EP2066821A1 - Poudre métallique - Google Patents

Poudre métallique

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Publication number
EP2066821A1
EP2066821A1 EP07803591A EP07803591A EP2066821A1 EP 2066821 A1 EP2066821 A1 EP 2066821A1 EP 07803591 A EP07803591 A EP 07803591A EP 07803591 A EP07803591 A EP 07803591A EP 2066821 A1 EP2066821 A1 EP 2066821A1
Authority
EP
European Patent Office
Prior art keywords
powder
iron
cobalt
nickel
binder
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
EP07803591A
Other languages
German (de)
English (en)
Other versions
EP2066821B9 (fr
EP2066821B1 (fr
Inventor
Benno Gries
Leo Prakash
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.)
HC Starck GmbH
Original Assignee
HC Starck GmbH
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Filing date
Publication date
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Application granted granted Critical
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Publication of EP2066821B9 publication Critical patent/EP2066821B9/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
    • C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
    • 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
    • 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
    • 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

  • Hard metals as a sintered and composite material consist of at least two phases, including a metallic binder phase, and one or more hard material phases. Due to the respective proportion of the metallic or hard phases, their different properties can be weighted and thus the desired properties of the hard metal, such as strength, hardness, modulus of elasticity, etc., can be attained.
  • the hard material phase usually consists of tungsten carbide, and depending on the application of the carbide tool also cubic carbides such as vanadium carbide, zirconium, tantalum or niobium carbide, their mixed carbides with each other or with tungsten carbide, as well as chromium carbide or Moiybdänkarbid, It can also nitrogen-containing cubic carbides ("carbonitrides Typical binder contents for hard metals are between 5 and 15% by weight, but may be up to 3% and more up to 40% by weight in special applications.
  • the metallic binder phase consists of predominantly cobalt in the classic carbide. Due to the liquid phase sintering and the carbide phase dissolution and deposition processes taking place, the metallic phase contains, after sintering, dissolved tungsten and carbon fractions, often also Cr - if e.g. Chromium carbide is used as an additive -, and for corrosion-resistant carbides also molybdenum. Very rarely, rhenium or ruthenium is used as an additive. The proportions of such metals in the binder which form cubic carbides are considerably lower because of their very low solubility.
  • the metallic binder phase in the sintered state comprises the hard material phase, forms a continuous network and is therefore often referred to as a "metallic binder” or as a "binder”. It is crucial for the strength of the carbide.
  • cobalt metal powder is usually mixed-milled with hard-material powders in ball mills or atres in liquids such as water, alcohols or acetone. In this case, a deforming stress of the cobalt metal powder takes place.
  • the resulting liquid suspension is dried, the resulting granules or powder ("hard metal mixture") pressed into compacts, and then sintered with at least teiiweisem melting of the metallic binder, subsequently ground if necessary to final gauge and / or provided with coatings
  • Technical effort because it produces fine, harmful dusts or generates grinding sludge, which represent a loss and their environmentally friendly handling costs, so it is desirable to control the size change of the compact during sintering so that grinding operations omitted as possible.
  • shrinkage In powder metallurgy, as well as in ceramics, the change in size of the compact during sintering is referred to as shrinkage or shrinkage.
  • the linear shrinkage ⁇ Si) of a dimension is calculated by the sinter-related dimensional change divided by the original dimension of the compact. Typical values for this so-called linear shrinkage in the hard metal industry are between 15 and 23%.
  • organic auxiliaries such as paraffin, low molecular weight polyethylenes or esters or amides of long-chain fatty acids as pressing aids
  • a form-forming agent for stabilizing granules after spray drying such as polyethylene glycol or Polyvinyialkohol, or antioxidants such as hydroxylamine or Ascorbic acid
  • organic adjuvants are also referred to as organic additives.
  • Weather factors affecting shrinkage and its isotropy are e.g. the grain size and size distribution of
  • anisotropies of the pressed density occur due to internal friction and wall friction during compaction, which can not be eliminated even by varying the parameters in the previous paragraph.
