EP2010687A2 - Procédé de production d'un corps en métal dur, poudre servant à la production d'un métal dur et corps en métal dur - Google Patents

Procédé de production d'un corps en métal dur, poudre servant à la production d'un métal dur et corps en métal dur

Info

Publication number
EP2010687A2
EP2010687A2 EP07724394A EP07724394A EP2010687A2 EP 2010687 A2 EP2010687 A2 EP 2010687A2 EP 07724394 A EP07724394 A EP 07724394A EP 07724394 A EP07724394 A EP 07724394A EP 2010687 A2 EP2010687 A2 EP 2010687A2
Authority
EP
European Patent Office
Prior art keywords
phase
metals
sintering
carbon
mass
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.)
Granted
Application number
EP07724394A
Other languages
German (de)
English (en)
Other versions
EP2010687B1 (fr
Inventor
Walter Lengauer
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.)
TUTEC GmbH
Original Assignee
Treibacher Industrie AG
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 Treibacher Industrie AG filed Critical Treibacher Industrie AG
Publication of EP2010687A2 publication Critical patent/EP2010687A2/fr
Application granted granted Critical
Publication of EP2010687B1 publication Critical patent/EP2010687B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • C22C29/02—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
    • C22C29/08—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 based on tungsten carbide
    • 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
    • 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
    • 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
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy

Definitions

  • the invention relates to a method for producing a hard metal body with a uniform microstructure, with a single- or multi-phase hard material phase consisting of 60% by mass to 100% by mass of WC, whose anisotropic crystallites make up less than 20% of all WC crystallites, and up to 40 %
  • the invention further relates to a powder having one or more, in principle ternary W-Co-C phases for producing a hard metal by reactive sintering in the presence of carbon and finally the hard metal body produced by said method or with said powder.
  • the grain size of hard metal bodies and their distribution in the hard metal are determined by many factors, including the starting materials, the composition and the production conditions, in particular the grinding and the sintering temperature.
  • the carbon balance of the hard metal approach plays a significant role.
  • lower grain growth tendency is found in carburized hard metal alloys than in hard metals with stoichiometric or superstoichiometric carbon content.
  • Additions of tantalum, vanadium, chromium or even titanium carbide can serve as grain growth inhibitors for WC.
  • the grain size and in particular the grain size distribution of a hard metal has a great influence on the mechanical properties.
  • coarse-grained WC-Co hard metals are generally tougher than fine-grained ones Wear resistance and hardness for it is higher.
  • Mixed crystal phases in Mehrcarbidlegie- ments can be used to improve the toughness.
  • additional carbides such as VC, Cr 3 C 2 , TaC, NbC, (Ta, Nb) C, or TiC
  • the additional carbides are added either in the form of a WC pre-doped with additional carbides or during the production of the hard metal batch, ie during mixing and grinding.
  • the aim is a uniform distribution of additional carbides as possible.
  • the mixture produced represents a mixture of WC and the additional carbides, which, however, is still inhomogeneous.
  • the additional carbides can not be incorporated into the crystal lattice of the WC on this production route.
  • WC agglomerates pose a particular problem, since these agglomerates are difficult to break up by grinding and thus the additional carbides are distributed irregularly on the WC crystallites and do not reach all crystallite surfaces. This leads to an undesirable inhomogeneous grain growth of the cemented carbide.
  • the present invention is based on the idea that the hard metal is produced by reactive sintering a powder mixture containing a W-Co-C phase in the form that the additional carbides incorporated in the crystal lattice of the W-Co-C phase, that is dissolved are or is homogeneously alloyed with these metals.
  • solubility of the ternary subcarbide for doping carbides is adequate to provide a suitable Total doping level to achieve in the finished sintered carbide.
  • additional carbides can be incorporated in a uniform distribution.
  • the hard metal is formed by reactive sintering a batch of a corresponding powder, for example W 9 C0 3 C4 together with carbon, which after the phase reaction
  • This cemented carbide has about 9 mass% Co when no additional phases are incorporated.
  • the additional carbides are not included in the above reaction equation;
  • the metals of the additional carbides are in the W 9 Co 3 C 4 as well as in all other W-Co-C phases either at the position of the W atoms and / or Co atoms in which these metals are substituted, or they are installed at other point locations in the crystal lattice.
  • these metals can be deposited as free carbides in the cemented carbide, optionally on WC crystallites and / or they are dissolved in the binder phase.
  • the metals of the additional carbides are incorporated into the ternary phase unit cell, they are already in the places where, in the ternary W-Co-C phase, by reactions with carbon WC corresponding to the above At best, the metals are separated by a distance of less lattice planes, so that they occur in the best possible distribution.
  • an optimum effect of the doping carbides is achieved not only with respect to the inhomogeneous grain growth to be suppressed, but also ensures economical use since the doping carbides are added only to the necessary extent. In particular, an overdoping of such additional carbides in the hard metal and thus embrittlement of the hard metal can thus be prevented.
  • a starting powder which not only has pure W-Co-C phases to which a grain growth inhibitor such as Cr3C2 is added, but uses a W-Co-C alloy alloy in advance, in which individual tungsten or cobalt atoms are represented by Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, Ni, Fe, Sc, Y, La, Ce, Re, Ru, Rh, Pt such that these metals are contained in a ternary W-Co-C phase in dissolved form.
  • the grain growth inhibitors are located in the same lattice as the tungsten, which reacts with WC in the presence of carbon.
  • At least one of the metals Ti, Zr, Hf, V, Nb, Ta, Cr, Mo 1 thereof, in particular V, Cr or Ta, and at least one of the metals Sc, Y, La, Ce, Re, Ru, Rh, Pt are preferred contained in dissolved form.
  • the starting mixture contains an amount of said ternary W-Co-C phase which corresponds to at least 10% by volume of the WC-sintered cemented carbide body.
  • the carbon necessary for the reaction sintering can be added to the batch in solid form as graphite, carbon black or another carbon modification (carbon nanotubes, Buckminster fullerenes) or in the form of another organic or inorganic carbon donor.
  • carbon nanotubes carbon nanotubes, Buckminster fullerenes
  • a part of the carbon required for reactive sintering is added by gas phase treatment with a carbon-containing gas in the pre-sintering or sintering process.
  • the desired total composition, in particular the 10 vol % of alloyed ternary phase corresponds, with at least two of the metals Ti, Zr, Hf, V, Nb, Ta, Cr, Mo or at least two oxides, carbides, oxicarbides, carbonitrides or oxicarbonitrides of these metals or an organic compound of these metals such Acetate, oxalate or citrate or another inorganic compound such as a fluoride or chloride and mixed by subsequent annealing in bulk or compressed form at temperatures up to 1900 0 C for up to 168 hours under vacuum, inert gas, C-containing Treated gases or hydrogen.
  • the starting mixture can be processed by reaction with carbon either by C-containing gases and / or by addition of carbon in solid form to a powder of the composition WC + Co + doping carbides by a controlled temperature control, preferably in a corresponding total composition necessary for the carbide to be produced ,
  • known sintering cycles which are tuned to a controlled uniform nucleation of the WC during heating, can be used, wherein the temperature is kept constant in the heating phase, the cooling phase and / or after reaching the maximum sintering temperature in hold times over periods ⁇ 5 min or the temperature change is reduced.
  • the starting mixture may contain AI in addition. The same applies to the powders according to claims 9 to 11 as explained for the above method.
  • End product is a hard metal body with a hard material phase of 60 to 100% by mass of WC (proportion of the hard material phase), up to 40% by mass (proportion of hard material phase) of a carbide, nitride, carbonitride or oxycarbonitride of at least one of the metals Ti 1 Zr, Hf 1 V, Nb, Ta, Cr, Mo, wherein at least 10% by volume of the WC have been formed by reaction of a ternary W-Co-C phase with carbon and this ternary phase before sintering at least two of the metals Ti, Zr, Hf , V, Nb, Ta, Cr, Mo, Fe, Ni 1 Sc, Y, La 1 Ce 1 Re 1 Ru, Rh contains 1 Pt in dissolved form and a binder phase with 4-20 mass% (proportion of carbide) from Co or Co with up to 50 mass% (proportion of the binder phase) Fe 1 Ni and / or Cr.
