EP0659507A1 - 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
EP0659507A1
EP0659507A1 EP94119399A EP94119399A EP0659507A1 EP 0659507 A1 EP0659507 A1 EP 0659507A1 EP 94119399 A EP94119399 A EP 94119399A EP 94119399 A EP94119399 A EP 94119399A EP 0659507 A1 EP0659507 A1 EP 0659507A1
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Prior art keywords
metal powder
cobalt metal
atomized
cobalt
ppm
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German (de)
French (fr)
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EP0659507B1 (en
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Matthias Dr. Höhne
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HC Starck GmbH
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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

Definitions

  • the present invention relates to cobalt metal powder as a binder metal for the production of diamond and / or hard metal tools and / or wear protection coatings and composite sintered bodies produced therefrom.
  • JP-A 53-093 165 discloses the production and use of atomized cobalt metal. After the atomization, the raw product is post-processed by grinding and shock annealing in order to achieve a desired hexagonal / cubic phase ratio. The grinding processes not only make the cobalt metal powders more expensive, they also contaminate them.
  • Cobalt metal powders can be produced very cheaply by atomization from the melt, but these powders are available as binder metals, e.g. completely unsuitable for the production of diamond tools, because due to the spheroidal grain shape and the grain size at the usual sintering temperatures between 800-900 ° C they do not produce dense composite sintered parts of sufficient hardness.
  • 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 / cm3 is also not achieved by hot pressing.
  • the porosity can reduce the strength if the above-mentioned impurities and sulfur are present in excessive amounts.
  • cobalt metal powders with low levels of impurities are therefore desirable.
  • the purity of the cobalt metal powder can be adapted to the requirements. The effort for the production of particularly pure cobalt metal powder is naturally cost-intensive and such powders are therefore very expensive.
  • the present invention relates to a cobalt metal powder as binder metal for the production of diamond and / or hard metal tools and / or wear protection coatings, which is characterized in that it contains 20 to 80% by weight. consists of an atomized cobalt metal powder with optically determined grain sizes of 5 to 150 ⁇ m and the remainder, which is missing by 100% by weight, of an optionally agglomerated cobalt metal powder with an optically determined primary size of less than 3 ⁇ m.
  • the cobalt metal powder according to the invention has the price advantage of the cobalt metal powder obtained from oxides or oxygen-containing compounds by reduction, but contains significantly smaller amounts of the above-mentioned critical impurities. It preferably contains less than 20 ppm Al, 20 ppm Ca, 30 ppm Na, 20 ppm Mg, 30 ppm S and 75 ppm Si.
  • the cobalt metal powder according to the invention is a mixture of atomized cobalt metal powder with fine cobalt powder from the hydrogen reduction.
  • the good technical suitability of the cobalt metal powder according to the invention starts with a mixture proportion of 20% by weight of atomized fine cobalt metal powder from the reduction in hydrogen, but from the aspect of the price advantage an upper limit of this proportion up to 80% by weight is still acceptable.
  • the powder metallurgical behavior of the mixtures is also very advantageous within the limits mentioned.
  • the amount of atomized cobalt metal powder is preferably 30 to 70% by weight.
  • Suitable as atomized cobalt metal powder are both a water atomized cobalt metal powder with predominantly spheroidal habit and a gas atomized cobalt metal powder with spheroidal habit.
  • 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.
  • the cobalt metal powder according to the invention has a bulk density of less than 1.4 kg / cm 3.
  • 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.
  • the cobalt metal powder according to the invention is outstandingly suitable for the powder metallurgical production of diamond tools and / or hard metals, in which the cobalt - optionally together with other customary matrix metals - represents the binder phase.
  • This invention therefore also relates to composite sintered bodies produced from hard material powder and / or diamond powder and binder metals, the cobalt metal powder according to the invention being used as the binder metal, if appropriate in addition to other metal powders.
  • Example 1 (mixture 70/30)
  • 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 / mm2 Stop time: 3 min
  • Fig. 4 clearly shows that large round cobalt particles in addition to fine primary crystals have been preserved in the polished and etched sample.
  • 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.
  • Comparative Example 1 (100% water-atomized cobalt metal powder ⁇ 63 ⁇ m):
  • Heating gradient 180 K / min
  • Sinter printing 350 N / mm2 Holding time: 3 min
  • Example 5 (100% water-atomized cobalt metal powder ⁇ 38 ⁇ m):
  • 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).
  • Table 1 (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 / cm3 8.54 g / cm3 8.54 g / cm3 8.5 g / cm3 8.45 80 HR B 101.6 HR B 101.2 HR B 100 HR B 97.7 HR B

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 production of diamond and / or hard metal tools and / or wear protection coatings and composite sintered bodies produced 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 produce cobalt metal powder by atomizing the molten metal. JP-A 53-093 165 discloses the production and use of atomized cobalt metal. After the atomization, the raw product is post-processed by grinding and shock annealing in order to achieve a desired hexagonal / cubic phase ratio. The grinding processes not only make the cobalt metal powders more expensive, they also contaminate them.

