EP4357471A1 - Nickel-chrom-legierungen - Google Patents

Nickel-chrom-legierungen Download PDF

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Publication number
EP4357471A1
EP4357471A1 EP22202777.3A EP22202777A EP4357471A1 EP 4357471 A1 EP4357471 A1 EP 4357471A1 EP 22202777 A EP22202777 A EP 22202777A EP 4357471 A1 EP4357471 A1 EP 4357471A1
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EP
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Prior art keywords
carbide
present
powder composition
nickel
molybdenum
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EP22202777.3A
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English (en)
French (fr)
Inventor
Oliver Lanz
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Hoganas Germany GmbH
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Hoganas Germany GmbH
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Priority to EP22202777.3A priority Critical patent/EP4357471A1/de
Priority to PCT/EP2023/079321 priority patent/WO2024084057A2/en
Publication of EP4357471A1 publication Critical patent/EP4357471A1/de
Pending legal-status Critical Current

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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/05Mixtures of metal powder with non-metallic powder
    • C22C1/051Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C22C1/053Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds
    • C22C1/055Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of hard compounds using carbon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C19/00Alloys based on nickel or cobalt
    • C22C19/03Alloys based on nickel or cobalt based on nickel
    • C22C19/05Alloys based on nickel or cobalt based on nickel with chromium
    • C22C19/051Alloys based on nickel or cobalt based on nickel with chromium and Mo or W
    • C22C19/055Alloys 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%
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C29/00Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/005Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C29/00Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C32/00Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
    • C22C32/0047Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents
    • C22C32/0052Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with carbides, nitrides, borides or silicides as the main non-metallic constituents only carbides

