, B: 0.005 to 0.015%, Zr: up to 0.05%, and the balance of Ni and inevitable impurities. Further, the weight % of Hf is preferably 0.5 to 1%.
  • the second Ni-base superalloy of the present invention consists of: by weight %, Co: 9 to 10%, Cr: 9 to 10%, Mo: 0.5 to 1%, W: 6 to 8%, Al: 4 to 5%, Ti: 4 to 5%, Ta: 2 to 3%, Hf: 0.5 to 2.5%, Re: 1 to 3%, C: 0.05 to 0.1%, B: 0.005 to 0.01%, Zr: up to 0.02%, and the balance of Ni and inevitable impurities. Further, the weight % of Hf is preferably 0.5 to 1%.
  • the third Ni-base superalloy of the present invention consists of: by weight %, Co: 10 to 11%, Cr: 10 to 12%, W: 8 to 9%, Al: 4 to 5%, Ti: 4 to 5%, Nb: up to 1%, Hf: 0.5 to 2.5%, C: 0.05 to 0.15%, B: 0.005 to 0.015%, Zr: 0.01 to 0.05%, and the balance of Ni and inevitable impurities. Further, the weight % of Hf is preferably 0.5 to 1%.
  • the gas turbine component of the present invention is manufactured by using any of the first to third Ni-base superalloys aforementioned and is preferably manufactured by using the directional solidification casting method.
  • the present invention was developed, to realize the coexistence of the resistance to corrosion at high temperatures and the resistance to oxidation at high temperatures and high-temperature strength, by producing and evaluating many alloys by way of trial, as a result, adjusting the quantity ratio of Cr, Al, and Ti to an appropriate range, within the composition range, finding that W is effective as an element for contributing to strength improvement and little badly affecting the resistance to corrosion, and furthermore taking the phase stability judged from the solid solution quantity to the ⁇ (gamma) phase and ⁇ ' (gamma prime) phase into account.
  • the quantity ratio of Cr contributing to the resistance to corrosion in a multiple environment of sulfidation and oxidation, Al for generating the ⁇ ' phase and contributing to the high-temperature strength and resistance to oxidation, and Ti for contributing to the resistance to corrosion is within an appropriate range, and the reinforced elements mainly W whose additional quantity is decided by contribution to strength improvement and influence on corrosion resistance are added to the concerned quantity ratio, thus the resistance to corrosion at high temperatures, the resistance to oxidation at high temperatures and high-temperature strength can be made excellent. Further, the Ni-base superalloys can obtain sufficiently high strength for practical use in the columnar grain material state, so that there is no need to set single crystallization as a precondition.
  • the second Ni-base superalloy is suitable for columnar crystalline blades or single crystalline blades by directional solidification casting and can exhibit the properties of corrosion resistance, oxidation resistance, and strength on a high level
  • the third Ni-base superalloy is suited for polycrystalline blades by conventional casting or columnar crystalline blades by directional solidification casting, and can suppress the material cost while maintaining the properties of corrosion resistance, oxidation resistance, and strength. Therefore, application of the present invention to turbine blades of an industrial gas turbine dealing with low-quality fuel is effective in improvement of the thermal efficiency and reliability of the gas turbine.
  • gas turbine component of the present invention has better tolerance than the exclusive single crystal material for the reduction in strength due to casting defects such as low-angle grain boundaries or high-angle grain boundaries, and the allowable restriction range is wide, so that a high yield can be ensured at the casting process of gas turbine component in complicated shapes.
  • Mo improves the high-temperature strength by solid solution reinforcement and deposition hardening, when the content thereof is more than 1 wt%, the resistance to corrosion is lowered. Further, the second alloy, when the content of Mo is less than 0.5 wt%, cannot obtain the aforementioned effect.
  • W improves the high-temperature strength by solid solution reinforcement and deposition hardening, when the content thereof is less than 6 wt% (for the third alloy, 8 wt%), the effect cannot be obtained, and when it is more than 9 wt% (for the second alloy, 8 wt%), the TCP phase is generated and the high-temperature strength is lowered. Further, although W is generally considered to lower the resistance to corrosion, knowledge that in the composition area of the present invention, there is few effect by W on the resistance to corrosion is obtained.
  • Al generates the ⁇ ' phase and improves the high-temperature strength and resistance to oxidation, when the content thereof is less than 4 wt%, the effect cannot be obtained, and when it is more than 5 wt%, the eutectic ⁇ ' phase is increased in amount, and the solution heat treatment becomes difficult to be performed, and the resistance to corrosion is lowered.
  • Ti improves the resistance to corrosion, when the content thereof is less than 4 wt%, the effect cannot be obtained, and when it is more than 5 wt%, the resistance to oxidation is lowered, and the heat treatment property is lowered.
