EP0423627B1 - 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

Info

Publication number
EP0423627B1
EP0423627B1 EP90119546A EP90119546A EP0423627B1 EP 0423627 B1 EP0423627 B1 EP 0423627B1 EP 90119546 A EP90119546 A EP 90119546A EP 90119546 A EP90119546 A EP 90119546A EP 0423627 B1 EP0423627 B1 EP 0423627B1
Authority
EP
European Patent Office
Prior art keywords
thf
metal
metals
amorphous
microcrystalline
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.)
Expired - Lifetime
Application number
EP90119546A
Other languages
German (de)
English (en)
Other versions
EP0423627A1 (fr
Inventor
Helmut Dr. Bönnemann
Werner Dr. Brijoux
Thomas Joussen
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.)
Studiengesellschaft Kohle gGmbH
Original Assignee
Studiengesellschaft Kohle gGmbH
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 Studiengesellschaft Kohle gGmbH filed Critical Studiengesellschaft Kohle gGmbH
Publication of EP0423627A1 publication Critical patent/EP0423627A1/fr
Application granted granted Critical
Publication of EP0423627B1 publication Critical patent/EP0423627B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/24—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. Also wildly claims the use of the powders produced according to the invention in powder technology (Ullmanns Encycl. Techn. Chemistry, 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. HJ Witzke, J. Mol. Catal. 1987, 41, 59 and cited therein ) or use as 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 Chertle, RS Rai, G. Thomas, J. Am. Chem. Soc. 1986, 108, 2608; PL Burk, RL Pruett, KS Campo, J. Mol. Catal. 1985, 33, 1 ).
  • EP-0 379 062 A2 published on July 25, 1990, describes a process for producing acicular, non-sintered iron-metal pigments.
  • These iron-metal pigments are produced by reducing iron oxide compounds in organic solvents with metal hydrides of metals from the first and second groups of the Periodic Table of the Elements, the metal hydrides being solvated with a carrier in the form of a carrier complex. This reaction becomes smooth at temperatures between 20 and 150 ° C in the presence of hydrogen from 1 to 200 bar to iron metal pigments.
  • the present invention relates to colloidal solutions of metals and / or alloys which can be obtained by the process described above.
  • Another aspect of the present invention comprises metal powders with a grain size of 0.01-200 »m, which can be obtained by the above method, which, according to their X-ray diffractogram, are microcrystalline to amorphous and have a boron content of less than 1% by weight.
  • the invention also includes metal alloy powders and the use of the microcrystalline to amorphous metal or alloy powders in powder technology.
  • metal hydrides of the first or second group of the PSE can be used with the help of organic boron or gallium complexing agents in the organic phase as reducing agents for metal salts without the use of a reducing H2 atmosphere, with boride- or gallium-free metals or metal alloys can be obtained in powder or colloidal form.
  • 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 arises 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 5 to 12 and 14 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 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, -at complexes of the type M [BR3 (anion)], M [BR n (OR ') 3 which are soluble in organic solvents -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.
  • Powder metals with a grain size of 0.01 »m (example) to 200» m 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. 44) results in a platinum powder with a much narrower grain size distribution and a pronounced maximum at 15 »m (see Fig. 2).
  • the metal powders produced according to the invention are microcrystalline to amorphous.
  • Fig. 3 shows the powder diffractograms of Fe powder produced according to the invention (Tab. 2, No. 3) measured by CoK ⁇ radiation before and after thermal treatment of the sample at 450 ° C.
  • the untreated original sample shows only 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 various metals 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.
  • 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 possible according to the invention with particular advantage by reducing metal salts and / or which have been drawn onto carrier materials insofar as they do not react with hydroethyl borates (for example Al2O3, SiO2 or organic polymers)
  • hydroethyl borates for example Al2O3, SiO2 or organic polymers
  • 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 (EP-A 0 379 062) 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).
  • 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. 4).
  • 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 swirled for 45 min at room temperature in a solution of 150 g (631.3 mmol) of NiCl2 ⁇ 6 H2O in 500 ml of ethanol, 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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)

Claims (14)