  • These density anisotropies lead to different shrinkages in two or even three spatial axes (anisotropic shrinkage), thus to tensions or even cracks in the sintered piece and must therefore be minimized as possible.
  • the empirical value is that the lower the shrinkage, ie the better the compactability during pressing, the better the shrinkage can be controlled within the desired tolerances, and the anisotropy of the shrinkage can be reduced.
  • EP 0 937 781 B1 describes how the undesired shrinkage anisotropy in the production of cobalt-bonded tungsten carbide hard metals below 1 ⁇ m can be influenced by uniaxial pressing by means of the grain size of the cobalt metal powder used as binder.
  • the value for K should be at least 0.988 to avoid reworking by grinding operations. For hard metals with 20% cobalt, a K value of 0.960 is given,
  • the K value can be calculated according to the following formula, the indices "s" being perpendicular to the pressing direction, "p" being parallel to the pressing direction:
  • the global shrinkage S 9 in percent can be calculated from the compact density and the sintered density according to the following formula: density Y * 1 sinter density ⁇
  • the global shrinkage does not consider possible differences in the 3 dimensions and is to be regarded as the average of the shrinkages in the three spatial axes. It enables a forecast of shrinkage based on the press density.
  • nickel-based binders are already being used, for example, for corrosion-resistant or nonmagnetic hardmetal types. by virtue of However, the low hardness and high ductility at higher temperatures are such Hartmetaüsorten not used for metal cutting.
  • EPA-1346074 discloses a FeNi-based cobalt-free binder type for coated hard metal cutting tools.
  • the case hardening can not occur due to the stable stability of the fcc binder phase over a wide temperature range from room temperature to the sintering temperature.
  • the lack of cobalt suggests that the high temperature properties (hot hardness) of the ductile binder can be exploited for certain applications, e.g. Turning metal are not sufficient.
  • Metal components mix by diffusion, such as mixing and annealing of oxides. If the equilibrium phase balance of these powders given by the gross composition is biphasic at room temperature, these powders often already contain portions of precipitated ferritic phase (cubic-body-centered, bcc) after production, with the fcc anteu (cubic-face centered) remaining , fcc) may be completely or partially metastable. Thus, the alloy powders may be supersaturated at room temperature with respect to the bcc portion to be precipitated, and the excretion of bcc portions may be promoted by mechanical activation of the powders even at room temperature.
  • This object is achieved by a method for producing a cemented carbide mixture by using a) at least one prealloyed powder selected from the group consisting of iron / nickel, iron / cobalt, iron / nickel / cobalt and nickel / cobalt; b) at least one element powder selected from the group consisting of iron, nickel and cobalt or a prealloyed powder selected from the group consisting of iron / nickel, iron / cobalt, iron / nickel / cobalt and nickel / cobalt, which is derived from component a) is different; c) hard material powder, wherein the gross composition of components a) and b) together contains a maximum of 90% cobalt and a maximum of 70 wt .-% nickel.
  • the iron content is advantageously at least 10 wt .-%.
  • this is a method for producing a hard metal mixture according to claim 1, wherein the gross composition of the binder of Co max. 90% by weight, Ni max. 70 wt .-% and Fe is at least 10 wt .-%, wherein the iron content of the inequality
  • At least two binder powders a) and b) being used, with one binder being less irony as the gross composition of the binder and the other binder powder is more ferrous than the gross composition of the binder and wherein at least one binder powder is pre-alloyed of at least two elements selected from the group consisting of iron, nickel and cobalt is used.
  • the component a) is advantageously a pre-alloyed metal powder and component b) is an element powder or a pre-alloyed powder having a different composition, wherein one of the components a) or b) in particular advantageously has a greater proportion of a fcc phase stable at room temperature than the gross composition of the binder, this would be completely pre-alloyed.
  • Particularly advantageous is one of the components a) or b) lower in iron than the gross composition of the binder powder. Accordingly, the respective other component is more iron-rich, with the contents of iron, nickel and cobalt complementing the desired overall composition of the binder (the composition of components a) and b) together).
