EP1520056B1 - Metal dur permettant de tailler la roche, le beton et l'asphalte - Google Patents

Metal dur permettant de tailler la roche, le beton et l'asphalte Download PDF

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Publication number
EP1520056B1
EP1520056B1 EP03763783A EP03763783A EP1520056B1 EP 1520056 B1 EP1520056 B1 EP 1520056B1 EP 03763783 A EP03763783 A EP 03763783A EP 03763783 A EP03763783 A EP 03763783A EP 1520056 B1 EP1520056 B1 EP 1520056B1
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Prior art keywords
hard metal
metal according
binder
nanoparticles
range
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EP03763783A
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German (de)
English (en)
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EP1520056A2 (fr
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Igor Konyashin
Bernd Ries
Roy Cooper
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Element Six Holding GmbH
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Barat Carbide Holding GmbH
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Priority claimed from DE10258537A external-priority patent/DE10258537B4/de
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    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F2005/001—Cutting tools, earth boring or grinding tool other than table ware
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles

Definitions

  • the invention relates to a hard metal for tools for the mechanical processing of particular rock, concrete and asphalt and a tool equipped with such a carbide.
  • tungsten carbide-cobalt hard metals For rock, concrete and asphalt cutting, coarse-grained tungsten carbide-cobalt hard metals (WC-Co hard metals) with a mean WC grain size of approx. 2 to 10 ⁇ m are used in practice.
  • the WC medium grain size in hard metals can be determined, for example, by the line cutting method.
  • WC hard metals mentioned here can have any desired combinations and ratios of tungsten and carbon (carbide).
  • the entirety of these combinations of tungsten carbide is abbreviated to WC in the following description as well as in the claims.
  • the coercitive field strength values of the hard metal indicate how thick the co-intermediate layers are.
  • the coercive force values of the coarse-grained hard metals are in a range up to 17.0 kA / m.
  • the carbon content of hard metals should be approximately in the middle of the two-phase field (without free carbon and ⁇ -phase) ( H. Suzuki, H. Kubota, "Plansee Reports Powder Metallurgy", 1966, Vol. 14, 2, pp. 96-109 ).
  • the best values of bending strength in combination with high hardness should be achievable.
  • the concentration of tungsten in the co-binder of the WC-Co hard metal depends on the carbon content. Thus, the tungsten concentration at low carbon content is much higher.
  • the W concentration or the carbon content in a WC-Co hard metal with a certain Co content can be defined by the value of the magnetic saturation.
  • the magnetic saturation of a hard metal is defined both as a magnetic moment per unit of weight ⁇ (magnetic moment / unit wt.) And as an inductance of saturation per unit weight 4 ⁇ (in English "saturation induction / unit wt.") (B. Roebuck. "Magnetic Moment (Saturation) Measurements on Hardmetals", Int. J. Refr. Met. Hard Mater., 14 (1996) 419).
  • the magnetic moment must be multiplied by 4 ⁇ to obtain the inductance of saturation, so that the magnetic moment ⁇ of pure Co is 16.1 ⁇ Tm 3 / kg and the inductance of the saturation 4 ⁇ of pure Co is 201, 9 ⁇ Tm 3 / kg ,
  • the EP 1 205 569 A2 and EP 1 043 415 A2 refer to carbides for metal cutting with low carbon content or low values of magnetic saturation. Both publications describe hard metals containing more than 1% by weight of cubic carbides (TaC, TiC and NbC). The use and said minimum amount of these cubic carbides is imperative for the application of hard metals for metal cutting tools.
  • cemented carbides for tools for the construction or mining industry must not contain such appreciable constituents of Ta, Ti or Nb, since their cubic carbides have a negative effect on the fracture toughness of the WC-Co hard metals.
