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WO2016016437A2 - Superalliage à base de cobalt - Google Patents

Superalliage à base de cobalt Download PDF

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Publication number
WO2016016437A2
WO2016016437A2 PCT/EP2015/067697 EP2015067697W WO2016016437A2 WO 2016016437 A2 WO2016016437 A2 WO 2016016437A2 EP 2015067697 W EP2015067697 W EP 2015067697W WO 2016016437 A2 WO2016016437 A2 WO 2016016437A2
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WO
WIPO (PCT)
Prior art keywords
cobalt
weight
alloys
temperature
phase
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.)
Ceased
Application number
PCT/EP2015/067697
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German (de)
English (en)
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WO2016016437A3 (fr
Inventor
Alexander Bauer
Mathias GÖKEN
Lisa FREUND
Steffen Neumeier
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.)
Friedrich Alexander Universitaet Erlangen Nuernberg
Original Assignee
Friedrich Alexander Universitaet Erlangen Nuernberg
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 Friedrich Alexander Universitaet Erlangen Nuernberg filed Critical Friedrich Alexander Universitaet Erlangen Nuernberg
Priority to US15/500,992 priority Critical patent/US20170342527A1/en
Priority to EP15750314.5A priority patent/EP3175008B1/fr
Publication of WO2016016437A2 publication Critical patent/WO2016016437A2/fr
Publication of WO2016016437A3 publication Critical patent/WO2016016437A3/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C30/00Alloys containing less than 50% by weight of each constituent
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/07Alloys based on nickel or cobalt based on cobalt

