EP0423627A1 - Procédé de préparation de poudre d'un métal ou d'un alliage microcristallin à amorphe, ainsi que des métaux ou alliages dissous dans des solvants organiques sans colloide protecteur - Google Patents

Procédé de préparation de poudre d'un métal ou d'un alliage microcristallin à amorphe, ainsi que des métaux ou alliages dissous dans des solvants organiques sans colloide protecteur Download PDF

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Publication number
EP0423627A1
EP0423627A1 EP90119546A EP90119546A EP0423627A1 EP 0423627 A1 EP0423627 A1 EP 0423627A1 EP 90119546 A EP90119546 A EP 90119546A EP 90119546 A EP90119546 A EP 90119546A EP 0423627 A1 EP0423627 A1 EP 0423627A1
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EP
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Prior art keywords
thf
metal
metals
powder
amorphous
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EP90119546A
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German (de)
English (en)
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EP0423627B1 (fr
Inventor
Helmut Dr. Bönnemann
Werner Dr. Brijoux
Thomas Joussen
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Studiengesellschaft Kohle gGmbH
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Studiengesellschaft Kohle gGmbH
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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
    • 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
    • B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
    • 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
    • B22F9/002—Making metallic powder or suspensions thereof amorphous or microcrystalline

Definitions

  • the present invention relates to a process for the production of finely divided, microcrystalline to amorphous metal or alloy powders or highly disperse colloids by reduction of metal salts with alkali or alkaline earth metal hydrides, which are kept in solution in organic solvents by means of special complexing agents.
  • the use of the powders produced according to the invention is also claimed in powder technology (Ullmanns Encycl. Techn. Chemie, 4th edition vol. 19, p. 563) or as catalysts in pure or supported form (Ullmanns Encycl. Techn. Chemistry, 9. Edition, vol. 13, p. 517; further: Kirk-Othmer, Encyclopedia of Chemical Technology, Vol. 19, p. 28 f.).
  • the colloids produced according to the invention can be used to apply metals in the form of fine cluster particles to surfaces (JS Bradley, E. Hill, ME Leonowicz. HJWitzke, J. Mol. Catal. 1987, 41, 59 and cited there ) use homogeneous catalysts. (JP Picard, J. Dunogues, A. Elyusufi, Synth. Commun. 1984, 14, 95; F. Freeman, JC Kappos, J. Am. Chem. Soc. 1985, 107, 6628; WF Maier, SJ Chettle, RS Rai, G. Thomas, J. Am. Chem. Soc. 1986, 108, 2608 ; PL Burk, RL Pruett, KS Campo, J. Mol. Catal. 1985, 33, 1 ).
  • metal hydrides of the first or second main group PSE can be used with the aid of organic boron or gallium complexing agents in the organic phase as reducing agents for metal salts, wherein boride- or gallium-free metals or metal alloys are obtained in powder or colloidal form will.
  • the advantages of the process according to the invention are that the reduction process can be carried out under very mild conditions (-30 ° C. to + 150 ° C.) in organic solvents, and furthermore in the good separability of the metal or alloy powders from the generally soluble ones By-products, as well as in the microcrystallinity of the powder and the fact that the particle size distribution can be controlled depending on the reaction temperature.
