EP2046522A1 - Mélanges de poudres métalliques - Google Patents

Mélanges de poudres métalliques

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Publication number
EP2046522A1
EP2046522A1 EP07787232A EP07787232A EP2046522A1 EP 2046522 A1 EP2046522 A1 EP 2046522A1 EP 07787232 A EP07787232 A EP 07787232A EP 07787232 A EP07787232 A EP 07787232A EP 2046522 A1 EP2046522 A1 EP 2046522A1
Authority
EP
European Patent Office
Prior art keywords
weight
powder
alloy
component
nickel
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Withdrawn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
EP07787232A
Other languages
German (de)
English (en)
Inventor
Roland Scholl
Ulf Waag
Aloys Eiling
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 EP2046522A1 publication Critical patent/EP2046522A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/0433—Nickel- or cobalt-based alloys
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
    • 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
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • B22F2009/041—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by mechanical alloying, e.g. blending, milling
    • 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

  • the invention relates to mixtures of metal, alloy or composite powders having a mean particle diameter D50 of at most 75, preferably at most 25 .mu.m, which are produced by a method in which a first
  • powders which are prepared by a process for the preparation of metal, alloy and composite powders having an average particle diameter D50 of at most 75, preferably at most 25 microns, determined by means of the particle measuring device Microtrac ® X 100 according to ASTM C 1070-01, are obtainable from a starting powder having a larger average particle diameter, wherein the particles of the starting powder are processed in a deformation step into platelet-shaped particles whose particle diameter to particle thickness ratio is between 10: 1 and 10000: 1 and these platelet-shaped particles be subjected in a further process step of a comminuting or a high energy stress in the presence of a grinding aid. This process is advantageously followed by a deagglomeration step.
  • This deagglomeration step in which the powder agglomerates are broken down into their primary particles, can be carried out, for example, in a counterblowing gas mill, an ultrasonic bath, a kneader or a rotor stator.
  • Such powders are referred to in this document as PZD powder.
  • PZD powders have various advantages over conventional metal, alloy and / or composite powders used for powder metallurgy applications, such as improved green strength, compressibility, sintering behavior, broadened temperature range for sintering and / or a lower sintering temperature, but also higher strength, better oxidation and corrosion behavior of the molded parts produced and lower production costs. Disadvantages of these powders are, for example, poorer flowability. Also, the altered shrinkage characteristics, coupled with the lower packing density in powder metallurgy processing in use, can lead to problems due to greater sintering shrinkage. These properties of the powders are described in DE-A-103 31 785, to which reference is made.
  • Object of the present invention is to provide metal powders for powder metallurgy, which do not have the aforementioned disadvantages of conventional metal powders (MLV) and PZD PuI ver, but their respective advantages, such as high sintering activity, good pressability, high green strength, good bulkiness , as far as possible to unite.
  • Another object of the present invention is to provide powders having functional additives which can impart characteristic properties to shaped articles made of PZD powder, such as additives that increase impact resistance or abrasion resistance, such as superhard powders, or additives facilitate the processing of greenware, or additives that act as a template for controlling the pore structure.
  • Another object of the present invention is to provide highly alloyed powders for the entire spectrum of powder metallurgy molding processes, so that applications are also possible in areas which are not accessible with conventional metal, alloy or composite powders.
  • This object is achieved by metallic powder mixtures containing a component I, a metal, alloy and composite powder having an average particle diameter D50 of at most 75, preferably at most 25 .mu.m, or even 25 .mu.m to 75 .mu.m, determined by means of the particle measuring device Microtrac ® X100 according to ASTM C 1070-01, obtainable by a process in which the particles of a starting powder having a larger or smaller average particle diameter are processed in a deformation step into platelet-shaped particles whose ratio of particle diameter to particle thickness is between 10: 1 and 10000: 1 and these platelet-shaped particles in a further process step are subjected to comminution grinding in the presence of a grinding assistant, a component II, which is a conventional metal powder (MLV) for powder metallurg
  • the phases formed eg oxides, nitrides, carbides, borides
  • the phases formed are considerably finer and more homogeneously distributed than with conventionally produced powders. This in turn leads to an increased sintering activity compared to discretely introduced similar phases. This also improves the sinterability of the metallic powder mixture according to the invention.
