EP0689617B1 - Cermet et son procede de production - Google Patents

Cermet et son procede de production Download PDF

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Publication number
EP0689617B1
EP0689617B1 EP94904953A EP94904953A EP0689617B1 EP 0689617 B1 EP0689617 B1 EP 0689617B1 EP 94904953 A EP94904953 A EP 94904953A EP 94904953 A EP94904953 A EP 94904953A EP 0689617 B1 EP0689617 B1 EP 0689617B1
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EP
European Patent Office
Prior art keywords
mass
cermet
hard material
powder
particle size
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.)
Expired - Lifetime
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EP94904953A
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German (de)
English (en)
Other versions
EP0689617A1 (fr
Inventor
Hans Kolaska
Klaus Dreyer
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.)
Widia GmbH
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Widia GmbH
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
Priority claimed from DE4344576A external-priority patent/DE4344576A1/de
Application filed by Widia GmbH filed Critical Widia GmbH
Publication of EP0689617A1 publication Critical patent/EP0689617A1/fr
Application granted granted Critical
Publication of EP0689617B1 publication Critical patent/EP0689617B1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/04—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
    • 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

Definitions

  • the invention relates to a cermet with 95 to 75% by mass of hard material phase, the remainder being cobalt and nickel.
  • the invention further relates to a process for the production of such a cermet by grinding a carbide, nitride and / or carbonitride of titanium and tungsten and, if appropriate, further elements of the IVa to VIa group of the periodic table, and a binder metal such as cobalt and / or nickel Mixture which is then pressed and sintered.
  • JP-A-60002646 describes a solution with a ternary hard material phase consisting of WC, (Ti, W, Ta / Nb) C and (Ti, W, Ta / Nb) CN, 5 to 15% by weight of Co , 5 to 50 wt .-% (Ti, W) C, 50 wt .-% (Ti, W) CN, 1 to 15 wt .-% TaC, NbC and / or (Ta, Nb) C, balance WC and Impurities are included.
  • Cermets consisting of 25 to 50% by weight of titanium nitride, 10 to 30% by weight of titanium carbide, 5 to 25% by weight of tantalum carbide, niobium carbide and / or zirconium carbide, 10 to 25% by weight of tungsten carbide and 7.5 to 25% by weight of cobalt and / or nickel binder and optionally 0.01 to 1% by weight of aluminum added to the binder, and a process for the production of cermet are known from DE 34 18 403 C2.
  • a molding is pressed and this molding is sintered above 1400 ° C. under a nitrogen atmosphere with a pressure between 0.13 and 133 mbar.
  • a cermet composition was proposed in US Pat. No. 4,778,521, which consists of 20 to 92% by weight of titanium carbonitride, 5 to 50% by weight of tungsten carbide and 3 to 30% by weight of a binder and has a three phase grain boundary microstructure comprising a core phase that is rich is titanium carbonitride, an intermediate phase which is rich in tungsten carbide and which frames the core phase mentioned and an outer phase made of titanium / tungsten carbonitride as the envelope of the aforementioned intermediate phase.
  • titanium carbonitride powder, tungsten carbide and nickel are mixed and, as mentioned above, further treated.
  • EP 0 270 509 B1 proposes, in order to improve the mechanical properties and in particular to improve the strength against plastic deformation, to heat a mixture of powders of TiC and (Ta, Nb) C and / or TaC after mixing and the mixture which forms after cooling crush solid solution into a powder.
