EP2066821B9 - Poudre métallique - Google Patents

Poudre métallique Download PDF

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Publication number
EP2066821B9
EP2066821B9 EP07803591.2A EP07803591A EP2066821B9 EP 2066821 B9 EP2066821 B9 EP 2066821B9 EP 07803591 A EP07803591 A EP 07803591A EP 2066821 B9 EP2066821 B9 EP 2066821B9
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Prior art keywords
powder
iron
nickel
cobalt
binder
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German (de)
English (en)
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EP2066821A1 (fr
EP2066821B1 (fr
Inventor
Benno Gries
Leo Prakash
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HC Starck GmbH
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HC Starck GmbH
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—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
    • 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
    • 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 set.
  • 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 molybdenum carbide.
  • Typical binder contents for cemented carbides are between 5 and 15% by weight, but in special applications they may be up to 3% and more up to 40% by weight.
  • the metallic binder phase consists of predominantly cobalt in the classic carbide. Due to the liquid phase sintering and the consequent dissolution and deposition processes of the carbide phase, 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 partial melting of the metallic binder, subsequently ground if necessary to final gauge and / or provided with coatings.
  • shrinkage In powder metallurgy as well as in ceramics, the size change of the compact during sintering is referred to as shrinkage or shrinkage.
  • S l linear shrinkage
  • Typical values for this so-called linear shrinkage in the hard metal industry are between 15 and 23%. This value is dependent on numerous parameters, such as added organic auxiliaries (such as paraffin, low molecular weight polyethylenes or esters or amides of long-chain fatty acids as pressing aids, a film-forming agent for stabilizing granules after spray drying, such as polyethylene glycol or polyvinyl alcohol, or antioxidants such as hydroxylamine or Ascorbic acid).
  • added organic auxiliaries such as paraffin, low molecular weight polyethylenes or esters or amides of long-chain fatty acids as pressing aids
  • a film-forming agent for stabilizing granules after spray drying such as polyethylene glycol or polyvinyl alcohol, or antioxidants such as hydroxylamine or Ascorbic acid.
  • organic aids are also referred to as organic additives.
  • Other influencing factors which influence the shrinkage and its isotropy are, for example, the particle size and size distribution of the hard material powders, the mixed grinding conditions and the geometry of the compact. The deeper reason is that these parameters and additives affect the compaction process when pressing the hard metal mixture to the compact.
  • elemental carbon or refractory metal powders are used as further additives (inorganic additives), which can likewise influence the shrinkage and its isotropy.
  • 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.
  • eridkonturnahe or accurate sintered parts can be produced. In the latter case, grinding operations are eliminated.
  • EP 0 937 781 B1 describes how the undesirable 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 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 non-magnetic carbide grades. by virtue of However, the low hardness and high ductility at higher temperatures such carbide types are not used for metal cutting.
  • Iron- and cobalt-containing metallic binder systems are therefore in the center of interest and are already available on a commercial basis.
  • feedstocks in the mixed grinding with the hard material powders usually either element powder such as cobalt, nickel or iron metal powder or prealloyed powders are used.
  • element powder such as cobalt, nickel or iron metal powder or prealloyed powders are used.
  • the latter already represent the desired composition of the FeCoNi portion of the binder after sintering as a pre-alloyed powder.
  • EPA 1346074 describes a cobalt-free FeNi-based binder type for coated carbide 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 are not sufficient for certain applications such as turning metal.
  • a metallic binder phase with about 70% iron, 10% cobalt and 20% nickel has proven to be particularly resistant to wear Characterized by a martensitic transformation on cooling. (B. Wittman, W.-D. Schubert, B. Lux, Euro PM 2002, Lausanne).
  • pre-alloyed metal powders from the FeCoNi alloy system are described. Here coprecipitated metal compounds or mixed oxides are reduced with hydrogen at temperatures between 300 ° C and 600 ° 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. If the equilibrium phase content of these powders given by the gross composition is biphasic at room temperature, these powders frequently already contain portions of excreted ferritic phase (cubic-body-centered, bcc) after production, the fcc portion still remaining (cubic face-centered , fcc) may be completely or partially metastable.