  1. Procédé de préparation de métaux et/ou d'alliages microcristallins à amorphes bien dispersés en forme de poudres, caractérisé en ce qu'on fait réagir sans atmosphère d'hydrogène, dans un solvant organique inerte non aqueux choisi parmi le THF, le diglyme et les hydrocarbures, des sels de métaux avec des hydrures de métaux du 1er et du 2ème groupe de la classification périodique des éléments qui sont conservés dans des solutions avec des agents complexants de formule générale BR₃, BRn(OR')3-n et/ou GaR₃, GaRn(OR')3-n, où R, R' représentent de l'alcoyle C₁ à C₆, du phényle ou de l'aralcoyle et où n est égal à 0, 1 ou 2, ou avec des tetraalkylammonium triorganoborates de formule NR''₄ (BR₃H) ou NR''₄ (BRn(OR')3-nH) (R = alcoyle C₁ à C₆, aryl-alcoyle C₁ à C₆; R' = alcoyle C₁ à C₆, aryle, aryl-alcoyle C₁ à C₆; R'' = alcoyle C₁ à C₆, aryle, aryl-alcoyle C₁ à C₆, tri(alkyl C₁ à C₆)silyle, n = 0, 1, 2.
  2. Procédé de préparation de métaux et/ou d'alliages dissous comme colloïdes dans du THF et/ou dans des hydrocarbures, caractérisé en ce qu'on fait réagir
    a) des donneurs complexants de sels de métaux variés et/ou nobles, séparément ou comme mélange, soit avec des tetraalkylammonium triorganohydroborates tels que définis dans la revendication 1, soit avec des triorganohydroborates de métaux alcalins ou alcalinoterreux dans du THF et/ou des hydrocarbures, ou
    b) des sels de métaux variés et/ou nobles seuls ou comme mélange avec des tetra-alkylammonium triorganohydroborates, tels que définis dans la revendication 1, dans du THF.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce qu'on met en oeuvre, comme sels métalliques en suspension ou dissous, séparément ou comme mélange, dans des solvants organiques, ceux des métaux des 5ème au 12ème et 14ème groupe de la classification périodique des éléments et que la réaction s'effectue avec des hydrures métalliques MHx (x = 1,2) du 1er et/ou du 2ème groupe de la classification périodique des éléments en présence de l'agent complexant entre -30°C et +150°C, de préférence de 0°C à + 80°C.
  4. Procédé selon la revendication 1 ou 3, caractérisé en ce que les sels métalliques sont ajoutés sous forme de complexants donneurs.
  5. Procédé selon les revendications 1 à 4, caractérisé en ce que les sels métalliques sont mis en réaction avec des hydrures métalliques et une hypodose de l'agent complexant.
  6. Procéde selon les revendications 1 à 5, caractérisé en ce que l'agent complexant est régénéré par acidification sous forme de BR₃ et/ou BRn(OR')3-n.
  7. Procédé selon les revendications 1 à 6, caractérisé en ce que la réduction s'effectue en présence de substances porteur.
  8. Procédé selon les revendications 2 et 7, caractérisé en ce qu'on prépare les métaux et/ou alliages dissous sous forme colloïdale dans du THF ou des hydrocarbures en présence de substances porteur organiques et anorganiques et/ou qu'on les lie par adsorption avec ces porteurs.
  9. Solutions colloïdales de métaux et/ou d'alliages dans du THF et/ou des hydrocarbures, obtenues selon les revendications 2, 7 et 8.
  10. Poudres métalliques obtenues selon la revendication 1 ou 2, avec la granulométrie 0,01 à 200 »m, qui sont microcristallines à amorphes d'après leur diagramme de diffraction des rayons X et ont une teneur de bore inférieure à 1% en poids.
  11. Poudres d'alliage métalliques obtenues selon la revendication 1 ou 2, avec la granulométrie 0,01 à 200 »m, qui sont microcristallines à amorphes d'après leur diagramme de diffraction diffus des rayons X et ont une teneur de bore inférieure à 1% en poids.
  12. Utilisation de poudres métalliques et/ou d'alliages microcristallines à amorphes selon les revendications 10 et 11 dans la technologie des poudres.
  13. Utilisation de poudres Pt microcristallines à amorphes ayant la granulométrie 2 à 200 »m, obtenues selon la revendication 1 ou 2, pour le revêtement des verres et de la céramique par la métallurgie des poudres.
  14. Utilisation d'alliages Fe-Ni-Co microcristallins à amorphes obtenus selon la revendication 1 ou 2 pour la métallisation des verres par la métallurgie des poudres.
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
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
DE3934351 1989-10-14

Publications (2)

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

Family

ID=6391482

Family Applications (1)

Application Number Title Priority Date Filing Date
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

Country Status (9)

Country Link
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 (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19756880A1 (de) * 1997-12-19 1999-07-01 Degussa Anodenkatalysator für Brennstoffzellen mit Polymerelektrolyt-Membranen
US7713910B2 (en) 2004-10-29 2010-05-11 Umicore Ag & Co Kg Method for manufacture of noble metal alloy catalysts and catalysts prepared therewith

