EP0839920B1 - Process for preparing a starting powder material for fine grained hard metal - Google Patents

Process for preparing a starting powder material for fine grained hard metal Download PDF

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Publication number
EP0839920B1
EP0839920B1 EP97203354A EP97203354A EP0839920B1 EP 0839920 B1 EP0839920 B1 EP 0839920B1 EP 97203354 A EP97203354 A EP 97203354A EP 97203354 A EP97203354 A EP 97203354A EP 0839920 B1 EP0839920 B1 EP 0839920B1
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Prior art keywords
powder
metal
reaction
cyclone
production
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German (de)
French (fr)
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EP0839920A2 (en
EP0839920A3 (en
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Günter Dr. Kneringer
Wolfgang Dr. Köck
Joachim Dr. Resch
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Plansee SE
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Plansee SE
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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
    • C22C1/053—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 hard compounds
    • C22C1/056—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 hard compounds using gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy

Definitions

  • the quality that can be achieved for a type of hard metal depends to a large extent on the nature of the starting powder, which is pressed and processed into a shaped hard metal body by sintering.
  • the chemical-metallurgical composition is just as important as the powder morphology, powder structure and consequently the powder preparation before pressing and sintem.
  • efforts to produce improved carbide grades have focused primarily on achieving fine grain and homogeneity of the carbide in the carbide.
  • the metallic components in the carbide hard material phase of the hard metal are mainly tungsten or titanium, in addition in the form of stabilizing Mixed carbides small amounts of the high-melting metals tantalum, niobium, Molybdenum, vanadium and chrome.
  • Metal oxides or comparable compounds familiar to the person skilled in the art are reduced to pure metal in one or more process stages and then the metal, usually in a separate process step, converted into metal carbide. Reduction and carburization are isolated also carried out in a common, ongoing process.
  • Metal oxides are used for metal oxide reduction in a solid-gas reaction on carrier ships in comparatively thin layers led a reduction furnace.
  • Usual processes for carbide formation are the intimate mixing of metal powder, for example tungsten metal powder, with carbon (soot particles) and subsequent reaction in a carburizing furnace.
  • metal powder for example tungsten metal powder
  • carbon silicates
  • commercial production also plays an important role in commercial production. It is determined by the price of the device in accordance with the complexity of the process, the amount of energy and reaction gas consumed per reaction unit and, above all, the factor of production time.
  • the reaction or throughput times of the powders in the devices listed are without exception in the range of hours, at best 1 to 2 hours, at worst 15 to 20 hours of reaction time.
  • the overall production also includes Reduction and carburization process steps such as grinding and mixing processes, which usually take many hours.
  • Powder preparation processes e.g. granulating the powder by means of Spray drying, largely indispensable in the carbide industry.
  • the object of the present invention is therefore to compare one with the state of the art Technology more economical process for the production of pressable To provide powder mixtures for hard metal production, which the Manufacture of high quality, especially fine-grained carbide grades allowed.
  • the object of the present invention is also to select one for Implementation of the method suitable device, such Devices for the chemical conversion of various organic and inorganic materials are known for the production of hard metal powder batches to achieve homogeneous, fine-grained carbide grades have not been used so far.
  • hard metal in claim 1 also includes materials known under the name of cermet, which in addition to carbides also contain substantial amounts of nitrides or carbonitrides in the hard material phase.
  • the inventive method requires the use of a Term "cyclone" common reaction chamber.
  • Cyclones are characterized in that they generally have axially or rotationally symmetrical chamber walls.
  • the material to be reacted in the form of solid particles is intimately mixed and swirled with carrier and / or reaction gas immediately upon entry into the reaction chamber and continuously blown in as a mixture in a direction deviating from the longitudinal axis of the chamber.
  • the substances introduced in this way move under the action of gravitation and centrifugal forces in accordance with the gas flow conditions prevailing in the chamber on essentially predetermined trajectories, that is to say not in a statistical movement, for example in a fluidized bed furnace.
  • the gas and particle flow is determined by the chamber walls, including any guide elements that may be attached there. There are high flow velocities tangential to these chamber walls. High relative speeds between solid and gaseous substances occur in the reaction chamber. High speed gradients between individual substances mean high turbulence intensities and result in high heat and mass transfer numbers for the individual reactants in the desired chemical reaction.
  • the duration of the reaction material in the chamber is device and process-related small.
  • the stay or reaction times depend on Plant design between tenths of a second and about a minute.
  • a major advantage of the present method over the known methods for producing submicron or nanophase powder for powder press approaches for the production of hard metal is that Raw material powder (metal compounds to be reduced) can be used can, as they do without special additional treatment from the ore processing be provided and after applying this procedure to carbide very uniform and fine-grained structure can be processed.
  • Powder batches allow hard metal qualities to reach those of those correspond to or are even superior to those after the ones above described method, production of nanophase composite powder, Manufacture of submicron carbides.
  • Metal oxides, or standard compounds which are alternatively available for the reduction to metal powder are usually provided in particle sizes between approximately 2 and 30 ⁇ m and, according to the process according to the invention, give metal powders with a particle size approximately comparable to the starting powder size, but with a significant proportion of agglomerated powders. Agglomerated powders are generally not a good starting point for the production of extremely fine-grained carbide. It was completely surprising, however, that the metal powders produced by chemical reduction according to the present invention consistently have an extremely high, sponge-like microporosity in the range of 0.1 ⁇ m. However, this means that the metal powder for further processing to carbide and hard metal has a quality that was previously known only approximately from the nanophase process mentioned as previously known. The entire volume of the metal powder can be completely carburized in a cyclone reaction and leads to a previously unattainable, fine-grained hard metal quality.
  • the chemical process step in Cyclone is the throughput time of the material to be reacted in the solid Phase 0.2 to 10 s, for at least 90% by volume of the solid phase complete chemical conversion to the predetermined reaction state.
  • the individual chemical process step in the cyclone optionally at least in repeated in another run.
  • the Metal oxide powder or the powdery metal compound as that too reducing material before the process step reduction metallic Filler materials added especially those in hard metal as binder metal metals Co and / or Ni used. This is done by adding metallic powder, or by making a solid beforehand Solution, that is, by introducing the filler materials into the solid phase of the good to be reduced.
  • the following result Variants for the invention comprising several partial steps Process for the production of powder press batches for further processing to fine-grain carbide.
