EP2835434B1 - Ni-basierte Schmiedelegierung, Herstellungsverfahren dafür und Turbinenkomponente - Google Patents

Ni-basierte Schmiedelegierung, Herstellungsverfahren dafür und Turbinenkomponente Download PDF

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EP2835434B1
EP2835434B1 EP14179191.3A EP14179191A EP2835434B1 EP 2835434 B1 EP2835434 B1 EP 2835434B1 EP 14179191 A EP14179191 A EP 14179191A EP 2835434 B1 EP2835434 B1 EP 2835434B1
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sample
based alloy
forging
treatment
temperature
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French (fr)
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EP2835434A2 (de
EP2835434A3 (de
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Shigekazu Miyashita
Kiyoshi Imai
Kuniyoshi Nemoto
Shun Oinuma
Shogo Iwai
Takeo Suga
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Toshiba Corp
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Toshiba Corp
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    • 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
    • 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
    • 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
    • C22C19/055—Alloys based on nickel or cobalt based on nickel with chromium and Mo or W with the maximum Cr content being at least 20% but less than 30%
    • 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

  • Embodiments described herein relate generally to an Ni-based alloy for forging, a method for manufacturing the same, and a turbine component.
  • a thermal power generation plant has been made highly efficient in recent years in view of reduction of carbon dioxide emissions into the atmosphere.
  • it is required to make a steam turbine and a gas turbine which are installed in the thermal power generation plant highly efficient.
  • a CO 2 turbine which is installable in the thermal power generation plant highly efficient.
  • the CO 2 turbine is one which drives a turbine, using CO 2 generated by combustion of fuel such as natural gas and oxygen as a working fluid.
  • fuel such as natural gas and oxygen
  • a component constructing a hot section of each turbine is desirable to be constituted with an Ni-based alloy, which is used for a component of a power generation gas turbine or an air plane engine, and is time-proven in usage in a high-temperature place.
  • Ni-based alloy As a representative example of the Ni-based alloy, there can be cited Inconel 718 and Inconel 617 (manufactured by Special Metals Corporation).
  • a strengthening mechanism of the Ni-based alloy can be broadly classified into a precipitation strengthening type and a solid solution strengthening type.
  • the precipitation strengthening type Ni-based alloy As a result that a precipitates called as a ⁇ ' (gamma prime: Ni 3 (Al, Ti)) phase or a ⁇ " (gamma double prime: Ni 3 Nb) phase is precipitated by adding Al, Ti, Ta, and Nb to Ni, a mechanical strength under a high temperature is improved.
  • a precipitates called as a ⁇ ' (gamma prime: Ni 3 (Al, Ti) phase or a ⁇ " (gamma double prime: Ni 3 Nb) phase is precipitated by adding Al, Ti, Ta, and Nb to Ni
  • a mechanical strength under a high temperature is improved.
  • the representative precipitation strengthening type Ni-based alloy the above-described Inconel 718 can be cited.
  • the solid solution strengthening type Ni-based alloy a matrix itself is strengthened by adding Co, Mo, and the like to Ni.
  • the above-described Inconel 617 can be cited.
  • Ni-based alloy As described above, as a material for a component of a turbine used under a high-temperature environment, application of an Ni-based alloy is discussed. As for the Ni-based alloy, a sufficient mechanical strength under the high-temperature environment is required, and further, productivity in manufacturing of a large-sized forged component and the like is required.
  • EP 2 233 594 A1 discloses a nickel (Ni)-base alloy for a turbine rotor of a steam turbine containing, in mass%, carbon (C): 0.01% to 0.15%, chromium (Cr): 18% to 28%, cobalt (Co): 10% to 15%, molybdenum (Mo): 8% to 12%, aluminum (Al): 0.5% to less than 1.5%, titanium (Ti): 0.7% to 3.0%, and boron (B): 0.001% to 0.006%, the balance being nickel (Ni) and unavoidable impurities.
  • a nickel (Ni)-based alloy for forging contains, in mass%, 0.01 to 0.07% of carbon (C), 14 to 26% of chromium (Cr), 10 to 15% of cobalt (Co), 5 to 12% of molybdenum (Mo), 0.8 to 3% of aluminum (Al), 0.8 to 3% of titanium (Ti), and 0.001 to 0.006% of boron (B), optionally 0.05 to 0.7% of tantalum (Ta), optionally 0.1 to 0.7% of niobium (Nb), and the balance being nickel (Ni) and unavoidable impurities, the relationship 11 mass% ⁇ Mo + 0.176Cr + 0.037Co ⁇ 13.5 mass% being satisfied, wherein an average thickness of a carbide precipitated along a grain boundary is 250 nm or less.
  • Ni-based alloy a material strength at a room temperature and a high temperature is improved by solid solution strengthening by a solid solution strengthening element such as Mo and W and by precipitation strengthening by fine precipitation of a ⁇ ' (gamma prime: Ni 3 (Al, Ti)) phase obtained by addition of Al, Ti and the like.
