EP4041927A1 - Hard metals and method for producing same - Google Patents

Hard metals and method for producing same

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Publication number
EP4041927A1
EP4041927A1 EP20786283.0A EP20786283A EP4041927A1 EP 4041927 A1 EP4041927 A1 EP 4041927A1 EP 20786283 A EP20786283 A EP 20786283A EP 4041927 A1 EP4041927 A1 EP 4041927A1
Authority
EP
European Patent Office
Prior art keywords
metals
hard
heh
subgroup
pse
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
EP20786283.0A
Other languages
German (de)
French (fr)
Inventor
Johannes Pötschke
Mathias Herrmann
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.)
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Forderung der Angewandten Forschung eV
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Publication of EP4041927A1 publication Critical patent/EP4041927A1/en
Pending legal-status Critical Current

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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
    • C22C29/005—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
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • B33Y70/10—Composites of different types of material, e.g. mixtures of ceramics and polymers or mixtures of metals and biomaterials
    • 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
    • C22C1/053—Making 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
    • 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
    • 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
    • C22C29/04—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 carbonitrides
    • 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
    • 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
    • C22C29/12—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on oxides
    • 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
    • C22C29/16—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on nitrides
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • 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
    • B22F10/00—Additive manufacturing of workpieces or articles from metallic powder
    • B22F10/20—Direct sintering or melting
    • B22F10/25—Direct deposition of metal particles, e.g. direct metal deposition [DMD] or laser engineered net shaping [LENS]
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/105—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding
    • B22F2003/1052—Sintering only by using electric current other than for infrared radiant energy, laser radiation or plasma ; by ultrasonic bonding assisted by energy absorption enhanced by the coating or powder
    • 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
    • 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
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/02—Compacting only
    • B22F3/04—Compacting only by applying fluid pressure, e.g. by cold isostatic pressing [CIP]
    • B22F3/045—Semi-isostatic pressure
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/12—Both compacting and sintering
    • B22F3/14—Both compacting and sintering simultaneously
    • B22F3/15—Hot isostatic pressing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y10/00—Processes of additive manufacturing
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency

Definitions

  • the invention relates to the fields of hard metal materials and ceramic and / or powder metallurgical process engineering and relates to hard metals such as those used, for example, as cutting materials for tools such as turning chisels, drills and milling tools, and as wear-resistant matrices e.g. B. can be used in forming or punching tools, as well as a method for their production.
  • Hard metals are metal matrix composites in which hard materials, which are present as small particles, are held together by a metal matrix. As a result, hard metals are a little less hard than pure hard materials, but much tougher. On the other hand, they are harder than pure metals, alloys and hardened steel, but more fragile (COMPREHENSIVE HARD MATERIALS, ISBN: 9780080965284)
  • hard metals always have metal-forming carbides (hard material) and in particular tungsten carbide-cobalt hard metals (WC-Co) are known as standard types that are of the greatest importance in terms of quantity.
  • WC-Co tungsten carbide-cobalt hard metals
  • they contain no or only small amounts ( ⁇ 1.8% by mass) of other carbides, such as vanadium carbide (VC), chromium carbide (Cr2C3), titanium carbide (TiC), molybdenum carbide (M02C) and tantalum-niobium carbide (Ta, Nb) C.
  • VC vanadium carbide
  • Cr2C3 chromium carbide
  • TiC titanium carbide
  • M02C molybdenum carbide
  • Ta, Nb tantalum-niobium carbide
  • cermet describes all types of hard materials, especially in the Anglo-American language. This is why hard metals, in particular tungsten carbide-free hard metal cutting materials, are cermets, although there are differences in the manufacturing process, in the mechanical behavior and in the interactions between the composite components.
  • the ceramic hard materials of cermets are often titanium carbide (TiC) and titanium carbonitride (TiCN), while nickel, cobalt, iron and others are used as metallic components. Furthermore, other carbides such as molybdenum carbide (M02C), tungsten carbide (WC) or chromium carbide (Cr3C2) are often added to improve the wetting during sintering and the mechanical and thermal properties.
  • the cermets are usually built up in a core-shell structure, the core always consisting of a single phase of a metal carbide, metal nitride or metal carbonitride and the shell also containing the other dissolved carbides.
  • High Entropy Alloys under development. (Lou: Journals of Alloys and Compounds; DOI: 10.1016 / j.jallcom.2019.03.328). Such special metallic binder alloys (High Entropy Alloys (HEA)) are not the subject of the present invention.
  • hard metal bodies which in the green state contain the hard metal starting powder in addition to organic binders, by means of pressing processes, extrusion, MIM / CIM or the 3D printing of green bodies and the subsequent sintering is known from the prior art.
  • hard metal components with different compositions can be produced.
  • the structure formation in the production of hard metals for example from WC-Co, the conventional production ideally results in a hard metal structure which consists of WC grains in a cobalt-rich matrix with dissolved tungsten and carbon.
  • Hard materials and hard metals have been known for a long time. According to Kiefer, R. et al: Hartstoffe und Hartmetalle, Vienna, Springer-Verlag, 1953, p. 196ff, numerous carbide multi-material systems are known as hard materials, including ternary and complex systems. "The alloying possibilities for hard carbides in triple and multiple systems are extraordinarily numerous.” “In general, one can again differentiate between two groups of alloys which are of technical interest. You can combine the carbides of the 4th and 5th group. Since these carbides are all isotypic, complete miscibility can also be expected in three and multi-component alloys, with the exception of systems with a high ZrC content. "
  • HEC high-entropy carbides
  • the particle size of the starting powder in particular is important for the homogeneous distribution of the individual elements in the HEC, whereas when using finer starting powders, the relative density decreases.
  • the materials examined showed an increased hardness.
  • the object of the present invention is to specify hard metals that have further improved mechanical properties and contain a new concept for the structural composition of the hard metals, as well as to specify a simple and inexpensive method for their production.
  • 50-100% by volume, advantageously 60-99% by volume, still advantageously 80-98% by volume, of the hard materials are an HEH composed of at least four metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of a solid solution of carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides.
  • hard materials in the hard metal from one, two or three metals of the 4th and / or 5th and / or 6th subgroup of the periodic table of the elements (PSE) composed in the form of a solid solution of carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides of the metals.
  • the hard materials are also advantageously composed of carbides or nitrides of the metals of the 4th and / or 5th and / or 6th subgroup of the PSE.
  • each proportion of a metal differs by a maximum of 20 at.% From the proportion which results from the same proportions for all metals in n metals.
  • the hard material HEH consists of five, six, seven or more metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of a solid solution of carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides is composed.
  • Metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of carbides, nitrides, carbonitrides and / or oxycarbonitrides are each essentially the same size.
  • Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W are present as metals of the hard materials.
  • the hard metals contain 5 to 32% by volume of binder metal, based on the hard metal.
  • PSE Periodic Table of the Elements
  • components are formed from the mixture with organic binders via a molding process, the organic binders are removed and the components are sintered.
  • the shaping is advantageously realized by means of pressing, extrusion, injection molding, CIP (Cold Isostatic Pressing) and / or by means of additive shaping.
  • the sintering is also advantageously carried out without pressure or with pressure support by means of sintering isostatic pressing, isostatic pressing (FIIP), industrial pressing or SPS.
  • FIIP isostatic pressing
  • SPS industrial pressing
  • At least five or six or seven or more powders of metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of carbides, nitrides, carbonitrides and / or oxycarbonitrides are mixed and the mixture is in-situ synthesized during sintering with binding metals to hard metals containing FHEFH.
  • hard metals which consist at least of hard materials in particle form and a binding metal arranged in between.
  • These hard metals contain at least the new hard material in particle form (High Entropy Hard Material - HEH) with a new structural composition and the binding metal.
  • binding metals known for hard metals are present as binding metals in the proportions known for hard metals of 0.1 to a maximum of 40% by volume, based on the hard metal.
  • the new high-entropy hard material HEH in the hard metal according to the invention which makes up at least 50% by volume of all hard materials, consists of at least four metals (Me) of the 4th and / or 5th and / or 6th Subgroup of the Periodic Table of the Elements (PSE) is composed in the form of a solid solution of carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides of the metals.
  • a solid solution is the name for homogeneous solids that consist of more than just one element or compound. There are several Types of atoms arranged randomly on a crystallographic position in the crystal lattice. As a result, the crystal structure of the phase is retained over a more or less large concentration range.
  • Such solid solutions are, for example, the transition metal carbides with a cubic NaCl structure. Different metals (Ti, Zr; V,.) Can take the position of the cation in the structure in a statistically distributed manner and carbon the position of the anion.
  • a solid solution is also present if the position of the anion is occupied by different amounts of carbon or by carbon, nitrogen or oxygen (even if the compound contains only one metal, for example Ti).
  • Such a statistical distribution of the respective atoms is only possible within certain limits, since it can be energetically more favorable if, with certain ratios of the atoms, the transition from the statistical distribution to an ordered arrangement of the atoms takes place, i.e. a new phase is eliminated, or the generation of superstructures takes place.
  • the size of the homogeneity areas of the solid phases increases with increasing similarity of the atoms or with the number of different types of atoms.
  • each of the metals should have a proportion of less than 70 at.%, better of ⁇ 60 at.%. It is therefore desired according to the invention that the proportions / concentrations of the individual metals are essentially the same, but deviations are possible.
  • the 50-0% by volume, advantageously 1 to 20% by volume, of further hard materials in the hard metal according to the invention can be composed of one, two or three metals of the 4th and / or 5th and / or 6th subgroup of the periodic table of the elements (PSE) in the form of a solid solution of carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides of the metals.
  • PSE periodic table of the elements
  • 50-100% by volume, advantageously 60-99% by volume, still advantageously 80-98% by volume, of the hard materials are an HEH composed of at least four metals of the 4th and / or 5th and / or 6th subgroup composed of the PSE in the form of a solid solution of carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides of the metals.
  • the hard material HEH is also advantageously in the hard metal according to the invention from five, six, seven or more metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of a solid solution of carbides, nitrides, carbonitrides, oxycarbides and / or Oxycarbonitrides composed of metals before.
  • the hard material also advantageously has Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W as metals of the hard materials.
  • the respective proportion of the metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the HEH containing at least four metals is essentially the same or the proportion of one or more of these metals deviates by a maximum of 20 atoms. % of it.
  • each proportion of a metal differs by a maximum of 20 at.% From the proportion which results from the same proportions for all metals in n metals.
  • the proportion of at least four metals of the at least four metals of the PSE in the form of a solid solution of carbides, nitrides, carbonitrides and / or oxycarbonitrides in the HEH consists of at least four metals of the 4th and / or 5th and / or 6th subgroup 4th and / or 5th and / or 6th subgroup of the PSE in the form of carbides, nitrides, carbonitrides and / or oxycarbonitrides is each the same size.
  • these different proportions mean that the proportion of all metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of carbides, nitrides, carbonitrides and / or oxycarbonitrides in the HEH is essentially the same.
  • Substantially equal proportions of metals in the HEH should, according to the invention, be those proportions which have slight fluctuations due to manufacturing-related and technically common deviations around the value of the same proportions.
  • the proportion of each of the metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of carbides, nitrides, carbonitrides and / or oxycarbonitrides are in each case 25%, with five metals in each case 20%.
  • the proportion of a metal can be a maximum of 20 at .-% from the same proportion of the four metals differ, i.e. 20 at .-% different from the proportion of 25% in HEH.
  • the proportion of at least four metals of the at least four metals of the PSE in the form of a solid solution of carbides, nitrides, carbonitrides and / or oxycarbonitrides in the HEH from at least four metals of the 4th and / or 5th and / or 6th subgroup 4th and / or 5th and / or 6th subgroup of the PSE in the form of carbides, nitrides, carbonitrides and / or oxycarbonitrides is each the same size.
  • the HEH have a single-phase structure and there is no or only very limited dissolution of the high entropy hard materials into the individual carbides, nitrides or carbonitrides and the high entropy hard materials in their solid solution even in the presence of different binding metals remain.
  • the solution according to the invention thus differs from the prior art at least in that, according to the invention, there is always an HEH of at least four metals in the hard material particles or hard material granules, and / or that the at least four metals are present in one phase in all HEH hard material particles or HEH hard material granules, and / or that the hard metals are also realized with metals in the form of a solid solution of nitrides, carbonitrides and / or oxycarbonitrides, and / or that in the case of a structure as a core-shell structure of the hard material particles or hard material granules in the core only the HEH according to the invention of at least four Metals are present in the form of a solid solution of carbides, nitrides, carbonitrides and / or oxycarbonitrides.
  • the solution according to the invention with regard to hard metals can also be described in terms of a formula, with:
  • PSE Periodic Table of the Elements
  • the HEH powder can also be produced from the reduction of oxides of metals of the 4th and / or 5th and / or 6th subgroup of the Periodic Table of the Elements (PSE) to metals and the subsequent co-carburization and / or nitration or can be synthesized by direct carburization and / or nitration of the mixed oxides.
  • PSE Periodic Table of the Elements
  • hard material powders or hard material granules are added to the HEH powders or the sintered granules of the HEH.
  • These hard materials are then mixed with powdery binding metal in a proportion of 0.1-40% by volume, based on the hard metal, and then sintered to either hard metal powder or hard metal granules.
  • the HEH-containing hard metals can also arise through an in-situ formation of the HEH, in which at least four powders of metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of carbides and / or nitrides mixed and the mixture is synthesized in-situ during sintering with binding metals to form HEH-containing hard metals.
  • a maximum of 50% by volume of other hard material powders can also be added to HEH powder, and these hard materials are mixed with powdered binding metal in a proportion of 0.1 to 40% by volume, based on the hard metal, and then partially or fully sintered Carbide granules are sintered.
