EP1378579B1 - Ausscheidungsgehärtete Kobalt-Nickel-Legierung mit guter Wärmebeständigkeit sowie zugehörige Herstellungsmethode - Google Patents

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

Info

Publication number
EP1378579B1
EP1378579B1 EP03015101A EP03015101A EP1378579B1 EP 1378579 B1 EP1378579 B1 EP 1378579B1 EP 03015101 A EP03015101 A EP 03015101A EP 03015101 A EP03015101 A EP 03015101A EP 1378579 B1 EP1378579 B1 EP 1378579B1
Authority
EP
European Patent Office
Prior art keywords
alloy
heat treatment
parent phase
twin structure
resistant alloy
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP03015101A
Other languages
English (en)
French (fr)
Other versions
EP1378579A1 (de
Inventor
Akihiko Chiba
Shirou Takeda
Michihiko Ayada
Shigemi Shato
Shigeki Ueta
Toshiharu Noda
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
NHK Spring Co Ltd
Original Assignee
NHK Spring Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by NHK Spring Co Ltd filed Critical NHK Spring Co Ltd
Publication of EP1378579A1 publication Critical patent/EP1378579A1/de
Application granted granted Critical
Publication of EP1378579B1 publication Critical patent/EP1378579B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • 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.
  • WO-A-0224967 discloses 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 production methods for the Co-Ni based heat-resistant alloys comprise 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.
  • 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, 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 between 100 and 400 MPa.
  • 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 of between 100 and 400 MPa, thereby forming a fine twin structure in a parent
  • 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
  • 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 between 100 and 400 MPa.
  • 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 is effectively used as a deoxidizer, and reduces stacking fault energy to improve the work hardening performance
  • this element is contained for this purpose.
  • 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 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%.
  • the content must not be less than 13%, more preferably, 16%. However, since 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%.
  • 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 and ⁇ 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 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%.
  • 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 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.
  • 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 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 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 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
  • 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%.

Landscapes

  • 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)
  • Heat Treatment Of Steel (AREA)
  • Turbine Rotor Nozzle Sealing (AREA)

Claims (6)

