EP0651067B1 - Keramik-Metallverbundkörper mit hoher Zähigkeit sowie Verfahren seiner Herstellung - Google Patents

Keramik-Metallverbundkörper mit hoher Zähigkeit sowie Verfahren seiner Herstellung Download PDF

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Publication number
EP0651067B1
EP0651067B1 EP94116793A EP94116793A EP0651067B1 EP 0651067 B1 EP0651067 B1 EP 0651067B1 EP 94116793 A EP94116793 A EP 94116793A EP 94116793 A EP94116793 A EP 94116793A EP 0651067 B1 EP0651067 B1 EP 0651067B1
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EP
European Patent Office
Prior art keywords
alumina
fact
process according
particles
sintering
Prior art date
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Expired - Lifetime
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EP94116793A
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English (en)
French (fr)
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EP0651067A2 (de
EP0651067A3 (de
Inventor
Denis Gonseth
Daniele Mari
Paul Bowen
Claude Paul Carry
Pascal Streit
Roberto Mulone
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Gonseth Denis
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Individual
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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
    • 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
    • B22F3/1003—Use of special medium during sintering, e.g. sintering aid
    • B22F3/1007—Atmosphere
    • 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
    • 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
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/02—Nitrogen
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12049—Nonmetal component
    • Y10T428/12056—Entirely inorganic
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12146—Nonmetal particles in a component
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/1216—Continuous interengaged phases of plural metals, or oriented fiber containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/1216—Continuous interengaged phases of plural metals, or oriented fiber containing
    • Y10T428/12167—Nonmetal containing

