EP0568863B1 - Poudre métallique finement divisée - Google Patents

Poudre métallique finement divisée Download PDF

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Publication number
EP0568863B1
EP0568863B1 EP93106466A EP93106466A EP0568863B1 EP 0568863 B1 EP0568863 B1 EP 0568863B1 EP 93106466 A EP93106466 A EP 93106466A EP 93106466 A EP93106466 A EP 93106466A EP 0568863 B1 EP0568863 B1 EP 0568863B1
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EP
European Patent Office
Prior art keywords
powders
less
reactor
particle size
metal
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Expired - Lifetime
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EP93106466A
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German (de)
English (en)
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EP0568863A1 (fr
Inventor
Theo Dr. König
Dietmar Dr. Fister
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HC Starck GmbH
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HC Starck GmbH
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    • 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
    • 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
    • B22F9/28—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from gaseous metal compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • 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
    • B22F1/14—Treatment of metallic powder
    • B22F1/145—Chemical treatment, e.g. passivation or decarburisation
    • 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 present invention relates to finely divided powders of the elements B, Al, Si, Ti, Zr, Hf, V, Nb, Ta and / or Cr with a defined particle size between 1.0 nm and less than 3 ⁇ m.
  • the properties of the starting powder are of crucial importance for the mechanical properties of powder-metallurgically manufactured components.
  • a narrow particle size distribution, high powder purity and a lack of coarse particles or agglomerates have a positive effect on the properties of corresponding components.
  • the particle size and particle size of the powders produced cannot be exactly controlled, and the reaction conditions usually lead to a wide particle size distribution and to the occurrence of individual particles whose diameter is a multiple of the average particle size.
  • EP-A 0 290 177 describes the decomposition of transition metal carbonyls for the production of fine metallic powders. Here, up to 200 nm fine powders can be obtained
  • the noble gas condensation process enables the production of the finest metal powders in the lower nanometer range. However, only quantities on a milligram scale can be obtained here. In addition, the powders produced in this way do not have a narrow particle size distribution.
  • the invention relates to finely divided powders of the metals B, Al, Si, Ti, Zr, Hf, V, Nb, Ta and / or Cr with a defined particle size between 1.0 nm and less than 3 ⁇ m, less than 1% of the individual particles a deviation of more than 40% and no individual particles have a deviation of more than 60% from the average grain size.
  • the individual particles Preferably, less than 1% of the individual particles have a deviation of more than 20% and no individual particles have a deviation of more than 50% from the mean grain size. Particularly preferably less than 1% of the individual particles have a deviation of more than 10% and no individual particles Deviation of more than 40% from the average grain size.
  • the powders according to the invention preferably have particle sizes from 1 to less than 500 nm, particularly preferably from 1 to less than 100 nm and very particularly preferably from 1 to less than 50 nm.
  • the metal powders according to the invention are distinguished by their high purity. They preferably have an oxygen content of less than 5,000 ppm and particularly preferably less than 1,000 ppm.
  • Particularly pure metal powders according to the invention are characterized in that they have an oxygen content of less than 100 ppm, preferably less than 50 ppm.
  • the non-oxide impurities are also very low.
  • the sum of their impurities, with the exception of the oxidic impurities, is preferably less than 5,000 ppm, particularly preferably less than 1,000 ppm.
  • the sum of their impurities, with the exception of the oxide impurities, is less than 200 ppm.
  • the powders according to the invention are available on an industrial scale. They are preferably present in amounts of more than 1 kg.
  • the powders according to the invention are obtainable in a process for the production of finely divided metal powders by reacting corresponding metal compounds and corresponding reactants in the gas phase -CVR-, the metal compound (s) and the further reactants being reacted in a gaseous state, directly from the gas phase are homogeneously condensed out with the exclusion of any wall reaction and then separated from the reaction medium, which is characterized in that the metal compounds and the reactants are introduced into the reactor separately from one another at at least the reaction temperature.
  • the respective gas mixtures should be selected so that no reaction occurs during the heating process. which leads to solid reaction products.
  • This process can be carried out particularly advantageously in a tubular reactor. It is particularly favorable if the metal compounds, the reactants and the product particles flow through the reactor in a laminar manner.
  • the location of the nucleation can be limited.
  • the laminar flow in the reactor ensures a narrow residence time distribution of the germs or the particles. A very narrow grain size distribution can be achieved in this way.
  • the metal compounds and the reactants should therefore preferably be introduced into the reactor as coaxial laminar partial streams.