Definitions

  • the invention relates to polycrystalline precipitation hardened and oxidation resistant ⁇ / ⁇ 'cobalt base superalloys for high temperature applications.
  • the mechanical properties of the specified cobalt-based superalloys exceed those of conventional carbide-hardened cobalt alloys. Up to a temperature of 800 ° C similar and at temperatures above 800 ° C even higher hot strengths than the nickel-based ⁇ / ⁇ 'forging alloys are achieved. The creep strengths are also significantly higher. In comparison to ⁇ / ⁇ 'nickel base superalloys are despite lower
  • Cobalt base and especially ⁇ / ⁇ 'nickel base superalloys are essential materials for a variety of components in jet engines of commercial aircraft or in stationary gas turbines for power conversion. Efforts to increase the efficiency of these turbines, cut costs and reduce fossil fuel consumption can all be achieved through new materials that offer higher temperature resistance, longer service life and lower manufacturing and processing costs.
  • ⁇ 'solvus temperature very high ⁇ ' volume fractions of more than 75% can be achieved at temperatures up to 900 ° C.
  • the ternary ⁇ / ⁇ 'cobalt base superalloys Co-9AI-9W (in atomic%), for example, despite a ⁇ ' solvus temperature of about only 975 ° C has a relatively high ⁇ 'excretion volume fraction of 58%. Owing to the large temperature range between solidus and ⁇ 'solvus temperature (forging window), the comparatively low ⁇ ' solvus temperatures and the high ⁇ 'volume fraction at application temperatures, the ⁇ / ⁇ ' cobalt base superalloys are thus suitable in particular as forging alloys. Nickel base superalloys, in comparison, either have a low ⁇ '
  • Solvus temperature 1038 ° C (Semiatin et al., Deformation behavior of Waspaloy at hot-working temperatures, Scripta Materialia 50 (2004) 625-629); ⁇ 'Voltage at application temperature: 25% (ASM Specialty Handbook: Nickel, Cobalt, and Their Alloys, Ed.
  • alloys are either malleable, but have a lower strength or that at forging temperatures of 1000 ° C to 1 150 ° C still have a relatively high proportion of the precipitation phase and thus only hardly or not at all are deformable and can only be processed powder metallurgy. This significantly increases the costs.
  • cobalt-based alloys are known to have higher hot-gas corrosion resistance than nickel-base alloys, since a liquid co-sulfur phase can occur only at 877 ° C, whereas a liquid Ni-S phase already occurs at 637 ° C ( see Bürgel, Maier, Niendorf, Handbuch Hochtemperaturtechnik, 4th Revised Edition 201 1, Vieheg + Teubner Verlag, Springer crampmedien Wiesbaden GmbH 201 1 or ASM Specialty Handbook: Nickel, Cobalt, and Their Alloys, Ed. Davies et al, ASM International, Materials Park, OH 44073, USA). Increased hot gas corrosion resistance can thus lead to a lifetime extension.
  • the object of the invention is the development of polycrystalline, high-strength, precipitation-hardened ⁇ / ⁇ 'cobalt-base superalloys, with very good oxidation properties, which can be processed by means of various forming processes, such as forging.
  • a cobalt-base superalloy comprising 32-45% by weight of Co, 28-40% by weight of Ni, 10-15% by weight of Cr, 2.5-5.5% by weight of Al, 6 , 5-1 6 wt% W, 0-9 wt% Ta, 0-8 wt% Ti, 0.1 -1 wt% Si, 0-0.5 wt% B , 0-0.5 wt% C, 0-2 wt% Hf, 0-0.1 wt% Zr, 0-8 wt% Fe, 0-6 wt% Nb, 0-7 wt .-% Mo, 0-4 wt .-% Ge and a balance of unavoidable impurities.
  • the cobalt-base superalloy comprises 32-45% by weight of Co, 28-40% by weight of Ni, 10-15% by weight of Cr, 2.5-5.5% by weight of Al, 6.5 1-6 wt% W, 0-9 wt% Ta, 0-8 wt% Ti, 0.1-1 wt% Si, 0-0.5 wt% B, 0 -0.5 wt% C, 0 to ⁇ 2 wt% Hf, 0 to ⁇ 0.1 wt% Zr, 0 to ⁇ 8 wt% Fe, 0 to ⁇ 6 wt% Nb, 0 to ⁇ 7 wt .-% Mo, 0 to ⁇ 4 wt .-% Ge and a balance of unavoidable impurities.
  • cobalt base superalloy in a further embodiment 32-45 wt .-% Co, 28-40 wt .-% Ni, 10-15 wt .-% Cr, 2.5-5.5 wt .-% Al, 6 , 5-1 6 wt .-% W, 0.2-9 wt .-% Ta, 0.2-8 wt .-% Ti, 0.1 -1 wt .-% Si, ⁇ 0.5 wt.