  • the alloy powders may be supersaturated at room temperature with respect to bcc fractions to be precipitated, and the excretion of bcc fractions may be promoted by mechanical activation of the powders even at room temperature.
  • the bcc-containing cemented carbide powder obtained after the mixing milling and drying can be pressed poorly. This results in low green densities, high and anisotropic shrinkages, and a greater dependence of compacted density on compacting pressure compared to elemental metal powders.
  • pre-alloyed FeCoNi powders which tend to biphase, could not be used as feedstock for carbide production due to process engineering reasons. Since the tungsten carbide is not deformed during pressing and only the metallic binder powder ensures the ductility required during pressing, the abovementioned problems with reduced binder content occur more frequently. Hard metals with a martensitic binder state - which require a pre-alloyed binder powder with very high iron contents and therefore high bcc contents - and low binder contents such as 6% are therefore only possible to produce under great process engineering effort.
  • This object is achieved by the method according to claim 7 for producing a hard metal 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 7, 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 Fe ⁇ 100 % - % Co • 90 % % Co + % Ni - % Ni • 70 % % Co + % Ni (with Fe: iron content in% by weight,% Co: cobalt content in% by weight,% Ni: nickel content in% by weight) is sufficient, with at least two binder powders a) and b) being used, with one binder powder having less iron 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.
  • Component a) is a prealloyed metal powder and component b) is an element powder or a prealloyed powder having a different composition, wherein one of the components a) or b) in particular advantageously has a greater proportion of a fcc phase which is stable at room temperature than the gross composition of Binders, 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.
  • 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).
  • volume percent (vol.), Mol percent (mol.%) And weight percent (wt.%) are used interchangeably.
  • the nickel content of the components is collectively 70% by weight of the powder mixture or less.
  • the nickel content of components a) and b) together amount to 45% by weight of the powder mixture or less if the cobalt content is less than 5% by weight.
  • 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 such as FeNi 50/50, FeCo 50/50 or FeCoNi 40/20/40.
  • the present invention also relates to a hard metal mixture obtainable by the method described above.
  • This hard metal mixture according to the invention can be used for the production of shaped articles, preferably by pressing and sintering.
  • the process for producing shaped articles is schematically shown in FIG. 6 shown.
  • the components a) and b), which are collectively referred to as binder powder 10, and the hard material powder 20 (component c) are mixed with a customary Mahl spasstechnik 30, for example water, hexane, ethanol, acetone and optionally other organic and / or inorganic additives (additives 40) subjected to a Mischmahlung 100, for example in a ball mill or an attritor.
  • the resulting suspension 50 is dried, removing the grinding fluid 90 and obtaining a hard metal mixture 60.
  • This cemented carbide mixture is pressed by a press 120 into the desired shape, whereby a compact 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 e.g. Paraffin, low molecular weight polyethylene or esters or amides of long-chain fatty acids, which are used as pressing aids; a film-forming agent for stabilizing granules after spray-drying, such as e.g. Polyethylene glycol or polyvinyl alcohol, or antioxidants such as hydroxylamine or ascorbic acid.
  • a film-forming agent for stabilizing granules after spray-drying such as e.g. Polyethylene glycol or polyvinyl alcohol, or antioxidants such as hydroxylamine or ascorbic acid.
  • low molecular weight organic compounds are suitable as organic additives.
  • polymers having a low ceiling temperature of preferably below 250 ° C. for example polyacrylates and polymethacrylates such as polymethyl methacrylate, polyethyl methacrylate, polymethyl acrylate, polyethyl acrylate or even polyvinyl acetate or polyacetal homo- or copolymers are suitable. These are generally used in amounts of from 1% by weight to 5% by weight, based on the total amount of components a, b and c.
  • Inorganic additives are, for example, elemental carbon or refractory metal powder added to control the carbon balance of sintering, which may also affect shrinkage and its isotropy.