  1. Ausscheidungsgehärtete warmfeste Legierung auf Co-Ni-Basis, welche gewichtsbezogen
       nicht mehr als 0,05 % C, nicht mehr als 0,5 % Si, nicht mehr als 1,0 % Mn, 25 bis 45 % Ni, 13 bis 22 % Cr, 10 bis 18 % Mo oder 10 bis 18 % Mo + 1/2 W, 0,1 bis 5,0 % Nb, 0,1 bis 5,0 % Fe;
       0,007 bis 0,10 % Seltenerdmetalle mindestens einer Art, 0,001 bis 0,010 % B, 0,0007 bis 0,010 % Mg, 0,001 bis 0,20 % Zr; und
       als Rest Co und unvermeidbare Verunreinigungen enthält, und welche
       eine feine Zwillingsstruktur;
       eine Stammphase; und
       an den Grenzen der feinen Zwillingsstruktur und der Stammphase ausgeschiedenes Co3Mo oder Co7Mo6
    aufweist.
  2. Ausscheidungsgehärtete warmfeste Legierung auf Co-Ni-Basis, welche gewichtsbezogen
       nicht mehr als 0,05 % C, nicht mehr als 0,5 % Si, nicht mehr als 1,0 % Mn, 25 bis 45 % Ni, 13 bis 22 % Cr, 10 bis 18 % Mo oder 10 bis 18 % Mo + 1/2 W, 0,1 bis 5,0 % Nb, 0,1 bis 5,0 % Fe, 0,1 bis 3,0 % Ti;
       0,007 bis 0,10 % Seltenerdmetalle mindestens einer Art, 0,001 bis 0,010 % B, 0,0007 bis 0,010 % Mg, 0,001 bis 0,20 % Zr; und
       als Rest Co und unvermeidbare Verunreinigungen enthält, und welche
       eine feine Zwillingsstruktur;
       eine Stammphase; und
       an den Grenzen der feinen Zwillingsstruktur und der Stammphase ausgeschiedenes Co3Mo oder Co7Mo6
    aufweist.
  3. Verfahren zur Herstellung einer ausscheidungsgehärteten warmfesten Legierung auf Co-Ni-Basis, welches Schritte umfasst, bei denen
    eine Legierung hergestellt wird, welche gewichtsbezogen
    nicht mehr als 0,05 % C, nicht mehr als 0,5 % Si, nicht mehr als 1,0 % Mn, 25 bis 45 % Ni, 13 bis 22 % Cr, 10 bis 18 % Mo oder 10 bis 18 % Mo + 1/2 W, 0,1 bis 5,0 % Nb, 0,1 bis 5,0 % Fe;
    0,007 bis 0,10 % Seltenerdmetalle mindestens einer Art, 0,001 bis 0,010 % B;
    0,0007 bis 0,010 % Mg, 0,001 bis 0,20 % Zr; und
    als Rest Co und unvermeidbare Verunreinigungen enthält, und bei denen
    die Legierung einer Festlösungs-Wärmebehandlung unterzogen wird; und
    die Legierung 0,5 bis 16 Stunden einer Alterungs-Wärmebehandlung bei 600 bis 800 °C unter einer ausgeübten Spannung von zwischen 100 und 400 MPa unterzogen wird, wodurch eine feine Zwillingsstruktur in einer Stammphase gebildet wird, und Co3Mo oder Co7Mo6 an einer Grenze der feinen Zwillingsstruktur und der Stammphase ausgeschieden wird.
  4. Verfahren zur Herstellung einer ausscheidungsgehärteten warmfesten Legierung auf Co-Ni-Basis, welches Schritte umfasst, bei denen
    eine Legierung hergestellt wird, welche gewichtsmäßig
    nicht mehr als 0,05 % C, nicht mehr als 0,5 % Si, nicht mehr als 1,0 % Mn, 25 bis 45 % Ni, 13 bis 22 % Cr, 10 bis 18 % Mo oder 10 bis 18 % Mo + 1/2 W, 0,1 bis 5,0 % Nb, 0,1 bis 5,0 % Fe, 0,1 bis 3,0 % Ti;
    0,007 bis 0,10 % Seltenerdmetalle mindestens einer Art, 0,001 bis 0,010 % B;
    0,0007 bis 0,010 % Mg, 0,001 bis 0,20 % Zr; und als Rest Co und unvermeidbare Verunreinigungen enthält, und bei denen
    die Legierung einer Festlösungs-Wärmebehandlung unterzogen wird; und
    die Legierung 0,5 bis 16 Stunden einer Alterungs-Wärmebehandlung bei 600 bis 800 °C unter einer ausgeübten Spannung von zwischen 100 und 400 MPa unterzogen wird, wodurch eine feine Zwillingsstruktur in einer Stammphase gebildet wird, und Co3Mo oder Co7Mo6 an einer Grenze der feinen Zwillingsstruktur und der Stammphase ausgeschieden wird.
  5. Verfahren zur Herstellung einer ausscheidungsgehärteten warmfesten Legierung auf Co-Ni-Basis, welches Schritte umfasst, bei denen
    eine Legierung hergestellt wird, welche gewichtsmäßig
    nicht mehr als 0,05 % C, nicht mehr als 0,5 % Si, nicht mehr als 1,0 % Mn, 25 bis 45 % Ni, 13 bis 22 % Cr, 10 bis 18 % Mo oder 10 bis 18 % Mo + 1/2 W, 0,1 bis 5,0 % Nb, 0,1 bis 5,0 % Fe;
    0,007 bis 0,10 % Seltenerdmetalle mindestens einer Art, 0,001 bis 0,010 % B;
    0,0007 bis 0,010 % Mg, 0,001 bis 0,20 % Zr; und
    als Rest Co und unvermeidbare Verunreinigungen enthält, und bei denen
    die Legierung einer Festlösungs-Wärmebehandlung unterzogen wird;
    die Legierung einer Kaltbearbeitung oder einer Warmbearbeitung mit einem Reduzierverhältnis von nicht weniger als 40 % unterzogen wird; und
    die Legierung 0,5 bis 16 Stunden einer Alterungs-Wärmebehandlung bei 600 bis 800 °C unter einer ausgeübten Spannung von zwischen 100 und 400 MPa unterzogen wird, wodurch eine feine Zwillingsstruktur in einer Stammphase gebildet wird, und Co3Mo oder Co7Mo6 an einer Grenze der feinen Zwillingsstruktur und der Stammphase ausgeschieden wird.
  6. Verfahren zur Herstellung einer ausscheidungsgehärteten warmfesten Legierung auf Co-Ni-Basis, welches Schritte umfasst, bei denen
    eine Legierung hergestellt wird, welche gewichtsmäßig
    nicht mehr als 0,05 % C, nicht mehr als 0,5 % Si, nicht mehr als 1,0 % Mn, 25 bis 45 % Ni, 13 bis 22 % Cr, 10 bis 18 % Mo oder 10 bis 18 % Mo + 1/2 W, 0,1 bis 5,0 % Nb, 0,1 bis 5,0 % Fe, 0,1 bis 3,0 % Ti;
    0,007 bis 0,10 % Seltenerdmetalle mindestens einer Art, 0,001 bis 0,010 % B;
    0,0007 bis 0,010 % Mg, 0,001 bis 0,20 % Zr; und
    als Rest Co und unvermeidbare Verunreinigungen; enthält, und bei denen
    die Legierung einer Festlösungs-wärmebehandlung unterzogen wird;
    die Legierung einer Kaltbearbeitung oder einer Warmbearbeitung mit einem Reduzierverhältnis von nicht weniger als 40 % unterzogen wird; und
    die Legierung 0,5 bis 16 Stunden einer Alterungs-Wärmebehandlung bei 600 bis 800 °C unter einer ausgeübten Spannung von zwischen 100 und 400 MPa unterzogen wird, wodurch eine feine Zwillingsstruktur in einer Stammphase gebildet wird, und Co3Mo oder Co7Mo6 an einer Grenze der feinen Zwillingsstruktur und der Stammphase ausgeschieden wird.
EP03015101A 2002-07-05 2003-07-03 Ausscheidungsgehärtete Kobalt-Nickel-Legierung mit guter Wärmebeständigkeit sowie zugehörige Herstellungsmethode Expired - Lifetime EP1378579B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2002197142A JP4264926B2 (ja) 2002-07-05 2002-07-05 析出強化型Ｃｏ−Ｎｉ基耐熱合金の製造方法
JP2002197142 2002-07-05