  • % B ⁇ 0.5% by weight C, 0-2% by weight Hf, 0-0.1% by weight Zr, 0-8% by weight Fe, 0-6% by weight Nb, 0-7 wt% Mo, 0-4 wt% Ge and a balance of unavoidable impurities.
  • the cobalt-base superalloy comprises 32-45% by weight of Co, 28-40% by weight of Ni, 10-15% by weight of Cr, 2.5-5.5% by weight of Al, 6, 5-1 6 wt% W, 0.2-9 wt% Ta, 0.2-8 wt% Ti, 0.1 -1 wt% Si, ⁇ 0.5 wt% % B, ⁇ 0.5 wt .-% C, 0 to ⁇ 2 wt .-% Hf, 0 to ⁇ 0.1 wt .-% Zr, 0 to ⁇ 8 wt .-% Fe, 0 to ⁇ 6 wt % Nb, 0 to ⁇ 7% by weight Mo, 0 to ⁇ 4% by weight Ge and a balance of unavoidable impurities.
  • the cobalt-base superalloy which comprises in particular an aforementioned composition, characterized by an intermetallic ⁇ 'phase of the composition (Co, Ni) 3 (Al, W, Ti, Ta), each of each bracket containing at least one of the elements listed in parentheses is.
  • the intermetallic ⁇ 'phase (precipitation phase) is contained with a volume fraction of more than 35%, preferably of more than 45%.
  • Co forms the cubic face-centered ⁇ -matrix phase as a basic element among other elements and is an important constituent of the hardening y '- (Co, Ni) 3 (Al, W, Ti, Ta) precipitation phase. Co also lowers the stacking fault energy.
  • Ni (nickel) 28-40% by weight
  • Ni in the specified range expands the ⁇ / ⁇ 'two-phase region to a sufficient extent, so that further alloying elements, in particular Cr, can be added to a sufficient extent.
  • Cr contents from about 4% by weight destabilize the biphasic ⁇ / ⁇ 'microstructure in ternary Co-Al-W alloys, and further undesirable intermetallic phases are formed.
  • Ni shifts the maximum possible concentration of Cr to higher concentrations. Furthermore, with Ni, the ⁇ 'solvus temperature can be increased.
  • the alloying element Cr should be added to the specified range.
  • Cr acts as a mixed crystal hardener.
  • Al forms the ⁇ 'precipitation phase (Co, Ni) 3 (Al, W, Ti, Ta), which contributes significantly to the increase in strength. Furthermore, AI increases the oxidation resistance. Higher levels of Al in the specified composition range can lead to the formation of additional intermetallic phases, such as CoAl, which can limit grain growth in forging alloys. As a result, smaller particle sizes and thus higher strengths can be achieved.
  • Si is a crucial element and significantly improves the oxidation resistance. However, excessive amounts of Si can lead to further undesirable intermetallic phases.
  • B acts as a grain boundary-strengthening alloying element and improves the oxidation properties. Too high concentrations lead to too high a proportion of borides.
  • B is contained at more than 0.01% by weight.
  • C acts as a grain boundary strengthening alloying element.
  • C forms carbides.
  • C is preferably contained with more than 0.01% by weight.
  • Ta (Tantalum): 0.2-9% by weight
  • Ta contributes to the formation of the ⁇ 'precipitation phase, increases the ⁇ ' soivus temperature and the ⁇ / ⁇ 'lattice mismatch. Ta hardens the ⁇ 'precipitation phase and leads to an increase in strength. In particular, when high toughness at 800 ° C is required, the two elements Ta and Ti are required.
  • Ti contributes to the formation of the ⁇ 'precipitation phase, increases the ⁇ ' soivus temperature and the ⁇ / ⁇ 'lattice mismatch. Ti hardens the ⁇ 'precipitation phase and leads to an increase in strength. In particular, when high toughness at 800 ° C is required, the two elements Ta and Ti are required. Ti can largely replace W, thereby significantly reducing the density.
  • Hf stabilizes the ⁇ 'excretion phase. Preference is given to Hf containing more than 0.2% by weight.
  • Zr serves to increase the grain boundary strength and to stabilize the ⁇ 'precipitation phase.
  • Zr is included at more than 0.01% by weight.
  • Fe lowers the ⁇ 'soivus temperature and can be used to adjust this especially for forging alloys. Fe is also a low cost element and can improve weldability. Too high concentrations destabilize the ⁇ / ⁇ 'microstructure. Preference is given to containing Fe more than 0.1% by weight.
