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EP0339366A1 - Process for preparing a metal-metalloid powder with a very fine to nanocrystalline structure - Google Patents

Process for preparing a metal-metalloid powder with a very fine to nanocrystalline structure Download PDF

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Publication number
EP0339366A1
EP0339366A1 EP89106477A EP89106477A EP0339366A1 EP 0339366 A1 EP0339366 A1 EP 0339366A1 EP 89106477 A EP89106477 A EP 89106477A EP 89106477 A EP89106477 A EP 89106477A EP 0339366 A1 EP0339366 A1 EP 0339366A1
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Prior art keywords
metal
metalloid
powder
metals
grinding
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German (de)
French (fr)
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EP0339366B1 (en
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Hans Dr. Ing. Grewe
Wolfgang Dr. Schlump
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Fried Krupp AG Hoesch Krupp
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Fried Krupp AG Hoesch Krupp
Fried Krupp AG
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • C22C1/057—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor with in situ formation of phases other than hard compounds by solid state reaction sintering, e.g. metal phase formed by reduction reaction
    • 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
    • B22F1/07—Metallic powder characterised by particles having a nanoscale microstructure
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/059—Making alloys comprising less than 5% by weight of dispersed reinforcing phases
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S75/00—Specialized metallurgical processes, compositions for use therein, consolidated metal powder compositions, and loose metal particulate mixtures
    • Y10S75/956—Producing particles containing a dispersed phase

Definitions

  • metal-metal metalloid powder the powder particles of which have the finest crystalline to nanocrystalline structure, are known from DE-OS 37 14 239.
  • the metal powders and metal metalloid powders of suitable particle size are ground with high energy.
  • the object of the present invention is to avoid the separate production of the metal metalloid powder.
  • the object is achieved in that the regrind in the initial state consists of metal powders and the metalloid elements C, B, Si, N, O and / or H are introduced into the regrind in a highly active form. Due to their physical state (e.g. gas under atmospheric pressure), the gaseous metalloids N, O, H are in a highly active form compared to the solids C, B, Si. This condition can be increased by a higher degree of dispersion, e.g. B. by using prettier Powder. The non-gaseous metalloids C, B, Si achieve a highly active form when they are transferred to a state with a high specific surface area, that is, when e.g. B. carbon is used in the form of lampblack.
  • Another or additional way of activating these metalloids is achieved by a high degree of disorder in the lattice of the solid components.
  • the high-energy grinding is converted into a reactive high-energy grinding.
  • the metal of the metal metalloid component reacts quantitatively with the metalloid during high-energy milling, so that after high-energy milling it only exists in the metal-metalloid compound.
  • the same result is achieved in the process of reactive high-energy grinding that has been achieved in the prior art by high-energy grinding of metal powder together with metal metalloid powder.
  • Reactive high-energy grinding in attritors or in planetary mills is particularly advantageous, in which grinding media (grinding balls) can be accelerated to at least 8 g.
  • the process is particularly favorable for those metals of the metal metalloid component whose enthalpy of formation with the relevant element from the group C, N, O, H, B and / or Si is noticeably negative at the process temperature which arises.
  • These include in particular the metals Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Si and Al.
  • a particularly fine-crystalline metal-metal-metalloid powder is obtained when the elements C, N, O, H, B and / or Si are only added to the regrind when metal alloys have already formed at least in part, as a result of which in the alloys due to the possible formation of compounds the reactivity of the metals for the formation of the metal metalloid component is reduced.
  • the result of the reactive milling process with respect to the metal metalloid is largely independent of the metal matrix, nickel or chromium according to Examples 1 and 2.
  • the resulting titanium carbide crystallites also become increasingly fine-grained, after all, in the final stage of the grinding process, only the finest-grained stoichiometric titanium carbide remains, that is becoming increasingly nanocrystalline.
  • the result after 48 hours is shown in the TEM image according to FIG. 4.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Nanotechnology (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)