  • the hard metals commonly used in mining are, without exception, tungsten carbide-cobalt alloys (H. Kolaska, "Pulvermetallurgie der Hartmetalle", Hagen, 1992, p.15 / 3).
  • the DE 198 10 533 A1 describes hard metals for milling titanium and titanium alloys with a Co-containing binder having relatively low levels of magnetic saturation. Here, however, there is no significant reinforcement of the binder.
  • the invention has for its object to provide a hard metal or carbide-tipped tool with improved properties and performance.
  • the WC medium grain size is preferably to be selected from a range of 0.2 ⁇ m to 20 ⁇ m, more preferably from a range of 2 ⁇ m to 20 ⁇ m, and particularly preferably from a range of 4 to 20 ⁇ m.
  • the condition of the binder plays a crucial role in the performance of coarse-grained hard metals.
  • the general view is that the WC or W concentration in the binder can not be higher than 20% by weight (about 9 atomic%) ( J. Willbrand, U. Wieland, "Techn.Mitt.Krupp.Forsch.-Ber.”, 1975, Vol. 33, 1, pp. 41-44 ), can be significantly strengthened in the carbide according to the invention by a high concentration of tungsten of 10 to 30 atomic% in the binder, the Co.
  • the largest value of the lattice constant of Co in WC-Co hard metals described in the literature is normally not higher than 0.357 nm (about 1% higher than the value of pure Co) ( H. Suzuki, H. Kubota, "Planseeberichte Pulvermetallurgie", 1966, Vol. 14, 2, pp. 96-109 ).
  • the lattice constant of the cobalt in the binder is greater than that of pure cobalt (0.3545 nm) by the higher concentration of tungsten over 1 to 5%.
  • the hard metal according to the invention can be further enhanced by nano-particles (particles finer than 100 nm) of tungsten and cobalt and / or carbon being embedded in the binder in the co-matrix.
  • nano-particles particles finer than 100 nm
  • the wear resistance and bending strength of the cemented carbide are substantially increased compared to conventional hard metals.
  • the bending strength of such hard metals is up to 30% higher than the conventional hard metals with similar WC grain size and the same Co content.
  • a cemented carbide according to the invention having at least 5% by volume of nanoparticles in the binder may preferably comprise up to 40% by weight of carbides, nitrides and / or carbonitrides of Ta, Nb, Ti, V, Cr, Mo, B, Zr and / or Hf included.
  • the nano-particles preferably furthermore contain Ni, Fe, Ta, Nb, Ti, V, Cr, Mo, Zr and / or Hf.
  • the nano-particles coherent with the cobalt matrix ensure stabilization of the binder and thus of those already described Improvements in the carbide properties and a tool provided with it.
  • the nano-particles have a hexagonal or cubic lattice structure, wherein the nano-particles are composed of one or more of the phases Co x W y C z with values X from 1 to 7, y is from 1 to 10, and Z from 0 to 4
  • the nano-particles may consist of a phase Co 2 W 4 C. It is also possible that the nano-particles consist of one or more intermetallic phases of tungsten and cobalt and thus contribute to a further improvement of the binder in the sense of the above object.
  • Reinforcing the binder can also have an effect if it has fcc-Co and / or hcp-Co in the form of a solid solution of W and / or C in Co.
  • the lattice constants of this solid solution are on the order of 1 to 5% greater than those of pure Co.
  • the binder may further contain up to 30% by weight of iron.
  • the hard metals according to the invention with a low carbon content or high concentration of W in the binder are also proportionally or all round toilet grains, which has a very positive effect on the life.
  • Round WC grains here are not only circular shapes, but even mostly irregular grain shapes with rounded corners, without sharp faceting.
  • fractions of up to 1.5% by weight each of Cr, No, V, Zr and / or Hf in the form of carbides and / or solid solutions in the binder lead to an improvement in the service life.