  • This powder is said to be mixed, pressed and sintered with carbides and nitrides or carbonitrides of metals from the IV to VI groups of the periodic table and a binder.
  • the body created in this way has a carbonitride component as a two-phase mixture with a nitrogen-poor, but titanium and tantalum-rich phase and a second phase, which is rich in Group VI metal components and nitrogen-rich.
  • the first phase forms the core and is surrounded by the second phase as an edge zone, which likewise forms the main interface with the binder metal alloy.
  • the first (core) phase has a carbonitride which is low in titanium and nitrogen
  • the second phase surrounding the core consists of carbonitrides which are rich in titanium and Are nitrogen.
  • a first powder is used to produce a cermet alloy to form a core structure from carbides and carbonitrides that contain titanium, as is a second powder to form an edge zone from titanium nitride, tantalum carbide and tungsten carbide, and a third powder prepared from a binding metal, such as cobalt and nickel, the entire mixture of which is pre-pressed and sintered.
  • a binding metal such as cobalt and nickel
  • EP 0 406 201 A1 describes a carbonitride alloy with at least 80% by volume of hard materials, which form duplex structures from the core and edge zones and which make up 10 to 80% by volume of the entire hard material phase.
  • the carbonitride metals are selected from groups IVa to VIa of the periodic table.
  • DE 40 00 937 A1 describes a process for the production of cermet, which starts from powdery titanium carbonitride, to which mixed carbides of the elements tantalum, niobium, tungsten or tantalum and tungsten or titanium, tantalum and tungsten are added in addition to the binder.
  • the titanium carbonitride can also be partially mixed with zirconium as the starting material.
  • the microstructure is uniformly fine-grained and essentially has a cubic NaCl crystal structure (B 1 structure) with an evenly distributed binder metal phase.
  • the hard material particles can contain a core composition of (Ti, W, Ta and / or Nb) C with 43 to 53% by mass of titanium, 35 to 50% by mass of tungsten, 4 to 8% by mass of tantalum and / or niobium, the edge zone corresponding to the aforementioned composition. This means that the interfaces of all hard material particles with respect to the binding phase have the same composition described above.
  • the hard material phase has only a cubic B 1 crystal structure and has an average grain diameter of ⁇ 1.5 ⁇ m with a uniform distribution of the binder metal phase.
  • the cermet alloy can additionally (in mass%) contain 0 to 12 molybdenum, 0 to 5 vanadium, 0 to 2 chromium and / or 0 to 2 aluminum.
  • the nitrogen content relative to the sum of carbon and nitrogen is preferably chosen between 0.2 and 0.8.
  • Substantially larger amounts of tungsten than titanium should preferably be dissolved in the binder metal phase, and the tungsten can be partially replaced by molybdenum, vanadium, chromium or aluminum.
  • This starting powder mixture is ground in a manner known in the prior art, pressed into a green compact and sintered.
  • TiAl 2 C, molybdenum and / or molybdenum carbide, chromium and / or chromium carbide and / or vanadium carbide can be up to 5% by mass in the starting mixture.
  • FIGS. La or 2a A respective comparison of FIGS. La or 2a with 3a or 1b or 2b with 3b reveals that the cermet alloy according to the invention is significantly more fine-grained than the alloys known according to the prior art and only particles with a dark core or particles with contains homogeneous composition.
  • backscattered electrons are used to generate the image, i.e. dark-colored structural components have a low density and are therefore Ti-rich, light-gray structural components have a higher density and are therefore W and Ta-rich.
  • the binding phase appears almost white.