  • Nb contributes to the formation of the ⁇ 'precipitation phase, leads to an increase in strength and increases the ⁇ ' soivus temperature. Higher concentrations within the given concentration range may lead to the formation of additional intermetallic phases which may limit grain growth in forging alloys. As a result, smaller particle sizes and thus higher strengths can be achieved.
  • Nb is contained at more than 0.1% by weight.
  • Mo serves as a solid-solution-hardening element and can partially replace W, thereby decreasing the density. Higher concentrations lead to the formation of additional intermetallic phases, which can limit grain growth in forging alloys. As a result, smaller particle sizes and thus higher strengths can be achieved.
  • Mo is contained with more than 0.1 wt .-%.
  • Ge forms the ⁇ 'precipitation phase Co 3 (Al, Ge, W), lowers the ⁇ ' solvus temperature and can be used to adjust this especially for forging alloys.
  • Ge preferably contains more than 0.1% by weight.
  • 1 is a graph showing the relationship between the precipitation rate at the application temperature and the solvus temperature of the ⁇ '-phase of ⁇ / ⁇ 'nickel-base superalloys in comparison with embodiments of the invention
  • FIG. 2 shows the microstructure of exemplary alloys of the invention.
  • 3 is an EBSD measurement for determining the grain size and the twin density of an exemplary alloy of the invention.
  • Fig. 5 is a graph showing the creep strength of an exemplary alloy of
  • FIG. 6 shows microstructural images of the ternary alloy Co9AI9W compared to an exemplary alloy of the invention
  • compositions of some embodiments of the present invention ⁇ / ⁇ 'cobalt base superalloys hereinafter referred to as CoWAIloyO, CoWAIloyl, and CoWAIIoy2, as well as some reference alloys are shown in Table 1 below.
  • CoWAIloyO CoWAIloyl
  • CoWAIIoy2 CoWAIIoy2
  • Table 1 the properties of exemplary embodiments of the invention will be described in more detail below with reference to the figures and investigations.
  • Table 1 Compositions of the here described ⁇ / ⁇ 'cobalt base superalloys CoWAIloyO, CoWAIloyl and CoWAIIoy2 as well as some polycrystalline, cobalt and nickel based reference alloys (in% by weight).
  • the developed alloys described here have the distinct advantage compared to nickel-based forging alloys that despite the relatively low ⁇ 'solvus temperatures of about 1050 ° C (CoWAIloyO), 1070 ° C (CoWAIloyl) or 1030 ° C (CoWAIIoy2) high Excretion volume ratios of more than 45% (CoWAIloyO) at 750 ° C can be achieved.
  • 1 shows the relationship between the excretion fraction at fürsstempe- and the solvus temperature of the ⁇ '-phase of ⁇ / ⁇ 'nickel-base superalloys and the presently stated ⁇ / ⁇ ' cobalt-base superalloy CoWAIloyO.
  • the relatively low ⁇ 'Solvus temperatures make easier forming possible at typical forging temperatures of 1000 ° C to 1 150 ° C.
  • FIG. 3 shows an EBSD measurement ("electron back scattering diffraction") for determining the grain size and twin density of the ⁇ / ⁇ cobalt-base superalloy CoWAIIoy2 described herein, the twin density of the CoWAIIoy2 alloy determined by EBSD. is much higher at 55% compared to the nickel base superalloy Udimet 720Li with only 33%. This is due to the lower stacking fault energy of the cobalt base superalloys.
  • EBSD measurement electron back scattering diffraction
  • Figure 4 shows the yield strength versus temperature of the CoWAIloyl and CoWAIIoy2 alloys herein compared to the Waspaloy and Udimet 720Li nickel based alloys and the Mar-M509 cobalt alloy.
  • Fig. 5 shows the creep strength of the ⁇ / ⁇ 'cobalt base superalloy CoWAIIoy2 compared to the polycrystalline ⁇ / ⁇ ' nickel base superalloys Waspaloy and Udimet 720LI at 700 ° C. Accordingly, the alloy CoWAIIoy2 at 700 ° C also has a significantly higher creep resistance than the nickel-based Waspaloy and Udimet 720Li alloys.
  • FIG. 6 shows microstructural images of the oxide layers of the ternary alloy Co9AI9W (a) and the alloy CoWAIIoy2 (b) given herein.