  • the high-W content carbides according to the invention in the binder can bring about a marked improvement in performance with the incorporation of coated diamond grains even in the group of the ultra-hard carbide materials and can be used successfully, since the combination of the high tungsten concentration in the binder at low magnetic saturation, a dissolution process of the coating Diamond grains significantly suppressed.
  • the hard metal 3 vol .-% to 60 vol .-% diamond grains having a coating of carbides, carbonitrides and / or nitrides of Ti, Ta, Nb, W, Co, Mo, V, Zr , Hf and / or Si.
  • a WC-Co cemented carbide was prepared with 6.5% by weight Co and low carbon content.
  • the coercitive field strength of this hard metal is 7.0 kA / m
  • the bending strength is 2400 MPa
  • TEM Transmission Electron Microscopy
  • Sample measured with EDX energy-dispersive X-ray microanalysis
  • the Co lattice constant was determined by TEM and X-ray studies.
  • the W concentration in the binder of the sample is 18 to 19 at.%
  • the binder contains nano-particles, which are shown in FIG.
  • the electron diffraction of the binder shows reflections of the tungsten-containing cubic cobalt matrix with fcc structure and the lattice constant of 0.366 nm as well as reflections of the intervening nano-particles, which are about 3 to 10 nm in size ( Figure 3).
  • the largest measurable D hkl value of the nanoparticles is 0.215 nm.
  • Mud-intensive asphalt was milled on average 20 cm above the concrete surface, with an average of 10 meters of feed per minute.
  • the milling cutter was half equipped with the chisels of the new carbide and the other half with those of conventional carbide. Results of the 1st field test: hard metal Chisel wear that made a turn, in mm Proportion of chisels that did not rotate (possible breaks) and wear, in mm Conventional 6.9 30% 8.6 New 3.4 6% 3.8
  • Fig. 4 shows the worn bits after the field test in comparison.
  • a WC-Co cemented carbide of 9.5% by weight Co and low carbon content was produced.
  • the coercive field strength is 6.1 kA / m
  • hardness HV30 990
  • flexural strength 2720 MPa.
  • the carbide contains round WC grains, co-binders and no ⁇ phase.
  • the TEM investigations of the new cemented carbide show that the W concentration in the binder is 19 to 21 atomic% and the binder contains nano-particles.
  • the lattice constant of fcc-Co in the binder is 0.368 nm.
  • Chisels with cutting elements made of the two hard metals were produced and tested in the laboratory for cutting abrasive concrete and granite.
  • the chisels were also tested in a coal mine when cutting high sandstone coal / sandstone. With the chisels with cutting elements made of the new carbide cutting performance of 700 m concrete could be achieved to wear of 1 mm, while in the chisels with conventional carbide with the same wear, the cutting performance was only 100 m.
  • the lifetime of the chisel in the granite cutting with the new carbide was about 2.5 times larger than that of the conventional hard metal chisel.
  • a WC-Co cemented carbide was prepared with 6.5% wt.% Co and low carbon content.
  • the coercitive field strength of this hard metal is 31.2 kA / m
  • the flexural strength is 2900 MPa
  • the fracture toughness K 1c 12.4 MPam 1/2 .
  • the W concentration in the binder of the sample is 17 to 18 at.%
  • the binder contains nano-particles embedded in fcc-Co.
  • the concentration of nano-particles in the binder was determined by the line-cut method.
  • the concentration of nano-particles is 7.0 ⁇ 0.5 vol.%.
  • the Dhkl value of the ordered phases is up to 0.215 nm ⁇ 0.007 nm.
  • the coarse-grained hard metals according to the invention have an improved combination of flexural strength, fracture toughness and wear resistance.
  • Tools with these hard metals have a very high performance in the field of rock and asphalt cutting and have a significantly extended service life as wearing parts.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Processing Of Stones Or Stones Resemblance Materials (AREA)
  • Powder Metallurgy (AREA)
  • Glass Compositions (AREA)

