EP3249063A1 - Hochfeste ni-basierte superlegierung - Google Patents

Hochfeste ni-basierte superlegierung Download PDF

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Publication number
EP3249063A1
EP3249063A1 EP16171670.9A EP16171670A EP3249063A1 EP 3249063 A1 EP3249063 A1 EP 3249063A1 EP 16171670 A EP16171670 A EP 16171670A EP 3249063 A1 EP3249063 A1 EP 3249063A1
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Prior art keywords
alloy
phase
temperature
high strength
based superalloy
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EP16171670.9A
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English (en)
French (fr)
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EP3249063B1 (de
Inventor
Koichi Takasawa
Takuya Ohkawa
Masato Yoshida
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Japan Steel Works M&E Inc
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Japan Steel Works Ltd
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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

Definitions

  • the present invention relates to a high strength Ni-based superalloy having a high strength.
  • a Ni-based superalloy shows excellent mechanical characteristics at high temperatures and is widely used as high-temperature members of aircraft jet engines, etc.
  • adding a small amount of Al, Ti as well as Nb and Ta to a Ni-based alloy brings about fine precipitation of a strengthening phase that is called a ⁇ ' (gamma prime) phase of Ni 3 (Al,Ti), or a ⁇ " (gamma double prime) phase of Ni 3 (Al,Ti,Nb) in crystal grains to express an excellent strength.
  • a technical tendency is toward an uncooled low-pressure turbine disk in jet engines.
  • a low-pressure turbine disk has become desired to have a high strength at higher temperatures, and development of an alloy having an increased strength by increasing the amount of the above-mentioned strengthening phase therein is being made.
  • the hot workability of the alloy lowers, and therefore, the alloy becomes difficult to work into a desired shape. Accordingly, it is important to secure hot workability of an alloy while increasing the strength thereof.
  • a Ni-based superalloy generally contains large quantities of alloying elements, and in smelting the alloy, there may occur in any way, unevenness in compositional distribution, that is, micro-segregation.
  • the solidus temperature is lower than that of the other part, and therefore, when overheated, the micro-segregated part may be partially melted to lower the hot workability of the alloy. Accordingly, before hot working, the alloy must be heat-treated under a suitable condition to relax the micro-segregation.
  • Patent Documents 1 to 3 Some proposes have been made for a Ni-based superalloy having excellent hot workability or a technique of improving the hot workability of a Ni-based alloy.
  • Patent Documents 1 and 2 propose a Ni-based superalloy excellent in weldability and hot workability.
  • these documents refer to nothing relating to hot workability from the viewpoint of the above-mentioned micro-segregation, and there is a possibility of absence of any suitable evaluation therein.
  • the contents of Al and Ti capable of contributing to formation of a strengthening phase are smaller than those in the present invention, and therefore, a strengthening phase in an amount required by low-pressure turbine disks to which the present invention is intended to be applied could not be formed, that is, there is a possibility that the strength of the alloys may be insufficient.
  • Patent Document 3 refers to nothing relating to the relationship between micro-segregation and hot workability, and it is unclear whether alloy production would be carried out under a suitable condition.
  • the present invention has been made in consideration of the above-mentioned situation, and an object thereof is to provide a Ni-based superalloy excellent in strength and hot workability.
  • the present invention relates to the following (1) to (7).
  • Ni-based superalloy having a high strength and excellent hot workability.