  • Such powders with finely dispersed deposits are accessible in particular during targeted supply of oxygen during the grinding process and lead to the formation of ultrafiltered oxides.
  • grinding aids which are suitable as ODS particles and undergo mechanical homogenization and dispersion during the milling process can be used in a targeted manner.
  • the metallic powder mixture according to the present invention is suitable for use in all powder metallurgy molding processes.
  • Powder metallurgical shaping processes in the sense of the invention are pressing, sintering, slip casting, film casting, wet powder spraying, powder rolling (both cold, hot or warm powder rolling), hot pressing and hot isostatic pressing (hot isostatic pressing, HIP for short), sintering HIP, sintering of powder fillings , Cold
  • Isostatic pressing especially with green machining, thermal spraying and build-up welding.
  • Pure thermal spray powders can also be used as a component repair solution.
  • the use of pure agglomerated / sintered powders according to the not yet disclosed patent application DE-A-103 31 785 as Therical spray powder allows the inherent coating of components with a surface layer, which shows a better abrasion and corrosion behavior than the base material. These properties result from extremely finely distributed ceramic inclusions (oxides of the oxygen-affinitive elements) in the alloy matrix as a result of the mechanical stress in the preparation of the powders according to DE-A-
  • Component I is an alloy powder which is obtainable by a two-stage process, wherein first a starting powder is shaped into platelet-shaped particles and then these are comminuted in the presence of grinding aids.
  • the component I is a metal, alloy and composite powder having an average particle diameter D50 of at most 75, preferably at most 25 microns, determined by means of the particle measuring device Microtrac ® X100 according to ASTM C 1070-01, obtainable by a method in which a starting powder With a larger average particle diameter particles are available with a smaller particle diameter, wherein the particles of the starting powder are processed in a deformation step into platelet-shaped particles, the ratio of particle diameter to particle thickness between 10: 1 and 10000: 1 and these platelet-shaped particles in a further process step Crushing be subjected in the presence of a grinding aid.
  • the particle measuring instrument Microtrac ® X100 is commercially available from Honeywell, USA.
  • the particle diameter and the particle thickness are determined by means of light-optical microscopy.
  • the platelet-shaped powder particles are first mixed with a viscous, transparent epoxy resin in a ratio of 2 parts by volume of resin and 1 part by volume of platelets. Thereafter, by evacuating this mixture, the air bubbles introduced during mixing are expelled. The then bubble-free mixture is poured on a flat surface and then rolled with a roller wide. In this way, the platelet-shaped particles in the flow field between the roller and the base are preferably oriented.
  • the Preferred position is expressed in that align the surface normals of the platelets on average parallel to the surface normal of the flat surface, so the platelets are arranged in layers flat on the substrate in the middle.
  • samples of suitable dimensions are worked out of the epoxy resin plate on the base. These samples are examined microscopically vertically and parallel to the substrate. Using a microscope with a calibrated optics and taking into account the sufficient particle orientation, at least 50 particles are measured and an average value is formed from the measured values. This mean value represents the particle diameter of the platelet-shaped particles.
  • the particle thickness is determined using the microscope with a calibrated optics, which was also used to determine the particle diameter.
  • ductile metal, alloy or composite powders can be produced by this method.
  • Ductile metal, alloy or composite powders are understood to mean those powders which undergo plastic strain or deformation under mechanical stress until they break, before significant material damage occurs (material embrittlement, material breakage). Such plastic material changes are material-dependent and are at OJ percent up to several 100 percent, based on the initial length.
  • the degree of ductility ie the ability of materials to plastically, ie permanently deform under the action of a mechanical stress, can be determined or described by means of mechanical tensile and / or pressure testing.
  • a so-called tensile test piece is prepared from the material to be evaluated. This may be, for example, a 2-cylindrical sample having a diameter reduction of about 30-50% over a length of about 30-50% of the total sample length in the middle region of the length.
  • the tensile specimen is clamped in a tensioning device of an electro-mechanical or electro-hydraulic tensile testing machine.