Definitions

  • the present disclosure concerns nickel-chrome alloys suitable for use as matrix alloys for holding particles of metal carbides for high abrasive wear resistance in high carbide volume fractions with high corrosion resistance. Further, direct synthesis of nickel-chrome alloys of the disclosure containing precipitates of metal carbides are detailed.
  • German patent application DE19901170A1 describes a Fe-based alloy, which is high in metal carbide formers like V, Cr, Mo, W, for providing a high carbide volume fraction that can provide an outstanding high abrasive wear resistance. Disadvantages are the missing corrosion resistance due to Cr depletion of the Fe-based matrix and the lack of impact tolerance of the Fe-based alloy.
  • Known alloys which are all Fe-based, contain the risk of undesired phase transformation such as martensite or delta ferrite, or the risk of incomplete martensitic phase transformation which retains residual austenite while applying them with casting/thermal spraying/surface welding/AM, leading for example to undesired level of hardness or undesirable brittleness.
  • Some particles act as hard phase components, other particles act as matrix with some corrosion resistance, making the coating properties locally inconsistent and the resulting coating sensitive to variations caused by inhomogeneities of the powder blend or due to inconsistent deposition efficacy. Additionally, the challenges due to Cr depletion from oxidation still exists.
  • the hardness of these Fe-based alloys and blends as described above is in the range of 615/670 HV0.3 for the FeCrMnBC/TiC coating and 67-68 HRC for the alloy in Patent DE19901170A1 .
  • AMPERWELD CCA4 respectively AMPERIT 380.088 (c.f. DE19901170A1 ) has a hardness of approx. 60 HRC after surface welding and 800-850 HV0.3 as HVOF sprayed.
  • Ni-based matrix alloy consisting by total weight of the alloy of: chromium (Cr) 12 wt% - 23 wt%, vanadium (V) 0.2 wt% - 3.1 wt%, tungsten (W) 1.0 wt% - 6.0 wt%, molybdenum (Mo) 0.6 wt% - 3.5 wt%, and optionally silicon (Si) 0 wt% - 2 wt%, manganese (Mn) 0 wt% - 2 wt%, aluminum (Al) 0 wt% - 1 wt%, the balance being nickel (Ni) and unavoidable impurities.
  • the present inventors have surprisingly found, that when alloys according to the present invention are formed by joint or stepwise melting of the constituent metals, a nickel-chrome alloy is formed which has improved corrosion resistive properties compared to reference products in the current market, while being very suitable for holding as micro-inclusions inside the formed alloy matrix, for example metal carbide particles in high volume fractions.
  • a further benefit of the present alloys is that some contamination with silicon, manganese, and aluminum is possible without loss of the beneficial properties of the present alloys, hence rendering sourcing of the constituent materials cheaper, since nickel-chrome scrap metal can be used to an extent as raw material or as an additive to the raw materials.
  • each of silicon, manganese, or aluminum is typically introduced into the present alloys by direct synthesis of a present alloys and on or more metal carbides taking place in e.g., in powder form from thermal spraying (e.g., HVOF or HVAF), surface welding (e.g., PTA welding or Laser Cladding) or Additive Manufacturing (e.g., Powder Bed Fusion or Direct Energy Deposition).
  • Iron which in the context of the present invention is considered an undesired impurity due to its high corrosive potential, may nonetheless be present in amounts up to 0.2 wt% without negative impact on the present alloys beyond miscoloring if exposed to corrosive conditions.
  • iron is not present in amounts exceeding 0.1 wt%, however scrap nickel-chrome alloys preferably used as source for the present alloys often contain this much of residual iron, and the present inventors consider it highly beneficial for cost that higher purity nickel-chrome source metals are not required.
  • chromium may be present in amounts from 12 wt% to 23 wt% based on the total weight of the present alloys.
  • chromium is present from 13 wt% to 22 wt%, from 14 wt% to 21 wt%, from 15 wt% to 20 wt%, from 16 wt% to 19 wt%, or from 17 wt% to 18 wt% in the present alloys.
  • vanadium (V) may be present in amounts from 0.2 wt% to 3.1 wt% based on the total weight of the present alloys.
  • vanadium is present from 0.3 wt% to 3.0 wt%, from 0.4 wt% to 2.9 wt%, from 0.5 wt% to 2.8 wt%, from 0.6 wt% to 2.7 wt%, from 0.6 wt% to 2.7 wt%, from 0.7 wt% to 2.6 wt%, from 0.8 wt% to 2.5 wt%, from 0.9 wt% to 2.4 wt%, from 1.0 wt% to 2.3 wt%, from 1.2 wt% to 2.1 wt%, from 1.4 wt% to 1.9 wt%, or from 1.6 wt% to 1.7 wt% in the present alloys.
  • tungsten may be present in amounts from 1.0 wt% to 6.0 wt% based on the total weight of the present alloys. Preferably, tungsten is present from 1.5 wt% to 5.5 wt%, from 2.0 wt% to 5.0 wt%, from 2.5 wt% to 4.5 wt%, from 3.0 wt% to 4.0 wt%, or from 3.3 wt% to 3.7 wt% in the present alloys.
  • molybdenum may be present in amounts from 0.6 wt% to 3.5 wt% based on the total weight of the present alloys.
  • molybdenum is present from 0.7 wt% to 3.4 wt%, from 0.8 wt% to 3.3 wt%, from 0.9 wt% to 3.2 wt%, from 1.0 wt% to 3.0 wt%, from 1.3 wt% to 2.7 wt%, from 1.6 wt% to 2.4 wt%, or from 1.8 wt% to 2.2 wt% in the present alloys.
