EP0659507B1 - Cobalt metal powder and composite sintered article made thereby - Google Patents

Cobalt metal powder and composite sintered article made thereby Download PDF

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Publication number
EP0659507B1
EP0659507B1 EP94119399A EP94119399A EP0659507B1 EP 0659507 B1 EP0659507 B1 EP 0659507B1 EP 94119399 A EP94119399 A EP 94119399A EP 94119399 A EP94119399 A EP 94119399A EP 0659507 B1 EP0659507 B1 EP 0659507B1
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metal powder
cobalt metal
cobalt
ppm
atomised
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German (de)
French (fr)
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EP0659507A1 (en
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Matthias Dr. Höhne
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HC Starck GmbH
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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
    • C22C1/0433—Nickel- or cobalt-based alloys
    • 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
    • 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
    • B22F1/05—Metallic powder characterised by the size or surface area of the particles
    • B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • 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
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/082—Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying atomising using a fluid
    • 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
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12049—Nonmetal component
    • Y10T428/12056—Entirely inorganic
    • 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
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12771—Transition metal-base component
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12931—Co-, Fe-, or Ni-base components, alternative to each other

Abstract

The invention relates to cobalt metal powders as a binder metal for the production of diamond and/or hard-metal tools and/or wear-resistant coatings and to composite sintered articles produced therefrom.

Description

Die vorliegende Erfindung betrifft Kobaltmetallpulver als Bindermetall für die Herstellung von Diamant- und/oder Hartmetallwerkzeugen und/oder Verschleißschutzbeschichtungen sowie daraus hergestellte Verbundsinterkörper.The present invention relates to cobalt metal powder as a binder metal for the Manufacture of diamond and / or hard metal tools and / or wear protection coatings and composite sintered bodies made therefrom.

Es ist bekannt, Kobaltmetallpulver durch Verdüsen des geschmolzenen Metalls herzustellen. Die JP-A 53-093 165 offenbart die Herstellung und Verwendung verdüsten Kobaltmetalls. Hierbei wird das Rohprodukt nach der Verdüsung durch Mahlen und Schocktempern nachbearbeitet, um ein gewünschtes hexagonal/kubisches Phasenverhältnis zu erreichen. Durch Mahlprozesse werden die Kobaltmetallpulver nicht nur verteuert, sondern auch zusätzlich verunreinigt.It is known to powder cobalt metal by atomizing the molten metal to manufacture. JP-A 53-093 165 discloses the manufacture and use atomize Cobalt metal. Here, the raw product after the atomization Milling and shock annealing post-processed to a desired hexagonal / cubic To achieve phase relationship. The cobalt metal powder is produced by grinding processes not only more expensive, but also contaminated.

Kobaltmetallpulver könen zwar durch Verdüsen aus der Schmelze recht kostengünstig hergestellt werden, diese Pulver sind jedoch als Bindermetalle, z.B. für die Herstellung von Diamantwerkzeugen völlig ungeeignet, da sie auf Grund der sphäroidischen Kornform und der Korngröße bei den anwendungsüblichen Sintertemperaturen zwischen 800-900°C keine dichten Verbundsinterteile von genügender Härte ergeben.Cobalt metal powders can be produced quite cheaply by atomization from the melt are produced, but these powders are available as binder metals, e.g. for the Manufacture of diamond tools completely unsuitable because of the spheroidal grain shape and grain size at the usual sintering temperatures between 800-900 ° C no dense composite sintered parts from result in sufficient hardness.

Hauptursache für die unzureichenden Gebrauchseigenschaften heißgepreßter Verbundsinterkörper aus verdüstem Kobaltmetallpulver ist die mangelnde Verpreßbarkeit der vorgepreßten Formkörper aufgrund der sphäroidischen Kornform, der relativ engen Korngrößenverteilung und der groben Primärpartikel (Fig. 2). Auch durch Heißpressen wird die notwendige Dichte von mindestens 8,5 g/cm3 nicht erreicht. The main reason for the inadequate performance properties of hot-pressed composite sintered bodies made of atomized cobalt metal powder is the lack of compressibility of the pre-pressed shaped bodies due to the spheroidal grain shape, the relatively narrow grain size distribution and the coarse primary particles (FIG. 2). The necessary density of at least 8.5 g / cm 3 is also not achieved by hot pressing.