Families Citing this family (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US5507973A (en) * 1991-04-26 1996-04-16 Board Of Regents Of The University Of Nebraska Highly reactive zerovalent metals from metal cyanides
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
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
WO1993005877A1 (fr) * 1991-09-25 1993-04-01 Research Corporation Technologies, Inc. Synthese sonochimique de metaux amorphes
ES2140733T3 (es) * 1995-05-26 2000-03-01 Goldschmidt Ag Th Proceso para la preparacion de polvo metalico amorfo a los rayos x y nanocristalino.
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
DE19806167A1 (de) * 1998-02-14 1999-08-19 Studiengesellschaft Kohle Mbh Edelmetall-geschützte, antikorrosive magnetische Nanokolloide
DE19821968A1 (de) * 1998-05-18 1999-11-25 Studiengesellschaft Kohle Mbh Verfahren zur Modifizierung der Dispergiereigenschaften von metallorganisch-prästabilisierten bzw. -vorbehandelten Nanometallkolloiden
US6262129B1 (en) * 1998-07-31 2001-07-17 International Business Machines Corporation Method for producing nanoparticles of transition metals
DE19853123A1 (de) * 1998-11-18 2000-05-25 Degussa Verfahren zur selektiven katalytischen Hydrierung von Fettsäuren
US7192778B2 (en) * 1999-10-06 2007-03-20 Natan Michael J Surface enhanced spectroscopy-active composite nanoparticles
US8497131B2 (en) * 1999-10-06 2013-07-30 Becton, Dickinson And Company Surface enhanced spectroscopy-active composite nanoparticles comprising Raman-active reporter molecules
KR100423030B1 (ko) * 2000-03-13 2004-03-12 캐논 가부시끼가이샤 재충전가능한 리튬배터리용 전극재료의 제조방법, 재충전가능한 리튬배터리의 전극구조체, 상기 전극구조체의 제조방법, 상기 전극구조체를 사용한 재충전 가능한 리튬배터리, 및 상기 재충전가능한 리튬배터리의 제조방법
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
US6861263B2 (en) * 2001-01-26 2005-03-01 Surromed, Inc. Surface-enhanced spectroscopy-active sandwich nanoparticles
US7282710B1 (en) 2002-01-02 2007-10-16 International Business Machines Corporation Scanning probe microscopy tips composed of nanoparticles and methods to form same
US6897650B2 (en) * 2002-02-11 2005-05-24 International Business Machines Corporation Magnetic-field sensor device
DE10227779A1 (de) * 2002-06-21 2004-01-08 Studiengesellschaft Kohle Mbh Monodisperse, magnetische Nanokolloide einstellbarer Größe und Verfahren zu deren Herstellung
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
JP4647906B2 (ja) * 2003-12-15 2011-03-09 日本板硝子株式会社 金属担持体の製造方法及び金属担持体。
JP2006218346A (ja) * 2005-02-08 2006-08-24 Honda Motor Co Ltd 水素吸着材及びその製造方法
US20070122620A1 (en) * 2005-11-02 2007-05-31 General Electric Company Nanoparticle-based imaging agents for x-ray / computed tomography and methods for making same
US9149545B2 (en) * 2005-11-02 2015-10-06 General Electric Company Nanoparticle-based imaging agents for X-ray/computed tomography and methods for making same
JP2009523406A (ja) * 2005-11-15 2009-06-25 オクソニカ・インコーポレーテッド 生体剤（ｂｉｏａｇｅｎｔｓ）の検出のためのＳＥＲＳに基づく方法
US8409863B2 (en) 2005-12-14 2013-04-02 Becton, Dickinson And Company Nanoparticulate chemical sensors using SERS
US7723100B2 (en) 2006-01-13 2010-05-25 Becton, Dickinson And Company Polymer coated SERS nanotag
EP1977242B1 (fr) * 2006-01-27 2016-08-03 Becton Dickinson and Company Immunoessai de flux latéral faisant intervenir des particules encapsulées en tant que modalite de détection
EP2044402B2 (fr) * 2006-07-24 2016-11-30 Becton Dickinson and Company Dispositif et procédé pour réaliser un dosage avec des particules magnétiques
US8003883B2 (en) 2007-01-11 2011-08-23 General Electric Company Nanowall solar cells and optoelectronic devices
US7977568B2 (en) * 2007-01-11 2011-07-12 General Electric Company Multilayered film-nanowire composite, bifacial, and tandem solar cells
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
US8772886B2 (en) * 2010-07-26 2014-07-08 Avalanche Technology, Inc. Spin transfer torque magnetic random access memory (STTMRAM) having graded synthetic free layer
EP3363538B1 (fr) 2017-02-20 2024-07-24 Technische Universität Berlin Procédé de préparation d'un matériau composite de carbone mésoporeux comportant des nanoparticules métalliques et usage dudit matériau comme catalyseur
EP4173701A1 (fr) 2021-10-29 2023-05-03 Technische Universität Berlin Procédé de fabrication de particule de carbone poreuse sphérique métallique