  • Nb is fused in the ⁇ ' phase and improves the high-temperature strength, when the content thereof is more than 1 wt%, it is deposited in the grain boundaries, and lowers the high-temperature strength.
  • Ta improves the high-temperature strength by solid solution reinforcement and deposition hardening, when the content thereof is more than 3 wt%, the eutectic ⁇ ' phase is increased in amount, and the solution heat treatment becomes difficult to be performed. Further, the second alloy, when the content of Ta is less than 2 wt%, cannot obtain the aforementioned effect.
  • Hf reinforces the grain boundaries and improves the high-temperature strength and ductility and is effective to prevent intergranular cracking during DS casting, when the content thereof is less than 0.5 wt%, the effect cannot be obtained, and when it is more than 2.5 wt%, it segregates in the grain boundaries, and lowers the high-temperature strength.
  • Re improves the high-temperature strength by solid solution reinforcement and particularly improves the resistance to corrosion at 900°C or higher, when the content thereof is more than 3 wt%, the ductility is deteriorated by deposition of the TCP phase, and the specific gravity is increased, and the cost is increased. Further, the second alloy cannot obtain the aforementioned effect when the content of Re is less than 1 wt%.
  • B forms boronides and reinforces the grain boundaries, when the content thereof is less than 0.005 wt%, the effect cannot be obtained, and when it is more than 0.015 wt% (for the second alloy, 0.01 wt%), the ductility and toughness are lowered, and the high-temperature strength is lowered.
  • Zr reinforces the grain boundaries, when the content thereof is more than 0.05 wt% (for the second alloy, 0.02 wt%), the ductility and toughness are lowered, and the high-temperature strength is lowered. Further, the third alloy cannot obtain the aforementioned effect when the content of Zr is less than 0.01 wt%.
  • Ni-base superalloys (alloys 1 to 3 of the present invention and comparison alloys 1 to 3) having the component composition shown in Table 1 (the component compositions of the existing alloy 1 (Rene80H) and existing alloy 2 (Mar-M247) are also shown) are prepared, and these Ni-base superalloys are solidified under the condition of withdrawing speed 200 mm/h using a directional solidification casting furnace, and columnar crystalline castings are manufactured. Next, the heat treatment indicated below is performed, thus the respective Ni-base superalloys are obtained.
  • test specimen shape Diameter of 10 mm, length of 100 mm
  • Test conditions In combustion gas with corrosive ingredients (sulfuric oil, artificial seawater) added into kerosene fuel, at a combustion gas temperature of 1050°C, air cooling after exposure for 100 hours, repeated 5 times (500 hours in total)
  • test specimen shape Diameter of 10 mm, length of 25 mm
  • Test conditions In the atmosphere, at 950°C, air cooling after exposure for 500 hours
  • test specimen shape Diameter of 4 mm, gauge length of 24 mm
  • Test conditions In the atmosphere, at 900°C, at 392 MPa
  • the alloy 1 of the present invention is excellent in the resistance to corrosion, resistance to oxidation, and strength and is particularly suited to use as a directional solidification material when higher strength is needed.
  • the alloy 2 of the present invention is suited to use under the condition that the resistance to oxidation and strength are needed, and the resistance to corrosion is within the tolerance to use the heavy oil fuel.
  • the alloy 3 of the present invention is suited to use under the condition that the resistance to corrosion is needed.
  • the existing alloy 1 is widely used as a turbine blade material of a gas turbine and is excellent in the resistance to corrosion, as compared with the composition range of the alloys 1 to 3 of the present invention, it contains much Cr and little Al, so that the resistance to oxidation is low, thus the existing alloy 1 cannot deal with high-temperature demands of combustion gas aiming at improvement of thermal efficiency.
  • the existing alloy 2 is excellent in the resistance to oxidation and strength, as compared with the composition range of the alloys 1 to 3 of the present invention, it contains little Cr and Ti and much Al, so that the resistance to corrosion is low, thus the existing alloy 2 cannot deal with heavy oil fuel.
  • the comparison alloy 1 (almost corresponding to the composition range described in Japanese Patent Laid-Open Publication No. 5-59473 and Japanese Patent Laid-Open Publication No. 9-170402 ), as compared with the composition range of the alloys 1 to 3 of the present invention, contains little Ti, so that the resistance to corrosion is insufficient.
  • the comparison alloy 2 (almost corresponding to the composition range described in Japanese Patent Laid-Open Publication No. 9-170402 ), as compared with the composition range of the alloys 1 to 3 of the present invention, contains much Cr and littleAl and W, so that the strength is insufficient.
  • the comparison alloy 3 (almost corresponding to the composition range described in Japanese Patent Laid-Open Publication No. 5-59473 ), as compared with the composition range of the alloys 1 to 3 of the present invention, contains much Mo, so that the resistance to corrosion is insufficient.