  • C is an additive element to form a carbide to suppress crystal grain coarsening of the alloy, and to precipitate in a grain boundary to improve the high-temperature strength of the alloy; but when the content thereof is small, it is not effective for sufficiently improving the strength, and therefore, the content of C must be 0.005% or more. However, when the content thereof is too large, an excessive carbide may be formed to have a negative influence of decreasing the amount of other useful precipitates such as a ⁇ '-phase, and therefore, the upper limit thereof is 0.05%. For the same reasons, the lower limit thereof is preferably 0.01% and the upper limit thereof is preferably 0.02%.
  • Fe is, when the content thereof is increased, effective for alloy cost reduction, but when Fe is incorporated excessively in an Nb-containing alloy, an intermetallic compound called a Laves phase is formed to cause worsening of material characteristics, for example, degradation of hot rollability, etc. Accordingly, the content of Fe is 0.1 to 2.0%. For the same reasons, the lower limit thereof is preferably 0.5% and the upper limit thereof is preferably 1.5%.
  • Co is an element of improving the segregation property of the alloy by bringing the partition coefficient of alloying elements such as Al, Ti, Nb and W close to 1.
  • the alloy does not contain Co in an amount of 10% or more, the effect could not be sufficiently realized.
  • the content of Co is more than 20%, not only the forgeability is worsened but also a Laves phase may be readily formed, whereby, the matrix texture at a high temperature would be rather destabilized and the high-temperature texture stability would be worsened. Accordingly, the content of Co is limited to a range of 10 to 20%.
  • the lower limit thereof is preferably 12% and the upper limit thereof is preferably 16%.
  • Mo mainly dissolves in a matrix to strengthen it, and also dissolves in a ⁇ ' phase to substitute for the Al site in this phase to thereby increase the stability of the phase, and is therefore effective for increasing both high-temperature strength and texture stability.
  • the content of Mo is less than 1.0%, the above-mentioned effect is insufficient, but when the content thereof is more than 8.0%, a Laves phase may be readily formed, whereby the matrix texture at a high temperature would be rather destabilized and the high-temperature texture stability would be worsened.
  • the content of Mo is limited to a range of 1.0 to 8.0%.
  • the lower limit thereof is preferably 2.0% and the upper limit thereof is preferably 6.0%.
  • W Like Mo, W also dissolves in a matrix to strengthen it, and dissolves in a ⁇ ' phase to substitute for the Al site in this phase to thereby increase the stability of the phase, and is therefore effective for increasing both high-temperature strength and texture stability.
  • W when W is incorporated excessively, not only ⁇ -W precipitates to lower texture stability but also hot workability is also noticeably worsened. Accordingly, the content of W is limited to a range of 1.0 to 8.0%.
  • the lower limit thereof is preferably 2.0% and the upper limit thereof is preferably 6.0%.
  • Cr is an element necessary for enhancing oxidation resistance, corrosion resistance and strength of the alloy. Also, it combines with C to form a carbide, thereby enhancing high-temperature strength. However, too large content thereof invites destabilization of matrix and promotes the formation of harmful TCP phases such as a ⁇ phase and ⁇ -Cr, resulting in adverse influences on ductility and toughness. Therefore, the content of Cr is limited to 10 to 20%. For the same reasons, the lower limit thereof is preferably 14% and the upper limit thereof is preferably 18%.
  • Ti mainly forms an MC carbide to suppress crystal grain coarsening of the alloy and also combines with Ni to precipitate a ⁇ ' phase, thereby contributing to precipitation strengthening of the alloy.
  • the stability of the ⁇ ' phase at a high temperature is lowered and an ⁇ phase is formed, thereby impairing strength, ductility, toughness, and high-temperature long-term texture stability. Therefore, the content ofTi is limited to a range of 0.1 to 2.0%.
  • the lower limit thereof is preferably 0.5% and the upper limit thereof is preferably 1.5%.
  • Al combines with Ni to precipitate a ⁇ ' phase, thereby contributing to precipitation strengthening of the alloy.
  • the content of Al is limited to 2.0 to 4.5%.
  • the lower limit thereof is preferably 3.0% and the upper limit thereof is preferably 4.0%.