Hingegen sind durch Wasserstoffreduktion von sauerstoffhaltigen Kobalt-Verbindungen bei erhöhter Temperatur als Matrixmaterial geeignete Kobaltmetallpulver mit einem FSSS-Wert von 3 bis 5 µm, sogenannte 400-mesh-Pulver (Fig. 1), erhältlich. Diese Bezeichnung erklärt sich aus dem Siebdurchgang dieser Pulver durch ein 400-mesh-Sieb. Derartige Pulver erfüllen Anforderungen, die an das Matrixmetall für Verbundwerkstoffe bezüglich Härte und Sinterdichte gestellt werden. Allerdings weisen die sogenannten 400-mesh-Pulver einen recht hohen Anteil an Verunreinigungen auf. Dabei ist allgemein bekannt, daß Aluminium, Kalzium, Natrium, Magnesium und Silizium leicht mit dem Sauerstoff des Kobaltmetallpulvers stabile Oxide bilden. Diese können in Diamantsegmenten eine unerwünschte Porosität verursachen.On the other hand, hydrogen reduction of oxygen-containing cobalt compounds suitable as matrix material at elevated temperature Cobalt metal powder with an FSSS value of 3 to 5 µm, so-called 400 mesh powder (Fig. 1) available. This designation is explained by the sieve passage this powder through a 400 mesh sieve. Such powders meet requirements that of the matrix metal for composite materials in terms of hardness and sintered density be put. However, the so-called 400-mesh powders are quite right high level of impurities. It is generally known that Aluminum, calcium, sodium, magnesium and silicon easily with the oxygen form stable oxides of the cobalt metal powder. These can be in diamond segments cause undesirable porosity.

Bei Hartmetallen können durch Porosität bedingt Festigkeitsverminderungen auftreten, wenn die oben genannten Verunreinigungen sowie Schwefel in zu hohen Mengen enthalten sind. In beiden Anwendungen sind daher Kobaltmetallpulver mit geringen Gehalten an Verunreinigungen erstrebenswert. Je nach Reinigungsaufwand in den metallurgischen Vorstufen kann die Reinheit der Kobaltmetallpulver den Erfordernissen angepaßt werden. Der Aufwand für die Herstellung besonders reiner Kobaltmetallpulver ist naturgemäß kostenintensiv und derartige Pulver sind demzufolge sehr teuer.Porosity can reduce the strength of hard metals, if the above impurities as well as sulfur in too high Amounts are included. Cobalt metal powder is therefore used in both applications low levels of impurities are desirable. Depending on the cleaning effort in the metallurgical precursors, the purity of the cobalt metal powder be adapted to requirements. The effort for the production Particularly pure cobalt metal powder is naturally expensive and such Powders are therefore very expensive.

Es ist nun Aufgabe dieser Erfindung, ein Kobaltmetallpulver zur Verfügung zu stellen, welches die Nachteile der beschriebenen Pulver nicht aufweisen.It is an object of this invention to provide a cobalt metal powder make, which do not have the disadvantages of the powder described.

Es wurde nun ein Kobaltmetallpulver gefunden, welches diese geforderten Eigenschaften aufweist Gegenstand dieser Erfindung ist ein Kobaltmetallpulver als Bindermetall für die Herstellung von Diamant- und/oder Hartmetallwerkzeugen und/oder Verschleißschutzbeschichtungen, welches dadurch gekennzeichnet ist, daß es zu 20 bis 80 Gew.-% aus einem verdüsten Kobaltmetallpulver mit optisch ermittelten Korngrößen von 5 bis 150 µm und dem zu 100 Gew.-% fehlenden Rest aus einem, gegebenenfalls agglomeriert vorliegenden, Kobaltmetallpulver einer optisch ermittelten Primärgröße von kleiner als 3 µm besteht. A cobalt metal powder was now found, which required this Properties This invention relates to a cobalt metal powder Binder metal for the production of diamond and / or hard metal tools and / or wear protection coatings, which is characterized by that it is 20 to 80 wt .-% of an atomized cobalt metal powder with optical determined grain sizes from 5 to 150 microns and the rest missing to 100 wt .-% from an optionally agglomerated cobalt metal powder optically determined primary size of less than 3 microns exists.