  • the oxide layer thickness after annealing at 900 ° C for 50 h is at least 10 times smaller in the alloy CoWAIIoy2 than in the ternary alloy Co9AI9W (see a with b).
  • the alloy CoWAIIoy2 ( Figure 6b) (has significantly better oxidation resistance.
  • FIG. 7 shows the element distributions in the various oxide layers of the alloy CoWAIIoy2 after annealing at 900 ° C. for 50 h, determined by energy-dispersive X-ray spectroscopy EDS in the scanning electron microscope SEM.
  • the relatively good oxidation properties result from the protective oxide layers rich in Al, Si and Cr.
  • the cobalt-base superalloys of the present invention are characterized by being based on the element cobalt, hardened with the intermetallic ⁇ 'phase (Co, Ni) 3 (Al, W, Ti, Ta) to have better mechanical properties than conventional ones
  • Carbide-hardened cobalt-base superalloys have higher strengths than comparable polycrystalline ⁇ / ⁇ 'nickel-based superalloys at temperatures above 800 ° C, having higher creep strengths than comparable polycrystalline ⁇ / ⁇ ' nickel-base superalloys at temperatures of 700 ° C, making them better
  • a ⁇ / ⁇ 'cobalt base superalloy with addition of molybdenum (CoWAIIoy3) is given.
  • the composition is shown in Table 2 again together with the other exemplary alloys CoWAIloyO, CoWAIloyl and CoWAIIoy2 described above.
  • the content of Mo is changed at the expense of Co.
  • Mo serves as a solid solution hardening element and can partially replace W, thereby reducing the density.
  • Mo results in the formation of additional "grain boundary pinning" intermetallic phases which can limit grain growth in forging alloys.
  • Table 2 Compositions of the y / ⁇ 'cobalt base superalloy CoWAIIoy3 together with CoWAlloyO, CoWAIloyl and CoWAIIoy2 (% by weight).
  • CoWAIIoy3 a relatively low solvus temperature of about 1050 ° C. is expected for CoWAIIoy3, while at the same time having a relatively high solidus temperature, which is advantageous for processing, in particular by casting and forging, since these two temperatures span the window for processing and heat treatment.
  • the alloy CoWAIIoy3 was after a homogenization annealed at 1250 ° C for 3h at 1 100 ° C for 1 h and then hot-rolled. The diameter was reduced in several passes from 40 mm to 15 mm. Subsequently, a recrystallization heat treatment was carried out to obtain a homogeneous, fine-grained texture.
  • Fig. 8 shows SEM micrographs of CoWAIIoy3 after recrystallization for 4 hours at (a) 1000 ° C and (b) 1100 ° C.
  • the predominantly grain boundary white contrast phase is the W and Mo containing ⁇ phase. It is clear that at a higher recrystallization temperature, the proportion of ⁇ -phase decreases and at the same time the grain size increases significantly.
  • the recrystallization at 1000 ° C leads to a ⁇ -phase content of about 3.2% and a median grain size of about 5 ⁇ .
  • the same heat-treated CoWAIIoy2 has a median of about 8 ⁇ , which illustrates the grain boundary pinning effect of the ⁇ -phase.
  • Another, two-stage heat treatment (900 ° C, 4 h + 750 ° C, 1 6 h) leads to the uniform elimination of ⁇ 'phase in the co-mixed crystal.
  • 9 shows the ⁇ / ⁇ 'microstructure after a two-stage heat treatment (900 ° C., 4 h + 750 ° C., 16 h): (a) SEM image with primary and secondary ⁇ '- Particles, (b) TEM dark field image with secondary and tertiary ⁇ '-particles.
  • the ⁇ 'particles are round, as in the comparative alloy CoWAIIoy2, indicating a low lattice mismatch.
  • the particle diameter is about 65 nm also in the range of the comparative alloy.
  • a difference can be seen in the ⁇ 'portion, which is about 37% lower than in CoWAIIoy2.
  • the reason for this can be assumed to be the formation of a ⁇ phase Co 7 (W, Mo) 6 , which reduces the W content available in the co-solid solution to form ⁇ '.
  • this slightly lower phase content does not adversely affect the high temperature strength.
  • FIG. 10 shows the yield stress above the temperature of the Mo-containing alloy CoWAIIoy3 with grain boundary pinning ⁇ phase in comparison to FIG. 10

