EP0319786B1 - Procédé pour la préparation de poudre secondaire à structure nanocristalline et à surface fermée - Google Patents

Procédé pour la préparation de poudre secondaire à structure nanocristalline et à surface fermée Download PDF

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Publication number
EP0319786B1
EP0319786B1 EP88119570A EP88119570A EP0319786B1 EP 0319786 B1 EP0319786 B1 EP 0319786B1 EP 88119570 A EP88119570 A EP 88119570A EP 88119570 A EP88119570 A EP 88119570A EP 0319786 B1 EP0319786 B1 EP 0319786B1
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EP
European Patent Office
Prior art keywords
secondary powder
powder particles
produced
composition
amorphous
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
EP88119570A
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German (de)
English (en)
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EP0319786A1 (fr
Inventor
Hans Dr-Ing. Grewe
Wolfgang Dr. Schlump
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.)
Fried Krupp AG Hoesch Krupp
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Fried Krupp AG Hoesch Krupp
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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
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • B22F9/004—Making metallic powder or suspensions thereof amorphous or microcrystalline by diffusion, e.g. solid state reaction
    • B22F9/005—Transformation into amorphous state by milling
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy

Definitions

  • the invention relates to a method for producing secondary powder particles with a nanocrystalline structure and with a sealed particle surface.
  • Materials with a nanocrystalline structure can be produced in such a way that crystals with a diameter of a few nanometers are compacted into a solid under high pressure (a few MPa). Basically, all methods of powder production are suitable with which sufficiently small crystals with a "clean" surface can be realized.
  • the problem is solved for powder mixtures whose composition tends to set amorphous structure, surprisingly by exposing the starting powder to high mechanical stress of at least 12 g at room temperature under neutral or reducing atmosphere over a longer period of time.
  • the composition is chosen such that, according to the corresponding metastable phase diagram, a multiphase region between the amorphous and crystalline phase is present in the secondary powder to be produced at a suitable temperature at this composition.
  • the duration for the production of the secondary powder is determined according to transmission electro-microscopic recordings (TEM); The desired final state is only achieved if these only have crystallites with a diameter of ⁇ 10 nm.
  • the starting powders are subjected to a grinding process, excessive heating must be avoided, since otherwise the metastable amorphous phase will not be preserved; so that the desired nanocrystalline structure forms, on the other hand, the grinding process must not be too slow.
  • the process can be carried out in particular using commercially available starting powders with a particle size between 2 and 250 ⁇ m.
  • the starting powder can consist of metallic materials, of materials with a metal character and of ceramic materials with several components.
  • the process can also be carried out using binary or multiphase substances which consist of at least one element from the group Y, Ti, Zr, Hf, Nb, Mo, Ta, W with at least one element from the group V, Cr, Mn, Fe, Co, Ni, Cu, Pd and optionally at least one accompanying element such as Si, Ge, B and / or oxides, nitrides, borides, carbides and their possible mixed crystals exist, the selected constituents in pure form or as master alloys in the manner mentioned above are mixed as a powder (claim 2 or 3).
  • the required high mechanical stress can be caused by cold working or by high-energy grinding (claim 4 or 5), the latter for example by impact grinding, especially in an attritor.
  • the specific surface area of the secondary powder particles produced according to the invention does not increase with the milling time, but remains the same size or decreases slightly, ie the sealing is gas-tight and there are no inner surfaces in the area of the nanocrystalline structural components which are accessible to the gases of the surrounding atmosphere.
  • the surfaces in the nanocrystalline area remain "clean"; the chemical resistance is unexpectedly high because the small crystallites are embedded in an amorphous phase.
  • the powder mixture used consists of 70% by weight of commercially available Ti powder (FSSS: 28 ⁇ m) and 30% by weight of commercially available Ni powder (FSSS: 4.7 ⁇ m).
  • the two powders are first mixed over a period of one hour in a (Turbula) mixer and then ground in a horizontally lying attritor; the powder batch weight is 1000 g. Grinding is carried out at an agitator arm speed of 200 rpm. over a period of 90 hours using rolling bearing balls with a diameter of approximately 6 mm and a mass ratio between balls and powder mixture of 20: 1.
  • the time required for the grinding process can be significantly reduced by using larger grinding units (batch use: 10 kg).
  • the measurement of the specific surface of a Ti / Ni powder mixture with 70/30 mass% according to the BET method gives the following values (depending on the grinding time): 0.152 m2 / g (0 h) or 0.140 m2 / g (90 h) or 0.137 m2 / g (180 h): The surprisingly, the specific surface decreases slightly with the grinding time.
  • FIG. 2a to 2c show the results of experiments in which 50 mg of the Ti / Ni powder with 70/30 mass% have been introduced into a 1N HNO3 solution, at 30 ° C (Fig. 2a) or 40 ° C (Fig. 2b) or 50 ° C (Fig. 2c).
  • the detached amount of Ni is shown as a function of time for powders obtained with different grinding times; These were first mixed in the Turbula mixer over a period of one hour and then ground in the attritor for 0 h - 180 h.
  • the diagrams in question show that the amount of Ni removed takes on significantly lower values as the grinding time increases. After a grinding time of 36 hours, the secondary powder produced shows a considerably higher chemical resistance than the untreated starting powder mixture.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
  • Carbon And Carbon Compounds (AREA)