Das erfindungsgemäße Kobaltmetallpulver weist den preislichen Vorteil der aus Oxiden oder sauerstoffhaltigen Verbindungen durch Reduktion erhaltenes Kobaltmetallpulver auf, enthält aber deutlich geringere Mengen der obengenannten kritischen Verunreinigungen. Vorzugsweise enthält es weniger als 20 ppm Al, 20 ppm Ca, 30 ppm Na, 20 ppm Mg, 30 ppm S und 75 ppm Si.The cobalt metal powder according to the invention has the price advantage of Oxides or oxygen-containing compounds by reduction of cobalt metal powder obtained on, but contains significantly smaller amounts of the above critical contaminants. It preferably contains less than 20 ppm Al, 20 ppm Ca, 30 ppm Na, 20 ppm Mg, 30 ppm S and 75 ppm Si.

Beim erfindungsgemäßen Kobaltmetallpulver handelt es sich um eine Aufmischung von verdüstem Kobaltmetallpulver mit feinem Kobaltpulver aus der Wasserstoffreduktion.The cobalt metal powder according to the invention is a Mixing of atomized cobalt metal powder with fine cobalt powder from the Hydrogen reduction.

Die gute technische Eignung des erfindungsgemäßen Kobaltmetallpulvers setzt bereits bei einem Mischungsanteil von 20 Gew.-% an verdüstem feinen Kobaltmetallpulver aus der Waserstoffreduktion ein, unter dem Aspekt des Preisvorteils ist aber eine Obergrenze dieses Anteils bis zu 80 Gew.-% noch vertretbar. Das pulvermetallurgische Verhalten der Mischungen ist innerhalb der genannten Grenzen ebenfalls sehr vorteilhaft.The good technical suitability of the cobalt metal powder according to the invention sets even with a mixture proportion of 20% by weight of atomized fine cobalt metal powder from the reduction of hydrogen, taking into account the price advantage however, an upper limit of this proportion up to 80% by weight is still acceptable. The Powder metallurgical behavior of the mixtures is within the above Limits are also very advantageous.

Bevorzugt beträgt die Menge des verdüsten Kobaltmetallpulvers 30 bis 70 Gew.-%. Als verdüstes Kobaltmetallpulver sind sowohl ein wasserverdüstes Kobaltmetallpulver mit überwiegend sphäroidischem Habitus als auch ein gasverdüstes Kobaltmetallpulver mit sphäroidischem Habitus geeignet.The amount of atomized cobalt metal powder is preferably 30 to 70% by weight. The atomized cobalt metal powder is both a water atomized cobalt metal powder with predominantly spheroidal habit as well as a gas atomized Cobalt metal powder with spheroidal habit suitable.

Das Kobaltmetallpulver mit kristalliner Struktur weist bevorzugt BET-Oberflächen, bestimmt nach der Stickstoff-1-Punkt-Methode (DIN 66 131), von größer als 0,8 m2/g auf. Das erfindungsgemäße Kobaltmetallpulver weist in einer bevorzugten Ausführungsform eine Schüttdichte von kleiner als 1,4 kg/cm3 auf.The cobalt metal powder with a crystalline structure preferably has BET surface areas, determined by the nitrogen 1-point method (DIN 66 131), of greater than 0.8 m 2 / g. In a preferred embodiment, the cobalt metal powder according to the invention has a bulk density of less than 1.4 kg / cm 3 .

Durch die günstige Kornverteilung des erfindungsgemäßen Kobaltmetallpulvers wird eine Dichte nach dem Heißpressen von mindenstens 8,5 g/cm3 erreicht, womit eine hervorragende Verpreßbarkeit des Pulvers einhergeht. Eine weitere bevorzugte Ausführungsform des erfindungsgemäßen Kobaltmetallpulvers besteht darin, daß das Pulver eine Rockwell-Härte, gemessen an heißgepreßten Prüfplatten, von mindestens 98 HRB aufweist. Due to the favorable particle size distribution of the cobalt metal powder according to the invention, a density after hot pressing of at least 8.5 g / cm 3 is achieved, which is associated with excellent compressibility of the powder. A further preferred embodiment of the cobalt metal powder of the invention is that the powder has a Rockwell hardness, as measured on hot-pressed test plates, of at least 98 HR B has.