  • a first method variant of the method according to the invention consists in the reduction of metal oxide or comparable metal compounds Cyclone metal powder in the cyclone process; at high Purity requirements for the metal powder to be produced also in one Repeat this reduction step.
  • the metal powder thus obtained is in a in Carbide manufacturing commonly used ball mill with carbon particles intimately mixed. In doing so, agglomerates of spongy Crushed metal powder.
  • This mixing and Milling process powdered additional metals (to form mixed carbides as Grain growth inhibitors in hard metal) added.
  • the powder mixture is further converted to metal carbide in the carburizing furnace by conventional methods converted, according to standard procedures with the binding metal (cobalt and / or Nickel powder) mixed and optionally over attritor grinding and Spray drying transferred into a ready-to-press powder batch.
  • the so obtained Powder press approach can be too much using conventional pressing and sintering processes Process fine-grain carbide with very high phase homogeneity.
  • the metal oxides are reduced to metal powder in the cyclone, as above.
  • the metal powder obtained in this way is also further processed in the cyclone to metal carbide by the cyclone process which is essential to the invention, namely in two sub-variants, either following prior external mixing with carbon particles (as above) by simultaneously blowing this mixture together with carrier gas and possibly with reaction gas into the reaction chamber, or according to a second sub-variant, by directly blowing the metal powder into the cyclone reactor together with gaseous carbon compounds, in particular hydrocarbon gases and / or CO.
  • This variant is also supplemented by customary grinding, mixing and granulating processes, with grinding and granulating processes not necessarily having to take place.
  • the Metal oxides together with a reducing gas and a carbon containing gas into the cyclone reaction chamber, or blown in and it takes place during a single overall run a first part of a spatially uniform overall reactor Reduction of the oxide to metal powder and immediately afterwards in one second chamber part to carburize the reduced metal powder Metal carbide.
  • additional metals for mixed carbide formation such as niobium, tantalum, vanadium and chromium, can also be added to the carburizing process in the cyclone and simultaneously converted to carbides with the main metal.
  • additional metals for mixed carbide formation such as niobium, tantalum, vanadium and chromium, can also be added to the carburizing process in the cyclone and simultaneously converted to carbides with the main metal.
  • a cyclone with the features of the present invention and corresponding to the representation in FIG. 1 is used as the device for carrying out the reduction process.
  • the overall system shown in FIG. 1 is composed of a steel reaction chamber designed as a cyclone, which is followed by a second reaction chamber designed as a downpipe for chemical aftertreatment of the reacted material, this aftertreatment and the associated reaction chamber not being part of the invention. It is a pilot plant that is smaller in comparison to plants for industrial production in terms of the throughput quantity of goods to be reduced per unit of time.
  • powdered W 4 O 11 is blown in via a feed device (1) together with reaction and / or carrier gas into the head part of a reaction chamber (2) which is approximately rotationally symmetrical with respect to the direction of fall.
  • the amount of gas is metered by means of a flow meter (7).
  • the reaction chamber is brought to a reaction temperature of 1100 ° C. by means of an electrical heating device (6).
  • the pulverulent reaction product leaves the chamber at the lower end, falls into a storage room with screw conveyor (3) and is introduced into the second reaction chamber (4) with heating device (6).
  • the exhaust gas (8), reaction and / or carrier gas and H 2 O vapor as the end product of the reaction leave the first chamber at the top.
  • the tungsten powder is collected in a container (5).
  • the temperature of the entire two-stage process is controlled by means of a thermocouple (9) at the exhaust outlet of the first reaction chamber.
  • a gas amount of 4000 l H 2 gas is used, ie a large excess of gas based on the stoichiometric reaction amounts.
  • Tungsten oxide as the material to be reduced and H 2 as the carrier or reducing gas are fed to the cyclone separately.
  • the carrier or reducing gas is preferably introduced horizontally into the chamber at the upper end at a high flow rate.
  • the pulverulent material to be reduced is brought up to the gas inlet nozzle in such a way that it is entrained by the gas jet as it enters the chamber, is swirled and mixed intensively with it, and passes through the chamber in accordance with the guidance of the gas flow on predetermined trajectories.
  • the material reduced to tungsten powder leaves the reduction chamber after a passage time of 1-2 s and has a residual oxygen content of 10,500 ⁇ g / g at the outlet.
  • the emerging tungsten powder has a grain size comparable to that of the powder taken in, of the order of 20 ⁇ m in diameter, but the individual powder particles or grains have a large porosity throughout their entire volume.
  • the spatial expansion of the substructure in the tungsten particle is 0.1 ⁇ m.
  • the tungsten powder obtained in this way is converted into carbide by customary methods.
  • the tungsten powder is first intensively mixed in the ball mill with a stoichiometric proportion of fine soot particles for tungsten carbide, WC. Individual agglomerates of the tungsten powder are crushed.
  • the batch obtained in this way is carburized in a graphite furnace with induction heating under an H 2 atmosphere at 1300 ° C. for 3 hours. Pure tungsten carbide with a carbon content of 6.12% and a residual oxygen content of 1200 ⁇ g / g is formed.
  • the carbide is made with binder metal and usual amounts of mixed carbides (Niobium carbide, tantalum carbide) mixed and optionally via attritor grinding and Spray drying processed into free-flowing granules.
  • the device used corresponds to that of Example 1 without a downpipe being connected downstream of the cyclone.
  • Tungsten oxide, blue is reduced to tungsten powder in the cyclone in accordance with the process conditions mentioned in Example 1.
  • the tungsten powder is then further processed into tungsten carbide in a cyclone reactor lined with graphite using carbon-containing gases plus carrier gas (CH 4 / H 2 mixture).
  • Carburization takes place in one step at a cyclone temperature of 1100 ° C.
  • a gas throughput of 6000 l / h is regulated for a tungsten powder throughput of 1000 g / h.
  • the methane concentration in the CH 4 / H 2 mixture is 1.1% by volume.
  • ready-to-press powder batches are produced by mixing the WC with binder material and small proportions of mixed carbides with optional granulation by means of spray drying.
  • the hard metal obtained from these powder batches corresponds in its fine-grained structure and homogeneity to that according to Example 1.
  • the subsequent carburization is again carried out in the cyclone reactor, but in contrast to Example 2, using CO as the carburizing and carrier gas.
  • the tungsten powder obtained from the cyclone reactor is continuously introduced into the chamber at a throughput of 1000 g / h with a gas quantity of 6000 l / h (CO gas) and at 1000 ° C. chamber temperature in a one-step process to produce W 2 C and WC (C content 4.2% by weight) and a residual oxygen content of 3240 ⁇ g / g reacts.
  • the X-ray diffractometer examination shows that in addition to W 2 C, small amounts of WC but no free carbon are present in the end product thus obtained.
  • the throughput time for the particles to be carburized in the cyclone reactor is 1-2 s.
  • the W 2 C-WC powder mixture obtained in this way is reacted in a second process step in the cyclone under approximately the same test conditions as for the first carburization step to pure tungsten carbide WC with only a very small residual oxygen content and without detectable free carbon residues.
  • the powder sets are completed by mixing and optionally granulating as in Examples 1 and 2.
  • a hard metal made from these powder batches by customary processes has a high degree of fine grain and a high degree of material homogeneity.

