US20140345752A1 - Precipitation hardened fe-ni alloy - Google Patents

Precipitation hardened fe-ni alloy Download PDF

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US20140345752A1
US20140345752A1 US14/278,179 US201414278179A US2014345752A1 US 20140345752 A1 US20140345752 A1 US 20140345752A1 US 201414278179 A US201414278179 A US 201414278179A US 2014345752 A1 US2014345752 A1 US 2014345752A1
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mass
alloy
precipitation hardened
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phase
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Mari Takahashi
Shigeki Ueta
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Daido Steel Co Ltd
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/54Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/18Hardening; Quenching with or without subsequent tempering
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/004Heat treatment of ferrous alloys containing Cr and Ni
    • CCHEMISTRY; METALLURGY
    • C21METALLURGY OF IRON
    • C21DMODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D6/00Heat treatment of ferrous alloys
    • C21D6/02Hardening by precipitation
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/056Alloys 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%
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • C22C30/02Alloys containing less than 50% by weight of each constituent containing copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/002Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/005Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/06Ferrous alloys, e.g. steel alloys containing aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/42Ferrous alloys, e.g. steel alloys containing chromium with nickel with copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/48Ferrous alloys, e.g. steel alloys containing chromium with nickel with niobium or tantalum
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/50Ferrous alloys, e.g. steel alloys containing chromium with nickel with titanium or zirconium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22FCHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/10Changing 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