Das erfindungsgemäße Kobaltmetallpulver eignet sich hervorragend für die pulvermetallurgische Herstellung von Diamantwerkzeugen und/oder Hartmetallen, in denen das Kobalt - gegebenenfalls zusammen mit weiteren üblichen Matrix-Metallen - die Binderphase darstellt.The cobalt metal powder according to the invention is outstandingly suitable for powder metallurgy Manufacture of diamond tools and / or hard metals, in which the cobalt - optionally together with other customary matrix metals - represents the binder phase.

Gegenstand dieser Erfindung sind somit auch Verbundsinterkörper, hergestellt aus Hartstoffpulver und/oder Diamantpulver und Bindermetallen, wobei als Bindermetall, gegebenenfalls neben anderen Metallpulvern, das erfindungsgemäße Kobaltmetallpulver verwendet wird.This invention therefore also relates to composite sintered bodies produced from Hard material powder and / or diamond powder and binder metals, whereby as binder metal, optionally the cobalt metal powder according to the invention in addition to other metal powders is used.

Im folgenden wird die Erfindung beispielhaft erläutert, ohne daß hierzu eine Einschränkung zu sehen ist. In the following, the invention is explained by way of example, without any restriction you can see.

Beispiel 1: (Mischung 70/30)Example 1: (mixture 70/30)

0,7 kg eines feinen Kobaltmetallpulvers aus der Reduktion von Kobaltoxid mit Wasserstoff mit einer durchschnittlichen Korngröße von 1,7 µm, gesiebt über ein 63-µm-Sieb mit einer Schüttdichte von 1,2 g/cm3 (Fig. 1), wurde mit 0,3 kg eines wasserverdüsten Kobaltmetallpulvers (11,7µm FSSS), gesiebt über ein 38-µm-Sieb mit einer Schüttdichte von 3,3 g/cm3 (Fig. 2), eine Stunde lang im Turbula-Mischer gemischt. Das so hergestellte Produkt wies einen FSSS-Wert von 2,25 µm und ein Schüttgewicht von 0,73 g/cm3 auf. Der Gehalt an kritischen Verunreinigungen im Vergleich zu einem 400-mesh-Kobaltmetallpulver gemäß dem Stand der Technik war deutlich erniedrigt (Tab. 2).0.7 kg of a fine cobalt metal powder from the reduction of cobalt oxide with hydrogen with an average grain size of 1.7 μm, was sieved through a 63 μm sieve with a bulk density of 1.2 g / cm 3 (FIG. 1) mixed with 0.3 kg of a water-atomized cobalt metal powder (11.7 μm FSSS), sieved through a 38 μm sieve with a bulk density of 3.3 g / cm 3 (FIG. 2), in a Turbula mixer. The product produced in this way had an FSSS value of 2.25 μm and a bulk density of 0.73 g / cm 3 . The content of critical impurities compared to a 400-mesh cobalt metal powder according to the prior art was significantly reduced (Table 2).

Sintertest:Sinter test:

Das gemischte Pulver wurde für den Sinterversuch in eine runde Graphitform mit ca. 30 mm Durchmesser gefüllt und unter folgenden Bedingungen heißgepreßt:

Aufheizgradient:
180 K/min
Sintertemperatur:
830°C (in der Graphitform gemessen)
Sinterdruck:
350 N/mm2
Haltzeit:
3 min
The mixed powder was filled into a round graphite mold with a diameter of approx. 30 mm for the sintering test and hot pressed under the following conditions:
Heating gradient:
180 K / min
Sintering temperature:
830 ° C (measured in the graphite form)
Sinter printing:
350 N / mm 2
Stop time:
3 min

Das so erhaltende Prüfplättchen hat eine End-Dichte von 8,54 g/cm3 und eine Härte (Rockwell-B) von HRB = 101,6.The test plate obtained in this way has a final density of 8.54 g / cm 3 and a hardness (Rockwell-B) of HR B = 101.6.

