EP4127258A1 - Matériau de métal dur à base de carbure de tungstène exempt de cobalt - Google Patents

Matériau de métal dur à base de carbure de tungstène exempt de cobalt

Info

Publication number
EP4127258A1
EP4127258A1 EP21711586.4A EP21711586A EP4127258A1 EP 4127258 A1 EP4127258 A1 EP 4127258A1 EP 21711586 A EP21711586 A EP 21711586A EP 4127258 A1 EP4127258 A1 EP 4127258A1
Authority
EP
European Patent Office
Prior art keywords
hard metal
metal material
tungsten carbide
content
cobalt
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.)
Pending
Application number
EP21711586.4A
Other languages
German (de)
English (en)
Inventor
Ralph USELDINGER
Claudio BERTALAN
Leonel Pereira Coelho
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.)
Ceratizit Luxembourg SARL
Original Assignee
Ceratizit Luxembourg SARL
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 Ceratizit Luxembourg SARL filed Critical Ceratizit Luxembourg SARL
Publication of EP4127258A1 publication Critical patent/EP4127258A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys 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
    • C22C29/08—Alloys 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 based on tungsten carbide
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys 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
    • C22C29/067—Alloys 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 comprising a particular metallic binder
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/44—Ferrous alloys, e.g. steel alloys containing chromium with nickel with molybdenum or tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
    • C22C38/46—Ferrous alloys, e.g. steel alloys containing chromium with nickel with vanadium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor

Definitions

  • the present invention relates to a cobalt-free tungsten carbide-based hardening material.
  • Tungsten carbide-based hard metal materials are composite materials in which hard material particles formed at least predominantly by tungsten carbide form the predominant part of the composite material and spaces between the hard material particles are filled by a ductile metallic binder.
  • Such hard metal materials have been used for many years due to their advantageous material properties, such as in particular high hardness in connection with good fracture toughness in a wide variety of areas, such as metal cutting, in wear parts, in woodworking tools, in forming tools, etc.
  • the material requirements when using such hard metal materials in the various areas of application are very different.
  • a high hardness is primarily decisive, for other applications, for example, good fracture toughness Ki c .
  • a high level of corrosion resistance and high flexural strength can also be important.
  • the ductile metallic binder is formed by cobalt or a cobalt-based alloy.
  • a basic alloy of an element is understood to mean that this element forms the largest component of the alloy.
  • hard metal materials with binders based on iron-nickel are also discussed, which basically have good mechanical properties at room temperature and therefore have the potential to replace conventional hard metal materials with cobalt-based binders.
  • these hard metal materials with iron-nickel-based binders show clear disadvantages compared to conventional hard metal materials with cobalt-based binders
  • the object of the present invention is to provide an improved cobalt-free tungsten carbide-based hard metal material which, in addition to high hardness, good fracture toughness Ki c and relatively high flexural strength BBF, also has good corrosion resistance and high heat resistance and is also reliable in one customary production plant for hard metal materials.
  • the object is achieved by a cobalt-free tungsten carbide-based hard metal material according to claim 1.
  • Advantageous further developments are given in the dependent claims.
  • the cobalt-free tungsten carbide-based hard metal material has: 70-97% by weight of hard material particles, which are at least predominantly formed by tungsten carbide, and 3-30% by weight of a metallic binder, which is an iron-nickel-based alloy, which is at least iron , Nickel and chromium.
  • the hard metal material has a ratio of Fe to (Ni + Fe) of 0.70 ⁇ Fe / (Fe + Ni) ⁇ 0.95 and a Cr content of
  • the hard metal material optionally has a Mo content in relation to (Fe + Ni + Cr) of 0% by weight ⁇ Mo / (Fe + Ni + Cr) ⁇ 10% by weight and optionally one
  • V content in relation to (Fe + Ni + Cr) of 0% by weight ⁇ V / (Fe + Ni + Cr) ⁇ 2% by weight; and unavoidable impurities up to a maximum of 1% by weight of the hard metal material.
  • the hard metal material would not have a satisfactory corrosion resistance and would have a pronounced plastic behavior at high temperatures, that is, a low creep resistance. To have a sufficient positive effect through the
  • the proportion of Cr / (Fe + Ni + Cr) of Cr to the total proportion of Fe, Ni and Cr is at least 0.5% by weight. It has been found that only such a minimum amount of Cr in the metallic binder leads to satisfactory corrosion resistance and sufficient improvement in creep resistance. However, the solubility of Cr in the metallic binder is limited. If Cr is added in excess of the solubility limit, Cr-containing precipitates occur in the form of mixed carbides, which have a very adverse effect on the mechanical properties of the hard metal material, in particular greatly reducing the flexural strength.
  • the solubility of Cr in the metallic binder is also dependent on the Fe content of the binder (or on the Fe / (Fe + Ni) ratio).
  • the higher the Fe content the lower the solubility of Cr in the metallic binder.
  • the carbon balance in the hard metal material in the powder metallurgical manufacturing process is also decisive.
  • the carbon balance in the hard metal work is also significantly reduced
  • Process atmosphere during manufacture influenced.
  • the process atmosphere cannot be set as precisely as desired, but in particular the carbon balance is subject to considerable tolerances.
  • the process window becomes the
  • the hard material particles are at least predominantly formed by tungsten carbide.
  • the hard material particles can preferably consist at least approximately only of tungsten carbide. However, small amounts of other hard material particles are also possible in addition to the tungsten carbide.
  • the hard metal material is preferably at least essentially free of silicon.
  • the silicon content is preferably ⁇ 0.08% by weight, more preferably ⁇ 0.05% by weight. Even more preferably, the hard metal material is completely free of silicon.
  • Fe / (Fe + Ni) ⁇ 0.90 applies.
  • high corrosion resistance can be achieved.
  • Ni ⁇ 0.90. In this case, good corrosion resistance and good creep resistance are achieved particularly reliably.
  • the content of the metallic binder is 5-25% by weight.
  • the hardness, the fracture toughness and the flexural strength can be set in a range that is advantageous for many different applications.
  • the Mo content Mo / (Fe + Ni + Cr) can preferably be> 0% by weight.
  • V content V / (Fe + Ni + Cr) ⁇ 1% by weight.
  • the metallic one formed by an iron-nickel base alloy Binder no pronounced grain growth of the tungsten carbide grains occurs during production, no significant vanadium contents are required. Furthermore, undesired embrittlement can be avoided by keeping the vanadium content as low as possible.
  • a good improvement in the corrosion resistance and creep resistance is achieved by a relatively high proportion of chromium dissolved in the iron-nickel base alloy.
  • Ratio Fe / (Fe + Ni) - the Cr content is chosen so that the following applies to the Cr content: Cr / (Fe + Ni + Cr) ⁇ 2.2% by weight, then the manufacturing process can be used for all iron contents can be carried out in a particularly reliable and stable manner with regard to tolerances.
  • the mean grain size of the tungsten carbide is 0.05-12 ⁇ m.
  • the properties of the cobalt-free tungsten carbide-based hard metal material can be specifically adapted to the respective application by adjusting the grain size. Since in the iron-nickel base alloy of the metallic binder, in contrast to cobalt-based binder systems, there is no strong grain growth of the tungsten carbide grains, even very small mean grain sizes can be set by selecting the tungsten carbide starting powder accordingly.