  • the mixture of hard metal powder or hard metal granules can also be processed into components by means of shaping and then sintered.
  • the molding processes used can advantageously be pressing, extrusion, injection molding, CIP (Cold Isostatic Pressing) and / or additive molding processes, as well as thermal spraying for the production of surface structures.
  • binders are advantageously added to the mixture and components are formed therefrom. The binders are then removed and the components can be sintered.
  • the sintering can advantageously take place without pressure or with pressure support by means of sintering hot isostatic pressing, hot isostatic pressing (HIP), hot pressing or PLC.
  • At least five or six or seven or more powders of metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides are mixed and the HEH are synthesized in situ during sintering with binder metals.
  • the HEH from metals of the 4th and / or 5th and / or 6th subgroup of the PSE are mixed in the form of a solid solution of carbides and / or nitrides.
  • the HEH phase is surprisingly stable, even if there is a clear dissolution of the HEH.
  • the amounts of WC found locally in the structure are due to the previous grinding of the HEH and can be avoided with further improved processing.
  • a single-phase high entropy hard material HEH of the composition (Tao, 2iNbo , 2iTio , 2iVo , produced by sintering at 1950 ° C in a vacuum and subsequent comminution in a ball mill from 20 at .-% TaC, NbC, TiC, VC and WC) i 9Wo , i 8) C was ground with 14 vol .-% cobalt (HalfMicron, from UmiCore) in a ball mill in a solvent (heptane) and a powder-to-grinding ball ratio of 1:20 for 48 h. After drying, bending rods with a geometry of 45 ⁇ 5 ⁇ 6 mm 3 were pressed from the powder by means of uniaxial pressing at 200 MPa.
  • the samples were sintered at 1280 ° C. for 45 min in a SinterHIP furnace with a HIP pressure of 10 MPa.
  • the test specimens were found to be completely tight under the light microscope.
  • the porosity according to ISO 4505 corresponded to> A02, B00, C00.
  • the Vickers hardness was determined to be 1620 HV10 and the fracture toughness (Kic) was calculated to be 8.5 MPa * m 1/2 by measuring the crack lengths and using the Shetty formula (Shetty 1985 - Indentation fracture of WC-Co cermets).
  • the structure consisted of the HEC hard material phase, another WC hard material phase with ⁇ 5% by mass and the cobalt binder.
  • the proportions of the HEH-containing hard metal determined by means of quantitative X-ray analysis (Rietveld analysis) and the lattice parameters determined for the HEH are given in Table 2.
  • the milled powder mixture described in Example 1 from the HEH hard material with the composition (Tao , 2Nbo , 2Tio , 2Vo , 2Wo , 2) C was added with 16% by volume of cobalt directly by means of a pressure-assisted sintering unit (SPS / FAST from FCT Syteme) A temperature of 1200 ° C and a holding time of 3 min to form disks with a diameter of 20 mm and a height of 6 mm and sintered.
  • SPS / FAST pressure-assisted sintering unit
  • the test specimens were found to be completely tight under the light microscope.
  • the porosity according to ISO 4505 corresponded to> A02, B00, C00.
  • the Vickers hardness was determined to be 1540 HV10 and the fracture toughness (Kic) was determined by measuring the crack lengths and using Shetty's formula (Shetty 1985 - Indentation fracture of WC-Co cermets, see reference above) calculated to be 10.1 MPa * m 1/2.
  • the structure consisted of the HEC hard material phase, another WC hard material phase with ⁇ 5% by mass and the cobalt binder enriched with W.
  • a single-phase high entropy hard material of the composition (Hfo, 2Tao , 2Zro , 2Nbo , produced by means of sintering at 1980 ° C in a vacuum and subsequent comminution in a ball mill from 20 at .-% each of HfC, TaC, ZrC, NbC and VC) 2Vo , 2) C was with 16 vol .-% cobalt (HalfMicron, from UmiCore) in a ball mill in heptane and a powder to grinding ball ratio of 1:20 for 48 h ground. After drying, the powder was pressed into flexural rods with a geometry of 45 x 5 x 6 mm 3 samples by means of uniaxial pressing at 200 MPa.
  • the samples were sintered at 1280 ° C. for 45 min in a SinterHIP furnace with a HIP pressure of 10 MPa.
  • the test specimens were found to be completely tight under the light microscope.
  • the porosity according to ISO 4505 corresponded to> A02, B00, C00.
  • the Vickers hardness was determined to be 1520 HV10 and the fracture toughness (Kic) was determined to be 8.9 MPa * m 1 by measuring the crack lengths and using the Shetty formula (Shetty 1985 - Indentation fracture of WC-Co cermets, see reference above) / 2 calculated.
  • the structure consisted of the HEC hard material phase, another (Hf, Ta) C hard material phase with ⁇ 2% by mass and the cobalt binder.
  • the test specimens were found to be completely tight under the light microscope.
  • the porosity according to ISO 4505 corresponded to> A04, B00, C00.
  • the Vickers hardness was determined to be 1720 HV10 and the fracture toughness (Kic) was determined to be 7.7 MPa * m 1 by measuring the crack lengths and using the Shetty formula (Shetty 1985 - Indentation fracture of WC-Co cermets, see reference above) / 2 calculated.
  • a single-phase high entropy hard material HEH of the composition (Hfo, 25Tao, produced by means of sintering at 2000 ° C in a vacuum and subsequent comminution in a ball mill from 25 at .-% H ⁇ Oo , q Oo , i, TaC, ZrC, and NbC) 25Zro, 25Nbo, 25) Co, 9750o, o25 was mixed with 16% by volume cobalt (HalfMicron, from UmiCore) in a ball mill in a solvent (heptane) and a powder-to-grinding ball ratio of 1:20 for 48 h ground.
  • bending rods with a geometry of 45 ⁇ 5 ⁇ 6 mm 3 were pressed from the powder by means of uniaxial pressing at 200 MPa.
  • the samples were sintered at 1280 ° C. for 60 min in a SinterHIP furnace with a HIP pressure of 10 MPa.
  • the test specimens were found to be completely tight under the light microscope.
  • the porosity according to ISO 4505 corresponded to> A02, B00, C00.
  • the Vickers hardness was determined to be 1420 HV10 and the fracture toughness (Kic) was calculated to be 8.0 MPa * m 1/2 using the Shetty's formula (Shetty 1985 - Indentation fracture of WC-Co cermets).
  • the structure consisted of the HEC hard material phase, further hard material phases containing Hf-Ta (in the form of an oxycarbide) with ⁇ 5% by mass and the cobalt binder.

Abstract

The invention relates to the field of hard metal materials and to hard metals, such as can be used, for example, as a cutting material for tools. The aim of the present invention is to provide hard metals which include a novel concept for the structural composition of the hard metals. The aim is achieved by hard metals which consist at least of hard materials in particulate form and binder metal arranged therebetween, wherein a high entropy hard material (HEH) is composed of at least four metals (Me) of the 4th and/or 5th and/or 6th subgroup of the periodic table of elements in the form of a solid solution of carbides, nitrides, carbonitrides, oxycarbides and/or oxycarbonitrides of the metals, wherein the respective fractions of the metals in the HEH are essentially the same.

Description

Hartmetalle und Verfahren zu ihrer Herstellung Hard metals and processes for their manufacture
Die Erfindung bezieht sich auf die Gebiete der Hartmetallwerkstoffe und der keramischen und/oder pulvermetallurgischen Verfahrenstechnik und betrifft Hartmetalle, wie sie beispielsweise als Schneidstoff für Werkzeuge, wie Drehmeißel, Bohrer und Fräswerkzeuge, und als verschleißfeste Matrizen z. B. in Umform- oder Stanzwerkzeugen verwendet werden können, sowie ein Verfahren zu ihrer Herstellung. The invention relates to the fields of hard metal materials and ceramic and / or powder metallurgical process engineering and relates to hard metals such as those used, for example, as cutting materials for tools such as turning chisels, drills and milling tools, and as wear-resistant matrices e.g. B. can be used in forming or punching tools, as well as a method for their production.
Hartmetalle sind Metallmatrix-Verbundwerkstoffe, bei denen Hartstoffe, die als kleine Partikel vorliegen, durch eine Matrix aus Metall zusammengehalten werden. Hartmetalle sind dadurch etwas weniger hart als die reinen Hartstoffe, aber deutlich zäher. Andererseits sind sie härter als reine Metalle, Legierungen und gehärteter Stahl, dafür aber bruchempfindlicher (COMPREHENSIVE HARD MATERIALS, ISBN: 9780080965284) Hard metals are metal matrix composites in which hard materials, which are present as small particles, are held together by a metal matrix. As a result, hard metals are a little less hard than pure hard materials, but much tougher. On the other hand, they are harder than pure metals, alloys and hardened steel, but more fragile (COMPREHENSIVE HARD MATERIALS, ISBN: 9780080965284)
Alle Hartmetalle weisen immer metallbildende Carbide (Hartstoff) auf und insbesondere Wolframcarbid-Cobalt-Hartmetalle (WC-Co) sind als Standardsorten bekannt, die mengenmäßig die größte Bedeutung haben. Sie enthalten neben WC keine oder nur geringe Mengen (< 1 ,8 Ma-%) anderer Carbide, wie Vanadiumcarbid (VC), Chromcarbid (Cr2C3), Titancarbid (TiC), Molybdäncarbid (M02C) und Tantal-Niob-Carbid (Ta,Nb)C. Weiterhin gibt es auch Hartmetalle mit weiteren Metallcarbiden von 5 bis zu 25 Ma-% die sich vor allem durch eine angepasste Wärmeleitfähigkeit auszeichnen. All hard metals always have metal-forming carbides (hard material) and in particular tungsten carbide-cobalt hard metals (WC-Co) are known as standard types that are of the greatest importance in terms of quantity. In addition to WC, they contain no or only small amounts (<1.8% by mass) of other carbides, such as vanadium carbide (VC), chromium carbide (Cr2C3), titanium carbide (TiC), molybdenum carbide (M02C) and tantalum-niobium carbide (Ta, Nb) C. Furthermore, there are also hard metals with other metal carbides of 5 to 25% by mass which are primarily characterized by an adapted thermal conductivity.
Der Begriff Cermet bezeichnet vor allem im anglo-amerikanischen Sprachgebrauch alle Arten von Hartstoffen. Deswegen zählen auch die Hartmetalle, insbesondere wolframcarbid-freie Hartmetall-Schneidstoffe, zu den Cermets, obwohl es Unterschiede im Herstellungsverfahren, im mechanischen Verhalten sowie in den Wechselwirkungen zwischen den Verbundkomponenten gibt. The term cermet describes all types of hard materials, especially in the Anglo-American language. This is why hard metals, in particular tungsten carbide-free hard metal cutting materials, are cermets, although there are differences in the manufacturing process, in the mechanical behavior and in the interactions between the composite components.
Die keramischen Hartstoffe von Cermets sind oft Titancarbid (TiC) und Titancarbonitrid (TiCN), während als metallische Komponenten Nickel, Cobalt, Eisen und andere eingesetzt werden. Weiterhin werden oft weitere Carbide wie z.B. Molybdäncarbid (M02C), Wolframcarbid (WC) oder Chromcarbid (Cr3C2) zugegeben um die Benetzung beim Sintern und die mechanischen als auch thermischen Eigenschaften zu verbessern. The ceramic hard materials of cermets are often titanium carbide (TiC) and titanium carbonitride (TiCN), while nickel, cobalt, iron and others are used as metallic components. Furthermore, other carbides such as molybdenum carbide (M02C), tungsten carbide (WC) or chromium carbide (Cr3C2) are often added to improve the wetting during sintering and the mechanical and thermal properties.
Dabei sind die Cermets meistens in einer Kern-Hülle-Struktur aufgebaut, wobei der Kern immer einphasig aus einem Metallcarbid, Metallnitride oder Metallcarbonitrid besteht und die Hülle auch die weiteren umgelösten Carbide beinhaltet. The cermets are usually built up in a core-shell structure, the core always consisting of a single phase of a metal carbide, metal nitride or metal carbonitride and the shell also containing the other dissolved carbides.
Als Alternative zu den genannten und vielfältig in der Industrie eingesetzten metallische Komponenten Nickel, Cobalt, Eisen als Bindemetall, sind in letzter Zeit auch komplexe Bindemetalllegierung, sogenannte Hoch Entropy Legierungen, engl. High Entropy Alloys (HEA) in der Entwicklung. (Lou: Journals of Alloys and Compounds; DOI: 10.1016/j.jallcom.2019.03.328). Solche speziellen metallischen Binderlegierungen (High Entropy Alloys (HEA) ) sind nicht Gegenstand der vorliegenden Erfindung. As an alternative to the metallic components mentioned and widely used in industry, nickel, cobalt, iron as binding metal, complex binding metal alloys, so-called high entropy alloys, have also recently become available. High Entropy Alloys (HEA) under development. (Lou: Journals of Alloys and Compounds; DOI: 10.1016 / j.jallcom.2019.03.328). Such special metallic binder alloys (High Entropy Alloys (HEA)) are not the subject of the present invention.
Die Herstellung von Hartmetallkörpern, die im Grünzustand neben organischen Bindemitteln die Hartmetallausgangspulver enthalten, mittels Pressverfahren, Extrusion, MIM/CIM oder dem 3D-Druck von Grünkörpern und dem anschließenden Sintern ist nach dem Stand der Technik bekannt. Dabei können Hartmetallbauteile mit verschiedener Zusammensetzung hergestellt werden. Bezüglich der Gefügeausbildung bei der Herstellung von Hartmetallen, beispielsweise aus WC-Co, entsteht bei der konventionellen Herstellung idealerweise ein Hartmetallgefüge, welches aus WC-Körnern in einer cobaltreichen Matrix mit gelöstem Wolfram und Kohlenstoff besteht. The production of hard metal bodies, which in the green state contain the hard metal starting powder in addition to organic binders, by means of pressing processes, extrusion, MIM / CIM or the 3D printing of green bodies and the subsequent sintering is known from the prior art. Here, hard metal components with different compositions can be produced. With regard to the structure formation in the production of hard metals, for example from WC-Co, the conventional production ideally results in a hard metal structure which consists of WC grains in a cobalt-rich matrix with dissolved tungsten and carbon.