Definitions

  • the present invention relates to a composite material high tenacity containing a strengthening phase based on oxide, and a method of manufacturing the same.
  • Ceramic-metallic composite materials can be used as well as materials structural (engine parts, aeronautical parts and the space industry) that as materials functional (cutting, drilling, drilling tools).
  • materials structural engine parts, aeronautical parts and the space industry
  • materials functional cutting, drilling, drilling tools.
  • Al 2 O 3 aluminum oxide or alumina
  • Al 2 O 3 aluminum oxide or alumina
  • the toughness and impact resistance of polycrystalline Al 2 O 3 are very low.
  • ceramics based on alumina are often added, for example, other ceramics such as ZrO 2 and Y 2 O 3 or carbides such as TiC. Even with such additions, however, the toughness of metals and ceramic-metal composites is never achieved.
  • the metals of the group Fe, Ni, Co, also called metals ferrous, are interesting for applications with high temperature, because their melting point is at temperatures well above those reached in the most industrial processes and yet easily obtainable during manufacture.
  • the alloys ferrous metals have excellent resistance to oxidation.
  • Ferrous metals form a pseudoeutectic lower than their melting point in the presence carbides and carbonitrides such as TiC, TaC, WC, TiCN. These carbides and carbonitrides in combination with ferrous metals (mainly Ni and Co) are the basis of the vast majority of cermets currently produced.
  • cermets nowadays, the application of cermets is targeting increasingly higher temperatures, which leads to problems of resistance to oxidation, resistance to creep and decohesion of interfaces.
  • the introduction of a strengthening phase based on aluminum oxide could give cermets better temperature resistance thanks to the chemical resistance of Al 2 O 3 and its refractory properties.
  • the document Us 3,098,723 discloses for example a composite material, more specifically intended for the manufacture of turbine blades, which comprises long alumina fibers in a steel matrix, these reinforcing filaments being able to be coated with titanium nitride before being introduced into said matrix.
  • the object of this invention therefore is to provide a composite material with high toughness and refractory properties which are specific to ceramic, by forming a layer around the ceramic oxide phase interfacial guaranteeing good wettability and good toughness of the interface.
  • the object of the invention aims at achieving the aim mentioned above, consists of a process for manufacturing a sintered ceramic-metallic material comprising a phase ceramic with alumina particles or solution solid based on alumina, a refractory phase comprising titanium nitride and / or carbonitride, and a matrix metallic based on Ni, Co and / or Fe, the interface between alumina particles or solid solution alumina and the metallic matrix being rich in nitrogen and made of titanium or compounds thereof, which is characterized by the fact that it includes the sintering of the elements components in a non-oxidizing nitrogen atmosphere, at a temperature from 1300 to 1600 ° C and under a pressure of 1 to 2000 MPa, and by the fact that we form, in situ during the sintering under nitrogen, around particles of alumina or solid alumina solution, said titanium-rich interface and nitrogen or their compounds at a temperature between 950 and 1600 ° C and in the presence of carbon.
  • the interface mentioned above is usually formed by a continuous TiN-rich layer around the particles alumina or solid alumina solution promoting a good wettability of the metal matrix, and which can contain aluminum, in the form of compounds with the titanium, nitrogen and / or a metal of the metallic phase, to proximity to this metallic matrix.
  • Alumina can be in the form of powder, whose grains have a diameter of 0.1 to 50 ⁇ m, preferably 0.5 to 10 ⁇ m, or platelets monocrystalline whose form factor varies between 5 and 20 and the diameter between 5 and 50 ⁇ m, or even whiskers or filaments.
  • the volume content of the ceramic phase can be between 10 and 80%, preferably between 20 and 50%, that of the phase refractory between 10 and 70% and that of the matrix metallic between 3 and 50%.
  • the content of the ceramic phase is between 5 and 30% vol., that of the phase refractory between 35 and 65% vol. and that of the matrix metallic between 5 and 25% vol.
  • the ceramic metal material may also contain as another main ingredient of titanium carbide in plus carbonitride or titanium nitride, or a mixture of the three.
  • the metal matrix may contain additional dissolved ingredients, such as metals that Sc, Y, Ti, Zr, Hf, V, Nb, Cr, Re, Ru, Al, C and N, between 0.1 and 5% vol. and the refractory phase of carbides of Mo, W, V, Hf, Nb, Cr, Ta, or nitrides such as AlN, TaN, ZrN and BN, between 0.5 and 15% vol.
  • additional dissolved ingredients such as metals that Sc, Y, Ti, Zr, Hf, V, Nb, Cr, Re, Ru, Al, C and N, between 0.1 and 5% vol. and the refractory phase of carbides of Mo, W, V, Hf, Nb, Cr, Ta, or nitrides such as AlN, TaN, ZrN and BN, between 0.5 and 15% vol.
  • the ceramic phase can also contain other oxides, such as ZrO 2 or Y 2 0 3 or a mixture of these oxides.
  • the sintering of constituent elements is carried out preferably from 1450 to 1500 ° C and under a pressure of 1 to 200 MPa. He can be combined with hot pressing or pressing hot isostatic.