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

Claims (10)

  1. Cermet comprenant de 75 à 95 pourcent en masse d'une phase de substance dure contenant du (Ti, W, Ta/Nb) C et (Ti, W, Ta/Nb) CN, le reste une phase liant avec une proportion ≥ 5 pourcent en masse de Co et/ou de Ni, caractérisé par une composition brute constituée de 30 à 60 pourcent en masse de Ti, de 5 à 20 pourcent en masse de W, de 5 à 15 pourcent en masse de Ta qui peut être remplacé jusqu'à 70% par du Nb, de 5 à 25 pourcent en masse de Ni et/ou de Co, avec plus de 80 pourcent molaire - relativement aux éléments de transition mentionnés - de carbone et d'azote, qui a été préparée à partir d'un mélange de départ solide pulvérulent avec une proportion de 15 à 45 pourcent en masse de (Ti, W, Ta) C et/ou (Ti, W, Ta, Nb) C, de 3 à 15 pourcent en masse de WC, de 5 à 25 pourcent en masse de Co et/ou de Ni, le reste Ti (C, N), respectivement d'une grosseur de grain de < 1,5 µm, par broyage, pressage et frittage et qui présente ou sur l'ensemble du corps de cermet des particules en substance dure dans la structure avec une structure noyau-bord avec des noyaux en Ti(C, N), N>C et des zones marginales homogènes en (Ti, W, Ta/Nb) C avec Ti = de 50 à 65 pourcent en masse, W = de 15 à 30 pourcent en masse, Ta = de 8 à 20 pourcent en masse, ou de 40 à 60 pourcent volumétrique de la phase de substance dure se compose de particules avec une structure noyau-bord avec un noyau en TiCN riche en azote avec N/(N+C) ≥ 0,7 et une zone marginale en (Ti, W, Ta) C avec Ti = de 50 à 65 pourcent en masse, W = de 15 à 30 pourcent en masse, Ta = de 8 à 20 pourcent en masse et de 60 à 40 pourcent volumétrique de la phase de substance dure se compose de particules d'une composition homogène correspondant à la zone marginale précédemment décrite.
  2. Cermet selon la revendication 1, caractérisé par la fait que la proportion de Ti(C, N) contenu dans le mélange de départ est comprise entre 25 et 65 pourcent en masse.
  3. Cermet selon la revendication 1 ou 2, caractérisé par le fait que, dans les phases de substance dure, jusqu'à 70% du Ta sont remplacés par du Nb.
  4. Cermet selon la revendication 3, caractérisé par le fait que, au détriement des particules avec une composition homogènes, en plus jusqu'à 5 pourcent volumétrique des particules en substance dure possèdent une composition de noyau de (Ti, W, Ta, Nb)C avec une proportion de 43 à 53 pourcent en masse de titane, de 35 à 50 pourcent en masse de tungstène, de 4 à 8 pourcent en masse de tantale et/ou de niobium.
  5. Cermet selon l'une des revendications 1 à 4, caractérisé par le fait que la phase de substance dure présente exclusivement une structure B1-cristalline cubique ainsi qu'un diamètre de grain moyen de < 1,5 µm avec une répartition uniforme de la phase de métal liant.
  6. Cermet selon l'une des revendications 1 à 5, caractérisé par le fait que, en plus, de 0 à 12 Mo, de 0 à 5 V, de 0 à 2 Cr et/ou de 0 à 2 Al sont contenus en pourcent en masse et/ou que le liant est présent en une proportion de Ni/(Ni+Co) = de 0,2 à 0,8, de préférence, dans la phase de métal liant, les quantités en tungstène étant plus importantes que celles en titane.
  7. Cermet selon la revendication 6, caractérisé par le fait que la quantité en molybdène, vanadium, chrome et tungstène dissolus est plus grande que celle en titane et/ou que la proportion en azote, par rapport à la somme de carbone et d'azote, est comprise entre 0,2 et 0,8.
  8. Procédé de fabrication d'un cermet selon l'une des revendications 1 à 7, par broyage d'un mélange contenant des carbures, des nitrures et/ou des carbonitrures du titane, du tungstène, du tantale et, le cas échéant, d'autres éléments du groupe lVa à Vla de la classification périodique des éléments ainsi que du cobalt et/ou du nickel, qui est par la suite pressé et fritté, caractérisé par le fait que le mélange de poudre de départ présente les composants suivants:
    (a) de 15 à 45 pourcent en masse de (Ti, W, Ta) C avec une grosseur de grain moyenne de < 1,5 µm, ce carbure mixte contenant de 20 à 50 pourcent en masse de TiC, de 20 à 40 pourcent en masse de WC et de 20 à 40 pourcent en masse de TaC, jusqu'à 70 pourcent en masse du Ta pouvant être remplacés par du Nb,
    (b) de 3 à 15 pourcent en masse de WC avec une grosseur de grain moyenne de < 1,5 µm,
    (c) de 5 à 25 pourcent en masse de nickel et/ou de cobalt et
    (d) de 0 à 5 pourcent en masse de l'un du moins des composants TiAl2C, Mo, Mo2C, Cr, Cr2C3 et V,
    (e) le reste Ti(C, N) avec une grosseur de grain moyenne de < 1,5 µm et un rapport de N/(C+N) ≥ 0,7.
  9. Procédé selon la revendication 8, caractérisé par le fait que le mélange de poudre de départ contient de 25 à 65 pourcent en masse de Ti(C, N).
  10. Procédé selon l'une des revendications 8 ou 9, caractérisé par le fait que le carbure mixte (W, Ti, Ta) C ou (W, Ti, Ta, Nb) C est présent en une structure à grains fins moyenne de 0,5 µm dans la proportion des carbures WC : TiC : TaC ou (Ta, Nb) C = 1 : 1 : et/ou que le Ti(C, N) est présent en une grosseur de grain moyenne de 1,2 µm avec une proportion de N/(C+N) = 0,75.
EP94904953A 1993-03-23 1994-01-22 Cermet et son procede de production Expired - Lifetime EP0689617B1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
DE4309261 1993-03-23
DE4309261 1993-03-23
DE4344576A DE4344576A1 (de) 1993-03-23 1993-12-24 Cermet und Verfahren zu seiner Herstellung
DE4344576 1993-12-24
PCT/DE1994/000048 WO1994021835A1 (fr) 1993-03-23 1994-01-22 Cermet et son procede de production

Publications (2)

Publication Number Publication Date
EP0689617A1 EP0689617A1 (fr) 1996-01-03
EP0689617B1 true EP0689617B1 (fr) 1997-03-05