Hartstoffe und Hartmetalle sind bereits seit langem bekannt. Nach Kiefer, R. et al: Hartstoffe und Hartmetalle, Wien, Springer-Verlag, 1953, S. 196ff sind zahlreiche Carbid-Mehrstoffsystemen als Hartstoffe bekannt, bis hin zu ternären und komplexen Systemen. „Die Legierungsmöglichkeiten für Hartkarbide in Drei- und Mehrfachsystemen sind außerordentlich zahlreich.“. „Allgemein kann man wieder zwei Gruppen von Legierungen unterscheiden, welche technisches Interesse haben. Man kann die Karbide der 4. und 5. Gruppe kombinieren. Da diese Karbide alle isotyp sind, ist auch in Drei- und Mehrstofflegierungen, mit Ausnahme hoch-ZrC-haltiger Systeme, vollständige Mischbarkeit zu erwarten.“. Hard materials and hard metals have been known for a long time. According to Kiefer, R. et al: Hartstoffe und Hartmetalle, Vienna, Springer-Verlag, 1953, p. 196ff, numerous carbide multi-material systems are known as hard materials, including ternary and complex systems. "The alloying possibilities for hard carbides in triple and multiple systems are extraordinarily numerous." “In general, one can again differentiate between two groups of alloys which are of technical interest. You can combine the carbides of the 4th and 5th group. Since these carbides are all isotypic, complete miscibility can also be expected in three and multi-component alloys, with the exception of systems with a high ZrC content. "
Untersucht wurden verschieden Dreifachsysteme, wie Titankarbid-Niobkarbid- Tantalkarbid oder Tantalkarbid-Molybdänkarbid-Wolframkarbid, aber auch die Vierfachsysteme Titankarbid-Vanadiumkarbid-Niobkarbid-Molybdänkarbid und Titankarbid-Vanadiumkarbid-Molybdänkarbid-Wolframkarbid. Various triple systems were examined, such as titanium carbide-niobium carbide-tantalum carbide or tantalum carbide-molybdenum carbide-tungsten carbide, but also the quadruple systems titanium carbide-vanadium carbide-niobium carbide-molybdenum carbide and titanium carbide-molybdenum carbide-tungsten carbide.
Weitere Informationen über die Eigenschaften dieser Systeme oder Anwendungen in der Praxis sind nicht erhältlich. Further information on the properties of these systems or practical applications is not available.
Bekannt ist weiter die Entwicklung von sogenannten „high-entropy carbides“ (HEC), die eine neue Klasse von Vielfachsystemen von Keramiken sind (Zhou, J. et al: Ceram. Internat. 44 (2018) 22014-22018). Die Untersuchungen sind an HEC mit equi- atomaren (Ti, Zr, Hf, Nb, Ta)C-high-entropy-Karbidpulver durchgeführt worden. Die Ausgangspulver TiC, ZrC, HfC, NbC, TaC sind im equi-molaren Verhältnis eingesetzt und mittels druckunterstützter Sintertechnik (spark plasma sintering - SPS) synthetisiert worden. Also known is the development of so-called “high-entropy carbides” (HEC), which are a new class of multiple systems of ceramics (Zhou, J. et al: Ceram. Internat. 44 (2018) 22014-22018). The investigations were carried out at HEC with equi-atomic (Ti, Zr, Hf, Nb, Ta) C high entropy carbide powder. The starting powders TiC, ZrC, HfC, NbC, TaC are used in an equi-molar ratio and synthesized using pressure-assisted sintering technology (spark plasma sintering - SPS).
Den Ergebnissen zufolge konnte bei 1950°C eine reine flächenzentrierte kubisch strukturierte feste Lösung erhalten werden, bei der Metallatome statistisch verteilt im metallischen Untergitter platziert wurden. According to the results, a pure face-centered cubic structured solid solution could be obtained at 1950 ° C, in which metal atoms were randomly placed in the metallic sublattice.
Dies führte zu der Aussage, dass HEC-Pulver thermisch stabiler als seine ursprünglichen Komponenten ist. Weiter sind durch Sarker, P. et al: Nature Communication DOI: 10.1038/s41467-018- 07160-7 HEC mit hoher Härte theoretisch vorhergesagt und einzelne HEC dann experimentell untersucht. Insbesondere wurde das System (Mo,Nb,Ta,V,W)C5 näher untersucht und eine hohe Härte festgestellt. This led to the statement that HEC powder is more thermally stable than its original components. Furthermore, Sarker, P. et al: Nature Communication DOI: 10.1038 / s41467-018-07160-7 theoretically predicted HEC with high hardness and then investigated individual HECs experimentally. In particular, the system (Mo, Nb, Ta, V, W) C5 was examined in more detail and a high hardness was found.
Nach Wie, X-F. et al: J.of the Europ. Ceram. Soc. 39 (2010). 2989-2994 sind ebenfalls HEC aus unterschiedlichen Ausgangspulvern hergestellt und untersucht worden. Dabei ist insbesondere (Tio,2Zro,2Nbo,2Tao,2Wo,2)C untersucht worden, welches ebenfalls mittels SPS hergestellt worden ist. After Wie, XF. et al: J. of the Europ. Ceram. Soc. 39 (2010). 2989-2994, HEC were also produced from different starting powders and investigated. In particular, (Tio , 2Zro , 2Nbo , 2Tao , 2Wo , 2) C was investigated, which was also produced by means of PLC.
Festgestellt wurde, dass insbesondere die Partikelgröße der Ausgangspulver für die homogene Verteilung der einzelnen Elemente im HEC von Bedeutung ist, wohingegen bei Einsatz feinerer Ausgangspulver die relative Dichte abnimmt. It was found that the particle size of the starting powder in particular is important for the homogeneous distribution of the individual elements in the HEC, whereas when using finer starting powders, the relative density decreases.
Gemäß Harrington, T.J. et al: Acta Materialia 166 (2019) 271-280 sind die Phasenstabilität der festen Lösung und die mechanischen Eigenschaften von HEC untersucht worden. Die Untersuchungen sind an Fünf-Metallcarbiden der Metalle der IVB-, VB- und VIB-Gruppe des PSE durchgeführt worden. According to Harrington, T.J. et al: Acta Materialia 166 (2019) 271-280, the phase stability of the solid solution and the mechanical properties of HEC have been investigated. The investigations were carried out on five-metal carbides of the metals of the IVB, VB and VIB groups of the PSE.
Die untersuchten Materialien zeigten eine erhöhte Härte. The materials examined showed an increased hardness.
Nachteilig an dem bekannten Stand der Technik zu HEC ist, dass diese als Hartstoffe bisher äußerst spröde sind. Ihr Einsatz als Hartstoff in Hartmetallen und deren Eigenschaften sind bis jetzt weder realisiert noch untersucht worden. Ebenso sind keine Herstellungsverfahren zur Herstellung solcher auf HEC basierender Hartmetalle bekannt. The disadvantage of the known prior art on HEC is that, as hard materials, these have so far been extremely brittle. Their use as hard material in hard metals and their properties have not yet been realized or investigated. Likewise, no manufacturing processes for manufacturing such HEC-based hard metals are known.
Aufgabe der vorliegenden Erfindung ist es, Hartmetalle anzugeben, die weiter verbesserte mechanische Eigenschaften aufweisen und ein neues Konzept für die strukturelle Zusammensetzung der Hartmetalle beinhalten, sowie ein einfaches und kostengünstiges Verfahren zu ihrer Herstellung anzugeben. The object of the present invention is to specify hard metals that have further improved mechanical properties and contain a new concept for the structural composition of the hard metals, as well as to specify a simple and inexpensive method for their production.
Die Aufgabe wird durch die in den Patentansprüchen angegebene Erfindung gelöst. Vorteilhafte Ausgestaltungen sind Gegenstand der Unteransprüche, wobei die Erfindung auch Kombinationen der einzelnen abhängigen Patentansprüche im Sinne einer Und-Verknüpfung mit einschließt, solange sie sich nicht gegenseitig ausschließen. The object is achieved by the invention specified in the patent claims. Advantageous refinements are the subject matter of the subclaims, the invention also including combinations of the individual dependent claims includes an AND link, as long as they are not mutually exclusive.
Die erfindungsgemäßen Hartmetalle bestehen mindestens aus Hartstoffen in Partikelform und dazwischen angeordnetem Bindemetall, wobei ein high-entropy- Hartstoff (HEH) dessen Gehalt im erfindungsgemäßen Hartmetall mindestens 50 Vol.- % beträgt, aus mindestens vier Metallen (Me) der 4. und/oder 5. und/oder 6. Nebengruppe des Periodensystems der Elemente (PSE) in Form einer festen Lösung von Carbiden, Nitriden, Carbonitriden, Oxycarbiden und/oder Oxycarbonitriden der Metalle zusammengesetzt ist, und wobei der jeweilige Anteil x, y und z in Summe des Kohlenstoff (C), des Stickstoffs (N) und des Sauerstoffs (0) in den Carbiden, Nitriden, Carbonitriden, Oxycarbiden und/oder Oxycarbonitriden der Metalle der 4. und/oder 5. und/oder 6. Nebengruppe des PSE gemäß MeCxNyOz = 0,7 < x+y+z <1 ist, und wobei die jeweiligen Anteile der Metalle der 4. und/oder 5. und/oder 6. Nebengruppe des PSE an den mindestens vier Metallen im HEH im Wesentlichen gleich groß sind oder der Anteil eines oder mehrerer dieser Metalle um maximal 20 At.-% davon abweicht, und wobei die Carbide, Nitride, Carbonitride, Oxycarbide und/oder Oxycarbonitride der Metalle der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in jedem Hartstoffpartikel als feste Lösung vorliegen, und weiterhin höchstens 50 Vol.-% der Hartstoffe eine andere Hartstoff-Zusammensetzung aufweisen, und wobei als Bindemetalle alle für Hartmetalle bekannten Bindemetalle in den für Hartmetalle bekannten Anteilen von 0,1 bis 40 Vol.-%, bezogen auf das Hartmetall, vorhanden sind. The hard metals according to the invention consist at least of hard materials in particle form and binding metal arranged in between, with a high-entropy hard material (HEH) whose content in the hard metal according to the invention is at least 50% by volume, of at least four metals (Me) of the 4th and / or 5th and / or 6th subgroup of the Periodic Table of the Elements (PSE) is composed in the form of a solid solution of carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides of the metals, and the respective proportion of x, y and z in the sum of the Carbon (C), nitrogen (N) and oxygen (0) in the carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides of the metals of the 4th and / or 5th and / or 6th subgroup of the PSE according to MeC x N y O z = 0.7 <x + y + z <1, and where the respective proportions of the metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the at least four metals in the HEH are essentially are equal or the share of one or more it deviates from these metals by a maximum of 20 at .-%, and the carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides of the metals of the 4th and / or 5th and / or 6th subgroup of the PSE in each hard material particle as solid Solution are present, and furthermore at most 50 vol .-% of the hard materials have a different hard material composition, and all binding metals known for hard metals in the proportions known for hard metals of 0.1 to 40 vol .-%, based on the hard metal , available.
Vorteilhafterweise sind 50 - 100 Vol.-%, vorteilhafterweise 60 - 99 Vol.-%, noch vorteilhafterweise 80 - 98 Vol.-% der Hartstoffe ein HEH aus mindestens vier Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form einer festen Lösung von Carbiden, Nitriden, Carbonitriden, Oxycarbiden und/oder Oxycarbonitriden. Advantageously, 50-100% by volume, advantageously 60-99% by volume, still advantageously 80-98% by volume, of the hard materials are an HEH composed of at least four metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of a solid solution of carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides.
Ebenfalls vorteilhafterweise sind 0 - 50 Vol.-%, vorteilhafterweise 1 bis 20 Vol.-%, an weiteren Hartstoffen im Hartmetall aus einem, zwei oder drei Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des Periodensystems der Elemente (PSE) in Form einer festen Lösung von Carbiden, Nitriden, Carbonitriden, Oxycarbiden und/oder Oxycarbonitriden der Metalle zusammengesetzt. Weiterhin vorteilhafterweise sind die Hartstoffe aus Carbiden oder Nitriden der Metalle der 4. und/oder 5. und/oder 6. Nebengruppe des PSE zusammengesetzt. Likewise advantageous are 0-50% by volume, advantageously 1 to 20% by volume, of further hard materials in the hard metal from one, two or three metals of the 4th and / or 5th and / or 6th subgroup of the periodic table of the elements (PSE) composed in the form of a solid solution of carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides of the metals. The hard materials are also advantageously composed of carbides or nitrides of the metals of the 4th and / or 5th and / or 6th subgroup of the PSE.
Und auch vorteilhafterweise ist der jeweilige Anteil x, y und z in Summe des Kohlenstoff (C), des Stickstoffs (N) und des Sauerstoffs (0) in den Carbiden, Nitriden, Carbonitriden , Oxycarbiden und/oder Oxycarbonitriden mit Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE gemäß MeCxNyOz = 0,9 < x+y+z <1 , vorteilhafterweise bei MeCxNyOz mit x = 0 -1 und/oder y = 0 - 1 und/oder z = 0 - 0,2. And also advantageously the respective proportions x, y and z in the sum of the carbon (C), the nitrogen (N) and the oxygen (0) in the carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides with metals of the 4th and / or 5th and / or 6th subgroup of the PSE according to MeC x N y O z = 0.9 <x + y + z <1, advantageously with MeC x N y O z with x = 0 -1 and / or y = 0-1 and / or z = 0-0.2.