  • a solid solution strengthening element such as Mo and W
  • precipitation strengthening by fine precipitation of a ⁇ ' (gamma prime: Ni 3 (Al, Ti)) phase obtained by addition of Al, Ti and the like.
  • excessive strengthening deteriorates hot workability of a material and reduces productivity.
  • Inconel 617 in which a precipitation strengthening amount by a ⁇ ' phase is minor has better forgeability compared with Udimet 520 (manufactured by Special Metals Corporation) or the like in which a precipitation strengthening amount by a ⁇ ' phase is large.
  • Inconel 738LC manufactured by Special Metals Corporation in which a precipitation amount of a ⁇ ' phase is large is not able to be formed by forging and is generally formed by casting.
  • a method for manufacturing an Ni-based alloy is determined mainly by a precipitation amount of a ⁇ ' phase.
  • an alloy composition is set in a manner not to generate excessive precipitation of a ⁇ ' phase during forging process.
  • a large-sized forging such as a turbine rotor of a steam turbine or a CO 2 turbine installed in a thermal power generation plant is larger compared with a forging such as a gas turbine or a jet engine for which an Ni-based alloy is conventionally used.
  • a forging of over 10 tons is necessary, for example.
  • Solid solution strengthening is obtained as a result that a different solute atom dissolves in a solvent atom constituting a matrix (solid solution) and that an internal strain occurring at that occasion prevents a motion of dislocation.
  • Solid solution strengthening is theoretically construed by a model in which dislocation moves while disengaging an obstacle of the solute atom. According to Friedel et al., a solid solution strengthening amount of a lean solid solution is proportional to the one-half power of a solute atom concentration and is proportional to the three-seconds power of a misfit strain due to an atom size difference (Advances in Physics, vol. 3, Issue 12, p 446-507 ).
  • a solid solution strengthening amount is proportional to the two-thirds power of a solute atom concentration and is proportional to the four-thirds power of a misfit strain due to an atom size difference (Phisica status solidi (b). Volume 41, Issue 2, p. 659-669 ).
  • a microstructure of a material can be cited.
  • a characteristic of a material is dependent on structures of not only within a grain but also in a grain boundary.
  • an M 23 C 6 type carbide precipitated on a grain boundary in a film shape reduces a toughness of a material. Therefore, in order to secure reliability of a material, it is necessary to control a microstructure properly by optimizing a heat treatment condition.
  • the present inventors find a parameter indicating a solid solution strengthening amount by quantitatively evaluating a solid solution amount of each additive element and a misfit strain which influence an Ni-based alloy. Further, the present inventors carry out various material testings about materials whose chemical compositions are changed, and find a chemical composition which has excellent forgeability while maintaining a sufficient material strength.
  • the present inventors find "an average thickness of a carbide on a grain boundary" as a factor dominating a toughness of an Ni-based alloy. Besides, the present inventors clarify a range of the carbide thickness on the grain boundary by which the toughness can be secured.
  • Fig. 1 is a diagram schematically showing a microstructure of an Ni-based alloy in the embodiment. Note that “%” indicating a composition component in the following explanation means “mass%” if not specifically mentioned.
  • the Ni-based alloy of the embodiment contains 0.01 to 0.07% of carbon (C), 14 to 26% of chromium (Cr), 10 to 15% of cobalt (Co), 5 to 12% of molybdenum (Mo), 0.8 to 3% of aluminum (Al), 0.8 to 3% of titanium (Ti), and 0.001 to 0.006% of boron (B), optionally 0.05 to 0.7% of tantalum (Ta), optionally 0.1 to 0.7% of niobium (Nb), and the balance being nickel (Ni) and unavoidable impurities, the relationship 11 mass% ⁇ Mo + 0.176Cr + 0.037Co ⁇ 13.5 mass% being satisfied.
  • a carbide 11 is precipitated along a grain boundary 10.
  • An average thickness t of the carbide 11 is preferable to be 250 nm or less.
  • the carbide 11 is continuously precipitated along the grain boundary 10.
  • a precipitate 13 is precipitated in a grain shape.
  • the carbide 11 is a carbide whose major constituents are Cr and Mo, and concretely, is an M 23 C 6 type carbide.
  • the reason why the average thickness t of the carbide 11 is preferable to be 250 nm or less is that, for example, such a thickness not reducing a toughness, a toughness for manufacturing a turbine component properly can be secured.
  • the precipitate 13 is constituted with a ⁇ ' (gamma prime: Ni 3 (Al, Ti)) phase.
  • a diameter of the ⁇ ' phase is preferable to be small, in view of precipitation strengthening.
  • An average diameter of the ⁇ ' phase is preferable to be 150 nm or less, for example.
  • the Ni-based alloy in the embodiment can contain 0.05 to 0.7% of Ta, in addition to the aforementioned chemical composition.
  • the Ni-based alloy in the embodiment can contain 0.1 to 0.7% of Nb.
  • the Ni-based alloy in the embodiment can contain 0.05 to 0.7% of Ta and 0.1 to 0.7% of Nb.
  • the unavoidable impurity there can be cited Si, Mn, N, Cu, Fe, S, and the like, for example.