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 very cheaply by atomization from the melt, but these powders are available as binder metals, e.g. completely unsuitable for the production of diamond tools, because due to the spheroidal grain shape and the grain size at the usual sintering temperatures between 800-900 ° C they do not produce dense composite sintered parts of 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 / cm³ 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, by reducing the oxygen content of cobalt compounds containing oxygen at elevated temperature, suitable cobalt metal powders with an FSSS value of 3 to 5 μm, so-called 400 mesh powders (FIG. 1), can be obtained as matrix material. This designation is explained by the passage of these powders through a 400 mesh sieve. Such powders meet the demands placed on the matrix metal for composite materials with regard to hardness and sintered density. However, the so-called 400-mesh powders have a fairly high proportion of impurities. It is generally known that aluminum, calcium, sodium, magnesium and silicon easily form stable oxides with the oxygen of the cobalt metal powder. These can cause undesirable porosity in diamond segments.

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.In the case of hard metals, the porosity can reduce the strength if the above-mentioned impurities and sulfur are present in excessive amounts. In both applications, cobalt metal powders with low levels of impurities are therefore desirable. Depending on the cleaning effort in the metallurgical precursors, the purity of the cobalt metal powder can be adapted to the requirements. The effort for the production of particularly pure cobalt metal powder is naturally cost-intensive 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 which does not have the disadvantages of the powders 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 has now been found which has these required properties. The present invention relates to a cobalt metal powder as binder metal for the production of diamond and / or hard metal tools and / or wear protection coatings, which is characterized in that it contains 20 to 80% by weight. consists of an atomized cobalt metal powder with optically determined grain sizes of 5 to 150 μm and the remainder, which is missing by 100% by weight, of an optionally agglomerated cobalt metal powder with an optically determined primary size of less than 3 μm.

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 the cobalt metal powder obtained from oxides or oxygen-containing compounds by reduction, but contains significantly smaller amounts of the above-mentioned critical impurities. 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 mixture 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 starts with a mixture proportion of 20% by weight of atomized fine cobalt metal powder from the reduction in hydrogen, but from the aspect of the price advantage an upper limit of this proportion up to 80% by weight is still acceptable. The powder metallurgical behavior of the mixtures is also very advantageous within the limits mentioned.

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. Suitable as atomized cobalt metal powder are both a water atomized cobalt metal powder with predominantly spheroidal habit and a gas atomized cobalt metal powder with spheroidal habit.

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 / cm³ 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 the powder metallurgical production 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, the cobalt metal powder according to the invention being used as the binder metal, if appropriate in addition to other metal powders.

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 limitation being seen.

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, sieved through a 63 μm sieve with a bulk density of 1.2 g / cm 3 (FIG. 1), was 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 / cm³ (Fig. 2), mixed in the Turbula mixer for one hour. The product thus produced had an FSSS value of 2.25 µm and a bulk density of 0.73 g / cm³. 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 / mm² 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 thus obtained has a final density of 8.54 g / cm³ 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 m² / g, an average grain size of 1.7 µm (FSSS), sieved through a 63 µm sieve with a bulk density of 1.2 g / cm³ ( 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 m² / g, determined by the N₂-1-point method (DIN 66 131), sieved through a 38 µm sieve with a bulk density of 3.3 g / cm³ (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 m² / g and a Bulk density of 0.8 g / cm³. 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 sample 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 m² / g, sieved through a 100 μm sieve (bulk density 0.8 g / cm³), was sieved with 0.5 kg of a water-atomized cobalt metal powder (11.7 μm FSSS) with a BET value of 0.73 m² / g, through a 38 μm sieve (bulk density 3.3 g / cm³) , 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 m² / g with a bulk density of 0.8 g / cm³.