  • the mean grain size of the tungsten carbide is preferably 0.1-6 ⁇ m.
  • the hard metal material has a specific composition, which is described in more detail below.
  • the hard metal material consists predominantly of 70-97% by weight of hard material particles, which are at least predominantly formed by tungsten carbide.
  • the hard material particles can consist of tungsten carbide.
  • the hard metal material also has 3-30% by weight of a metallic binder.
  • the proportion of the metallic binder can preferably be 5 to 25% by weight of the hard metal material.
  • the metallic binder is an iron-nickel base alloy, so it has iron and nickel as the main components. In addition to iron and nickel, the metallic binder has at least chromium.
  • the hard metal material is cobalt-free, i.e. does not show any cobalt or at most traces of cobalt as unavoidable impurities.
  • the hard metal material can optionally also contain up to 10% by weight of molybdenum in relation to the total content of iron, nickel and chromium, ie Mo / (Fe + Ni + Cr) ⁇ 10% by weight, up to a maximum of 2% by weight.
  • the iron-nickel base alloy of the metallic binder has a higher proportion of iron than nickel.
  • the iron content is 70-95% by weight of the total iron and nickel content (Fe + Ni).
  • the iron content is preferably a maximum of 90% by weight of the total iron and nickel content, particularly preferably 75-90% by weight of the total iron and nickel content.
  • the chromium content of the hard metal material is at least 0.5% by weight of the total content (Fe + Ni + Cr) of iron, nickel and chromium.
  • the chromium content can preferably be at least 1.5% by weight of the total iron, nickel and chromium content, more preferably at least 2.0% by weight.
  • phase diagrams of FIGS. 1 to 3 the problems that arise for the industrial production of cobalt-free tungsten carbide-based hard metal material with a metallic binder formed by an iron-nickel-based alloy are explained in greater detail.
  • chromium is added.
  • the carbon content in% by weight is plotted on the horizontal axis.
  • Area 10 with a chromium content of Cr / (Fe + Ni + Cr) of 3.0% by weight is only very narrow.
  • the phase diagram in FIG. 3 at 1000 ° C. it only extends between carbon contents of approx. 5.565% by weight to approx. 5.605% by weight.
  • the risk of undesired mixed carbide or phase precipitations increases rapidly if the process atmosphere and thus the carbon balance cannot be kept within tight tolerances.
  • the cobalt-free tungsten carbide-based hard metal material can - depending on the intended area of application - have a mean grain size of
  • Tungsten carbide from 0.05 to 12 pm, preferably from 0.1 to 6 pm.
  • the mean grain size of the tungsten carbide grains in the hard metal material can be determined using the "equivalent circle diameter (ECD)” method from EBSD (electron backscatter diffraction) recordings. This method is for example in “Development of a quantitative method for grain size measurement using EBSD”; Master of Science Thesis, Sweden 2012, described by Frederik Josefsson.
  • the cobalt-free tungsten carbide-based hard metal material according to the embodiment was produced by powder metallurgy using WC powder with a particle size (FSSS, Fisher sieve sizes) of 0.6 ⁇ m or
  • Chromium can be added in the powder metallurgical production of the hard metal material, for example as pure metal or in the form of Cr3C2 or Cr2N powder.
  • Mo can preferably be added in the form of Mo2C powder, but it is also possible, for example, to add it as pure metal or as, for example, (W, Mo) C mixed carbide.
  • Fe, Ni, Cr can be added individually or in pre-alloyed form.
  • Cobalt-free tungsten carbide-based hard metal materials and comparative examples according to the invention were produced by the method described above.
  • the hard metal materials produced in the examples and comparative examples were each examined with regard to the mean grain size. Furthermore, the Vickers hardness HV10, the fracture toughness Kic and the bending strength BBF were determined on the hard metal materials produced.
  • the Vickers hardness HV10 was determined in accordance with ISO 3878: 1991 (“Hardmetals - Vickers hardness test”).
  • the fracture toughness Kic in MPa m 1/2 was determined according to ISO 28079: 2009 with an indentation load of 10 kgf (corresponding to 98.0665 N).
  • the bending strength BBF was determined according to the ISO 3327: 2009 standard using a test object with a cylindrical cross-section (shape C).
  • the conventional cobalt-containing hard metal materials of the types N and O which also contain chromium and vanadium in addition to cobalt, also show both good and good corrosion resistance
  • Creep resistance Due to their smaller mean grain size and their lower proportion of metallic binder, these grades N and O show a higher hardness and higher flexural strength, but on the other hand also a significantly reduced fracture toughness compared to grade A.
  • the L grade of a cobalt-containing tungsten carbide-based hard metal material which also serves as a comparative example and which has neither chromium nor vanadium in addition to cobalt, has very high fracture toughness due to its higher content of metallic binder, but the corrosion resistance and creep resistance are both poor .
  • the comparative examples of types B, C, D and E are each cobalt-free tungsten carbide-based hard metal materials in which the metallic binder is an iron-nickel-based alloy that has no chromium.
  • the types B, C, D and E differ in the iron-nickel ratio of the metallic binder.
  • the total iron and nickel content (Fe + Ni) was adjusted in such a way that the resulting volume of the binder is essentially that of a conventional cobalt-containing binder Tungsten carbide-based hard metal material with 10% by weight cobalt binder.
  • a comparison of the example of the type M with the comparative example of the cobalt-containing type L shows that acceptable physical properties can be achieved compared to conventional cobalt-containing hard metal materials even with higher proportions of the metallic binder in the hard metal material.
  • Grain size of the tungsten carbide grains achieved an acceptable corrosion resistance and an acceptable creep resistance. Due to the smaller mean grain size and the lower proportion of the metallic binder, a higher hardness is achieved on the one hand and an increased flexural strength is achieved due to the smaller mean grain size, but on the other hand the fracture toughness Kic decreases as expected. Overall, however, the physical properties achieved are quite acceptable compared to conventional cobalt-containing tungsten carbide-based hard metal materials of the types N and O.