Definitions

  • the present invention relates to a precipitation hardened Fe—Ni alloy. More specifically, the invention relates to a precipitation hardened Fe—Ni alloy having high strength and excellent corrosion resistance.
  • a precipitation hardened stainless steel is a steel in which elements such as Cu, Al, Ti, Nb, and Mo are added to achieve precipitation hardening and has both of high corrosion resistance and high strength.
  • an austenite precipitation hardened stainless steel represented by A286 alloy (SUH660) is an alloy excellent in both of corrosion resistance and strength among Fe based alloys.
  • A286 alloy SBA-65 alloy
  • Patent Document 1 discloses a nickel-iron based alloy comprising, in terms of % by weight, 0.027% of C, 0.08% of Mn, 0.10% of Si, 0.001% of P, 0.005% of S, 15.81% of Cr, 39.89% of Ni, 2.83% of Nb, 1.61% of Ti, 0.3% of Al, and 0.0041% of B, with the balance being Fe and unavoidable impurities.
  • Patent Document 2 discloses an Ni based alloy comprising, in terms of % by weight, 0.017% of C, 0.15% of Si, 0.14% of Mn, 0.010% of P, 0.003% of S, 40.32% of Ni, 16.20% of Cr, 1.02% of Mo, 0.25% of Al, 0.95% of Ti, and 2.71% of Nb, with the balance being Fe and unavoidable impurities.
  • the document describes a fact that the alloy has high strength from room temperature till extremely low temperature and can suppress HAZ cracking by such a composition.
  • Patent Document 3 discloses a high-strength corrosion-resistant alloy comprising, in terms of % by weight, 44.2% of Ni, 19.5% of Cr, 3.4% of Mo, 2.0% of Cu, 0.006% of C, 0.3% of Al, 3.8% of Nb, and 1.6% of Ti, with the balance being Fe.
  • the document describes a fact that high strength is obtained by precipitating predetermined amounts of the ⁇ ′ phase and the ⁇ ′′ phase by annealing and aging treatments.
  • Patent Document 1 Mo and Cu are not added and corrosion resistance is insufficient.
  • strength is insufficient owing to the balance among Ni, Nb, Ti, and Al.
  • Patent Document 3 strength of Ni and Nb are high and the raw material costs and the production costs thereof are high.
  • JP-T-2009-515053 (the term “JP-T” as used herein means a published Japanese translation of a PCT patent application)
  • a problem to be solved by the present invention is to provide a precipitation hardened Fe—Ni alloy having both of high corrosion resistance and high hardness.
  • the gist of the invention is that the precipitation hardened Fe—Ni alloy according to the invention has the following constitutions.
  • the precipitation hardened Fe—Ni alloy comprising:
  • the precipitation hardened Fe—Ni alloy satisfies the following formula (3):
  • the ⁇ ′ phase (Ni 3 (Al, Ti, Nb)) and the ⁇ ′′ phase (Ni 3 Nb) containing Nb as a constituent element are precipitated by a solution heat treatment and an aging treatment.
  • the Laves phase (Fe 2 Nb) is prone to remain after the solution heat treatment.
  • the Nb amount necessary for precipitation hardening in the matrix decreases. As a result, necessary hardness cannot be obtained even when the aging treatment is performed.
  • the remaining of the Laves phase can be suppressed after the solution heat treatment.
  • FIG. 1 shows optical microscopic pictures of the materials after a solution heat treatment obtained in Example 5 and Comparative Example 4.
  • the precipitation hardened Fe—Ni alloy according to the invention contains the following elements, with the balance being Fe and unavoidable impurities.
  • Kinds of the addition elements, composition ranges thereof, and reasons for the limitation thereof are as follows.
  • the C is an element effective for forming a carbide together with Nb and Ti to enhance the strength. Moreover, it suppresses crystal grain coarsening at a solution heat treatment. For obtaining such effects, the C content is necessarily 0.01% by mass or more. The C content is further preferably 0.04% by mass or more.
  • the C content when the C content becomes excessive, toughness and ductility are lowered. Moreover, when a large amount of the carbide is formed, corrosion resistance is remarkably lowered.
  • the C content is necessarily 0.08% by mass or less.
  • the C content is preferably 0.07% by mass or less.
  • Si is effective as a deoxidizing element at the time of ingoting.
  • the Si content is necessarily 0.02% by mass or more.
  • the Si content when the Si content becomes excessive, the toughness is lowered. Therefore, the Si content is necessarily 1.0% by mass or less.
  • Mn is effective as a deoxidizing element at the time of ingoting.
  • oxidation resistance at a high temperature is lowered.
  • excessive Mn also lowers corrosion resistance. Therefore, the Mn content is necessarily 1.0% by mass or less.
  • Ni is essential as an austenite-forming element. Also, Ni makes the alloy age-hardened through precipitation of the ⁇ ′ phase (Ni 3 (Al, Ti, Nb)) and the ⁇ ′′ phase (Ni 3 Nb) together with Ti, Al, and Nb by the aging treatment. For obtaining such an effect, the Ni content is necessarily 36.0% by mass or more. The Ni content is more preferably 37.0% by mass or more.
  • the Ni content when the Ni content becomes excessive, the raw material costs are increased. Therefore, the Ni content is necessarily 41.0% by mass or less.
  • the Ni content is more preferably 40.0% by mass or less, further preferably 39.0% by mass or less.
  • the Cr content is necessarily 14.0% by mass or more.
