WO2010034369A1 - Corps en métal dur et son procédé de fabrication - Google Patents

Corps en métal dur et son procédé de fabrication Download PDF

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Publication number
WO2010034369A1
WO2010034369A1 PCT/EP2009/005090 EP2009005090W WO2010034369A1 WO 2010034369 A1 WO2010034369 A1 WO 2010034369A1 EP 2009005090 W EP2009005090 W EP 2009005090W WO 2010034369 A1 WO2010034369 A1 WO 2010034369A1
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WO
WIPO (PCT)
Prior art keywords
phase
microns
binder
layer
mass
Prior art date
Application number
PCT/EP2009/005090
Other languages
German (de)
English (en)
Inventor
Klaus RÖDIGER
Hendrikus Van Den Berg
Walter Lengauer
Klaus Dreyer
Dominic Janisch
Original Assignee
Kennametal Inc.
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 Kennametal Inc. filed Critical Kennametal Inc.
Priority to US13/061,593 priority Critical patent/US20110150692A1/en
Priority to CN2009801358675A priority patent/CN102159743A/zh
Publication of WO2010034369A1 publication Critical patent/WO2010034369A1/fr

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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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor

Definitions

  • the invention relates to a hard metal body with 1-30 mass% binder of Co, Co / Ni, Co / Fe, Co / Ni / Fe or Ni / Fe and a hard material.
  • the invention further relates to a method for producing such a cemented carbide body by powder metallurgy, in which a starting powder mixture is mixed, ground, precompressed into a green compact and finally sintered.
  • Cemented carbide bodies with a binder phase and a hard material phase which comprise carbides, nitrides, carbonitrides or oxycarbonitrides of the elements Ti 1 Zr, Hf, V, Nb, Ta, Cr, Mo and / or W are known in principle from the prior art. It is also known that the hardness and wear resistance of a cemented carbide body can be influenced by the particle size and the particle size distribution in the finished sintered body. Decisive factors include the composition of the starting materials, the production conditions, in particular the grain sizes of the starting powder, their grinding and the sintering temperature. In the production of hard metal bodies by powder metallurgy, the carbon balance of the hard metal approach also plays a significant role.
  • the hexagonal phase and cubic face centered phase microstructure has a mean grain size between 0.2 ⁇ m and 1 ⁇ m, and the mean hexagonal and cubic face centered grain sizes differ by no more than 30%.
  • the cubic face-centered phase additionally contains at least one of the elements Ta, Nb, Hf, Cr, Mo or V.
  • chromium and vanadium serve here as grain growth inhibitors.
  • the face-centered cubic phase consists of a carbonitride having a molar C content between 80% and 40% and a molar N content between 20% and 60%.
  • the cemented carbide body has a marginal zone which is free of cubic face-centered carbides or carbonitrides. A method for producing such a low-mix boundary zone is described in DE 197 52 298 C1.
  • a substantially pure WC-Co composition adjoins and what c) in a third lowermost layer with a thickness of at least 10 microns and a maximum of 650 microns the proportions of the binder phase and the IVa and / or Va-EIe- elements change to the present in the body, substantially constant value increasing and the tungsten content drops to the substantially constant inside the body value.
  • a peripheral zone formation in which a) in an outer, adjoining the body surface or an edge zone with a penetration depth of 1 .mu.m to a maximum of 3 .mu.m and to a depth of between 10 ⁇ m to 200 ⁇ m in the hard material phase, the tungsten and the binder phase content is at most 0.8 times the proportion resulting from the total composition, and in this layer the tungsten and binder phase content increases substantially continuously towards the interior of the body and the nitrogen content to the interior of the body decreases substantially continuously, b) in an underlying middle layer of a thickness between 20 microns and 400 microns tungsten and binder phase contents with progressive penetration depth a maximum and the contents of the elements of the IVa and / or Va group of the Periodic Table go through a minimum and c) in a third lowermost layer which reaches up to a depth of penetration of up to 1 mm measured by the body surface, the tungsten and
  • first layer with increased binder content and a reduced proportion of mixed carbides another, 2-40 microns thick second layer follows which has a higher nitrogen content than the first layer and which consists essentially of nitrides and / or carbonitrides of the metals of the IVa group of the Periodic Table and phase fractions of up to 10% by volume of carbides, nitrides, carbonitrides or oxicarbonitrides of the elements W, Mo , V, Ta, Nb, Cr, and / or has dissolved in the hard phase portions of up to 5 mass% V, Nb, Ta and up to 2 mass% Cr, Mo, W and contains up to 15 mass% binder.
  • a transition zone with a thickness of 2 .mu.m to 100 .mu.m is formed, in which the composition gradually changes to a homogeneous composition in the interior of the core of the cemented carbide body.
  • a relatively tough and abrasive resistant zone with high levels of WC is given
  • underlying layer is a diffusion-resistant, hard layer with a high nitride or carbonitride content.