  • tungsten, chromium or molybdenum metal powders can be used as the refractory metal powder. In general, they are used in amounts of less than 1: 5, in particular less than 1:10 in a weight ratio to the total binder content of the hard metal.
  • Suitable graphite powders generally have BET surface areas of 10 to 30 m 2 / g, in particular 15 to 25 m 2 / g, advantageously 15 to 20 m 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 they were completely prealloyed, 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 (eg, 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 has a higher stable fcc content than the gross composition would have been, it would be completely prealloyed.
  • Another aspect of the invention is that when pressed, the least amount of bcc phase is present on such binder compositions, as compared to those which would have been produced entirely from elemental powders.
  • the invention is preferably relevant to the composition range FeCoNi of the binder (gross composition) which is pre-alloyed at room temperature (it is assumed that the temperature prevailing in the mixed grinding is between room temperature and a maximum of 80 ° C) according to the phase diagram in the two-phase region bcc (cubic-body centered ) / 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 larger, the general rule is that pre-alloyed metal powders in the FeCoNi system - provided the composition is in the two-phase region at room temperature - due to the usual manufacturing temperatures between 400 and 900 ° C.
  • iron powder FeCo powder with up to 90% Co, FeNi 82/18 or FeCoNi 90/5/5, constructed.
  • 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 Share.
  • 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 Fe ⁇ 100 % - % Co • 90 % % Co + % Ni - % Ni • 70 % % Co + % Ni
  • the boundary line A is in FIG. 4 described mathematically.
  • iron powder is used as the element powder in component b), but it is also possible to use an iron-rich alloy powder. You can get out of the Phase diagrams show that this preferred range for the bcc powder stable at room temperature satisfies the conditions "Ni max 10%” and "Co max 70%". 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 content of oxygen, nitrogen, carbon or any passivating organic nature (for example, waxes, polymers or antioxidants such as ascorbic acid) is not taken into account. This must be taken into account, in particular, in the commercially available iron carbonyl powders, which may well have carbon and nitrogen of more than one percent by weight. Nevertheless, they are called element powder.
  • 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-alloyed powders is known in principle to a person skilled in the art and is described, for example, in US Pat EP-A-1079950 and EP-A-865 511 described, to which reference is made.
  • These pre-alloyed powders can be prepared by reduction of coprecipitated metal compounds or mixed oxides with hydrogen at temperatures between 300 ° C and 600 ° 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. Such methods are known to the person skilled in the art or can be achieved by a small number of corresponding experiments.
  • 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.
  • an aqueous solution containing metal salts of the desired metals in the appropriate proportions to each other with an aqueous solution, for. a carboxylic acid, a hydroxide, carbonate or basic carbonate mixed.
  • 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 precipitation product may optionally be subjected to thermal decomposition at a temperature of 200 to 1000 ° C in an oxygen-containing atmosphere (calcination).
  • the precipitate can be reduced to the prealloyed metal powder after precipitation and drying or after a calcination step in a hydrogen atmosphere at a temperature of 300 ° C to 1000 ° C.
  • Component a) contains at least two metals selected from the group consisting of iron, nickel and cobalt.
  • pre-alloyed 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 powder 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. More preferably, 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 to those skilled in the art and are commercially 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 often used for the production of "conventional powders", but results in a non-spherical morphology of the powder particles.
  • Pre-alloyed powders are powders which consist of punctually sintered primary grains and therefore have an internal porosity and can therefore be comminuted in the case of mixed grinding, as 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.
  • mixed grinding for the production of the hard metal mixture occurs in the case of the use of atomized metal powders not for comminution, but for the ductile deformation of the powder particles, which causes microstructural defects in the sintered cemented carbide.
  • binder pools which contain no hard material, as well as elongated pores, which are formed by the fact that deformed metal particles melt with high aspect ratio in the liquid phase sintering and absorbed by the surrounding hard material powder via capillary forces, then leaving a pore which has the shape of the deformed metal particle.
