EP1378579A1 - Ausscheidungsgehärtete Kobalt-Nickel-Legierung mit guter Wärmebeständigkeit sowie zugehörige Herstellungsmethode - Google Patents

Ausscheidungsgehärtete Kobalt-Nickel-Legierung mit guter Wärmebeständigkeit sowie zugehörige Herstellungsmethode Download PDF

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EP1378579A1
EP1378579A1 EP03015101A EP03015101A EP1378579A1 EP 1378579 A1 EP1378579 A1 EP 1378579A1 EP 03015101 A EP03015101 A EP 03015101A EP 03015101 A EP03015101 A EP 03015101A EP 1378579 A1 EP1378579 A1 EP 1378579A1
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alloy
heat treatment
twin structure
parent phase
subjecting
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French (fr)
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EP1378579B1 (de
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Akihiko Chiba
Shirou Takeda
Michihiko Ayada
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NHK Spring Co Ltd
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NHK Spring Co Ltd
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    • 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
    • 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%
    • 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
    • C22C19/07—Alloys based on nickel or cobalt based on cobalt
    • 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

Definitions

  • the present invention relates to a precipitation hardened Co-Ni based heat-resistant alloy and to a production method therefor, and more particularly, relates to a precipitation hardened Co-Ni based heat-resistant alloy in which Co 3 Mo or Co 7 Mo 6 is precipitated at boundaries between a fine twin structure and a parent phase.
  • the structure is suitable for springs, bolts, etc., that are used in parts, such as engine exhaust systems and peripheral devices in gas turbines, which are exposed to high temperatures.
  • heat-resistant parts which are used in parts, such as engine exhaust systems and peripheral devices in gas turbines, that are exposed to high temperatures, are manufactured by using Ni-based super heat-resistant alloys such as Inconel X-750 (Ni: 73.0 mass%, Cr: 15.0 mass%, Al: 0.8 mass%, Ti: 2.5 mass%, Fe: 6.8 mass%, Mn: 0.70 mass%, Si: 0.25 mass%, C: 0.04, Nb+Ta: 0.9 mass%) and Inconel 718 (Ni: 53.0 mass%, Cr: 18.6 mass%, Mo: 3.1 mass%, Al: 0.4 mass%, Ti: 0.9 mass%, Fe: 18.5 mass%, Mn: 0.20 mass%, Si: 0.18 mass%, C: 0.04 mass%, Nb+Ta: 5.0 mass%).
  • Ni-based super heat-resistant alloys such as Inconel X-750 (Ni: 73.0 mass%, Cr: 15.0 mass%, Al: 0.8 mass%, Ti: 2.5 mass%
  • Ni-based super-heat-resistant alloys are reinforced by precipitating ⁇ ' phase (Ni 3 (Al, Ti, Nb) and ⁇ " phase (Ni 3 Nb).
  • ⁇ ' phase Ni 3 (Al, Ti, Nb)
  • ⁇ " phase Ni 3 Nb
  • the ⁇ ' phase and ⁇ " phase become coarse due to overaging, thereby causing a decrease in strength.
  • stress relaxation is large, and thereby there is failure to maintain initial performance originally required for the parts.
  • Co-Ni based heat-resistant alloys comprising, all by weight, not more than 0.05 mass% of C; not more than 0.5 mass% of Si; not more than 1.0 mass% of Mn; 25 to 45 mass% of Ni; 13 to less than 18 mass% of Cr; 7 to 20 mass% of Mo + 1/2W of at least one of Mo and W; 0.1 to 3.0 mass% of Ti; 0.1 to 5.0 mass% of Nb; 0.1 to 5.0 mass% of Fe; and the balance substantially of Co and inevitable impurities, the Co-Ni based heat-resistant alloy, as necessary, further comprising: 0.007 to 0.10 mass% of REM, further comprising, all by weight, at least one selected from the group consisting of 0.001 to 0.010 mass% of B; 0.0007 to 0.010 mass% of Mg; 0.001 to 0.20 mass% of Zr.
  • the inventors also previously developed production methods for Co-Ni based heat-resistant alloys, comprising the steps of subjecting the alloy to a solid solution heat treatment at 1000 to 1200°C or a hot working at this temperature, then subjecting the alloy to a cold working or a warm working having a reduction ratio of not less than 40% and then subjecting the alloy to an aging heat treatment at 500 to 800°C for 0.1 to 50 hours.
