WO1998021147A1 - Procede de production de matieres dures renfermant de l'oxygene et leur utilisation - Google Patents

Procede de production de matieres dures renfermant de l'oxygene et leur utilisation Download PDF

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Publication number
WO1998021147A1
WO1998021147A1 PCT/EP1997/006137 EP9706137W WO9821147A1 WO 1998021147 A1 WO1998021147 A1 WO 1998021147A1 EP 9706137 W EP9706137 W EP 9706137W WO 9821147 A1 WO9821147 A1 WO 9821147A1
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WIPO (PCT)
Prior art keywords
pse
metals
oxides
oxygen
subgroup
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PCT/EP1997/006137
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German (de)
English (en)
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WO1998021147A9 (fr
Inventor
Lutz-Michael Berger
Andreas Krell
Eckart Langholf
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Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V.
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Publication of WO1998021147A1 publication Critical patent/WO1998021147A1/fr
Publication of WO1998021147A9 publication Critical patent/WO1998021147A9/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B21/00—Nitrogen; Compounds thereof
    • C01B21/082—Compounds containing nitrogen and non-metals and optionally metals
    • C01B21/0828—Carbonitrides or oxycarbonitrides of metals, boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/013—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics containing carbon

Definitions

  • the invention relates to the field of ceramics and hard metals and relates to a method for producing oxygen-containing hard materials which are used in composite materials, e.g. for bearings, for indexable inserts, as an abrasive or as a magnetic head substrate.
  • the first basic process relates to the direct carburization / nitration of metals and their hydrides. This process has the disadvantage that it is very difficult to carry out and this also leads to a strong agglomeration of the reaction products. Long periods of time are needed to destroy the agglomerates
  • deposition processes e.g. CVD known, which are mainly used for surface coating.
  • oxide-containing titanium layers have become known (EP 537 741, JP 02057616, JP 02015159, JP 01197364, JP 61272343, JP 53-60808). These oxide-containing layers increase the oxidation resistance, hardness and abrasion resistance of cutting tools. Larger amounts of hard materials cannot be produced with this process.
  • the carbothermal reduction of the oxides of the metals by carbon is known as the third method.
  • This process is known as the simplest and most economically effective process, but it also has disadvantages in terms of purity, grain size and their distributions or grain shape of the hard materials.
  • EP 693 456 specifies a process for producing spherical nitride and / or carbonitride powder of titanium, in which the oxide of the metal is intimately mixed with carbon and then reacted at temperatures between 1400 ° C. and 2000 ° C. The reaction space is then evacuated and the reaction mixture is then flooded several times with a nitrogen-containing atmosphere at a pressure of 5 to 100 kPa and temperatures between 2000 and 2400 ° C. and evacuated again.
  • composition of this powder is at 11, 7% Cg it; ⁇ 0.05% Cf re j; 9.1% N; 0.12% O given.
  • a spherical grain shape is not achieved by the long meals, rather a powder is added split-edged grain shape and possibly produced with a broad grain spectrum
  • the average grain sizes are in a range> 2 ⁇ m, preferably> 3 ⁇ m
  • the disadvantage of this method is essentially that a stochiometric composition is to be achieved, the oxygen content in the hard material being assumed to be as low as possible ⁇ 0.5% by weight. Such an oxygen content leads to a z value when converted into stochiometric information of at most 0.05, the stochiometric composition is essentially achieved by the long synthesis times and the high temperatures that are used in this process
  • No. 5,314,656 describes a process for the production of TICQ 5N0 5, which is characterized by two successive steps.
  • the transition metal in the example titanium
  • SHS self-propagating high-temperature synthesis
  • DD 287 959 describes the formation of low-oxygen, coarse substochiometric carbides, which coarsen at temperatures above 2000 ° C. Subsequently, carbonitrides with a composition MeC x N v with y> 0, 1 and x + y> 0.7. Overall, the method is aimed at achieving stoichiometric or near-stoichiometric compositions, an intermediate sub-stoichiometry being accepted in the course of the method. This can also be seen from the exemplary embodiments given.
  • the object of the invention is then to provide a simple process for the production of oxygen-containing hard materials in a stochiometric and substochiometric composition
  • the powder mixture is first heated in a reducing atmosphere to a temperature between 1150 ° C. and 1600 ° C., then kept at this temperature for up to 1 h and then cooled to room temperature, and then this powder mixture is in the Vacuum heated to a temperature between 1350 ° C and 1800 ° C, held there for 2 h and then cooled back to room temperature.