  • the nickel content of components a) and b) together amount to 45% by weight of
  • the nickel content of both components a) and b) together is 45% by weight of the powder mixture or less if the
  • Cobaltgehalt less than 5 wt .-% is.
  • component a) is a prealloyed powder such as FeNi 50/50, FeCo 50/50 or FeCoNi 40/20/40.
  • the present invention also relates to a hardmetal mixture obtainable by the method described above.
  • This hard metal mixture according to the invention can be used for the production of molded
  • the present invention therefore also relates to shaped articles containing a sintered metallic powder mixture according to the invention.
  • the molded article contains one
  • the invention also relates to a hard metal obtainable by sintering a
  • the present invention also relates to a process for the production of molded
  • the process for producing shaped articles is shown schematically in FIG.
  • the components a) and b), which are jointly designated as binder powder 10, and the hard material powder 20 (component c) are mixed with a conventional grinding fluid 30, for example water, hexane, ethanol, acetone and optionally further organic and / or inorganic additives (additives 40) subjected to a Mischmahlung 100, for example in a ball mill or an attritor.
  • the suspension 50 obtained is dried, the grinding fluid 90 being removed and a hard metal mixture 60 being obtained.
  • This hard metal mixture is pressed by a press 120 into the desired shape, wherein a pressure 70 is obtained.
  • This is sintered by a conventional method, as described in detail below, (sintering 130).
  • a molded article 90 is obtained, which consists of a hard metal.
  • Organic additives are, for example, paraffin, low molecular weight polyethylenes or esters or amides of long-chain fatty acids, which are used as a compression aid! be used; a fumrelienden means for stabilizing granules after spray drying, such as polyethylene glycol or pofyvinyl alcohol, or antioxidants such as hydroxylamine or ascorbic acid.
  • low molecular weight organic compounds are suitable as organic additives.
  • Suitable graphite powders generally have BET surface areas of 10 to 30 m.sup.2 / g, in particular 15 to 25 m.sup.2 / g, advantageously 15 to 20 m.sup.2 / g.
  • the particle size distributions have a d50 value of usually 2 to 10 .mu.m, advantageously from 3 to 7 .mu.m, the d90 value is generally from 5 to 15 .mu.m.
  • the basic feature of the invention is to have the lowest possible proportion of room-temperature-stable bcc phase in pressing on such binder compositions, which, if fully pre-alloyed, would be in the two-phase region bcc / fcc at room temperature.
  • This is achieved by adjusting the gross composition of the binder to at least two different powders, one of which is stable at room temperature bcc (for example, iron powder or an iron-rich composition which is stable at room temperature and single-phase bcc), and another stable at room temperature fcc or At room temperature it has a higher stable fcc content than the gross composition would have been it is completely prealloyed.
  • the invention is thus preferably for those composition range FeCoNi of the binder (overall composition) relevant, which voriegiert at room temperature (it is assumed that the predominant in the mix-milling temperature between room temperature and a maximum of 80 0 C) bcc in the two-phase region according to the phase diagram (body-centered cubic ) / fcc (face-centered cubic), which is the prerequisite for the mechanically activated excretion of bcc phases. Since the fcc phases are more stable at high temperatures or their area of existence is greater, the general rule is that pre-alloyed metal powders in the system FeCoNi - provided the composition is in the two-phase region at room temperature - due to the usual manufacturing temperatures between 400 and 900 0 C.
  • FeCo powder with up to 90% Co, FeNi 82/18 or FeCoNi 90/5/5 constructed.
  • cubic face-centered phase is already found by X-ray diffraction at room temperature, although published phase diagrams for this composition alone show the face-centered cubic phase to be stable.
  • the very high proportion of cubic-face-centered phase after the mixed grinding of Beispie! 1 further indication that the boundary line of the two-phase region bcc / fcc to the fcc phase has to run at much lower iron values than indicated in the literature.
  • the boundary line two-phase region / fcc in the edge system FeNi is about 26% Ni, it is in the edge system FeNi at 70% Ni. If you connect these two points on the edge systems (FeNi 30/70 and FeCo 10/90) in the ternary system, you can draw the approximate course of the boundary line two-phase area / fcc at room temperature as a line and thus obtains its approximate course in the ternary system.