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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)
  • Cutting Tools, Boring Holders, And Turrets (AREA)

Abstract

L'invention concerne un matériau de métal dur à base de carbure de tungstène exempt de cobalt comprenant de 70 à 97 % en poids de particules de matériau dur qui sont au moins majoritairement formées par du carbure de tungstène et de 3 à 30 % en poids d'un liant métallique qui est un alliage à base de fer-nickel comprenant au moins du fer, du nickel et du chrome avec un rapport de Fe à (Ni + Fe) de 0,70 ≤ Fe / (Fe + Ni) ≤ 0,95 ; une teneur en Cr de 0,5 % en poids ≤ Cr / (Fe + Ni + Cr) et (i) pour la plage 0,7 ≤ Fe / (Fe + Ni) ≤ 0,83 : Cr / (Fe + Ni + Cr) ≤ (-0,625 * (Fe / (Fe + Ni)) + 3,2688) % en poids ; (ii) pour la plage 0,83 ≤ Fe / (Fe + Ni) ≤ 0,85 : Cr / (Fe + Ni + Cr) ≤ (-27,5 * (Fe / (Fe + Ni)) + 25,575) % en poids et (iii) pour la plage 0,85 ≤ Fe / (Fe + Ni) ≤ 0,95 : Cr / (Fe + Ni + Cr) ≤ 2,2 % en poids ; éventuellement avec une teneur en Mo par rapport à (Fe + Ni + Cr) de 0 % en poids ≤ Mo / (Fe + Ni + Cr) ≤ 10 % en poids ; éventuellement avec une teneur en V par rapport à (Fe + Ni + Cr) de 0 % en poids ≤ V / (Fe + Ni + Cr) ≤ 2 % en poids ; et les impuretés inévitables jusqu'à une proportion totale inférieure ou égale à 1 % en poids du matériau de métal dur.
EP21711586.4A 2020-03-26 2021-03-17 Matériau de métal dur à base de carbure de tungstène exempt de cobalt Pending EP4127258A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP20165742.6A EP3885459A1 (fr) 2020-03-26 2020-03-26 Matériau métallique dur à base de carbure de tungstène exempt de cobalt
PCT/EP2021/056762 WO2021191009A1 (fr) 2020-03-26 2021-03-17 Matériau de métal dur à base de carbure de tungstène exempt de cobalt

Publications (1)

Publication Number Publication Date
EP4127258A1 true EP4127258A1 (fr) 2023-02-08

Family

ID=70008405

Family Applications (2)

Application Number Title Priority Date Filing Date
EP20165742.6A Withdrawn EP3885459A1 (fr) 2020-03-26 2020-03-26 Matériau métallique dur à base de carbure de tungstène exempt de cobalt
EP21711586.4A Pending EP4127258A1 (fr) 2020-03-26 2021-03-17 Matériau de métal dur à base de carbure de tungstène exempt de cobalt

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP20165742.6A Withdrawn EP3885459A1 (fr) 2020-03-26 2020-03-26 Matériau métallique dur à base de carbure de tungstène exempt de cobalt

Country Status (5)

Country Link
US (1) US20230151461A1 (fr)
EP (2) EP3885459A1 (fr)
JP (1) JP7490075B2 (fr)
CN (1) CN115349023B (fr)
WO (1) WO2021191009A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB202204522D0 (en) * 2022-03-30 2022-05-11 Element Six Gmbh Cemented carbide material
DE102023135181A1 (de) 2022-12-15 2024-06-20 Hochschule Aalen, Körperschaft des öffentlichen Rechts Hartmetall
EP4389923A1 (fr) * 2022-12-20 2024-06-26 AB Sandvik Coromant Outil de coupe en carbure cémenté

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001081526A (ja) 1999-09-13 2001-03-27 Kohan Kogyo Kk 鉄基超硬合金およびその製造方法
US7163657B2 (en) * 2003-12-03 2007-01-16 Kennametal Inc. Cemented carbide body containing zirconium and niobium and method of making the same
CN101560623B (zh) * 2009-05-22 2011-07-20 华南理工大学 一种WC-增韧增强Ni3Al硬质合金及其制备方法
WO2018025848A1 (fr) 2016-08-01 2018-02-08 日立金属株式会社 Carbure cimenté, son procédé de fabrication et rouleau de laminoir
US11434549B2 (en) * 2016-11-10 2022-09-06 The United States Of America As Represented By The Secretary Of The Army Cemented carbide containing tungsten carbide and finegrained iron alloy binder
US20200024702A1 (en) * 2017-11-09 2020-01-23 U.S. Army Research Laboratory Attn: Rdrl-Loc-I Cemented carbide containing tungsten carbide and iron alloy binder

Also Published As

Publication number Publication date
WO2021191009A1 (fr) 2021-09-30
CN115349023A (zh) 2022-11-15
CN115349023B (zh) 2024-06-04
JP2023518477A (ja) 2023-05-01
US20230151461A1 (en) 2023-05-18
EP3885459A1 (fr) 2021-09-29
JP7490075B2 (ja) 2024-05-24

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