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
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Abstract

In the production of a starting powder for fine grained cemented carbide manufacture from a metal oxide or reducible metal compound powder by reducing to metal, carburizing and subjecting to a mechanical-chemical powder treatment and/or mixing operation, the reduction and/or carburization step employs a cyclone unit which is a heated rotationally symmetrical reaction chamber having inlet and outlet openings for the powder, reagent and carrier gas. The continuously supplied powder retains its solid state during high velocity passage through the reaction chamber along predetermined flight paths which are tangential to the chamber wall and which are controlled by means of the powder flight direction and velocity at the inlet and by means of the flow parameters of the carrier and/or reaction gas. The unit produces ≥ 90 vol.% chemical reaction of the powder in a dwell time of 0.1-60 (preferably 0.2-10) s.

Description

Die Erfindung betrifft ein Verfahren zur Herstellung von Pulver-Preßansätzen für feinkörniges Hartmetall auf Metallkarbidbasis, das von Metalloxidpulver oder von reduzierbaren festen Metallverbindungen ausgeht und die Verfahrensstufen

  • Reduktion des Oxids oder der Metallverbindung zu Metall
  • Karburierung des Metalls
  • mechanisch-chemisches Pulverkomaufbereitungs- und/oder Mischverfahren mit einschließt.
The invention relates to a method for producing powder press batches for fine-grained hard metal based on metal carbide, which starts from metal oxide powder or reducible solid metal compounds, and the process stages
  • Reduction of the oxide or metal compound to metal
  • Carburizing the metal
  • includes mechanical-chemical powder preparation and / or mixing processes.

Die für eine Hartmetallsorte erzielbare Qualität hängt ganz wesentlich von der Beschaffenheit der Ausgangspulver ab, die verpreßt und durch Sintern zu einem Hartmetall-Formkörper verarbeitet werden. Dabei ist die chemischmetallurgische Zusammensetzung ebenso bedeutsam wie die Pulvermorphologie, Pulverstruktur und demzufolge die Pulveraufbereitung vor dem Verpressen und Sintem.
In den vergangenen Jahren konzentrierten sich die Anstrengungen zur Herstellung verbesserter Hartmetall-Qualitäten vor allem auf die Erzielung von Feinkörnigkeit und Homogenität der Hartstoffe im Hartmetall.The quality that can be achieved for a type of hard metal depends to a large extent on the nature of the starting powder, which is pressed and processed into a shaped hard metal body by sintering. The chemical-metallurgical composition is just as important as the powder morphology, powder structure and consequently the powder preparation before pressing and sintem.
In recent years, efforts to produce improved carbide grades have focused primarily on achieving fine grain and homogeneity of the carbide in the carbide.

Die metallischen Komponenten in der Karbid-Hartstoffphase des Hartmetalls sind vor allem Wolfram oder Titan, daneben in Form von komstabilisierenden Mischkarbiden kleine Mengen der hochschmelzenden Metalle Tantal, Niob, Molybdän, Vanadium und Chrom.The metallic components in the carbide hard material phase of the hard metal are mainly tungsten or titanium, in addition in the form of stabilizing Mixed carbides small amounts of the high-melting metals tantalum, niobium, Molybdenum, vanadium and chrome.

In der langen Verfahrensreihe der Erzaufbereitung dieser Metalle sind die Verarbeitungsschritte, beginnend mit der Reduktion pulverförmiger Metalloxide bzw. vergleichbare Verbindungen wie Ammoniummetallat und Metallsäure, bis hin zur Metallkarbid-Gewinnung wesentlich für die spätere Qualität von Hartmetallsorten, insbesondere hinsichtlich deren Gefügestruktur.In the long series of processes for ore processing these metals are Processing steps, starting with the reduction of powdered metal oxides or comparable compounds such as ammonium metallate and metallic acid, to towards metal carbide extraction essential for the later quality of Carbide grades, especially with regard to their structure.

Metalloxide oder dem Fachmann geläufige, vergleichbare Verbindungen werden in einer oder mehreren Prozeßstufen zum reinen Metall reduziert und anschließend wird das Metal, üblicherweise in einem getrennten Prozeßschritt, in Metallkarbid überführt. Vereinzelt werden Reduzierung und Karburierung auch in einem gemeinsamen, fortlaufenden Prozeß durchgeführt.Metal oxides or comparable compounds familiar to the person skilled in the art are reduced to pure metal in one or more process stages and then the metal, usually in a separate process step, converted into metal carbide. Reduction and carburization are isolated also carried out in a common, ongoing process.

