EP0537502B1 - Poudre de métal ou d'alliage métallique sous forme microcristalline, sphérique et dense ainsi que procédé et installation pour sa préparation - Google Patents

Poudre de métal ou d'alliage métallique sous forme microcristalline, sphérique et dense ainsi que procédé et installation pour sa préparation Download PDF

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Publication number
EP0537502B1
EP0537502B1 EP92116067A EP92116067A EP0537502B1 EP 0537502 B1 EP0537502 B1 EP 0537502B1 EP 92116067 A EP92116067 A EP 92116067A EP 92116067 A EP92116067 A EP 92116067A EP 0537502 B1 EP0537502 B1 EP 0537502B1
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EP
European Patent Office
Prior art keywords
powder
powders
particles
spherical
metal
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Expired - Lifetime
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EP92116067A
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German (de)
English (en)
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EP0537502A1 (fr
Inventor
Alain Dauger
Gerard Labregere
Guy Roche
Rene Guinebretiere
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.)
Evonik Operations GmbH
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Degussa 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06—Metallic powder characterised by the shape of the particles
    • B22F1/065—Spherical particles

Definitions

  • the invention relates to powders of metals and binary and ternary metal alloys in the form of microcrystalline, spherical and dense particles.
  • microcrystalline metal and metal alloy powders that are approximately spherical, free of cracks and pores, that is to say dense with a surface that is as smooth as possible.
  • Metal powders can be produced using chemical and physical processes that have a decisive influence on the properties of the powders.
  • the known processes consist in the production of the powders by atomizing the metal or metal alloy melts in a liquid or gaseous medium (see, for example, DE-OS 33 24 188, DE-OS 33 45 983, GB 952 457, GB 1 123 825 and EP- A 0 120 506).
  • the metal powder particles atomized with water according to DE-OS 33 24 188 have very irregular surfaces, and their specific surface area is considerably larger than that calculated geometrically.
  • metal powder with spherical particles is obtained, the particle size of which is described in GB 952 457, e.g. is between 10 and 50 ⁇ m.
  • EP-A 0 120 506 describes a special process for producing even finer metal powder by atomizing a melt stream using a gas.
  • the powder particles obtained with this method are dense and non-porous; they are approximately spherical with an average diameter between 5 and 35 microns.
  • a completely different method for producing spherical metal particles according to DE-OS 33 45 985 consists in a certain amount of coarse metal particles, for. B. scrap, chips or castings in the melting zone of a fluidized bed furnace, melt the particles, atomize the melt product in a hot gas stream in droplets and solidify the droplets.
  • This method which is just as expensive as the one described above, is suitable for the production of abrasives, but not for the production of microcrystalline powders.
  • EP-A 0 282 945 teaches a hydrometallurgical process for producing finely divided spherical precious metal powders. Starting from an aqueous solution containing a noble metal compound, a solid reducible salt or oxide is formed, this is reduced and the product obtained is passed through an oven by means of a carrier gas, in which the particles melt at least 50%; then it is cooled. Particles with a diameter of less than 20 ⁇ m are obtained.
  • metal powder such as the powder of precious metals and their alloys, which are produced by simple chemical reduction of the metal salts, very fine with a particle diameter between 0.001 and 0.1 ⁇ m. They have a large specific surface area of 10 to 40 m 2 / g, depending on which reducing agent was used.
  • the primary particles of these powders can be agglomerated by thermomechanical treatment. However, these particles are structured so that they usually have a small grain size with a large specific surface area. Under these conditions the powders are very reactive; this is disadvantageous for the production of sintered metals as well as electronic components and microelectronic hybrid circuits.
  • the two metals form slightly continuous series of single-phase solutions.
  • the temperature of the solid state and that of the liquid is between the melting point of the palladium at 1552 ° C and the melting point of the silver at 961 ° C.
  • the ratio Pd / Ag is chosen so that the melting point is above the sintering temperature of the non-conductor in order to prevent the electrode from melting during the sintering process.
  • the two metals form oxides when sintered in air.
  • Ag 2 O is the most stable oxidation level of silver at room temperature and up to 300 ° C.
  • the formation of oxide is impeded by the air and the decrease in the specific surface area of the silver during the first sintering phase.
  • Palladium on the other hand, easily forms the oxide PdO in the initial phase of the sintering process. The extent depends on the specific surface of the metal, the heating rate and the partial pressure of atmospheric oxygen. PdO with a tetragonal crystalline structure is thermodynamic up to approx. 800 ° C. stable and returns to the metallic state at higher temperatures.
  • the oxidation of the palladium can be accompanied by a volume expansion of up to 40%. Above 800 ° C the reduction of PdO to Pd is noticeable in a volume reduction. Both reactions cause tension, which is a reason for the flaking.