Publications (2)

Publication Number Publication Date
EP1378579A1 EP1378579A1 (de) 2004-01-07
EP1378579B1 true EP1378579B1 (de) 2005-11-02

Family

ID=29720314

Family Applications (1)

Application Number Title Priority Date Filing Date
EP03015101A Expired - Lifetime EP1378579B1 (de) 2002-07-05 2003-07-03 Ausscheidungsgehärtete Kobalt-Nickel-Legierung mit guter Wärmebeständigkeit sowie zugehörige Herstellungsmethode

Country Status (5)

Country Link
US (1) US20040033158A1 (de)
EP (1) EP1378579B1 (de)
JP (1) JP4264926B2 (de)
DE (1) DE60302108T8 (de)
ES (1) ES2250793T3 (de)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11306372B2 (en) 2019-03-07 2022-04-19 Mitsubishi Power, Ltd. Cobalt-based alloy powder, cobalt-based alloy sintered body, and method for producing cobalt-based alloy sintered body
US11325189B2 (en) 2017-09-08 2022-05-10 Mitsubishi Heavy Industries, Ltd. Cobalt based alloy additive manufactured article, cobalt based alloy product, and method for manufacturing same
US11414728B2 (en) 2019-03-07 2022-08-16 Mitsubishi Heavy Industries, Ltd. Cobalt based alloy product, method for manufacturing same, and cobalt based alloy article
US11427893B2 (en) 2019-03-07 2022-08-30 Mitsubishi Heavy Industries, Ltd. Heat exchanger
US11499208B2 (en) 2019-03-07 2022-11-15 Mitsubishi Heavy Industries, Ltd. Cobalt based alloy product
US11613795B2 (en) 2019-03-07 2023-03-28 Mitsubishi Heavy Industries, Ltd. Cobalt based alloy product and method for manufacturing same

Families Citing this family (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
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
JP5582532B2 (ja) * 2010-08-23 2014-09-03 大同特殊鋼株式会社 Ｃｏ基合金
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
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
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
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
US20180340438A1 (en) * 2017-05-01 2018-11-29 General Electric Company Turbine Nozzle-To-Shroud Interface
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
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
US10533571B2 (en) * 2018-01-20 2020-01-14 Carolyn Rende Fortin Pump systems with variable diameter impeller devices
CN111187999B (zh) * 2020-02-17 2020-12-08 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
CN113073234B (zh) * 2021-03-23 2022-05-24 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
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

Family Cites Families (4)