  • This starting mixture is ground, pre-pressed into a green compact and finally sintered.
  • hexagonal WC or a tungsten-containing phase such as pure W, W 2 C or WO 3 , which reacts by carbon uptake to hexagonal WC, is additionally used in the starting mixture.
  • the supply of nitrogen to the sintering process is carried out in such a way that a hard-material skeleton with at least one face-centered cubic phase is formed.
  • the hard-material skeleton of the finished sintered body may contain more or less hexagonal WC.
  • the content of metals of the IVa, Va and / or Vla group of the Periodic Table in the cubic face-centered phase need not coincide with the content of the finished sintered cemented carbide body.
  • the hard material skeleton may have a non-metal / metal content ratio of 0.8 to 1.0, where the non-metal content is the sum of all nonmetals of the individual phases of the hard material skeleton (C + N + O) in mol and the metal content is the sum of all Metals of the phases of the hard material skeleton denoted in mol.
  • the nitrogen pressure and the exposure time of the nitrogen therefore, the coefficients in the reaction equation given above are different.
  • An influence in terms of structure optimization and adjustment a specially constructed binder phase can additionally by adding carbon, carbides, oxides, oxicarbides, Oxicarbonitriden the metals Ti, Zr, Hf, V 1 Nb, Ta 1 Cr, Mo, W or carbon nitrides to carbide approach or by supplying carbon-emitting gases at Dewaxing, pre-sintering or sintering process done.
  • Hard metals which are produced by the described starting materials and processes, have a finer structure, a z. T. substantially higher hardness at about the same fracture toughness K 1c and are conventional, non-reaction sintered and produced from non-prealloyed powders hard metals of the same overall composition superior.
  • the nitrogen atmosphere is maintained even during cooling at least until reaching 1000 0 C.
  • the method can be extended to the effect that after cooling to at least 1000 0 C, the sintered body additionally in a nitrogen atmosphere under a nitrogen pressure of 5 x 10 3 Pa to 10 7 Pa at temperatures between 1000 ° C and a temperature below the eutectic, preferably below 1200 0 C, is treated.
  • at least part of the nitrogen is introduced by nitrides, carbonitrides and / or oxicarbonitrides contained in the starting mixture of at least one of the metals V, Nb 1 Ta, Cr, Mo and W or by means of solid carbon nitrides.
  • the powdery starting mixture at least z. T. resorted to powdered hard materials, which have been obtained from recycled carbide bodies.
  • the maximum Temperature of 1450 0 C was maintained for 30 minutes, after which the body was cooled to room temperature at a cooling rate of 4 ° C / min.
  • the average nitrogen content of the cemented carbide body was 0
  • the hardness HV 30 could be increased from 1560 to the stated value of 1840 compared to such cemented carbide bodies which have an identical overall composition but have been produced using non-prealloyed hard material powders.
  • a powder mixture of 18.8 mass% of a multiphase prealloyed carbide powder of the type (Ti 1 Ta, Nb.Cr, W) C with low levels of WC and W 2 C, which originated from a synthesis process, and 8 mass% Co, 6.2 mass% W, rest WC was made a green product.
  • the pre-pressed green compact was heated in a vacuum sintering furnace at 1100 0 C under vacuum at a heating rate of 8 ° C / min. This temperature was maintained for 15 minutes, after which a nitrogen pressure of 2.5 to 2.75 x 10 4 Pa was set.
  • the body was then heated to 1300 0 C, held this temperature for 15 min, before the same heating rate, the body was heated to 1450 ° C. This temperature of 1450 0 C was maintained for 30 min, after which the sintered body at a cooling rate of 4 ° C / min was cooled to room temperature.
  • the resulting sintered body had a hardness of 1730 HV30, a fracture toughness K
  • the average nitrogen content of the cemented carbide body was 0.5% by mass
  • Sintered bodies of the same overall composition were prepared, but in the starting mixture, only those hard powder powders were used which were not pre-alloyed Such a sintered body had a hardness HV30 of 1510.
  • the maximum temperature of 1450 ° C was maintained for 30 minutes, after which the body was cooled to room temperature at a cooling rate of 4 ° C / min.
  • the average nitrogen content of the hard material body was 2 mass%.
  • a hard material powder composed of two phases (Ti 1 Ta 1 Nb 1 Cr 1 W) C and originating from a synthesis process with 25 mass% of a recycling powder consisting essentially of WC and Co, 27 mass% W, 8 mass% Co, remainder WC, and pressed to a cemented carbide green body, which was then heated in a vacuum sintering furnace under vacuum at 8 ° C / min to 1100 0 C.
  • nitrogen was placed 10 4 Pa under a pressure of 2.5 to 2.75 x and then heated the body at a rate of 3 ° C / min to 1450 0 C, interrupted by another 15-minute hold time at 1300 0 C.
  • the average nitrogen content of the hard material body was 2
  • the hardness HV30 could be increased from 1580 to 1760 compared to a cemented carbide body of the same total chemical composition, but using a starting powder mixture containing no prealloyed hard powder powders.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Cutting Tools, Boring Holders, And Turrets (AREA)
  • Ceramic Products (AREA)