Beispiel 2: (Mischung 60/40)Example 2: (Mix 60/40)

0,6 kg eines feinen Kobaltmetallpulvers mit einem BET-Wert von 1,11 m2/g, einer durchschnittlichen Korngröße von 1,7 µm (FSSS), gesiebt über ein 63-µm Sieb mit einer Schüttdichte von 1,2 g/cm3 (Fig. 1), wurden mit 0,4 kg eines wasserverdüsten Kobaltmetallpulvers (11,7 µm FSSS) mit einem BET-Wert von 0,73 m2/g, bestimmt nach der N2-1-Punkt-Methode (DIN 66 131), gesiebt über ein 38-µm-Sieb mit einer Schüttdichte von 3,3 g/cm3 (Fig. 2) in einem Pflugschar-Mischer 60 Minuten lang gemischt. Das so erhaltene Kobaltmetallpulver (Fig. 3) hatte einen FSSS-Wert von 2,6 µm, einen BET-Wert von 0,74 m2/g sowie ein Schüttgewicht von 0,8 g/cm3. Der Gehalt an chemischen Verunreinigungen ist gegenüber einem üblichen 400-mesh-Kobaltmetallpulver deutlich erniedrigt (Tab. 2).0.6 kg of a fine cobalt metal powder with a BET value of 1.11 m 2 / g, an average grain size of 1.7 µm (FSSS), sieved through a 63 µm sieve with a bulk density of 1.2 g / cm 3 (Fig. 1), were with 0.4 kg of a water-atomized cobalt metal powder (11.7 µm FSSS) with a BET value of 0.73 m 2 / g, determined by the N 2 -1-point method (DIN 66 131), sieved through a 38-µm sieve with a bulk density of 3.3 g / cm 3 (Fig. 2) mixed in a ploughshare mixer for 60 minutes. The cobalt metal powder obtained in this way (FIG. 3) had an FSSS value of 2.6 μm, a BET value of 0.74 m 2 / g and a bulk density of 0.8 g / cm 3 . The level of chemical impurities is significantly reduced compared to a conventional 400 mesh cobalt metal powder (Tab. 2).

Ein, wie bei Beispiel 1 beschriebenes, heißgepreßtes Probeplättchen wies eine Dichte von 8,54 g/cm3 und eine Härte von HRB = 101,2 auf. Fig. 4 zeigt deutlich, daß in der polierten und geätzten Probe noch große runde Kobaltpartikel neben feinen Primärkristallen erhalten geblieben sind.A hot-pressed test plate as described in Example 1 had a density of 8.54 g / cm 3 and a hardness of HR B = 101.2. Fig. 4 clearly shows that large round cobalt particles in addition to fine primary crystals have been preserved in the polished and etched sample.

Beispiel 3: (Mischung 50/50)Example 3: (Mix 50/50)

0,5 kg eines feinen Kobaltmetallpulvers, erhalten aus der Reduktion von Kobalthydroxid mit einer durchschnittlichen Korngröße von 0,9 µm, einem BET-Wert von 1,85 m2/g, gesiebt über ein 100-µm-Sieb (Schüttdichte 0,8 g/cm3), wurde mit 0,5 kg eines wasserverdüsten Kobaltmetallpulvers (11,7 µm FSSS) mit einem BET-Wert von 0,73 m2/g, gesiebt über ein 38-µm-Sieb (Schüttdiche 3,3 g/cm3), in einem "Turbula-Mischer" 15 Minuten lang gemischt. Die so entstandene Mischung hatte einen FSSS-Wert von 1,5 µm FSSS, einen BET-Wert von 1,06 m2/g bei einem Schüttgewicht von 0,8 g/cm3.0.5 kg of a fine cobalt metal powder, obtained from the reduction of cobalt hydroxide with an average grain size of 0.9 μm, a BET value of 1.85 m 2 / g, sieved through a 100 μm sieve (bulk density 0.8 g / cm 3 ), was sieved with 0.5 kg of a water-atomized cobalt metal powder (11.7 μm FSSS) with a BET value of 0.73 m 2 / g, through a 38 μm sieve (bulk density 3.3 g / cm 3 ), mixed in a "Turbula mixer" for 15 minutes. The resulting mixture had an FSSS value of 1.5 µm FSSS, a BET value of 1.06 m 2 / g with a bulk density of 0.8 g / cm 3 .

Aus einem heißgepreßten Probeplättchen entsprechend Beispiel 1 wurde eine Härte von HRB 100,4 und eine Dichte von 8,5 g/cm3 gemessen.A hardness of HR B 100.4 and a density of 8.5 g / cm 3 were measured from a hot-pressed sample plate according to Example 1.