Von Vorteil ist es auch, wenn die Anteile der Metalle vorhanden sind gemäß: It is also advantageous if the proportions of metals are present according to:
HEH aus einer Anzahl von n Metallen der 4. und/oder 5. und/oder 6. Nebengruppe desHEH from a number of n metals of the 4th and / or 5th and / or 6th subgroup of the
PSE mit n = 4 bis 9, wobei im Falle von n = 4 bis 6 die Anteile der jeweiligen Metalle nach (1/n 100) + 10 At.-%, vorteilhafterweise + 5 At.-%, noch vorteilhafterweise + 2 At.-%, und/oder im Falle von n = 7 bis 9 die Anteile der jeweiligen Metalle nach (1/n 100) + 5 At.-%, vorteilhafterweise + 2 At.-%, und/oder die Anteile von n-3 (n minus 3) der Metalle auch um Anteile von jeweils > 10 At.-% bezogen auf den Gesamtmetallgehalt im HEH abweichen können, wobei der Anteil eines der Metalle maximal 70 At.-%, vorteilhafterweise 60 At.-% bezogen auf den Gesamtmetallgehalt der HEH, betragen kann. PSE with n = 4 to 9, where in the case of n = 4 to 6 the proportions of the respective metals according to (1 / n 100) + 10 at .-%, advantageously + 5 at .-%, still advantageously + 2 at. -%, and / or in the case of n = 7 to 9 the proportions of the respective metals according to (1 / n 100) + 5 at.%, advantageously + 2 at.%, and / or the proportions of n-3 (n minus 3) of the metals can also differ by proportions of> 10 at.% based on the total metal content in the HEH, the proportion of one of the metals being a maximum of 70 at.%, advantageously 60 at.% based on the total metal content the HEH, can be.
Weiterhin von Vorteil ist es, wenn jeder Anteil eines Metalls um maximal 20 At.-% von dem Anteil abweicht, der sich aus den gleichen Anteilen für alle Metalle bei n Metallen ergibt. It is also advantageous if each proportion of a metal differs by a maximum of 20 at.% From the proportion which results from the same proportions for all metals in n metals.
Ebenfalls von Vorteil ist es, wenn der Hartstoff HEH aus fünf, sechs, sieben oder mehr Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form einer festen Lösung von Carbiden, Nitriden, Carbonitriden, Oxycarbiden und/oder Oxycarbonitriden zusammengesetzt vorliegt. Und auch von Vorteil ist es, wenn im HEH aus mindestens vier Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form einer festen Lösung von Carbiden, Nitriden, Carbonitriden und/oder Oxycarbonitriden der Anteil der mindestens vier Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form von Carbiden, Nitriden, Carbonitriden und/oder Oxycarbonitriden jeweils im Wesentlichen gleich groß sind. It is also advantageous if the hard material HEH consists of five, six, seven or more metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of a solid solution of carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides is composed. And it is also advantageous if in the HEH the proportion of at least four metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of a solid solution of carbides, nitrides, carbonitrides and / or oxycarbonitrides Metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of carbides, nitrides, carbonitrides and / or oxycarbonitrides are each essentially the same size.
Vorteilhaft ist es auch, wenn Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W als Metalle der Hartstoffe vorhanden sind. It is also advantageous if Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W are present as metals of the hard materials.
Und auch vorteilhaft ist es, wenn Co, Ni, Fe, Mn, Cu, Cr, Ti oder deren Mischungen, wie kohlenstoffarme und kohlenstoffreiche Stähle und high entropy Metalllegierungen, als Bindemetalle vorhanden sind. And it is also advantageous if Co, Ni, Fe, Mn, Cu, Cr, Ti or their mixtures, such as low-carbon and high-carbon steels and high entropy metal alloys, are present as binding metals.
Weiterhin vorteilhaft ist es, wenn 5 bis 32 Vol.-% Bindemetall, bezogen auf das Hartmetall, in den Hartmetallen enthalten ist. It is also advantageous if the hard metals contain 5 to 32% by volume of binder metal, based on the hard metal.
Bei dem erfindungsgemäßen Verfahren zur Herstellung von Hartmetallen werden Pulver von mindestens vier Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des Periodensystems der Elemente (PSE) in Form von Carbiden, Nitriden, Carbonitriden und/oder Oxycarbonitriden gemischt und zu einem HEH-Pulver oder zu HEH- Granalien synthetisiert und nachfolgend werden zu den HEH-Pulvern oder den Granalien des HEHs maximal 50 Vol.-% weitere Hartstoffpulver oder Hartstoff- Granalien zugegeben, und diese Hartstoffe werden mit pulverförmigem Bindemetall in einem Anteil von 0,1 bis 40 Vol.-%, bezogen auf das Hartmetall, gemischt und zu Hartmetallpulver oder Hartmetallgranalien und nach einer Formgebung zu Bauteilen gesintert. In the method according to the invention for producing hard metals, powders of at least four metals of the 4th and / or 5th and / or 6th subgroup of the Periodic Table of the Elements (PSE) in the form of carbides, nitrides, carbonitrides and / or oxycarbonitrides are mixed and added a HEH powder or HEH granules and then a maximum of 50% by volume of further hard material powders or hard material granules are added to the HEH powders or the HEH granules, and these hard materials are mixed with powdery binding metal in a proportion of 0, 1 to 40% by volume, based on the hard metal, mixed and sintered to hard metal powder or hard metal granules and after shaping into components.
Vorteilhafterweise werden über ein Formgebungsverfahren aus der Mischung mit organischen Bindemitteln Bauteile geformt werden, die organischen Bindemittel entfernt und die Bauteile gesintert. Weiterhin vorteilhafterweise wird die Formgebung mittels Pressen, Extrudieren, Spritzgießen, CIP (Cold Isostatic Pressing) und/oder mittels Additiver Formgebung realisiert. Advantageously, components are formed from the mixture with organic binders via a molding process, the organic binders are removed and the components are sintered. Furthermore, the shaping is advantageously realized by means of pressing, extrusion, injection molding, CIP (Cold Isostatic Pressing) and / or by means of additive shaping.
Auch vorteilhafterweise erfolgt die Sinterung drucklos oder druckunterstützt mittels Sinter-Fleißisostatischem Pressen, Fleißisostatischem Pressen(FIIP), Fleißpressen oder SPS. The sintering is also advantageously carried out without pressure or with pressure support by means of sintering isostatic pressing, isostatic pressing (FIIP), industrial pressing or SPS.
Ebenfalls vorteilhafterweise werden mindestens fünf oder sechs oder sieben oder mehr Pulver aus Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form von Carbiden, Nitriden, Carbonitriden und/oder Oxycarbonitriden gemischt und die Mischung wird in-situ während der Sinterung mit Bindemetallen zu FHEFH- haltigen Hartmetallen synthetisiert. Likewise advantageously, at least five or six or seven or more powders of metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of carbides, nitrides, carbonitrides and / or oxycarbonitrides are mixed and the mixture is in-situ synthesized during sintering with binding metals to hard metals containing FHEFH.
Vorteilhaft ist es auch, wenn vier Pulver aus Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form von Carbiden, und/oder Nitriden gemischt werden und die Mischung in-situ während der Sinterung mit Bindemetallen zu HEH- haltigen Hartmetallen synthetisiert wird. It is also advantageous if four powders of metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of carbides and / or nitrides are mixed and the mixture is mixed in situ during sintering with binding metals to form HEH - containing hard metals is synthesized.
Weiterhin vorteilhaft ist es, wenn 0 - < 50 Vol.-%, noch vorteilhafterweise 1 bis 20 Vol.- %, an Pulvern von Hartstoffen aus einem oder zwei oder drei Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form einer festen Lösung von Carbiden, Nitriden, Carbonitriden und/oder Oxycarbonitriden eingesetzt werden. It is also advantageous if 0- <50% by volume, still advantageously 1 to 20% by volume, of powders of hard materials from one or two or three metals of the 4th and / or 5th and / or 6th subgroup of the PSE can be used in the form of a solid solution of carbides, nitrides, carbonitrides and / or oxycarbonitrides.
Ebenfalls vorteilhaft ist es, wenn die Synthese der HEH-Pulver aus der Reduktion von Oxiden von Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE zu Metallen und der anschließenden Co-Karburierung und/oder Nitrierung durchgeführt wird oder durch eine Direkte Karburierung und/oder Nitrierung der Mischoxide erfolgt. It is also advantageous if the synthesis of the HEH powder from the reduction of oxides of metals of the 4th and / or 5th and / or 6th subgroup of the PSE to metals and the subsequent co-carburization and / or nitration is carried out or takes place by direct carburization and / or nitration of the mixed oxides.
Und auch vorteilhaft ist es, wenn zu HEH-Pulver maximal 50 Vol.-% weitere Hartstoffpulver zugegeben werden, und diese Hartstoffe mit pulverförmigem Bindemetall in einem Anteil von 0,1 bis 40 Vol.-%, bezogen auf das Hartmetall, gemischt und nachfolgend zu teilweise oder vollständig gesinterten Hartmetall- Granalien gesintert werden. Mit der erfindungsgemäßen Lösung wird es erstmals möglich Hartmetalle anzugeben, die weiter verbesserte mechanische Eigenschaften aufweisen und ein neues Konzept für die strukturelle Zusammensetzung der Hartmetalle beinhalten. Ebenso ist es erstmals möglich, ein Herstellungsverfahren für derartige Hartmetalle anzugeben. It is also advantageous if a maximum of 50% by volume of further hard material powders are added to HEH powder, and these hard materials are mixed with powdered binding metal in a proportion of 0.1 to 40% by volume, based on the hard metal, and then mixed be sintered to partially or fully sintered hard metal granules. With the solution according to the invention, it is possible for the first time to specify hard metals that have further improved mechanical properties and contain a new concept for the structural composition of the hard metals. It is also possible for the first time to specify a manufacturing method for hard metals of this type.
Erreicht wird dies durch Hartmetalle, die mindestens aus Hartstoffen in Partikelform und dazwischen angeordnetem Bindemetall bestehen. This is achieved by hard metals, which consist at least of hard materials in particle form and a binding metal arranged in between.
Diese Hartmetalle enthalten mindestens den neuen Hartstoff in Partikelform (High Entropy Hartstoff - HEH) mit einer neuen strukturelle Zusammensetzung und das Bindemetall. These hard metals contain at least the new hard material in particle form (High Entropy Hard Material - HEH) with a new structural composition and the binding metal.
Als Bindemetalle sind dabei alle für Hartmetalle bekannten Bindemetalle in den für Hartmetalle bekannten Anteilen von 0,1 bis maximal 40 Vol.-%, bezogen auf das Hartmetall, vorhanden. All of the binding metals known for hard metals are present as binding metals in the proportions known for hard metals of 0.1 to a maximum of 40% by volume, based on the hard metal.
Vorteilhafterweise sind dies Co, Ni, Fe, Mn, Cu, Cr, Ti oder deren Mischungen wie kohlenstoffarme und kohlenstoffreiche Stähle und high entropy Metalllegierungen, die vorteilhafterweise in einem Anteil von 5 - 32 Vol.-%, bezogen auf das Hartmetall, in den erfindungsgemäßen Hartmetallen vorhanden sind. These are advantageously Co, Ni, Fe, Mn, Cu, Cr, Ti or their mixtures, such as low-carbon and high-carbon steels and high entropy metal alloys, which are advantageously used in a proportion of 5-32% by volume, based on the hard metal Hard metals according to the invention are present.
Während des Sinterprozesses kommt es zum Anlösen der HEH. Dadurch können sich auch diese Elemente in geringer Konzentration im metallischen Binder befinden, ähnlich wie das bei konventionellen Hartmetallen der Fall ist, bei denen der Co-Binder Kohlenstoff und Wolfram enthält. The HEH loosens during the sintering process. As a result, these elements can also be found in low concentrations in the metallic binder, similar to the case with conventional hard metals, in which the Co-binder contains carbon and tungsten.
Von erfindungsgemäßer Bedeutung ist aber, dass der neue high-entropy-Hartstoff HEH im erfindungsgemäßen Hartmetall, der zu mindestens 50 Vol.-% aller Hartstoffe ausmacht, aus mindestens vier Metallen (Me) der 4. und/oder 5. und/oder 6. Nebengruppe des Periodensystems der Elemente (PSE) in Form einer festen Lösung von Carbiden, Nitriden, Carbonitriden, Oxycarbiden und/oder Oxycarbonitriden der Metalle zusammengesetzt ist. What is important according to the invention, however, is that the new high-entropy hard material HEH in the hard metal according to the invention, which makes up at least 50% by volume of all hard materials, consists of at least four metals (Me) of the 4th and / or 5th and / or 6th Subgroup of the Periodic Table of the Elements (PSE) is composed in the form of a solid solution of carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides of the metals.