Claims (25)

  1. Métal dur en WC pour des outils destinés à l'usinage mécanique en particulier de roche, de béton et d'asphalte, avec 5 à 25% en poids de liant à base de Co ou de Co et de Ni, l'intensité du champ coercitif du métal dur étant d'au maximum 9,5 kA/m, le liant contenant jusqu'à 30% en poids de Fe et le métal dur présentant une saturation magnétique (σ ou 4πσ, à chaque fois en unités de microtesla multipliés par des mètres cubes par kilogramme) en fonction de la proportion de Co (X) en % en poids du métal dur dans une plage de σ = 0 , 11 ⁢ X à σ = 0 , 137 ⁢ X
    Figure imgb0005
    ou 4 ⁢ πσ = 0 , 44 ⁢ πX à 4 ⁢ πσ = 0 , 548 ⁢ πX .
    Figure imgb0006
  2. Métal dur selon la revendication 1, caractérisé en ce que son intensité du champ coercitif est d'au maximum 8,0 kA/m.
  3. Métal dur selon l'une quelconque des revendications 1 ou 2, caractérisé en ce que son intensité du champ coercitif est d'au maximum 7,2 kA/m.
  4. Métal dur selon l'une quelconque des revendications 1 à 3, caractérisé en ce que son intensité de champ coercitif se situe dans une plage de 1,6 kA/m à 6,4 kA/m.
  5. Métal dur selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le liant contient des nanoparticules, qui sont plus fines que 100 nm et qui sont constituées par une ou plusieurs des phases ordonnées CoxWyCz avec x = 1 à 7, y = 1 à 10 et z = 0 à 4.
  6. Métal dur selon l'une quelconque des revendications 1 à 5, caractérisé en ce que la taille moyenne de ses particules de WC se situe dans une plage de 0,2 µm à 20 µm.
  7. Métal dur selon l'une quelconque des revendications 1 à 6, caractérisé en ce que la taille moyenne de ses particules de WC se situe dans une plage de 2 µm à 20 µm.
  8. Métal dur selon l'une quelconque des revendications 1 à 7, caractérisé en ce que la taille moyenne de ses particules de WC se situe dans une plage de 4 µm à 20 µm.
  9. Métal dur selon l'une quelconque des revendications 1 à 8, caractérisé en ce qu'il contient au total jusqu'à 0,4% en poids de Ta, de Nb et/ou de Ti sous forme de carbures cubiques et/ou de solution solide dans le liant.
  10. Métal dur selon l'une quelconque des revendications 1 à 9, caractérisé en ce qu'il contient à chaque fois jusqu'à 1,5% en poids de Cr, de Mo, de V, de Zr et/ou de Hf sous forme de carbures et/ou de solutions solides dans le liant.
  11. Métal dur selon la revendication 5, caractérisé en ce que le liant contient au moins 5% en volume de nanoparticules, qui sont plus fines que 100 nm et qui sont constituées par une ou plusieurs des phases CoxWyCz avec x = 1 à 7, y = 1 à 10 et z = 0 à 4.
  12. Métal dur selon la revendication 11, caractérisé en ce qu'il contient jusqu'à 40% en poids de carbures, de nitrures et/ou de carbonitrures de Ta, Nb, Ti, V, Cr, Mo, B, Zr et/ou Hf.
  13. Métal dur selon la revendication 11 ou 12, caractérisé en ce que les nanoparticules contiennent Ni, Fe, Ta, Nb, Ti, V, Cr, Mo, Zr et/ou Hf.
  14. Métal dur selon l'une quelconque des revendications 5 à 13, caractérisé en ce que les nanoparticules sont cohérentes avec la matrice de cobalt.
  15. Métal dur selon l'une quelconque des revendications 5 à 14, caractérisé en ce que la valeur Dhkl la plus grande mesurable des phases ordonnées des nanoparticules est de 0,215 nm ± 0,007 nm.
  16. Métal dur selon l'une quelconque des revendications 5 à 15, caractérisé en ce qu'au moins des parties des nanoparticules présentent une structure de réseau hexagonale.
  17. Métal dur selon l'une quelconque des revendications 5 à 16, caractérisé en ce qu'au moins des parties des nanoparticules présentent une structure de réseau cubique.
  18. Métal dur selon l'une quelconque des revendications 5 à 17, caractérisé en ce que les nanoparticules sont constituées par une phase de Co2W4C.
  19. Métal dur selon l'une quelconque des revendications 5 à 18, caractérisé en ce que les nanoparticules sont constituées par une ou plusieurs phases intermétalliques de W et de Co.
  20. Métal dur selon l'une quelconque des revendications 1 à 19, caractérisé en ce que les particules de WC sont partiellement ou totalement rondes.
  21. Métal dur selon l'une quelconque des revendications 1 à 20, caractérisé en ce que la concentration en W dans le liant se situe dans une plage de 10 à 30% en atome.
  22. Métal dur selon l'une quelconque des revendications 1 à 21, caractérisé en ce qu'il contient 3 à 60% en volume de particules de diamant avec un revêtement de carbures, de carbonitrures et/ou de nitrures de Ti, Ta, Nb, W, Cr, Mo, V, Zr, Hf et/ou Si.
  23. Métal dur selon l'une quelconque des revendications 1 à 22, caractérisé en ce que le liant présente du fcc-Co et/ou du hcp-Co sous forme d'une solution solide de W et/ou C dans du Co.
  24. Métal dur selon la revendication 10 ou 23, caractérisé en ce que les constantes de réseau de la solution solide sont supérieures de 1% à 5% à celles du Co pur.
  25. Outil pour l'usinage mécanique, en particulier de roche, de béton et d'asphalte, avec au moins un élément de coupe, caractérisé en ce que l'élément de coupe est constitué par un métal dur selon l'une quelconque des revendications 1 à 24.
EP03763783A 2002-07-10 2003-07-10 Metal dur permettant de tailler la roche, le beton et l'asphalte Revoked EP1520056B1 (fr)

Applications Claiming Priority (7)

