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EP4041927A1 - Métaux durs et leur procédé de production - Google Patents

Métaux durs et leur procédé de production

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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)
English (en)
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 Foerderung der Angewandten Forschung eV
Original Assignee
Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV filed Critical Fraunhofer Gesellschaft zur Foerderung der Angewandten Forschung eV
Publication of EP4041927A1 publication Critical patent/EP4041927A1/fr
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.

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Abstract

L'invention concerne le domaine des matériaux métalliques durs et des métaux durs, tels que ceux qui peuvent être utilisés, par exemple, en tant que matériau de coupe pour des outils. L'objectif de la présente invention est de fournir des métaux durs qui comprennent un nouveau concept pour la composition structurale des métaux durs. L'objectif est réalisé par des métaux durs qui sont constitués au moins de matériaux durs sous forme particulaire et d'un métal liant agencé entre ceux-ci, un matériau dur à entropie élevée (HEH) étant composé d'au moins quatre métaux (Me) des 4e et/ou 5e et/ou 6e sous-groupes de la classification périodique des éléments sous la forme d'une solution solide de carbures, de nitrures, de carbonitrures, d'oxycarbures et/ou d'oxycarbonitrures des métaux, les fractions respectives des métaux dans le HEH étant pratiquement identiques.
EP20786283.0A 2019-10-11 2020-10-05 Métaux durs et leur procédé de production Pending EP4041927A1 (fr)

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CN114196914B (zh) * 2021-12-14 2022-09-02 中国科学院兰州化学物理研究所 一种碳化物高熵陶瓷材料、碳化物陶瓷层及其制备方法和应用
CN115305403A (zh) * 2022-08-18 2022-11-08 中南大学 一种超强超硬高断裂韧性的硬质合金及其制备方法
CN115386777B (zh) * 2022-09-02 2023-07-18 石家庄铁道大学 一种过渡金属碳氮化物基高熵金属陶瓷及其制备方法
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CN115595463B (zh) * 2022-10-26 2023-07-18 山东大学 一种高熵硬质合金刀具材料及其制备方法与应用
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