  • binder pools which contain no hard material, as well as elongated pores, which are formed by the fact that deformed metal particles melt with high aspect ratio in the liquid phase sintering and absorbed by the surrounding hard material powder via capillary forces, then leaving a pore which has the shape of the deformed metal particle.
  • a point sintered cobalt metal powder produced by hydrogen reduction of oxides or oxalates. Sputtered cobalt metal powders, although easier to produce, have not been able to assert themselves from the problems described above for producing hard metal blends.
  • 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 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 (US Pat. 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 produced by the combination of vaporization and condensation processes of metals as well as by gas phase reactions (US Pat. 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 of less than 5 .mu.m being often suitable for hard metal production, such as, for example, the commercially available CM-type carbonyl iron powders 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 compounds mentioned above can be used.
  • component c) in the ratio of 1: 100 to 100: 1 or of 1:10 to 10: 1 or of 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 hard metal mixture is a mixture of components a) and b) and component c) with the proviso that the ratio of component I to component III at 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 hard metal mixture according to the invention may contain conventional organic and inorganic additives, such as organic film-forming binders, as already described above.
  • Component a), the pre-alloyed powder, and component b), the element powder or the further pre-alloyed powder, complement the desired composition of the binder metal ("gross composition") for the component c), the hard material.
  • the components a) and b) together contain at least 10 wt .-% iron, the nickel content is not more than 70 wt .-%, advantageously, the maximum cobalt content is 90%.
  • the proviso that the iron content of the gross composition of both components a) and b) together satisfies the following inequality is particularly advantageous: Fe ⁇ 100 - % Co • 90 % Co + % Ni - % Ni • 70 % Co + % Ni (with Fe: iron content in wt%,% Co: cobalt content in wt%,% Ni: nickel content in wt%)
  • 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.
  • the components of the pre-alloyed powder are indicated by the element abbreviations and the numbers indicate the amount of the corresponding metal in weight percent.
  • component b) is a conventional one Iron powder, or a prealloyed powder of the composition FeCo 50/50, FeCoNi 90/5/5 or FeNi 90/10.
  • the hard metal mixture is used according to the invention for the production of shaped articles by sintering.
  • the hard metal mixture is pressed and sintered.
  • the cemented carbide composition according to the invention can be made into green bodies by known powder metallurgical processing methods, and is then sintered at a temperature of 1220 ° C to 1600 ° C for a period of 0.1 hour to 20 hours to form a 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 ° 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.
  • the powder was examined by X-ray diffraction analysis.
  • 100 g of the binder metal powder 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 area: 9.6 m 2 / g) with 570 ml of spirit and 30 ml of water a ball mill (content 2 l) with 5 kg of 15 mm diameter hard metal balls at 63 rpm for 14 h mixed milled.
  • 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. Was obtained a hard metal powder, which was sieved over 400 microns.
  • the height ratio of the main reflections bcc / fcc was determined by X-ray diffraction analysis to be 14.3, ie the bcc content is about 94% by volume and the fcc content is about 6% by volume. 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 a firm punch at 100, 150 and 200 MPa, determined the densities of the compacts, and sintered in vacuo at 1400 ° C for 1 h.
  • the following table shows the results thus obtained: Pressing pressure (MPa) 100 150 200 Press density (g / cm 3 ) 6.01 6.25 6.45 Global shrinkage (calculated from pressed density and sintered density, in%) 22.87 21.86 21,04
  • the change in phase balance is presumably due to supersaturation of the fully prealloyed binder powder at room temperature with respect to the face centered cubic content, and acceleration of the conversion rate from fcc to bcc due to the mechanical activation in the mixed grinding.
  • Example 1 was repeated, but instead of the pre-alloyed binder powder, the following elemental metal powders were used: amount element Manufacturer FSSS * Phase inventory according to X-ray diffraction analysis 70 g iron BASF, D 2.47 Pure bcc 10g cobalt Umicore, B 0.9 Hexagonal: fcc 1:25 20 g nickel Inco Specialties, UK 2.8 Pure fcc * ASTM B330
  • 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 portion stable at room temperature is 20% since the fcc portion in the cobalt metal powder is metastable at room temperature while iron is stably hexagonal at room temperature bcc and cobalt.