  • Ni-based matrix alloys that these can be formed in-situ by from a powder form by e.g., thermal spraying (e.g., HVOF or HVAF), surface welding (e.g., PTA welding or Laser Cladding) or Additive Manufacturing (e.g., Powder Bed Fusion or Direct Energy Deposition) .
  • thermal spraying e.g., HVOF or HVAF
  • surface welding e.g., PTA welding or Laser Cladding
  • Additive Manufacturing e.g., Powder Bed Fusion or Direct Energy Deposition
  • a Ni-based powder composition at least comprising: chromium (Cr) from 12 wt% to 23 wt%, vanadium (V) from 0.2 wt% to 3.1 wt%, tungsten (W) from 1.0 wt% to 6.0 wt%, molybdenum (Mo) from 0.6 wt% to 3.5 wt%, and optionally silicon (Si) from 0 wt% to 2 wt%, manganese (Mn) from 0 wt% to 2 wt%, aluminum (Al) from 0 wt% to 1 wt%, the balance being nickel (Ni) and unavoidable impurities, for forming a Ni-based matrix alloy according to any of the preceding embodiments.
  • the Ni-based matrix alloy is a pre-alloyed powder.
  • the Ni-based powder composition and consequently, the Ni-based matrix alloy composition once formed further comprise from 1 vol% to 70 vol% of a metal carbide powder comprising at least one metal carbide.
  • Ni-based matrix alloys of the present disclosure can be formulated as pre-alloyed powders and desired amounts of metal carbide powders added, e.g., by in-mixing. This not only broadens the range and the composition of metal carbide powders, which can be added, making the hard-coatings independent on the formation chemistry of the constituent powders, but also it allows for lower deposition temperatures, since rather than providing coating temperatures necessary for metal carbide formation, it is now only necessary to provide energy for melting the Ni-based matrix alloy powder and not the metal carbides.
  • the at least one metal carbide is selected from one or more of a nickel carbide, a chromium carbide, a vanadium carbide, a tungsten carbide (WC), a molybdenum carbide, a silicon carbide, a manganese carbide, an aluminum carbide, a titanium carbide, a niobium carbide, a tantalum carbide, a hafnium carbide, or a zirconium carbide, preferably is selected from one or more of a nickel carbide, a chromium carbide, a vanadium carbide, a tungsten carbide (WC), a molybdenum carbide, a silicon carbide, a manganese carbide, or an aluminum carbide, more preferably is selected from one or more of a nickel carbide, a chromium carbide, a vanadium carbide, a tungsten carbide (WC), a molybdenum carbide, a silicon carbide, a manganes
  • Ni-based matrix alloys of the present disclosure concomitantly with metal carbides of chromium, vanadium, tungsten, molybdenum, and when present in the Ni-based powder composition, also of silicon, manganese, and aluminum.
  • the Ni-based matrix alloys then deposit from the gas-phase containing inclusions of the desired metal carbides.
  • Ni-based powder composition consisting by total weight of the powder composition of chromium (Cr) 20 wt% - 30 wt%, vanadium (V) 5 wt% - 20 wt%, carbon (C) 2 wt% - 4 wt%, tungsten (W) 1 wt% - 10 wt%, molybdenum (Mo) 0.6 wt% - 10 wt%, silicon (Si) 0 wt% - 2 wt%, manganese (Mn) 0 wt% - 2 wt%, aluminum (Al) 0 wt% - 1 wt%, the balance being nickel (Ni) and unavoidable impurities.
  • a Ni-based powder composition wherein chromium is present from 21 wt% to 29 wt%, from 22 wt% to 28 wt%, from 23 wt% to 27 wt%, or from 24 wt% to 26 wt%, preferably from 25 wt% to 30 wt%, from 26 wt% to 29 wt%, or from 27 wt% to 28 wt%.
  • a Ni-based powder composition wherein vanadium is present from 6 wt% to 19 wt%, from 7 wt% to 18 wt%, from 8 wt% to 17 wt%, from 9 wt% to 16 wt%, from 10 wt% to 15 wt%, from 10 wt% to 14 wt%, or from 12 wt% to 13 wt%.
  • a Ni-based powder composition wherein carbon is present from 2.3 wt% to 3.7 wt%, from 2.6 wt% to 3.4 wt%, or from 2.9 wt% to 3.1 wt%.
  • a Ni-based powder composition wherein tungsten is present from 1 wt% to 9 wt%, from 2 wt% to 8 wt%, from 3 wt% to 7 wt%, or from 4 wt% to 6 wt%.
  • a Ni-based powder composition wherein molybdenum is present from 1 wt% to 9 wt%, from 2 wt% to 8 wt%, from 3 wt% to 7 wt%, or from 4 wt% to 6 wt%.
  • a Ni-based powder composition wherein molybdenum is present from 1 wt% to 9 wt%, from 2 wt% to 8 wt%, from 3 wt% to 7 wt%, or from 4 wt% to 6 wt%.
  • a Ni-based powder composition wherein silicon is present in an amount of at least 0.1 wt%.
  • a Ni-based powder composition wherein manganese is present in an amount of not more than 1.5 wt%, not more than 1.0 wt%, not more than 0.75 wt%, or not more than 0.5 wt%.
  • a Ni-based powder composition wherein aluminum is present in an amount of not more than 0.75 wt%, or not more than 0.5 wt%.
  • Ni-based powder composition consisting by total weight of the powder composition of chromium (Cr) 25 wt% - 30 wt%, vanadium (V) 7 wt% - 13 wt%, carbon (C) 2 wt% - 3 wt%, tungsten (W) 3 wt% - 7 wt%, molybdenum (Mo) 3 wt% - 7 wt%, silicon (Si) 0.1 wt% - 2 wt%, aluminum (Al) 0 wt% - 1 wt%, the balance being nickel (Ni) and unavoidable impurities including manganese.
  • Ni-based powder composition consisting by total weight of the powder composition of chromium (Cr) 25 wt% - 30 wt%, vanadium (V) 13 wt% - 19 wt%, carbon (C) 3 wt% - 4 wt%, tungsten (W) 3 wt% - 7 wt%, molybdenum (Mo) 3 wt% - 7 wt%, silicon (Si) 0.1 wt% - 2 wt%, aluminum (Al) 0 wt% - 1 wt%, the balance being nickel (Ni) and unavoidable impurities including manganese.