  • a remaining content ratio of the unavoidable impurity as above is preferable to be approximated to 0% to the extent possible.
  • Ni-based alloy of the embodiment is suitable as a material constituting a turbine component constructed by forging, such as a power generation turbine, for example, which is used under a temperature of 650°C or higher, for example.
  • a turbine component there can be cited a turbine rotor, a rotor blade, a stationary blade, a screwing member, a pipe, and the like, for example.
  • Those forged components are each disposed in a high temperature and high pressure environment.
  • the screwing member there can be exemplified a bolt and a nut fixing a turbine casing or various component parts inside the turbine, for example.
  • the pipe there can be exemplified a pipe which is disposed in a power generation turbine plant or the like and through which a high temperature and high pressure working fluid passes, for example.
  • the Ni-based alloy for forging of the embodiment described above is superior to a conventional Ni-based alloy for forging in a strength characteristic and is superior in forgeability.
  • the turbine components fabricated by using the Ni-based alloy for forging of the embodiment such as a turbine rotor, a rotor blade, a stationary blade, a screwing member, and a pipe, have high reliability even under a high temperature environment.
  • C is effective as a constituent element of a carbide being a strengthening phase. Further, C has a function to suppress coarsening of a grain under a high temperature, by a pinning effect of the carbide to prevent movement of a grain boundary.
  • a content ratio of C is less than 0.01%, strengthening by the carbide is not sufficient.
  • the content ratio of C is less than 0.01%, there is a possibility that failure in securing of a sufficient precipitation amount of the carbide causes coarsening of the grain.
  • the content ratio of C is over 0.07%, forgeability is reduced.
  • the content ratio of C is set to be 0.01 to 0.07%. Further, the more preferable content ratio of C is 0.03 to 0.07%.
  • Cr is an element indispensable for heightening an oxidation resistance, a corrosive resistance, and a high temperature strength characteristic of an Ni-based alloy.
  • a content ratio of Cr is less than 14%, the oxidation resistance and the corrosive resistance are reduced.
  • the content ration of Cr is over 26%, precipitation of a ⁇ phase which causes reduction of a creep strength becomes prominent and forgeability is deteriorated.
  • the content ratio of Cr is set to be 14 to 26%. Further, the more preferable content ratio of Cr is 16 to 20%.
  • a content ratio of Co is less than 10%, a sufficient mechanical strength cannot be obtained.
  • the content ratio of Co is over 15%, forgeability is reduced.
  • the content ratio of Co is set to be 10 to 15%. Further, the more preferable content ratio of Co is 11 to 14%.
  • Mo solid-dissolves in an Ni matrix and improves a creep strength and a tensile strength. Further, by part of Mo substituting in an M 23 C 6 type carbide, stability of the carbide is heightened. When a content ratio of Mo is over 12%, hot workability is reduced. On the other hand, when the content ratio of Mo is less than 5%, improvement of a mechanical strength cannot be obtained. Thus, the content ratio of Mo is set to be 5 to 12%. Further, the more preferable content ratio of Mo is 7 to 10%.
  • A1 generates a ⁇ ' (Ni 3 Al) phase with Ni and improves a mechanical strength of an Ni-based alloy by precipitation.
  • a content ratio of A1 is less than 0.8%, an effect by precipitation of the ⁇ ' phase is not exhibited.
  • the content ratio of A1 is over 3%, precipitation of a ⁇ phase is promoted, and the mechanical strength is reduced.
  • the content ratio of A1 is set to be 0.8% to 3%.
  • the more preferable content ratio of A1 is 1 to 2%.
  • Ti similarly to A1, generates a ⁇ ' (Ni 3 (Al, Ti)) phase with Ni, and improves a mechanical strength of an Ni-based alloy.
  • a content ratio of Ti is less than 0.8%., an effect by precipitation of the ⁇ ' phase is not exhibited.
  • the content ratio of Ti is set to be 0.8 to 3%. Further, the more preferable content ratio of Ti is 1 to 2%.
  • B segregates in a grain boundary and improves a high temperature strength characteristic.
  • a content ratio of B is less than 0.001%, such an effect to improve the high temperature strength characteristic is not exhibited.
  • the content ratio of B is over 0.006%, intergranular embrittlement occurs.
  • the content ratio of B is set to be 0.001 to 0.006%. Further, the more preferable content ratio of B is 0.002 to 0.004%.
  • Ta solid-dissolves in a ⁇ ' (Ni 3 (Al,Ti)) phase and stabilizes the ⁇ ' phase.
  • a content ratio of Ta is less than 0.05%, the above-described effect is not exhibited.
  • the content ratio of Ta is over 0.7%, forgeability is reduced.
  • the content ratio of Ta is set to be 0.05% to 0.7%. Further, the more preferable content ratio of Ta is 0.08 to 0.12%.
  • Nb similarly to Ta, solid-dissolves in a ⁇ ' (Ni 3 (Al,Ti)) phase and stabilizes the ⁇ ' phase.
  • a content ratio of Nb is less than 0.1%, the above-described effect is not exhibited.
  • the content ratio of Nb is over 0.7%, segregation occurs at a time of dissolving or forging, and forgeability is reduced.
