WO2006104059A1 - SUPERALLIAGE A BASE DE Ni EXEMPT DE COBALT - Google Patents

SUPERALLIAGE A BASE DE Ni EXEMPT DE COBALT Download PDF

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Publication number
WO2006104059A1
WO2006104059A1 PCT/JP2006/306022 JP2006306022W WO2006104059A1 WO 2006104059 A1 WO2006104059 A1 WO 2006104059A1 JP 2006306022 W JP2006306022 W JP 2006306022W WO 2006104059 A1 WO2006104059 A1 WO 2006104059A1
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WIPO (PCT)
Prior art keywords
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base superalloy
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free
Prior art date
Application number
PCT/JP2006/306022
Other languages
English (en)
Japanese (ja)
Inventor
Toshiharu Kobayashi
Yutaka Koizumi
Hiroshi Harada
Tadaharu Yokokawa
Original Assignee
National Institute For Materials Science
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by National Institute For Materials Science filed Critical National Institute For Materials Science
Priority to JP2007510462A priority Critical patent/JP5024797B2/ja
Priority to US11/887,221 priority patent/US20080240926A1/en
Publication of WO2006104059A1 publication Critical patent/WO2006104059A1/fr
Priority to GB0720743A priority patent/GB2439071B/en

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
    • B22D27/045—Directionally solidified castings
    • 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
    • C22C19/007—Alloys based on nickel or cobalt with a light metal (alkali metal Li, Na, K, Rb, Cs; earth alkali metal Be, Mg, Ca, Sr, Ba, Al Ga, Ge, Ti) or B, Si, Zr, Hf, Sc, Y, lanthanides, actinides, as the next major constituent
    • 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
    • C22C30/00—Alloys containing less than 50% by weight of each constituent
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2300/00—Materials; Properties thereof
    • F05D2300/10—Metals, alloys or intermetallic compounds
    • F05D2300/12—Light metals
    • F05D2300/121—Aluminium
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2300/00—Materials; Properties thereof
    • F05D2300/10—Metals, alloys or intermetallic compounds
    • F05D2300/13—Refractory metals, i.e. Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2300/00—Materials; Properties thereof
    • F05D2300/10—Metals, alloys or intermetallic compounds
    • F05D2300/13—Refractory metals, i.e. Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W
    • F05D2300/131—Molybdenum
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F05—INDEXING SCHEMES RELATING TO ENGINES OR PUMPS IN VARIOUS SUBCLASSES OF CLASSES F01-F04
    • F05D—INDEXING SCHEME FOR ASPECTS RELATING TO NON-POSITIVE-DISPLACEMENT MACHINES OR ENGINES, GAS-TURBINES OR JET-PROPULSION PLANTS
    • F05D2300/00—Materials; Properties thereof
    • F05D2300/10—Metals, alloys or intermetallic compounds
    • F05D2300/13—Refractory metals, i.e. Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W
    • F05D2300/132—Chromium