Zur Metalloxid-Reduktion in einer Feststoff-Gas-Reaktion werden Metalloxide auf Trägerschiffchen in vergleichsweise dünnen Lagen kontinuierlich durch einen Reduktionsofen geführt. Ebenso geläufig ist die Reduktion im Drehrohrofen und in der Wirbelschicht.Metal oxides are used for metal oxide reduction in a solid-gas reaction on carrier ships in comparatively thin layers led a reduction furnace. The reduction in the Rotary kiln and in the fluidized bed.

Übliche Verfahren zur Karbidbildung sind das innige Vermischen von Metallpulver, z.B. Wolframmetallpulver, mit Kohlenstoff (Rußpartikeln) und anschließende Reaktion in einem Karburierungsofen.
Bei der kommerziellen Fertigung spielt neben der Pulverqualität auch die Wirtschaftlichkeit der Fertigung eine wichtige Rolle. Sie wird bestimmt vom Preis der Vorrichtung entsprechend der Komplexität des Verfahrens, von der verbrauchten Menge an Energie und Reaktionsgas je Reaktionseinheit und vor allem von Faktor Fertigungszeit.
Die Reaktions- bzw. Durchlaufzeiten der Pulver in den jeweils angeführten Vorrichtungen liegen ausnahmslos im Bereich von Stunden, günstigstenfalls bei 1 bis 2 Stunden, ungünstigstenfalls bei 15 bis 20 Stunden Reaktionszeit.Usual processes for carbide formation are the intimate mixing of metal powder, for example tungsten metal powder, with carbon (soot particles) and subsequent reaction in a carburizing furnace.
In addition to powder quality, commercial production also plays an important role in commercial production. It is determined by the price of the device in accordance with the complexity of the process, the amount of energy and reaction gas consumed per reaction unit and, above all, the factor of production time.
The reaction or throughput times of the powders in the devices listed are without exception in the range of hours, at best 1 to 2 hours, at worst 15 to 20 hours of reaction time.

Zur Gesamtfertigung gehören neben den chemischen Verfahrensschritten Reduktion und Karburierung Verfahrensschritte wie Mahl- und Mischvorgänge, die in der Regel wiederum viele Stunden beanspruchen. Daneben sind Pulveraufbereitungsverfahren, wie z.B. das Granulieren der Pulver mittels Sprühtrockung, in der Hartmetall-Industrie weitgehend unverzichtbar.In addition to the chemical process steps, the overall production also includes Reduction and carburization process steps such as grinding and mixing processes, which usually take many hours. Are next to it Powder preparation processes, e.g. granulating the powder by means of Spray drying, largely indispensable in the carbide industry.

In Verbindung mit der Forderung nach Submikron- und Nanophasenpulver für Hartmetall-Pulveransätze wurden neue Verfahren entwickelt, bei denen die übliche Reduktion und Karburierung, einschließlich besonderer Pulvervorbereitungs- und -aufbereitungsverfahren, gleichzeitig oder in einer zwingenden Schrittfolge nacheinander ablaufen.In connection with the demand for submicron and nanophase powder for Tungsten carbide powder batches, new processes were developed in which the usual reduction and carburization, including special ones Powder preparation and preparation processes, simultaneously or in one mandatory sequence of steps.

Stellvertretend für derartige Prozesse und dazu verwendete Vorrichtungen seien genannt die WO 91/07244 mit dem Titel "Sprühumwandlungsprozeß für die Herstellung von Nanophasen-Verbundpulver" und die WO 95/04703 mit dem Titel "Verfahren zur Herstellung von Submikrometer-Karbiden, Submikrometer-Mischkristallkarbiden und daraus entstehende Materialien", wobei in dieser Patentschrift auf die US 5 110 565 verwiesen ist, in der ein Reaktor beschrieben ist, wie er zur Durchführung des Verfahrens gemäß WO-Anmeldung verwendet wurde.Representing such processes and devices used for them may be mentioned WO 91/07244 with the title "spray conversion process for the production of nanophase composite powder "and WO 95/04703 with entitled "Process for the Production of Submicrometer Carbides, Submicrometer mixed crystal carbides and resulting materials ", in this patent reference is made to US 5 110 565, in which a Reactor is described as it is for carrying out the process WHERE application was used.

Nachteilig bei diesen Verfahren sind die hohen Fertigungs- und Vorrichtungskosten. In Summe sind die Reaktionszeiten bei den unverzichtbar durchzuführenden Verfahrensschritten trotz einzelner Verkürzungen gegenüber dem bis dahin bekannten Stand der Technik immer noch in der Größenordnung von einer bis mehrere Stunden und damit ein wesentlicher Kostenfaktor. Diese Verfahren sind somit in Summe unwirtschaftlich, insbesondere was den Gewinn an Pulverfeinkörnigkeit gegenüber weiter vorne beschriebenen Standardverfahren anbetrifft.The disadvantage of these processes is the high manufacturing and Device costs. In total, the response times are indispensable process steps to be carried out despite individual reductions the previously known state of the art is still in the order of magnitude from one to several hours and thus an essential cost factor. This All in all, procedures are uneconomical, especially when it comes to profit powder fine grain compared to that described above Standard procedure applies.

Aufgabe vorliegender Erfindung ist es daher, ein im Vergleich zum Stand der Technik wirtschaftlicheres Verfahren zur Herstellung von preßfähigen Pulvermischungen für die Hartmetall-Fertigung bereitzustellen, welches die Fertigung qualitativ hochwertiger, insbesondere feinkörniger Hartmetall-Sorten erlaubt.The object of the present invention is therefore to compare one with the state of the art Technology more economical process for the production of pressable To provide powder mixtures for hard metal production, which the Manufacture of high quality, especially fine-grained carbide grades allowed.