  • the content ratio of Nb is set to be 0.1 to 0.7%. Further, the more preferable content ratio ofNb is 0.2 to 0.5%.
  • a solid solution strengthening amount in a highly concentrated solid solution is proportional to the two-thirds power of a solute atom concentration and is proportional to the four-thirds power of a misfit strain due to an atom size difference.
  • a parameter representing solid solution strengthening is defined from the number of atoms per one mass% and each atomic radius. Note that since the content ratio of C (carbon) is small in the present embodiment, C is excluded from the parameter.
  • Atomic weights of Mo, Cr, and Co are 95.9, 52.0, and 58.9, respectively.
  • a ratio of the number of atoms in a case where the same amounts of the respective elements are added is, in a case of Mo being 1, Cr and Co being 1.84 and 1.62, respectively. Values of the two-thirds power of this ratio are 1, 1.50, and 1.38, respectively.
  • a misfit strain occurring at a time that each element is added is determined by an atomic size difference from an Ni atom. Atomic radius differences between the Ni atom and Mo, Cr, Co atoms is 0.15 A (angstrom), 0.03 A, and 0.01 A, respectively.
  • a ratio of the misfit strain amounts in a case where the respective elements are added is, in a case of Mo being 1, Cr and Co being 0.200 and 0.067, respectively. Values of the four-thirds power of this ratio are 1, 0.117, and 0.027, respectively.
  • the value of the above-described parameter is set to be 11 to 13.5%.
  • misfit strain by addition of an element is considered, in a strict sense, to be influenced not only by an atomic size but also by interaction or the like with Ni and other atoms.
  • a misfit strain value is determined from a difference between each solute atom and an Ni atom.
  • Si silicon
  • Mn manganese
  • N nitrogen
  • Cu copper
  • Fe iron
  • S sulfur
  • Si, Mn, N, Cu, Fe, and S are classified into unavoidable impurities in the Ni-based alloy for forging of the embodiment. Remaining content ratios of those unavoidable impurities are desirable to be approximated to 0% to the extent possible. Further, it is preferable that among those unavoidable impurities, at least Si and Mn are restricted to be 0.1% or less and that N is restricted to be 0.01% or less.
  • Si is added in order to supplement a corrosive resistance in a case of ordinary steel.
  • an Ni-based alloy has a large Cr content and a sufficient corrosive resistance can be secured.
  • a remaining content ratio of Si is set to be 0.1% or less and that the remaining content ratio thereof is approximated to 0% to the extent possible.
  • Mn makes S (sulfur) causing brittleness into MnS, to prevent brittleness, in a case of ordinary steel.
  • a content of S in an Ni-based alloy is quite low and it is not necessary to add Mn.
  • a remaining content ratio of Mn is set to be 0.1% or less and that the remaining content ratio thereof is approximated to 0% to the extent possible.
  • N forms TiN by reacting with Ti in a material and decreases Ti which contributes to generation of a ⁇ ' phase. Consequently, a mechanical strength is reduced.
  • a remaining content ratio of N is set to be 0.01% or less and that the remaining content ratio thereof is approximated to 0% to the extent possible.
  • Ni-based alloy for forging of the embodiment is manufactured as follows, for example.
  • composition components to constitute the Ni-based alloy are vacuum induction melted (VIM) and molten metal thereof is poured into a predetermined mold form, to form an ingot. Then, the ingot is soaking treated and hot forged, and subjected to a solution treatment, an ageing treatment, and the like, so that the Ni-based alloy for forging is fabricated.
  • VIP vacuum induction melted
  • a turbine rotor being a turbine component is fabricated as below, for example.
  • composition components to constitute the Ni-based alloy for forging of the embodiment are vacuum induction melted (VIM), electroslag remelted (ESR), and poured into a predetermined mold form. Subsequently, a soaking treatment, a forging treatment, a solution treatment, an aging treatment, and the like are carried out, so that the turbine rotor is fabricated.
  • VIP vacuum induction melted
  • ESR electroslag remelted
  • a soaking treatment, a forging treatment, a solution treatment, an aging treatment, and the like are carried out, so that the turbine rotor is fabricated.
  • composition components to constitute the Ni-based alloy for forging of the embodiment are vacuum induction melted (VIM), vacuum arc remelted (VAR), and poured into a predetermined mold form. Subsequently, a soaking treatment, a forging treatment, a solution treatment, an aging treatment, and the like are carried out, so that the turbine rotor is fabricated.
  • VIP vacuum induction melted
  • VAR vacuum arc remelted
  • a soaking treatment, a forging treatment, a solution treatment, an aging treatment, and the like are carried out, so that the turbine rotor is fabricated.
  • composition components to constituted the Ni-based alloy for forging of the embodiment are vacuum induction melted (VIM), electroslag remelted (ESR), vacuum arc remelted (VAR), and poured into a predetermined mold form. Subsequently, a soaking treatment, a forging treatment, a solution treatment, an aging treatment, and the like are carried out, so that the turbine rotor is fabricated.