  • the resulting Ni-based matrix alloys form as eutectics from the gas-phase, the formed eutectics being essentially devoid of carbon.
  • the abovementioned two preferred embodiments of the Ni-based powder compositions were tested for their suitability for thermal spraying (e.g., HVOF or HVAF), surface welding (e.g., PTA welding or Laser Cladding) or Additive Manufacturing (e.g., Powder Bed Fusion or Direct Energy Deposition).
  • thermal spraying e.g., HVOF or HVAF
  • surface welding e.g., PTA welding or Laser Cladding
  • Additive Manufacturing e.g., Powder Bed Fusion or Direct Energy Deposition
  • the resulting microstructure after thermal spraying was characterized by fine carbide precipitations as shown in the figures, embedded in a corrosion resistant Ni based matrix to resist mechanical wear and corrosion.
  • the carbides such as Vanadium carbides and Chromium carbides (and mixed carbides) provide the necessary hard phases to resist mechanical wear like abrasion or erosion.
  • the Ni based matrix is alloyed with elements such as Cr, Mo, W, Si and/or Al to provide solid solution strengthening and corrosion resistance. It is proved by similar alloys that the type and volume fraction of the hard phase precipitants provide an essential high resistance against mechanical wear (such as abrasion, sliding, erosion).
  • the level of hard phases also influences the properties in terms of brittle nature at dynamics forces or crack-sensitivity in the application process. It is followed that the Ni based matrix provides some impact tolerance compared to existing solutions.
  • FIG 1 to 4 is shown comparative example using a Fe containing composition of Ni (bal.), Cr 16wt%, V 11wt%, W 4.0wt%, Mo 3.0wt%, C 2.5wt%, Fe 7.0wt%, which has been vacuum atomized with KVA.
  • the composition provides a corrosion resistant alloy with a high degree of melting with a target of 45 HRC by VC and eutectic precipitants.
  • Figure 2 shows the composition with a 30-33 HRC as welded and was not considered relevant for further testing.
  • the composition has a hardness of approx. 700 HV0.3 as HVOF-sprayed and 33 HRC as welded, and there is some porosity due to unoptimized particle size distribution.
  • figure 4 is shown a salt spray testing of the composition of figure 3 where weakness in corrosion is seen due to open cavities and Cr depletion as result of oxidation.
  • Figure 11 is shown an alloy composition Ni (bal.), Cr 27wt%, V 10wt%, Mo 5.5wt%, C 2.5wt%, Al 0.4wt%, Si 0.2wt%, in the present context having a high Cr and medium V content. There is a homogeneous chemical distribution and no large unwanted precipitants.
  • Figure 12 is shown an alloy composition with Ni (bal.), Cr 28wt%, V 16wt%, Mo 5.7wt%, C 3.7wt%, Al 0.4wt%, Si 0.3wt%, in the present context having a high Cr and high V content.
  • the invented alloy is based on Ni, it always stays in FCC lattice and therefore an imbalance with hard HCP phase does not occur (c.f. "Amperweld Ni-CCA4 med Phase Simulation" with simulation results of such a Ni based alloy and the received stable FCC phase in comparison to a V and Cr-rich carbide strengthened Fe based alloys called AMPERWELD CCA4) .
  • Hardness is gained by precipitating out fine hard phases such as Cr- and V-rich carbides so that the martensitic phase transformation is not needed. This has a simplifying effect on the powder atomization and the required window of the chemical composition.
  • Ni-based powders of the present disclosure were also independent to the processing technology and the characterizing cooling speed when it comes to the required hardness by martensitic phase transformation. Since the since the invention is hard phase strengthened, different cooling speeds will affect the size (and therefore the mean free path between the individual hard phases) of the precipitants.
  • phase compositions for REF1 (Table 2) and REF2 (Table 3) can be expected; Matrix alloy, FCC, M23C6, and HCP.
  • nickel does not present in the FCC and HCP phases (in the simulations to a total content below 0.1 wt%), rather nickel stays in the matrix alloy, and only to a smaller content (between 1.0 wt% to 8.5 wt%) contributes to the M23C6 hard phase.
  • the simulation confirms the experiments that the high corrosion resistance is due to the advantageous distribution of nickel into the matrix alloy, when Ni-Cr-powders as detailed herein are melted.
  • Table 3 -Sample REF2 Results [wt%/part] Total Composition Ni Cr V W Mo C Matrix Alloy MIN 61.4 72.1 14.9 0.3 2.0 1.0 0.0 MAX 70.5 79.1 20.7 2.9 5.0 3.2 0.0 FCC MIN 1.1 0.0 1.5 67.5 1.4 0.8 15.0 MAX 9.8 0.1 6.7 81.1 7.1 3.2 15.7 M23C6 MIN 20.7 1.1 54.3 4.7 4.3 10.3 4.8 MAX 29.9 8.5 62.2 14.4 15.0 15.8 5.0 HCP MIN 0.2 0.0 9.7 44.8 3.6 17.4 8.6 MAX 8.6 0.0 10.2 59.3 5.7 31.2 9.4 In the table, the phase-distribution is wt% based on total weight of the composition, whereas the elements are listed based on their relative distribution in the respective phases.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
EP22202777.3A 2022-10-20 2022-10-20 Nickel-chrom-legierungen Pending EP4357471A1 (de)