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Abstract

Superalliage à base de cobalt comprenant de 32 à 45 % en poids de Co, de 28 à 40 % en poids de Ni, de 10 à 15 % en poids de Cr, de 2,5 à 5,5 % en poids d'Al, de 6,5 à 16 % en poids de W, de 0 à 9 % en poids de Ta, de 0 à 8 % en poids de Ti, de 0,1 à 1 % en poids de Si, de 0 à 0,5 % en poids de B, de 0 à 0,5 % en poids de C, de 0 à 2 % en poids de Hf, de 0 à 0,1 % en poids de Zr, de 0 à 8 % en poids de Fe, de 0 à 6 % en poids de Nb, de 0 à 7 % en poids de Mo, de 0 à 4 % en poids de Ge, le reste étant constitué d'impuretés inévitables.
PCT/EP2015/067697 2014-08-01 2015-07-31 Superalliage à base de cobalt Ceased WO2016016437A2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US15/500,992 US20170342527A1 (en) 2014-08-01 2015-07-31 Cobalt-based super alloy
EP15750314.5A EP3175008B1 (fr) 2014-08-01 2015-07-31 Alliage a base de cobalt

Applications Claiming Priority (2)

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DE102014011249.7 2014-08-01
DE102014011249 2014-08-01

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WO2019233693A1 (fr) * 2018-06-04 2019-12-12 Siemens Aktiengesellschaft ALLIAGE À BASE DE COBALT-NICKEL À DURCISSEMENT γ, γ', POUDRE, COMPOSANT ET PROCÉDÉ
WO2019233692A1 (fr) * 2018-06-04 2019-12-12 Siemens Aktiengesellschaft ALLIAGE À BASE DE COBALT-NICKEL À DURCISSEMENT γ, γ', POUDRE, COMPOSANT ET PROCÉDÉ
CN111051548A (zh) * 2017-04-21 2020-04-21 Crs 控股公司 可沉淀硬化的钴-镍基高温合金和由其制造的制品
DE102020203436A1 (de) 2020-03-18 2021-09-23 Siemens Aktiengesellschaft Kobaltbasislegierung, Pulvermischung, Verfahren und Bauteil
EP4306236A1 (fr) * 2022-07-11 2024-01-17 Liburdi Engineering Limited Matériau de soudage à base de nickel à haute teneur en gamma prime

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DE102016200135A1 (de) * 2016-01-08 2017-07-13 Siemens Aktiengesellschaft Gamma, Gamma'-kobaltbasierte Legierungen für additive Fertigungsverfahren oder Löten, Schweißen, Pulver und Bauteil
WO2018193036A1 (fr) * 2017-04-21 2018-10-25 Oerlikon Surface Solutions Ag, Pfäffikon Cible de pulvérisation en superalliage
KR20200133386A (ko) 2018-04-04 2020-11-27 더 리전츠 오브 더 유니버시티 오브 캘리포니아 고온 내산화성 Co 기반 감마/감마 프라임 합금 DMREF-Co
CN113684398B (zh) * 2021-08-26 2022-05-13 大连理工大学 900℃组织稳定的立方形γ′纳米粒子共格析出强化的高温合金及制备方法
CN114086049B (zh) * 2021-11-17 2022-08-23 沈阳航空航天大学 2.0GPa级超高屈服强度塑性CoCrNi基中熵合金及其制备方法
CN115233074A (zh) * 2022-07-12 2022-10-25 北京科技大学 一种燃机动叶片用钴镍基高温合金及其制备方法

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111051548A (zh) * 2017-04-21 2020-04-21 Crs 控股公司 可沉淀硬化的钴-镍基高温合金和由其制造的制品
EP3612656B1 (fr) * 2017-04-21 2024-08-07 CRS Holdings, LLC Superalliage à base de cobalt-nickel à durcissement par précipitation et article fabriqué à partir de celui-ci
WO2019233693A1 (fr) * 2018-06-04 2019-12-12 Siemens Aktiengesellschaft ALLIAGE À BASE DE COBALT-NICKEL À DURCISSEMENT γ, γ', POUDRE, COMPOSANT ET PROCÉDÉ
WO2019233692A1 (fr) * 2018-06-04 2019-12-12 Siemens Aktiengesellschaft ALLIAGE À BASE DE COBALT-NICKEL À DURCISSEMENT γ, γ', POUDRE, COMPOSANT ET PROCÉDÉ
DE102020203436A1 (de) 2020-03-18 2021-09-23 Siemens Aktiengesellschaft Kobaltbasislegierung, Pulvermischung, Verfahren und Bauteil
EP4306236A1 (fr) * 2022-07-11 2024-01-17 Liburdi Engineering Limited Matériau de soudage à base de nickel à haute teneur en gamma prime

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US20170342527A1 (en) 2017-11-30
WO2016016437A3 (fr) 2016-04-07
EP3175008B1 (fr) 2018-10-17
EP3175008A2 (fr) 2017-06-07

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