  • Another advantage results from the fact that, under certain conditions (use of donor metal salt complexes and / or ammonium triorganohydroborates), colloidal solutions of metals or alloys are obtained in ethers or even pure hydrocarbons without the addition of further protective colloids.
  • the elements of groups IVA, IB, IIB, VB, VIB, VIIB and VIIIB of the PSE are preferably used as metals of the metal salts.
  • metals of the mentioned groups of PSE are Sn, Cu, Ag, Au, Zn, Cd, Hg, Ta, Cr, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt.
  • Metal salts or compounds used are those which contain either inorganic or organic anions, preferably those which are solvated in the systems used as solvents, such as hydroxides, oxides, halides, cyanides, cyanates, thiocyanates and alcoholates and salts of organic acids.
  • M-hydroxides, alcoholates, cyanides, cyanates and thiocyanates form with the boron and gallium organic complexing agents soluble -at complexes of the type M [BR3 (anion)], M [BR n (OR ′) 3 -n (anion)] or M [GaR3 (anion)], M [GaR n (OR ′) 3-n (anion)].
  • the metal or alloy powder can be isolated according to the invention with particular advantage by simple filtration from the clear organic solution in pure form after the reaction has ended.
  • M halides generally do not form any such complexes; however, in many cases they remain dissolved in the organic solvent, for example THF, after the reaction. This applies in particular to CsF, LiCl, MgCl2, LiBr, MgBr2, LiI, NaI, and MgI2.
  • the choice of the cation in the hydride is therefore decisive for the production of metal and alloy powders from corresponding metal halide compounds according to the invention.
  • M-halides which precipitate from the organic solvent after the reaction according to the invention for example NaCl
  • M-halides which precipitate from the organic solvent after the reaction according to the invention can be separated from the metal or alloy powder by washing with, for example, water.
  • a characteristic of the process carried out according to the invention is that the organic boron or gallium complexing agent can be recovered in free form after the reaction or after the complexes by-products M (anion) x have been decomplexed.
  • Reactions of Ni (OH) 2 with Na (BEt3H) in THF for example according to 11B-NMR spectrum (11B signal at 1 ppm) in solution Na (BEt3OH). From this -at complex present in the reaction solution, the complexing agent BEt3 is obtained by hydrolysis with HCl / THF according to gas chromatographic analysis in 97.6% yield (Example 15).
  • Powder metals with a grain size of 0.01 ⁇ m (Example 11) to 200 ⁇ m (Tab. 2, No. 46) are obtained by the process according to the invention.
  • the particle size distribution can be controlled by the reaction parameters. Given a combination of starting materials and The lower the reaction temperature, the finer the metal particles obtained according to the invention.
  • the reaction of PtCl2 with Li (BEt3H) in THF at 80 ° C provides a platinum powder with a relatively broad particle size distribution from 5 to 100 ⁇ m (see Fig. 1).
  • the same reaction at 0 ° C (Tab 2, No. 45) results in a platinum powder with a much narrower grain size distribution and a pronounced maximum at 15 ⁇ m (see Fig. 2)
  • FIG 1 A first figure.
  • the metal powders produced according to the invention are microcrystalline to amorphous.
  • Fig. 3 shows the powder diffractograms measured by CoK ⁇ radiation of Fe powder produced according to the invention (Tab. 2, No. 3) before and after thermal treatment of the sample at 450 ° C.
  • the untreated original sample only shows a very broad line (Fig.3a), proof of the presence of microcrystalline to amorphous phases (HP Klug, LE Alexander, X-ray Diffraction Procedures for Polycrystalline and Amorphous Materials, 2nd edn ., Wiley, New York, 1974).
