EP0319786A1 - 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
EP0319786A1
EP0319786A1 EP88119570A EP88119570A EP0319786A1 EP 0319786 A1 EP0319786 A1 EP 0319786A1 EP 88119570 A EP88119570 A EP 88119570A EP 88119570 A EP88119570 A EP 88119570A EP 0319786 A1 EP0319786 A1 EP 0319786A1
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EP
European Patent Office
Prior art keywords
secondary powder
nanocrystalline structure
powder
elements
nanocrystalline
Prior art date
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EP88119570A
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German (de)
English (en)
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EP0319786B1 (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
Fried Krupp AG
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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

  • 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).
  • all methods that enable the production of sufficiently small crystals with a "clean" surface are suitable for the production of nanocrystalline materials.
  • the chemical processes primarily involve the thermal decomposition of solid or gaseous compounds and the reduction of solid substances or metal ions in solutions.
  • a major disadvantage of many chemical manufacturing processes is that the free surface of the crystallites is covered with foreign atoms or molecules.
  • the problem is solved for powder mixtures which tend to set amorphous structural components in their composition, surprisingly by mechanical stressing of at least 12 g of commercial starting powder between 2 and 250 ⁇ m over a long period of time under a neutral or reducing atmosphere at room temperature.
  • the duration for the production of the secondary powder according to the invention is determined according to transmission electromicroscopic recordings (TEM).
  • TEM transmission electromicroscopic recordings
  • the state according to the invention for the secondary powder particles is only reached when these images only show crystallites ⁇ 10 mm. Strong heating must be avoided during the grinding process, since otherwise the metastable amorphous phase will not be preserved. On the other hand, the grinding process must not be too slow, since then no nanocrystalline structure will be formed.
  • a composition of the secondary powder is particularly advantageous in which, according to the corresponding metastable phase diagram at a suitable temperature, there is a multiphase region between the amorphous and the crystalline phase.
  • These secondary powder particles can be processed under the conditions of the surrounding atmosphere without special precautions.
  • the material made from these secondary powder particles compacted by known methods shows a nanocrystalline structure.
  • the method is suitable according to claim 1 for starting powder from metallic materials, from materials with a metal character and from ceramic materials with multiple components.
  • Binary or multiphase substances consisting of at least one element from the group Y, Ti, Zr, Hf, Mo, Nb, Ta, W and at least one element from the group V, Cr, Mn, Fe, Co, Ni, Cu, are particularly advantageous.
  • Pd without or with the addition of accompanying elements such as Si, Ge, B and / or oxides, nitrides, borides, carbides and their possible mixed crystals exist either in pure form or as corresponding master alloys of these groups.
  • the extreme degrees of deformation can be particularly advantageous by high energy milling e.g. can be achieved by impact grinding, particularly 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 or decreases slightly, that is to say that the seal is gas-tight and that there are no internal surfaces in the region 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 surprisingly high, since the small crystallites are embedded in an amorphous phase.
  • the object of the invention is illustrated using the example of a titanium-nickel powder mixture as the starting material.
  • the powder mixture consists of 70% by weight of commercially available Ti powder (FSSS 28 ⁇ m) and 30% by weight of commercially available nickel powder (FSSS 4.7 ⁇ m).
  • the Powders are first mixed in an (Turbula) mixer for one hour and then ground in a horizontally located attritor.
  • the powder batch weight is 1000 g.
  • the grinding takes place using rolling bearing balls with a diameter of approx. 6 mm.
  • the mass ratio of balls to powder is 20: 1.
  • the grinding time is 90 hours with a stirrer arm rotation of 200 rpm.
  • the grinding times can be significantly reduced by using larger grinding units (batch load 10 kg).
  • Fig. 1 and 2 show TEM images with a magnification of 200,000: 1 of Ti Ni secondary powder with 70/30 mass%.
  • the crystallites embedded in an amorphous phase are clearly visible on the images.
  • Fig. 1 shows the grinding result after 40 hours of grinding. Although the amorphous phase is already present here, some of the crystallites are still> 10 nm in size. At 90 hours milling time (Fig. 2), only crystallites ⁇ 10 nm can be seen.
  • the measurement of the specific surface of a Ti Ni powder with 70/30 mass% according to the BET method shows the following values: 0.152 m2 / g (0 h), 0.140 m2 / g (90 h), 0.137 m2 / g (180 h) .
  • the specific surface surprisingly decreases slightly with the grinding time.
  • Figures 3a to 3c show the results of tests in which 50 mg of the Ti Ni powder with 70/30 mass% in a 1 NHNo3 solution at 30 ° C (Fig. 3a), at 40 ° C (Fig. 3b) and at 50 ° C (Fig. 3c) were introduced.
  • the detached amount of Ni as a function of time is shown for powders with different grinding times were obtained.
  • the powders were first mixed in a Turbula mixer for 1 h and then ground in an attritor for 0 h - 180 h. It can be clearly seen that the detached amount of Ni becomes much smaller with longer grinding times. After 36 hours of grinding, the secondary powder shows significantly 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)
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 true EP0319786A1 (fr) 1989-06-14
EP0319786B1 EP0319786B1 (fr) 1993-10-27

Family

ID=6341878

Family Applications (1)

Application Number Title Priority Date Filing Date
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)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0507364A1 (fr) * 1991-03-30 1992-10-07 PM HOCHTEMPERATUR-METALL GmbH Alliage durcissable par precipitation à base de nickel-chrome durci par dispersion d'oxydes

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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
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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GB1298944A (en) * 1969-08-26 1972-12-06 Int Nickel Ltd Powder-metallurgical products and the production thereof
DE2412022A1 (de) * 1974-03-13 1975-09-25 Krupp Gmbh Verfahren zur herstellung hochwarmfester, dispersionsgehaerteter, aushaertbarer legierungen
EP0219582A1 (fr) * 1983-08-17 1987-04-29 Exxon Research And Engineering Company Poudre métallique composite renforcée par dispersion, et sa méthode de fabrication
EP0232772A1 (fr) * 1986-02-05 1987-08-19 Siemens Aktiengesellschaft Procédé de préparation d'un matériau pulvérulent amorphe par un procédé de broyage

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GB1298944A (en) * 1969-08-26 1972-12-06 Int Nickel Ltd Powder-metallurgical products and the production thereof
DE2412022A1 (de) * 1974-03-13 1975-09-25 Krupp Gmbh Verfahren zur herstellung hochwarmfester, dispersionsgehaerteter, aushaertbarer legierungen
EP0219582A1 (fr) * 1983-08-17 1987-04-29 Exxon Research And Engineering Company Poudre métallique composite renforcée par dispersion, et sa méthode de fabrication
EP0232772A1 (fr) * 1986-02-05 1987-08-19 Siemens Aktiengesellschaft Procédé de préparation d'un matériau pulvérulent amorphe par un procédé de broyage

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0507364A1 (fr) * 1991-03-30 1992-10-07 PM HOCHTEMPERATUR-METALL GmbH Alliage durcissable par precipitation à base de nickel-chrome durci par dispersion d'oxydes

Also Published As

Publication number Publication date
EP0319786B1 (fr) 1993-10-27
JPH01208401A (ja) 1989-08-22
CA1320940C (fr) 1993-08-03
DE3741119A1 (de) 1989-06-15
US5149381A (en) 1992-09-22

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