Vergleichs-Beispiel 1 (100 % wasserverdüstes Kobaltmetallpulver < 63 µm):Comparative Example 1 (100% water-atomized cobalt metal powder <63 µm):

Reines wasserverdüstes Kobaltmetallpulver, gesiebt über ein 63- µm-Sieb, mit einem FSSS-Wert von 12 µm wurde gemäß Beispiel 1 heißgepreßt, wobei die Heißpreßtemperatur variiert wurde. An den so erhaltenen Prüfplättchen wurden folgende Härtewerte ermittelt:Pure water atomized cobalt metal powder, sieved through a 63 µm sieve, With an FSSS value of 12 μm was hot-pressed according to Example 1, the Hot pressing temperature was varied. On the test slides thus obtained following hardness values determined:

Sintertest mittels Heißpressen:Sintering test using hot pressing:

Aufheizgradient:Heating gradient:
180 K/min180 K / min
Sinterdruck:Sinter printing:
350 N/mm2 350 N / mm 2
Haltezeit:Holding time:
3 min3 min
Ergebnisse:Results:

SintertemperaturSintering temperature Härtewerte (HRB)Hardness values (HR B ) Dichtedensity 800°C800 ° C Preßkörper zerfällt, Härte nicht bestimmbarPress body disintegrates, hardness cannot be determined n.b.n.b. 850°C850 ° C 2525th 7,07.0 900°C900 ° C 4040 7,57.5 950°C950 ° C 4747 7,87.8

In keinem Fall gelang es, mit dem verdüsten Kobaltmetallpulver die geforderte Mindestdichte von 8,5 g/cm3 und die Mindesthärte von 98 HRB zu erreichen.In no case did the atomized cobalt metal powder achieve the required minimum density of 8.5 g / cm 3 and the minimum hardness of 98 HRB.

Beispiel 5 (100 % wasserverdüstes Kobaltmetallpulver < 38 µm):Example 5 (100% water-atomized cobalt metal powder <38 µm):

Reines wasserverdüstes Kobaltmetallpulver, gesiebt über ein 38- µm-Sieb (Fig. 2), mit einem FSSS-Wert von 11,8 µm wurde nach den unter Beispiel 1 beschriebenen Bedingungen heißgepreßt, wobei die Härte von HRB 80 an den Probeplättchen gemessen wurde.Pure water-atomized cobalt metal powder, sieved through a 38 μm sieve (FIG. 2), with an FSSS value of 11.8 μm, was hot-pressed according to the conditions described in Example 1, the hardness of HR B 80 being measured on the test platelets .

Auch bei dieser noch feineren Absiebung war es nicht möglich, die geforderte Mindestdichte und Mindesthärte zu erreichen.Even with this even finer screening, it was not possible to to achieve the required minimum density and minimum hardness.

In Tabelle 1 sind die Daten aus den Beispielen 1 bis 3 und die Vergleichsdaten zu dem 400-mesh-Kobaltpulver und dem verdüsten Pulver (gemäß Stand der Technik) zusammengefaßt. (Versuchsergebnisse aus dem Härtetest): Heißpreßtemperatur Sinterdichten/Rockwell-Härten (HRB) (°C) Verdüstes Co-Pulver Beispiel 5 Mischung aus Beispiel 1 (70/30) Mischung aus Beispiel 2 (60/40) Mischung aus Beispiel 3 (50/50) Co 400 mesh St.d.T. 830 8,1 g/cm3 8,54 g/cm3 8,54 g/cm3 8,5 g/cm3 8,45 80 HRB 101,6 HRB 101,2 HRB 100 HRB 97,7 HRB Table 1 summarizes the data from Examples 1 to 3 and the comparative data for the 400-mesh cobalt powder and the atomized powder (according to the prior art). (Test results from the endurance test): Hot pressing temperature Sintered densities / Rockwell hardness (HR B ) (° C) Atomized co-powder Example 5 Mixture from example 1 (70/30) Mixture from example 2 (60/40) Mixture from example 3 (50/50) Co 400 mesh St.dT 830 8.1 g / cm 3 8.54 g / cm 3 8.54 g / cm 3 8.5 g / cm 3 8.45 80 HR B 101.6 HR B 101.2 HR B 100 HR B 97.7 HR B

Vergleichsbeispiel (400 mesh-Pulver)Comparative example (400 mesh powder) Tabelle 2 : Vergleichsdaten kritischer Verunreinigungen in KobaltmetallpulvernTable 2: Comparative data of critical impurities in cobalt metal powders