  • a Karman vortex street defined in terms of intensity and expansion, is generated by installing a disturbing body in the otherwise strictly laminar flow.
  • a preferred embodiment of this method is therefore that the coaxial, laminar partial flows of the metal compound (s) and the reactants are mixed in a defined manner by means of a Karman vortex.
  • the reaction medium is preferably shielded from the reaction wall by an inert gas layer.
  • an inert gas layer This can be done by introducing an inert gas stream into the reactor wall through specially shaped annular gaps, which is applied to the reactor wall via the Coanda effect.
  • the metal powder particles created in the reactor by a homogeneous separation from the gas phase with typical residence times between 10 and 300 msec leave this together with the gaseous reaction products (e.g. HCl), the unreacted reactants and the inert gases, which act as carrier gas, purge gas and for the purpose of reduction the HCl adsorption are blown in.
  • yields, based on the metal component, of up to 100% can be achieved.
  • the metal powders are then preferably separated off at temperatures above the boiling or sublimation temperatures of the metal compounds, reactants and / or by-products formed during the reaction.
  • the separation can advantageously be carried out in a blow-back filter. If this at high temperatures of e.g. 600 ° C is operated, the adsorption of the gases, especially the non-inert gases such as HCl on the very large surface of the powder can be kept low.
  • the remaining interfering substances adsorbed on the powder surface can be added in a downstream Vacuum containers are further removed, preferably again at temperatures of approx. 600 ° C.
  • the finished powders should then be discharged from the system in the absence of air.
  • Preferred metal compounds for the purposes of this invention are one or more from the group consisting of metal halides, partially hydrogenated metal halides, metal hydrides, metal alcoholates, metal alkyls, metal amides, metal azides and metal carbonyls.
  • Hydrogen is used as a further reaction partner.
  • Other characteristics of the powders are their high purity, high surface purity and good reproducibility.
  • the powders according to the invention can be very sensitive to air or pyrophoric. In order to eliminate this property, these powders can be surface-modified in a defined manner by exposure to gas / steam mixtures.
  • Fig. 1 is a schematic representation of a device with which the powders according to the invention can be produced. The implementation of this method is explained below with reference to FIG. 1. The process, material and / or device parameters explicitly mentioned here represent only selected options among many and thus do not limit the invention.
  • the solid, liquid or gaseous metal compounds are metered into an outside evaporator (1) or inside the high temperature furnace (1a), evaporated there at temperatures from 200 ° C to 2000 ° C and with an inert carrier gas (N 2 , Ar or He) transported into the gas preheater (2a).
  • the further reactant (3) H 2 is also heated in a gas preheater (2).
  • the turbulent individual flow threads emerging from the gas preheaters (2) are formed into two coaxial, laminar and rotationally symmetrical flow threads in a nozzle (5).
  • the middle flow thread (6) which contains the metal component
  • the enveloping flow thread (7) which contains the hydrogen, mix under defined conditions.
  • the reaction occurs at temperatures between 500 ° C and 2000 ° C, for example according to the following case studies; TaCl 5 + 2 1/2 H 2nd ⁇ Ta + 5 HCl BCl 3rd + 1 1/2 H 2nd ⁇ B + 3 HCl
  • a Karman vortex street can be created by installing a disturbing body (17) in the otherwise strictly laminar flow.
  • the two coaxial flow threads are separated at the nozzle outlet by a weak inert gas flow (16) in order to prevent growth at the nozzle (5).
  • the latter is flushed through annular gaps (8) with an inert gas stream (9) (N 2 , Ar or He) which is applied to the reactor wall via the Coanda effect.
  • an inert gas stream (9) N 2 , Ar or He
  • the metal powder particles formed in the reactor by a homogeneous separation from the gas phase leave it together with the gaseous reaction products (e.g. HCl), the inert gases and the unreacted reactants and go directly into a blow-back filter (10) in which they are separated.
  • gaseous reaction products e.g. HCl
  • the blow-back filter (10) is operated at temperatures between 300 ° C and 1000 ° C, whereby the adsorption of the gases, especially the non-inert gases such as HCl on the very large surface of these powders is kept at a low level.
  • the residues of the adsorbed gases on the powders are further reduced by preferably alternately applying vacuum and flooding with various gases at 300 ° C. to 1000 ° C. Good effects are achieved if gases such as N 2 , Ar or Kr are used. SF 6 is particularly preferably used.
  • Metastable material systems are obtained by setting very high cooling rates in the lower part of the reactor.
  • the particles with a core / shell structure are obtained by introducing additional reaction gases into the lower part of the reactor.
  • the powders pass from the evacuation container (11) into the cooling container (12) before they pass through the lock (13) into the collection and shipping container (14).
  • the particle surfaces can be surface-modified in a defined manner in the cooling container (12) by blowing in various gas / steam mixtures
  • Coated graphite in particular fine-grain graphite, can preferably be used as the material for those components which are exposed to temperatures of up to 2000 ° C. and more, such as heat exchangers (2) and (3), nozzle (5), reactor (4) and reactor jacket tube (15). be used.