  • Nb is an element that stabilizes the ⁇ ' phase and contributes to strength enhancement, but when Nb is exceedingly incorporated, the precipitation of the ⁇ phase, the ⁇ phase, and the Laves phase that are harmful phases is promoted, thereby remarkably lowering texture stability. Therefore, the content ofNb is limited to 0.1 to 2.0%. For the same reasons, the lower limit thereof is preferably 0.5% and the upper limit thereof is preferably 1.5%.
  • P is considered to have an effect of reducing local strain accumulation near grain boundaries to prevent creep deformation by depositing precipitates containing P at grain boundaries, thereby lowering the minimum creep speed and prolonging the creep rupture time.
  • P when P is exceedingly incorporated, there is a possibility that grain boundary segregation of P becomes excessive to lower the consistency of the grain boundaries, thereby causing ductility reduction and the like. Therefore, when P is incorporated according to the necessity, it is desirable that the lower limit of the content of P is 30 ppm and the upper limit thereof is 100 ppm.
  • the lower limit thereof is more preferably 40 ppm and the upper limit thereof is more preferably 80 ppm.
  • B segregates at grain boundaries to contribute to high-temperature characteristics, and is therefore incorporated according to the necessity.
  • the content of B is preferably 250 ppm or less.
  • the content thereof is preferably 50 ppm or more, and for the same reasons as above, the lower limit thereof is more preferably 100 ppm and the upper limit thereof is more preferably 200 ppm.
  • Mg mainly combines with S to form a sulfide and enhances hot workability, so that Mg is incorporated according to the necessity.
  • the content of Mg is preferably 0.01% or less.
  • the lower limit of the Mg content is preferably 0.0005% or more.
  • Zr segregates at grain boundaries to contribute to an improvement in high-temperature characteristics, so that Zr is incorporated according to the necessity.
  • the content of Zr is preferably 0.50% or less. In order to obtain the above-described effect, it is preferable to incorporate Zr in an amount of 0.01% or more.
  • ⁇ ' phase amount at 700°C being 40 to 43% in terms of volume fraction.
  • the ⁇ ' phase amount at 700°C in terms of volume fraction is appropriate, a desired strength can be realized. When it is lower than 40%, the strength would be too low and desired characteristics of members could not be satisfied. On the other hand, when it is more than 43%, the strength would be excessive to lower the toughness of members. Accordingly, it is desirable that the ⁇ ' phase amount at 700°C is 40 to 43% in terms of volume fraction.
  • the ⁇ ' phase amount in terms of volume fraction may be controlled by varying the balance of Al and Ti that are the constituent elements of the ⁇ ' phase.
  • ⁇ ' phase solution temperature being 1100°C or lower.
  • the temperature range within which the alloy exhibits good hot workability can be expanded to lower temperatures, thereby enabling effective bloom-forging at lower temperatures.
  • the ⁇ ' phase solution temperature can be controlled by varying the balance of Al and Ti that are the constituent elements of the ⁇ ' phase. Temperature range within which reduction of area is 50% or more being 120°C or higher.
  • the temperature range that realizes excellent hot workability is expanded, and in a one-time bloom-forging step, a cast structure can be more effectively destroyed.
  • the temperature range is less than 120°C, the temperature range capable of realizing excellent hot workability may narrow, and multiple bloom-forging steps would be necessary for sufficiently destroying a cast structure, thereby resulting in cost increase.
  • Hot working can be carried out, for example, in a temperature range of 900°C to 1150°C.
  • the temperature range for hot working is not limited to the above-described temperature range.
  • the temperature range within which the reduction of area is 50% or more is preferably 120°C or higher, and the temperature range can be controlled by varying the balance of Al and Ti that are the constituent elements of the ⁇ ' phase, and the balance of Cr, Mo and Nb that are micro-segregation elements.
  • the Ni-based alloy of the present invention is controlled to have a composition including, in terms of % by mass, C: 0.005 to 0.05%, Fe: 0.1 to 2.0%, Cr: 10 to 20%, Co: 10 to 20%, Mo: 1.0 to 8.0%, W: 1.0 to 8.0%, Ti: 0.1 to 2.0%, Al: 2.0 to 4.5%, and Nb: 0.1 to 2.0%, with the balance being Ni and unavoidable impurities.