  • Cr is a ferrite-forming element and, when the Cr content becomes excessive, structural stability is lowered. Also, excessive Cr lowers hot workability. Therefore, the Cr content is necessarily less than 20.0% by mass.
  • the Cr content is more preferably 18.0% by mass or less, further preferably 17.0% by mass or less.
  • Mo improves the corrosion resistance (particularly pitting resistance) through solution into the parent phase.
  • the Mo content is necessarily 0.01% by mass or more.
  • the Mo content becomes excessive, the Laves phase (Fe 2 (Mo, Nb)) is precipitated at the time of the aging treatment and the precipitation amounts of the ⁇ ′ phase and the ⁇ ′′ phase are decreased. As a result, the strength of the alloy is lowered. Therefore, the Mo content is necessarily 3.0% by mass or less. The Mo content is preferably 2.0% by mass or less.
  • Al makes the alloy age-hardened through precipitation of the ⁇ ′ phase (Ni 3 (Al, Ti, Nb)) together with Ni, Ti, and Nb.
  • the Al content is necessarily 0.1% by mass or more.
  • the Al content When the Al content becomes excessive, the hot workability is lowered. Therefore, the Al content is necessarily 1.0% by mass or less.
  • the Al content is preferably 0.5% by mass or less.
  • Ti makes the alloy age-hardened through precipitation of the ⁇ ′ phase (Ni 3 (Al, Ti, Nb)) together with Ni, Al, and Nb.
  • the Ti content is necessarily 1.0% by mass or more.
  • the Ti content is preferably 1.5% by mass or more, more preferably 1.8% by mass or more.
  • the Ti content becomes excessive, the hot workability is lowered. Therefore, the Ti content is necessarily 2.5% by mass or less.
  • Nb makes the alloy age-hardened through precipitation of the ⁇ ′ phase (Ni 3 (Al, Ti, Nb)) and the ⁇ ′′ phase (Ni 3 Nb) together with Ni.
  • the Nb content is necessarily 2.0% by mass or more.
  • the Nb content is necessarily 3.5% by mass or less.
  • the Nb content is more preferably 3.0% by mass or less.
  • the precipitation hardened Fe—Ni alloy according to the invention may further contain one kind or two or more kinds of the following auxiliary constituent elements in addition to the aforementioned main constituent elements.
  • auxiliary constituent elements Kinds of the addition elements, composition ranges thereof, and reasons for the limitation thereof are as follows.
  • the B has an effect of enhancing the hot workability by adding B in a small amount. Also, the precipitation of the ⁇ phase at a grain boundary can be suppressed by the presence of B at the grain boundary.
  • the B content is preferably 0.0005% by mass or more.
  • the B content is further preferably 0.0010% by mass or more.
  • the B content is particularly preferably 0.0020% by mass or more.
  • the B content is preferably 0.01% by mass or less.
  • the B content is further preferably 0.008% by mass or less.
  • the Cu has an effect of enhancing the corrosion resistance in a non-oxidative corrosive environment.
  • the Cu content is preferably 0.05% by mass or more.
  • the Cu content is further preferably 0.10% by mass or more.
  • the Cu content is preferably 1.0% by mass or less.
  • V forms a carbide to enhance the strength. Also, the precipitation amounts of the ⁇ ′ phase and the ⁇ ′′ phase are increased through reducing the ratio of Nb in the carbide. For obtaining such effects, the V content is preferably 0.05% by mass or more.
  • the V content is preferably 1.0% by mass or less.
  • Zr, Ta, W, Hf, Mg, and REM have an effect on micronization of the carbide and micronization of crystal grains.
  • a total content of these elements is preferably 0.001% by mass or more.
  • the total content of these elements is preferably 0.50% by mass or less.
  • any one of these elements may be added or two or more thereof may be used in combination.
  • the Ca content is preferably 0.0005% by mass or more.
  • the Ca content is preferably 0.01% by mass or less.
  • the precipitation hardened stainless steel according to the invention necessarily satisfies the following formulae (1) and (2), in addition to the requirement that the constituent elements are present in the aforementioned ranges.
  • the precipitation hardened stainless steel preferably further satisfies the following formula (3).
  • the formula (1) is relevant to the amount of the Laves phase after the solution heat treatment.
  • the Laves phase Fe 2 Nb
  • the precipitation amounts of the ⁇ ′ phase and the ⁇ ′′ phase at the time of the aging treatment are increased and thereby the strength of the alloy is enhanced.
  • the formula (1) is more preferably Ni ⁇ 6 ⁇ Nb+18.0, further preferably Ni ⁇ 6 ⁇ Nb+20.0.
  • the formula (2) is relevant to the amount of the ⁇ ′′ phase at the time of the aging treatment.
  • the amounts of Nb, Ti, and Al are optimized so as to satisfy the formula (2), the precipitation amount of the ⁇ ′′ phase is increased and thereby further enhancing the strength of the alloy.
  • the formula (3) is relevant to the corrosion resistance of the precipitation hardened Fe—Ni alloy. Cr, Mo, and Cu all have an effect of enhancing the corrosion resistance of the precipitation hardened Fe—Ni alloy. Particularly, when the contents of these elements are optimized so as to satisfy the formula (3), high corrosion resistance is exhibited with maintaining high strength.
  • the Laves phase is almost completely dissolved in the matrix.