  • a coating may be necessary, for example, if the necessary chemical resistance of the graphite against the gases used such as metal chlorides, HCl, H 2 and N 2 is not sufficient at the given temperatures or if erosion occurs at higher flow rates (0.5 to 50 m / sec) is quite considerable or if the gas tightness of the graphite can be increased as a result or if the surface roughness of the reactor components can thus be reduced.
  • SiC, B 4 C, TiN, TiC and Ni can be used as layers. Combinations of different layers, for example with a "specific" top layer, are also possible. These layers can advantageously be applied by means of CVD, plasma spraying and electrolysis (Ni).
  • An important advantage of the variability of the temperature-residence time profile is the possibility of decoupling the nucleation zone from the nucleation zone. This makes it possible to produce "coarser” powders at a very low temperature and with a short residence time (ie small reactor cross-section for one certain length) to allow the formation of only a few nuclei, which can then grow into "coarse” particles at high temperature and a long residence time (large reactor cross section). It is also possible to produce very “fine” powders: in a region of high temperature and a relatively long residence time, a large number of nuclei are formed, which grow only slightly in the further reactor at low temperatures and a short residence time (small reactor cross section). It is possible to set all transitions between the borderline cases shown here qualitatively.
  • the cooling container (12) In the cooling container (12), a passivation of the partly. very air sensitive to pyrophoric powder possible.
  • the particle surfaces of these metal powders can be coated with an oxide layer of defined thickness as well as with suitable organic compounds such as higher alcohols, amines or sintering aids such as paraffins in an inert carrier gas stream.
  • suitable organic compounds such as higher alcohols, amines or sintering aids such as paraffins in an inert carrier gas stream.
  • the coating can also be carried out with regard to the further processing possibilities of the powders.
  • the nanoscale powders according to the invention are suitable for the production of novel sensors, actuators, structural metals and cermets.
  • Ta became according to the reaction equation TaCl 5 + 2 1/2 H 2nd ⁇ Ta + 5HCl produced in an apparatus according to FIG. 1, an excess of H 2 being maintained.
  • the turbulent individual flow threads emerging from the gas preheaters (2) were formed in the outer part of the nozzle (5) to form a homogeneous, rotationally symmetrical and laminar ring flow.
  • the gas stream emerging from the gas preheater (2a) was also laminarized in the nozzle (5) and introduced into the ring flow.
  • the nozzle (5) consisted of three coaxial nozzles.
  • An inert gas stream (16) emerged from the central part nozzle, which moved the location of the start of the reaction, ie the meeting of the two partial flows (6) and (7) away from the nozzle into the reaction tube.
  • the tubular reactor had an inner diameter of 40 mm at the nozzle outlet, 200 mm below the nozzle an inner diameter of 30 mm and 50 mm at the outlet.
  • the reaction tube (4) was composed of 18 segments, the segments being connected by a spacer and centering ring. An annular gap (8) was realized at each of these locations.
  • the temperature of the reaction tube (4) was set at 1230 ° C., measured on the outer wall of the reactor, 400 mm below the nozzle, using the W5Re-W26Re thermocouple (19).
  • the pressure in the reaction tube (4) was practically identical to the pressure in the blow-back filter (10). This was 250 mbar overpressure.
  • the reactor wall was flushed through 18 ring gaps (8) with 200 Nl / min Ar. If the reactor wall is not flushed with an inert gas, accretions can occur which can sometimes lead to the reactor closure and thus to the process being terminated very quickly; in any case, because of the changing reactor geometry, a likewise changing product is produced.
  • 200 Nl / min Ar was blown into the reaction tube (4) through the 6th annular gap from below using an additional gas inlet device.
  • the product (Ta with a uniform particle size of ⁇ 25 nm) was separated from the gases (H 2 , HCl, Ar) in the blow-back filter (10) at a temperature of 600 ° C.
  • This temperature was selected in order to keep the primary coverage of the very large particle surfaces (18 m 2 / g) with HCl at a low level ( ⁇ 0.8% Cl).
  • the Ta produced in this way was collected for 40 min (ie 2000 g) in the blow-back filter, in order to then be transferred to the evacuation container (11).
  • 8 pump flood cycles with a final vacuum of 0.1 mbar abs were carried out over a period of 35 min . run through.
  • the container was filled with Ar up to a pressure of 1100 mbar abs. flooded, after 35 min. the Ta powder treated in this way was transferred to the cooling container (12).
  • Targeted surface tailoring is also possible in this container by blowing in various gas / steam mixtures. After the powder had cooled to ⁇ 50 ° C, it was transferred through the lock (13) into the collection and shipping container without contact with the outside air.
  • the pyrophoric Ta powder showed an extremely narrow particle size distribution with a specific surface area of 17 m 2 / g, according to BET, measured according to the N 2 -1-point method (DIN 66 131), corresponding to 25 nm.
  • a SEM image of this Ta powder with a specific surface area of 25 m 2 / g showed the very narrow distribution of the particle dimensions and the absence of oversize particles. Accordingly, less than 1% of the individual particles have a deviation of more than 10% and no individual particles have a deviation of more than 40% from the mean grain size. According to the current state of measurement technology, reliable statements about a Particle size distribution of such extremely fine powders can only be obtained using imaging methods (e.g. B, SEM, TEM).

