EP2097549A2 - Poudre métallique - Google Patents

Poudre métallique

Info

Publication number
EP2097549A2
EP2097549A2 EP07847463A EP07847463A EP2097549A2 EP 2097549 A2 EP2097549 A2 EP 2097549A2 EP 07847463 A EP07847463 A EP 07847463A EP 07847463 A EP07847463 A EP 07847463A EP 2097549 A2 EP2097549 A2 EP 2097549A2
Authority
EP
European Patent Office
Prior art keywords
weight
molybdenum
alloyed
metal powder
carboxylic acid
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.)
Withdrawn
Application number
EP07847463A
Other languages
German (de)
English (en)
Inventor
Bernd Mende
Gerhard Gille
Ines Lamprecht
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
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 HC Starck GmbH filed Critical HC Starck GmbH
Publication of EP2097549A2 publication Critical patent/EP2097549A2/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0207—Using a mixture of prealloyed powders or a master alloy
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C33/00—Making ferrous alloys
    • C22C33/02—Making ferrous alloys by powder metallurgy
    • C22C33/0257—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements
    • C22C33/0278—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5%
    • C22C33/0285—Making ferrous alloys by powder metallurgy characterised by the range of the alloying elements with at least one alloying element having a minimum content above 5% with Cr, Co, or Ni having a minimum content higher than 5%
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/10—Ferrous alloys, e.g. steel alloys containing cobalt
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium

Definitions

  • Alloy powders have many applications for the production of sintered moldings by powder metallurgy.
  • the main feature of powder metallurgy is that corresponding powdered alloy or metal powders are pressed and then sintered at a sufficiently high temperature.
  • This method is introduced on an industrial scale for the production of complicated moldings which can otherwise only be produced with a high degree of complex finishing or, as in the case of liquid phase sintering, e.g. Hard or heavy metals where no technological alternatives exist.
  • the sintering temperature is chosen as high as possible and also the adjustment of certain phases, compositions, etc. requires correspondingly high sintering temperatures and times.
  • the hardness of the metallic matrix drops above an optimum temperature again, since it comes as a result of grain growth to a coarsening of the structure (Ostwald ripening).
  • such powders are advantageous for sintered bodies which already achieve their theoretical density and suitable phase formation at the lowest possible sintering temperatures.
  • the object of the invention is to provide alloy powder, ie pre-alloyed metal powder containing at least the metals iron, cobalt and molybdenum, which meet the stated requirements for sintered materials available.
  • FeCoMo-based steels within certain compositional ranges, with appropriate heat treatment, form the intermetallic compounds (FeCo) 7M ⁇ 6, which provide very high hardnesses and strengths and are an alternative to the steels produced by certain applications carbidic precipitates are hardened (Köster f W .: Mechanical and magnetic precipitation hardening of the iron-cobra-Woifram- and iron-cobalt-molybdenum alloys, Archive for the iron and steel industry, 1932, No. 1 / JuIi, p 17-23).
  • the production of such steels by melting the components and casting in an inert atmosphere is complicated and has hitherto found no entry into industrial practice.
  • Puivern In the previously known Puivern is particularly disadvantageous that they contain the components in inhomogeneous distribution and therefore require high temperatures to homogenize the components to achieve diffusion.
  • the sintering behavior depends on the heating rate (rapid heating requires higher final temperatures or longer holding times) and the sintered bodies only achieve insufficient sintering densities, ie they have a corresponding porosity.
  • the invention is first a method for producing the pre-alloyed metal powder by mixing aqueous Metallallsalziösungen with a Klailungsstoff, preferably a carboxylic acid solution, separating the precipitate of the mother liquor and reduction of the precipitate to the metal, wherein advantageously the Kayliungsstoff superstoichiometric and as concentrated aqueous Solution is used.
  • the metal salt solutions and / or the aqueous solution of the precipitating agent may additionally contain dispersed solid compounds.
  • the aqueous solution or suspension of a carboxylic acid, a hydroxide, carbonate or basic carbonate can be used.
  • the metal salt solution can be mixed with the precipitant, but advantageously the metal salt solution is added to the Klailungssch.
  • the precipitate is washed after separation from the mother liquor with water and dried.
  • the reduction of the precipitate is preferably carried out in a hydrogen-containing atmosphere at temperatures between 600 0 C and 850 ° C.
  • the reduction can be carried out in indirectly heated rotary kilns or in push-through furnaces.
  • Other ways to carry out the reduction are readily apparent to those skilled in the art, such. B. in deck ovens or fluidized bed ovens. This is surprising, since Mo oxides can be reduced with hydrogen only above 1000 ° C to Mo metal powders with sufficiently low oxygen contents, which are necessary for a powder metallurgical further processing and sintering.
  • the moist or dried precipitate is calcined before reduction in an oxygen-containing atmosphere at temperatures between 250 0 C and 600 0 C.
  • the calcination causes the precipitate product consisting of polycrystalline particles or agglomerates to be comminuted by decrepitation by the gases released in the decomposition (of the carboxylic acid residue), so that larger surfaces and shorter diffusion paths are available for the subsequent, diffusion-controlled gas phase reaction (reduction) and a finer-grained end product is obtained.
  • a pre-alloyed metal powder with significantly reduced porosity is obtained.
  • the precipitated product [(mixed) metal carboxylic acid salt] to the pre-alloyed metal powder
  • a significant volume reduction of the particles continues to occur, which leads to the formation of pores.
  • the precipitated product is first transferred into the (mixed) rnetalloxid and annealed, so that a pre-compression takes place with the healing of defects clusters and micropores.
  • the subsequent reduction in a hydrogen-containing atmosphere accordingly, only the volume shrinkage from the oxide to the metal has to be overcome.
  • the intermediate calcination step accordingly a stepwise volume shrinkage is achieved, each taking place with structural stabilization of the intermediate crystals.
  • Suitable precipitants are carboxylic acids, but also hydroxides, carbonates or basic carbonates, in particular of the alkali or alkaline earth metals, advantageously of sodium or potassium. These are in particular hydroxides of the alkali or alkaline earth metals, very particularly sodium or potassium hydroxide.