Application Number Priority Date Filing Date Title
DE10231303 2002-07-10
DE10231303 2002-07-10
DE10248898 2002-10-18
DE10248898 2002-10-18
DE10258537A DE10258537B4 (de) 2002-07-10 2002-12-14 Hartmetall für insbesondere Gestein-, Beton- und Asphaltschneiden
DE10258537 2002-12-14
PCT/EP2003/007462 WO2004007784A2 (fr) 2002-07-10 2003-07-10 Metal dur permettant de tailler la roche, le beton et l'asphalte

Publications (2)

Publication Number Publication Date
EP1520056A2 EP1520056A2 (fr) 2005-04-06
EP1520056B1 true EP1520056B1 (fr) 2008-01-30

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EP03763783A Revoked EP1520056B1 (fr) 2002-07-10 2003-07-10 Metal dur permettant de tailler la roche, le beton et l'asphalte

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US (1) US20060093859A1 (fr)
EP (1) EP1520056B1 (fr)
AT (1) ATE385262T1 (fr)
AU (1) AU2003250024A1 (fr)
DE (1) DE50309106D1 (fr)
ES (1) ES2300616T3 (fr)
WO (1) WO2004007784A2 (fr)

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Publication number Priority date Publication date Assignee Title
EP1971462B1 (fr) * 2005-11-14 2020-02-26 National University of Science and Technology MISiS Liant pour la fabrication d'outils diamantés
US7275566B2 (en) * 2006-02-27 2007-10-02 Weavexx Corporation Warped stitched papermaker's forming fabric with fewer effective top MD yarns than bottom MD yarns
DE102006018947A1 (de) * 2006-04-24 2007-10-25 Tutec Gmbh Verfahren zur Herstellung eines Hartmetallkörpers, Pulver zur Herstellung eines Hartmetalls und Hartmetallkörper
US9015051B2 (en) 2007-03-21 2015-04-21 Fraunhofer-Gesellschaft Zur Foerderung Der Angewandten Forschung E.V. Reconstruction of audio channels with direction parameters indicating direction of origin
GB0816837D0 (en) * 2008-09-15 2008-10-22 Element Six Holding Gmbh A Hard-Metal
DE112009002204T5 (de) * 2008-09-24 2011-07-07 Smith International, Inc., Tex. Neuartiges Hartmetall für eine Verwendung bei Erdöl- und Gasbohrungen
GB0903322D0 (en) * 2009-02-27 2009-04-22 Element Six Holding Gmbh Hard-metal substrate with graded microstructure
GB0915971D0 (en) * 2009-09-11 2009-10-28 Element Six Ltd Polycrysalline diamond composite compact elements, tools incorporating same, method for making same and method for using same
US20110061944A1 (en) * 2009-09-11 2011-03-17 Danny Eugene Scott Polycrystalline diamond composite compact
GB201105150D0 (en) 2011-03-28 2011-05-11 Element Six Holding Gmbh Cemented carbide material and tools comprising same
GB201209482D0 (en) * 2012-05-29 2012-07-11 Element Six Gmbh Polycrystalline material,bodies comprising same,tools comprising same and method for making same
DE102014204277B4 (de) 2014-03-07 2023-06-15 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. VERSCHLEIßFESTE WOLFRAMCARBID-KERAMIKEN UND VERFAHREN ZU IHRER HERSTELLUNG
AU2016236146B2 (en) * 2015-03-26 2020-09-03 Sandvik Intellectual Property Ab A rock drill button
AU2017333850B2 (en) * 2016-09-28 2021-05-20 Sandvik Intellectual Property Ab A rock drill insert
GB201713532D0 (en) * 2017-08-23 2017-10-04 Element Six Gmbh Cemented carbide material
JP7087596B2 (ja) * 2018-04-04 2022-06-21 住友電気工業株式会社 切削工具

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SE9004123D0 (sv) * 1990-12-21 1990-12-21 Sandvik Ab Diamantimpregnerat haardmaterial
US5992546A (en) * 1997-08-27 1999-11-30 Kennametal Inc. Rotary earth strata penetrating tool with a cermet insert having a co-ni-fe-binder

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WO2004007784A2 (fr) 2004-01-22
EP1520056A2 (fr) 2005-04-06
DE50309106D1 (de) 2008-03-20
ATE385262T1 (de) 2008-02-15
AU2003250024A1 (en) 2004-02-02
ES2300616T3 (es) 2008-06-16
WO2004007784A3 (fr) 2004-04-08
AU2003250024A8 (en) 2004-02-02
US20060093859A1 (en) 2006-05-04

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