Claims (12)

  1. Poudres fines des éléments B, Al, Si, Ti, Zr, Hf, V, Nb, Ta et/ou Cr avec une taille de particules définie comprise entre 1,0 nm et 3 µm, caractérisées en ce que moins de 1% des particules individuelles présentent un écart de plus de 40% et aucune particule individuelle ne présente un écart de plus de 60% par rapport à la taille de grains moyenne.
  2. Poudres selon la revendication 1, caractérisées en ce que moins de 1% des particules individuelles présentent un écart de plus de 20% et aucune particule individuelle ne présente un écart de plus de 50% à la taille de grains moyenne.
  3. Poudres selon l'une des revendications 1 ou 2, caractérisées en ce que moins de 1% des particules individuelles présentent un écart de plus de 10% et aucune particule individuelle ne présente un écart de plus de 40% à la taille de grains moyenne.
  4. Poudres selon l'une ou plusieurs des revendications 1 à 3, caractérisées en ce que la taille de particules est comprise entre 1 et moins de 500 nm.
  5. Poudres selon l'une ou plusieurs des revendications 1 à 4, caractérisées en ce que la taille de particules est comprise entre 1 et moins de 100 nm, de préférence 1 à moins de 50 nm.
  6. Poudres selon l'une ou plusieurs des revendications 1 à 5, caractérisées en ce qu'elles présentent une teneur en oxygène inférieure à 5 000 ppm.
  7. Poudres selon l'une ou plusieurs des revendications 1 à 6, caractérisées en ce qu'elles présentent une teneur en oxygène inférieure à 1 000 ppm.
  8. Poudres selon l'une ou plusieurs des revendications 1 à 7, caractérisées en ce qu'elles présentent une teneur en oxygène inférieure à 100 ppm, de préférence inférieure à 50 ppm.
  9. Poudres selon l'une ou plusieurs des revendications 1 à 8, caractérisées en ce que la somme de leurs impuretés à l'exception des impuretés oxydes, est inférieure à 5 000 ppm.
  10. Poudres selon l'une ou plusieurs des revendications 1 à 9, caractérisées en ce que la somme de leurs impuretés, à l'exception des impuretés oxydes, est inférieure à 1 000 ppm.
  11. Poudres selon l'une ou plusieurs des revendications 1 à 10, caractérisées en ce que la somme de leurs impuretés, à l'exception des impuretés oxyde est inférieure à 200 ppm.
  12. Poudres selon l'une ou plusieurs des revendications 1 à 11, caractérisées en ce qu'elles se présentent en des quantités supérieures à 1 kg.
EP93106466A 1992-05-04 1993-04-21 Poudre métallique finement divisée Expired - Lifetime EP0568863B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4214722 1992-05-04
DE4214722A DE4214722C2 (de) 1992-05-04 1992-05-04 Feinteilige Metallpulver