Definitions

  • the invention of this application relates to a Ni-base superalloy that is a heat-resistant alloy used in high-temperature equipment such as jet engines and industrial gas turbines, and more specifically, as turbine blades and turbine vanes for nuclear power generation, etc.
  • Ni-based superalloys are widely used as materials for high-temperature equipment due to their excellent structure stability and creep properties at high temperatures, and patent applications have been filed (Patent Documents 1 and 2).
  • Ni-based superalloys with excellent heat resistance contain a large amount of Co (cobalt).
  • Co increases the solid solubility limit of Al, Ta, and other gamma matrixes at high temperatures, and disperses and precipitates fine gamma prime phases by heat treatment to improve high-temperature strength! ⁇ ⁇ Has excellent functions! / It has been considered an indispensable component for Ni-base superalloys that are used at high temperatures.
  • Co has a long half-life, if the Ni-base superalloy containing Co is radioactively contaminated, maintenance becomes very troublesome.
  • Patent Document 1 U.S. Pat.Nos. 5,366,695
  • Patent Document 2 European Patent Publication No. 1,262,569
  • the invention of this application was made on the basis of the background as described above, and has high yarn and woven stability over a long period of time suitable for a turbine blade or turbine vane for nuclear power generation, and at high temperatures.
  • Cobalt-free (Co-free) Ni-based super composite with excellent creep properties The challenge is to provide money.
  • the invention of this application is to solve the above problems.
  • Cr l. 0-10.
  • W 7.5 to : LO.
  • Al 4.0 to 8-8.
  • Owt%, at least one of Ta, Nb and Ti 12. Owt% or less
  • Hf 0 to 2.
  • Owt%, Re 0. 1 to 5
  • a Ni-base superalloy having a composition containing Owt% and the balance being Ni and inevitable impurities.
  • the yarn is further composed of Si: 0.3 wt% or less, V: 3 wt% or less, Zr: 3 wt% or less, C: 0.3 wt%
  • a Ni-base superalloy characterized by containing at least one of B: 0.2 wt% or less, Y: 0.2 wt% or less, La: 0.2 wt% or less, Ce: 0.2 wt% or less provide.
  • a method for producing a Ni-base superalloy characterized in that any one of the above-mentioned Ni-base superalloys is forged by a normal forging method, a unidirectional solidification method, or a single crystal solidification method.
  • preliminary heat treatment is performed at 1260-1300 ° C for 20 minutes to 2 hours, solution treatment at 1300-1350 ° C for 3-10 hours, 1050-1150 ° C 1 to 8 hours primary aging treatment and 800 to 900 ° C secondary aging treatment for 10 to 24 hours.
  • FIG. 1 is a diagram showing the results of comparison of the creep life of the existing strongest Ni-base superalloy containing Co and the invention of this application.
  • Co increases the solid solubility limit of Al, Ta, and other gamma matrixes at high temperatures and heat treatment. It is considered to be an indispensable component for Ni-base superalloys that have excellent structure stability and creep properties at high temperatures because they have the function of improving the high-temperature strength by dispersing and precipitating fine gamma prime phases. It was. However, in the invention of this application, even without adding Co, which has been considered indispensable in high-strength Ni-base superalloys so far, by making the Ni-base superalloy a specific composition, that is, Cr: 0 to: LO. Owt%, Mo: 0.1 to 3.5 wt%, W: 7.6 to: LO.
  • CMSX-4 containing Co which has been used as an alloy, it is possible to produce a Ni-base superalloy with high creep strength.
  • the cobalt-free Ni-base superalloy of the invention of this application has excellent structure stability and creep characteristics at high temperatures, and is particularly suitable for the manufacture of turbine blades or turbine vane parts.
  • Cr chromium
  • the Cr content is preferably in the range of 1.0-10. Owt%, and more preferably 4.0-6. Owt%.
  • Mo mobdenum
  • the content of Mo is 0.1 -.! 3.1.1 0-3 gesture, et al preferred is 5wt% of the range Owt 0/0 preferably from force / ⁇ .
  • W tungsten
  • the W content is preferably in the range of 7.5 to 10.0%, more preferably 7.6 to 8.5 wt%.
  • A1 (aluminum) forms a gamma prime phase that combines with Ni and precipitates in the gamma matrix.
  • the intermetallic compound represented by Ni Al is formed at a volume fraction of 50-70% and is high.
  • the content of A1 is 4.0-8. (A range of ⁇ % is preferable, and 4.5 to 6. Owt% is more preferable.
  • Ta tantalum
  • Nb niobium
  • ⁇ titanium
  • Hf hafnium
  • Hf has an effect of improving oxidation resistance. If the content exceeds 2 wt%, the formation of harmful phases is promoted, so it is necessary to make it less than this.
  • Hf may be 0 wt% for turbine blades and turbine vane parts produced by the single crystal solidification method, but 0.1 to 1.6 wt% is more preferable.
  • Re rhenium not only improves the high-temperature strength by solid solution strengthening in the gamma phase, but also has an effect of improving corrosion resistance. However, if a large amount of Re is contained, the TCP phase may precipitate at high temperatures to reduce the high temperature strength, so the range of 0.1 to 5 wt% is preferable, and 1.5 to 3.5 wt% is more preferable.
  • Si (Ca) improves the acid resistance as a protective film by forming a SiO film on the alloy surface.
  • V vanadium
  • vanadium is dissolved in the gamma prime phase to strengthen the gamma prime phase.
  • an excessive content of 3 wt% or less is preferable because it reduces the creep strength.
  • Zr zirconium reinforces grain boundaries in the same way as B (boron) and C.
  • an excessive content is preferably 3 wt% or less because it reduces the creep strength.
  • C carbon
  • an excessive content of 0.3 wt% or less is preferable because it impairs ductility.
  • B boron
  • C boron
  • Y yttrium
  • La lanthanum
  • Ce cerium
  • Y 0.2 wt% or less
  • La 0.2 wt% or less
  • Ce 0.2 wt% or less
  • Ni-base superalloy of the present invention having the above elemental composition can be fabricated.
  • a Ni-based superalloy can be manufactured as a polycrystalline alloy, a unidirectionally solidified alloy, or a single crystal alloy by a normal forging method, a unidirectional solidification method, or a single crystal solidification method.
  • the ordinary forging method is basically forging using an ingot prepared to a desired composition, but after the mold temperature is heated to a solidification temperature of the alloy of about 1500 ° C or higher and the superalloy is introduced, For example, it is a method in which a large number of crystals are grown in one direction by applying a temperature gradient by gradually increasing the furnace power.
  • the single crystal solidification method is almost the same as the unidirectional solidification method, but a zigzag or spiral type selector is provided before the desired product is solidified, and a number of crystals that have solidified in one direction are integrated with the selector. One crystal is produced to produce the desired product.
  • the Ni-base superalloy of the present invention can have high tally strength by heat treatment after fabrication.
  • Standard heat treatment after performing preliminary heat treatment of 20 minutes to 2 hours at 1,260 to 1,300 ° C, from 1300 to 1350 0 ⁇ a 1,050 to 1,150 0 ⁇ 2-8 hours Caro heat in a temperature range of the air-cooled Do.
  • This treatment can also be used as a coating treatment for heat and acid resistance.
  • secondary aging treatment for gamma prime phase stabilization is performed at 800-900 ° C for 10-24 hours, followed by air cooling treatment. Each air cooling may be replaced with an inert gas.
  • High temperature parts such as turbine blades or turbine vanes of gas turbines are realized by the Ni-base superalloy produced by this manufacturing method.
  • the creep strength was measured for the sample of this example that had undergone solution treatment and aging treatment.
  • the creep test is 800. C—735 MPa, 900. C—392MPa, 1000. C-245MPa, 1100 ° C-137MPa.
  • the time until the specimen creep rupture was defined as the lifetime.
  • nine types of samples ( ⁇ .1 to ⁇ .12) with different compositions were used, but there were no significant differences in the samples of ⁇ .1 to ⁇ .12.
  • Fig. 3 shows the results of a comparison of the creep test results using No. 5 sample and CMSX-4 in terms of the creep life.
  • the Ni-based superalloy of the invention of this application contains Co, which has been used as a second-generation Ni-based single crystal alloy, even though it does not contain Co.
  • CMSX-4 Compared to the above, it has a creep strength that is equal to or higher than that, and it is extremely difficult.
  • the invention of the first Ni-base superalloy described above it is possible to provide an alloy having a good balance up to a medium temperature part high temperature part suitable as a turbine blade or turbine vane such as a jet engine or a gas turbine for power generation.
  • a medium temperature part high temperature part suitable as a turbine blade or turbine vane such as a jet engine or a gas turbine for power generation.
  • it has a long half-life and does not contain Co. Therefore, it can be put to practical use as a material for nuclear power generation.
  • the cobalt-free Ni-base superalloy produced in claim 1 or 2 is subjected to normal solidification, single crystal solidification, and unidirectional solidification.
  • normal solidification, single crystal solidification, and unidirectional solidification By molding using this method, it becomes possible to produce turbine blades or turbine vane parts that have excellent creep characteristics at high temperatures with high structural stability over a long period of time.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)