Der Gehalt an kritischen Verunreinigungen war im Vergleich zu einem üblichen 400-mesh-Kobaltmetallpulver deutlich vermindert ( Tab. 2)The level of critical contaminants was compared to one usual 400-mesh cobalt metal powder significantly reduced (Tab. 2)

Verunreinigungen 400-mesh-Kobalt (400 mesh-Kobaltmetallpulver ("Cobalt Powder 400-mesh" der Fa. Hoboken Overpelt, Belgien)) und Mischungen gemäß den erfindungsgemäßen Beispielen 1, 2 und 3: Verunreinigungen 400 mesh-Co (100/0) Mischung Beispiel 1 (70/30) Mischung Beispiel 2 (60/40) Mischung Beispiel 3 (50/50) Al (ppm) 180 6 7 6 Ca (ppm) 320 12 12 13 Na (ppm) 55 25 22 9 Mg (ppm) 150 8 8 3 S (ppm) 140 13 14 15 Si (ppm) 310 34 36 41 Impurities 400-mesh cobalt (400-mesh cobalt metal powder ("Cobalt Powder 400-mesh" from Hoboken Overpelt, Belgium)) and mixtures according to Examples 1, 2 and 3 according to the invention: Impurities 400 mesh-Co (100/0) Mixture example 1 (70/30) Mixture example 2 (60/40) Mixture example 3 (50/50) Al (ppm) 180 6 7 6 Ca (ppm) 320 12th 12th 13 Na (ppm) 55 25th 22 9 Mg (ppm) 150 8th 8th 3rd S (ppm) 140 13 14 15 Si (ppm) 310 34 36 41

Claims (9)

  1. A cobalt metal powder as binder metal for the production of diamond tools and/or hard metal tools and/or wear-resistant coatings, characterised in that 20 to 80 wt.% of the powder consists of an atomised cobalt metal powder having optically determined particle sizes of from 5 to 150 µm and the balance to 100 wt.% consists of an optionally agglomerated cobalt powder having an optically determined primary particle size of less than 3 µm.
  2. A cobalt metal powder according to claim 1, characterised in that the quantity of atomised cobalt metal powder is from 30 to 70 wt.%.
  3. A cobalt metal powder according to one of claims 1 or 2, characterised in that the cobalt metal powder of crystalline structure has BET surface areas, as measured by the nitrogen one-point method (DIN 66131), of greater than 0.8 m2/g.
  4. A cobalt metal powder according to one or more of claims 1 to 3, characterised in that the atomised cobalt metal powder is a water-atomised cobalt metal powder having a predominantly spheroidal habit.
  5. A cobalt metal powder according to one or more of claims 1 to 3, characterised in that the atomised cobalt metal powder is a gas-atomised cobalt metal powder having a spheroidal habit.
  6. A cobalt metal powder according to one or more of claims 1 to 5, characterised in that it has a bulk density of less than 1.4 g/cm3.
  7. A cobalt metal powder according to one or more of claims 1 to 6, characterised in that it contains less than 20 ppm of aluminium, 20 ppm of calcium, 30 ppm of sodium, 20 ppm of magnesium, 30 ppm of sulphur, 75 ppm of silicon.
  8. A cobalt metal powder according to one or more of claims 1 to 7, characterised in that it has a Rockwell hardness, as measured on hot-pressed test plates, of at least 98 HRB.
  9. Composite sintered articles produced from hard material powders and/or diamond powder and from binder metals, wherein the cobalt metal powder according to one or more of claims 1 to 6 is used as binder metal, optionally together with other metal powders.
EP94119399A 1993-12-21 1994-12-08 Cobalt metal powder and composite sintered article made thereby Expired - Lifetime EP0659507B1 (en)

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DE19540076C1 (en) * 1995-10-27 1997-05-22 Starck H C Gmbh Co Kg Ultrafine cobalt metal powder, process for its preparation and use of the cobalt metal powder and the cobalt carbonate
DE19544107C1 (en) * 1995-11-27 1997-04-30 Starck H C Gmbh Co Kg Metal powder granules, process for its preparation and its use
SE9703204L (en) * 1997-09-05 1999-03-06 Sandvik Ab Tools for drilling / milling circuit board material
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DE59406412D1 (en) 1998-08-13
CN1112466A (en) 1995-11-29
US5482530A (en) 1996-01-09
CN1070094C (en) 2001-08-29
DE4343594C1 (en) 1995-02-02

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