  • KKAI Japanese Unexamined Patent application
  • Co-Ni based heat-resistant alloys Cr which precipitates as a ⁇ phase is at least needed, solute elements such as Mo, Fe, and Nb, which are segregated in stacking faults of extended dislocation to block dislocation movements, are increased to achieve high work hardening performance.
  • solute elements such as Mo, Fe, and Nb, which are segregated in stacking faults of extended dislocation to block dislocation movements, are increased to achieve high work hardening performance.
  • These alloys have higher strengths at room temperature and can inhibit decrease in strength even after long-periods of use under high temperatures in comparison with conventional Ni-based super-heat-resistant alloys.
  • objects of the present invention are to provide a heat resistant alloy which exhibits higher strength than the above-mentioned Ni-based super-heat-resistant alloy and which can inhibit decrease in strength even after a long-period of use under high temperatures, and to provide a production method therefor.
  • the inventors of the present invention have carried out various research and studies on the composition and aging heat treatment conditions of the Co-Ni based heat-resistant alloys which exhibit higher strengths than the above-mentioned Ni-based super-heat-resistant alloy, and can inhibit decrease in strength even after a long-period of use under high temperatures.
  • the inventors found that when a Co-Ni based heat-resistant alloy is subjected to an aging heat treatment under conditions of applying stress or high temperature, a fine twin structure having an average grain size of several microns is formed, and Co 3 Mo or Co 7 Mo 6 with sizes from several micron to several tens of nanometers is precipitated in boundaries between the fine twin structure and a parent phase (refer to Fig. 1 and Fig. 2 showing structure photographs of Practical Example 22 of the present invention).
  • the inventors also found that when the above-mentioned structure is formed, a heat-resistant alloy which has high strength and which can inhibit decrease in strength even after a long-period of use under high temperatures can be obtained.
  • the inventors also found that when Co-Ni based heat-resistant alloy is first subjected to a cold working or a warm working having a reduction ratio of not less than 40% after a solid solution heat treatment and is secondly subjected to an aging heat treatment, a dislocation with high density is formed in a matrix by the cold working or the warm working, whereby strength under high temperatures is improved by anchoring the dislocation by precipitates formed by an aging heat treatment after the solid solution heat treatment. Furthermore, a solute element such as Mo is segregated in stacking fault surfaces of dislocation, and the dislocation is anchored. Therefore, an improvement effect in the strength at room temperature and under high temperatures is obtained.
  • an aging heat treatment is performed in which heat-resistant alloy is heated in an adequate time to a temperature of 600 to 800°C in a condition of applying stress after the solid solution heat treatment.
  • a working and an aging heat treatment is performed in which a heat-resistant alloy is first subjected to a cold working or a warm working having a reduction ratio of not less than 40% after a solid solution heat treatment and is secondly heated in an adequate time at a temperature of 600 to 800°C in a condition of applying stress.
  • a working and an aging heat treatment is performed in which a heat-resistant alloy is first subjected to a cold working or a warm working having a reduction ratio of not less than 40% after a solid solution heat treatment and is secondly heated in an adequate time at a temperature of 800°C to 950°C.
  • the present invention provides a precipitation hardened Co-Ni based heat-resistant alloy comprising, all by weight, not more than 0.05% of C; not more than 0.5% of Si; not more than 1.0% of Mn; 25 to 45% of Ni; 13 to 22% of Cr; 10 to 18% of Mo or 10 to 18% of Mo + 1/2W; 0.1 to 5.0% of Nb; 0.1 to 5.0% of Fe; if any 0.1 to 3.0% of Ti; at least one kind of 0.007 to 0.10% of REM; 0.001 to 0.010% of B; 0.0007 to 0.010% of Mg and 0.001 to 0.20% of Zr; the balance of Co and inevitable impurities; a fine twin structure; a parent phase; and Co 3 Mo or Co 7 Mo 6 is precipitated at boundaries of the fine twin structure and the parent phase.