  • VIP vacuum induction melted
  • ESR electroslag remelted
  • VAR vacuum arc remelted
  • At least a predetermined portion of the turbine rotor is manufactured by the above-described method for manufacturing the turbine rotor.
  • the predetermined portion there can be cited a portion exposed to a high temperature of 700°C or higher, for example, of the turbine rotor.
  • a portion exposed to a temperature of about 600°C, for example, of the turbine rotor is manufactured with a conventional heat resistant alloy.
  • a component made of the Ni-based alloy for forging of the embodiment manufactured by the above-described manufacturing method and a component made of the conventional heat resistant alloy are joined by welding, for example, to construct a turbine rotor.
  • a method for joining the component made of the Ni-based alloy for forging of the embodiment and the component made of the conventional heat resistant alloy is not limited to welding, but the components can be fastened by a bolt and a nut, for example.
  • a rotor blade, a stationary blade, and a screwing member being turbine components are fabricated as below, for example.
  • composition components to constitute the Ni-based alloy for forging of the embodiment are vacuum induction melted (VIM) and electroslag remelted (ESR).
  • VIP vacuum induction melted
  • ESR electroslag remelted
  • a molten alloy is poured into a predetermined mold form under a reduced pressure atmosphere to fabricate an ingot, and a soaking treatment is performed.
  • the ingot is disposed in a mold form corresponding to a shape of the above-described turbine component and a forging treatment, a solution treatment, an aging treatment, and the like are carried out, so that the rotor blade, the stationary blade, and the screwing member are fabricated.
  • the rotor blade, the stationary blade, and the screwing member are fabricated by die forging.
  • composition components to constitute the Ni-based alloy for forging of the embodiment are vacuum induction melted (VIM) and vacuum arc remelted (VAR), for example.
  • VIP vacuum induction melted
  • VAR vacuum arc remelted
  • a molten alloy is poured into a predetermined mold form under a reduced pressure atmosphere to fabricate an ingot.
  • a soaking treatment is applied to the ingot, and similarly to the above, a forging treatment, a solution treatment, an aging treatment, and the like are carried out, so that the rotor blade, the stationary blade, and the screwing member can be fabricated.
  • composition components to constitute the Ni-based alloy for forging of the embodiment are vacuum induction melted (VIM), electroslag remelted (ESR), and vacuum arc remelted (VAR), for example.
  • VIP vacuum induction melted
  • ESR electroslag remelted
  • VAR vacuum arc remelted
  • a molten alloy is poured into a predetermined mold form under a reduced pressure atmosphere to fabricate an ingot.
  • a soaking treatment is applied to the ingot, and similarly to the above, a forging treatment, a solution treatment, an aging treatment, and the like are carried out, so that the rotor blade, the stationary blade, and the screwing member can be fabricated.
  • a pipe being a forged component of the embodiment is fabricated as below, for example.
  • composition components to constitute the Ni-based alloy for forging of the embodiment are electric furnace melted (EF) and argon-oxide decarburization (AOD) is performed, so that an ingot is fabricated.
  • EF electric furnace melted
  • AOD argon-oxide decarburization
  • a soaking treatment is applied to the ingot.
  • the ingot is drilled by a vertical press, so that an element pipe of a cup shape is fabricated.
  • treatment and reheating by a mandrel and a die are repeated by a horizontal press, so that the element pipe is formed in a shape of a pipe.
  • This treatment method is an Ehrhardt push bench pipe manufacturing method.
  • a solution treatment, an aging treatment, and the like are carried out, so that the pipe is fabricated.
  • the methods for fabricating the turbine rotor, the rotor blade, the stationary blade, the screwing member, and the pipe are not limited to the methods described above.
  • the above-described forged components such as a turbine rotor, a rotor blade, a stationary blade, a screwing member, and a pipe can be applied to power generation turbines, such as a steam turbine, a gas turbine, and a CO 2 turbine, for example.
  • each heat treatment performed in manufacturing the Ni-based alloy for forging and the turbine component will be explained.
  • a temperature in each heat treatment is set in each range described below, in correspondence with the Ni-based alloy for forging, the turbine component, and the like to be treated.
  • a time for each treatment is set properly in correspondence with the Ni-based alloy for forging, the turbine component, and the like to be treated.
  • the soaking treatment it is necessary to heat the alloy at a high temperature for a sufficient time, in order to decrease segregation of a chemical component by thermal diffusion.
  • the soaking treatment is preferable to be performed in a temperature range of 1000 to 1200°C.
  • Forging is required to be performed in a range of temperature where sufficient ductility of a material can be obtained to a zero ductility temperature. Thus, forging is preferable to be performed in a temperature range of 950 to 1100°C.
  • the solution treatment a temperature range of 1050 to 1200°C is preferable to be maintained for 1 to 24 hours.
  • the solution treatment is performed for the purpose of solid dissolving an alloy element into a matrix sufficiently to obtain an effect of solid solution strengthening sufficiently, and of enabling precipitation control of a precipitate by a heat treatment thereafter. Further, the solution treatment is sometimes performed for the purpose of adjusting a grain size.