  • the dashed line A shows the boundary, the hatched area to the left of the dashed line A represents the gross composition area according to the invention.
  • the determined line also provides a means to obtain binder powder having the highest possible room temperature stable fcc - Select proportion.
  • the composition FeCoNi 40/20/40 must be biphasic.
  • the invention is carried out in such gross compositions FeCoNi of the binder, which satisfies the conditions Co a maximum of 90% and Ni a maximum of 70%, with the additional condition
  • iron powder is used as element powder, but it can also be an iron-rich Verä mecanicspuiver can be used. You can get out of the Phase diagrams show that this preferred range for the room temperature stable bcc powder of the conditions "Ni max. 10% "and” Co max 70% "is enough. In addition, any iron-rich prealloyed powder having a higher bcc stable at room temperature than the gross pre-alloyed powder composition may be used.
  • the gross composition of the binder which is calculated from the chemical compositions of the element or alloy powders used, takes into account only the metal content of the powders used.
  • the elements copper, zinc or tin are preferably present at most in the trace range, ie in amounts of at most 1000 ppm.
  • Component a) are so-called pre-alloyed powders.
  • the preparation of pre-coated powders is known in principle to a person skilled in the art and is described, for example, in EP-A-1079950 and EP-A-865511, to which reference is made.
  • These prealloyed powders can be prepared by reduction of coprecipitated metal compounds or mixed oxides with hydrogen at temperatures between 300 0 C and 600 0 C to the metal powder.
  • pre-alloyed metal powders may also be made by other methods in which there is a possibility that the metal components will be mixed by diffusion, such as mixing and annealing of oxides. The reduction can also be achieved in other reducing gases at a corresponding temperature.
  • pre-alloyed powders eg atomised pre-alloy
  • Such powders are expressly excluded from the term of pre-alloyed powders used herein and differ greatly in their properties.
  • the metal salts may advantageously be nitrates, sulfates or halides (especially chlorides) of iron, cobalt or nickel. This forms insoluble compounds of the metals, which precipitate from the solution and can be filtered off.
  • the precipitate is hydroxides, carbonates, or oxalates of the metals.
  • This precipitate may optionally be subjected to thermal decomposition (calcination) at a temperature of from 200 to 1000 ° C. in an oxygen-containing atmosphere.
  • Precipitation product can be after precipitation and drying, or after a calcination step in a hydrogen atmosphere at a temperature of 300 0 C to 1000 ° C reduced to the pre-alloyed metal powder.
  • the component a), the pre-alloyed powder contains at least two metals selected from the group consisting of iron, Nicke! and cobalt.
  • Examples of prealloyed powders in component a) are: pre-alloyed CoNi powders with any ratio Co: Ni between 0 and 200, also pre-alloyed with up to 10% Fe, FeNi-Pufver with up to 30% Fe, FeNi 50/50.
  • component b) are FeCo 50/50, FeCo 20/80, FeCoNi 90/5/5, FeNi 95/5.
  • Component b) is an element powder selected from the group consisting of iron, nickel and cobalt, alternatively another prealloyed powder.
  • component b) is a prealloyed powder selected from the group consisting of iron / nickel, iron / cobalt, iron / nickel / cobalt and nickel / cobalt, which is different from component a).
  • the gross composition of components a) and b) together contains at least 10% by weight of iron and not more than 70% by weight of nickel.
  • the proportion of room-temperature-stable fcc phase of both components a) and b) is different from each other, and is higher than that of components a) and b), if they were completely pre-alloyed together to the desired gross composition of the binder. Also advantageous is a content of not more than 90% cobalt.
  • components a) or b) can in turn also be made up of components having different compositions, so that theoretically the number of binder powders used is not limited.
  • the choice of binder powder is also here according to the invention, i. the proportion of fcc phase stable at room temperature is greater than that of the gross composition as prealloyed powder.