Abstract

La présente invention propose un superalliage à base de Ni exempt de Co comprenant de 1,0 à 10 % en poids de Cr, de 0,1 à 3,5 % en poids de Mo, de 7,5 à 10 % en poids de W, de 4,0 à 8 % en poids de Al, ≤ 12 % en poids d'au moins un élément parmi Ta, Nb et Ti, de 0 à 2,0 % en poids de Hf, de 0,1 à 5,0 % en poids de Re, le reste étant représenté par Ni et les impuretés inévitables. Ce superalliage à base de Ni exempt de Co présente une stabilité structurelle élevée pendant une période prolongée, des caractéristiques de fluage excellentes à haute température et il facilite la maintenance destinée à lutter contre la contamination radiative, etc. Il convient donc pour une utilisation dans une ailette ou une aube de turbine de génération d'électricité nucléaire, etc.
PCT/JP2006/306022 2005-03-28 2006-03-24 SUPERALLIAGE A BASE DE Ni EXEMPT DE COBALT WO2006104059A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2007510462A JP5024797B2 (ja) 2005-03-28 2006-03-24 コバルトフリーのＮｉ基超合金
US11/887,221 US20080240926A1 (en) 2005-03-28 2006-03-24 Cobalt-Free Ni-Base Superalloy
GB0720743A GB2439071B (en) 2005-03-28 2007-10-23 Colbalt-free Ni base superalloy

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005090451 2005-03-28
JP2005-090451 2005-03-28

Publications (1)

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WO2006104059A1 true WO2006104059A1 (fr) 2006-10-05

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PCT/JP2006/306022 WO2006104059A1 (fr) 2005-03-28 2006-03-24 SUPERALLIAGE A BASE DE Ni EXEMPT DE COBALT

Country Status (4)