  • the oxidation reduction of the palladium is accelerated by adding silver.
  • powders consisting of 70 wt% Ag and 30 wt% Pd reach the oxidation maximum at 520 ° C compared to 790 ° C without silver.
  • the reduction end of PdO is reduced in the same way from 900 ° C to 700 ° C.
  • the fine powder can react catalytically with the organic medium to form warm spots, which leads to rapid degassing, bubble formation and the condensers peeling.
  • the shrinkage properties of very fine metal powders are usually very pronounced and cannot compensate for the properties of the surrounding dielectric materials. As a result, tiny metal "islands" form from the discontinuous metal groups with weaker conductivity.
  • the object of the invention is to provide inactive noble metal powders which are fine enough for use in screen printing pastes, but whose specific surface area has to be small enough so that the catalytic effect is slowed down.
  • Another object of this invention is to develop a method and an apparatus for producing such powders, starting from microcrystalline powders from non-spherical particles, the specific surface area of which is larger than the theoretically calculated value.
  • the invention therefore relates to powders made of noble metals or of binary and ternary noble metal alloys in the form of microcrystalline, completely spherical and dense particles, which are characterized in that the mean particle diameter is between 0.1 ⁇ m and less than 5 ⁇ m and the grain spectrum within 0.1 ⁇ m and 10 ⁇ m.
  • a process for the production of powders from precious metals and precious metal alloys in the form was also found microcrystalline, completely spherical and dense particles with an average grain diameter between 0.1 and 5 ⁇ m and a grain spectrum within 0.1 and 10 ⁇ m from starting powders of the precious metals or their alloys in the form of microcrystalline, non-spherical particles with a larger specific surface than that of the powders to be prepared, comprising suspending the starting powder in an inert carrier gas, passing the suspension (powder cloud) through a tubular oven with external heating, wherein the powder particles are at a temperature within the heating zone of the oven of 100 to 250 ° C above the melting temperature of the Powder particles are heated to a temperature above the melting point, cooling the suspension to solidify the molten powder particles by means of one or more cooling devices which are located between the heating zone and the outlet of the tubular furnace outside it and / or outside e it is arranged at the exit of the tubular furnace, the diameter of which is larger than that of the tubular furnace, and
  • a metal or metal alloy powder is used as the starting product, which was produced by chemical synthesis, preferably by chemical reduction of metal salts with possibly subsequent thermomechanical treatment.
  • all powders that can be suspended in the carrier gas can be used as the starting product.
  • the flow rate of the suspension through the furnace and the temperature of the heating zone are controlled so that the molten particles are spherical as they enter the cooling zone.
  • the heating zone is preferably set to a temperature which is 100 to 250 ° C above the melting temperature.
  • the particles solidify in a cooling device, which can be attached to the outside of the furnace tube or in a part of the tube and / or outside the furnace.
  • powders of base metals such as. B. copper, lead, tin, zinc, aluminum and powder of precious metals, preferably silver, gold, palladium and platinum.
  • the method is also applicable to binary and ternary metal alloys.
  • a powder of an Ag-Pd alloy produced by chemical reduction of a silver-palladium mixed carbonate using a reducing agent of the aldehyde type in the aqueous phase has a specific surface area of 10 m 2 / g (measured by means of N 2 gas adsorption after the BET method) and a particle diameter of less than 0.1 ⁇ m.
  • a powder with a specific surface area of 1 to 2 m 2 / g is obtained by thermomechanical treatment of the powder produced. With the method according to the invention, the specific surface area of the latter powder can be reduced to approximately 0.3 to 0.5 m 2 / g.
  • the 3 contains a device for suspending the powder (1), a tubular furnace (8), one or more devices for cooling the suspension (11) and a device (13) in which the powder consists of spherical particles Carrier gas is separated and recovered;
  • the device (1) consists of an airtight housing (2), a filling system the starting powder (3), at least one carrier gas supply (4), a device (5, 6) for intensive mixing of the powder with the gas and an outlet (7) connected to the beginning (9a) of the tube (9) of the tubular furnace (8) is connected;
  • the area (9b) of the pipe (9) is surrounded by one or more heating devices (10), the cooling device or devices (11) are inside and / or outside of the pipe (9) between the heating zone (9b) and the pipe outlet ( 9c) and / or inside and / or outside on the chimney (12), which is located between the pipe end (9c) and the recovery chamber (13).
  • the device (1) and its parts (2) to (6) can be designed in various ways.
  • the powder feed (3) can take place, for example, by conventional metering systems which are used for fine powders, such as cellular wheel sluices, metering screws or vibration chutes.
  • Fig. 3 shows a particularly suitable mixing device (5, 6); (5) is a rotor (5) driven by a motor (6).