  • Example 1 Example 1) was repeated, except that 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 reduced by the same amount , The results obtained are shown in the following table: Pressing pressure (MPa) 100 150 200 Press density (g / cm 3 ) 6.27 6.49 6.68 Global shrinkage (calculated from pressed density and sintered density, in%) 21.78 20.87 20.11
  • Example 1 was repeated, but the following amounts of prealloyed binder powder or Fe metal powder were added instead of the prealloyed binder powder: amount Manufacturer FSSS * Phase inventory according to X-ray diffraction analysis 40 g FeNi 50/50 HC Starck 2.01 Pure fcc 20 g FeCo 50/50 HC Starck 1.26 Pure bcc 40 g Fe powder BASF 2.47 Pure bcc • ASTM B330
  • the addition of carbon black was 1.94 g to set the same carbon content in the formulation as in Example 1.
  • 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 the pre-alloyed binder content is difficult to estimate, since the phase diagram FeCoNi is not known in this alloy composition at room temperature, but should be well below 50%, since the starting powder FeCoNi 40/20/40 precipitates below about 500 ° C already bcc phase , Thus, the stable at room temperature fcc content of the binder would be less than 25%.
  • Example 2 was repeated. A portion of the hard metal powder was pressed directly after drying, another part was according to WO 2004 014586 with 2 parts by weight of paraffin infiltrated 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.
  • Example 1 The hard metal powder from Example 1 was infiltrated with paraffin wax to give a content of 2%. Press densities corrected for wax content were 5.99 (100 MPa), 6.39 (150 MPa), and 6.61 (200 MPa). Comparison with Example 1 shows that there is only a slight improvement in the green density due to the added wax.
  • 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 of the invention show in comparison to the use of elemental powders a significantly lower shrinkage at the same time higher K value.
  • the fully pre-alloyed powder causes a much smaller K value at high shrinkages, which is even below the K value for 20% cobalt cemented carbides.
  • the K values which were obtained according to the invention and with elemental powders are above the value of 0.988 EP 0 937 781 B1 and it is therefore believed that these three cemented carbide 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-body-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 in FIG. 5 shown.
  • FIG. 7 shows the results obtained for the dependence of the shrinkage on the pressing pressure, the alloy state of the binding metal powder and in the direction perpendicular and parallel to the pressing direction.
  • the lines are practically superimposed.
  • the expected, very high anisotropy of shrinkage results, in the direction parallel to the pressing direction a much higher shrinkage is found.
  • c) according to the invention (“FeNi 50/50 + Fe")

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Claims (17)

  1. Mélange de poudres métalliques, contenant a) au moins une poudre alliée au préalable, choisie dans le groupe constitué par le fer/nickel, le fer/cobalt, le fer/nickel/cobalt et le nickel/cobalt; b) au moins une poudre élémentaire, choisie dans le groupe constitué par le fer, le nickel et le cobalt ou une poudre alliée au préalable choisie dans le groupe constitué par le fer/nickel, le fer/cobalt, le fer/nickel/cobalt et le nickel/cobalt, qui est différente du composant a).
  2. Mélange de poudres métalliques selon la revendication 1, la composition brute des composants a) et b) contenant ensemble au maximum 90% en poids de cobalt et au maximum 70% en poids de nickel et la teneur en fer satisfaisant à l'inégalité Fe ≥ 100 % - % Co • 90 % % Co + % Ni - % Ni • 70 % % Co + % Ni .
    Figure imgb0012
  3. Mélange de poudres métalliques selon l'une ou plusieurs des revendications 1 à 2, contenant des additifs organiques et/ou inorganiques.
  4. Mélange de poudres métalliques selon l'une ou plusieurs des revendications 1 à 3, contenant un composant c), une substance dure.
  5. Mélange de poudres métalliques selon l'une ou plusieurs des revendications 1 à 4, qui est un mélange de liant métallique.