Die Aufgabe vorliegender Erfindung besteht weiters in der Auswahl einer zur Durchführung des Verfahrens geeigneten Vorrichtung, wobei derartige Vorrichtungen zwar für die chemische Umsetzung verschiedener organischer und anorganischer Werkstoffe bekannt sind, für die Herstellung von Hartmetall-Pulveransätzen zur Erzielung homogener, feinkörniger Hartmetall-Sorten bisher aber nicht genutzt wurden.The object of the present invention is also to select one for Implementation of the method suitable device, such Devices for the chemical conversion of various organic and inorganic materials are known for the production of hard metal powder batches to achieve homogeneous, fine-grained carbide grades have not been used so far.

Die vorgenannte Aufgabe wird erfindungsgemäß durch ein Verfahren nach Anspruch 1 gelöst.
Der Begriff "Hartmetall" in Anspruch 1 schließt auch unter dem Namen Cermet gebräuchliche Werkstoffe mit ein, welche neben Karbiden auch wesentliche Anteile an Nitriden oder Karbonitriden in der Hartstoff-Phase enthalten. The above object is achieved according to the invention by a method according to claim 1.
The term "hard metal" in claim 1 also includes materials known under the name of cermet, which in addition to carbides also contain substantial amounts of nitrides or carbonitrides in the hard material phase.

Das erfindungsgemäße Verfahren erfordert die Verwendung einer unter dem Begriff "Zyklon" geläufigen Reaktionskammer.The inventive method requires the use of a Term "cyclone" common reaction chamber.

Zyklone sind dadurch charakterisiert, daß sie in der Regel achs- bzw. rotationssymmetrische Kammerwände besitzen. Das zu reagierende Gut in Form von festen Teilchen wird unmittelbar beim Einlaß in die Reaktionskammer mit Träger- und/oder Reaktionsgas innig vermischt und verwirbelt und als Gemisch in einer von der Kammerlängsachse abweichenden Richtung kontinuierlich eingeblasen. Die derart eingebrachten Stoffe bewegen sich unter der Wirkung von Gravitation und Fliehkräften entsprechend der in der Kammer herrschenden Gasströmungsverhältnisse auf im wesentlichen vorbestimmten Flugbahnen, das heißt also nicht in einer statistischen Bewegung, wie beispielsweise in einem Wirbelschichtofen. Der Gas- und Teilchenstrom wird durch die Kammerwandungen, einschließlich dort eventuell angebrachter Leitelemente vorgegeben.
Es kommt zu hohen Strömungsgeschwindigkeiten tangential zu diesen Kammerwänden. In der Reaktionskammer treten hohe Relativgeschwindigkeiten zwischen festen und gasförmigen Stoffen auf. Hohe Geschwindigkeitsgradienten zwischen einzelnen Stoffen bedeuten hohe Turbulenzintensitäten und bewirken hohe Wärme- und Stoffaustauschzahlen für die einzelnen Reaktanden an der angestrebten chemischen Reaktion.Cyclones are characterized in that they generally have axially or rotationally symmetrical chamber walls. The material to be reacted in the form of solid particles is intimately mixed and swirled with carrier and / or reaction gas immediately upon entry into the reaction chamber and continuously blown in as a mixture in a direction deviating from the longitudinal axis of the chamber. The substances introduced in this way move under the action of gravitation and centrifugal forces in accordance with the gas flow conditions prevailing in the chamber on essentially predetermined trajectories, that is to say not in a statistical movement, for example in a fluidized bed furnace. The gas and particle flow is determined by the chamber walls, including any guide elements that may be attached there.
There are high flow velocities tangential to these chamber walls. High relative speeds between solid and gaseous substances occur in the reaction chamber. High speed gradients between individual substances mean high turbulence intensities and result in high heat and mass transfer numbers for the individual reactants in the desired chemical reaction.

Die Aufenthaltsdauer des Reaktionsgutes in der Kammer ist vorrichtungs- und prozeßbedingt klein. Die Aufenthalts- bzw. Reaktionszeiten liegen je nach Anlagenausgestaltung zwischen Zehntelsekunden und etwa einer Minute.The duration of the reaction material in the chamber is device and process-related small. The stay or reaction times depend on Plant design between tenths of a second and about a minute.

Derartige Zyklon-Reaktoren finden bereits Verwendung bei der Pyrolyse von Sägespänen: J. Lede et al, "Flash Pyrolysis of Wood in a Cyclone Reactor", Chem. Eng. Proc. 20 (1986), Seiten 309-317; J. Cousins et al, "Gasification of Sawdust in an air blown cyclone Gasifier", Ind. Eng. Chem. Process Des. Dev.24 (1985), Seiten 1281-1287; bei der Schlackenverbrennung sowie der Verbrennung von Schlammrückständen, T. Murakami et al, "Characteristics of Melting Process for Sewage Sludge", Wat. Sci, Tech. 23 (1991), Seiten 2019-2028. Die Prozesse finden schließlich auch für exotherme metallurgische Prozesse, z.B. für das Erschmelzen von kupfer-, blei- und zinkhaltigen Kupferkonzentraten Anwendung, wie vorbeschrieben in der DE 33 41 154 und im Fachaufsatz "Das Schwebeschmelzen und andere leistungsintensive Prozesse", A. Lange, Erzmetall 13 (1960), Seiten 151-159.Such cyclone reactors are already used in the pyrolysis of Sawdust: J. Lede et al, "Flash Pyrolysis of Wood in a Cyclone Reactor", Chem. Eng. Proc. 20 (1986), pp. 309-317; J. Cousins et al, "Gasification of Sawdust in an air blown cyclone gasifier ", Ind. Eng. Chem. Process Des. Dev. 24 (1985), pages 1281-1287; in the slag combustion and the Incineration of sludge residues, T. Murakami et al, "Characteristics of Melting Process for Sewage Sludge ", Wat. Sci, Tech. 23 (1991), pages From 2019 to 2028. The processes ultimately also find for exothermic metallurgical Processes, e.g. for melting copper, lead and zinc Copper concentrates application, as described in DE 33 41 154 and in the technical essay "The levitation and other performance-intensive Processes ", A. Lange, Erzmetall 13 (1960), pages 151-159.