Claims (5)

  1. Procédé pour la préparation de particules de poudre secondaire comportant une structure nanocristalline et une surface fermée, à partir de poudre comportant au moins deux matériaux des groupes des métaux, des combinaisons à caractère métallique et des matériaux céramiques, pour former une composition qui tend à créer des fractions de structure amorphes, les poudres étant mélangées de telle façon que, d'après le diagramme de phases métastables correspondant, on se trouve, dans la poudre secondaire à préparer, en présence d'un domaine multiphase entre phase amorphe et phase cristalline, à la température appropriée pour cette combinaison, et le mélange étant soumis à une sollicitation mécanique élevée d'au moins 12 g jusqu'à ce qu'il se soit produit des particules de poudre secondaire, comportant des cristallites, dans le domaine de quelques micromètres, pour lesquelles on ne puisse déceler au microscope électronique que des diamètres inférieurs à 10 nm.
  2. Procédé pour la préparation de particules de poudre secondaire à structure nanocristalline et à surface fermée, à partir de matériaux binaires ou multiphases, qui, à partir d'au moins l'un des éléments Y, Ti, Zr, Hf, Nb, Mo, Ta et W et au moins l'un des éléments V, Cr, Mn, Fe, Co, Ni, Cu et Pd, constituent une composition qui tend à créer des fractions de structure amorphes, les éléments choisis sous forme pure ou sous la forme de préalliages étant mélangés sous forme de poudre de telle façon que, d'après le diagramme de phases métastables correspondant, on se trouve, dans la poudre secondaire à préparer, en présence d'un domaine multiphase entre phase amorphe et phase cristalline à la température appropriée pour cette combinaison, et le mélange étant soumis à une sollicitation mécanique élevée d'au moins 12 g jusqu'à ce qu'il se soit produit des particules de poudre secondaire, comportant des cristallites, dans le domaine de quelques micromètres, pour lesquelles on ne puisse déceler au microscope électronique que des diamètres inférieurs à 10 nm.
  3. Procédé pour la préparation de particules de poudre secondaire à structure nanocristalline et à surface fermée, à partir de matériaux binaires ou multiphases, qui, à partir d'au moins l'un des éléments Y, Ti, Zr, Hf, Nb, Mo, Ta et W avec au moins l'un des éléments V, Cr, Mn, Fe, Co, Ni, Cu et Pd, et au moins un élément d'accompagnement comme Si, Ge, B et/ou des oxydes, nitrures, borures carbures ainsi que leurs solutions solides possibles, constituent une combinaison qui tend à créer des fractions de structure amorphes, les éléments choisis sous forme pure ou sous la forme de préalliages étant mélangés sous forme de poudre de telle façon que, d'après le diagramme de phases métastables correspondant, on se trouve, dans la poudre secondaire à préparer, en présence d'un domaine multiphase entre phase amorphe et phase cristalline à la température appropriée pour cette combinaison, et le mélange étant soumis à une sollicitation mécanique élevée d'au moins 12 g jusqu'à ce qu'il se soit produit des particules de poudre secondaire, comportant des cristallites, dans le domaine de quelques micromètres, pour lesquelles on ne puisse déceler au microscope électronique que des diamètres inférieurs à 10 nm.
  4. Procédé suivant les revendications 1 à 3, caractérisé en ce que la sollicitation mécanique élevée est produite par matriçage à froid.
  5. Procédé suivant les revendications 1 à 3, caractérisé en ce que la sollicitation mécanique élevée est produite par broyage à haute énergie.
EP88119570A 1987-12-04 1988-11-24 Procédé pour la préparation de poudre secondaire à structure nanocristalline et à surface fermée Expired - Lifetime EP0319786B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE3741119 1987-12-04
DE19873741119 DE3741119A1 (de) 1987-12-04 1987-12-04 Erzeugung von sekundaerpulverteilchen mit nanokristalliner struktur und mit versiegelten oberflaechen