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EP94904953A Expired - Lifetime EP0689617B1 (fr) 1993-03-23 1994-01-22 Cermet et son procede de production

Country Status (7)

Country Link
US (1) US5670726A (fr)
EP (1) EP0689617B1 (fr)
JP (1) JPH08508066A (fr)
CN (1) CN1054164C (fr)
AT (1) ATE149580T1 (fr)
ES (1) ES2102200T3 (fr)
WO (1) WO1994021835A1 (fr)

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RU2209128C1 (ru) * 2002-06-05 2003-07-27 Научно-исследовательский институт механики МГУ им. М.В. Ломоносова Устройство для обработки материалов
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SE527173C2 (sv) * 2003-07-25 2006-01-17 Sandvik Intellectual Property Sätt att tillverka en finkorning hårdmetall
US7700038B2 (en) * 2005-03-21 2010-04-20 Ati Properties, Inc. Formed articles including master alloy, and methods of making and using the same
WO2006134936A1 (fr) * 2005-06-14 2006-12-21 Ngk Spark Plug Co., Ltd. Insert en cermet et outil de coupe
RU2307012C1 (ru) * 2006-03-27 2007-09-27 Научно-исследовательский институт механики Московского государственного университета им. М.В. Ломоносова Твердосплавный инструмент
RU2307013C1 (ru) * 2006-03-27 2007-09-27 Научно-исследовательский институт механики Московского государственного университета им. М.В. Ломоносова Инструмент из твердого сплава, содержащего карбиды вольфрама и титана
CN100484661C (zh) * 2006-08-16 2009-05-06 山东大学 一种含碳化硅、铁、碳、铬的钼基金属陶瓷
CN101210291B (zh) * 2006-12-26 2010-12-01 四川理工学院 一种超细晶粒金属陶瓷的生产方法
WO2010035824A1 (fr) * 2008-09-26 2010-04-01 京セラ株式会社 Cermet fritté et outil de coupe
EP2465960B1 (fr) * 2010-12-17 2014-10-08 Sandvik Intellectual Property AB Corps en cermet et procédé de fabrication d'un corps en cermet
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CN103521770B (zh) * 2013-09-22 2015-10-28 成都工具研究所有限公司 TiCN基金属陶瓷
JP5989930B1 (ja) * 2014-11-27 2016-09-07 京セラ株式会社 サーメットおよび切削工具
JP2015107525A (ja) * 2014-12-18 2015-06-11 住友電気工業株式会社 回転ツール
CN106801180B (zh) * 2017-01-12 2018-03-16 安徽三联学院 一种高韧性低应力金属陶瓷
WO2018193659A1 (fr) * 2017-04-19 2018-10-25 住友電気工業株式会社 Carbure cémenté, outil de coupe comprenant du carbure cémenté, procédé de production de carbure cémenté
CN107760955B (zh) * 2017-11-29 2019-07-02 成都创客之家科技有限公司 一种氮化硅基金属陶瓷材料
CN109972014A (zh) * 2017-12-28 2019-07-05 厦门钨业股份有限公司 一种TiCN基金属陶瓷
CN108637338A (zh) * 2018-05-21 2018-10-12 浙江普菲特切削工具有限公司 一种强韧化金属陶瓷材料及由其制成的立铣刀
CN109128136B (zh) * 2018-08-22 2021-06-29 株洲欧科亿数控精密刀具股份有限公司 一种钢件加工用涂层刀片及其制备方法
CN109338198A (zh) * 2018-12-26 2019-02-15 河源普益硬质合金厂有限公司 一种高性能yc50硬质合金及其加工方法
CN113999013A (zh) * 2021-11-03 2022-02-01 哈尔滨理工大学 一种反应热压烧结法低温制备碳氮化物-硅化物固溶体复相陶瓷的方法
CN115233073B (zh) * 2022-07-07 2023-02-24 九江学院 一种具有芯-环结构的(W,Ti)(C,N)基金属陶瓷材料及其原位合成方法
CN115650236B (zh) * 2022-12-13 2023-04-07 淄博高新技术产业开发区Mems研究院 一种碳化钛-碳化钽固溶体、制备方法及其用途

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Also Published As

Publication number Publication date
CN1054164C (zh) 2000-07-05
ES2102200T3 (es) 1997-07-16
JPH08508066A (ja) 1996-08-27
CN1093121A (zh) 1994-10-05
US5670726A (en) 1997-09-23
WO1994021835A1 (fr) 1994-09-29
EP0689617A1 (fr) 1996-01-03
ATE149580T1 (de) 1997-03-15

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