Abstract

Es wird ein Verfahren zur Herstellung von Metall-Metallmetalloid-Pulver angegeben, dessen Pulverteilchen feinstkristalline bis nanokristalline Struktur haben, wobei die Metallmetalloid-Komponente aus einer oder mehreren Metallverbindungen mit einem oder mehreren Elementen der Gruppe C, N, O, H, B, Si besteht. Die Elemente C, N, O, H, B, Si werden soweit sie in der Metallmetalloid-Komponente auftreten, als hochaktive Komponenten ins Mahlgut, das aus Pulvern der Metalle der Metallmatrix und der Metalle der Metallmetalloid-Komponenten besteht, eingebracht.A process for the production of metal-metal metalloid powder is specified, the powder particles of which have very fine-crystalline to nanocrystalline structure, the metal-metaloid component consisting of one or more metal compounds with one or more elements from the group C, N, O, H, B, Si consists. The elements C, N, O, H, B, Si, as far as they occur in the metal metalloid component, are introduced as highly active components into the regrind, which consists of powders of the metals of the metal matrix and the metals of the metal metalloid components.

Description

Verfahren zur Herstellung von Metall-Metallmetalloid-Pulver, dessen Pulverteilchen feinstkristalline bis nanokristalline Struktur haben, sind nach der DE-OS 37 14 239 bekannt. Hierbei werden die Metall-Pulver und Metallmetalloid-Pulver von geeigneter Teilchengröße hochenergiegemahlen.Processes for the production of metal-metal metalloid powder, the powder particles of which have the finest crystalline to nanocrystalline structure, are known from DE-OS 37 14 239. Here, the metal powders and metal metalloid powders of suitable particle size are ground with high energy.

Aufgabe der vorliegenden Erfindung ist es, die gesonderte Herstellung des Metallmetalloid-Pulvers zu vermeiden.The object of the present invention is to avoid the separate production of the metal metalloid powder.

Erfindungsgemäß wird die Aufgabe nach Anspruch 1 dadurch gelöst, daß das Mahlgut im Ausgangszustand aus Metall -Pulvern besteht und die Metalloidelemente C, B, Si, N, O und/oder H in hochaktiver Form in das Mahlgut eingebracht werden. Die gasförmigen Metalloide N, O, H sind durch ihren Aggregatzustand (z. B. Gas unter Atmosphärendruck) verglichen mit den Festkörpern C, B, Si in jedem Fall in hochaktiver Form. Dieser Zustand kann noch erhöht werden durch einen höheren Dispersionsgrad, z. B. durch Verwendung spratziger Pulver. Die nicht gasförmigen Metalloide C, B, Si erreichen eine hochaktive Form, wenn sie in einen Zustand mit möglichst hoher spezifischer Oberfläche überführt werden, wenn also z. B. Kohlenstoff in der Form von Lampenruß eingesetzt wird. Eine andere oder zusätzliche Möglichkeit, diese Metalloide zu aktivieren, wird durch einen hohen Fehlordnungsgrad im Gitter der festen Komponenten erreicht. Bei Einsatz der hochaktiven Metalloide C, B, Si, N, O und/oder H wird das Hochenergiemahlen in ein reaktives Hochenergiemahlen überführt. Das Metall der Metallmetalloid-Komponente reagiert bei dem Hochenergiemahlen quantitativ mit dem Metalloid, so daß es nach dem Hochenergiemahlen nur noch in der Metallmetalloid-Verbindung existiert. Es wird also bei dem Prozeß des reaktiven Hochenergiemahlens das gleiche Ergebnis erreicht, das bisher nach dem Stand der Technik durch Hochenergiemahlen von Metallpulver zusammen mit Metallmetalloid-Pulver erzielt worden ist.According to the invention the object is achieved in that the regrind in the initial state consists of metal powders and the metalloid elements C, B, Si, N, O and / or H are introduced into the regrind in a highly active form. Due to their physical state (e.g. gas under atmospheric pressure), the gaseous metalloids N, O, H are in a highly active form compared to the solids C, B, Si. This condition can be increased by a higher degree of dispersion, e.g. B. by using prettier Powder. The non-gaseous metalloids C, B, Si achieve a highly active form when they are transferred to a state with a high specific surface area, that is, when e.g. B. carbon is used in the form of lampblack. Another or additional way of activating these metalloids is achieved by a high degree of disorder in the lattice of the solid components. When using the highly active metalloids C, B, Si, N, O and / or H, the high-energy grinding is converted into a reactive high-energy grinding. The metal of the metal metalloid component reacts quantitatively with the metalloid during high-energy milling, so that after high-energy milling it only exists in the metal-metalloid compound. The same result is achieved in the process of reactive high-energy grinding that has been achieved in the prior art by high-energy grinding of metal powder together with metal metalloid powder.