  • Suitable carboxylic acids are aliphatic or aromatic, saturated or unsaturated mono- or dicarboxylic acids, in particular those having 1 to 8 carbon atoms. Due to their reducing action, formic acid, oxalic acid, acrylic acid and crotonic acid are preferred, and because of their availability, especially formic and oxalic acid, most preferably oxalic acid are used.
  • the carboxylic acids can be used as aqueous solution or suspension, but also in pure form as precipitant, when the carboxylic acid is liquid.
  • the carboxylic acid with 1.1 to 1, 6-fold stoichiometric excess, based on the metals used. Particularly preferred is a 1, 2-1, 5-fold excess.
  • a carboxylic acid solution is used as the suspension agent as a suspension containing undissolved carboxylic acid (as a suspension).
  • the preferred carboxylic acid suspension contains a depot of undissolved carboxylic acid, from which the carboxylic acid removed by precipitation of the solution is replenished, so that a high concentration of carboxylic acid is maintained in the mother liquor during the entire precipitation reaction.
  • the concentration of dissolved carboxylic acid in the mother liquor at the end of the precipitation reaction is still at least 10% of the saturation concentration of the carboxylic acid in water, in particular 20% of the saturation concentration of the carboxylic acid in water. This will be a complete and largely identical precipitation of the MetaJisalze ensured.
  • the alloy composition of the pre-alloyed powders can thus be determined by the choice of the composition of the metal salt solution.
  • Suitable precipitants are hydroxides, carbonates or basic carbonates. These are, in particular, hydroxides of the alkali metal or alkaline earth metals, with sodium or potassium hydroxide being advantageous. These can be used analogously to carboxylic acids, also with respect to their use in the form of a solution or suspension as described above for the carboxylic acid.
  • the precipitant may indeed be added to Metailsalzates, but advantageously the solution or suspension of the precipitant is presented and added the metal salt solution.
  • the addition of the Metallisäiziösung to the carboxylic acid suspension is carried out gradually, in such a way that the content of dissolved carboxylic acid in the mother liquor during the feeding of Metailsalzaims a value of 50% of the solubility of the Carboxylic acid in water does not fall below.
  • the addition of the metal salt solution is particularly preferably carried out gradually so that the concentration of dissolved carboxylic acid does not fall below 80% of the solubility in water until the suspended carboxylic acid is dissolved.
  • the rate of addition of the metal salt solution to the carboxylic acid suspension thus takes place in such a manner that the removal of carboxylic acid from the mother liquor, including concentration reduction by dilution by the water supplied with the metal salt solution, is compensated by the dissolution of undissolved, suspended carboxylic acid.
  • the chlorides or sulfates of the metals are used, so that in each case a metal chloride or sulfate solution is used. It is also possible to use mixed chlorides and sulfates, in which, for example Ferric chloride and cobalt sulfate are used to prepare the metal salt solution.
  • the concentration of the metal salt solution is about 1.6 to 2.8 moles of metal per liter.
  • the metal salt solution has a content of 20 wt .-% to 90 wt .-% iron, based on the Intelmetallgehatt, and the elements cobalt and molybdenum.
  • the content of iron in the metal salt solution is particularly preferably between 25% by weight and 85% by weight, very particularly preferably more than 30% by weight to 70% by weight, in each case based on the total metal content.
  • the metal salt solutions contain up to 65 wt .-% cobalt, based on the Intelmetallgehait, advantageously 5 wt .-% to 50 wt .-%, in particular 10 wt .-% to 30 wt .-%.
  • the molybdenum content of the metal salt solution is 3% by weight to 60% by weight, preferably 4% by weight to 50% by weight, in particular 5% by weight to 40% by weight, particularly advantageously 6% by weight to 35% by weight, 9% by weight to 30% by weight, 12% by weight to 20% by weight or 14% by weight to 19% by weight.
  • MoO 2 is insoluble, it can be suspended in the metal salt solution. However, it may also be suspended in the solution or suspension of the precipitant to which the metal salt solution is preferably added as described above.
  • a concentrated carboxylic acid solution has the "activity 1"
  • a half-concentrated carboxylic acid solution has the "activity 0.5”. Accordingly, the activity of the mother liquor should preferably not fall below 0.8 during the addition of the metal salt solution.
  • solubility is preferably used
  • Oxalic acid in water about 1, 1 moles per liter of water (room temperature), corresponding to 138 g of oxalic acid (with 2 moles of water of crystallization).
  • the oxalic acid should be presented as an aqueous suspension containing from 2.3 to 4.5 moles of oxalic acid per liter of water. This suspension contains about 1.2 to 3.4 moles of undissolved oxalic acid per liter of water.
  • After initiation of the Metal salt solution and completed precipitation should be the content of oxalic acid in the mother liquor still 15 to 30 g / l.
  • the precipitated oxalic acid is constantly replaced by dissolution of suspended oxalic acid.