Eine feste Lösung ist die Bezeichnung für homogene Festkörper, die aus mehr als nur einem Element oder einer Verbindung bestehen. Dabei befinden sich mehrere Atomarten statistisch angeordnet auf einer kristallographischen Position im Kristallgitter. Dadurch bleibt über einen mehr oder weniger großen Konzentrationsbereich die Kristallstruktur der Phase erhalten. Solche feste Lösungen sind zum Beispiel die Übergangsmetallcarbide mit kubischer NaCI Struktur. Dabei können verschiedene Metalle ( Ti, Zr; V, . ) die Position des Kations in der Struktur statistisch verteilt einnehmen und Kohlenstoff die Position des Anions. Eine feste Lösung liegt auch vor, wenn die Position des Anions mit unterschiedlichen Mengen an Kohlenstoff oder durch Kohlenstoff, Stickstoff oder Sauerstoff besetzt ist (auch wenn die Verbindung nur ein Metall zum Beispiel Ti enthält). Eine solche statistische Verteilung der jeweiligen Atome geht nur in bestimmten Grenzen, da es energetisch günstiger sein kann, wenn bei bestimmten Verhältnissen der Atome der Übergang von der statistischen Verteilung zu einer geordneten Anordnung der Atome erfolgt, es also zum Ausscheiden einer neuen Phase kommt, oder die Generierung von Überstrukturen erfolgt. Die Größe der Homogenitätsbereiche der festen Phasen nimmt mit zunehmender Ähnlichkeit der Atome bzw. mit der Anzahl der unterschiedlichen Atomsorten zu. A solid solution is the name for homogeneous solids that consist of more than just one element or compound. There are several Types of atoms arranged randomly on a crystallographic position in the crystal lattice. As a result, the crystal structure of the phase is retained over a more or less large concentration range. Such solid solutions are, for example, the transition metal carbides with a cubic NaCl structure. Different metals (Ti, Zr; V,.) Can take the position of the cation in the structure in a statistically distributed manner and carbon the position of the anion. A solid solution is also present if the position of the anion is occupied by different amounts of carbon or by carbon, nitrogen or oxygen (even if the compound contains only one metal, for example Ti). Such a statistical distribution of the respective atoms is only possible within certain limits, since it can be energetically more favorable if, with certain ratios of the atoms, the transition from the statistical distribution to an ordered arrangement of the atoms takes place, i.e. a new phase is eliminated, or the generation of superstructures takes place. The size of the homogeneity areas of the solid phases increases with increasing similarity of the atoms or with the number of different types of atoms.
Daher ist es erfindungsgemäß wichtig, dass in den HEH vier oder mehr Metalle im Gitter vorhanden sind, da das die statistische Anordnung der Metallatome unterstützt und dann zu einer Reduktion von Versetzungsbewegungen und damit zur Erhöhung der Härte führt. Daher ist es erfindungsgemäß auch wichtig, dass die Metalle in im Wesentlichen gleichen Anteilen/Konzentrationen im HEH vorhanden sind und keines der Metalle in einem zu hohen Anteil/Konzentration vorliegt, da dann dieser Effekt nicht mehr genügend ausgeprägt ist, d. h. dass jedes der Metalle einen Anteil von kleiner als 70 At.-%, besser von < 60 At.-%, aufweisen sollte. Daher ist es erfindungsgemäß gewünscht, dass die Anteile/Konzentrationen der einzelnen Metalle im Wesentlichen gleich sind, aber Abweichungen möglich sind. It is therefore important according to the invention that four or more metals are present in the lattice in the HEH, since this supports the statistical arrangement of the metal atoms and then leads to a reduction in dislocation movements and thus to an increase in hardness. It is therefore also important according to the invention that the metals are present in essentially the same proportions / concentrations in the HEH and none of the metals is present in too high a proportion / concentration, since this effect is then no longer sufficiently pronounced, i.e. H. that each of the metals should have a proportion of less than 70 at.%, better of <60 at.%. It is therefore desired according to the invention that the proportions / concentrations of the individual metals are essentially the same, but deviations are possible.
Zu den festen Lösungen gehören z. B. die meisten Legierungen und Mischkristalle. Fixed solutions include B. most alloys and mixed crystals.
Die 50 - 0 Vol.-%, vorteilhafterweise 1 bis 20 Vol.-%, an weiteren Hartstoffen im erfindungsgemäßen Hartmetall können aus einem, zwei oder drei Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des Periodensystems der Elemente (PSE) in Form einer festen Lösung von Carbiden, Nitriden, Carbonitriden, Oxycarbiden und/oder Oxycarbonitriden der Metalle zusammengesetzt sein. Vorteilhafterweise sind 50 - 100 Vol.-%, vorteilhafterweise 60 - 99 Vol.-%, noch vorteilhafterweise 80 - 98 Vol.-% der Hartstoffe ein HEH aus mindestens vier Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form einer festen Lösung von Carbiden, Nitriden, Carbonitriden, Oxycarbiden und/oder Oxycarbonitriden der Metalle zusammengesetzt. The 50-0% by volume, advantageously 1 to 20% by volume, of further hard materials in the hard metal according to the invention can be composed of one, two or three metals of the 4th and / or 5th and / or 6th subgroup of the periodic table of the elements (PSE) in the form of a solid solution of carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides of the metals. Advantageously, 50-100% by volume, advantageously 60-99% by volume, still advantageously 80-98% by volume, of the hard materials are an HEH composed of at least four metals of the 4th and / or 5th and / or 6th subgroup composed of the PSE in the form of a solid solution of carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides of the metals.
Auch vorteilhafterweise liegt der Hartstoff HEH im erfindungsgemäßen Hartmetall aus fünf, sechs, sieben oder mehr Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form einer festen Lösung von Carbiden, Nitriden, Carbonitriden, Oxycarbiden und/oder Oxycarbonitriden der Metalle zusammengesetzt vor. The hard material HEH is also advantageously in the hard metal according to the invention from five, six, seven or more metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of a solid solution of carbides, nitrides, carbonitrides, oxycarbides and / or Oxycarbonitrides composed of metals before.
Weiter vorteilhafterweise weist der Hartstoff Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W als Metalle der Hartstoffe auf. The hard material also advantageously has Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W as metals of the hard materials.
Erfindungsgemäß ist der jeweilige Anteil x, y und z in Summe des Kohlenstoff (C), des Stickstoffs (N) und des Sauerstoffs (O) in den Carbiden, Nitriden, Carbonitriden und/oder Oxycarbonitriden mit Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE gemäß MeCxNyOz = 0,7 < x+y+z <1 . According to the invention, the respective proportion x, y and z is the sum of the carbon (C), the nitrogen (N) and the oxygen (O) in the carbides, nitrides, carbonitrides and / or oxycarbonitrides with metals of the 4th and / or 5th. and / or 6th subgroup of the PSE according to MeC x N y O z = 0.7 <x + y + z <1.
Vorteilhafterweise beträgt der jeweilige Anteil x, y und z in Summe des Kohlenstoff (C), des Stickstoffs (N) und des Sauerstoffs (O) in den Carbiden, Nitriden, Carbonitriden, Oxycarbiden und/oder Oxycarbonitriden der Metalle mit Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE gemäß MeCxNyOz = 0,9 < x+y+z <1 , vorteilhafterweise bei MeCxNyOz mit x = 0 -1 und/oder y = 0 - 1 und/oder z = 0 - 0,2. Advantageously, the respective proportion x, y and z is the sum of the carbon (C), the nitrogen (N) and the oxygen (O) in the carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides of the metals with metals of the 4th and 4th / or 5th and / or 6th subgroup of the PSE according to MeC x N y O z = 0.9 <x + y + z <1, advantageously with MeC x N y O z with x = 0 -1 and / or y = 0-1 and / or z = 0-0.2.
Ebenfalls erfindungsgemäß ist der jeweilige Anteil der Metalle der 4. und/oder 5. und/oder 6. Nebengruppe des PSE an dem mindestens vier Metalle enthaltenen HEH im Wesentlichen gleich groß oder der Anteil eines oder mehrerer dieser Metalle weicht um maximal 20 At.-% davon ab. Also according to the invention, the respective proportion of the metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the HEH containing at least four metals is essentially the same or the proportion of one or more of these metals deviates by a maximum of 20 atoms. % of it.
Erfindungsgemäß vorteilhaft ist es, wenn die Anteile der Metalle vorhanden sind gemäß: It is advantageous according to the invention if the proportions of the metals are present according to:
HEH aus einer Anzahl von n Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE mit n = 4 bis 9, wobei im Falle von n = 4 bis 6 die Anteile der jeweiligen Metalle nach (1/n 100) + 10 At.-%, vorteilhafterweise + 5 At.-%, noch vorteilhafterweise + 2 At.-%, und/oder im Falle von n = 7 bis 9 die Anteile der jeweiligen Metalle nach (1/n 100) + 5 At.-%, vorteilhafterweise + 2 At.-%, und/oder die Anteile von n-3 (n minus 3) der Metalle auch um Anteile von jeweils > 10 At.-% bezogen auf den Gesamtmetallgehalt im HEH abweichen können, wobei der Anteil eines der Metalle maximal 70 At.-%, bezogen auf den Gesamtmetallgehalt der HEH, betragen kann. Vorteilhafterweise sind es weniger als 60 At.-%, noch mehr zu bevorzugen ist < 50 At.-%. HEH from a number of n metals of the 4th and / or 5th and / or 6th subgroup of the PSE with n = 4 to 9, where in the case of n = 4 to 6 the proportions of the respective metals according to (1 / n 100) + 10 at.%, advantageously + 5 at.%, still advantageously + 2 at.%, and / or in the case from n = 7 to 9 the proportions of the respective metals according to (1 / n 100) + 5 at .-%, advantageously + 2 at .-%, and / or the proportions of n-3 (n minus 3) of the metals as well may differ by proportions of> 10 at .-% based on the total metal content in the HEH, the proportion of one of the metals being a maximum of 70 at .-%, based on the total metal content of the HEH. It is advantageously less than 60 at%, and <50 at% is even more preferred.
Weiterhin ist es vorteilhaft, wenn jeder Anteil eines Metalls um maximal 20 At.-% von dem Anteil abweicht, der sich aus den gleichen Anteilen für alle Metalle bei n Metallen ergibt. Furthermore, it is advantageous if each proportion of a metal differs by a maximum of 20 at.% From the proportion which results from the same proportions for all metals in n metals.
Vorteilhaft ist es auch, wenn im HEH aus mindestens vier Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form einer festen Lösung von Carbiden, Nitriden, Carbonitriden und/oder Oxycarbonitriden der Anteil der mindestens vier Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form von Carbiden, Nitriden, Carbonitriden und/oder Oxycarbonitriden jeweils gleich groß ist. It is also advantageous if the proportion of at least four metals of the at least four metals of the PSE in the form of a solid solution of carbides, nitrides, carbonitrides and / or oxycarbonitrides in the HEH consists of at least four metals of the 4th and / or 5th and / or 6th subgroup 4th and / or 5th and / or 6th subgroup of the PSE in the form of carbides, nitrides, carbonitrides and / or oxycarbonitrides is each the same size.
Erfindungsgemäß ist mit diesen unterschiedlichen Anteilen gemeint, dass der Anteil aller Metalle der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form von Carbiden, Nitriden, Carbonitriden und/oder Oxycarbonitriden im HEH im Wesentlichen gleich groß ist. According to the invention, these different proportions mean that the proportion of all metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of carbides, nitrides, carbonitrides and / or oxycarbonitrides in the HEH is essentially the same.
Im Wesentlichen gleiche Anteile an Metallen im HEH sollen erfindungsgemäß solche Anteile sein, die geringe Schwankungen durch herstellungsbedingte und technisch übliche Abweichungen um den Wert der gleichen Anteile aufweisen. Substantially equal proportions of metals in the HEH should, according to the invention, be those proportions which have slight fluctuations due to manufacturing-related and technically common deviations around the value of the same proportions.
Bei beispielsweise vier Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form von Carbiden, Nitriden, Carbonitriden und/oder Oxycarbonitriden würde der Anteil jedes der Metalle der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form von Carbiden, Nitriden, Carbonitriden und/oder Oxycarbonitriden jeweils 25 % betragen, bei fünf Metallen jeweils 20 %. For example, with four metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of carbides, nitrides, carbonitrides and / or oxycarbonitrides, the The proportion of each of the metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of carbides, nitrides, carbonitrides and / or oxycarbonitrides are in each case 25%, with five metals in each case 20%.
Dabei kann erfindungsgemäß bei vier Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form von Carbiden, Nitriden, Carbonitriden und/oder Oxycarbonitriden der Anteil eines Metalls sich um maximal 20 At.-% von dem gleichen Anteil der vier Metalle unterscheiden, also um 20 At.-% unterschiedlich von dem Anteil von 25 % am HEH. According to the invention, with four metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of carbides, nitrides, carbonitrides and / or oxycarbonitrides, the proportion of a metal can be a maximum of 20 at .-% from the same proportion of the four metals differ, i.e. 20 at .-% different from the proportion of 25% in HEH.
Vorteilhaft ist es weiterhin, wenn im HEH aus mindestens vier Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form einer festen Lösung von Carbiden, Nitriden, Carbonitriden und/oder Oxycarbonitriden der Anteil der mindestens vier Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form von Carbiden, Nitriden, Carbonitriden und/oder Oxycarbonitriden jeweils gleich groß ist. It is also advantageous if the proportion of at least four metals of the at least four metals of the PSE in the form of a solid solution of carbides, nitrides, carbonitrides and / or oxycarbonitrides in the HEH from at least four metals of the 4th and / or 5th and / or 6th subgroup 4th and / or 5th and / or 6th subgroup of the PSE in the form of carbides, nitrides, carbonitrides and / or oxycarbonitrides is each the same size.
Von erfindungsgemäß besonderer Bedeutung ist, dass die HEH einphasig aufgebaut sind und es zu keiner oder nur sehr begrenzten Auflösung der High Entropy Hartstoffe in die Einzelkarbide, -Nitride oder -carbonitride kommt und die High Entropy Hartstoffe auch in Gegenwart von verschieden Bindemetallen in ihrer festen Lösung bestehen bleiben. According to the invention, it is particularly important that the HEH have a single-phase structure and there is no or only very limited dissolution of the high entropy hard materials into the individual carbides, nitrides or carbonitrides and the high entropy hard materials in their solid solution even in the presence of different binding metals remain.