  • the component b) according to the invention is a conventional iron powder, or the component b) is a conventional one Nickel metal powder, for example for powder metallurgical applications, or component b) is a conventional cobalt powder.
  • component b) is a conventional iron or nickel powder.
  • These metal powders are elemental powders, that is, these powders consist essentially of one, advantageously pure, metal.
  • the powder may contain common impurities.
  • These powders are known in the art and commercial! available. For their preparation, numerous metallurgical or chemical processes are known. If fine powders are to be produced, the known methods often begin with the melting of a metal.
  • the mechanical coarse and fine comminution of metals or alloys is also frequently used for the production of "conventional powders", but results in a non-spherical morphology of the powder particles, and, if functioning well, is a very simple and efficient method of powder production (W. Schatt, K.-P. Wieters in "Powder Metallurgy - Processing and Materials", EPMA European Powder Metallurgy / Association, 1997, 5-10).
  • the morphology of the particles is also determined by the type of atomization.
  • Pre-powdered powders are those powders which consist of punctually sintered primary grains, therefore have an internal porosity and can therefore be comminuted in the case of mixed grinding, as described in WO 00/23631 A1, p. 1, lines 26-30.
  • melted metal powders are not suitable for the disclosed process since they have no internal porosity.
  • comminution does not take place for comminution but for ductile deformation of the powder particles, which causes microstructural defects in the sintered hard metal.
  • binder pools which contain no hard material, as well as elongated pores, which are created by the fact that deformed metal particles melt with high aspect ratio in the liquid phase sintering and are absorbed by the surrounding hard material pu I ver via Kapiilar machine remains then a pore having the shape of the deformed metal particle.
  • binder pools which contain no hard material, as well as elongated pores, which are created by the fact that deformed metal particles melt with high aspect ratio in the liquid phase sintering and are absorbed by the surrounding hard material pu I ver via Kapiilar development remains then a pore having the shape of the deformed metal particle.
  • a point sintered cobalt metal powder produced by hydrogen reduction of oxides or oxalates.
  • Atomized cobalt metal powder although easier to produce, has not been able to establish itself from the above-described problems for producing hardmetal mixtures.
  • melt-spinning ie Pouring a melt onto a cooled roll to form a thin, generally easily shredded strip
  • crucible-melt-extraction ie immersing a cooled, profiled, high-speed roll into a molten metal, whereby particles or fibers are recovered become.
  • a suitable variant of the production of conventional powder element powders for powder metallurgy applications which are suitable for the production of the hard metal mixture according to the invention is the chemical route via reduction of metal oxides or metal salts (W. Schatt, K.-P. Wieters in "Powder Metallurgy”). Processing and Materials, EPMA European Powder Metallurgy Association, 1997, 23-30), so that the procedure (apart from the use of the starting metal) is identical to the preparation of component a) Extremely fine particles having particle sizes below one micrometer can also be generated by the combination of vaporization and condensation processes of metals as well as by gas phase reactions (W. Schatt, K.-P. Wieters in "Powder Metallurgy - Processing and Materials", EPMA European Powder Metallurgy Association, 1997, 39-41 ).
  • One known industrial process for the production of iron, nickel and FeNi powders is the so-called carbonyl process, in which metal carbonyls are thermally decomposed.
  • the particle sizes here are between 0.3 and 10 .mu.m, with powders having particle sizes below 5 .mu.m being often suitable for hard metal production, such as, for example, the commercially available carbonyl iron phosphors of the type CM from BASF AG, Germany.
  • Component c) the hard material powder
  • these hard material powders are powders of, for example, carbides, borides, nitrides, metals of groups 4, 5 and 6 of the Periodic Table of the Elements.
  • the hard powder in the powder mixture according to the invention in particular carbides, borides and nitrides of the elements of Groups 4, 5 and 6 of the Periodic Table; in particular carbides, borides and nitrides of the elements molybdenum, tungsten, chromium, hafnium, vanadium, tantalum, niobium, zirconium.
  • Advantageous hard materials are in particular titanium nitride, titanium boride, boron nitride, titanium carbide, chromium carbide or tungsten carbide.