  • the invention provides a production method for precipitation hardened Co-Ni based heat-resistant alloy, the method comprising the steps of: preparing an alloy comprising, all by weight, not more than 0.05% of C; not more than 0.5% of Si; not more than 1.0% of Mn; 25 to 45% of Ni; 13 to 22% of Cr; 10 to 18% of Mo or 10 to 18% of Mo + 1/2W; 0.1 to 5.0% of Nb; 0.1 to 5.0% of Fe; if any 0.1 to 3.0% of Ti; at least one kind of 0.007 to 0.10% of REM; 0.001 to 0.010% of B; 0.0007 to 0.010% of Mg and 0.001 to 0.20% of Zr; the balance of Co and inevitable impurities; subjecting the alloy to a solid solution heat treatment; and subjecting the alloy to an aging heat treatment at 600 to 800°C for 0.5 to 16 hours in a condition of applying stress, thereby forming a fine twin structure in a parent phase, and precipitating Co 3
  • the invention provides a production method for precipitation hardened Co-Ni based heat-resistant alloy, the method comprising the steps of: preparing an alloy comprising, all by weight, not more than 0.05% of C; not more than 0.5% of Si; not more than 1.0% of Mn; 25 to 45% of Ni; 13 to 22% of Cr; 10 to 18% of Mo or 10 to 18% of Mo + 1/2W; 0.1 to 5.0% of Nb; 0.1 to 5.0% of Fe; if any 0.1 to 3.0% of Ti; at least one kind of 0.007 to 0.10% of REM; 0.001 to 0.010% of B; 0.0007 to 0.010% of Mg and 0.001 to 0.20% of Zr; the balance of Co and inevitable impurities; subjecting the alloy to a solid solution heat treatment; subjecting the alloy to a cold working or a warm working having a reduction ratio of not less than 40%; and subjecting the alloy to an aging heat treatment at 600 to 800°C for 0.5 to 16 hours
  • the invention provides a production method for precipitation hardened Co-Ni based heat-resistant alloy, the method comprising the steps of: preparing an alloy comprising, all by weight, not more than 0.05% of C; not more than 0.5% of Si; not more than 1.0% of Mn; 25 to 45% of Ni; 13 to 22% of Cr; 10 to 18% of Mo or 10 to 18% of Mo + 1/2W; 0.1 to 5.0% of Nb; 0.1 to 5.0% of Fe; if any 0.1 to 3.0% of Ti; at least one kind of 0.007 to 0.10% of REM; 0.001 to 0.010% of B; 0.0007 to 0.010% of Mg and 0.001 to 0.20% of Zr; the balance of Co and inevitable impurities; subjecting the alloy to a solid solution heat treatment; subjecting the alloy to a cold working or a warm working having a reduction ratio of not less than 40%; and subjecting the alloy to an aging heat treatment at 800°C to 950°C for 0.5 to
  • fine precipitates are formed at boundaries between the fine twin structure and a parent phase.
  • the precipitates are not grown to be coarse at high temperatures of about 700°C, an effect on anchoring dislocation is performed even at high temperatures of not less than 700°C due to interaction between the precipitates and the dislocation.
  • the precipitates are formed in grain boundaries of a fine twin structure having average grain size of several microns. Therefore, the precipitates suppress grain boundary sliding as a obstacle when the grain boundary moves at high temperatures of not less than 700°C, and prevents coursening of the grains. Accordingly, high strength, such as creep strength, is excellent.
  • the heat-resistant alloy is subjected to an aging heat treatment for 0.5 to 16 hours at a temperature of 600 to 800°C in a condition of applying stress after a solid solution heat treatment by heating at 1000 to 1200°C.
  • the heat-resistant alloy is first subjected to a cold working or a warm working having a reduction ratio of not less than 40% after the solid solution heat treatment and is secondly subjected to an aging heat treatment for 0.5 to 16 hours at a temperature of 600 to 800°C in a condition of applying stress.
  • the heat-resistant alloy is first subjected to a cold working or a warm working having a reduction ratio of not less than 40% after the solid solution heat treatment and secondly to an aging heat treatment by heating for 0.5 to 16 hours at temperature of 800°C to 950°C. Therefore, the fine twin structure can be formed and at least one kind of Co 3 Mo and Co 7 Mo 6 can be precipitated in boundaries between the fine twin structure and a parent phase.
  • Carbon C is bound to Nb and Ti to form carbides to prevent grains from becoming coarse at the time of a solid solution heat treatment, and also to strengthen the grain boundary; thus, this element is contained for these purposes.
  • the content must be not less than 0.005%.
  • a content exceeding 0.05%, more specifically, 0.03% would cause decrease in the toughness and corrosion resistance, and would also form a carbide with a dislocation anchoring element such as Mo, thereby resulting in interference with the dislocation anchoring, the content must not be more than 0.05%.
  • the preferable range is 0.005 to 0.03%.
  • Si is effectively used as a deoxidizer, this element is contained for this purpose. However, since a content exceeding 0.5%, more specifically, 0.3%, would cause decrease toughness, the content is not more than 0.5%. The preferable range is not more than 0.3%.