Damit unterscheidet sich die erfindungsgemäße Lösung vom Stand der Technik mindestens dadurch, dass erfindungsgemäß in den Hartstoffpartikeln oder Hartstoffgranalien immer ein HEH aus mindestens vier Metallen vorliegt, und/oder dass die mindestens vier Metalle in allen HEH Hartstoffpartikel oder HEH Hartstoffgranalien einphasig vorhanden sind, und/oder dass die Hartmetalle auch mit Metallen in Form einer festen Lösung von Nitriden, Carbonitriden und/oder Oxycarbonitriden realisiert sind, und/oder dass im Falle eines Aufbaus als Kern- Schale-Struktur der Hartstoffpartikel oder Hartstoffgranalien im Kern nur die erfindungsgemäßen HEH aus mindestens vier Metallen in Form einer festen Lösung von Carbiden, Nitriden, Carbonitriden und/oder Oxycarbonitriden vorhanden sind. Die erfindungsgemäße Lösung bezüglich der Hartmetalle kann auch formelmäßig beschrieben werden, mit: The solution according to the invention thus differs from the prior art at least in that, according to the invention, there is always an HEH of at least four metals in the hard material particles or hard material granules, and / or that the at least four metals are present in one phase in all HEH hard material particles or HEH hard material granules, and / or that the hard metals are also realized with metals in the form of a solid solution of nitrides, carbonitrides and / or oxycarbonitrides, and / or that in the case of a structure as a core-shell structure of the hard material particles or hard material granules in the core only the HEH according to the invention of at least four Metals are present in the form of a solid solution of carbides, nitrides, carbonitrides and / or oxycarbonitrides. The solution according to the invention with regard to hard metals can also be described in terms of a formula, with:
Hartmetall = HEH + BM (+MeHS) wobei: Carbide = HEH + BM (+ MeHS) where:
HEH - High Entropy Hartstoff (Mei,Me2...Men)CxNyOz =0,7 < x+y+z <1 m t i Mei='\HEH - High Entropy Hard Material (Mei, Me2 ... Me n ) CxN y Oz = 0.7 <x + y + z <1 mti Me i = '\
BM - Bindemetall BM - binding metal
MeHS- Metall-Hartstoff MeHS metal hard material
Me, - Metalle sind. Me, - metals are.
Weiter werden bei den erfindungsgemäßen Verfahren zur Herstellung von Hartmetallen Pulver aus mindestens vier verschiedenen Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des Periodensystems der Elemente (PSE) in Form von Carbiden, Nitriden, Carbonitriden, Oxycarbiden und/oder Oxycarbonitriden gemischt und zu einem HEH-Pulver oder zu HEH-Granalien gesintert. Furthermore, in the method according to the invention for the production of hard metals, powders of at least four different metals of the 4th and / or 5th and / or 6th subgroup of the Periodic Table of the Elements (PSE) in the form of carbides, nitrides, carbonitrides, oxycarbides and / or Oxycarbonitrides mixed and sintered to form an HEH powder or HEH granules.
Dabei kann das HEH-Pulver auch aus der Reduktion von Oxiden von Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des Periodensystems der Elemente (PSE) zu Metallen und der anschließenden Co-Karburierung und/oder Nitrierung hergestellt werden oder durch eine direkte Karburierung und/oder Nitrierung der Mischoxide synthetisiert werden. The HEH powder can also be produced from the reduction of oxides of metals of the 4th and / or 5th and / or 6th subgroup of the Periodic Table of the Elements (PSE) to metals and the subsequent co-carburization and / or nitration or can be synthesized by direct carburization and / or nitration of the mixed oxides.
Nachfolgend werden zu den HEH-Pulvern oder den gesinterten Granalien des HEHs maximal < 50 Vol.-% weitere Hartstoffpulver oder Hartstoff-Granalien zugegeben. Diese Hartstoffe werden danach mit pulverförmigem Bindemetall in einem Anteil von 0,1 - 40 Vol.-%, bezogen auf das Hartmetall, gemischt und nachfolgend entweder zu Hartmetallpulver oder Hartmetallgranulaten gesintert. Subsequently, a maximum of <50% by volume of further hard material powders or hard material granules are added to the HEH powders or the sintered granules of the HEH. These hard materials are then mixed with powdery binding metal in a proportion of 0.1-40% by volume, based on the hard metal, and then sintered to either hard metal powder or hard metal granules.
Weiterhin können die HEH-haltigen Hartmetalle auch durch eine in-situ Bildung der HEH entstehen, bei der mindestens vier Pulver aus Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form von Carbiden, und/oder Nitriden gemischt und die Mischung in-situ während der Sinterung mit Bindemetallen zu HEH haltigen Hartmetallen synthetisiert wird. Ebenso kann zu HEH-Pulver maximal 50 Vol.-% weitere Hartstoffpulver zugegeben werden, und diese Hartstoffe mit pulverförmigem Bindemetall in einem Anteil von 0,1 bis 40 Vol.-%, bezogen auf das Hartmetall, gemischt und nachfolgend zu teilweise oder vollständig gesinterten Hartmetall-Granalien gesintert werden. Furthermore, the HEH-containing hard metals can also arise through an in-situ formation of the HEH, in which at least four powders of metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of carbides and / or nitrides mixed and the mixture is synthesized in-situ during sintering with binding metals to form HEH-containing hard metals. A maximum of 50% by volume of other hard material powders can also be added to HEH powder, and these hard materials are mixed with powdered binding metal in a proportion of 0.1 to 40% by volume, based on the hard metal, and then partially or fully sintered Carbide granules are sintered.
Die Mischung aus Hartmetallpulver oder Hartmetallgranalien kann auch mittels Formgebung zu Bauteilen verarbeitet und dann gesintert werden. The mixture of hard metal powder or hard metal granules can also be processed into components by means of shaping and then sintered.
Als Formgebungsverfahren können vorteilhafterweise Pressen, Extrudieren, Spritzgießen, CIP (Cold Isostatic Pressing) und/oder Additive Formgebungsverfahren sowie das thermische Spritzen zur Herstellung von Oberflächenstrukturen eingesetzt werden. The molding processes used can advantageously be pressing, extrusion, injection molding, CIP (Cold Isostatic Pressing) and / or additive molding processes, as well as thermal spraying for the production of surface structures.
Bei der Formgebung werden vorteilhafterweise der Mischung Bindemittel zugegeben und daraus Bauteile geformt. Nachfolgend werden die Bindemittel entfernt und die Bauteile können gesintert werden. During shaping, binders are advantageously added to the mixture and components are formed therefrom. The binders are then removed and the components can be sintered.
Die Sinterung kann vorteilhafterweise drucklos oder druckunterstützt mittels Sinter- Heißisostatischem Pressen, Heißisostatischem Pressen(HIP), Heißpressen oder SPS erfolgen. The sintering can advantageously take place without pressure or with pressure support by means of sintering hot isostatic pressing, hot isostatic pressing (HIP), hot pressing or PLC.
Vorteilhafterweise werden mindestens fünf oder sechs oder sieben oder mehr Pulver aus Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form von Carbiden, Nitriden, Carbonitriden, Oxycarbiden und/oder Oxycarbonitriden gemischt und die HEH werden in-situ während der Sinterung mit Bindemetallen synthetisiert. Advantageously, at least five or six or seven or more powders of metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides are mixed and the HEH are synthesized in situ during sintering with binder metals.
Besonders vorteilhaft ist es, wenn die HEH aus Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form einer festen Lösung von Carbiden, und/oder Nitriden gemischt werden. It is particularly advantageous if the HEH from metals of the 4th and / or 5th and / or 6th subgroup of the PSE are mixed in the form of a solid solution of carbides and / or nitrides.
Weiterhin ist es vorteilhaft, dass 0 bis 50 Vol.-%, vorteilhafterweise 1 bis 20 Vol.-%, an Pulvern von Hartstoffen aus einem oder zwei oder drei Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form einer festen Lösung von Carbiden, Nitriden, Carbonitriden und/oder Oxycarbonitriden eingesetzt werden. Nachfolgend wird die Erfindung an einem Ausführungsbeispiel näher erläutert. It is also advantageous that 0 to 50% by volume, advantageously 1 to 20% by volume, of powders of hard materials from one or two or three metals of the 4th and / or 5th and / or 6th subgroup of the PSE can be used in the form of a solid solution of carbides, nitrides, carbonitrides and / or oxycarbonitrides. The invention is explained in more detail below using an exemplary embodiment.
Die Nachfolgenden Beispiele zeigen, dass bei den gewählten Bedingungen die HEH Phase erstaunlicher Weise stabil ist, auch wenn es zu einem klaren Umlösen der HEH kommt. Die in den Gefügen lokal gefundenen Mengen von WC sind durch die vorherige Aufmahlung der HEH bedingt und können bei weiter verbessertem Processing vermieden werden. Ähnliches gilt für die teilweise gefundenen Hf(0,C) Phase, die durch die nicht vollständigen Reduktion des relativ stabilen Hf02, das im Ausgangspulver vorhanden ist, bedingt ist. The following examples show that under the chosen conditions the HEH phase is surprisingly stable, even if there is a clear dissolution of the HEH. The amounts of WC found locally in the structure are due to the previous grinding of the HEH and can be avoided with further improved processing. The same applies to the partially found Hf (0, C) phase, which is due to the incomplete reduction of the relatively stable Hf0 2 that is present in the starting powder.
Beispiel 1 example 1
Ein mittels einer Sinterung bei 1950 °C im Vakuum und einer nachfolgenden Zerkleinerung in einer Kugelmühle aus je 20 At.-% TaC, NbC, TiC, VC und WC erzeugter einphasiger High Entropy Hartstoff HEH der Zusammensetzung (Tao,2iNbo,2iTio,2iVo,i9Wo,i8)C wurde mit 14 Vol.-% Cobalt (HalfMicron, von UmiCore) in einer Kugelmühle in einem Lösungsmittel (Heptan) und einem Pulver-zu-Mahlkugel- Verhältnis von 1 :20 für 48 h gemahlen. Nach dem Trocknen wurden aus dem Pulver Biegebruchstäbe der Geometrie 45 x 5 x 6 mm3 mittels des Uniaxialen Pressens bei 200 MPa gepresst. A single-phase high entropy hard material HEH of the composition (Tao, 2iNbo , 2iTio , 2iVo , produced by sintering at 1950 ° C in a vacuum and subsequent comminution in a ball mill from 20 at .-% TaC, NbC, TiC, VC and WC) i 9Wo , i 8) C was ground with 14 vol .-% cobalt (HalfMicron, from UmiCore) in a ball mill in a solvent (heptane) and a powder-to-grinding ball ratio of 1:20 for 48 h. After drying, bending rods with a geometry of 45 × 5 × 6 mm 3 were pressed from the powder by means of uniaxial pressing at 200 MPa.
Die Proben wurden bei 1280 °C für 45 min in einem SinterHIP-Ofen mit einem HIP- Druck von 10 MPa gesintert. The samples were sintered at 1280 ° C. for 45 min in a SinterHIP furnace with a HIP pressure of 10 MPa.
Die Probenkörper erwiesen sich im Lichtmikroskop als vollständig dicht. Die Porosität gemäß ISO 4505 entsprach > A02, B00, C00. Die Vickershärte wurde zu 1620 HV10 bestimmt und die Bruchzähigkeit (Kic) wurde mittels der Ausmessung der Risslängen und unter Verwendung der Formel von Shetty (Shetty 1985 - Indentation fracture of WC-Co cermets) zu 8,5 MPa*m1/2 berechnet. The test specimens were found to be completely tight under the light microscope. The porosity according to ISO 4505 corresponded to> A02, B00, C00. The Vickers hardness was determined to be 1620 HV10 and the fracture toughness (Kic) was calculated to be 8.5 MPa * m 1/2 by measuring the crack lengths and using the Shetty formula (Shetty 1985 - Indentation fracture of WC-Co cermets).
Ergebnisse dieser Untersuchungen zur Dichte, Porosität, magnetischer Sättigung, Koerzitivfeldstärke, Härte und Bruchzähigkeit sind in Tabelle 1 gegeben. Tab. 1 The results of these investigations on density, porosity, magnetic saturation, coercive field strength, hardness and fracture toughness are given in Table 1. Tab. 1
Das Gefüge bestand nach dem Sintern aus der HEC-Hartstoffphase, einer weiteren WC- Hartstoffphase mit < 5 Ma.-% und dem Cobaltbinder. After sintering, the structure consisted of the HEC hard material phase, another WC hard material phase with <5% by mass and the cobalt binder.
Die mittels quantitativer Röntgenanalyse (Rietveldanalyse) bestimmten Anteile des HEH-haltigen Hartmetalls und der für das HEH bestimmte Gitterparameter sind dabei in Tab. 2 gegeben. The proportions of the HEH-containing hard metal determined by means of quantitative X-ray analysis (Rietveld analysis) and the lattice parameters determined for the HEH are given in Table 2.
Tab.2 Tab. 2
Beispiel 2 Example 2
Die in Beispiel 1 beschriebe gemahlenen Pulvermischung aus dem HEH Hartstoff der Zusammensetzung (Tao,2Nbo,2Tio,2Vo,2Wo,2)C wurde mit 16 Vol.-% Cobalt direkt mittels eines druckunterstützen Sinteraggregates (SPS/FAST der Firma FCT Syteme) bei einer Temperatur von 1200 °C und einer Haltezeit von 3 min zu Scheiben mit einem Durchmesser von 20 mm und einer Höhe von 6 mm gepresst und gesintert. The milled powder mixture described in Example 1 from the HEH hard material with the composition (Tao , 2Nbo , 2Tio , 2Vo , 2Wo , 2) C was added with 16% by volume of cobalt directly by means of a pressure-assisted sintering unit (SPS / FAST from FCT Syteme) A temperature of 1200 ° C and a holding time of 3 min to form disks with a diameter of 20 mm and a height of 6 mm and sintered.