Allen bisher in Zyklonen durchgeführten Prozessen, insbesondere auch metallurgischen Prozessen, ist jedoch gemeinsam, daß das zu reagierende Gut als Feststoffpartikel in den Zyklon eingebracht wird, daß die Festpartikel zur Durchführung der gewünschten Reaktion jedoch in die flüssige oder meist gasförmige Phase überführt werden und daß die am Ende gewünschten Reaktionsstoffe, insbesondere auch reduzierte Metalle, den Zyklon gasförmig oder schmelzflüssig verlassen.
Chemische Reaktionen laufen in aller Regel in der schmelzflüssigen oder gasförmigen Phase aber schneller ab als in der festen Phase und kommen damit den kurzen Verweilzeiten und Reaktionszeiten im Zyklon entgegen bzw. erschienen dem Fachmann unverzichtbar.
Erfahrungswerte aus Zyklonreaktionen unter Beibehaltung der festen Phase für mindestens einen Reaktanden lagen daher nicht vor. Die technisch und kommerziell zufriedenstellende Durchführung eines so gesteuerten Zyklonverfahrens war daher weder vorgegeben noch nahegelegtHowever, all processes previously carried out in cyclones, in particular also metallurgical processes, have in common that the material to be reacted is introduced into the cyclone as solid particles, but that the solid particles are converted into the liquid or mostly gaseous phase in order to carry out the desired reaction and that in the end, the desired reactants, especially also reduced metals, leave the cyclone in gaseous or molten form.
As a rule, chemical reactions take place faster in the molten or gaseous phase than in the solid phase and thus meet the short dwell times and reaction times in the cyclone or appeared indispensable to the person skilled in the art.
Experience from cyclone reactions while maintaining the solid phase for at least one reactant was therefore not available. The technically and commercially satisfactory implementation of such a cyclone process was therefore neither specified nor suggested

Anders als bei chemischen Reaktionen im Zyklon nach dem Stand der Technik muß die Reduktion und/oder Karburierung entsprechender fester Teilchen unter Beibehaltung der festen Phase erfolgen. Verflüssigung und/oder Verflüchtigung der festen Teilchen und anschließende Sublimierung würden bei der Zyklon-Reaktion zu Endprodukten (Pulvern) führen, die aufgrund ihrer strukturellen Pulverbeschaffenheit nicht zur Weiterverarbeitung zu Hartmetall heute üblicher Qualität geeignet sind.Unlike with chemical reactions in the cyclone according to the prior art must reduce and / or carburize corresponding solid particles done while maintaining the solid phase. Liquefaction and / or Volatilization of the solid particles and subsequent sublimation would occur lead to end products (powders) in the cyclone reaction which, owing to their structural powder texture not for further processing into hard metal usual quality are suitable today.

Ein wesentlicher Vorteil des gegenständlichen Verfahrens gegenüber den bekannten Verfahren zur Erzeugung von Submikron- oder Nanophasenpulver für Pulver-Preßansätze zur Herstellung von Hartmetall liegt darin, daß Vormaterialpulver (zu reduzierende Metallverbindungen) verwendet werden können, wie sie ohne besondere Zusatzbehandlung aus der Erzaufbereitung bereitgestellt werden und nach Anwendung dieses Verfahrens zu Hartmetall sehr gleichmäßiger und feinkörniger Struktur verarbeitbar sind.A major advantage of the present method over the known methods for producing submicron or nanophase powder for powder press approaches for the production of hard metal is that Raw material powder (metal compounds to be reduced) can be used can, as they do without special additional treatment from the ore processing be provided and after applying this procedure to carbide very uniform and fine-grained structure can be processed.

Die aus nach dem gegenständlichen Verfahren sehr wirtschaftlich gefertigten Pulveransätze lassen Hartmetall-Qualitäten erreichen, die denjenigen entsprechen oder jenen sogar überlegen sind, die nach den weiter vorne beschriebenen Verfahren, Herstellung von Nanophasen-Verbundpulver, Herstellung von Submikrometer-Karbiden, erreicht werden.Those made very economically from the process in question Powder batches allow hard metal qualities to reach those of those correspond to or are even superior to those after the ones above described method, production of nanophase composite powder, Manufacture of submicron carbides.

Die Reaktionszeiten bei den chemischen Verfahrensschritten Reduktion und Karburierung gemäß vorliegender Erfindung bis zur vollständigen Reaktion für mindestens 90 % Volumenanteil des zu reagierenden Gutes in der festen Phase liegen aber wesentlich unter denen der bekannten Verfahren. Dadurch ist eine wesentlich höhere Wirtschaftlichkeit des gegenständlichen Verfahrens gegenüber dem bekannten Stand der Technik gegeben. Die Kostenvorteile des gegenständlichen Verfahrens vergrößern sich noch aufgrund einer vergleichsweise bautechnisch einfachen Ausgestaltung von Zyklon-Reaktionskammern, sowie wegen vergleichsweise günstigerer Energie- und Gas-Verbrauchsdaten.The reaction times in the chemical process steps reduction and Carburization according to the present invention until complete reaction for at least 90% by volume of the material to be reacted in the solid However, the phase is significantly lower than that of the known processes. Thereby is a much higher cost-effectiveness of the process in question given compared to the known prior art. The cost advantages of the subject procedure are enlarged due to a comparatively simple construction of cyclone reaction chambers, and because of comparatively cheaper energy and Gas consumption data.