  • hard material powder one or more of the above-mentioned compounds can be used.
  • component c) in the ratio of 1: 100 to 100: 1 or from 1:10 to 10: 1 or from 1: 2 to 2 : 1 or 1: 1 used.
  • tungsten carbide, boron nitride or titanium nitride these are advantageously used in amounts of from 3: 1 to 1: 100 or from 1: 1 to 1:10 or from 1: 2 to 1: 7 or from 1: 3 to 1: 6.3 used.
  • the hard material is advantageously used in amounts of from 3: 1 to 1: 100 or from 1: 1 to 1:10 or from 1: 2 to 1: 7 or from 1: 3 to 1: 6.3 ,
  • the hardmetal mixture is a mixture of components a) and b) and component c), with the proviso that the ratio of component I to component III is from 3: 1 to 1: 100, or from 1: 1 to 1: 10, or from 1: 2 to 1: 7, or from 1: 3 to 1: 6.3.
  • the mean particle sizes before use in the process according to the invention are generally between 0.1 ⁇ m to 100 ⁇ m
  • the hardmetal mixture according to the invention may contain conventional organic and inorganic additives, such as organic fiim-forming binders, as already described above.
  • the iron content of the gross composition of both components a) and b) is combined the following inequality suffices:
  • the nickel content of components a) and b) together is advantageously 70% by weight or less.
  • the nickel content of both components a) and b) together is 45% by weight of the powder mixture or less if the cobalt content is less than 5% by weight.
  • component a) is a prealloyed powder consisting of iron and nickel and component b) is a conventional elemental powder of iron.
  • component a) is a prealloyed powder selected from the group consisting of FeNi 50/50 and FeCoNi 40/20/40 or a
  • Nickel metal powder Here, the components of the pre-alloyed powder are indicated by the element abbreviations and the numbers indicate the amount of the corresponding Metailes in
  • component b) is a conventional one Eisenpuiver, or a prealloyed powder composition FeCo 50/50, FeCoNi 90/5/5 or FeNi 90/10.
  • the hard metal compound is used according to the invention for the production of shaped articles by sintering.
  • the Hartmetaümischung is pressed and sintered.
  • the hard metal mixture according to the invention can be processed into green bodies by known methods of powder metallurgical processing and is then sintered at a temperature of 1220 0 C to 1600 0 C for a time of 0.1 hours to 20 hours with the appearance of liquid metal binder phase.
  • the green body Before sintering, the green body must be debinded in the presence of an organic additive, which is achieved for example by heating to a temperature of 200 to 450 0 C, but is also possible by other methods.
  • the sintering takes place advantageously in an inert or reducing atmosphere or in a vacuum.
  • an inert gas can be noble gases such as helium or argon, in some cases also use nitrogen, as reducing gases hydrogen or its mixtures with nitrogen, noble gases. In some cases, hydrocarbons are also used.
  • the design of the entire sintering cycle has great significance for the mechanical properties of the cemented carbides, but not for the shrinkage, provided the densification during sintering is close to the theoretical one.
  • Comparative Example 1 The metallic binder powder used was a prealloyed one prepared according to EP-A-1079950
  • Bindermetal Spulvers was mixed with 400 g of WC (FSSS 0.6 (ASTM B330), type WC DS 60, manufacturer: HC Starck GmbH) and 2.13 g of carbon black (specific surface: 9.6 nf7g) with 570 ml of spirit and 30 ml of water in a ball mill (Contents 2 I) mixed with 5 kg of 15 mm diameter carbide balls at 63 rpm for 14 h.
  • the hard metal balls were mechanically separated, and the suspension obtained in a glass flask at 65 ° C and 175 mbar absolute pressure heated under rotation to separate the grinding liquid by distillation.
  • the height ratio of the main reflections bcc / fcc was determined by means of X-ray diffraction analysis to be 14.3, ie the bcc fraction is about 94% by volume and the fcc anion is about 6% by vol. Based on this result, it can be assumed that the fcc phase stable at room temperature for a FeCoNi 70/10/20 is at most 6% by volume.