  • the method produces fine ductile alloy powders having a ductility level of at least 5%.
  • the comminution of alloy or metal powders which in themselves can not be further comminuted, is achieved by the use of mechanically, mechanochemically and / or chemically acting grinding aids, which are purposefully added or in the milling process be generated, improved.
  • An essential aspect of this approach is not to alter or even influence the overall chemical "target composition" of the powder so produced, in order to improve the processing properties, such as sintering behavior or flowability.
  • the process is suitable for producing a wide variety of fine metal, alloy or composite powders having an average particle diameter D50 of at most 75, preferably at most 25 ⁇ m.
  • the metal, alloy or composite powders produced are usually distinguished by a small mean particle diameter D50.
  • the average particle diameter D50 is not more than 15 microns, preferably, determined according to ASTM C 1070-01 (measuring device: Microtrac ® X 100).
  • ASTM C 1070-01 measuring device: Microtrac ® X 100.
  • powders which already have the composition of the desired metal, alloy or composite powder can be used as the starting powder.
  • the composition of the produced metal, alloy or composite powder can also be influenced by the choice of grinding aid, if it remains in the product.
  • the starting powders used are powders with spherically or sparingly shaped particles and an average particle diameter D50 of more than 75 ⁇ m, in particular greater than 25 ⁇ m, preferably from 30 to 2000 ⁇ m or from 30 to 1000 ⁇ m, of ASTM C 1070-01 75 ⁇ m to 2000 ⁇ m or 75 ⁇ m to 1000 ⁇ m.
  • the required starting powders can be obtained, for example, by atomization of molten metals and, if necessary, subsequent sifting or sieving.
  • the starting powder is first subjected to a deformation step.
  • the deformation step can be carried out in known devices, for example in a rolling mill, a Hametag mill, a high-energy mill or an attritor or agitating ball mills.
  • a rolling mill for example in a rolling mill, a Hametag mill, a high-energy mill or an attritor or agitating ball mills.
  • the individual particles are reshaped so that they ultimately have platelet shape, the thickness of the platelets preferably 1 is up to 20 microns.
  • This may for example by a single load in a roller or a hammer mill, by multiple stressing in "small" deformation steps, for example by impact milling in a Hametag mill or Simoloyer ® or by a combination of impact and frictional grinding, for example in an attritor or
  • the high material load during this forming leads to structural damage and / or material embrittlement, which can be used in the following steps for comminuting the material.
  • the milling media and the other grinding conditions are preferably chosen so that the impurities are as low as possible by abrasion and / or reactions with oxygen or nitrogen and below the critical for the application of the product size or within the specification applicable to the material. This is possible, for example, by a suitable choice of the grinding container and grinding media materials, and / or the use of gases which hinder the oxidation and nitriding and / or the addition of protective solvents during the deformation step.
  • the platelet-shaped particles are dried in a rapid solidification step, e.g. produced by so-called “melt spinning” directly from the melt by cooling on or between one or more, preferably cooled rolls, so that directly flakes (flakes) are formed.
  • a rapid solidification step e.g. produced by so-called “melt spinning” directly from the melt by cooling on or between one or more, preferably cooled rolls, so that directly flakes (flakes) are formed.
  • the platelet-shaped particles obtained in the deformation step are subjected to comminution grinding.
  • the ratio of particle diameter to particle thickness changes, as a rule primary particles (obtained after deagglomeration) having a particle diameter to particle particle ratio of 1: 1 to 100: 1, advantageously 1: 1 to 10: 1, are obtained .
  • the desired mean particle diameter of not more than 75, preferably not more than 25 microns is set without again difficult to comminute particle agglomerates occur.
  • the comminution grinding can be carried out for example in a mill, such as an eccentric vibrating mill, but also in Gutbett- rollers, extruders or similar devices that cause a material breakdown due to different movement and stress rates in platelets.
  • the comminution grinding is carried out in the presence of a grinding aid.
  • a grinding aid for example, liquid grinding aids, waxes and / or brittle powders can be used.