  • the principle of mixing devices without mobile parts, whereby powder and carrier gas are introduced on one side of the fixed mixer, has also proven itself. Instead of via the feed line (4), the carrier gas can also be fed into the mixing chamber (2) via other connections.
  • the tube (9) of the tubular furnace (8) has a heating zone (9c) which is heated by one or more heating registers (10).
  • the heating can be done electrically or with gas; however, an electric heater is preferred because it enables the regulation and setting of the temperature program for the entire heating zone in a simple manner.
  • the pipe (9) is connected at one end (9a) to the mixing chamber (2) and at the other end (9c) to the recovery chamber (13) or any chimney (12) between the recovery chamber and the pipe (9).
  • the cooling system (s) (11) can be of different types and can be arranged at the end of the pipe (9) and / or in the vicinity of the possible chimney (12).
  • the suspension can be cooled in one or more steps respectively.
  • the cooling device (11) is at the end of the tube (9); this cooling system consists of a heat exchanger that is placed around the pipe and works with a refrigerant; (11a) and (11b) represent the supply or discharge of the refrigerant.
  • the optional cooling system (14) with supply and discharge (14a and 14b) of the refrigerant serves to stably close the pipe (9) with the chamber (2) connect. If a pipe element (12), which has the shape of a chimney and is equipped with a cooling device, can be installed between the pipe (9) and the recovery system (13), it will, due to its significantly larger diameter than the pipe (9), cause that the flow rate of the suspension decreases.
  • the powder can be separated from the carrier gas by settling in the simply constructed chamber (13); the powder moves towards the outlet (13b); the carrier gas escapes via the outlet (13a), which is optionally provided with dust filters, or it is completely or partially returned to the mixing chamber.
  • the continuous separation of the powder from the cooled suspension can also take place by means of other known devices, for example by means of a dust separator and / or dust filter.
  • microcrystalline metal or metal alloy powders which are present as non-spherical particles can, according to the invention, be converted into powders with spherical particles and a smooth surface in a production device specially developed for this process.
  • This process is particularly advantageous because it is much simpler and can work more economically than the known processes, which also start from solids.
  • the amount of gas required is considerably less than in the named methods; the energy and raw material costs are lower.
  • the powders produced by the process according to the invention have proven to be particularly suitable for the production of electronic components, such as ceramic multilayer capacitors. Due to its simple construction, the device is particularly suitable for the production of small powder batches of very expensive metals, such as precious metals and their alloys.
  • a device for producing the powders according to the invention can also be used to improve the crystal structure of the metal and metal alloy powders, even if they are treated at temperatures which are 100 to 200 ° C. below the melting temperature.
  • the starting powder can be in the form of spherical or non-spherical particles.
  • the starting powder - see FIG. 1 - is a silver / palladium alloy with 30% by weight of Pd, which was produced chemically and by thermomechanical treatment.
  • the particles are completely spherical - see Fig. 2; the grain size is between 0.2 and 3 ⁇ m, the specific surface is 0.43 m 2 / g (electron microscope).
  • the particles of the powder are completely homogeneous; the chemical composition has not changed.
  • the starting powder and the powder obtained were used to produce the internal electrodes of ceramic multilayer capacitors; Manufacture of capacitors using known methods:
  • the chips based on the starting powder showed some tiny metal islands as well as partial exfoliation of the layers after sintering at 1150 ° C.
  • the chips based on the spherical powder according to Example 1 showed no exfoliation after sintering at 1150 ° C.
  • Example 2 Starting powder and test conditions are identical to Example 1, the only difference is that the oven temperature is set to 1320 ° C.
  • the particles are completely spherical, the grain size is between 0.4 and 4 ⁇ m, the specific surface area is 0.34 m 2 / g.
  • the particles of the powder are completely homogeneous; the chemical composition has not changed.
  • the degree of oxidation of the palladium contained is 30% at the maximum oxidation temperature of 575 ° C.
  • the shrinkage measured at 1100 ° C is 12% compared to 40% of the starting powder.
  • the linear coefficient of thermal expansion at 0 and 900 ° C is close to that of the layer connection, ie 1.68 x 10 -5 / ° C.
  • the chips used for the production of the inner electrodes of ceramic multilayer capacitors, the chips showed no peeling after sintering at 1150 ° C.
  • the starting powder is a silver / palladium alloy with 70% by weight Pd, which was produced chemically and by thermomechanical treatment.
  • the particles are perfectly spherical; the grain size is between 0.2 and 3 ⁇ m, the specific surface is 0.5 m 2 / g.
  • the particles of the powder are completely homogeneous; the chemical composition has not changed.
  • the particles are perfectly spherical; the grain size is between 2 and 5 ⁇ m.
  • the particles are perfectly spherical; the average grain size is 8 ⁇ m, the specific surface 0.2 m 2 / g.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)