Publications (2)

Publication Number Publication Date
EP0319786A1 EP0319786A1 (fr) 1989-06-14
EP0319786B1 true EP0319786B1 (fr) 1993-10-27

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EP88119570A Expired - Lifetime EP0319786B1 (fr) 1987-12-04 1988-11-24 Procédé pour la préparation de poudre secondaire à structure nanocristalline et à surface fermée

Country Status (5)

Country Link
US (1) US5149381A (fr)
EP (1) EP0319786B1 (fr)
JP (1) JPH01208401A (fr)
CA (1) CA1320940C (fr)
DE (1) DE3741119A1 (fr)

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WO1990007012A1 (fr) * 1988-12-22 1990-06-28 The University Of Western Australia Procede de production de metaux, d'alliages et de matieres ceramiques
EP0406580B1 (fr) * 1989-06-09 1996-09-04 Matsushita Electric Industrial Co., Ltd. Matériau composite et son procédé de préparation
DE4110543A1 (de) * 1991-03-30 1992-10-01 Pm Hochtemperatur Metall Gmbh Oxiddispersionsgehaertete ausscheidungshaertbare nickel-chromlegierung
US5877437A (en) * 1992-04-29 1999-03-02 Oltrogge; Victor C. High density projectile
JP2892231B2 (ja) * 1992-09-16 1999-05-17 健 増本 Ｔｉ−Ｓｉ−Ｎ系複合硬質膜及びその製造方法
US5433797A (en) * 1992-11-30 1995-07-18 Queen's University Nanocrystalline metals
US5984996A (en) * 1995-02-15 1999-11-16 The University Of Connecticut Nanostructured metals, metal carbides, and metal alloys
US6033624A (en) * 1995-02-15 2000-03-07 The University Of Conneticut Methods for the manufacturing of nanostructured metals, metal carbides, and metal alloys
US5589011A (en) * 1995-02-15 1996-12-31 The University Of Connecticut Nanostructured steel alloy
JP2899682B2 (ja) * 1996-03-22 1999-06-02 科学技術庁金属材料技術研究所長 Ｔｉ−Ｎｉ系形状記憶合金とその製造方法
US6933331B2 (en) 1998-05-22 2005-08-23 Nanoproducts Corporation Nanotechnology for drug delivery, contrast agents and biomedical implants
US5905000A (en) * 1996-09-03 1999-05-18 Nanomaterials Research Corporation Nanostructured ion conducting solid electrolytes
JPH10218700A (ja) * 1997-02-07 1998-08-18 Natl Res Inst For Metals 合金系ナノ結晶集合体とその製造方法
DE69805553T2 (de) * 1998-09-30 2002-12-19 Hydro-Quebec Corp., Montreal Herstellung von nanokristallinen legierungen durch mechanisches legieren bei erhöhten temperaturen
US6472632B1 (en) 1999-09-15 2002-10-29 Nanoscale Engineering And Technology Corporation Method and apparatus for direct electrothermal-physical conversion of ceramic into nanopowder
US6600127B1 (en) 1999-09-15 2003-07-29 Nanotechnologies, Inc. Method and apparatus for direct electrothermal-physical conversion of ceramic into nanopowder
US6855426B2 (en) 2001-08-08 2005-02-15 Nanoproducts Corporation Methods for producing composite nanoparticles
US7708974B2 (en) 2002-12-10 2010-05-04 Ppg Industries Ohio, Inc. Tungsten comprising nanomaterials and related nanotechnology
US6858173B2 (en) * 2003-01-30 2005-02-22 The Regents Of The University Of California Nanocrystalline ceramic materials reinforced with single-wall carbon nanotubes
US7556982B2 (en) * 2003-08-07 2009-07-07 Uchicago Argonne, Llc Method to grow pure nanocrystalline diamond films at low temperatures and high deposition rates
DE102010050771B4 (de) * 2010-11-10 2014-05-08 Schott Ag Erzeugnis aus Glas oder Glaskeramik mit hochtemperaturstabiler Niedrigenergie-Schicht, Verfahren zur Herstellung derselben und Verwendung des Erzeugnisses

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EP0288785A2 (fr) * 1987-04-29 1988-11-02 Fried. Krupp AG Hoesch-Krupp Procédé de préparation de matériau ayant une structure nanocristalline

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Also Published As

Publication number Publication date
JPH01208401A (ja) 1989-08-22
CA1320940C (fr) 1993-08-03
DE3741119A1 (de) 1989-06-15
EP0319786A1 (fr) 1989-06-14
US5149381A (en) 1992-09-22

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