Metalloxide, bzw. für die Reduktion zu Metallpulver alternativ erhältliche Standardverbindungen, werden üblicherweise in Teilchengrößen zwischen etwa 2 und 30 µm bereitgestellt und ergeben nach dem erfindungsgemäßen Verfahren Metallpulver mit zur Ausgangspulvergröße etwa vergleichbarer Teilchengröße, allerdings bei einem signifikanten Anteil an agglomerierten Pulvern.
Agglomerierte Pulver sind grundsätzlich keine gute Ausgangsbasis für die Fertigung von höchst feinkörnigem Hartmetall. Es war indes völlig überraschend, daß die durch chemische Reduktion nach vorliegender Erfindung hergestellten Metallpulver durchgehend eine extrem hohe, schwammartige Mikroporosität im Bereich von 0,1 µm aufweisen. Damit besitzt aber das Metallpulver für die weitere Verarbeitung zu Karbid und Hartmetall eine Qualität, wie es bisher allenfalls annähernd von dem als vorbekannt genannten Nanophasen-Verfahren her bekannt war. Das Metallpulver läßt sich in einer Zyklon-Reaktion in seinem gesamten Volumen vollständig karburieren und führt zu einer bisher nicht erreichten, feinkörnigen Hartmetall-Qualität.Metal oxides, or standard compounds which are alternatively available for the reduction to metal powder, are usually provided in particle sizes between approximately 2 and 30 μm and, according to the process according to the invention, give metal powders with a particle size approximately comparable to the starting powder size, but with a significant proportion of agglomerated powders.
Agglomerated powders are generally not a good starting point for the production of extremely fine-grained carbide. It was completely surprising, however, that the metal powders produced by chemical reduction according to the present invention consistently have an extremely high, sponge-like microporosity in the range of 0.1 μm. However, this means that the metal powder for further processing to carbide and hard metal has a quality that was previously known only approximately from the nanophase process mentioned as previously known. The entire volume of the metal powder can be completely carburized in a cyclone reaction and leads to a previously unattainable, fine-grained hard metal quality.

Nach einer bevorzugten Ausführung des chemischen Verfahrensschrittes im Zyklon beträgt die Durchlaufzeit des zu reagierenden Gutes in der festen Phase 0,2 bis 10 s, und zwar bei für mindestens 90 Vol.% der festen Phase vollständiger chemischer Überführung in den vorbestimmten Reaktionszustand. Zur Erhöhung des Volumenanteils mit vollständiger chemischer Reaktion wird der einzelne chemische Verfahrensschritt im Zyklon wahlweise mindestens in einem weiteren Durchlauf wiederholt.According to a preferred embodiment of the chemical process step in Cyclone is the throughput time of the material to be reacted in the solid Phase 0.2 to 10 s, for at least 90% by volume of the solid phase complete chemical conversion to the predetermined reaction state. To increase the volume fraction with complete chemical reaction the individual chemical process step in the cyclone optionally at least in repeated in another run.

Nach einer weiteren bevorzugten Ausführung des Verfahrens werden dem Metalloxidpulver oder der pulverförmigen Metallverbindung als dem zu reduzierenden Gut vor dem Verfahrensschritt Reduktion metallische Zusatzwerkstoffe beigegeben, insbesondere die in Hartmetall als Bindermetall verwendeten Metalle Co und/oder Ni. Dies geschieht durch Zugabe metallischer Pulver, oder aber durch vorherige Herstellung einer festen Lösung, das heißt durch Einbringen der Zusatzwerkstoffe in die feste Phase des zu reduzierenden Gutes.According to a further preferred embodiment of the method, the Metal oxide powder or the powdery metal compound as that too reducing material before the process step reduction metallic Filler materials added, especially those in hard metal as binder metal metals Co and / or Ni used. This is done by adding metallic powder, or by making a solid beforehand Solution, that is, by introducing the filler materials into the solid phase of the good to be reduced.

Gemäß einzelner bevorzugter Ausführungen ergeben sich die folgenden Varianten für das mehrere Teilschritte umfassende erfindungsgemäße Verfahren zur Herstellung von Pulver-Preßansätzen für die Weiterverarbeitung zu feinkörnigem Hartmetall.According to individual preferred embodiments, the following result Variants for the invention comprising several partial steps Process for the production of powder press batches for further processing to fine-grain carbide.

Eine erste Verfahrensvariante des erfindungsgemäßen Verfahrens besteht in der Reduktion von Metalloxid oder von vergleichbaren Metallverbindungen zu Metallpulver im Zyklon nach dem Zyklonverfahren; bei hohen Reinheitsansprüchen an das zu erzeugende Metallpulver auch in einer Wiederholung dieses Reduktionsschrittes.A first method variant of the method according to the invention consists in the reduction of metal oxide or comparable metal compounds Cyclone metal powder in the cyclone process; at high Purity requirements for the metal powder to be produced also in one Repeat this reduction step.

Anschließend wird das so erhaltene Metallpulver in einer in der Hartmetallfertigung häufig verwendeten Kugelmühle mit Kohlenstoffpartikeln innigst vermischt. Dabei werden Agglomerate des schwammartigen Metallpulvers zerkleinert. Vorzugsweise werden bei diesem Misch- und Mahlprozeß pulverförmige Zusatzmetalle (zur Bildung von Mischkarbiden als Komwachstums-Inhibitoren im Hartmetall) beigegeben. Die Pulvermischung wird weiter nach üblichen Verfahren im Karburierungsofen zu Metallkarbid umgewandelt, nach üblichen Standardverfahren mit dem Bindemetall (Kobaltund/oder Nickelpulver) vermischt und wahlweise über Attritormahlen und Sprühtrocknen in einen preßfertigen Pulveransatz überführt. Der so erhaltene Pulverpreßansatz läßt sich mittels üblicher Preß- und Sinterverfahren zu sehr feinkörnigem Hartmetall mit sehr hoher Phasenhomogenität verarbeiten.Then the metal powder thus obtained is in a in Carbide manufacturing commonly used ball mill with carbon particles intimately mixed. In doing so, agglomerates of spongy Crushed metal powder. This mixing and Milling process powdered additional metals (to form mixed carbides as Grain growth inhibitors in hard metal) added. The powder mixture is further converted to metal carbide in the carburizing furnace by conventional methods converted, according to standard procedures with the binding metal (cobalt and / or Nickel powder) mixed and optionally over attritor grinding and Spray drying transferred into a ready-to-press powder batch. The so obtained Powder press approach can be too much using conventional pressing and sintering processes Process fine-grain carbide with very high phase homogeneity.