  • a temperature of the solution treatment When a temperature of the solution treatment is lower than 1050°C, an alloy element is not solid dissolved into the matrix completely, and strengthening by a solid solution strengthening element is not carried out sufficiently. Further, it also becomes difficult to control a precipitated form of a precipitates by the heat treatment after the solution treatment. On the other hand, when the temperature of the solution treatment is over 1200°C, coarsening of the grain size is brought about, and a mechanical strength is reduced. Thus, the temperature of the solution treatment is set to be 1050 to 1200°C. Further, it is further preferable that the temperature of the solution treatment is set to be 1050 to 1150°C. Note that the Ni-based alloy and the turbine component having been subjected to the solution treatment are cooled to a room temperature by water cooling, forced air cooling, or the like, for example.
  • a temperature range of 700 to 800°C is preferable to be maintained for 5 to 50 hours.
  • the aging treatment can be performed in multiple stages. Note that after the aging treatment the Ni-based alloy and the turbine component are cooled to the room temperature by water cooling or furnace cooling, for example.
  • a major object of the aging treatment is control of a precipitation form of a ⁇ ' phase precipitated in a grain. Further, the aging treatment influences a property of a grain boundary. Therefore, for the aging treatment, the temperature and the time condition are required to be determined in consideration of structures in the grain and the grain boundary.
  • Fig. 2 and Fig. 3 are views showing electron micrographs of Ni-based alloys in order to explain precipitation forms of carbides precipitated into grain boundaries by conditions of the aging treatments.
  • a composition of the Ni-based alloy shown here is 0.04% of C, 18% of Cr, 12% of Co, 9% of Mo, 1.3% of Al, 1.4% of Ti, 0.003% of B, 0.1% of Ta, 0.3% of Nb, and the balance being Ni.
  • Fig. 2 shows the microstructure having been subjected to the aging treatment of 850°C for 10 hours
  • Fig. 3 shows the microstructure having been subjected to the aging treatment of 750°C for 10 hours. Further, the soaking treatment and the solution treatment are performed in the above-described ranges. Note that Fig. 2 and Fig. 3 also show precipitates 13 ( ⁇ ' phase).
  • a film-shaped carbide 11 is precipitated in a manner to cover the grain boundary of the N-based alloy.
  • the film-shaped carbide 11 is a brittle carbide (M 23 C 6 type carbide) whose major constituents are Cr and Mo.
  • the carbide 11 promotes destruction of the grain boundary and substantially reduces a toughness of the material. Therefore, it has been considered that it is necessary to perform the aging treatment preventing precipitation of such a film-shaped carbide 11 covering the grain boundary.
  • a thickness of the film-shaped carbide covering the grain boundary becomes small, depending on the condition of the aging treatment. Note that the carbide is continuously precipitated along the grain boundary. As a result of a material testing, the inventors clarify that reduction of ductility/toughness does not occur in a case where a thickness of a carbide is sufficiently small.
  • the above-described temperature and time are specified to a range satisfying both fine precipitation of a ⁇ ' phase and suppression of coarsening of the carbide covering the grain boundary.
  • the temperature of the aging treatment is set to be 700 to 800°C.
  • heat treatments of multiple stages for example, two stages, can be performed in the aging treatment.
  • the temperature is set within the above-described temperature range of the aging treatment.
  • the whole heat treatment time in multiple stages is also set within the above-described time range of the aging treatment.
  • Cooling after the aging treatment is performed by furnace cooling or air cooling, for example.
  • cooling between each aging treatment is performed by furnace cooling, for example, as described above. Then, cooling is not performed to reach a room temperature but the aging treatment is performed continuously.
  • an intermediate heat treatment can be applied, before the aging treatment is performed, to the Ni-based alloy and the turbine component which are cooled to the room temperature after the solution treatment.
  • An object of the intermediate heat treatment is to form a block-shaped carbide intermittently along a grain boundary, first, before the aging treatment, in order to suppress precipitation or coarsening of a film-shaped carbide covering the grain boundary.
  • This carbide is also a carbide whose major constituents are Cr and Mo.
  • the intermediate heat treatment is preferable to be performed in a temperature range of 1000 to 1050°C. In cases where the intermediate heat treatment temperature is lower than 1000°C and where the intermediate heat treatment temperature is over 1050°C, the block-shaped carbide is not precipitated. A time of the intermediate treatment is set properly in correspondence with the Ni-based alloy and the turbine component to be treated.
  • the Ni-based alloy for forging of the embodiment is excellent in a strength characteristic and forgeability.
  • Table 1 shows chemical compositions of a sample 1 to a sample 21 used for evaluation of a strength characteristic, forgeability, and the like. Note that the samples 1, 4, 5, 8 and 13 shown in Table 1 are Ni-based alloys within a chemical composition range of the Ni-based alloy for forging of the embodiment, and the samples 2, 3, 6, 7, 9 to 12 and 14 to 21 are Ni-based alloys whose compositions are not within the chemical composition range of the Ni-based alloy for forging of the embodiment, and are comparative examples.