  • the grinding aids can act mechanically, chemically or mechanically-chemically. If the metal powder is brittle enough, any additions to other grinding aids are unnecessary; The metal powder is in this case, so to speak, its own grinding aid.
  • the grinding aid can be paraffin oil, paraffin wax, metal powder, alloy powder, metal sulfides, metal salts, salts of organic acids and / or hard material powder.
  • Brittle powders or phases act as mechanical grinding aids and can be used, for example, in the form of alloy, element, hard material, carbide, suicide, oxide, boride, nitride or salt powders.
  • pre-shredded elemental and / or alloy powders are used which, together with the starting powder which is difficult to comminute, give the desired composition of the product powder.
  • the brittle powders used are preferably those which consist of binary, ternary and / or higher compositions of the elements occurring in the starting alloy used, or else the starting alloy itself.
  • liquid and / or easily deformable grinding aids for example waxes.
  • hydrocarbons such as hexane, alcohols, amines or aqueous media. These are preferably compounds which are needed for the subsequent steps of further processing and / or which can be easily removed after the comminution grinding.
  • grinding aids are used which enter into a targeted chemical reaction with the starting powder to achieve the grinding progress and / or to set a specific chemical composition of the product.
  • These may be, for example, decomposable chemical compounds, of which only one or more constituents are required for setting a desired composition, wherein at least one component or constituent can be largely removed by a thermal process.
  • the grinding aid is not added separately, but is generated in-situ during the crushing grinding. In this case, for example, it is possible to proceed in such a way that the production of the grinding aid takes place by adding a reaction gas which reacts with the starting powder under the conditions of the comminution grinding to form a brittle phase.
  • the reaction gas used is preferably hydrogen.
  • the brittle phases resulting from the treatment with the reaction gas can generally be removed again by appropriate process steps after comminution grinding or during the processing of the resulting fine metal, alloy or composite powder.
  • grinding aids which are not or only partially removed from the produced metal, alloy or composite powder, these are preferably chosen so that the remaining constituents affect a property of the material in a desired manner, such as the improvement of the mechanical properties Reduction of corrosion susceptibility, increase of hardness and improvement of the abrasion behavior or the friction and sliding properties.
  • a hard material may be mentioned here, which is increased in its proportion in a subsequent step so far that the hard material together with the alloy component can be further processed to form a hard metal or a hard-material alloy composite material.
  • the primary particles of the metal, alloy or composite powder have a mean particle diameter D50, determined according to ASTM C 1070-01 (Microtrac ® X 100) of usually 25 .mu.m, advantageously less than 75 microns, in particular less or equal to 25 microns.
  • the comminution grinding preferably follows a deagglomeration step - if the product to be produced does not permit or require no (coarse) agglomerate - in which the agglomerates are broken up and the primary particles are released.
  • the deagglomeration can be carried out, for example, by applying shear forces in the form of mechanical and / or thermal stresses and / or by removing previously in the process between primary particles
  • the particular deagglomeration method to be used depends on the degree of agglomeration, the intended use and the susceptibility to oxidation of the ultrafine powders and the permissible impurities in the finished product.
  • the deagglomeration can be done for example by mechanical methods, such as by treatment in a gas counter jet mill, screening, sifting or treatment in an attritor, a kneader or a rotor-stator-disperser. It is also possible to use a field of stress, as generated in an ultrasonic treatment, a thermal treatment, for example, dissolution or conversion of a previously introduced separation layer between the primary particles by cryogenic or high temperature treatments, or a chemical conversion introduced or selectively generated phases.
  • the deagglomeration is carried out in the presence of one or more liquids, dispersing aids and / or binders.
  • a slurry, a paste, a plasticine or a suspension having a solids content between 1 and 95 wt .-% can be obtained.
  • solids contents of between 30 and 95% by weight
  • these can be directly processed by known powder technology methods, such as injection molding, film casting, coating, hot casting, for example, to form a suitable drying, debindering and sintering step Final product to be implemented.
  • a gas jet jet mill which is operated under inert gases, for example argon or nitrogen.
  • the metal, alloy or composite powders produced are distinguished from conventional powders of the same mean particle diameter and chemical composition, which are produced, for example, by atomization, by a number of special properties.