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 being varied. The following hardness values were determined on the test platelets obtained in this way:

Sintertest mittels Heißpressen:Sintering test using hot pressing:

Aufheizgradient:Heating gradient: 180 K/min180 K / min Sinterdruck:Sinter printing: 350 N/mm²350 N / mm² 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 was it possible to achieve the required minimum density of 8.5 g / cm³ and the minimum hardness of 98 HRB with the atomized cobalt metal powder.

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 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. Tabelle 1 (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). Table 1 (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 / cm³ 8.54 g / cm³ 8.54 g / cm³ 8.5 g / cm³ 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)

Figure imgb0001
Figure imgb0001
Figure imgb0002
Figure imgb0002

Claims (9)

Kobaltmetallpulver als Bindermetall für die Herstellung von Diamant- und/oder Hartmetallwerkzeugen und/oder Verschleißschutzbeschichtungen, dadurch gekennzeichnet, 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.Cobalt metal powder as binder metal for the production of diamond and / or hard metal tools and / or wear protection coatings, characterized in that it consists of 20 to 80% by weight of an atomized cobalt metal powder with optically determined grain sizes of 5 to 150 µm and 100% by weight. % missing remainder consists of an optionally agglomerated cobalt metal powder with an optically determined primary size of less than 3 µm. Kobaltmetallpulver gemaß Anspruch 1, dadurch gekennzeichnet, daß die Menge des verdüsten Kobaltmetallpulvers 30 bis 70 Gew.-% beträgt.Cobalt metal powder according to claim 1, characterized in that the amount of atomized cobalt metal powder is 30 to 70% by weight. Kobaltmetallpulver gemäß einem der Ansprüche 1 oder 2, dadurch gekennzeichnet daß das Kobaltmetallpulver mit kristalliner Struktur BET-Oberflächen, gemessen nach der Stickstoff-1-Punkt-Methode (DIN 66131), von größer als 0,8 m²/g aufweist.Cobalt metal powder according to one of claims 1 or 2, characterized in that the cobalt metal powder with a crystalline structure has BET surface areas, measured by the nitrogen 1-point method (DIN 66131), of greater than 0.8 m² / g. Kobaltmetallpulver gemäß einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das verdüste Kobaltmetallpulver ein wasserverdüstes Kobaltmetallpulver mit überwiegend sphäroidischem Habitus ist.Cobalt metal powder according to one or more of claims 1 to 3, characterized in that the atomized cobalt metal powder is a water atomized cobalt metal powder with a predominantly spheroidal habit. Kobaltmetallpulver gemäß einem oder mehreren der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das verdüste Kobaltmetallpulver ein gasverdüstes Kobaltmetallpulver mit sphäroidischem Habitus ist.Cobalt metal powder according to one or more of claims 1 to 3, characterized in that the atomized cobalt metal powder is a gas atomized cobalt metal powder with a spheroidal habit. Kobaltmetallpulver gemäß einem oder mehreren der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß es ein Schüttgewicht von kleiner als 1,4 g/cm³ aufweist.Cobalt metal powder according to one or more of claims 1 to 5, characterized in that it has a bulk density of less than 1.4 g / cm³. Kobaltmetallpulver gemäß einem oder mehreren der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß es weniger als 20 ppm Aluminium, 20 ppm Kalzium, 30 ppm Natrium, 20 ppm Magnesium, 30 ppm Schwefel und 75 ppm Silizium enthält.Cobalt metal powder according to one or more of claims 1 to 6, characterized in that it contains less than 20 ppm aluminum, 20 ppm calcium, 30 ppm sodium, 20 ppm magnesium, 30 ppm sulfur and 75 ppm silicon. Kobaltmetallpulver gemäß einem oder mehreren der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß es eine Rockwell-Härte, gemessen an heißgepreßten Prüfplättchen, von mindestens 98 HRB aufweist.Cobalt metal powder according to one or more of claims 1 to 7, characterized in that it has a Rockwell hardness, as measured on hot-pressed test plates, of at least 98 HRB. Verbundsinterkörper, hergestellt aus Hartstoffpulvern und/oder Diamantpulver und Bindermetallen, wobei als Bindermetall, gegebenenfalls neben anderen Metallpulvern das Kobaltmetallpulver gemäß einem oder mehreren der Ansprüche 1 bis 6 verwendet wird.Composite sintered body, produced from hard material powders and / or diamond powder and binder metals, the cobalt metal powder according to one or more of Claims 1 to 6 being used as the binder metal, optionally in addition to other metal powders.
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