  • Mn Not more than 1.0%
  • Mn is effectively used as a deoxidizer, and reduces stacking fault energy to improve the work hardening performance, this element is contained for this purpose. However, since a content exceeding 1.0%, more specifically, 0.7%, would cause decrease in corrosion resistance, the content must not be more than 1.0%. The preferable range is not more than 0.7%. Ni: 25 to 45%
  • Ni is an element that is used for stabilizing austenite serving as a matrix and improves heat resistance and corrosion resistance of the alloy, this element is contained for these purposes.
  • the content must not be less than 25%, more preferably, 27%. However, since a content exceeding 45%, would cause decrease in work hardening performance, the content must be 25 to 45%. The preferable range is 27 to 45%.
  • Cr 13% to less than 22%
  • Cr is an element that is used for improving the heat resistance and corrosion resistance, this element is contained for these purposes.
  • the content must not be less than 13%, more preferably, 16%.
  • a content exceeding 22%, more specifically, 21% tends to cause precipitation of a ⁇ phase, the content must be in a range of 13 to 22%.
  • the preferable range is 16 to 21%.
  • the content must not be less than 10%, more preferably, 11%, and preferably the Mo content must not be less than 8.0% in the case of containing Mo and W.
  • the content must be in a range of 10 to 18%. The preferable range is 11 to 18%.
  • Nb is bound to C to form carbides to prevent grains from becoming coarse in a solid solution heat treatment and to strengthen the grain boundary, and also solid solution-treated in the matrix to strengthen the matrix, thereby improving the work hardening performance.
  • this element is contained for these purposes.
  • the content must not be less than 0.1%, more preferably, 0.8%. However, since the content exceeding 5.0%, more specifically, 3.0%, would cause precipitation of a ⁇ phase (Ni 3 Nb) resulting in decrease in workability and toughness, the content must be in a range of 0.1 to 5.0%. The preferable range is 0.8 to 3.0%.
  • Fe 0.1 to 5.0%
  • the content must not be less than 0.1%, and more preferably, 0.5%. However, since a content exceeding 5.0%, more specifically, 4.8%, causes decrease in oxidation resistance property, the content must be in a range of 0.1 to 5.0%. The preferable range is 0.5 to 4.8%.
  • the content must not be less than 0.1%, more preferably, 0.5%. However, since a content exceeding 3.0%, more specifically, 2.5%, would cause precipitation of an ⁇ phase (Ni 3 Ti) resulting in decrease in workability and toughness, the content must be in a range of 0.1 to 3.0%. The preferable range is 0.5 to 2.5%.
  • REM 0.007 to 0.10%
  • REM which is at least one rare-earth elements such as Y, Ce, and misch metal, improves the hot workability and oxidation resistance property
  • the content must not be less than 0.007%, more preferably, 0.01%.
  • a content exceeding 0.10%, more specifically, 0.04% causes decrease in hot workability and oxidation resistance property in an inverse manner, the content must be in a range of 0.007 to 0.10%. The preferable range is 0.01 to 0.04%.
  • Mg 0.0007 to 0.010%
  • Zr 0.001 to 0.20%.
  • B Since B, Mg, and Zr improve the hot workability and strengthen the grain boundary, these elements are contained for these purposes. In order to obtain these effects, B must be 0.001%, more preferably, 0.002%, Mg must be 0.0007%, more preferably, 0.001%, and Zr must be 0.001%, more preferably, 0.01%. However, since B exceeding 0.010%, more specifically, 0.006%, Mg exceeding 0.010%, more specifically, 0.004% and Zr exceeding 0.20%, more specifically 0.05%, would cause decrease in hot workability and oxidation resistance property, the ranges of the contents must be respectively in the above-mentioned ranges. More preferably, B is in a range of 0.002 to 0.006%, Mg is in a range of 0.001 to 0.004%, and Zr is in a range of 0.01 to 0.05%. Co: Balance
  • Co which has a close-packed hexagonal lattice structure, is allowed to contain Ni so as to have a face-centered cubic lattice structure, that is, austenite, thereby exerting a high work hardening performance.
  • the precipitation hardened Co-Ni based heat-resistant alloy of the present invention comprises the above-mentioned composition, and has a structure in which Co 3 Mo or Co 7 Mo 6 is precipitated in boundaries between a fine twin structure and a parent phase.