  • the metal powders of component I show, for example, an excellent sintering behavior. At low sintering temperatures, it is usually possible to achieve approximately the same sintering densities as powders produced by atomization. At the same sintering temperature, starting from powder compacts having the same compacting density, higher sintered densities can be achieved, based on the metallic proportion in the compact. This increased sintering activity is also evident, for example, in the fact that, until the main shrinkage maximum of the powder according to the invention is reached, the shrinkage during the sintering process is higher than with conventionally produced powders and / or the (normalized) temperature at which the shrinkage maximum occurs in the Case of PZD powder is lower.
  • the shrinkage curve is calculated by adding the shrinkages at the respective temperature.
  • the shrinkage in the pressing direction contributes to one third and the shrinkage perpendicular to the pressing direction to two-thirds of the shrinkage curve.
  • the metal powders of component I are metal powders whose shrinkage, determined by means of a dilatometer in accordance with DIN 51045-1, until reaching the temperature of the first shrinkage maximum is at least 1.05 times the shrinkage of a metal-alloyed alloy produced by atomization. or composite powder of the same chemical composition and the same average particle diameter D50, wherein the powder to be examined before Measurement of shrinkage is compressed to a compact density of 50% of the theoretical density.
  • the sintering behavior of powders of component I can also be specifically influenced by the choice of grinding aid.
  • one or more alloys can be used as Mahloskar, which already form liquid phases due to their low melting point compared to the Ninlegierimg during heating, which improve the particle rearrangement and material diffusion and thus the sintering behavior or shrinkage behavior and thus higher sintering densities at the same Sintering temperature or at lower sintering temperature can achieve the same sintered density as in the comparison powders.
  • the component II of the metallic powder mixture according to the invention are conventional alloy powders for powder metallurgical applications. These are powders which have a substantially spherical or blistered form of the particles, as shown, for example, in FIG. 1 of DE-A-103 31 785.
  • the chemical identity of the alloy powder is determined by an alloy of at least two metals.
  • conventional impurities may be included.
  • 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 prepared, the known methods often begin with the melting of a metal or an alloy.
  • 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.
  • the powder particles form directly from the molten droplets produced by solidification.
  • the process parameters used such as the nozzle geometry, gas velocity, gas temperature or the nozzle material, and the material parameters of the melt, such as melting and solidification point, solidification behavior, viscosity, chemical composition and reactivity with the process media, there are a number of possibilities, but also limitations of the method (W. Schatt, K.-P. Wieters in "Powder Metallurgy - Processing and Materials", EPMA European Powder Metallurgy Association, 1997, 10-23 ).
  • melt-spinning ie the casting of a melt on a cooled roll, whereby a thin, usually easy to comminute band
  • crucible-melt extraction ie immersing a cooled, profiled, high speed rotating roll into a molten metal to recover particles or fibers.
  • the mechanical comminution especially in mills, as the oldest method of particle size adjustment, is very advantageous from a technical point of view, because it is less expensive and applicable to a variety of materials. However, it makes certain demands on the feed, for example, in terms of size of the pieces and brittleness of the material. In addition, the crushing does not work continue as desired. Rather, a grinding equilibrium is formed, which also sets in when the grinding process begins with finer powders. The conventional milling processes are then modified when the physical limits of comminution for the respective regrind are reached, and certain phenomena such as low-temperature embrittlement or the
  • the component III of the metallic powder mixture according to the invention are conventional element powders for powder metallurgical applications. These are powders which have a substantially spherical, chapped or fractal shape of the particles, as shown for example in FIG. 1 of DE-A-103 31 785. 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. The preparation of these powders can be carried out analogously to the alloy powders of component II, in addition to the reduction of oxide powders of the metal, so that the procedure (apart from the use of the starting metal) is identical. For their preparation, numerous metallurgical or chemical processes are known.
  • melt-spinning ie the casting of a melt on a cooled roll, whereby a thin, usually easily comminuted band is formed
  • crucible-melt extraction ie immersing a cooled, profiled, high speed rotating roll into a molten metal to recover particles or fibers.