  • one of the main characteristics of the present invention consists in forming on the surface of the ceramic phase an intermediate layer having affinities with the matrix, this layer being rich in nitrogen and titanium. It is well known that metals wet ceramics by forming chemical bonds. When the wetting is poor, the reaction between the metal and the atoms on the surface of the ceramic is not thermodynamically favorable. The presence of a reactive prelayer can thus provide the driving force necessary for the wetting reaction. Maintaining the reactive preliminary layer during sintering thus allows the formation of the interface is done by the addition of nitrogen and a metallic element, preferably titanium, in solution in the matrix. There is thus the deposition of a nitride.
  • the energy supplied by this reaction during sintering increases the wetting and the epitaxial precipitation of the nitride guarantees the homogeneity and the tenacity of the interface.
  • the reactive preliminary layer can be obtained by PVD or CVD deposition, in which case it leads to an interface thickness between 0.5 and 5 ⁇ m, or by nitriding of Al 2 O 3 before sintering, in which case it leads to a interface thickness between 10 and 1000 nm. Nitriding can be helped by the addition of carbon which allows the reduction of alumina.
  • Another possibility is the deposition of a TiN layer or of TiCN on the ceramic before sintering. In this case the wetting is ensured by the maintenance reactions 3a, b.
  • the manufacturing of the composite material generally includes first mixing the powders of the binding phase. More particularly, a slip is first prepared by mixing the binding phase in the form of powders with a liquid organic product such as polyethylene glycol. The slurry is mixed for 12 h in a mill beads, then degassed to adjust the viscosity. We add to this mixes the ceramic with oxides. Light grinding of the total mass is necessary to obtain good homogeneity. We then move on to formatting which can be performed by dry pressing, filter pressing, pouring in slip, extrusion or injection. The exhibits form are then sintered. Pre-sintering at one temperature between 300 and 700 ° C may be necessary to release the organic binder completely. Sintering is carried out at a temperature between 1300 and 1600 ° C, for 1-4 hours, under nitrogen at a pressure between 1 and 2000 MPa.
  • the thickness of the interface between the alumina particles and the metal matrix is 100 to 10,000 Angstroms when obtained by prior surface nitriding of said particles. This thickness can be by against 0.1 to 1 ⁇ m if the interface is obtained after deposition chemical of a titanium compound on the particles alumina, and from 0.05 to 5 ⁇ m in the case where this interface is obtained during sintering without a prior reactive layer.
  • the powders of the composite matrix were previously mixed with 2% polyethylene glycol and ground for 12 h in a ball mill.
  • the Al 2 O 3 plates are added to the slip and the whole is mixed in a ball mill for 2 hours.
  • This mixture is then dried in air at 50 ° C., deagglomerated in a ball mixer and dry press with a pressure of 140 MPa. Sintering is then carried out at 1500 ° C. for 1 hour under a nitrogen atmosphere.
  • the composite powders are mixed with 2% polyethylene glycol and ground for 12 hours in a mill ball. This mixture is then dried in air at 50 ° C, deagglomerated in a ball mixer and dry pressed with a pressure of 140 MPa. We then proceed to sintering at 1500 ° C for 1 h under nitrogen atmosphere.
  • the same shaped mixing process is used here, sintering and the same matrix composition as in Example 1.
  • the alumina strengthening phase is formed wafers coated with a TiN layer according to the method described below.
  • Platelets of Al 2 O 3 suspended in hexane are introduced into a laboratory autoclave.
  • the Al 2 O 3 platelets are dispersed in hexane for 15 minutes with an ultrasonic probe.
  • a 10% solution of TiCl 4 in hexane is introduced, and simultaneously a stream of ammonia is passed through for 10 minutes.
  • the TiCl 4 .NH 3 complex is thus precipitated on the platelets.
  • the powders obtained are then dried under vacuum. After this treatment, the powders are oxidized in an oven in air at 900 ° C. for 1 h.
  • the powders obtained are mixed at equal weight with powdered graphite powder and heated to 1150 ° C. under a flow of nitrogen. We stay at this temperature for 4 h.
  • a TiN layer of less than about 1 ⁇ m was thus obtained on the surface of the Al 2 0 3 powders according to the reaction: 2Ti0 2 + 4C + N 2 ⁇ 2TiN + 4CO ⁇
  • Sample 8 TiCN 65%, TiN 20%, Mo 2 C 5%, Ni 10% Absence of reinforcement phase (Al 2 0 3 ); obtained by sintering under nitrogen.
  • microstructure of composite materials according to the invention shows the particles of aluminum oxide uniformly dispersed in one phase made up of metal islands in a ceramic skeleton of titanium carbonitride. Metal also surrounds the oxide particles.
  • the interface between metal and the oxide which has a thickness between 0.03 and 0.1 ⁇ m is mainly consisting of titanium nitride.
  • the present invention significantly improves toughness cermets, while keeping a high hardness, by the introduction of alumina particles, provided that whether the alumina is treated before or during the sintering of so as to favor the formation of an interface rich in nitrogen and titanium. It can also be noted that sintering under pressure (Sample 4) provides properties excellent mechanical properties with a significant reduction the duration of said sintering.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Products (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Manufacture Of Alloys Or Alloy Compounds (AREA)
  • Powder Metallurgy (AREA)