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0379062A2 (fr) * 1989-01-14 1990-07-25 Studiengesellschaft Kohle mbH Pigments aciculaires magnétiques du fer avec force coercitive ajustable et son procédé de fabrication, pigments métalliques du fer pour l'enregistrement magnétique avec force coercitive ajustable

Family Cites Families (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3180835A (en) * 1962-07-17 1965-04-27 California Research Corp Stable metal sols and method for producing the same
GB1047933A (en) * 1962-09-12 1966-11-09 Exxon Research Engineering Co Catalysts
FR2041076A1 (en) * 1969-03-15 1971-01-29 Stamicarbon Submicroscopic metallic particles in the - form of needles and capable of being perm
US3672867A (en) * 1970-12-07 1972-06-27 Du Pont Submicron ferromagnetic alloy particles containing cobalt,boron,and zinc
US3814696A (en) * 1972-06-19 1974-06-04 Eastman Kodak Co Colloidal metal in non-aqueous media
US4096316A (en) * 1973-08-18 1978-06-20 Fuji Photo Film Co., Ltd. Method of producing magnetic material with alkaline borohydrides
US4080177A (en) * 1975-04-17 1978-03-21 Winston Boyer Colloidal magnesium suspension in critical low concentration in jet fuel
JPS6018902A (ja) * 1983-07-13 1985-01-31 Toyota Motor Corp 磁性流体の製造方法
US4537625A (en) * 1984-03-09 1985-08-27 The Standard Oil Company (Ohio) Amorphous metal alloy powders and synthesis of same by solid state chemical reduction reactions
US4624797A (en) * 1984-09-17 1986-11-25 Tdk Corporation Magnetic fluid and process for preparing the same
DE3513132A1 (de) * 1985-04-12 1986-10-23 Peter Dr. 4000 Düsseldorf Faber Elektrochemisch aktive nickelmasse
US4877647A (en) * 1986-04-17 1989-10-31 Kansas State University Research Foundation Method of coating substrates with solvated clusters of metal particles
JPS6475601A (en) * 1987-09-18 1989-03-22 Tanaka Precious Metal Ind Fine composite silver-palladium powder and production thereof
EP0363552B1 (fr) * 1988-07-27 1993-10-13 Tanaka Kikinzoku Kogyo K.K. Procédé de fabrication de poudre métallique
EP0417253A1 (fr) * 1989-04-04 1991-03-20 Sri International Procede a basse temperature de formation de materiaux en utilisant un ou plusieurs agents de reaction metalliques et un agent de reaction contenant de l'halogene pour former un ou plusieurs intermediaires reactifs
US5034313A (en) * 1989-04-28 1991-07-23 Eastman Kodak Company Metastable metal colloids and preparation
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

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0379062A2 (fr) * 1989-01-14 1990-07-25 Studiengesellschaft Kohle mbH Pigments aciculaires magnétiques du fer avec force coercitive ajustable et son procédé de fabrication, pigments métalliques du fer pour l'enregistrement magnétique avec force coercitive ajustable

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19756880A1 (de) * 1997-12-19 1999-07-01 Degussa Anodenkatalysator für Brennstoffzellen mit Polymerelektrolyt-Membranen
US7713910B2 (en) 2004-10-29 2010-05-11 Umicore Ag & Co Kg Method for manufacture of noble metal alloy catalysts and catalysts prepared therewith
US8017548B2 (en) 2004-10-29 2011-09-13 Umicore Ag & Co. Kg Method for manufacture of noble metal alloy catalysts and catalysts prepared therewith