  • a simple reduction of salts of different metals or of mixed oxides by the process according to the invention provides fine-particle two-metal and multi-metal alloys under mild conditions.
  • the reduction of FeSO4 and CoCl2 with tetrahydroborate in aqueous solution describe J. v. Wontherghem, St. Morup et al. ( Nature, 1986, 322, p. 622 ).
  • the result of this procedure is, according to the elementary composition and the saturation magnetization of 89 JT ⁇ 1kg ⁇ 1, an Fe / Co / B alloy with the composition Fe44Co19B37.
  • a 1: 1 amount of amorphous Fe and Co powder produced according to the invention was measured at 450 ° C. before and after the heat treatment ( Fig. 5).
  • the untreated batch again shows a diffuse line (a).
  • a comparison of Figs. 4 and 5 shows that a microcrystalline to amorphous alloy is formed during the reduction according to the invention, which recrystallizes only after heat treatment.
  • single-phase two-component and multi-component systems in microcrystalline to amorphous form can be freely combined by reducing the salts of main and sub-group elements, non-ferrous and / or noble metals. It is also possible according to the invention with particular advantage, by reducing metal salts and / or on carrier materials, provided they do not react with hydroethyl borates (eg Al2O3, SiO2 or organic polymers) To produce metal compounds or salt mixtures to form shell-shaped amorphous metals and / or alloys on supports.
  • hydroethyl borates eg Al2O3, SiO2 or organic polymers
  • Amorphous alloys in pure or supported form are of great technical interest as catalysts.
  • metals and / or alloys in organic solvents can be obtained with particular advantage under certain conditions without the addition of a protective colloid in colloidal solution.
  • the conversion of non-ferrous or noble metal salts (individually or as a mixture) with the tetraalkylammonium triorganohydroborates accessible according to German patent application P 39 01 027.9 leads to stable, transparent red, colloidal solutions of the metals at room temperature in THF.
  • the metal salts are used in the form of donor complexes, the colloidal metals can also be prepared according to the invention with alkali metal or alkaline earth metal triorganohydroborates in THF or hydrocarbons (see Table 6, No. 15, 16, 17).
  • metal alloy powder It is washed again with 200 ml each of THF and pentane and, after drying in a high vacuum (10 ⁇ 3 mbar), 2.45 g of metal alloy powder are obtained (see Table 5, No. 6).
  • Metal content of the sample 47.0% Fe, 47.1% Co Boron content of the sample: 0.0%
  • the solution is removed and the Al2O3 carrier again dried in a high vacuum (10 ⁇ 3 mbar) for three hours.
  • the impregnation is carried out again overnight with 330 ml FeCl3 / CoCl2 solution.
  • the color of the solution no longer occurs.
  • the solution is removed and the Al2O3 pellets are treated with 63.6 g (600 mmol) of LiBEt3H in 400 ml of THF at 23 ° C for 16 hours, the pellets turning black with evolution of H2.
  • the reaction solution is removed and the pellets are washed with 300 ml of THF, THF / ethanol (2: 1), THF and dried in a high vacuum (10 ⁇ 3 mbar) for four hours.
  • Al2O3 pellets are obtained which are coated with an Fe / Co alloy only on the surface of the shell. Elemental analysis: 1.13% Fe, 0.50% Co
  • 270 g of spherical, neutral aluminum oxide are rotated at room temperature in a solution of 150 g (631.3 mmol) of NiCl2 ⁇ 6 H2O in 500 ml of ethanol for 45 min, freed from the supernatant solution and at 24 h in a high vacuum (10 ⁇ 3 mbar) 250 ° C dried. After cooling, 1 l of 1.5 molar LiBEt3H solution in THF is added under a protective gas, and the clear reaction solution is separated off after 16 hours of swirling.