  • the composition may further include according to the necessity, in terms of ppm by mass, at least one of P: 30 to 100 ppm, and B: 50 to 250 ppm, and also according to the necessity, at least one of Mg: 0.01% or less, and Zr: 0.01 to 0.50%.
  • the Ni-based alloy of the present invention can be produced according to an ordinary smelting method and, as the invention, the smelting method is not particularly limited.
  • the Ni-based alloy may be subjected to diffusion heat treatment.
  • an ingot of 5 tons or more is expected in smelting.
  • the size of products is not specifically limited, the effect of improving hot workability for large-size members of 5 tons or more brings about especially favorable results.
  • Diffusion heat treatment can be carried out under the condition at 1200°C for 50 hours or more.
  • the treatment time is preferably 100 hours or less.
  • diffusion heat treatment may be omitted.
  • the Ni-based alloy may be worked for forging or the like, according to the necessity.
  • the condition in working is not specifically limited in the present invention.
  • the ⁇ ' phase amount at 700°C is 40 to 43% in terms of volume fraction
  • the ⁇ ' phase solution temperature is 1100°C or lower
  • the temperature range within which the reduction of area of the alloy in a tensile test is 50% or more, is 120°C or higher; and the alloy realizes good hot workability.
  • an Ni-based superalloy that has improved hot workability and contains a sufficient amount of a strengthening phase to secure the strength thereof can be obtained.
  • the strength is, for example, 1050 MPa or more at 750°C, but is not limited thereto.
  • Ni-based alloy is favorably used in the field where a temperature of 600°C or higher is expected, such as low-pressure turbine disks of jet engines and gas turbine disks for high-efficiency power generation.
  • the material was a 25-kg round ingot produced according to a vacuum induction melting method, and nine invention alloys and one comparative alloy were produced.
  • the chemical components (with the balance being unavoidable impurities) of the invention alloys and the comparative alloy are shown in Table 1.
  • the ⁇ ' phase amount at 700°C and the ⁇ ' phase solution temperature of the invention alloys and the comparative alloy are calculated using a general-purpose thermodynamic calculation software (Thermo-Calc). Table 2 collectively shows them.
  • the tensile test was performed as follows.
  • each test piece had a diameter in the parallel part of 6 mm and a mark-to-mark distance of 30 mm.
  • the test temperature range was 950 to 1225°C, and the following method was employed for avoiding the influence to be provided by the difference in the crystal grain size. Specifically, in the case where the test temperature was 1150°C or higher, the test piece was kept at the test temperature for 30 minutes and then subjected to the tensile test.
  • the test piece was once kept at 1150°C for 30 minutes, then cooled down to the test temperature, and further kept at the test temperature for 15 minutes to thereby stabilize the temperature thereof, and thereafter subjected to the tensile test.
  • the strain speed in the tensile test was 3 x 10 -2 s -1 in every case.
  • all the invention alloys have a larger ⁇ ' phase amount at 700°C, from 42.0 to 43.1%, than the comparative alloy.
  • the ⁇ ' phase solution temperature in the invention alloys is lower than that in the comparative alloy, that is, lower than 1100°C.
  • Fig. 1 and Fig. 2 each show a relationship between a reduction of area and a temperature of the invention alloys and the comparative alloy.
  • the maximum reduction of area is almost the same between the invention alloys and the comparative alloy, but the temperature range within which the reduction of area is 50% or more is broader for the invention alloys than that for the comparative alloy.
  • the broader temperature range means that the forgeable temperature range is broad and the hot workability of the alloy is good.
  • Fig. 3 shows the temperature range within which the reduction of area is 50% or more for the invention alloys and the comparative alloy.
  • the temperature range for the comparative alloy is 120°C, but all the invention alloys shown in Fig. 3 show a temperature range higher than that for the comparative alloy. Accordingly, it becomes clear that the invention alloys are excellent in hot workability.