  • the addition of the metal salt solution is carried out gradually such that the oxalic acid concentration in the mother liquor during the addition does not fall below 69 g, more preferably not below 110 g per liter of mother liquor. This causes a sufficiently high supersaturation is constantly achieved during the addition of the metal salt solution, which is sufficient for nucleation, ie for the production of additional precipitation particles.
  • the inventively preferred high carboxylic acid concentration during the precipitation also causes the precipitate with respect to the relative contents of metals has largely the same composition as the metal salt solution, d. H. a homogeneous precipitate with respect to its composition and thus alloy metal powder is produced.
  • the invention furthermore relates to pre-alloyed metal powders which contain the elements iron, cobalt and molybdenum and which advantageously have an average particle size according to ASTM B330 (FSSS) of less than 8 ⁇ m, advantageously from 0.1 ⁇ m to 8 ⁇ m, in particular 0, 5 ⁇ m to 3 ⁇ m,
  • FSSS ASTM B330
  • the BET surface area of the pre-alloyed powders is generally more than 0.5 m 2 / g, advantageously 0.7 m 2 / g to 5 m 2 / g, in particular 1 m 2 / g to 3 m 2 / g ,
  • the alloy powders contain 20 wt .-% to 90 wt .-% iron, preferably 25 wt .-% to 85 wt .-% and particularly preferably 30 wt .-% to 70 wt .-% iron, based on the total metal content. More preferably, the pre-alloyed Metaüpulver contain up to 65 wt .-% Co 1 advantageously 5 wt. ⁇ % wt to 50 wt .-%, in particular 10. '% to 30 wt .-%.
  • the molybdenum content of the metal powders is 3 wt .-% to 60 wt .-%, preferably 4 wt .-% to 50 wt .-%, in particular 5 wt .-% to 40 wt .-%, particularly advantageously 6 or 7 wt. % to 35% by weight, 9% by weight to 30% by weight, 12% by weight to 20% by weight or 14% by weight to 19% by weight, further constituents of the alloying powder be unavoidable impurities.
  • the present invention therefore also relates to alloy powder containing
  • alloy powders in which the molybdenum content is less than 25 wt .-%, when the iron content is greater than 50 wt .-%; and or Alloy powder in which the cobalt content at 10 wt .-% to 30 wt.
  • % is when the sum of the molybdenum content and the iron content is less than 90% by weight.
  • the X-ray diffractograms of the pre-alloyed powders according to the invention differ markedly from those prepared from purely mechanically mixed elemental powders.
  • the prealloyed metal powders according to the invention achieve a higher hardness than metallic powder mixtures of the same chemical composition (see Table 2).
  • the sintered bodies obtained from the pre-alloyed metal powder have densities of at least 97%, advantageously greater than 98.5%, but in particular values greater than 99% of the theoretical density. These values can rarely be achieved in powder metallurgy processes.
  • the shaped articles obtained by sintering the pre-alloyed powder have high Rockwell hardnesses of more than 50 HRC, in particular more than 55 HRC, and very particularly preferably after sintering more than 60 HRC.
  • the metal powders pre-alloyed according to the invention have a low carbon content of less than 0.04% by weight, preferably less than 0.02% by weight and most preferably less than 0.005% by weight to the temperature carried out between precipitation and reduction treatment in an oxygen-containing atmosphere, in which the organic carbon present after the precipitation is removed.
  • Preferred pre-alloyed metal powders furthermore have an oxygen content of less than 1% by weight.
  • the composition of the powders according to the invention is not limited to the elements iron, cobalt and molybdenum.
  • additional metals M selected from the group consisting of tungsten, copper, nickel, vanadium, titanium, tantalum, niobium, manganese, and aluminum may additionally be contained.
  • tungsten or copper may be contained in amounts of up to 25 wt .-%.
  • Copper is advantageously contained in amounts of up to 10% by weight, in particular 6.5 to 10% by weight.
  • Nickel may also be present in amounts of up to 10% by weight, advantageously from 1% by weight to 10% by weight, in particular from 6.5 to 10% by weight.
  • the alloy powder according to the invention particularly advantageously contains no nickel except for unavoidable impurities. Further Constituents of the alloy powder may still be unavoidable impurities
  • the alloy powder according to the invention may contain vanadium, titanium, tantalum, niobium, manganese and aluminum. These additives are advantageously up to a maximum of 3 wt .-%, in particular 0.5 wt .-% to 3 wt .-% contained. Thus, a targeted adjustment of mechanical, thermal or electrical properties is possible.
  • the alloy powder is free of the metals M selected from the group consisting of vanadium, titanium, tantalum, niobium, manganese and aluminum.
  • the remaining components of the alloy powder are unavoidable impurities.
  • the pre-alloyed metal powders are excellently usable for the powder metallurgical production of components.
  • the invention therefore also relates to shaped articles obtainable by sintering a pre-alloyed metal powder according to the invention.
  • These molded objects are suitable for applications that require high-temperature resistant components ⁇ mechanical stress at a continuous temperature greater than 500 0 C) and are characterized by a high hot hardness (even at temperatures greater than 600 0 C), high creep resistance, good heat conduction and good chemical Corrosion resistance. Therefore, these shaped articles are particularly well suited as cutting tools for austenitic steels or for parts of internal combustion engines, turbines, turbochargers, jet engines and the like.