  • the cemented carbide powder was pressed uniaxially with firm stamping at 100, 150 and 200 MPa, determined the densities of the compacts, and sintered in vacuo at 1400 0 C for 1 h. The following table shows the results thus obtained:
  • the change in the phase state is presumed to be due to supersaturation of the fully pre-alloyed binder powder with respect to the cubic face-centered phase content, and acceleration of the conversion rate from fcc to bcc due to mechanical activation in the mixed milling.
  • Example 1 was repeated, but instead of the pre-alloyed binder powder, the following elemental metal powders were used:
  • the amount of carbon black added had to be reduced to 0.84 g to achieve the same carbon content of the formulation as in Example 1. Since only the Ni powder is stable at room temperature fcc and the co-powder is predominantly hexagonal , results for the binder powder used On the other hand, the fcc content stable at room temperature is 20% because the fcc content in the cobalt metal powder is metastable at room temperature while iron is stably hexagonal at room temperature bcc and cobalt. The following results were obtained:
  • Example 1 Comparative Example 3 a) Example 1) was repeated, but 0.71 g of graphite powder having a BET surface area of 20 m 2 / g, a d50 of 3.3 ⁇ m and d90 of 6.5 ⁇ m were added as internal lubricant and the amount of carbon black added was the same Amount reduced. The results obtained are shown in the following table:
  • Example 1 was repeated, but the following amounts of prealloyed binder powder or Fe metal powder were added instead of the prealloyed binder powder:
  • the addition of carbon black was 1.94 g to set the same carbon content in the formulation as in Example 1.
  • the results are summarized in the following table:
  • Example 1 was repeated, but instead of the prealloyed binder powder, the following quantities of prealloyed binder powder or Fe powder were added:
  • the carbon black addition was 2.03 g to adjust the same carbon content in the formulation as in Example 1.
  • the proportion of stable at room temperature fcc phase after the Mixed grinding in pre-alloyed binder content is bad estimate, since the phase diagram FeCoNi is not known at this Leg istszusammens ⁇ tzung at room temperature, but should be well below 50%, as the starting powder FeCoNi 40/20/40 below about 500 0 C already eliminated bcc phase , Thus, the stable at room temperature fcc content of the binder would be less than 25%.
  • the results obtained are summarized in the following table:
  • Example 2 was repeated. A portion of the hard metal powder was pressed directly after drying, another part was infiltrated according to WO 2004 014586 with 2 parts by weight of paraffin to 98 parts by weight of hard metal powder to achieve a homogeneous wax distribution. The results "waxed” and “unwaxed” are compared in the following table. At the values for the density "waxed” the measured value for the density was multiplied by the factor 0.98, because the wax is expelled during sintering.
  • the sintering density was 14.80 g / cm3 +/- 0.03, but variant b) showed porosity and therefore reached only 14.54 g / cm3.
  • the variant a) shows a lower anisotropy of the shrinkage compared to the variant c).
  • Variant b) could not be densely sintered, which is an indication of a poor homogeneity of the green density and an indication of very high internal friction during pressing. The values for the shrinkage can therefore not be evaluated.
  • Examples 9 to 12 illustrate the essence of the invention particularly clearly.
  • the two embodiments according to the invention show, in comparison to the use of egg powder, a significantly lower shrinkage and at the same time a higher K value.
  • the completely pre-alloyed powder causes a much smaller K value at high shrinkages, which is even below the K value for hard metals at 20%. Cobalt lies.
  • the K values which were obtained according to the invention and with eggplant powders are above the value 0.988 according to EP 0 937 781 B1 and it is therefore to be assumed that these three hard meta mixtures are suitable for the production of sintered hard metal parts without post-processing.
  • the two embodiments of the invention provide in Compared to the use of pure element powders additionally the advantage of an overall lower shrinkage, which additionally facilitates the production of final contour sintering and the advantages of pre-alloyed powders in the sintering.