Die Probenkörper erwiesen sich im Lichtmikroskop als vollständig dicht. Die Porosität gemäß ISO 4505 entsprach > A02, B00, C00. Die Vickershärte wurde zu 1540 HV10 bestimmt und die Bruchzähigkeit (Kic) wurde mittels der Ausmessung der Risslängen und unter Verwendung der Formel von Shetty (Shetty 1985 - Indentation fracture of WC-Co cermets, siehe Referenz oben) zu 10,1 MPa*m 1/2 berechnet. The test specimens were found to be completely tight under the light microscope. The porosity according to ISO 4505 corresponded to> A02, B00, C00. The Vickers hardness was determined to be 1540 HV10 and the fracture toughness (Kic) was determined by measuring the crack lengths and using Shetty's formula (Shetty 1985 - Indentation fracture of WC-Co cermets, see reference above) calculated to be 10.1 MPa * m 1/2.
Ergebnisse dieser Untersuchungen zur Dichte, Porosität, magnetischer Sättigung, Koerzitivfeldstärke, Härte und Bruchzähigkeit sind in Tabelle 3 gegeben. Results of these investigations on density, porosity, magnetic saturation, coercive field strength, hardness and fracture toughness are given in Table 3.
Tab. 3 Tab. 3
Das Gefüge bestand nach dem Sintern aus der HEC-Hartstoffphase, einer weiteren WC-Hartstoffphase mit < 5 Ma.-% und dem mit W angereicherten Cobaltbinder. After sintering, the structure consisted of the HEC hard material phase, another WC hard material phase with <5% by mass and the cobalt binder enriched with W.
Die mittels Röntgenanalyse bestimmten Anteile des HEH-haltigen Hartmetalls und der für das HEH bestimmte Gitterparameter sind dabei in Tab. 4 gegeben. The proportions of the HEH-containing hard metal determined by means of X-ray analysis and the lattice parameters determined for the HEH are given in Table 4.
Tab.4 Tab. 4
Beispiel 3 Example 3
Ein mittels einer Sinterung bei 1980 °C im Vakuum und einer nachfolgenden Zerkleinerung in einer Kugelmühle aus je 20 At.-% HfC, TaC, ZrC, NbC und VC, erzeugter einphasiger High Entropy Hartstoff der Zusammensetzung (Hfo,2Tao,2Zro,2Nbo,2Vo,2)C wurde mit 16 Vol.-% Cobalt (HalfMicron, von UmiCore) in einer Kugelmühle in Heptan und einem Pulver zu Mahlkugel Verhältnis von 1 :20 für 48 h gemahlen. Nach dem Trocknen wurde das Pulver zu Biegebruchstäben der Geometrie 45 x 5 x 6 mm3 Proben mittels des uniaxialen Pressens bei 200 MPa gepresst. A single-phase high entropy hard material of the composition (Hfo, 2Tao , 2Zro , 2Nbo , produced by means of sintering at 1980 ° C in a vacuum and subsequent comminution in a ball mill from 20 at .-% each of HfC, TaC, ZrC, NbC and VC) 2Vo , 2) C was with 16 vol .-% cobalt (HalfMicron, from UmiCore) in a ball mill in heptane and a powder to grinding ball ratio of 1:20 for 48 h ground. After drying, the powder was pressed into flexural rods with a geometry of 45 x 5 x 6 mm 3 samples by means of uniaxial pressing at 200 MPa.
Die Proben wurden bei 1280 °C für 45 min in einem SinterHIP-Ofen mit einem HIP- Druck von 10 MPa gesintert. The samples were sintered at 1280 ° C. for 45 min in a SinterHIP furnace with a HIP pressure of 10 MPa.
Die Probenkörper erwiesen sich im Lichtmikroskop als vollständig dicht. Die Porosität gemäß ISO 4505 entsprach > A02, B00, C00. Die Vickershärte wurde zu 1520 HV10 bestimmt und die Bruchzähigkeit (Kic) wurde mittels der Ausmessung der Risslängen und unter Verwendung der Formel von Shetty (Shetty 1985 - Indentation fracture of WC-Co cermets, siehe Referenz oben) zu 8,9 MPa*m 1/2 berechnet. The test specimens were found to be completely tight under the light microscope. The porosity according to ISO 4505 corresponded to> A02, B00, C00. The Vickers hardness was determined to be 1520 HV10 and the fracture toughness (Kic) was determined to be 8.9 MPa * m 1 by measuring the crack lengths and using the Shetty formula (Shetty 1985 - Indentation fracture of WC-Co cermets, see reference above) / 2 calculated.
Ergebnisse dieser Untersuchungen zur Dichte, Porosität, magnetischer Sättigung, Koerzitivfeldstärke, Härte und Bruchzähigkeit sind in Tabelle 5 gegeben. The results of these investigations on density, porosity, magnetic saturation, coercive field strength, hardness and fracture toughness are given in Table 5.
Tab. 5 Tab. 5
Das Gefüge bestand nach dem Sintern aus der HEC-Hartstoffphase, einer weiteren (Hf,Ta)C- Hartstoffphase mit < 2 Ma.-% und dem Cobaltbinder. After sintering, the structure consisted of the HEC hard material phase, another (Hf, Ta) C hard material phase with <2% by mass and the cobalt binder.
Beispiel 4 Example 4
Ein mittels einer Sinterung bei 2000 °C unter Stickstoff und einer nachfolgenden Zerkleinerung in einer Kugelmühle aus je 20 At.-% HfC, TaC, ZrC, NbC und TiCo,3Noj erzeugter einphasiger High Entropy Hartstoff der Zusammensetzung (Hfo,2Tao,2Zro,2Nbo,2Tio,2)Co,84No,u wurde mit 8 Vol.-% Cobalt (HalfMicron, von UmiCore) und 8 Vol.-% Nickel (2800, von EuroTungsten) in einer Kugelmühle in Heptan und einem Pulver-zu-Mahlkugel-Verhältnis von 1 :20 für 48 h gemahlen. Nach dem Trocknen wurden aus dem Pulver Biegebruchstäbe der Geometrie 45 x 5 x 6 mm3 Proben mittels des Uniaxialen Pressens bei 200 MPa gepresst. A generated by a sintering at 2000 ° C under nitrogen, and subsequent comminution in a ball mill of 20 At .-% HfC, TaC, ZrC, NbC and TiCo, 3Noj single-phase High Entropy hard material of the composition (Hfo, 2Tao, 2Zro, 2Nbo , 2Tio, 2) Co, 84No, u was mixed with 8% by volume of cobalt (HalfMicron, from UmiCore) and 8 vol .-% nickel (2800, from EuroTungsten) ground in a ball mill in heptane and a powder-to-grinding ball ratio of 1:20 for 48 h. After drying, bending rods with a geometry of 45 x 5 x 6 mm 3 samples were pressed from the powder by means of uniaxial pressing at 200 MPa.
Die Probenkörper erwiesen sich im Lichtmikroskop als vollständig dicht. Die Porosität gemäß ISO 4505 entsprach > A04, B00, C00. Die Vickershärte wurde zu 1720 HV10 bestimmt und die Bruchzähigkeit (Kic) wurde mittels der Ausmessung der Risslängen und unter Verwendung der Formel von Shetty (Shetty 1985 - Indentation fracture of WC-Co cermets, siehe Referenz oben) zu 7,7 MPa*m 1/2 berechnet. The test specimens were found to be completely tight under the light microscope. The porosity according to ISO 4505 corresponded to> A04, B00, C00. The Vickers hardness was determined to be 1720 HV10 and the fracture toughness (Kic) was determined to be 7.7 MPa * m 1 by measuring the crack lengths and using the Shetty formula (Shetty 1985 - Indentation fracture of WC-Co cermets, see reference above) / 2 calculated.
Ergebnisse dieser Untersuchungen zur Dichte, Porosität, magnetischer Sättigung, Koerzitivfeldstärke, Härte und Bruchzähigkeit sind in Tabelle 6 gegeben. Results of these investigations on density, porosity, magnetic saturation, coercive field strength, hardness and fracture toughness are given in Table 6.
Tab. 6 Tab. 6
Beispiel 5 Example 5
Ein mittels einer Sinterung bei 2000 °C im Vakuum und einer nachfolgenden Zerkleinerung in einer Kugelmühle aus je 25 At.-% HίOo,qOo,i, TaC, ZrC, und NbC erzeugter einphasiger High Entropy Hartstoff HEH der Zusammensetzung (Hfo,25Tao,25Zro,25Nbo,25)Co,9750o,o25 wurde mit 16 Vol.-% Cobalt (HalfMicron, von UmiCore) in einer Kugelmühle in einem Lösungsmittel (Heptan) und einem Pulver-zu- Mahlkugel-Verhältnis von 1 :20 für 48 h gemahlen. Nach dem Trocknen wurden aus dem Pulver Biegebruchstäbe der Geometrie 45 x 5 x 6 mm3 mittels des Uniaxialen Pressens bei 200 MPa gepresst. Die Proben wurden bei 1280 °C für 60 min in einem SinterHIP-Ofen mit einem HIP- Druck von 10 MPa gesintert. A single-phase high entropy hard material HEH of the composition (Hfo, 25Tao, produced by means of sintering at 2000 ° C in a vacuum and subsequent comminution in a ball mill from 25 at .-% HίOo , q Oo , i, TaC, ZrC, and NbC) 25Zro, 25Nbo, 25) Co, 9750o, o25 was mixed with 16% by volume cobalt (HalfMicron, from UmiCore) in a ball mill in a solvent (heptane) and a powder-to-grinding ball ratio of 1:20 for 48 h ground. After drying, bending rods with a geometry of 45 × 5 × 6 mm 3 were pressed from the powder by means of uniaxial pressing at 200 MPa. The samples were sintered at 1280 ° C. for 60 min in a SinterHIP furnace with a HIP pressure of 10 MPa.
Die Probenkörper erwiesen sich im Lichtmikroskop als vollständig dicht. Die Porosität gemäß ISO 4505 entsprach > A02, B00, C00. Die Vickershärte wurde zu 1420 HV10 bestimmt und die Bruchzähigkeit (Kic) wurde mittels der Ausmessung der Risslängen und unter Verwendung der Formel von Shetty (Shetty 1985 - Indentation fracture of WC-Co cermets) zu 8,0 MPa*m 1/2 berechnet. The test specimens were found to be completely tight under the light microscope. The porosity according to ISO 4505 corresponded to> A02, B00, C00. The Vickers hardness was determined to be 1420 HV10 and the fracture toughness (Kic) was calculated to be 8.0 MPa * m 1/2 using the Shetty's formula (Shetty 1985 - Indentation fracture of WC-Co cermets).
Ergebnisse dieser Untersuchungen zur Dichte, Porosität, magnetischer Sättigung, Koerzitivfeldstärke, Härte und Bruchzähigkeit sind in Tabelle 7 gegeben. Results of these investigations on density, porosity, magnetic saturation, coercive field strength, hardness and fracture toughness are given in Table 7.
Tab. 7 Tab. 7
Das Gefüge bestand nach dem Sintern aus der HEC-Hartstoffphase, weiterer Hf-Ta- haltigen Hartstoffphasen (in Form eines Oxycarbids) mit < 5 Ma.-% und dem Cobaltbinder. After sintering, the structure consisted of the HEC hard material phase, further hard material phases containing Hf-Ta (in the form of an oxycarbide) with <5% by mass and the cobalt binder.

Claims

Patentansprüche Claims
1. Hartmetalle mindestens bestehend aus Hartstoffen in Partikelform und dazwischen angeordnetem Bindemetall, wobei ein high-entropy-Hartstoff (HEH) dessen Gehalt im erfindungsgemäßen Hartmetall mindestens 50 Vol.-% beträgt, aus mindestens vier Metallen (Me) der 4. und/oder 5. und/oder 6. Nebengruppe des Periodensystems der Elemente (PSE) in Form einer festen Lösung von Carbiden, Nitriden, Carbonitriden, Oxycarbiden und/oder Oxycarbonitriden der Metalle zusammengesetzt ist, und wobei der jeweilige Anteil x, y und z in Summe des Kohlenstoff (C), des Stickstoffs (N) und des Sauerstoffs (0) in den Carbiden, Nitriden, Carbonitriden, Oxycarbiden und/oder Oxycarbonitriden der Metalle der 4. und/oder 5. und/oder 6. Nebengruppe des PSE gemäß MeCxNyOz = 0,7 < x+y+z <1 ist, und wobei die jeweiligen Anteile der Metalle der 4. und/oder 5. und/oder 6. Nebengruppe des PSE an den mindestens vier Metallen im HEH im Wesentlichen gleich groß sind oder der Anteil eines oder mehrerer dieser Metalle um maximal 20 At.-% davon abweicht, und wobei die Carbide, Nitride, Carbonitride, Oxycarbide und/oder Oxycarbonitride der Metalle der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in jedem Hartstoffpartikel als feste Lösung vorliegen, und weiterhin höchstens 50 Vol.-% der Hartstoffe eine andere Hartstoff-Zusammensetzung aufweisen, und wobei als Bindemetalle alle für Hartmetalle bekannten Bindemetalle in den für Hartmetalle bekannten Anteilen von 0,1 bis 40 Vol.-%, bezogen auf das Hartmetall, vorhanden sind. 1. Hard metals at least consisting of hard materials in particle form and binding metal arranged in between, with a high-entropy hard material (HEH) whose content in the hard metal according to the invention is at least 50% by volume, of at least four metals (Me) of the 4th and / or 5th and / or 6th subgroup of the Periodic Table of the Elements (PSE) is composed in the form of a solid solution of carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides of the metals, and the respective proportion of x, y and z in the sum of the Carbon (C), nitrogen (N) and oxygen (0) in the carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides of the metals of the 4th and / or 5th and / or 6th subgroup of the PSE according to MeC x N y O z = 0.7 <x + y + z <1, and where the respective proportions of the metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the at least four metals in the HEH are essentially are the same or the proportion of one or more of these metals around a maximum of 20 at .-% deviates therefrom, and where the carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides of the metals of the 4th and / or 5th and / or 6th subgroup of the PSE are present in each hard material particle as a solid solution, and furthermore at most 50% by volume of the hard materials have a different hard material composition, and all binding metals known for hard metals are present as binding metals in the proportions known for hard metals of 0.1 to 40% by volume, based on the hard metal.