Abstract

La présente invention concerne un corps en métal dur comprenant 1 à 30 % massiques de liant, le reste étant une matière dure ayant une phase WC hexagonale et une phase cubique à faces centrées de forme (M1, M2, M3)C ou (M1, M2, M3)(C, N) ou encore (M1, M2, M3)(O, C, N), où M1 = Ti et/ou Zr et M2 = W et M3 désigne éventuellement aucun ou bien un ou plusieurs des éléments Ta, Nb, Hf, Cr, Mo ou V. La proportion de phase cubique à faces centrées rapportée à la masse totale s’élève à 2 %-97 %, de préférence à 5-12 % massiques, et la microstructure de la phase hexagonale et de la phase cubique à faces centrées présente une granulométrie moyenne comprise entre 0,2 μm et 1 μm, de préférence ≤ 0,9 μm et les granulométries moyennes de la phase hexagonale et de la phase cubique à faces centrées diffèrent de 30 % au plus. L’invention concerne en outre un procédé pour fabriquer le corps en métal dur ayant la composition mentionnée. Selon ce procédé, le mélange de départ contient, outre le métal liant ou les métaux liants, une phase pré-alliée du type (M1, M2, M3)C ou (M1, M2, M3)(C, N) ou encore (M1, M2, M3)(O, C, N), où M1 = Ti et/ou Zr et M2 = W et M3 désigne éventuellement aucun ou bien un ou plusieurs des éléments Ta, Nb, Hf, Cr, Mo ou V.
PCT/EP2009/005090 2008-09-25 2009-07-14 Corps en métal dur et son procédé de fabrication WO2010034369A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US13/061,593 US20110150692A1 (en) 2008-09-25 2009-07-14 Submicron Cemented Carbide with Mixed Carbides
CN2009801358675A CN102159743A (zh) 2008-09-25 2009-07-14 烧结碳化物体以及用于生产它的方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102008048967A DE102008048967A1 (de) 2008-09-25 2008-09-25 Hartmetallkörper und Verfahren zu dessen Herstellung
DE102008048967.0 2008-09-25

Publications (1)

Publication Number Publication Date
WO2010034369A1 true WO2010034369A1 (fr) 2010-04-01

Family

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PCT/EP2009/005090 WO2010034369A1 (fr) 2008-09-25 2009-07-14 Corps en métal dur et son procédé de fabrication

Country Status (4)

Country Link
US (1) US20110150692A1 (fr)
CN (1) CN102159743A (fr)
DE (1) DE102008048967A1 (fr)
WO (1) WO2010034369A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102012018067A1 (de) * 2012-09-13 2014-03-13 Tutec Gmbh Hexagonales WC-Pulver, Verfahren zu dessen Herstellung sowie Verwendung dieses Pulvers
BR112015029883A2 (pt) * 2013-05-31 2017-07-25 Sandvik Intellectual Property novo processo de manufaturação de metal duro e um produto obtido a partir do mesmo
KR102231553B1 (ko) * 2013-05-31 2021-03-23 산드빅 인터렉츄얼 프로퍼티 에이비 초경합금의 신규 제조 방법 및 그로부터 획득되는 제품
GB201900988D0 (en) * 2019-01-24 2019-03-13 Hyperion Materials & Tech Sweden Ab Lightweight cemented carbide

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EP0913489A1 (fr) * 1996-12-16 1999-05-06 Sumitomo Electric Industries, Limited Carbure fritte, procede de production de celui-ci et outils en carbure fritte
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EP0591121A1 (fr) * 1992-09-30 1994-04-06 Sandvik Aktiebolag Alliage de carbonitrure à base de titanium ayant une structure commandée
WO1996024454A1 (fr) * 1995-02-09 1996-08-15 Sandvik Ab Procede de production de materiaux metalliques composites
WO1998003691A1 (fr) * 1996-07-19 1998-01-29 Sandvik Ab (Publ) Plaquette de carbure fritte destinee au tournage, au fraisage et au perçage
EP0913489A1 (fr) * 1996-12-16 1999-05-06 Sumitomo Electric Industries, Limited Carbure fritte, procede de production de celui-ci et outils en carbure fritte
DE19752289C1 (de) * 1997-11-26 1999-04-22 Hartmetall Beteiligungs Gmbh Gesinterter Hartmetall-Formkörper
DE19845376A1 (de) * 1998-07-08 2000-01-13 Widia Gmbh Hartmetall- oder Cermet-Körper

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Also Published As

Publication number Publication date
CN102159743A (zh) 2011-08-17
US20110150692A1 (en) 2011-06-23
DE102008048967A1 (de) 2010-04-01

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