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US (1) US20080240926A1 (fr)
JP (1) JP5024797B2 (fr)
GB (1) GB2439071B (fr)
WO (1) WO2006104059A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011001590A (ja) * 2009-06-18 2011-01-06 National Institute For Materials Science Ｎｉ基超合金
WO2014024734A1 (fr) * 2012-08-09 2014-02-13 独立行政法人物質・材料研究機構 Superalliage monocristallin à base de nickel
JP2014070231A (ja) * 2012-09-28 2014-04-21 National Institute For Materials Science Ｎｉ基単結晶超合金部品の直接リサイクル法
WO2017154809A1 (fr) * 2016-03-07 2017-09-14 国立研究開発法人物質・材料研究機構 Alliage à solidification unidirectionnelle à base de nickel
CN110396624A (zh) * 2019-08-13 2019-11-01 上海大学 核屏蔽用富硼镍钨基合金材料及其制备方法

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Publication number Priority date Publication date Assignee Title
IT1394975B1 (it) * 2009-07-29 2012-08-07 Nuovo Pignone Spa Superlega a base di nichel, componente meccanico realizzato con detta superlega, turbomacchina comprendente tale componente e metodi relativi
US20160214350A1 (en) 2012-08-20 2016-07-28 Pratt & Whitney Canada Corp. Oxidation-Resistant Coated Superalloy
FR3057880B1 (fr) * 2016-10-25 2018-11-23 Safran Superalliage a base de nickel, aube monocristalline et turbomachine
US20200255924A1 (en) 2019-02-08 2020-08-13 United Technologies Corporation High Temperature Combustor and Vane Alloy
FR3097879B1 (fr) * 2019-06-28 2021-05-28 Safran Aircraft Engines Procede de fabrication d’une piece en superalliage monocristallin

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US5611670A (en) * 1993-08-06 1997-03-18 Hitachi, Ltd. Blade for gas turbine
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US5611670A (en) * 1993-08-06 1997-03-18 Hitachi, Ltd. Blade for gas turbine
EP0767252A1 (fr) * 1995-10-02 1997-04-09 United Technologies Corporation Superalliage à base de nickel résistant aux propagations de fissures
US6051083A (en) * 1996-02-09 2000-04-18 Hitachi, Ltd. High strength Ni-base superalloy for directionally solidified castings
US6673803B2 (en) * 1996-09-25 2004-01-06 Zeneca Limited Quinazoline derivatives and pharmaceutical compositions containing them
EP0971041A1 (fr) * 1998-07-07 2000-01-12 ONERA (Office National d'Etudes et de Recherches Aérospatiales) Superalliage monocristallin à base de nickel à haut solvus phase gamma prime
JP2000063969A (ja) * 1998-08-13 2000-02-29 Toshiba Corp Ｎｉ基超合金、その製造方法およびガスタービン部品
EP1201778A2 (fr) * 2000-10-30 2002-05-02 United Technologies Corporation Matériaux en superalliage résistant à l'oxydation et de faible densité capables de retenir un revêtement de barrière thermique sans couche de liaison

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011001590A (ja) * 2009-06-18 2011-01-06 National Institute For Materials Science Ｎｉ基超合金
WO2014024734A1 (fr) * 2012-08-09 2014-02-13 独立行政法人物質・材料研究機構 Superalliage monocristallin à base de nickel
JP2014034720A (ja) * 2012-08-09 2014-02-24 National Institute For Materials Science Ｎｉ基単結晶超合金
CN104520457A (zh) * 2012-08-09 2015-04-15 独立行政法人物质·材料研究机构 Ni基单晶超合金
CN104520457B (zh) * 2012-08-09 2017-03-15 独立行政法人物质·材料研究机构 Ni基单晶超合金
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JP2014070231A (ja) * 2012-09-28 2014-04-21 National Institute For Materials Science Ｎｉ基単結晶超合金部品の直接リサイクル法
WO2017154809A1 (fr) * 2016-03-07 2017-09-14 国立研究開発法人物質・材料研究機構 Alliage à solidification unidirectionnelle à base de nickel
CN110396624A (zh) * 2019-08-13 2019-11-01 上海大学 核屏蔽用富硼镍钨基合金材料及其制备方法
CN110396624B (zh) * 2019-08-13 2021-04-09 上海大学 核屏蔽用富硼镍钨基合金材料及其制备方法

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Publication number Publication date
US20080240926A1 (en) 2008-10-02
GB0720743D0 (en) 2007-12-05
JPWO2006104059A1 (ja) 2008-09-04
JP5024797B2 (ja) 2012-09-12
GB2439071B (en) 2010-09-22
GB2439071A (en) 2007-12-19

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