  • a strength characteristic was evaluated by a tensile test, a toughness was evaluated by a Charpy impact test, and forgeability was evaluated by visual observation. Further, a thickness of a film-shaped carbide covering a grain boundary was measured by microstructure observation.
  • test piece used in each test was fabricated as follows.
  • Each of the Ni-based alloys of the sample 1 to the sample 21 having the chemical compositions shown in Table 1 was melted in a vacuum induction melting furnace, to fabricate an ingot.
  • a soaking treatment was applied to the ingot at 1050°C for 5 hours. Thereafter, forging was performed in a temperature range of 950 to 1100°C (reheating temperature was 1100°C) by a 500 kgf hammer forging machine. After forging, a solution treatment was performed at a temperature of 1100°C for 4 hours, and thereafter, cooling to a room temperature was carried out by air cooling. After cooling, an intermediate heat treatment was performed at a temperature of 1025°C for 10 hours, and thereafter, cooling to the room temperature was carried out by furnace cooling. After cooling, a two-stage aging treatment at a temperature of 800°C for 10 hours and subsequently at a temperature of 750°C for 20 hours was performed continuously. Thereafter, cooling to the room temperature was performed by air cooling, so that a forged product was made.
  • the tensile test was performed in accordance with JIS Z 2241, and measurement of 0.2% proof stress and a tensile strength at the room temperature was performed.
  • the Charpy impact test was performed in accordance with JIS Z 2242, and measurement of a Charpy impact value was performed.
  • the sample after the soaking treatment described above was forged by a 500 kgf hammer forging machine, to fabricate a test piece of a solid columnar shape with a diameter of 125 mm and a length of 210 mm. Further, the forging treatment was performed until a forging ratio (a forging ratio based on JIS G 0701 (representation of a forging ratio of a steel product forging operation) became 3. Note that the forging treatment was performed in a range of 950 to 1100°C. When a temperature of the test piece being an object to be forged was reduced, that was, when the object to be forged was being cured, reheating to the reheating temperature of 1100°C was performed and the forging treatment was repeated. The evaluation of forgeability was performed by visual observation of existence/absence of a forging crack after the test piece was cooled.
  • the forging ratio is obtained by dividing a cross-sectional area of the object to be forged before application of the forging treatment, the cross-sectional area being vertical in a direction where the object to be forged is to be expanded, by a cross-sectional area of the object to be forged after the forging treatment, the cross-sectional area being vertical in a direction where the object to be forged has been expanded.
  • the forged product cooled to the room temperature after the aging treatment was used.
  • the thickness of the carbide was obtained by image-analyzing an electron micrograph photographed at 20000 magnification by using a field-emission scanning electron microscope.
  • 5 representative grain boundaries were selected, and thicknesses of 20 points of the carbide were measured per each grain boundary. Then, the above thicknesses were arithmetically averaged, to obtain an average thickness of the carbide.
  • Table 2 Test results and observation results are shown in Table 2.
  • a case where a forging crack does not exist is denoted as "No”, and further, evaluation of forgeability is denoted as " ⁇ " in order to indicate that forgeability is excellent.
  • a case where a forging crack exists is denoted as "Yes”, and evaluation of forgeability is denoted as "x" to indicate that forgeability is inferior.
  • the sample 1 to the sample 13 are higher in both 0.2% proof stresses and tensile strengthes compared with the sample 14. It is considered that in the sample 1 to the sample 13, the 0.2% proof stresses and the tensile strengths are high in values because sufficient solid solution strengthening and precipitation strengthening are enhanced. Further, the sample 1 to the sample 13 are excellent in forgeability, and thicknesses of the carbides are 250 nm or less. Further, results of Charpy impact values of the sample 1 to the sample 13 each indicate a value of 50 J/cm 2 or more. Therefore, it is confirmed that the sample 1 to the sample 13 have practically sufficient toughnesses.
  • the sample 1, and a sample 22 to a sample 31 shown in Table 3 are heat-treated under the heat treatment condition of the present embodiment, and the other samples are comparative examples heat-treated under a condition departing from a range of the heat treatment condition of the present embodiment. Test results and observation results are shown in Table 4.
  • the sample 1 and the sample 22 to the sample 31 are higher in both 0.2% proof stresses and tensile strengths compared with samples 32 to samples 39.
  • Average thicknesses of film-shaped carbides covering grain boundaries in the sample 1 and the sample 22 to the sample 31 are each 250 nm or less.

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

Claims (7)

  1. Nickelbasierte (Ni) Schmiedelegierung, beinhaltend, in Gewichtsprozent:
    0,01 bis 0,07 % Kohlenstoff (C),
    14 bis 26 % Chrom (Cr),
    10 bis 15 % Kobalt (Co),
    5 bis 12 % Molybdän (Mo),
    0,8 bis 3 % Aluminium (Al),
    0,8 bis 3 % Titan (Ti),
    0,001 bis 0,006 % Bor (B),
    optionsweise, 0,05 bis 0,7 % Tantal (Ta),
    optionsweise, 0,1 bis 0,7 % Niob (Nb), und
    wobei der Rest aus Nickel (Ni) und aus unvermeidbaren Verunreinigungen besteht,
    wobei das Verhältnis 11 Gewichtsprozent ≤ Mo + 0,176 Cr + 0,037 Co ≤ 13,5 Gewichtsprozent erfüllt wird,
    wobei eine mittlere Dicke eines entlang einer Korngrenze ausgefällten Karbids 250 nm oder darunter beträgt.