Claims (4)

  1. Poudres de métaux nobles ou d'alliages de métaux nobles binaires ainsi que ternaires sous forme de particules microcristalline, parfaitement sphériques et denses,
    caractérisées en ce que
    le diamètre moyen d'argent, d'or, de palladium ou de platine ou de leurs alliages.
  2. Poudres selon la revendication 1,
    caractérisées en ce qu'
    elles se composent d'argent, d'or, de palladium ou de platine ou de leurs alliages.
  3. Procédé de production de poudres en métaux nobles et en alliages de métaux nobles sous la forme de particules microcristallines, parfaitement sphériques et denses ayant un diamètre de grain moyen compris entre 0,1 et 5 µm et un spectre granulométrique compris entre 0,1 et 10 µm, à partir de poudres d'origine de métaux nobles ou de leurs alliages sous la forme de particules microcristallines, non sphériques ayant une surface spécifique plus grande que celle de la poudre à fabriquer, comportant le passage de la suspension (nuage de poudre) à travers un four tubulaire avec chauffage externe, dans lequel les particules de poudre sont chauffées avec une température à l'intérieur de la zone de chauffage du four de 100 à 250°C au dessus de la température au dessus du point de fusion, le refroidissement de la suspension en vue de solidifier les particules de poudre fondues au moyen d'un ou de plusieurs dispositifs refroidisseurs, qui sont disposés entre la zone de chauffage et la sortie du four tubulaire, à l'extérieur de celui-ci et/ou à l'extérieur d'une cheminée se raccordant à la sortie du four tubulaire, dont le diamètre est plus grand que celui du four tubulaire et séparation des particules de poudre sphériques de la suspension au moyen de méthodes connues.
  4. Procédé selon la revendication 3,
    caractérisé en ce qu'
    on utilise comme produit d'origine une poudre de métal noble ou d'un alliage de métal noble, qui a été obtenue par synthèse chimique, de préférence par réduction chimique de sels métalliques avec un traitement suivant thermomécanique.
EP92116067A 1991-10-18 1992-09-19 Poudre de métal ou d'alliage métallique sous forme microcristalline, sphérique et dense ainsi que procédé et installation pour sa préparation Expired - Lifetime EP0537502B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9112890 1991-10-18
FR9112890A FR2682625B1 (fr) 1991-10-18 1991-10-18 Poudres de metaux et d'alliages de metaux sous forme de grains microcristallins spheriques et compacts, et procede et dispositif pour la fabrication des poudres.