  • the production method of the precipitation hardened Co-Ni based heat-resistant alloy of the present invention In the production method of the precipitation hardened Co-Ni based heat-resistant alloy of the present invention, a fine twin structure having average grain size of several microns is formed in a precipitation hardened Co-Ni based heat-resistant alloy having the above-mentioned composition, Co 3 Mo or Co 7 Mo 6 of sizes from several microns to several tens of nanometers is precipitated in boundaries between the fine twin structure and a parent phase, and thereby a heat-resistant alloy which has high strength and which can inhibit decrease in strength even after a long-period of use under high temperatures can be obtained.
  • the production method of the precipitation hardened Co-Ni based heat-resistant alloy of the present invention is characterized in that the above-mentioned Co-Ni based heat-resistant alloy is first subjected to a solid solution heat treatment by heating to 1000 to 1200°C, etc., and secondly to an aging heat treatment by heating for 0.5 to 16 hours at temperature of 600 to 800°C in a condition of applying stress.
  • another production method of the precipitation hardened Co-Ni based heat-resistant alloy of the present invention is characterized in that the above-mentioned Co-Ni based heat-resistant alloy is first subjected to a solid solution heat treatment, secondly to a cold working or a warm working having a reduction ratio of not less than 40%, and thirdly to an aging heat treatment by heating for 0.5 to 16 hours to a temperature of 600 to 800°C in a condition of applying stress.
  • another production method of the precipitation hardened Co-Ni based heat-resistant alloy of the present invention is characterized in that the above-mentioned Co-Ni based heat-resistant alloy is first subjected to a solid solution heat treatment, secondly to a cold working or a warm working having a reduction ratio of not less than 40%, and thirdly to an aging heat treatment by heating for 0.5 to 16 hours to a temperature of 800°C to 950°C in an unloaded condition.
  • the solid solution heat treatment is performed in order to make the structure uniform and to lower the hardness to facilitate working. Therefore, the solid solution heat treatment is preferably performed by heating to 1000 to 1200°C.
  • a temperature lower than 1000°C fails to provide a sufficiently uniform structure and also fails to lower the hardness, thereby causing difficulty in working.
  • a temperature lower than 1000°C might cause precipitation of a compound such as Mo that exerts an anchoring effect on dislocations, and a subsequent reduction in the age hardening property.
  • a temperature exceeding 1200°C makes crystal grains coarse, resulting in decrease in toughness and strength.
  • the heat-resistant alloy is subjected to an aging heat treatment by heating for 0.5 to 16 hours to a temperature of 600 to 800°C in a condition of applying stress in order to form a fine twin structure having an average grain size of several microns and to precipitate Co 3 Mo or Co 7 Mo 6 of sizes from several microns to several tens of nanometers in boundaries between the fine twin structure and a parent phase.
  • the applied stress in the aging heat treatment is preferably about 100 to 400MPa.
  • An applied stress less than 100MPa fails to sufficiently precipitate fine Co 3 Mo or Co 7 Mo 6 in boundaries between a fine twin structure and a parent phase.
  • the applied stress exceeding 400MPa results in saturation and transforms the alloy which is subjected to the aging heat treatment.
  • the heat-resistant alloy is subjected to an aging heat treatment by heating for 0.5 to 16 hours at a temperature of 600 to 800°C because a temperature lower than 600°C or a time shorter than 0.5 hours fails to sufficiently precipitate a fine twin structure and fine Co 3 Mo or Co 7 Mo 6 in boundaries between the fine twin structure and a parent phase, and a temperature higher than 800°C or a time longer than 16 hours results in saturation and makes the precipitates rather coarse, thereby causing decrease in strength, and this also causes greater creep elongation by causing decrease in hardness and strength by causing the dislocation to reform when the aging heat treatment is additionally performed after performing a cold working or a warm working having a reduction ratio of not less than 40%.
  • the heat-resistant alloy is subjected to a cold working or a warm working having a reduction ratio of not less than 40% before an aging heat treatment in a condition of applying stress because forming dislocations at high density is necessary, and a density lower than 40% fails to form dislocations at high density.
  • solute atoms such as Mo and Fe are segregated in stacking faults formed between half-dislocations of extended dislocations; thus, the dislocation movements are blocked so that stress relaxation, that is, reoccurrence of dislocations, is suppressed.
  • the heat-resistant alloy is subjected to an aging heat treatment by heating for 0.5 to 16 hours at a higher temperature of 800°C to 950°C after the cold working or warm working having a reduction ratio of not less than 40% after the solid solution heat treatment because a fine twin structure having average grain size of several microns must be formed and Co 3 Mo or Co 7 Mo 6 of sizes from several microns to several tens of nanometers must be precipitated in boundaries between the fine twin structure and a parent phase.