  6. Utilisation d'un mélange de poudres métalliques selon l'une ou plusieurs des revendications 1 à 5, pour la préparation de liants métalliques pour des métaux durs.
  7. Procédé pour la préparation d'un mélange pour métaux durs par l'utilisation de a) au moins une poudre alliée au préalable, choisie dans le groupe constitué par le fer/nickel, le fer/cobalt, le fer/nickel/cobalt et le nickel/cobalt ; b) au moins une poudre élémentaire, choisie dans le groupe constitué par le fer, le nickel et le cobalt ou une poudre alliée au préalable choisie dans le groupe constitué par le fer/nickel, le fer/cobalt, le fer/nickel/cobalt et le nickel/cobalt, qui est différente du composant a) ; c) une poudre de substance dure, la composition brute des composants a) et b) contenant ensemble au maximum 90% en poids de cobalt et au maximum 70% en poids de nickel et la teneur en fer satisfaisant à l'inégalité Fe ≥ 100 % - % Co • 90 % % Co + % Ni - % Ni • 70 % % Co + % Ni .
    Figure imgb0013
  8. Procédé pour la préparation d'un mélange pour métaux durs selon la revendication 7, la composition brute du liant étant Ni maximum 70% en poids et Fe au moins 10% en poids, la teneur en fer satisfaisant à l'inégalité Fe ≥ 100 % - % Co • 90 % % Co + % Ni - % Ni • 70 % % Co + % Ni
    Figure imgb0014
    au moins deux poudres de liant a) et b) étant utilisées, la première poudre de liant étant plus pauvre en fer que la composition brute du liant et la deuxième poudre de liant étant plus riche en fer que la composition brute du liant et au moins une poudre de liant étant alliée au préalable, constituée par au moins deux éléments choisis dans le groupe constitué par le fer, le nickel et le cobalt.
  9. Procédé selon l'une quelconque des revendications 7 ou 8, la teneur en nickel des composants valant ensemble 60% en poids du mélange de poudres ou moins.
  10. Procédé selon l'une quelconque des revendications 7 à 9, la teneur en fer des deux composants valant ensemble 5% en poids du mélange de poudres ou plus.
  11. Procédé selon l'une ou plusieurs des revendications de procédé ci-dessus, la teneur en nickel des deux composants valant ensemble 45% en poids du mélange de poudres ou moins, lorsque la teneur en cobalt est inférieure à 5% en poids.
  12. Procédé selon l'une ou plusieurs des revendications de procédé précédentes, le composant a) étant une poudre métallique alliée au préalable et le composant b) étant une poudre élémentaire, les teneurs en fer, en nickel et en cobalt se complétant en formant la composition globale souhaitée de la poudre de liant.
  13. Procédé selon l'une ou plusieurs des revendications de procédé précédentes, a) étant une poudre alliée au préalable constituée par du fer/nickel et b) étant une poudre de fer.
  14. Procédé selon l'une ou plusieurs des revendications de procédé précédentes, le composant a) étant une poudre alliée au préalable constituée par du FeNi 50/50, FeCo 50/50 ou FeCoNi 40/20/40.
  15. Mélange pour métaux durs, pouvant être obtenu selon l'une ou plusieurs des revendications de procédé précédentes.
  16. Utilisation d'un mélange pour métaux durs selon la revendication 15 pour la production d'objets façonnés, de préférence par frittage.
  17. Procédé pour la production d'objets façonnés à partir d'un mélange pour métaux durs tel que défini dans l'une ou plusieurs des revendications précédentes 7-14, comprenant les étapes suivantes
    - mise à disposition d'une première poudre métallique alliée au préalable,
    - mise à disposition d'une poudre élémentaire ou d'une deuxième poudre métallique alliée au préalable,
    - mélange-broyage des deux composants avec une poudre de substance dure pour obtenir un mélange pour métaux durs,
    - pressage et frittage du mélange pour métaux durs, ce qui permet d'obtenir un objet façonné constitué par un métal dur.
EP07803591.2A 2006-09-22 2007-09-21 Poudre métallique Not-in-force EP2066821B9 (fr)

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