  • the powder mixture is first heated to a temperature of up to 2000 ° C. in a reducing or inert atmosphere, then kept at this temperature for up to 3 hours and then this powder mixture is vacuumed to a temperature above 1600 ° C. preferably between 2000 ° C and 2500 ° C, heated, held there for 5 h and then cooled again to room temperature.
  • a carbon with a proportion of oxygen in the range from 0.1 to 25% by mass is used as carbon.
  • a molar ratio R x C 1 1 to 1 (x + p-0.05) is set in order to set a stoichiometric oxygen-containing or a substoichiometric oxygen-containing composition, where R is one or more metals of IV, and / or V.
  • the hard materials produced according to the invention are used in composite materials for bearings, for indexable inserts, as an abrasive or as a magnetic head substrate.
  • oxygen-containing hard materials are advantageously used in composite materials made of oxygen-containing hard materials and oxides, in particular for a black ceramic. It is also advantageous if oxygen-containing hard materials according to claim 12 with an average grain size of> 5 ⁇ m are used for coating steels.
  • the invention is based on the surprising finding that a previously unknown sub-stoichiometry can be set for the oxygen-containing hard materials produced according to the invention and that a stoichiometric composition can also be produced in this way.
  • Oxygen-containing hard materials according to the present invention are to be understood as meaning oxicarbides, oxynitrides, oxicarbonitrides, mixed oxyarbides, mixed oxynitrides and mixed oxycarbonitrides.
  • oxygen-containing hard materials produced according to the invention is that even coarser-grained starting powders can be used for their production without this having any negative effects on the use of the hard materials.
  • sintered ceramics with a relatively dense, fine-grained structure and comparatively high hardness can be produced from coarse-grained, oxygen-containing hard materials.
  • the process according to the invention produces oxygen-containing hard materials which have a relatively low proportion of free carbon, which has a very advantageous effect on the process implementation, since higher temperatures, long synthesis times and / or subsequent additional reactions can be avoided.
  • oxygen-containing hard materials produced according to the invention not only cause no deterioration in properties when used in sintered ceramics, as would be expected according to the general expert opinion, but sometimes even improvements in properties.
  • a two-stage process is used to produce fine-grained hard material powder, in particular ⁇ 2 ⁇ m.
  • the starting powder mixture is heated to a temperature between 1150 ° C. and 1600 ° C. in a reducing atmosphere and held there for 1 hour.
  • This powder mixture is then heated in a vacuum to a temperature between 1350 ° C. and 1800 ° C., held for 2 hours and then cooled to room temperature. This has resulted in a very fine-grained hard material powder with a comparatively high oxygen content and a low free carbon content.
  • the free carbon content of the end product is advantageously influenced and reduced overall.
  • the starting powder mixture is to be heated to a temperature of up to 2000 ° C. in a first synthesis step under a reducing or inert atmosphere and held there for 3 hours.
  • the powder mixture is then heated under vacuum to temperatures above 1600 ° C., preferably between 2000 ° C. and 2500 ° C., held there for up to 5 hours and then cooled to room temperature.
  • the desired grain growth takes place primarily in the second stage.
  • Coarser hard material powder in particular with an average grain size of> 5 ⁇ m, is used, for example, in the coating of steels. This coating is carried out by means of laser entry.
  • This coarser hard material powder is advantageous in this method because the hard material grains are not melted during the coating and thus improve the surface strength and wear resistance of the steels. Best way to carry out the invention
  • Temperature treatment is carried out in an oven with graphite heating elements with 30 g portions stuffed in graphite crucibles.
  • the furnace is heated to a temperature of 1500 ° C. at a heating rate of 50 K / min and then to a temperature of 1600 ° C. at 20 K / min.
  • 100 l / h of argon are flowed through the furnace.
  • the pressure at the end of the holding time is 8.5 x 10 -2 MPa.
  • the temperature is kept at 1600 ° C. for 15 minutes and the furnace is evacuated during this time.
  • the mixture is then heated to 2000 ° C. under constant evacuation at a heating rate of 20 K / min and held there for 60 min.
  • the pressure is 5.5 x 10 ⁇ 5 MPa.
  • the oven is evacuated for 15 minutes at a temperature of 1600 ° C.
  • the mixture is then heated to 1800 ° C. under constant evacuation at a heating rate of 20 K / min and held there for 30 minutes.
  • the samples are quickly cooled to room temperature.
  • the temperature is maintained at this temperature for 120 minutes and then the samples are cooled in the cooling chamber.
  • the samples are then heated under vacuum to a temperature of 1600 ° C. at a heating rate of 50 K / min and held at this temperature for 60 min.
  • the pressure at the end of the holding time is 6 x10 " 5 MPa.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