  • an aging heat treatment is performed at a higher temperature of 800°C to 950°C instead of using the condition of applying stress in this production method of the precipitation hardened Co-Ni based heat-resistant alloy of the present invention.
  • the aging heat treatment is performed at a higher temperature of 800°C or more and for not less than 0.5 hours because a temperature below 800°C or a time shorter than 0.5 hours fails to sufficiently precipitate a fine twin structure and fine Co 3 Mo or Co 7 Mo 6 in boundaries between the fine twin structure and a parent phase.
  • the aging heat treatment is performed at a temperature not more than 950°C and for not more than 16 hours because a temperature higher than 950°C or a time longer than 16 hours results in saturation and makes the precipitates solve or become coarse, thereby causing decrease in strength.
  • the alloy is melted and prepared through a typical method by using a vacuum high-frequency induction furnace, etc., and is forged into an ingot through a typical forging method.
  • the ingot is subjected to a hot working and solid solution heat treatment at 1000 to 1200°C, and the ingot is then subjected to an aging heat treatment by heating for 0.5 to 16 hours at a temperature of 600 to 800°C in a condition of applying stress of 100 to 140MPa.
  • the alloy is subjected to a cold working or warm working having a reduction ratio of not less than 40% after the above-mentioned solid solution heat treatment, and then the alloy is subjected to an aging heat treatment by heating for 0.5 to 16 hours at a temperature of 600 to 800°C in a condition of applying stress of 100 to 140MPa.
  • the alloy is subjected to a cold working or warm working having a reduction ratio of not less than 40% after the above-mentioned solid solution heat treatment, and then the alloy is subjected to an aging heat treatment by heating for 0.5 to 16 hours at a temperature of 800°C to 950°C.
  • the precipitation hardened Co-Ni based heat-resistant alloys of the present invention may be applied to parts and devices such as exhaust-related parts such as engine exhaust manifolds, peripheral devices of gas turbines, furnace chamber materials, heat-resistant springs and heat-resistant bolts, for which Inconel X750 or Inconel X718 has been used. They may also be used for parts and devices used under higher temperatures. Specifically, they may be preferably applied to springs and bolts in which stress is usually applied in high temperatures.
  • Cylindrical bars having a diameter of 20 mm of No. 5 and No. 6 alloy of the present invention shown in Table 1 were subjected to a solid solution heat treatment at 1100°C. Then, as examples of the present invention, the cylindrical bars were subjected to an aging heating treatment of 620°C ⁇ 15 hours at a tensile stress of 250MPa, an aging heat treatment of 720°C ⁇ 8 hours at a tensile stress of 200MPa, or an aging heat treatment of 770°C ⁇ 4 hours at a tensile stress of 120MPa.
  • the cylindrical bars were subjected to an aging heating treatment of 850°C ⁇ 4 hours at a tensile stress of 80MPa, or an aging heat treatment of 550°C ⁇ 15 hours at a tensile stress of 250MPa. Creep test pieces were obtained from these elements in the same manner as in Example 1, and creep tests were carried out under the same conditions as in Example 1 to measure creep. Table 3 shows the results of the tests. No.
  • Cylindrical bars having a diameter of 20 mm of No. 5 and No. 6 alloy of the present invention shown in Table 1 were subjected to a solid solution heat treatment at 1100°C. Then, as examples of the present invention, the cylindrical bars were subjected to a cold working at reduction ratios of 45, 60 or 75%, and were then subjected to an aging heat treatment under conditions shown in Table 4 (applied stress, heating temperature and heating time). As a comparative example, the cylindrical bars were subjected to a cold working at a reduction ratio of 45%, and were then subjected to an aging heat treatment of 720°C ⁇ 8 hours in an unloaded condition.
  • the cylindrical bars were subjected to a cold working at a reduction ratio of 60%, and were then subjected to an aging heat treatment of 720°C ⁇ 8 hours in an unloaded condition. Creep test pieces were obtained from these elements in the same manner as in Example 1, and creep tests were carried out under the same conditions as in Example 1 to measure creep. Table 4 shows the results of the tests. No.