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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)

Claims (6)

  1. Nickelbasis-Superlegierung, bestehend aus:
    in Gew.-%, Co: 9 bis 11%, Cr: 9 bis 12%, Mo: bis zu 1%, W: 6 bis 9 %, Al: 4 bis 5%, Ti: 4 bis 5%, Nb: bis zu 1 %, Ta: bis zu 3%, Hf: 0,5 bis 2,5%, Re: bis zu 3%, C: 0,05 bis 0,15%, B: 0,005 bis 0,015%, Zr: bis zu 0,05%, und der Restanteil Ni und unvermeidbare Verunreinigungen.
  2. Nickelbasis-Superlegierung nach Anspruch 1, bestehend aus:
    in Gew.-%, Co: 9 bis 10%, Cr: 9 bis 10%, Mo: 0,5 bis 1%, W: 6 bis 8 %, Al: 4 bis 5%, Ti: 4 bis 5%, Ta: 2 bis 3%, Hf: 0,5 bis 2,5%, Re: 1 bis 3%, C: 0,05 bis 0,1 %, B: 0,005 bis 0,01 %, Zr: bis zu 0,02%, und der Restanteil Ni und unvermeidbare Verunreinigungen.
  3. Nickelbasis-Superlegierung nach Anspruch 1, bestehend aus:
    in Gew.-%, Co: 10 bis 11%, Cr: 10 bis 12%, W: 8 bis 9 %, Al: 4 bis 5%, Ti: 4 bis 5%, Nb: bis zu 1 %, Hf: 0,5 bis 2,5%, C: 0,05 bis 0,15%, B: 0,005 bis 0,015%, Zr: 0,01 bis 0,05%, und der Restanteil Ni und unvermeidbare Verunreinigungen.
  4. Nickelbasis-Superlegierung nach einem der Ansprüche 1 bis 3, wobei die Gew.-% an Hf 0,5 bis 1% betragen.
  5. Gasturbinenbauteil, dadurch gekennzeichnet, dass es unter Verwendung der Nickelbasis-Superlegierung nach einem der Ansprüche 1 bis 4 gefertigt wird.
  6. Gasturbinenbauteil nach Anspruch 5, wobei das Gasturbinenbauteil mittels eines Gießverfahrens mit gerichtetem Erstarren gefertigt wird.
EP04807451A 2003-12-26 2004-12-21 Auf nickel basierende superwärmebeständige legierung und gasturbinenbauteil damit Active EP1715068B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2003435037 2003-12-26
PCT/JP2004/019094 WO2005064027A1 (ja) 2003-12-26 2004-12-21 Ｎｉ基超耐熱合金及びそれを用いたガスタービン部品

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EP1715068A1 EP1715068A1 (de) 2006-10-25
EP1715068A4 EP1715068A4 (de) 2009-11-11
EP1715068B1 true EP1715068B1 (de) 2012-08-01

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US20100034692A1 (en) * 2008-08-06 2010-02-11 General Electric Company Nickel-base superalloy, unidirectional-solidification process therefor, and castings formed therefrom
EP2823074A4 (de) 2012-03-09 2016-01-13 Indian Inst Scient Nickel-aluminium-zirkoniumlegierungen
ITUA20161551A1 (it) * 2016-03-10 2017-09-10 Nuovo Pignone Tecnologie Srl Lega avente elevata resistenza all’ossidazione ed applicazioni di turbine a gas che la impiegano
GB2554898B (en) * 2016-10-12 2018-10-03 Univ Oxford Innovation Ltd A Nickel-based alloy
RU2633679C1 (ru) * 2016-12-20 2017-10-16 Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") Литейный жаропрочный сплав на никелевой основе и изделие, выполненное из него
CN115572861B (zh) * 2022-09-23 2024-02-23 北京北冶功能材料有限公司 一种易于加工成型的镍基高温合金及其制备方法和应用

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RU2215804C2 (ru) * 2001-10-08 2003-11-10 Государственное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" Жаропрочный сплав на основе никеля и изделие, выполненное из него

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JP4911753B2 (ja) 2012-04-04
WO2005064027A1 (ja) 2005-07-14
EP1715068A4 (de) 2009-11-11
JPWO2005064027A1 (ja) 2007-12-20
US20100047110A1 (en) 2010-02-25
EP1715068A1 (de) 2006-10-25
US20080008618A1 (en) 2008-01-10

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