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  • Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)
EP90119546A 1989-10-14 1990-10-12 Procédé de préparation de poudre d'un métal ou d'un alliage microcristallin à amorphe, ainsi que des métaux ou alliages dissous dans des solvants organiques sans colloide protecteur Expired - Lifetime EP0423627B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3934351 1989-10-14
DE3934351A DE3934351A1 (de) 1989-10-14 1989-10-14 Verfahren zur herstellung von mikrokristallinen bis amorphen metall- bzw. legierungspulvern und ohne schutzkolloid in organischen solventien geloesten metallen bzw. legierungen

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EP0423627A1 true EP0423627A1 (fr) 1991-04-24
EP0423627B1 EP0423627B1 (fr) 1995-04-19

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EP90119546A Expired - Lifetime EP0423627B1 (fr) 1989-10-14 1990-10-12 Procédé de préparation de poudre d'un métal ou d'un alliage microcristallin à amorphe, ainsi que des métaux ou alliages dissous dans des solvants organiques sans colloide protecteur

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US (2) US5308377A (fr)
EP (1) EP0423627B1 (fr)
JP (1) JPH03134106A (fr)
AT (1) ATE121330T1 (fr)
CA (1) CA2027257C (fr)
DE (2) DE3934351A1 (fr)
DK (1) DK0423627T3 (fr)
ES (1) ES2070970T3 (fr)
IE (1) IE67173B1 (fr)

Cited By (9)

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WO1993005877A1 (fr) * 1991-09-25 1993-04-01 Research Corporation Technologies, Inc. Synthese sonochimique de metaux amorphes
WO1993024263A1 (fr) * 1992-06-04 1993-12-09 Board Of Regents Of The University Of Nebraska Metaux de valence zero tres reactifs derives de cyanures metalliques adaptes a la preparation de composes organometalliques
US5330687A (en) * 1991-08-01 1994-07-19 Board Of Regents Of The University Of Nebraska Preparation of functionalized polymers utilizing a soluble highly reactive form of calcium
EP0744234A1 (fr) * 1995-05-26 1996-11-27 Th. Goldschmidt AG Procédé pour la fabrication de poudres métalliques nanocristallines et amorphes aux rayons X
WO1999041758A1 (fr) * 1998-02-14 1999-08-19 Studiengesellschaft Kohle Mbh Nanocolloides magnetiques anticorrosion proteges par des metaux precieux
US6066410A (en) * 1997-12-19 2000-05-23 Degussa Aktiengesellschaft Anode catalyst for fuel cells with polymer electrolyte membranes
EP1002578A2 (fr) * 1998-11-18 2000-05-24 Degussa-Hüls Aktiengesellschaft Procédé pour l'hydrogénation sélective catalytique d'acides gras
WO2004001776A1 (fr) * 2002-06-21 2003-12-31 Studiengesellschaft Kohle Mbh Nanocolloides magnetiques a dispersion uniforme et de taille ajustable, et leur procede de production
EP2060323A1 (fr) 2007-11-12 2009-05-20 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Procédé pour la préparation de composés intermétalliques ordonnés de palladium et gallium, optionellement supportés, les composés mêmes et leur utilisation en catalyse