  • the paraffin wax commonly used as a lubricant in the hard metal industry improves the green density and the shrinkage, but does not increase the K value. This is explained by the fact that the lubricant facilitates the rotation or displacement of particles occurring during pressing against each other, but of course not the equally necessary deformation of metallic binder particles.
  • the examples show that the alloy state of the binder is the largest major factor influencing shrinkage and K value. This is even more true, the higher the binder content. In the case of 6% binder, the influence decreases significantly, which confirms the assumption that the role of the binder is crucial. Thus, the deformability of the binder particles would be crucial.
  • phase transformations or precipitates presumably caused by mechanical activation of precipitation processes or phase transformations of pre-alloyed powders in the mixed grinding with tungsten carbide, lead to an aggravation of compaction during pressing, by deteriorating the deformability.
  • proportion of cubic-centered phase increases, it can be assumed that a mechanically activated precipitation hardening occurs.
  • cubic body-centered metal alloys are less deformable than face-centered cubic because they have less crystallographic slip planes. The green density increases disproportionately with the stable at room temperature fraction of fcc phase. This is shown in FIG.
  • Ratio at room temperature stable fcc phase to the bcc phase must be 2.5: 1, resulting in a proportion of 71, 4%.
  • FIG. 7 shows the results obtained for the dependence of the shrinkage on

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
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  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)

Abstract

La présente invention concerne un mélange de poudres métalliques, utilisé pour la fabrication de corps frittés. Le mélange de poudres est utilisé comme liant pour les métaux durs, et contient : a) au moins une poudre choisie dans le groupe comprenant fer/nickel, fer/cobalt, fer/nickel/cobalt et nickel/cobalt ; b) au moins une poudre d'un élément choisi dans le groupe comprenant fer, nickel et cobalt ou une poudre choisie dans le groupe comprenant fer/nickel, fer/cobalt, fer/nickel/cobalt et nickel/cobalt, différente du composant (a).
EP07803591.2A 2006-09-22 2007-09-21 Poudre métallique Not-in-force EP2066821B9 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006045339A DE102006045339B3 (de) 2006-09-22 2006-09-22 Metallpulver
PCT/EP2007/060060 WO2008034903A1 (fr) 2006-09-22 2007-09-21 Poudre métallique

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EP2066821A1 true EP2066821A1 (fr) 2009-06-10
EP2066821B1 EP2066821B1 (fr) 2013-03-27
EP2066821B9 EP2066821B9 (fr) 2013-07-24

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EP (1) EP2066821B9 (fr)
JP (1) JP2010504427A (fr)
KR (1) KR20090053934A (fr)
CN (1) CN101528961B (fr)
DE (1) DE102006045339B3 (fr)
IL (1) IL197307A0 (fr)
MX (1) MX2009002790A (fr)
RU (1) RU2468889C2 (fr)
WO (1) WO2008034903A1 (fr)
ZA (1) ZA200901577B (fr)

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EP4034323A1 (fr) * 2019-09-25 2022-08-03 Evonik Operations GmbH Corps métalliques et procédé de production de ceux-ci
KR20220078640A (ko) * 2019-10-03 2022-06-10 유미코아 다이아몬드 공구용 예비 합금 분말의 제조 방법, 및 이로 수득된 분말
KR102254512B1 (ko) * 2020-01-31 2021-05-21 부경대학교 산학협력단 열차폐용 복합재료 제조방법 및 이에 의해 제조된 열차폐용 복합재료
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US8523976B2 (en) 2013-09-03
CN101528961B (zh) 2013-07-17
MX2009002790A (es) 2009-03-30
RU2468889C2 (ru) 2012-12-10
US20090285712A1 (en) 2009-11-19
IL197307A0 (en) 2009-12-24
JP2010504427A (ja) 2010-02-12
RU2009114862A (ru) 2010-10-27
CN101528961A (zh) 2009-09-09
EP2066821B9 (fr) 2013-07-24
ZA200901577B (en) 2010-05-26
DE102006045339B3 (de) 2008-04-03
EP2066821B1 (fr) 2013-03-27
KR20090053934A (ko) 2009-05-28
WO2008034903A1 (fr) 2008-03-27

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