  • the metallic powder mixture according to the invention contains
  • component I which is an alloy containing 15 to 76% by weight of nickel, 15 to 45% by weight of chromium, 0 to 12% by weight of aluminum, and 0 to
  • Alloy powder which is an alloy containing 15 to 76 wt .-% nickel, 15 to
  • the metallic powder mixture according to the invention contains
  • the component I which is an alloy containing 15 to 76 wt .-% nickel, 15 to 45 wt .-% chromium, 0 to 12 wt .-% aluminum and 0 to 10% by weight of titanium;
  • component II 20% by weight to 55% by weight of component II, of a conventional alloy powder j which is an alloy containing 15 to 76% by weight of nickel, 15 to 45% by weight of chromium, 0 to 12% by weight Aluminum and 0 to 10 wt .-% titanium; From 25% to 50% by weight of component III, a conventional elemental powder of nickel.
  • a conventional alloy powder j which is an alloy containing 15 to 76% by weight of nickel, 15 to 45% by weight of chromium, 0 to 12% by weight Aluminum and 0 to 10 wt .-% titanium
  • Components I and II may additionally contain 5 to 40% by weight of cobalt, 4 to 15% by weight of molybdenum and / or tungsten, 1 to 5% by weight of tantalum and / or Mob or mixtures thereof.
  • the powder mixture according to the present invention may also contain as component IV 0 wt .-% to 3 wt .-% carbon, in particular 0.1 wt .-% to 1.5 wt .-%.
  • the alloy additionally contains 1 to 5 wt .-% tantalum. In an advantageous embodiment of such tantalum alloys, the alloy additionally contains 10 to 20% by weight of cobalt; or in a further embodiment of the invention, the alloy contains 5 to 25 wt .-% cobalt. In an advantageous embodiment of such cobalt alloys, the content of aluminum is from 2 to 12% by weight and the content of titanium is from 2 to 10% by weight.
  • the alloy which determines the chemical identity of components I and II may advantageously be an alloy containing the following alloy constituents: 15 to 40% by weight of nickel,
  • a molded article obtained by subjecting a metallic powder mixture according to the invention to a powder metallurgy molding process has a composition which is composed of the percentage of the sum of the introduced components I to IV.
  • FIG. 1 shows the microstructure of a typical micro-cut material produced from the metallic powder mixture according to the invention. Characteristic are the circular to oval pores (black in the picture), which are evenly distributed in the volume. The size of the pores is typically between 1 .mu.m to 10 .mu.m, advantageously 1 .mu.m to 5 .mu.m.
  • the molded article, component I and / or component II consists essentially of an alloy selected from the group consisting of Nil7Co20Crl, 5A12.5Ti, Nil7Mol5Cr6Fe5WlCo ⁇ Ni20Crl6Co2.5Til s 5Al
  • the powder mixture according to the invention comprises additives which are largely or completely removed from the product and thus act as a template.
  • additives which are largely or completely removed from the product and thus act as a template.
  • These may be hydrocarbons or plastics.
  • Suitable hydrocarbons are long-chain hydrocarbons such as low molecular weight, waxy polyolefins, such as low molecular weight polyethylene or polypropylene, but also saturated, wholly or partially unsaturated hydrocarbons having 10 to 50 carbon atoms or having 20 to 40 carbon atoms, waxes and paraffins.
  • Suitable plastics are in particular those having a low ceiling temperature, in particular a ceiling temperature of less than 400 ° C or lower than 300 0 C or lower than 200 0 C.
  • plastics are thermodynamically unstable and tend to Decomposed into monomers (depolymerization).
  • Suitable plastics are, for example, polyurethanes, polyacetals, polyacrylates and - methacrylates or polystyrene.