  • Nitrogen may also be present in bound form in the powdery starting mixture, in particular as nitride or carbonitride. This nitrogen has a grain refining effect in the further production of the cemented carbide body in the finished product.
  • the following procedure was used to produce an alloyed subcarbide powder: First, the solubilities of V, Ta and Cr on both hot-pressed samples and carburized Co-rich alloys of the W-Co-CV-Cr-Ta system were determined by high performance microprobe analysis using chemically analyzed external standards.
  • the hot pressed samples had a sub-carbide phase content of> 95% and had traces of free VC, Cr 3 C 2 and TaC to ensure reaching the solubility limit for the corresponding metals in the subcarbide phase.
  • alloy powder subcarbide an alloy phase (W, Ta, V, Cr) 2 were used for the production weighed, wherein Ta content based on the total Weighing 0.9% by weight and the V and Cr content in each case 0.4% by weight.
  • the powders were homogenized in the planetary ball mill in cyclohexane for 20 minutes using carbide grinding media and ground.
  • the dried and sieved powder mixture was placed in a molybdenum boat under a hydrogen atmosphere at a rate of 5 ° C / min heated to 1350 ° C and held the temperature there for 100 min.
  • the cooling rate was initially 12 ° C / min, from 800 0 C 3 ° C / min.
  • the result was a X-ray single-phase powder of (W, Ta, V, Cr) 2 , 5 iC ⁇ o. 82 C.
  • a third embodiment for producing rare earth alloyed subcarbide powder the following proportions were weighed into a mixture of tungsten carbide, tungsten and cobalt powders, tantalum, vanadium and chromium carbide powders and yttrium nitride: 0.6% by mass TaC, 0.3 Mass% VC, 0.3 mass% Cr 3 C 2 and 0.1 mass% YN, again using the general formula (W, Ta 1 V 1 Cr, Y) 2 , 5 iC ⁇ o, 82 C.
  • YN donates Y by elimination of nitrogen, which dissolves as well as V, Ta, and Cr in the alloyed subcarbide phase.
  • This mixture was homogenized in the planetary ball mill in cyclohexane for 20 minutes by means of carbide grinding bodies and ground.
  • the dried and sieved powder mixture was heated in a molybdenum boat under hydrogen atmosphere at 5 ° C / min to 1350 0 C and kept the temperature there for 100 min.
  • the cooling curve was initially 12 ° C / min, from 800 ° C 3 ° C / min.
  • Example 1 To the above-described powders (W, Ta 1 V 1 Cr, Y) 2, 5 iCo 0, 82 C or (W, Ta, V, Cr) 2, 5 iC ⁇ o, 82 C So much carbon black was weighed in that, after sintering, a molar [W + V + Ta + Cr] / [C] ratio of 1 was achieved. By means of test sintering and measurement of the specific saturation magnetization, the carbon doping was set exactly. The mixture was homogenized in the drum mill under cyclohexane with hard metal grinding media for 20 h and ground.
  • Example 2 After drying the powder cylindrical shapes were pressed at a pressure of 150 MPa, placed in a graphite crucible and heated under vacuum at a rate of 5 ° C / minute to 128o C 0. The temperature was held there for 30 min and added 20 mbar Ar as protective gas at the end of this holding plateau. The mixture was then heated at a rate of 5 ° C / min to 1400 0 C and cooled min after holding a plateau of 30 min at a rate of 5 ° C /. Sintering hard metals with carbon black addition, Example 2
  • the atmosphere was pumped down to a rotary pump vacuum (about 0.01 mbar) and then made up to 100 mbar Ar.
  • the mixture was then heated at a rate of 5 ° C / min to 1400 0 C and cooled min after holding a plateau of 30 min at a rate of 5 ° C /.
  • Example 5 From the above-described, ground powder (W, Ta, V, Cr) 2.5 iC ⁇ o, 82 C green compacts were pressed by means of pressing aids with a soot amount significantly below the [W + V + Cr] / [C] ratio of 1, pressed and placed in a graphite crucible. With the addition of a methane / Ar mixture was heated at a rate of 5 ° C / min to 1280 0 C, wherein the Ar / methane ratio was successively increased. The temperature was maintained at 1280 ° for 30 minutes. At the end of this holding plateau there was a pure Ar atmosphere. At a rate of 5 ° C / min was further heated to 1400 ° C and cooled after a holding plateau of 30 min at 5 ° C / min.
  • the substances and methods described are equally suitable for improving the properties of ultrafine to coarse carbide carbides as well as for the improvement of hard metals with a high proportion of cubic phases (P and M hard metals).
  • the improved characteristics are due to a more uniform hard metal structure resulting from a uniform distribution of the grain growth inhibiting metals V, Ta and / or Cr.
  • the significantly improved properties are due to the uniform distribution of Co, which originates entirely from the subcarbide in the cited embodiments. Only by using alloyed subcarbide phases in the approach, this distribution is ideal, since W, Co and the grain growth inhibitors are dissolved in the same crystal lattice of the precursor.
  • the addition of rare earth elements such as Y additionally increases the connection of the interfaces of the WC to Co.
  • the use of nitrogen already in the heating phase and even in the presence of the open-pore structure of the green compacts additionally refines the hard metal structure. This indicates a solution of nitrogen in the alloyed subcarbide phases, which can already be achieved in powder production.
  • Tungsten carbide, tungsten, cobalt, tantalum carbide, vanadium carbide and chromium carbide powders having average grain sizes in the range of 0.6-1.7 ⁇ m have been converted to a powder of total composition Co. 82 (W 2.4 Ta 0. o 2 Vo.o 4 Cro.o 4 ) Weighed 2.5 iC.
  • the starting mixture was homogenized in the planetary ball mill in cyclohexane for 20 min and ground.
  • the dried and sieved powder mixture was heated in a molybdenum boat under hydrogen atmosphere at 5 ° C / min to 1350 0 C and kept the temperature there for 100 min. Up to 800 0 C was cooled at 11 ° C / min, then at 3 ° C / min.
  • soot was weighed to obtain a stoichiometric amount of carbon, this mixture was homogenized and ground in the planetary ball mill in hard metal grinding bowls using tungsten carbide balls in cyclohexane for 20 minutes. After drying and granulation were washed with a Pressure of 150 MPa cylindrical molds pressed in a carbide die placed in a graphite crucible.
  • the hardness HV30 of this cemented carbide was 1690 and the fracture toughness was
  • Tungsten carbide, tungsten, cobalt, Tantalcarbid-, vanadium carbide and chromium carbide powder having average particle sizes in the range of 0.6-1, 7 .mu.m Cro 4 were added to a powder of the total composition C ⁇ o. ⁇ 2 (W 2. 42 Vo.o. O 4 ) 2.5 iC weighed.
  • the mixture of the starting powders was homogenized in the planetary ball mill in cyclohexane for 20 min and ground.
  • the dried and sieved powder mixture was heated in a molybdenum boat under hydrogen atmosphere at 5 ° C / min to 1350 0 C and kept the temperature there for 100 min. Up to 800 0 C was cooled at 11 ° C / min, then at 3 ° C / min.
  • carbon black was weighed to a theoretical (W, Cr, V) / C ratio of 0.94, homogenized and ground in the planetary ball mill in hard metal grinding jars using hard metal balls in cyclohexane for 20 minutes.
  • cylindrical molds were pressed in a carbide die at a pressure of 150 MPa and placed in a graphite crucible.
  • the green compacts were heated at 93O 0 C with 5 ° C / min. There, a holding plateau of 45 min was inserted and then also heated at 5 ° C / min to 1280 0 C on.
  • the temperature was maintained for 30 min and then 20mbar argon added as a protective gas.
  • the hardness HV30 of this cemented carbide was 1430 and the fracture toughness according to Palmqvist / Shetty was 15.5 MPa.m- 172 .