2. Hartmetalle nach Anspruch 1, bei denen 50 - 100 Vol.-%, vorteilhafterweise 60 - 99 Vol.-%, noch vorteilhafterweise 80 - 98 Vol.-% der Hartstoffe ein HEH aus mindestens vier Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form einer festen Lösung von Carbiden, Nitriden, Carbonitriden, Oxycarbiden und/oder Oxycarbonitriden sind. 2. Hard metals according to claim 1, in which 50-100% by volume, advantageously 60-99% by volume, still advantageously 80-98% by volume of the hard materials is a HEH of at least four metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of a solid solution of carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides.
3. Hartmetalle nach Anspruch 1, bei denen 0- 50 Vol.-%, vorteilhafterweise 1 bis 20 Vol.-%, an weiteren Hartstoffen im Hartmetall aus einem, zwei oder drei Metallen der3. Hard metals according to claim 1, in which 0-50% by volume, advantageously 1 to 20% by volume, of further hard materials in the hard metal of one, two or three metals
4. und/oder 5. und/oder 6. Nebengruppe des Periodensystems der Elemente (PSE) in Form einer festen Lösung von Carbiden, Nitriden, Carbonitriden, Oxycarbiden und/oder Oxycarbonitriden der Metalle zusammengesetzt sind. 4th and / or 5th and / or 6th subgroup of the Periodic Table of the Elements (PSE) are composed in the form of a solid solution of carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides of the metals.
4. Hartmetalle nach Anspruch 1, bei denen die Hartstoffe aus Carbiden oder Nitriden der Metalle der 4. und/oder 5. und/oder 6. Nebengruppe des PSE zusammengesetzt sind. 4. Hard metals according to claim 1, in which the hard materials are composed of carbides or nitrides of the metals of the 4th and / or 5th and / or 6th subgroup of the PSE.
5. Hartmetalle nach Anspruch 1, bei denen der jeweilige Anteil x, y und z in Summe des Kohlenstoff (C), des Stickstoffs (N) und des Sauerstoffs (0) in den Carbiden, Nitriden, Carbonitriden , Oxycarbiden und/oder Oxycarbonitriden mit Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE gemäß MeCxNyOz = 0,9 < x+y+z <1, vorteilhafterweise bei MeCxNyOz mit x = 0 -1 und/oder y = 0 - 1 und/oder z = 0 - 0,2, ist. 5. Hard metals according to claim 1, in which the respective proportion x, y and z in the sum of the carbon (C), the nitrogen (N) and the oxygen (0) in the carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides Metals of the 4th and / or 5th and / or 6th subgroup of the PSE according to MeC x N y O z = 0.9 <x + y + z <1, advantageously with MeC x N y O z with x = 0 - 1 and / or y = 0-1 and / or z = 0-0.2.
6. Hartmetalle nach Anspruch 1, bei denen die Anteile der Metalle vorhanden sind gemäß: 6. Hard metals according to claim 1, in which the proportions of the metals are present according to:
HEH aus einer Anzahl von n Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE mit n = 4 bis 9, wobei im Falle von n = 4 bis 6 die Anteile der jeweiligen Metalle nach (1/n 100) + 10 At.-%, vorteilhafterweise + 5 At.-%, noch vorteilhafterweise + 2 At.-%, und/oder im Falle von n = 7 bis 9 die Anteile der jeweiligen Metalle nach (1/n 100) + 5 At.-%, vorteilhafterweise + 2 At.-%, und/oder die Anteile von n-3 (n minus 3) der Metalle auch um Anteile von jeweils > 10 At.-% bezogen auf den Gesamtmetallgehalt im HEH abweichen können, wobei der Anteil eines der Metalle maximal 70 At.-%, vorteilhafterweise 60 At.-% bezogen auf den Gesamtmetallgehalt der HEH, betragen kann. HEH from a number of n metals of the 4th and / or 5th and / or 6th subgroup of the PSE with n = 4 to 9, whereby in the case of n = 4 to 6 the proportions of the respective metals according to (1 / n 100 ) + 10 at.%, Advantageously + 5 at.%, Still advantageously + 2 at.%, And / or in the case of n = 7 to 9 the proportions of the respective metals according to (1 / n 100) + 5 At .-%, advantageously + 2 At .-%, and / or the proportions of n-3 (n minus 3) of the metals can also differ by proportions of> 10 At .-% based on the total metal content in the HEH, with the proportion of one of the metals can be a maximum of 70 at.%, advantageously 60 at.%, based on the total metal content of the HEH.
7. Hartmetalle nach Anspruch 1, bei dem jeder Anteil eines Metalls um maximal 20 At.-% von dem Anteil abweicht, der sich aus den gleichen Anteilen für alle Metalle bei n Metallen ergibt. 7. Hard metals according to claim 1, in which each proportion of a metal differs by a maximum of 20 at .-% from the proportion which results from the same proportions for all metals in n metals.
8. Hartmetalle nach Anspruch 1, bei denen der Hartstoff HEH aus fünf, sechs, sieben oder mehr Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form einer festen Lösung von Carbiden, Nitriden, Carbonitriden, Oxycarbiden und/oder Oxycarbonitriden zusammengesetzt vorliegt. 8. Hard metals according to claim 1, in which the hard material HEH consists of five, six, seven or more metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of a solid solution of carbides, nitrides, carbonitrides, oxycarbides and / or oxycarbonitrides is composed.
9. Hartmetalle nach Anspruch 1, bei denen im HEH aus mindestens vier Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form einer festen Lösung von Carbiden, Nitriden, Carbonitriden und/oder Oxycarbonitriden der Anteil der mindestens vier Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form von Carbiden, Nitriden, Carbonitriden und/oder Oxycarbonitriden jeweils im Wesentlichen gleich groß sind. 9. Hard metals according to claim 1, in which in the HEH of at least four metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of a solid solution of carbides, nitrides, carbonitrides and / or oxycarbonitrides, the proportion of at least four metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of carbides, nitrides, carbonitrides and / or oxycarbonitrides are each essentially the same size.
10. Hartmetalle nach Anspruch 1, bei denen Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W als Metalle der Hartstoffe vorhanden sind. 10. Hard metals according to claim 1, in which Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W are present as metals of the hard materials.
11. Hartmetalle nach Anspruch 1, bei denen Co, Ni, Fe, Mn, Cu, Cr, Ti oder deren Mischungen, wie kohlenstoffarme und kohlenstoffreiche Stähle und high entropy Metalllegierungen, als Bindemetalle vorhanden sind. 11. Hard metals according to claim 1, in which Co, Ni, Fe, Mn, Cu, Cr, Ti or mixtures thereof, such as low-carbon and high-carbon steels and high entropy metal alloys, are present as binder metals.
12. Hartmetalle nach Anspruch 1, bei denen 5 bis 32 Vol.-% Bindemetall, bezogen auf das Hartmetall, in den Hartmetallen enthalten ist. 12. Hard metals according to claim 1, in which 5 to 32 vol .-% binder metal, based on the hard metal, is contained in the hard metals.
13. Verfahren zur Herstellung von Hartmetallen, bei denen Pulver von mindestens vier Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des Periodensystems der Elemente (PSE) in Form von Carbiden, Nitriden, Carbonitriden und/oder Oxycarbonitriden gemischt und zu einem HEH-Pulver oder zu HEH-Granalien synthetisiert werden und nachfolgend zu den HEH-Pulvern oder den Granalien des HEHs maximal 50 Vol.-% weitere Hartstoffpulver oder Hartstoff-Granalien zugegeben werden, und diese Hartstoffe mit pulverförmigem Bindemetall in einem Anteil von 0,1 bis 40 Vol.-%, bezogen auf das Hartmetall, gemischt und zu Hartmetallpulver oder Hartmetallgranalien und nach einer Formgebung zu Bauteilen gesintert werden. 13. Process for the production of hard metals, in which powders of at least four metals of the 4th and / or 5th and / or 6th subgroup of the Periodic Table of the Elements (PSE) in the form of carbides, nitrides, carbonitrides and / or oxycarbonitrides are mixed and are synthesized into an HEH powder or into HEH granules and subsequently a maximum of 50% by volume of further hard material powders or hard material granules are added to the HEH powders or the granules of the HEH, and these hard materials with powdery binding metal in a proportion of 0 , 1 to 40 vol .-%, based on the hard metal, mixed and sintered to hard metal powder or hard metal granules and after shaping into components.
14. Verfahren nach Anspruch 13, bei dem über ein Formgebungsverfahren aus der Mischung mit organischen Bindemitteln Bauteile geformt werden, die organischen Bindemittel entfernt und die Bauteile gesintert werden. 14. The method according to claim 13, in which components are formed from the mixture with organic binders via a molding process, the organic binders are removed and the components are sintered.
15. Verfahren nach Anspruch 13, bei dem die Formgebung mittels Pressen, Extrudieren, Spritzgießen, CIP (Cold Isostatic Pressing) und/oder mittels Additiver Formgebung realisiert wird. 15. The method according to claim 13, in which the shaping is realized by means of pressing, extrusion, injection molding, CIP (Cold Isostatic Pressing) and / or by means of additive shaping.
16. Verfahren nach Anspruch 13, bei dem die Sinterung drucklos oder druckunterstützt mittels Sinter-Fleißisostatischem Pressen, Fleißisostatischem Pressen(FIIP), Fleißpressen oder SPS erfolgt. 16. The method according to claim 13, in which the sintering takes place without pressure or with pressure support by means of sintering isostatic pressing, isostatic pressing (FIIP), industrial pressing or SPS.
17. Verfahren nach Anspruch 13, bei dem mindestens fünf oder sechs oder sieben oder mehr Pulver aus Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form von Carbiden, Nitriden, Carbonitriden und/oder Oxycarbonitriden gemischt und die Mischung in-situ während der Sinterung mit Bindemetallen zu FHEFH- haltigen Hartmetallen synthetisiert wird. 17. The method according to claim 13, in which at least five or six or seven or more powders of metals of the 4th and / or 5th and / or 6th subgroup of the PSE in the form of carbides, nitrides, carbonitrides and / or oxycarbonitrides are mixed and the mixture is synthesized in-situ during sintering with binding metals to form FHEFH-containing hard metals.
18. Verfahren nach Anspruch 13, bei dem vier Pulver aus Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form von Carbiden, und/oder Nitriden gemischt und die Mischung in-situ während der Sinterung mit Bindemetallen zu HEH- haltigen Hartmetallen synthetisiert wird. 18. The method according to claim 13, in which four powders of metals of the 4th and / or 5th and / or 6th subgroup of the PSE are mixed in the form of carbides and / or nitrides and the mixture is mixed in-situ during sintering with binding metals is synthesized into HEH-containing hard metals.
19. Verfahren nach Anspruch 13, bei dem 0 - < 50 Vol.-% vorteilhafterweise 1 bis 20 Vol.-% an Pulvern von Hartstoffen aus einem oder zwei oder drei Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE in Form einer festen Lösung von Carbiden, Nitriden, Carbonitriden und/oder Oxycarbonitriden eingesetzt werden. 19. The method according to claim 13, wherein 0 - <50 vol .-%, advantageously 1 to 20 vol .-% of powders of hard materials from one or two or three metals of the 4th and / or 5th and / or 6th subgroup of the PSE can be used in the form of a solid solution of carbides, nitrides, carbonitrides and / or oxycarbonitrides.
20. Verfahren nach Anspruch 13, bei dem die Synthese der HEH-Pulver aus der Reduktion von Oxiden von Metallen der 4. und/oder 5. und/oder 6. Nebengruppe des PSE zu Metallen und der anschließenden Co-Karburierung und/oder Nitrierung durchgeführt wird oder durch eine Direkte Karburierung und/oder Nitrierung der Mischoxide erfolgt. 20. The method according to claim 13, in which the synthesis of the HEH powder from the reduction of oxides of metals of the 4th and / or 5th and / or 6th subgroup of the PSE to metals and the subsequent co-carburization and / or nitration is carried out or is carried out by direct carburization and / or nitration of the mixed oxides.
21. Verfahren nach Anspruch 13, bei dem zu HEH-Pulver maximal 50 Vol.-% weitere Hartstoffpulver zugegeben werden, und diese Hartstoffe mit pulverförmigem Bindemetall in einem Anteil von 0,1 bis 40 Vol.-%, bezogen auf das Hartmetall, gemischt und nachfolgend zu teilweise oder vollständig gesinterten Hartmetall- Granalien gesintert werden. 21. The method as claimed in claim 13, in which a maximum of 50% by volume of further hard material powders are added to HEH powder, and these hard materials are mixed with powdery binding metal in a proportion of 0.1 to 40% by volume, based on the hard metal and subsequently sintered to partially or fully sintered cemented carbide granules.
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