Publications (2)

Publication Number Publication Date
EP0568863A1 EP0568863A1 (fr) 1993-11-10
EP0568863B1 true EP0568863B1 (fr) 1997-02-26

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US (1) US5407458A (fr)
EP (1) EP0568863B1 (fr)
JP (1) JP3356325B2 (fr)
KR (1) KR100251664B1 (fr)
AT (1) ATE149110T1 (fr)
DE (2) DE4214722C2 (fr)

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JPS597765B2 (ja) * 1980-09-13 1984-02-21 昭宣 吉澤 微粉末金属の製造方法
DE3119635A1 (de) * 1981-05-16 1982-12-02 Degussa Ag, 6000 Frankfurt "verfahren und vorrichtung zur herstellung von silberpulver"
JPS6039106A (ja) * 1983-08-10 1985-02-28 Res Dev Corp Of Japan 微粒子の製造方法
US4994107A (en) * 1986-07-09 1991-02-19 California Institute Of Technology Aerosol reactor production of uniform submicron powders
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US4808216A (en) * 1987-04-25 1989-02-28 Mitsubishi Petrochemical Company Limited Process for producing ultrafine metal powder
US4769064A (en) * 1988-01-21 1988-09-06 The United States Of America As Represented By The United States Department Of Energy Method for synthesizing ultrafine powder materials
DE3820960A1 (de) * 1988-06-22 1989-12-28 Starck Hermann C Fa Feinkoernige hochreine erdsaeuremetallpulver, verfahren zu ihrer herstellung sowie deren verwendung
DE3937740A1 (de) * 1989-11-13 1991-05-16 Rudolf C Dr Alberti Verfahren zur herstellung von nanokristallinen pulvern aus metallen, legierungen bzw. keramikwerkstoffen

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DE4214722C2 (de) 1994-08-25
DE4214722A1 (de) 1993-11-11
US5407458A (en) 1995-04-18
KR930023095A (ko) 1993-12-18
JPH0625701A (ja) 1994-02-01
ATE149110T1 (de) 1997-03-15
EP0568863A1 (fr) 1993-11-10
DE59305509D1 (de) 1997-04-03
JP3356325B2 (ja) 2002-12-16
KR100251664B1 (ko) 2000-04-15

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