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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)
  • Powder Metallurgy (AREA)

Abstract

L'invention concerne un procédé de production d'un corps en métal dur, une poudre servant à la production du métal dur ainsi qu'un corps en métal dur produit. Selon ladite invention, ce corps en métal dur possède une phase dure, qui contient 60 % en masse à 100 % en masse de carbure de tungstène (WC) et jusqu'à 40 % en masse d'un carbure, d'un nitrure, d'un carbonitrure ou d'un oxycarbonitrure d'au moins un des métaux suivants : Ti, Zr, Hf, V, Ta, Cr, Mo, ainsi qu'une phase liante composée de Co ou d'un alliage de Co et d'au maximum 50 % en masse de Ni, Fe ou Cr, laquelle phase liante constitue 4 à 20 % en masse du métal dur. Selon ladite invention, au moins 10 % en volume du carbure de tungstène s'obtiennent en faisant réagir une phase W-Co-C en principe ternaire avec du carbone, cette phase W-Co-C ternaire contenant sous forme dissoute, avant le frittage, au moins deux des métaux suivants : Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, Fe, Ni, Sc, Y, La, Ce, Re, Ru, Rh, Pt.
EP07724394.7A 2006-04-24 2007-04-20 Corps en métal dur et procédé de son production Not-in-force EP2010687B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006018947A DE102006018947A1 (de) 2006-04-24 2006-04-24 Verfahren zur Herstellung eines Hartmetallkörpers, Pulver zur Herstellung eines Hartmetalls und Hartmetallkörper
PCT/EP2007/003457 WO2007121931A2 (fr) 2006-04-24 2007-04-20 Procédé de production d'un corps en métal dur, poudre servant à la production d'un métal dur et corps en métal dur

Publications (2)

Publication Number Publication Date
EP2010687A2 true EP2010687A2 (fr) 2009-01-07
EP2010687B1 EP2010687B1 (fr) 2013-06-05

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Application Number Title Priority Date Filing Date
EP07724394.7A Not-in-force EP2010687B1 (fr) 2006-04-24 2007-04-20 Corps en métal dur et procédé de son production

Country Status (3)

Country Link
EP (1) EP2010687B1 (fr)
DE (1) DE102006018947A1 (fr)
WO (1) WO2007121931A2 (fr)

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Also Published As

Publication number Publication date
WO2007121931A3 (fr) 2008-03-06
DE102006018947A1 (de) 2007-10-25
WO2007121931A2 (fr) 2007-11-01
EP2010687B1 (fr) 2013-06-05

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