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DE3934351A1 (de) * 1989-10-14 1991-04-18 Studiengesellschaft Kohle Mbh Verfahren zur herstellung von mikrokristallinen bis amorphen metall- bzw. legierungspulvern und ohne schutzkolloid in organischen solventien geloesten metallen bzw. legierungen
US5384078A (en) * 1991-08-01 1995-01-24 Board Of Regents Of The University Of Nebraska Soluble highly reactive form of calcium and reagents thereof
FR2768638B1 (fr) * 1997-09-23 1999-12-17 Centre Nat Rech Scient Particules polymetalliques ultrafines, leur preparation et leur utilisation pour l'hydrogenation d'olefines ou pour le couplage de derives halogenes aromatiques
DE19821968A1 (de) * 1998-05-18 1999-11-25 Studiengesellschaft Kohle Mbh Verfahren zur Modifizierung der Dispergiereigenschaften von metallorganisch-prästabilisierten bzw. -vorbehandelten Nanometallkolloiden
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US8497131B2 (en) * 1999-10-06 2013-07-30 Becton, Dickinson And Company Surface enhanced spectroscopy-active composite nanoparticles comprising Raman-active reporter molecules
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WO2002079764A1 (fr) * 2001-01-26 2002-10-10 Nanoplex Technologies, Inc. Nanoparticules sandwich a spectrometrie active exaltees de surface
US6835332B2 (en) * 2000-03-13 2004-12-28 Canon Kabushiki Kaisha Process for producing an electrode material for a rechargeable lithium battery, an electrode structural body for a rechargeable lithium battery, process for producing said electrode structural body, a rechargeable lithium battery in which said electrode structural body is used, and a process for producing said rechargeable lithium battery
KR100358853B1 (ko) * 2000-04-04 2002-10-31 광주과학기술원 무수 금속 염화물을 사용한 직접 메탄올 연료전지용 백금합금 전극촉매의 제조방법
DE10024776C1 (de) 2000-05-19 2001-09-06 Goldschmidt Ag Th Verwendung von Metallhydrid-behandeltem Zink in der metallorganischen Synthese
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WO2005056222A1 (fr) * 2003-12-15 2005-06-23 Nippon Sheet Glass Co., Ltd. Liquide nanocolloidal metallique, procede pour produire un support metallique et support metallique associe
US7713910B2 (en) 2004-10-29 2010-05-11 Umicore Ag & Co Kg Method for manufacture of noble metal alloy catalysts and catalysts prepared therewith
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EP3363538A1 (fr) 2017-02-20 2018-08-22 Technische Universität Berlin Procédé de préparation d'un matériau composite de carbone mésoporeux comportant des nanoparticules métalliques et usage dudit matériau comme catalyseur
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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5330687A (en) * 1991-08-01 1994-07-19 Board Of Regents Of The University Of Nebraska Preparation of functionalized polymers utilizing a soluble highly reactive form of calcium
WO1993005877A1 (fr) * 1991-09-25 1993-04-01 Research Corporation Technologies, Inc. Synthese sonochimique de metaux amorphes
WO1993024263A1 (fr) * 1992-06-04 1993-12-09 Board Of Regents Of The University Of Nebraska Metaux de valence zero tres reactifs derives de cyanures metalliques adaptes a la preparation de composes organometalliques
EP0744234A1 (fr) * 1995-05-26 1996-11-27 Th. Goldschmidt AG Procédé pour la fabrication de poudres métalliques nanocristallines et amorphes aux rayons X
US5951739A (en) * 1995-05-26 1999-09-14 Th. Goldschmidt Ag Process for preparing x-ray amorphous and nanocrystalline metal powders
US6066410A (en) * 1997-12-19 2000-05-23 Degussa Aktiengesellschaft Anode catalyst for fuel cells with polymer electrolyte membranes
WO1999041758A1 (fr) * 1998-02-14 1999-08-19 Studiengesellschaft Kohle Mbh Nanocolloides magnetiques anticorrosion proteges par des metaux precieux
US6491842B1 (en) * 1998-02-14 2002-12-10 Studiengesellschaft Kohle Mbh Anticorrosive magnetic nanocolloids protected by precious metals
EP1002578A2 (fr) * 1998-11-18 2000-05-24 Degussa-Hüls Aktiengesellschaft Procédé pour l'hydrogénation sélective catalytique d'acides gras
EP1002578A3 (fr) * 1998-11-18 2002-04-10 Degussa-Hüls Aktiengesellschaft Procédé pour l'hydrogénation sélective catalytique d'acides gras
WO2004001776A1 (fr) * 2002-06-21 2003-12-31 Studiengesellschaft Kohle Mbh Nanocolloides magnetiques a dispersion uniforme et de taille ajustable, et leur procede de production
EP2060323A1 (fr) 2007-11-12 2009-05-20 Max-Planck-Gesellschaft zur Förderung der Wissenschaften e.V. Procédé pour la préparation de composés intermétalliques ordonnés de palladium et gallium, optionellement supportés, les composés mêmes et leur utilisation en catalyse

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Publication number Publication date
US5580492A (en) 1996-12-03
ATE121330T1 (de) 1995-05-15
JPH03134106A (ja) 1991-06-07
CA2027257C (fr) 2001-05-29
CA2027257A1 (fr) 1991-04-15
DE3934351A1 (de) 1991-04-18
IE903660A1 (en) 1991-04-24
ES2070970T3 (es) 1995-06-16
DK0423627T3 (da) 1995-09-04
IE67173B1 (en) 1996-03-06
EP0423627B1 (fr) 1995-04-19
US5308377A (en) 1994-05-03
DE59008929D1 (de) 1995-05-24

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