  • FIG. 1 shows an X-ray diffractogram of the mechanical powder mixture according to Example 5.
  • FIG. 2 shows an X-ray diffractogram of the powder according to the invention according to Example 4.
  • FIG. 3 compares the results of thermodilatometric measurements during sintering of the mechanical powder mixture and of the
  • FIG. 4 shows the results of thermodiamtometric measurements in FIG.
  • FIG. 5 shows the results of thermodilatometric measurements in FIG
  • FIG. 6 compares the sintering behavior of the mechanical powder mixture according to Example 5 and of the alloy powder according to the invention
  • FIG. 7 compares the behavior with repeated cooling of the mechanical powder mixture according to Example 5 and FIG.
  • FIG. 8 compares the residual porosities of the sintered bodies ex mechanical
  • Molybdenum contents of greater than 6 or 7 wt .-% can be seen.
  • Way (s) for carrying out the invention The invention will be explained below by means of examples.
  • the precipitation suspension was stirred for a further 30 min to adjust the equilibrium and then filtered to separate the precipitate from the mother liquor through a suction filter and washed free of deionized water of chloride and sulfate ions.
  • the nutschfeuchte precipitated product was calcined in a push-through furnace at about 550 0 C with air in countercurrent and reduced in a subsequent push-through furnace at 750 0 C in a hydrogen atmosphere to the metal powder.
  • the analytical test gave the following values: 58.38 wt.% Fe / 24.65 wt.% Co / 15.27 wt.% Mo / 0.63 wt.% Oxygen.
  • the content of carbon was 17 ppm.
  • the FeCo mixed salt solution was pumped with a metering pump with a Voiumenstrom of about 2 L / min in the template of oxalic acid and Moiybdändioxid. After completion of precipitation, the precipitate suspension was stirred for a further 30 min to adjust the equilibrium, then filtered to remove the precipitate from the mother liquor through a suction filter and washed free of deionized water of chloride and sulfate ions.
  • the nutschfeuchte precipitated product was calcined in a push-through furnace at about 550 0 C with air in countercurrent and in a subsequent Push-through furnace at 750 ° C in a hydrogen atmosphere reduced to metal powder.
  • the following values were measured: 69.11% by weight of Fe / 17.73% by weight of Co / 12.21% by weight of Mo / 0.46% by weight of oxygen.
  • the content of carbon was 21 ppm.
  • the FeCoCu mixed salt solution with the dispersed MoO 2 was pumped into the original of oxalic acid with a metering pump. After completion of precipitation, the precipitation suspension was stirred for a further 30 min, then filtered through a suction filter and washed free of deionized water of chloride and sulfate ions.
  • the wet-moist precipitate was calcined in a chamber furnace in the presence of air at 550 0 C and reduced in a second chamber furnace in H2 atmosphere at 725 0 C to MetallpuSver.
  • Example 1 After the procedure and conditions of Example 1 was a
  • the analytical control gave 59.94 wt.% Fe / 24.80 wt.% Co / 14.46 wt.% Mo / 0.61 wt.% Oxygen and 141 ppm carbon.
  • the grain size was measured at 1.88 ⁇ m (FSSS) and the specific surface at 0.78 m 2 / g.
  • the powders according to Examples 4 and 5 show very different X-ray diffraction patterns.
  • the mechanical powder mixture according to Example 5 shows distinct, separate reflections for the components Fe, Co and Mo (see FIG. 1), which are virtually no longer detectable in the prealloyed inventive powder according to Example 4 (FIG. 2); obviously, the components Co and Mo are dissolved in the Fe matrix.
  • thermo-parametric analysis see Figure 3.
  • green bodies were prepared by cold isostatic pressing at 221 MPa and in dilatometer 402 E Netzsch apparatus construction GmbH sintered under hydrogen atmosphere.
  • the mechanical powder mixture shows several shrinkage levels
  • the powder according to Example 4 according to Example 4 shows in addition to the ⁇ / ⁇ phase transition ⁇ cubic body-centered in the cubic surface-centered crystal lattice) of FeCo matrix at about 900 ° C, only one, very sharply defined, shrinkage level between 1000-1200 0 C. Der Phase transition occurs in the mechanical powder mixture with a widening of the volume, in the powder according to the invention, however, with a shrinkage.
  • the sintering behavior of the mechanical powder mixture according to Example 5 depends on the heating rate, see FIG. 4. Faster heating rates shift the shrinkage in the direction of higher temperatures. Surprisingly, the shrinkage of the powder according to the invention according to Example 4, in contrast, practically independent of the heating rate, see Figure 5.
  • Table 2 sintered densities and curing of the thermodilatometric
  • Example 5 according to Example 4 theoretical density: 8.40 g / cm 3 theoretical density: 8.40 g / cm 3
  • alloy powders were prepared by the process of Example 1 via the Oxalatmatlung, calcination and reduction under hydrogen, whose compositions are listed in Table 3 and wherein all alloying elements are present in pre-alloyed form.
  • the molybdenum content was as in the Salt solution suspended molybdenum dioxide introduced during the oxalate precipitation.
  • the alloy powders became "as produced" below to rectangular