  • Example 5 of the present invention 45 400 720°C ⁇ 8hr 1.8 15 Example 5 of the present invention 45 350 770°C ⁇ 4hr 1.9 16 Example 5 of the present invention 60 400 700°C ⁇ 8hr 1.3 17 Example 5 of the present invention 60 350 720°C ⁇ 4hr 1.5 18 Example 5 of the present invention 75 400 650°C ⁇ 8hr 1.0 19 Example 5 of the present invention 75 350 650°C ⁇ 4hr 1.2 20 Example 6 of the present invention 45 400 650°C ⁇ 8hr 1.0 21 Example 6 of the present invention 60 400 650°C ⁇ 8hr 0.9 22 Example 6 of the present invention 75 400 650°C ⁇ 8hr 1.2 Comparative Examples 7 Example 5 of the present invention 45 ⁇ 700°C ⁇ 4hr 4.8 8 Example 5 of the present invention 60 .
  • Cylindrical bars having a diameter of 20 mm of No. 5 and No. 6 alloy of the present invention shown in Table 1 were subjected to a solid solution heat treatment at 1100°C. Then, as examples of the present invention, the cylindrical bars were subjected to a cold working at reduction ratios of 60 or 75%, and were then subjected to an aging heat treatment of 850°C ⁇ 4 hours or 920°C ⁇ 2 hours in an unloaded condition. As a comparative example, the cylindrical bars were subjected to a cold working at a reduction ratio of 35%, and were then subjected to an aging heat treatment of 920°C ⁇ 2 hours in an unloaded condition.
  • the cylindrical bars were subjected to a cold working at a reduction ratio of 75%, and were then subjected to an aging heat treatment of 990°C ⁇ 2 hours in an unloaded condition. Creep test pieces were obtained from these elements in the same manner as in Example 1, and creep tests were carried out under the same conditions as in Example 1 to measure creep. Table 5 shows the results of the tests. No.
  • Example 5 of the present invention 60 ⁇ 850°C ⁇ 4hr 1.7 24
  • Example 5 of the present invention 60 ⁇ 920°C ⁇ 2hr 1.9 25
  • Example 5 of the present invention 75 ⁇ 850°C ⁇ 4hr 1.4
  • Example 5 of the present invention 75 ⁇ 920°C ⁇ 2hr 1.5
  • Example 6 of the present invention 60 ⁇ 920°C ⁇ 4hr 1.7
  • Example 6 of the present invention 75 ⁇ 850°C ⁇ 2hr 1.3 Comparative Examples 9
  • Example 5 of the present invention 35 ⁇ 920°C ⁇ 2hr 4.6 10
  • Example 5 of the present invention 75 ⁇ 990°C ⁇ 2hr rupture Creep elongation was measured by creep tests carried out under conditions of 700°C, 330MPa
  • Example No. 8 to 13 of the present invention (Table 3), fine twin structure was formed when the structures of test pieces were observed by a SEM (scanning electron microscope). Moreover, Co 3 Mo or Co 7 Mo 6 was precipitated in boundaries between the fine twin structure and a parent phase. Furthermore, the creep elongation in the creep test was 2.0 to 2.9%.

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100590210C (zh) * 2007-09-19 2010-02-17 中国科学院金属研究所 一种提高γ＇沉淀强化型铁基合金中孪晶界数量的工艺方法
EP2610360A1 (de) * 2010-08-23 2013-07-03 Hitachi, Ltd. Co-basislegierung
CN106756404A (zh) * 2016-11-29 2017-05-31 四川六合锻造股份有限公司 一种用于燃烧室零部件的Co基合金及其制备方法
CN107127343A (zh) * 2017-05-05 2017-09-05 桂林电子科技大学 一种镍基合金结构件的电子束增材制造方法
CN107208892A (zh) * 2014-12-24 2017-09-26 安萨尔多能源公司 用于燃气轮机燃烧室的隔热瓦的支撑构件
CN111187999A (zh) * 2020-02-17 2020-05-22 河北工业大学 一种增强多晶Ni-Cr-Al基合金抗燃气腐蚀性能的热处理方法
CN113073234A (zh) * 2021-03-23 2021-07-06 成都先进金属材料产业技术研究院股份有限公司 镍铬系高电阻电热合金及其制备方法