L'invention concerne le domaine des matières dures renfermant de l'oxygène, un procédé de production et leur utilisation p.ex. pour les paliers. L'invention a pour objet de créer un procédé simple pour la production de matières dures renfermant de l'oxygène entrant dans des compositions stoechiométriques et substoechiométriques. Selon ce procédé, un oxyde des métaux des sous-groupes IV. et V. de la classification périodique ou des mélanges d'oxydes des métaux des sous-groupes IV., V., et VI. ou au moins un métal des sous-groupes IV. et/ou V. ou des sous-groupes IV. et V. et VI. ou des sous-groupes IV. et VI. ou bien V. et VI et au moins un oxyde des métaux des sous-groupes IV, V et VI sont broyés avec du carbone et homogénéisés. Ensuite, le mélange pulvérulent est chauffé en continu ou discontinu à une température maximale de 2500 °C.
PCT/EP1997/006137 1996-11-09 1997-11-06 Procede de production de matieres dures renfermant de l'oxygene et leur utilisation WO1998021147A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19646333.5 1996-11-09
DE1996146333 DE19646333C2 (de) 1996-11-09 1996-11-09 Verfahren zur Herstellung von sauerstoffhaltigen Hartstoffen und deren Verwendung

Publications (2)

Publication Number Publication Date
WO1998021147A1 true WO1998021147A1 (fr) 1998-05-22
WO1998021147A9 WO1998021147A9 (fr) 1998-08-27

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DE (1) DE19646333C2 (fr)
WO (1) WO1998021147A1 (fr)

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0464396A1 (fr) * 1990-06-20 1992-01-08 H.C. Starck GmbH & Co. KG Carbonitrures à partir des métaux de transition (M, M*, M**) des groupes 4 (M), 5 (M*) et 6 (M**) du système périodique des éléments, procédé pour leur production et application des carbonitrures

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DD287959A5 (de) * 1989-09-20 1991-03-14 Zi F. Festkoerperphysik U. Werkstofforschung Der Adw,De Verfahren zur herstellung von grobem karbonitridpulver
JP2775955B2 (ja) * 1990-01-31 1998-07-16 三菱マテリアル株式会社 耐摩耗性に優れたコーティングサーメットの製造法
AT394188B (de) * 1990-03-14 1992-02-10 Treibacher Chemische Werke Ag Verfahren zur herstellung von feinkoernigen, sinteraktiven nitrid- und carbonitridpulvern des titans
DE4125505A1 (de) * 1990-08-08 1992-02-13 Sueddeutsche Kalkstickstoff Verfahren zur herstellung von metallcarbiden
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FR2684091B1 (fr) * 1991-11-21 1994-02-25 Pechiney Recherche Procede de fabrication de carbures metalliques a grande surface specifique sous balayage de gaz inerte a pression atmospherique.
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US5314656A (en) * 1992-11-20 1994-05-24 The Regents Of The University Of California Synthesis of transition metal carbonitrides
US5380688A (en) * 1993-08-09 1995-01-10 The Dow Chemical Company Method for making submicrometer carbides, submicrometer solid solution carbides, and the material resulting therefrom
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Publication number Priority date Publication date Assignee Title
EP0464396A1 (fr) * 1990-06-20 1992-01-08 H.C. Starck GmbH & Co. KG Carbonitrures à partir des métaux de transition (M, M*, M**) des groupes 4 (M), 5 (M*) et 6 (M**) du système périodique des éléments, procédé pour leur production et application des carbonitrures

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Publication number Publication date
DE19646333C2 (de) 1999-01-14
DE19646333A1 (de) 1998-05-14

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