* 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
JP4315582B2 (ja) * 2000-09-19 2009-08-19 日本発條株式会社 Ｃｏ−Ｎｉ基耐熱合金およびその製造方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11325189B2 (en) 2017-09-08 2022-05-10 Mitsubishi Heavy Industries, Ltd. Cobalt based alloy additive manufactured article, cobalt based alloy product, and method for manufacturing same
US11306372B2 (en) 2019-03-07 2022-04-19 Mitsubishi Power, Ltd. Cobalt-based alloy powder, cobalt-based alloy sintered body, and method for producing cobalt-based alloy sintered body
US11414728B2 (en) 2019-03-07 2022-08-16 Mitsubishi Heavy Industries, Ltd. Cobalt based alloy product, method for manufacturing same, and cobalt based alloy article
US11427893B2 (en) 2019-03-07 2022-08-30 Mitsubishi Heavy Industries, Ltd. Heat exchanger
US11499208B2 (en) 2019-03-07 2022-11-15 Mitsubishi Heavy Industries, Ltd. Cobalt based alloy product
US11613795B2 (en) 2019-03-07 2023-03-28 Mitsubishi Heavy Industries, Ltd. Cobalt based alloy product and method for manufacturing same

Also Published As

Publication number Publication date
DE60302108T2 (de) 2006-07-27
EP1378579A1 (de) 2004-01-07
ES2250793T3 (es) 2006-04-16
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

Similar Documents

Publication Publication Date Title
EP1378579B1 (de) Ausscheidungsgehärtete Kobalt-Nickel-Legierung mit guter Wärmebeständigkeit sowie zugehörige Herstellungsmethode
US7156932B2 (en) Nickel-base alloys and methods of heat treating nickel-base alloys
JP4996468B2 (ja) 高耐熱性，高強度Ｃｏ基合金及びその製造方法
EP1591548A1 (de) Verfahren zur Herstellung einer wärmedehnungsarmen Superlegierung auf Ni-basis
EP1900835A1 (de) Für die Festigkeitssteigerung durch Nitride geeignete Kobalt-Chrom-Eisen-Nickel-Legierungen
EP2610360A1 (de) Co-basislegierung
EP1340825A2 (de) Nickelbasislegierung, heissbeständige Feder aus dieser Legierung und Verfahren zur Herstellung dieser Feder
EP3526357B1 (de) Hochtemperatur- und beschädigungsbeständige superlegierung, aus der legierung hergestellter fertigungsartikel und verfahren zur herstellung der legierung
KR20200002965A (ko) 석출 경화성의 코발트-니켈 베이스 초합금 및 이로부터 제조된 물품
CN106167877B (zh) 马氏体时效钢
JP6315319B2 (ja) Ｆｅ−Ｎｉ基超耐熱合金の製造方法
KR101603049B1 (ko) 고온 특성 및 내수소취성 특성을 구비한 Fe-Ni계 합금 및 그의 제조방법
USH2245H1 (en) Age-hardenable, nickel-base superalloy with improved notch ductility
EP1329528B1 (de) Hitzebeständige co-ni-basis-legierung und entsprechende herstellung
WO2017123186A1 (en) Tial-based alloys having improved creep strength by strengthening of gamma phase
CA2930153A1 (en) Maraging steel
Hagiwara et al. Microstructure, Tensile and Creep Properties of Minor B-Modified Orthorhombic-Type Ti–27.5 Al–13Nb Alloy and Its Nb-Replaced Mo-and Fe-Containing Derivatives
JP6025216B2 (ja) Ｆｅ−Ｎｉ基合金およびＦｅ−Ｎｉ基合金の製造法

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IT LI LU MC NL PT RO SE SI SK TR

AX Request for extension of the european patent

Extension state: AL LT LV MK

17P Request for examination filed

Effective date: 20040109

17Q First examination report despatched

Effective date: 20040225

AKX Designation fees paid

Designated state(s): DE ES FR GB SE

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

RIN1 Information on inventor provided before grant (corrected)

Inventor name: NODA, TOSHIHARU

Inventor name: UETA, SHIGEKI

Inventor name: SHATO, SHIGEMI

Inventor name: AYADA, MICHIHIKO

Inventor name: TAKEDA, SHIROU

Inventor name: CHIBA, AKIHIKO

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): DE ES FR GB SE

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REF Corresponds to:

Ref document number: 60302108

Country of ref document: DE

Date of ref document: 20051208

Kind code of ref document: P

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

RIN2 Information on inventor provided after grant (corrected)

Inventor name: NODA, TOSHIHARU

Inventor name: UETA, SHIGEKI

Inventor name: SATO, SHIGEMI

Inventor name: AYADA, MICHIHIKO

Inventor name: TAKEDA, SHIROU

Inventor name: CHIBA, AKIHIKO

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2250793

Country of ref document: ES

Kind code of ref document: T3

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20060629

Year of fee payment: 4

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20060719

Year of fee payment: 4

ET Fr: translation filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20060724

Year of fee payment: 4

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20060803

EUG Se: european patent has lapsed
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20070703

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070704

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20080201

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070703

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20080331

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20060705

Year of fee payment: 4

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070731

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20070704

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20070704