Publications (2)

Publication Number Publication Date
EP0537502A1 EP0537502A1 (fr) 1993-04-21
EP0537502B1 true EP0537502B1 (fr) 1997-07-23

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EP92116067A Expired - Lifetime EP0537502B1 (fr) 1991-10-18 1992-09-19 Poudre de métal ou d'alliage métallique sous forme microcristalline, sphérique et dense ainsi que procédé et installation pour sa préparation

Country Status (4)

Country Link
EP (1) EP0537502B1 (fr)
JP (1) JPH05214410A (fr)
DE (1) DE59208720D1 (fr)
FR (1) FR2682625B1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7128852B2 (en) 1997-02-24 2006-10-31 Cabot Corporation Aerosol method and apparatus, particulate products, and electronic devices made therefrom
US7749299B2 (en) 2005-01-14 2010-07-06 Cabot Corporation Production of metal nanoparticles
US8167393B2 (en) 2005-01-14 2012-05-01 Cabot Corporation Printable electronic features on non-uniform substrate and processes for making same
US8334464B2 (en) 2005-01-14 2012-12-18 Cabot Corporation Optimized multi-layer printing of electronics and displays
US8383014B2 (en) 2010-06-15 2013-02-26 Cabot Corporation Metal nanoparticle compositions
US8597397B2 (en) 2005-01-14 2013-12-03 Cabot Corporation Production of metal nanoparticles

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6165247A (en) 1997-02-24 2000-12-26 Superior Micropowders, Llc Methods for producing platinum powders
US6159267A (en) * 1997-02-24 2000-12-12 Superior Micropowders Llc Palladium-containing particles, method and apparatus of manufacture, palladium-containing devices made therefrom
US6699304B1 (en) 1997-02-24 2004-03-02 Superior Micropowders, Llc Palladium-containing particles, method and apparatus of manufacture, palladium-containing devices made therefrom
DE10120484A1 (de) * 2001-04-25 2002-10-31 Degussa Verfahren und Vorrichtung zur thermischen Behandlung von pulverförmigen Stoffen
EP3216545B2 (fr) * 2016-03-07 2022-09-28 Heraeus Deutschland GmbH & Co. KG Poudre en metal noble et son utilisation pour la fabrication de composants
WO2024204211A1 (fr) * 2023-03-29 2024-10-03 昭栄化学工業株式会社 Procédé pour la production de poudre métallique et poudre métallique

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2038251A (en) * 1933-01-03 1936-04-21 Vogt Hans Process for the thermic treatment of small particles
FR823216A (fr) * 1936-06-18 1938-01-17 Lignes Telegraph Telephon Traitement thermique des poudres
US4731110A (en) * 1987-03-16 1988-03-15 Gte Products Corp. Hydrometallurigcal process for producing finely divided spherical precious metal based powders

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7128852B2 (en) 1997-02-24 2006-10-31 Cabot Corporation Aerosol method and apparatus, particulate products, and electronic devices made therefrom
US8333820B2 (en) 1997-02-24 2012-12-18 Cabot Corporation Forming conductive features of electronic devices
US7749299B2 (en) 2005-01-14 2010-07-06 Cabot Corporation Production of metal nanoparticles
US8167393B2 (en) 2005-01-14 2012-05-01 Cabot Corporation Printable electronic features on non-uniform substrate and processes for making same
US8334464B2 (en) 2005-01-14 2012-12-18 Cabot Corporation Optimized multi-layer printing of electronics and displays
US8597397B2 (en) 2005-01-14 2013-12-03 Cabot Corporation Production of metal nanoparticles
US8668848B2 (en) 2005-01-14 2014-03-11 Cabot Corporation Metal nanoparticle compositions for reflective features
US8383014B2 (en) 2010-06-15 2013-02-26 Cabot Corporation Metal nanoparticle compositions

Also Published As

Publication number Publication date
FR2682625A1 (fr) 1993-04-23
FR2682625B1 (fr) 1997-04-11
DE59208720D1 (de) 1997-08-28
EP0537502A1 (fr) 1993-04-21
JPH05214410A (ja) 1993-08-24

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