  • a suitable solution heat treatment When individual components are optimized as mentioned above and a suitable solution heat treatment is performed, the Laves phase is almost completely dissolved in the matrix.
  • large amounts of the ⁇ ′ phase and the ⁇ ′′ phase are precipitated.
  • the 0.2% offset yield strength at room temperature becomes 850 MPa or more.
  • the 0.2% offset yield strength at room temperature becomes 900 MPa or more or 950 MPa or more.
  • the precipitation hardened Fe—Ni alloy according to the invention is preferably one in which an area percentage of the carbide after the solution heat treatment is 0.4% or more. At the time of the solution heat treatment, the coarsening of crystal grains can be suppressed when a predetermined amount of the carbide is dispersed in the matrix.
  • the “area percentage of the carbide” means a ratio of area of the carbide to the total area of cross-sectional microstructure (0.034 mm 2 ⁇ 30 viewing fields).
  • the method for manufacturing the precipitation hardened Fe—Ni alloy according to the invention comprises a melting and casting process, a hot working process, a solution heat treatment process, and an aging treatment process.
  • the melting and casting process is a process of dissolving a raw material blended in a predetermined composition and performing casting.
  • the dissolving method and the casting method are not particularly limited and various methods can be used according to the purpose.
  • the hot working process is a process of hot-working an ingot obtained in the melting and casting process.
  • the hot working is performed for destroying cast structure and casting defect.
  • Hot working conditions are not particularly limited and most suitable conditions can be selected according to the purpose.
  • the solution heat treatment process is a process of heating a hot-worked material at a predetermined temperature.
  • the solution heat treatment is performed mainly for dissolving a precipitate dispersed in the steel.
  • heat treatment temperature is preferably 900° C. or higher.
  • the heat treatment temperature is preferably 1,200° C. or lower.
  • Heat treatment time may be suitably a time sufficient for dissolving the precipitate. Most suitable heat treatment time varies depending on the heat treatment temperature but is usually from about 30 minutes to about 2 hours. After the heat treatment, the material is quenched.
  • the aging treatment process is a process of subjecting the material after the solution heat treatment to an aging treatment at a predetermined temperature.
  • the aging treatment temperature is preferably from 600° C. to 750° C.
  • Aging treatment time may be suitably a time sufficient for precipitating a sufficient amount of the precipitate. Most suitable aging treatment time varies depending on the aging treatment temperature but is usually from about 8 hours to about 24 hours.
  • the ⁇ ′ phase (Ni 3 (Al, Ti, Nb)) and the ⁇ ′′ phase (Ni 3 Nb) containing Nb as a constituent element are precipitated by the solution heat treatment and the aging treatment.
  • the Laves phase (Fe 2 Nb) tends to remain after the solution heat treatment.
  • the Nb amount in the matrix necessary for precipitation hardening decreases. As a result, necessary hardness is not obtained even when the aging treatment is performed.
  • each steel was cooled to prepare an ingot. After hot working, the ingot was thermally refined by a solution heat treatment and an aging treatment.
  • Solution heat treatment temperature was set to 900 to 1,200° C. Also, the aging treatment temperature was set to 600 to 750° C.
  • Evaluation of the corrosion resistance was performed on a corrosion rate at the time of immersion for 6 h in 10% hydrochloric acid at 80° C.
  • the case where the corrosion rate was 100 g/m 2 /h or less was designated as “A”
  • the case where the rate was more than 100 g/m 2 /h and 200 g/m 2 /h or less was designated as “B”
  • the case where the rate was more than 200 g/m 2 /h was designated as “C”.
  • area percentage was measured at 30 visual fields on a microstructure photograph with a magnification of 400 times (1 visual field: 0.034 mm 2 ) using an image-analyzing software.
  • Table 3 shows results. From Table 3, the following are realized.
  • FIG. 1 shows optical microscopic photographs of materials after solution heat treatment obtained in Example 5 and Comparative Example 4. From FIG. 1 , it is realized that the Laves phase is observed besides the carbide in Comparative Example 4 but the Laves phase is not observed in Example 5.
  • the precipitation hardened Fe—Ni alloy according to the invention can be used as members for excavation, automobile engine parts, thermal power generation plant members, and the like.

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JP2013106957 2013-05-21
JP2013-106957 2013-05-21
JP2014-039222 2014-02-28
JP2014039222A JP6337514B2 (ja) 2013-05-21 2014-02-28 析出硬化型Fe−Ni合金及びその製造方法

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Cited By (1)

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US10119182B2 (en) 2016-02-18 2018-11-06 Daido Steel Co., Ltd. Ni-based superalloy for hot forging

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RU2650353C1 (ru) * 2017-09-18 2018-04-11 Юлия Алексеевна Щепочкина Сталь

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