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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)
EP16171670.9A 2016-05-27 2016-05-27 Hochfeste ni-basierte superlegierung Active EP3249063B1 (de)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109504879A (zh) * 2018-12-28 2019-03-22 西安欧中材料科技有限公司 一种航空发动机用镍基高温合金
RU2686831C1 (ru) * 2018-03-22 2019-04-30 Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") Металлокерамический композиционный материал на основе интерметаллидной матрицы и способ его получения
US11634792B2 (en) 2017-07-28 2023-04-25 Alloyed Limited Nickel-based alloy

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2246449A1 (de) * 2008-02-13 2010-11-03 The Japan Steel Works, Ltd. Superlegierung auf ni-basis mit hervorragenden segregationseigenschaften
WO2012047352A2 (en) * 2010-07-09 2012-04-12 General Electric Company Nickel-base alloy, processing therefor, and components formed thereof
WO2014124626A1 (de) * 2013-02-14 2014-08-21 VDM Metals GmbH Nickel-kobalt-legierung
EP2940174A1 (de) * 2012-12-28 2015-11-04 The Japan Steel Works, Ltd. Legierung auf fe-ni-basis mit hervorragenden hochtemperatureigenschaften und beständigkeit gegen wasserstoffversprödung und verfahren zur herstellung davon

Family Cites Families (6)

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Publication number Priority date Publication date Assignee Title
FR1227686A (fr) 1958-06-17 1960-08-22 Mond Nickel Co Ltd Perfectionnements aux alliages de nickel-chrome
WO2001053548A2 (en) 2000-01-24 2001-07-26 Inco Alloys International, Inc. Ni-Co-Cr HIGH TEMPERATURE STRENGTH AND CORROSION RESISTANT ALLOY
JP5201708B2 (ja) 2006-04-14 2013-06-05 三菱マテリアル株式会社 Ｎｉ基耐熱合金溶接用ワイヤー
KR20120053645A (ko) 2010-11-18 2012-05-29 한국기계연구원 고온에서의 기계적 특성이 우수한 다결정 니켈기 초내열합금
US9738953B2 (en) 2013-07-12 2017-08-22 Daido Steel Co., Ltd. Hot-forgeable Ni-based superalloy excellent in high temperature strength
US10487384B2 (en) 2013-07-17 2019-11-26 Mitsubishi Hitachi Power Systems, Ltd. Ni-based alloy product and method for producing same, and Ni-based alloy member and method for producing same

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2246449A1 (de) * 2008-02-13 2010-11-03 The Japan Steel Works, Ltd. Superlegierung auf ni-basis mit hervorragenden segregationseigenschaften
WO2012047352A2 (en) * 2010-07-09 2012-04-12 General Electric Company Nickel-base alloy, processing therefor, and components formed thereof
EP2940174A1 (de) * 2012-12-28 2015-11-04 The Japan Steel Works, Ltd. Legierung auf fe-ni-basis mit hervorragenden hochtemperatureigenschaften und beständigkeit gegen wasserstoffversprödung und verfahren zur herstellung davon
WO2014124626A1 (de) * 2013-02-14 2014-08-21 VDM Metals GmbH Nickel-kobalt-legierung

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11634792B2 (en) 2017-07-28 2023-04-25 Alloyed Limited Nickel-based alloy
RU2686831C1 (ru) * 2018-03-22 2019-04-30 Федеральное государственное унитарное предприятие "Всероссийский научно-исследовательский институт авиационных материалов" (ФГУП "ВИАМ") Металлокерамический композиционный материал на основе интерметаллидной матрицы и способ его получения
CN109504879A (zh) * 2018-12-28 2019-03-22 西安欧中材料科技有限公司 一种航空发动机用镍基高温合金

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