Besonders vorteilhaft ist das reaktive Hochenergiemahlen in Attritoren oder in Planetenmühlen, in denen Mahlkörper (Mahlkugeln) mindestens bis auf 8 g beschleunigt werden können.Reactive high-energy grinding in attritors or in planetary mills is particularly advantageous, in which grinding media (grinding balls) can be accelerated to at least 8 g.

Besonders günstig ist das Verfahren für solche Metalle der Metallmetalloid-Komponente, deren Bildungsenthalpie mit dem betreffenden Element aus der Gruppe C, N, O, H, B und/oder Si bei der sich einstellenden Prozeßtemperatur merklich negativ ist. Dazu gehören insbesondere die Metalle Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Si und Al.The process is particularly favorable for those metals of the metal metalloid component whose enthalpy of formation with the relevant element from the group C, N, O, H, B and / or Si is noticeably negative at the process temperature which arises. These include in particular the metals Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Si and Al.

Ein besonders feinstkristallines Metall-Metallmetalloid-Pulver erhält man, wenn die Elemente C, N, O, H, B und/oder Si erst dann dem Mahlgut zugefügt werden, wenn sich bereits zumindest teilweise Metallegierungen eingestellt haben, wodurch in den Legierungen infolge möglicher Verbindungsbildung die Reaktionsbereitschaft der Metalle für die Bildung der Metallmetalloid-Komponente verringert wird.A particularly fine-crystalline metal-metal-metalloid powder is obtained when the elements C, N, O, H, B and / or Si are only added to the regrind when metal alloys have already formed at least in part, as a result of which in the alloys due to the possible formation of compounds the reactivity of the metals for the formation of the metal metalloid component is reduced.

Im folgenden werden einige Beispiele zum Gegenstand der Erfindung aufgeführt, wobei die Strukturuntersuchungen und Phasenanalysen elektronenmikroskopisch erfolgt sind.Some examples of the subject matter of the invention are listed below, the structural investigations and phase analyzes being carried out using electron microscopy.

Beispiel 1example 1

Ausgangspulver Titan-Nickel-Pulver (70:30 Massen-%), Mahlvorgang an Luft unter Atmosphärendruck, Mahldauer 8 h in einer Planetenmühle mit 12 g Beschleunigung der Mahlkugeln. Die TEM-Aufnahme gemäß Fig. 1 zeigt die Struktur des hergestellten Pulvers. TiO hat sich quantitativ in metallischer Matrix gebildet. Die Aufnahme zeigt ein ein feinstkristallines Gefüge.Starting powder titanium-nickel powder (70:30 mass%), grinding process in air under atmospheric pressure, grinding time 8 hours in a planetary mill with 12 g acceleration of the grinding balls. 1 shows the structure of the powder produced. TiO has formed quantitatively in a metallic matrix. The picture shows a microcrystalline structure.