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

La présente invention concerne de nouvelles poudres métalliques préalliées, un procédé de production de celles-ci, ainsi que leur utilisation.
EP07847463A 2006-12-02 2007-11-28 Poudre métallique Withdrawn EP2097549A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102006057004A DE102006057004A1 (de) 2006-12-02 2006-12-02 Metallpulver
PCT/EP2007/062940 WO2008065136A2 (fr) 2006-12-02 2007-11-28 Poudre métallique

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EP2097549A2 true EP2097549A2 (fr) 2009-09-09

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US (2) US8133297B2 (fr)
EP (1) EP2097549A2 (fr)
JP (2) JP2010511782A (fr)
DE (1) DE102006057004A1 (fr)
IL (1) IL198570A0 (fr)
MX (1) MX2009005542A (fr)
NO (1) NO20092142L (fr)
RU (1) RU2468111C2 (fr)
UA (1) UA95824C2 (fr)
WO (1) WO2008065136A2 (fr)
ZA (1) ZA200903076B (fr)

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DE102008052559A1 (de) 2008-10-21 2010-06-02 H.C. Starck Gmbh Metallpulver
EP2337874B1 (fr) 2008-10-20 2015-08-26 H.C. Starck GmbH Poudre métallique
JP5530270B2 (ja) * 2010-06-29 2014-06-25 Ｊｘ日鉱日石金属株式会社 コバルト粉末及びその製造方法
JP5878325B2 (ja) * 2011-09-30 2016-03-08 日東電工株式会社 永久磁石の製造方法
JP5991645B2 (ja) * 2012-12-28 2016-09-14 住友電気工業株式会社 金属粉末の製造方法
CN107673354A (zh) * 2017-11-17 2018-02-09 芜湖人本合金有限责任公司 碳化钒及其制备方法
JP2020084286A (ja) * 2018-11-29 2020-06-04 株式会社日立製作所 合金粉末、造形体
CN113025859B (zh) * 2021-03-05 2021-12-14 北京理工大学 一种高强度高塑性钨合金材料及其制备方法
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DE102006057004A1 (de) 2008-06-05
US20120132033A1 (en) 2012-05-31
RU2009125183A (ru) 2011-01-10
NO20092142L (no) 2009-08-28
IL198570A0 (en) 2010-02-17
WO2008065136A3 (fr) 2008-07-24
UA95824C2 (ru) 2011-09-12
JP2010511782A (ja) 2010-04-15
ZA200903076B (en) 2010-07-28
US20100061879A1 (en) 2010-03-11
JP2013224491A (ja) 2013-10-31
WO2008065136A2 (fr) 2008-06-05
MX2009005542A (es) 2009-06-05
US8133297B2 (en) 2012-03-13
RU2468111C2 (ru) 2012-11-27

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