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JP4421877B2 (ja) * 2003-03-26 2010-02-24 セイコーインスツル株式会社 Ｃｏ−Ｎｉ基高弾性合金及びＣｏ−Ｎｉ基高弾性合金を用いた動力ぜんまいとその製造方法
JP5736140B2 (ja) * 2010-09-16 2015-06-17 セイコーインスツル株式会社 Ｃｏ−Ｎｉ基合金およびその製造方法
US10385622B2 (en) 2014-09-18 2019-08-20 Halliburton Energy Services, Inc. Precipitation hardened matrix drill bit
JP6358246B2 (ja) 2015-01-08 2018-07-18 セイコーエプソン株式会社 粉末冶金用金属粉末、コンパウンド、造粒粉末、焼結体および装飾品
US20180340438A1 (en) * 2017-05-01 2018-11-29 General Electric Company Turbine Nozzle-To-Shroud Interface
WO2019031577A1 (ja) 2017-08-09 2019-02-14 日立金属株式会社 合金部材、該合金部材の製造方法、および該合金部材を用いた製造物
JP6509290B2 (ja) 2017-09-08 2019-05-08 三菱日立パワーシステムズ株式会社 コバルト基合金積層造形体、コバルト基合金製造物、およびそれらの製造方法
US10533571B2 (en) * 2018-01-20 2020-01-14 Carolyn Rende Fortin Pump systems with variable diameter impeller devices
KR102422684B1 (ko) 2019-03-07 2022-07-20 미츠비시 파워 가부시키가이샤 코발트기 합금 제조물, 해당 제조물의 제조 방법, 및 코발트기 합금 물품
WO2020179082A1 (ja) 2019-03-07 2020-09-10 三菱日立パワーシステムズ株式会社 コバルト基合金粉末、コバルト基合金焼結体およびコバルト基合金焼結体の製造方法
CN111918976B (zh) 2019-03-07 2022-05-17 三菱重工业株式会社 钴基合金制造物
WO2020179083A1 (ja) 2019-03-07 2020-09-10 三菱日立パワーシステムズ株式会社 コバルト基合金製造物およびその製造方法
EP3733885A4 (de) 2019-03-07 2020-12-30 Mitsubishi Power, Ltd. Wärmetauscher
CN115522148B (zh) * 2021-06-25 2023-05-23 中国科学院金属研究所 钴基复合材料的精细组织调控方法
CN115747688B (zh) * 2022-11-16 2023-10-20 西北工业大学 一种提高镍基高温合金蠕变持久寿命的时效热处理方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002024967A1 (fr) * 2000-09-19 2002-03-28 Nhk Spring Co., Ltd. Alliage thermoresistant a base de co-ni et son procede de fabrication

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4795504A (en) * 1984-08-08 1989-01-03 Latrobe Steel Company Nickel-cobalt base alloys
US5476555A (en) * 1992-08-31 1995-12-19 Sps Technologies, Inc. Nickel-cobalt based alloys
US5725692A (en) * 1995-10-02 1998-03-10 United Technologies Corporation Nickel base superalloy articles with improved resistance to crack propagation

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002024967A1 (fr) * 2000-09-19 2002-03-28 Nhk Spring Co., Ltd. Alliage thermoresistant a base de co-ni et son procede de fabrication

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CN100590210C (zh) * 2007-09-19 2010-02-17 中国科学院金属研究所 一种提高γ＇沉淀强化型铁基合金中孪晶界数量的工艺方法
EP2610360A1 (de) * 2010-08-23 2013-07-03 Hitachi, Ltd. Co-basislegierung
EP2610360A4 (de) * 2010-08-23 2014-03-19 Hitachi Ltd Co-basislegierung
CN107208892A (zh) * 2014-12-24 2017-09-26 安萨尔多能源公司 用于燃气轮机燃烧室的隔热瓦的支撑构件
CN107208892B (zh) * 2014-12-24 2019-11-26 安萨尔多能源公司 用于燃气轮机燃烧室的隔热瓦的支撑构件
CN106756404A (zh) * 2016-11-29 2017-05-31 四川六合锻造股份有限公司 一种用于燃烧室零部件的Co基合金及其制备方法
CN106756404B (zh) * 2016-11-29 2019-01-01 四川六合锻造股份有限公司 一种用于燃烧室零部件的Co基合金及其制备方法
CN107127343A (zh) * 2017-05-05 2017-09-05 桂林电子科技大学 一种镍基合金结构件的电子束增材制造方法
CN111187999A (zh) * 2020-02-17 2020-05-22 河北工业大学 一种增强多晶Ni-Cr-Al基合金抗燃气腐蚀性能的热处理方法
CN113073234A (zh) * 2021-03-23 2021-07-06 成都先进金属材料产业技术研究院股份有限公司 镍铬系高电阻电热合金及其制备方法

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ES2250793T3 (es) 2006-04-16
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DE60302108T8 (de) 2006-11-30
JP4264926B2 (ja) 2009-05-20
DE60302108D1 (de) 2005-12-08
JP2004035974A (ja) 2004-02-05
US20040033158A1 (en) 2004-02-19

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