Beispiel 2Example 2

Ausgangspulver Titan-Chrom-Pulver (70:30 Massen-%), Mahlvorgang an Luft unter Atmosphärendruck, Mahldauer 24 h in einer Planetenmühle mit 12 g Beschleunigung der Mahlkugeln. Die TEM-Aufnahme gemäß Fig. 2 zeigt die Struktur des hergestellten Pulvers. Auch hier hat sich TiO quantitativ in metallischer Matrix gebildet.Starting powder titanium-chrome powder (70:30 mass%), grinding process in air under atmospheric pressure, grinding time 24 h in a planetary mill with 12 g acceleration of the grinding balls. 2 shows the structure of the powder produced. Here, too, TiO has formed quantitatively in a metallic matrix.

Das Ergebnis des reaktiven Mahlvorgangs bezüglich des Metallmetalloids ist nach den Beispielen 1 und 2 weitgehend unabhängig von der Metallmatrix, Nickel oder Chrom.The result of the reactive milling process with respect to the metal metalloid is largely independent of the metal matrix, nickel or chromium according to Examples 1 and 2.

Beispiel 3Example 3

Ausgangspulver Titan-Cobalt-Pulver (70:30 Massen-%), Mahlvorgang mit Stickstoff unter Atmoshärendruck, Mahldauer 90 h im Attritor mit 8 g Beschleunigung der Mahlkugeln. Als Ergebnis hat sich quantitativ Titannitrid gebildet. Die TEM-Aufnahme gemäß Fig. 3 zeigt Titannitrid in metallischer Matrix. Matrix und Nitridphase sind nanokristall in.Starting powder titanium cobalt powder (70:30 mass%), grinding process with nitrogen under atmospheric pressure, grinding time 90 h in the attritor with 8 g acceleration of the grinding balls. As a result, titanium nitride was formed quantitatively. 3 shows titanium nitride in a metallic matrix. Matrix and nitride phase are in nanocrystals.

Beispiel 4Example 4

Ausgangspulver Titan-Cobalt-Pulver mit Kohlenstoff in Form von Lampenruß (62:26,5:11,5 Massen-%), Mahldauer 48 h in einer Planetenmühle mit 12 g Beschleunigung der Mahlkugeln. Die hohe spezifische Oberfläche (35 bis 40 m²/g) weist den Ruß als hoch-aktive Komponente aus. Die Hochenergie-Beanspruchung des Mahlgutes während des Mahlens in der Planetenmühle führt im Anfangsstatium zur Ausbildung von relativ groben Titancarbiden (0,5 - 1 µm Kristallitgröße), die offensichtlich in bezug auf den Kohlenstoffgehalt unterstöchiometrisch sind. Im Fortgang des Mahlvorganges wird das Titan sowohl mit Cobalt legiert als auch zugleich feinkristalliner. Gleichzeitig werden die entstehenden Titancarbid-­Kristallite ebenfalls zunehmend feinkörniger, schließlich bleibt im Endstadium des Mahlprozesses nur noch feinstkörniges stöchiometrisches Titancarbid, das zunehmend nanokristallin wird. Das Ergebnis nach 48 h zeigt die TEM-Aufnahme gemäß Fig. 4.Starting powder titanium cobalt powder with carbon in the form of lampblack (62: 26.5: 11.5 mass%), grinding time 48 hours in a planetary mill with 12 g acceleration of the grinding balls. The high specific surface (35 to 40 m² / g) shows the soot as a highly active component. The high-energy stress on the ground material during grinding in the planetary mill leads in the initial stage to the formation of relatively coarse titanium carbides (0.5 - 1 µm crystallite size), which are obviously substoichiometric with regard to the carbon content. As the milling process progresses, the titanium is alloyed with cobalt as well as being more finely crystalline. At the same time, the resulting titanium carbide crystallites also become increasingly fine-grained, after all, in the final stage of the grinding process, only the finest-grained stoichiometric titanium carbide remains, that is becoming increasingly nanocrystalline. The result after 48 hours is shown in the TEM image according to FIG. 4.