  • the plastic in the form of preferably foamed particles is used, such as foamed polystyrene beads, as they are as a precursor or intermediate in the
  • sublimation-prone inorganic compounds may function as wildcards, such as some oxides of refractory metals, particularly oxides of rhenium and molybdenum, as well as partially or fully decomposable compounds such as hydrides (Ti hydride, Mg hydride, Ta hydride), organic (Metal stearates) or inorganic salts
  • hydrides Ti hydride, Mg hydride, Ta hydride
  • organic (Metal stearates) or inorganic salts By adding these additives, which are largely or completely removed from the product and thus act as a template, can be largely dense components (90 to 100% of the theoretical density), low-porosity (70 to 90% the theoretical density) and highly porous (5 to 70% of the theoretical density) components by subjecting a metallic powder mixture according to the invention containing such functional additive as a dummy to a powder metallurgy molding process.
  • the additives that are largely or completely removed from the product and thus act as a template in proportions of metal powder (sum of components I 5 II and III) to additives, from 1: 100 to 100: 1 or 1: 10 to 10: 1 or from 1: 2 to 2: 1 or 1: 1 used.
  • additives which alter the properties of the sintered body obtained from the powder mixture according to the invention.
  • hard materials oxides, in particular aluminum oxide, zirconium oxide or yttrium oxide or carbides, such as tungsten carbide, boron nitride or titanium nitride, which are advantageous in amounts of from 100: 1 to 1: 100 or from 1: 1 to 1:10 or 1: 2 to 1: 7 or from 1: 3 to 1: 6.3 (ratio of sum of components I, II and III: hard material) are used.
  • the metallic powder mixture is a mixture of the sum of the components I, II and / or component III to the hard material, with the proviso that the ratio at 100: 1 to 1: 100 or from 3: 1 to
  • the metallic powder mixture is such a mixture, with the proviso that the ratio at 100: 1 to 1: 100 or from 1: 1 to 1:10 or from 1: 2 to 1: 7 or 1: 3 to 1: 6.3.
  • the metallic powder mixture is such a mixture with the proviso that in the presence of tungsten carbide as hard material, the ratio at 100: 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.
  • additives there may be present those which have the processing properties such as the pressing behavior, strength of the agglomerates,
  • waxes such as polyethylene waxes or oxidized polyethylene waxes, ester waxes such as montan acid esters, oleic esters, esters of linoleic acid or linolenic acid or mixtures thereof, paraffins, plastics, resins such as rosin, salts of long-chain organic acids such
  • Metal salts of montanic acid, oleic acid, linoleic acid or linolenic acid, metal stearates and metal palmitates for example zinc stearate, in particular the alkali metals and alkaline earth metals, for example magnesium stearate, sodium palmitate, Calcium stearate, or lubricants.
  • these are substances which are customary in powder processing (pressing, MIM, film casting, slip casting) and which are known to the person skilled in the art.
  • the compaction of the powder to be examined can be carried out with the addition of conventional press-promoting agents, such as paraffin wax or other waxes or salts of organic acids, for example zinc stearate.
  • reducing and / or decomposable compounds such as hydrides, oxides, sulfides, salts, sugars can be mentioned, which are at least partially removed from the millbase in a subsequent processing step and / or the powder metallurgical processing of the product powder and the remainder Chemically complete powder composition in the desired manner.
  • these may also be hydrocarbons or plastics.
  • Suitable hydrocarbons are long-chain hydrocarbons, such as low molecular weight, waxy polyolefins, low molecular weight polyethylene or polypropylene, but also saturated, wholly or partially unsaturated hydrocarbons having 10 to 50 carbon atoms or having 20 to 40 carbon atoms, waxes and paraffins.
  • Suitable plastics are, in particular, those with a low ceiling temperature, in particular with one
  • Ceiling temperature of less than 400 ° C, or lower than 300 0 C or lower than 200 0 C.
  • plastics are thermodynamically unstable and prone to disintegration into monomers (depolymerization).
  • Suitable plastics are, for example, polyurethanes, polyacetal, polyacrylates and polymethacrylates or polystyrene. These hydrocarbons or plastics are particularly suitable for improving the green strength of molded articles obtained from the powder mixes according to the invention.
  • Suitable additives are further described in W. Schatt, K.-P. Wieters in "Powder Metallurgy - Processing and Materials", EPMA European Powder Metallurgy Association, 1997, 49-51, to which reference is made.
  • Fraction 1 is, as described in DE-A-103 31 785, processed into a fine powder.
  • the powder has a D50: 20 ⁇ m.