Also Published As

Publication number Publication date
IE903660A1 (en) 1991-04-24
US5580492A (en) 1996-12-03
US5308377A (en) 1994-05-03
IE67173B1 (en) 1996-03-06
JPH03134106A (ja) 1991-06-07
DE3934351A1 (de) 1991-04-18
CA2027257C (fr) 2001-05-29
DE59008929D1 (de) 1995-05-24
EP0423627A1 (fr) 1991-04-24
ATE121330T1 (de) 1995-05-15
ES2070970T3 (es) 1995-06-16
CA2027257A1 (fr) 1991-04-15
DK0423627T3 (da) 1995-09-04

Similar Documents

Publication Publication Date Title
EP0423627B1 (fr) 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
DE1467175C3 (de) Zeolithisches Molekularsieb
DE60037881T2 (de) Promovierter poröser katalysator
EP0490156B1 (fr) Procédé de préparation d'un système de stockage hydrure de magnésium-magnésium-hydrogène, accepteur d'hydrogène, actif et réversible
DE102007038045B4 (de) Verfahren zur Herstellung eines Palladium/Kohle-Katalysators
EP0112548B1 (fr) Procédé pour la production de systèmes actifs pour l'emmagasinage de l'hydrogène par hydrures de magnésium
EP0151991B1 (fr) Composés ammonium-organopolysiloxanes contenant du platine et/ou du palladium, procédé pour leur fabrication et utilisation
DE3347677C2 (de) Verfahren zur Herstellung eines Katalysators
DE3347676C2 (fr)
WO2005087374A1 (fr) Preparation de catalyseurs supportes a base de metal/oxyde metallique par nanometallurgie des produits chimiques precurseurs dans des chambres de reaction definies de supports poreux au moyen de precurseurs organometalliques et/ou inorganiques et d'agents de reduction metalliques
EP0911079A2 (fr) Catalyseurs supportés présentant une résistance améliorée au frittage et leur méthode de préparation
DE2748210A1 (de) Teilchen von legierungen von platinmetallen mit nichtplatinmetallen, verfahren zu ihrer herstellung und ihre verwendung
DE69024884T2 (de) Verfahren zur Herstellung von feinem Kupferpulver
US4454246A (en) Highly dispersed supported group VIII noble metal phosphorus compounds
EP1299191B1 (fr) Catalyseurs de nickel metalliques d'hydrogenation, leur production et leur utilisation
DE3687447T2 (de) Verfahren zur herstellung von feinverteilten metallpulvern.
DE102006013794A1 (de) Verfahren zur Herstellung kolloidaler Nanokatalysatoren
WO2009000526A1 (fr) Catalyseur colloïdal et procédé pour sa production
DE1297792B (de) Verfahren zum katalytischen Kracken eines Kohlenwasserstoffoels
DE4336829A1 (de) Verfahren zur Herstellung von dotierten Metall-Trägerkatalysatoren aus einem organischen oder anorganischen Trägermaterial und deren Verwendung
AT287156B (de) Dreidimensionales, kristallines, zeolithisches molekularsieb zum veredeln von kohlenwasserstoffen
EP0976450A1 (fr) Catalyseurs bimétalliques ruthenium/cuivre supportés présentant une résistance améliorée au frittage et leur méthode de préparation
EP4353869A2 (fr) Matériau inorganique particulaire comprenant de l'argent élémentaire et du ruthénium élémentaire
DE1145152B (de) Verfahren zur Herstellung von metallbeladenen zeolithischen Molekularsieben
DE1302402C2 (de) Entwaessertes synthetisches zeolithisches molekularsieb

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL

17P Request for examination filed

Effective date: 19910518

17Q First examination report despatched

Effective date: 19930405

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE DK ES FR GB IT LI LU NL

REF Corresponds to:

Ref document number: 121330

Country of ref document: AT

Date of ref document: 19950515

Kind code of ref document: T

ET Fr: translation filed
REF Corresponds to:

Ref document number: 59008929

Country of ref document: DE

Date of ref document: 19950524

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2070970

Country of ref document: ES

Kind code of ref document: T3

ITF It: translation for a ep patent filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19950710

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19970919

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 19970924

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19970925

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19970926

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19971003

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19971010

Year of fee payment: 8

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19971021

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981012

Ref country code: DK

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981012

Ref country code: AT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981012

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF THE APPLICANT RENOUNCES

Effective date: 19981013

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981031

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981031

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19981031

BERE Be: lapsed

Owner name: STUDIENGESELLSCHAFT KOHLE M.B.H.

Effective date: 19981031

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19990501

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 19990501

REG Reference to a national code

Ref country code: DK

Ref legal event code: EBP

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20001102

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20020925

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20021009

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20021017

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20031012

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040501

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20031012

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20040630

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20051012