Beispiel 5Example 5

Ausgangspulver Titan-Nickel-Kohlenstoff (62:26,5:11,5 Massen-%). Durch Vormahlen des Titan-Nickel-Pulvergemisches (ca. 48 h) wird die teilweise Bildung eines Legierungspulvers erreicht und damit die Reaktionsbereitschaft des Titans herabgesetzt. Sodann wird Kohlenstoff in Form von hoch-aktivem Lampenruß dem Mahlgut beigegeben und das Mahlgut wird weitere 90 h im Attritor gemahlen. Nach insgesamt ca. 130 h Hochenergie-Beanspruchung hat sich quantitativ feinst- bis nanokristallines Titancarbid in einer Nickelmatrix gebildet. Diese ist ebenfalls weitgehend nanokristallin. TEM-Aufname gemäß Fig. 5 zeigt das Ergebnis.Starting powder titanium-nickel-carbon (62: 26.5: 11.5 mass%). By pre-grinding the titanium-nickel powder mixture (approx. 48 h) the partial formation of an alloy powder is achieved and the titanium's willingness to react is reduced. Then carbon is added to the regrind in the form of highly active lampblack and the regrind is ground for a further 90 hours in the attritor. After a total of approx. 130 h of high energy exposure, quantitatively fine to nanocrystalline titanium carbide has formed in a nickel matrix. This is also largely nanocrystalline. 5 shows the result.

Beispiel 6Example 6

Ausgangspulver Wolfram-Cobalt-Nickel-Kohlenstoff (79,5:7, 95:7, 95:4,6 Massen-%), Mahldauer 90 h im Attritor mit 8 g Beschleunigung der Mahlkugeln. Der Kohlenstoff wurde wiederum in Form von hoch-aktivem Lampenruß zugegeben. Die TEM-Aufnahme gemäß Fig. 6 zeigt Carbide, die überwiegend nanokristallin sind.Starting powder tungsten-cobalt-nickel-carbon (79.5: 7, 95: 7, 95: 4.6 mass%), grinding time 90 h in the attritor with 8 g acceleration of the grinding balls. The carbon was again added in the form of highly active lampblack. 6 shows carbides which are predominantly nanocrystalline.

Claims (6)