  • the powder thus produced corresponds to the component I in the above description.
  • 663 g of the mixture to be produced were fed.
  • 337 g of a fine nickel powder IN 210 from INCO was added to the mixture with a D50 value of 4 ⁇ m. This corresponds to component III.
  • 13 g of paraffin ( ⁇ 200 ⁇ m) were added to the powder and mixed by mixing for 10 minutes in portions in a planetary ball mill with 250 ml content at a speed of 120 rpm (50% ball filling, 10 mm steel balls).
  • Shaped body was thus the same.
  • test specimens according to DIN / ISO 3995 "green strength test” by uniaxial pressing in accordance with DIN / ISO 3995 on a hydraulic press at a pressure of 600 MPa
  • the green density of the moldings was determined from the volume (30 mm ⁇ 12 mm ⁇ 12 mm) and the mass (weighing with microbalance, resolution 0.1 mg) of the sample. The green density results from the ratio of mass and volume.
  • the density of the sintered samples is also determined, but the samples are ground plane-parallel on all sides before the length measurement.
  • the green strength is determined according to DIN / ISO 3995 by 3-point bending tests. The results are summarized in Table 2.
  • the moldings are then debind in a tube furnace in a train under hydrogen (heating to 600 0 C at 2 K / min) and immediately sintered (heating at 10 K / min to 1250 0 C, 1285 0 C and 1300 0 C) ,
  • the sintering temperature was held for one hour.
  • the samples were then cooled at an average cooling rate of 5 K / min until they reached room temperature.
  • Example 1 has advantages in terms of green strength, yield strength and breaking strength. Disadvantages arise in the green density.
  • the sintered density reached 95% of the theoretical density at 125O 0 C. Particularly relevant is the high green strength, which allows only a powder metallurgical processing .2 -

Abstract

L'invention concerne des mélanges de poudres de métaux, d'alliages ou de matériaux composites présentant un diamètre de particules moyen compris entre D50 et 75, de préférence 25 μm, qui sont produites selon un procédé de l'invention. Selon le procédé de l'invention, une poudre de départ est transformée en particules se présentant sous la forme de plaquettes et ces dernières sont ensuite broyées en présence d'agents de mouture. Lesdits mélanges comprennent d'autres adjuvants (tels qu'une poudre élémentaire de nickel) ainsi que l'utilisation desdits mélanges de poudres ainsi que des articles obtenus à partir desdits mélanges.
EP07787232A 2006-07-12 2007-07-09 Mélanges de poudres métalliques Withdrawn EP2046522A1 (fr)

Applications Claiming Priority (2)

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PCT/EP2007/056956 WO2008006801A1 (fr) 2006-07-12 2007-07-09 Mélanges de poudres métalliques

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EP2046522A1 true EP2046522A1 (fr) 2009-04-15

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EP2439300A1 (fr) 2010-10-08 2012-04-11 Sandvik Intellectual Property AB Carbure cémenté
KR101248996B1 (ko) * 2012-10-10 2013-04-02 한국지질자원연구원 바인더가 포함된 탄화물 및 탄질화물 분말 합성 방법 및 이에 따라 얻어지는 서멧트
EP3790692A4 (fr) * 2018-05-11 2022-01-19 Equispheres Inc. Poudre de fabrication additive et pièce de fabrication additive fabriquée à l'aide de celle-ci
WO2020172744A1 (fr) * 2019-02-25 2020-09-03 Rio Tinto Iron And Titanium Canada Inc. Poudre de fer métallique
DE102020116865A1 (de) 2019-07-05 2021-01-07 Vdm Metals International Gmbh Nickel-Basislegierung für Pulver und Verfahren zur Herstellung eines Pulvers
DE102020116868A1 (de) 2019-07-05 2021-01-07 Vdm Metals International Gmbh Pulver aus einer Nickel-Kobaltlegierung, sowie Verfahren zur Herstellung des Pulvers

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DE102009057127A1 (de) 2009-12-08 2011-06-09 H.C. Starck Gmbh Teilchenfilter, Filterkörper, deren Herstellung und Verwendung

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