  2. Nickelbasierte (Ni) Schmiedelegierung nach Anspruch 1, beinhaltend 0,05 bis 0,7 Gewichtsprozent Tantal (Ta).
  3. Nickelbasierte (Ni) Schmiedelegierung nach Anspruch 1, beinhaltend 0,1 bis 0,7 Gewichtsprozent Niob (Nb).
  4. Nickelbasierte (Ni) Schmiedelegierung nach Anspruch 1, beinhaltend 0,05 bis 0,7 Gewichtsprozent Tantal (Ta) und 0,1 bis 0,7 Gewichtsprozent Niob (Nb).
  5. Nickelbasierte (Ni) Schmiedelegierung nach einem der Ansprüche 1 bis 4, wobei das Karbid durch Vornahme einer Lösungsbehandlung bei einer Temperatur zwischen 1050 und 1200 °C und einer Alterungsbehandlung bei einer Temperatur zwischen 700 und 800 °C ausgefällt wird.
  6. Verfahren zur Herstellung einer nickelbasierten (Ni) Schmiedelegierung, Folgende Schritte beinhaltend:
    Bilden einer Struktur einer vorbestimmten Form durch Schmelzen eines nickelbasierten (NI) Legierungsmaterials, beinhaltend, in Gewichtsprozent:
    0,01 bis 0,07 % Kohlenstoff (C),
    14 bis 26 % Chrom (Cr),
    10 bis 15 % Kobalt (Co),
    5 bis 12 % Molybdän (Mo),
    0,8 bis 3 % Aluminium (Al),
    0,8 bis 3 % Titan (Ti),
    0,001 bis 0,006 % Bor (B),
    optionsweise, 0,05 bis 0,7 % Tantal (Ta),
    optionsweise, 0,1 bis 0,7 % Niob (Nb), und
    wobei der Rest aus Nickel (Ni) und aus unvermeidbaren Verunreinigungen besteht,
    wobei das Verhältnis 11 Gewichtsprozent ≤ Mo + 0,176 Cr + 0,037 Co ≤ 13,5 Gewichtsprozent erfüllt wird;
    Lösungsbehandeln der Struktur bei einer Temperatur zwischen 1050 und 1200°C; und
    Alterungsbehandeln der lösungsbehandelten Struktur bei einer Temperatur zwischen 700 und 800 °C.
  7. Turbinenkomponente, Folgendes beinhaltend:
    mindestens einen vorbestimmten Abschnitt, hergestellt unter Verwendung der nickelbasierten (Ni) Schmiedelegierung nach einem der Ansprüche 1 bis 5.
EP14179191.3A 2013-08-07 2014-07-30 Ni-basierte Schmiedelegierung, Herstellungsverfahren dafür und Turbinenkomponente Active EP2835434B1 (de)

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TWI564398B (zh) * 2015-11-18 2017-01-01 中國鋼鐵股份有限公司 鎳基合金及其製造方法
CN105543748B (zh) * 2015-12-30 2018-10-02 无锡透平叶片有限公司 一种Nimonic101镍基合金的热处理方法
JP6419102B2 (ja) * 2016-04-13 2018-11-07 株式会社日本製鋼所 Ｎｉ基超合金およびＮｉ基超合金の製造方法
JP6842316B2 (ja) * 2017-02-17 2021-03-17 日本製鋼所Ｍ＆Ｅ株式会社 Ｎｉ基合金、ガスタービン材およびクリープ特性に優れたＮｉ基合金の製造方法
JP7431730B2 (ja) * 2017-11-10 2024-02-15 ヘインズ インターナショナル，インコーポレーテッド Ｎｉ－Ｃｒ－Ｃｏ－Ｍｏ－Ｔｉ－Ａｌ合金の延性を向上させるための熱処理
CN108330334A (zh) * 2018-03-15 2018-07-27 江苏理工学院 一种火电机组用高温合金及其制造方法
CN109576621B (zh) * 2019-01-18 2020-09-22 中国航发北京航空材料研究院 一种镍基变形高温合金制件的精确热处理方法
DE102020106433A1 (de) * 2019-03-18 2020-09-24 Vdm Metals International Gmbh Nickel-Legierung mit guter Korrosionsbeständigkeit und hoher Zugfestigkeit sowie Verfahren zur Herstellung von Halbzeugen
EP4023779A4 (de) 2019-08-28 2023-09-20 Gaona Aero Material Co., Ltd. Schmelzverfahren für niobreichen grossen gussblock aus hochtemperaturlegierung sowie niobreicher grosser gussblock aus hochtemperaturlegierung
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JP6223743B2 (ja) 2017-11-01
KR20160046770A (ko) 2016-04-29
CN104342585A (zh) 2015-02-11

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