1. Verfahren zur Herstellung eines Metall-Metallmetalloid-Pulvers, dessen Pulverteilchen feinstkristalline bis nannokristalline Struktur sowohl in der metallischen Matrix als auch in der Metallmetalloid-Komponente aufweisen, wobei die Metallmetalloid-Komponente aus einer oder mehreren Metallverbindungen mit einem oder mehreren Elementen der Gruppe C, N, O, H, B, Si als Metalloid besteht, durch Hochenergiemahlen,
dadurch gekennzeichnet, daß die Metalloide der Metallmetalloid-Komponenten als hochaktive Komponenten ins Mahlgut, das aus Pulvern der Metalle der Metallmatrix und der Metalle der Metallmetalloid-Komponenten besteht, eingebracht werden.1. A process for producing a metal-metal metalloid powder, the powder particles of which have the finest crystalline to nano-crystalline structure both in the metallic matrix and in the metal metalloid component, the metal metalloid component consisting of one or more metal compounds with one or more elements from group C , N, O, H, B, Si as a metalloid, by high-energy grinding,
characterized in that the metalloids of the metal metalloid components are introduced as highly active components into the regrind, which consists of powders of the metals of the metal matrix and the metals of the metal metalloid components. 2. Verfahren zur Herstellung eines Metall-Metallmetalloid-Pulvers nach Anspruch 1, dadurch gekennzeichnet, daß das Hochenergiemahlen in Attritoren, in Planetenmühlen oder in anderen Mühlen durchgeführt wird, in denen geeignete Mahlkörper (Mahlkugeln) auf mindestens 8 g beschleunigt werden.2. A method for producing a metal-metal metalloid powder according to claim 1, characterized in that the high-energy grinding is carried out in attritors, in planetary mills or in other mills in which suitable grinding media (grinding balls) are accelerated to at least 8 g. 3. Verfahren zur Herstellung eines Metall-Metallmetalloid-Pulvers nach den Ansprüchen 1 und 2, dadurch gekennzeichnet, daß die Metalle der Metallmetalloid-Komponente bezüglich der jeweils verwendeten Elemente C, N, O, H, B und/oder Si eine deutlich negative Bildungsenthalpie bei der sich einstellenden Prozeßtemperatur haben.3. Process for the production of a metal-metal metalloid powder according to the Claims 1 and 2, characterized in that the metals of the metal metalloid component with respect to the elements C, N, O, H, B and / or Si used have a clearly negative enthalpy of formation at the process temperature which arises. 4. Verfahren zur Herstellung eines Metall-Metallmetalloid-Pulvers nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß die Metalle der Metallmetalloid-Komponente Ti, Zr, Hf, V, Nb, Ta, Cr, Mo und/oder W sind.4. A method for producing a metal-metal metalloid powder according to claims 1 to 3, characterized in that the metals of the metal metalloid component are Ti, Zr, Hf, V, Nb, Ta, Cr, Mo and / or W. 5. Verfahren zur Herstellung eines Metall-Metallmetalloid-Pulvers nach den Ansprüchen 1 bis 3, dadurch gekennzeichnet, daß das Metall der Metallmetalloid-Komponente Aluminium und/oder Silicium ist.5. A method for producing a metal-metal metalloid powder according to claims 1 to 3, characterized in that the metal of the metal metalloid component is aluminum and / or silicon. 6. Verfahren zur Herstellung eines Metall-Metallmetalloid-Pulvers nach den Ansprüchen 1 bis 5, dadurch gekennzeichnet, daß die Elemente C, N, O, H, B und/oder Si in das Mahlgut eingebracht werden, wenn sich während des Hochenergie-Mahlens bei den Metallen Legierungsbildung eingestellt hat.6. A method for producing a metal-metal metalloid powder according to claims 1 to 5, characterized in that the elements C, N, O, H, B and / or Si are introduced into the regrind if during the high-energy grinding alloy formation in metals.
EP89106477A 1988-04-20 1989-04-12 Process for preparing a metal-metalloid powder with a very fine to nanocrystalline structure Expired - Lifetime EP0339366B1 (en)

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DE3813224 1988-04-20
DE3813224A DE3813224A1 (en) 1988-04-20 1988-04-20 METHOD FOR ADJUSTING FINE CRYSTALLINE TO NANOCRISTALLINE STRUCTURES IN METAL-METAL METALOID POWDER

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KR960014946B1 (en) * 1988-12-22 1996-10-21 더 유니버어스티 오브 웨스트런 오스트레일리아 Method for manufacturing metals, alloys and ceramic materials
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US5460701A (en) * 1993-07-27 1995-10-24 Nanophase Technologies Corporation Method of making nanostructured materials
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US5984996A (en) * 1995-02-15 1999-11-16 The University Of Connecticut Nanostructured metals, metal carbides, and metal alloys
US6193844B1 (en) 1995-06-07 2001-02-27 Mclaughlin John R. Method for making paper using microparticles
US5704556A (en) * 1995-06-07 1998-01-06 Mclaughlin; John R. Process for rapid production of colloidal particles
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US5968316A (en) * 1995-06-07 1999-10-19 Mclauglin; John R. Method of making paper using microparticles
US5935890A (en) 1996-08-01 1999-08-10 Glcc Technologies, Inc. Stable dispersions of metal passivation agents and methods for making them
US5900116A (en) 1997-05-19 1999-05-04 Sortwell & Co. Method of making paper
DE19758384C2 (en) * 1997-12-23 2002-08-01 Geesthacht Gkss Forschung Process for the production of nanocrystalline metal hydrides
US6086242A (en) * 1998-02-27 2000-07-11 University Of Utah Dual drive planetary mill
CA2341779A1 (en) * 2001-03-20 2002-09-20 Marco Blouin Inert electrode material in nanocrystalline powder form
US6970162B2 (en) * 2001-08-03 2005-11-29 Canon Kabushiki Kaisha Image display apparatus
US20070265354A1 (en) * 2004-10-21 2007-11-15 Canham Leigh T Silicon Structure
DE102006005225B3 (en) * 2006-01-26 2007-04-05 Technische Universität Dresden Titanium material and process for its preparation
US9150442B2 (en) 2010-07-26 2015-10-06 Sortwell & Co. Method for dispersing and aggregating components of mineral slurries and high-molecular weight multivalent polymers for clay aggregation
US8721896B2 (en) 2012-01-25 2014-05-13 Sortwell & Co. Method for dispersing and aggregating components of mineral slurries and low molecular weight multivalent polymers for mineral aggregation
KR101248996B1 (en) * 2012-10-10 2013-04-02 한국지질자원연구원 Production of carbide and carbonitride powders containing binder, and cermet therefrom