Priority Applications (2)

Application Number Priority Date Filing Date Title
EP22202777.3A EP4357471A1 (de) 2022-10-20 2022-10-20 Nickel-chrom-legierungen
PCT/EP2023/079321 WO2024084057A2 (en) 2022-10-20 2023-10-20 Nickel-chrome alloys

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EP22202777.3A EP4357471A1 (de) 2022-10-20 2022-10-20 Nickel-chrom-legierungen

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3890816A (en) * 1973-09-26 1975-06-24 Gen Electric Elimination of carbide segregation to prior particle boundaries
DE19901170A1 (de) 1998-10-21 2000-04-27 Reiloy Metall Gmbh Verwendung einer Eisenbasishartlegierung
EP1052305A2 (de) * 1999-05-10 2000-11-15 Böhler Edelstahl GmbH & Co KG Metallischer Werkstoff mit hoher Härte, hohem Verschleisswiderstand und hoher Zähigkeit
JP2016056436A (ja) * 2014-09-12 2016-04-21 新日鐵住金株式会社 Ni基耐熱合金
CN106424714A (zh) * 2016-11-18 2017-02-22 中国矿业大学 一种复合wc合金粉末及其制备方法和用途
JP6609727B1 (ja) * 2018-03-28 2019-11-20 日鉄ステンレス株式会社 合金板及びその製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3890816A (en) * 1973-09-26 1975-06-24 Gen Electric Elimination of carbide segregation to prior particle boundaries
DE19901170A1 (de) 1998-10-21 2000-04-27 Reiloy Metall Gmbh Verwendung einer Eisenbasishartlegierung
EP1052305A2 (de) * 1999-05-10 2000-11-15 Böhler Edelstahl GmbH & Co KG Metallischer Werkstoff mit hoher Härte, hohem Verschleisswiderstand und hoher Zähigkeit
JP2016056436A (ja) * 2014-09-12 2016-04-21 新日鐵住金株式会社 Ni基耐熱合金
CN106424714A (zh) * 2016-11-18 2017-02-22 中国矿业大学 一种复合wc合金粉末及其制备方法和用途
JP6609727B1 (ja) * 2018-03-28 2019-11-20 日鉄ステンレス株式会社 合金板及びその製造方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
K. BOBZIN: "New Possibilities for Fe-based HVAF-sprayed coatings", 11. KOLLOQUIUM HVOF SPRAYING 2018, CONFERENCE PROCEEDINGS, pages 19 - 30

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