Claims (12)

  1. Herstellungsverfahren für einen gesinterten metallkeramischen Verbundwerkstoff, der eine keramische Phase mit Teilchen aus Aluminiumoxid oder einer festen Lösung auf der Basis von Aluminiumoxid, eine hochwarmfeste Phase mit Titannitrid und/oder Titancarbonitrid sowie eine Metallmatrix auf der Basis von Ni, Co und/oder Fe umfasst, wobei die Grenzfläche zwischen den Teilchen aus Aluminiumoxid oder der festen Aluminiumoxidlösung und der Metallmatrix reich an Stickstoff und Titan oder deren Verbindungen ist, dadurch gekennzeichnet, dass es das Sintern der Bestandteile in nichtoxidierender Stickstoffatmosphäre bei einer Temperatur von 1300 bis 1600 °C und unter einem Druck von 1 bis 2000 MPa umfasst und dass während des Sinterns unter Stickstoff um die Teilchen aus Aluminiumoxid oder fester Aluminiumoxidlösung herum die benannte, an Titan und Stickstoff oder an Verbindungen dieser Elemente reiche Grenzfläche bei einer Temperatur zwischen 950 und 1600 °C sowie in Gegenwart von Kohlenstoff in situ gebildet wird.
  2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, dass die benannte Grenzfläche durch eine durchgehende, an TiN reiche Schicht um die Teilchen aus Aluminiumoxid oder fester Aluminiumoxidlösung herum gebildet wird und Aluminium in Gestalt der Verbindungen zumindest mit Titan und Stickstoff nahe der Metallmatrix enthalten kann.
  3. Verfahren nach Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, dass die Al2O3-Teilchen in der Form von Pulver vorliegen, dessen Körner einen Durchmesser von 0,1 bis 50 µm und vorzugsweise von 0,5 bis 10 µm haben.
  4. Verfahren nach Anspruch 1 oder Anspruch 2, dadurch gekennzeichnet, dass die Al2O3-Teilchen in Form von einkristallinen Plättchen, deren Seitenverhältnis zwischen 5 und 20 und deren Durchmesser zwischen 5 und 50 µm schwankt, oder in Form von Whiskers oder Fäden vorliegen.
  5. Verfahren nach Anspruch 3, dadurch gekennzeichnet, dass der Volumenanteil der keramischen Phase zwischen 10 und 80 % und vorzugsweise zwischen 20 und 50 %, der der hochwarmfesten Phase zwischen 10 und 70 % und der der Metallmatrix zwischen 3 und 50 % liegt.
  6. Verfahren nach Anspruch 4, dadurch gekennzeichnet, dass der Volumenanteil der keramischen Phase zwischen 5 und 30 %, der der hochwarmfesten Phase zwischen 35 und 65 % und der der Metallmatrix zwischen 5 und 25 % liegt.
  7. Verfahren nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, dass die keramische Phase andere Oxide wie ZrO2 und Y2O3 umfasst.
  8. Verfahren nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, dass die Metallmatrix gelöste Elemente enthält, die unter Sc, Y, Ti, Zr. Hf, V, Nb, Cr, Mo, W, Re, Ru, Al, C und N ausgewählt sind.
  9. Verfahren nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, dass die hochwarmfeste Phase zusätzlich zu TiCN und NiN noch TiC und/oder eine oder mehrere Verbindungen enthält, die unter den Carbiden von W, Cr, V, Mo, Ta, Hf, Nb und den Nitriden ZrN, TaN, AlN und BN ausgewählt sind.
  10. Verfahren nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, dass die Grenzfläche zwischen den Teilchen aus Aluminiumoxid oder fester Aluminiumoxidlösung und der Metallmatrix eine Dicke zwischen 0,01 und 5 µm hat.
  11. Verfahren nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, dass das Sintern der Bestandteile bei einer Temperatur von 1450 bis 1500 °C und unter einem Druck von 1 bis 200 MPa erfolgt.
  12. Verfahren nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, dass vor dem Sintern eine Formung durch einachsiges Pressen bei etwa 100 MPa, isostatisches Pressen bei etwa 300 MPa, Filterpressen oder Schlickerguss erfolgt.
EP94116793A 1993-11-01 1994-10-25 Keramik-Metallverbundkörper mit hoher Zähigkeit sowie Verfahren seiner Herstellung Expired - Lifetime EP0651067B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CH03288/93A CH686888A5 (fr) 1993-11-01 1993-11-01 Matériau composite céramo-métallique à haute tenacité et procédé pour sa fabrication.
CH328893 1993-11-01
CH3288/93 1993-11-01

Publications (3)

Publication Number Publication Date
EP0651067A2 EP0651067A2 (de) 1995-05-03
EP0651067A3 EP0651067A3 (de) 1996-12-18
EP0651067B1 true EP0651067B1 (de) 2000-03-22

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EP94116793A Expired - Lifetime EP0651067B1 (de) 1993-11-01 1994-10-25 Keramik-Metallverbundkörper mit hoher Zähigkeit sowie Verfahren seiner Herstellung

Country Status (6)

Country Link
US (1) US5682595A (de)
EP (1) EP0651067B1 (de)
JP (1) JPH07188803A (de)
AT (1) ATE191015T1 (de)
CH (1) CH686888A5 (de)
DE (1) DE69423565D1 (de)

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US8449991B2 (en) 2005-04-07 2013-05-28 Dimicron, Inc. Use of SN and pore size control to improve biocompatibility in polycrystalline diamond compacts
JP5604981B2 (ja) * 2009-05-28 2014-10-15 Ｊｆｅスチール株式会社 粉末冶金用鉄基混合粉末
US8663359B2 (en) 2009-06-26 2014-03-04 Dimicron, Inc. Thick sintered polycrystalline diamond and sintered jewelry
KR102478654B1 (ko) 2017-07-11 2022-12-16 한국재료연구원 계면 물질을 포함하는 복합재료 및 이의 제조방법
RU2707216C1 (ru) * 2019-09-27 2019-11-25 Федеральное Государственное Бюджетное Образовательное Учреждение Высшего Образования "Новосибирский Государственный Технический Университет" СПОСОБ ПОЛУЧЕНИЯ КОМПОЗИЦИОННОГО МАТЕРИАЛА НА ОСНОВЕ Al2O3 -TiCN
EP3974405A1 (de) * 2020-09-25 2022-03-30 The Swatch Group Research and Development Ltd Dekoratives keramikartikel

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Publication number Publication date
ATE191015T1 (de) 2000-04-15
DE69423565D1 (de) 2000-04-27
EP0651067A2 (de) 1995-05-03
US5682595A (en) 1997-10-28
JPH07188803A (ja) 1995-07-25
EP0651067A3 (de) 1996-12-18
CH686888A5 (fr) 1996-07-31

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