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2239535A1 (en) * 1973-08-02 1975-02-28 Vmw Ranshofen Berndorf Ag
US4623705A (en) * 1980-03-05 1986-11-18 Anic S.P.A. Process for synthesizing allyl carbonates by polyhydric alcohols and their derivatives
EP0203311A1 (en) * 1985-05-24 1986-12-03 Kernforschungszentrum Karlsruhe Gmbh Process for manufacturing articles with isotropic properties
EP0232772A1 (en) * 1986-02-05 1987-08-19 Siemens Aktiengesellschaft Process for preparing a pulverulent amorphous material by way of a milling process
US4737340A (en) * 1986-08-29 1988-04-12 Allied Corporation High performance metal alloys

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3167605D1 (en) * 1980-07-31 1985-01-17 Mpd Technology Dispersion-strengthened aluminium alloys
US4758273A (en) * 1984-10-23 1988-07-19 Inco Alloys International, Inc. Dispersion strengthened aluminum alloys
DE3525056A1 (en) * 1985-07-13 1987-01-22 Metallgesellschaft Ag METHOD FOR PRODUCING A MECHANICALLY ALLOYED COMPOSITE POWDER
US4624705A (en) * 1986-04-04 1986-11-25 Inco Alloys International, Inc. Mechanical alloying
DE3714239C2 (en) * 1987-04-29 1996-05-15 Krupp Ag Hoesch Krupp Process for the production of a material with a structure of nanocrystalline structure

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2239535A1 (en) * 1973-08-02 1975-02-28 Vmw Ranshofen Berndorf Ag
US4623705A (en) * 1980-03-05 1986-11-18 Anic S.P.A. Process for synthesizing allyl carbonates by polyhydric alcohols and their derivatives
EP0203311A1 (en) * 1985-05-24 1986-12-03 Kernforschungszentrum Karlsruhe Gmbh Process for manufacturing articles with isotropic properties
EP0232772A1 (en) * 1986-02-05 1987-08-19 Siemens Aktiengesellschaft Process for preparing a pulverulent amorphous material by way of a milling process
US4737340A (en) * 1986-08-29 1988-04-12 Allied Corporation High performance metal alloys

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
E. KLAR: "Metals handbook", 9. Auflage, Band 7, "Powder Metallurgy", Seiten 66-67 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5709786A (en) * 1992-11-17 1998-01-20 Robert Bosch Gmbh Sintered solid electrolyte having a high oxygen-ion conductivity
CN112342432A (en) * 2020-09-29 2021-02-09 中国科学院金属研究所 High-thermal-stability equiaxial nanocrystalline Ti-W alloy and preparation method thereof

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JPH01309901A (en) 1989-12-14
US5147449A (en) 1992-09-15
DE3813224A1 (en) 1988-08-25
DE58905300D1 (en) 1993-09-23

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