Nach einer zweiten Variante werden die Metalloxide, wie oben, im Zyklon zu Metallpulver reduziert. Im Unterschied zum oben beschriebenen Verfahren wird das so erhaltene Metallpulver ebenfalls nach dem erfindungswesentlichen Zyklon-Verfahren im Zyklon zu Metallkarbid weiterverarbeitet, und zwar gemäß zweier Untervarianten,
entweder im Anschluß an vorheriges externes Vermischen mit Kohlenstoffpartikeln (wie oben) durch gleichzeitiges Einblasen dieser Mischung zusammen mit Trägergas und eventuell mit Reaktionsgas in die Reaktionskammer,
oder nach einer zweiten Untervariante über direktes Einblasen des Metallpulvers gemeinsam mit gasförmigen Kohlenstoffverbindungen, insbesondere Kohlenwasserstoffgasen und/oder CO in den Zyklonreaktor. Auch diese Variante wird durch übliche Mahl-, Misch- und Granulierprozesse ergänzt, wobei Mahl- und Granuliervorgänge nicht zwingend erfolgen müssen.According to a second variant, the metal oxides are reduced to metal powder in the cyclone, as above. In contrast to the process described above, the metal powder obtained in this way is also further processed in the cyclone to metal carbide by the cyclone process which is essential to the invention, namely in two sub-variants,
either following prior external mixing with carbon particles (as above) by simultaneously blowing this mixture together with carrier gas and possibly with reaction gas into the reaction chamber,
or according to a second sub-variant, by directly blowing the metal powder into the cyclone reactor together with gaseous carbon compounds, in particular hydrocarbon gases and / or CO. This variant is also supplemented by customary grinding, mixing and granulating processes, with grinding and granulating processes not necessarily having to take place.

Gemäß einer dritten bevorzugten Variante des Verfahrens werden die Metalloxide gemeinsam mit einem Reduktionsgas und einem Kohlenstoff enthaltenden Gas in die Zyklon-Reaktionskammer eingelassen, bzw. eingeblasen und es erfolgt während eines einzigen Gesamtdurchlaufes in einem ersten Teil eines räumlich einheitlichen Gesamtreaktors zunächst die Reduktion des Oxides zu Metallpulver und unmittelbar anschließend in einem zweiten Kammerteil die Aufkohlung des reduzierten Metallpulvers zu Metallkarbid. According to a third preferred variant of the method, the Metal oxides together with a reducing gas and a carbon containing gas into the cyclone reaction chamber, or blown in and it takes place during a single overall run a first part of a spatially uniform overall reactor Reduction of the oxide to metal powder and immediately afterwards in one second chamber part to carburize the reduced metal powder Metal carbide.

Wie für die erste Variante ausgeführt, können auch beim Karburierungsprozeß im Zyklon neben dem Grundmetall, z.B. Wolfram und/oder Titan, Zusatzmetalle für die Mischkarbidbildung, wie Niob, Tantal, Vanadium und Chrom, beigegeben und gleichzeitig mit dem Hauptmetall zu Karbiden umgewandelt werden.
Für die begleitenden Misch-, Mahl- und Granuliervorgänge, sowie deren zwingende oder wahlweise Anwendung, gilt ebenfalls das Obengesagte.As stated for the first variant, in addition to the base metal, for example tungsten and / or titanium, additional metals for mixed carbide formation, such as niobium, tantalum, vanadium and chromium, can also be added to the carburizing process in the cyclone and simultaneously converted to carbides with the main metal.
The above also applies to the accompanying mixing, grinding and granulating processes, as well as their mandatory or optional use.

Das erfindungsgemäße Verfahren wird anhand der nachfolgenden Beispiele näher beschrieben.The process according to the invention is illustrated by the examples below described in more detail.

BEISPIEL 1:EXAMPLE 1:

Zur Durchführung des Reduktionsverfahrens wird als Vorrichtung ein Zyklon mit den Merkmalen vorliegender Erfindung und entsprechend der Darstellung in Figur 1 eingesetzt. Die in Figur 1 dargestellte Gesamtanlage setzt sich zusammen aus einer als Zyklon ausgestalteten Reaktionskammer aus Stahl, welcher eine zweite als Fallrohr ausgestaltete Reaktionskammer zur chemischen Nachbehandlung des reagierten Gutes nachgeschaltet ist, wobei diese Nachbehandlung und die zugehörige Reaktionskammer nicht Teil der Erfindung sind.
Es handelt sich dabei um eine im Vergleich mit Anlagen für industrielle Fertigung verkleinerte Pilotanlage, was die Durchsatzmenge an zu reduzierendem Gut pro Zeiteinheit anbelangt.A cyclone with the features of the present invention and corresponding to the representation in FIG. 1 is used as the device for carrying out the reduction process. The overall system shown in FIG. 1 is composed of a steel reaction chamber designed as a cyclone, which is followed by a second reaction chamber designed as a downpipe for chemical aftertreatment of the reacted material, this aftertreatment and the associated reaction chamber not being part of the invention.
It is a pilot plant that is smaller in comparison to plants for industrial production in terms of the throughput quantity of goods to be reduced per unit of time.

In der ersten Stufe wird erfindungsgemäß pulverförmiges W4O11 über eine Einspeisevorrichtung (1) gemeinsam mit Reaktions- und/oder Trägergas in den Kopfteil einer zur Fallrichtung etwa rotationssymmetrischen Reaktionskammer (2) eingeblasen. Die Gasmenge wird mittels eines Flußmeters (7) dosiert. Die Reaktionskammer wird mittels einer elektrischen Heizeinrichtung (6) auf Reaktionstemperatur von 1100°C gebracht. Das pulverförmige Reaktionsprodukt verläßt die Kammer am unteren Ende, fällt in einen Vorratsraum mit Förderschnecke (3) und wird über diese in die zweite Reaktionskammer (4) mit Heizeinrichtung (6) eingeleitet. Das Abgas (8), Reaktions- und/oder Trägergas sowie H2O-Dampf als Reaktions-Endprodukt, verlassen die erste Kammer an ihrem Kopfteil.
In der zweiten Prozeßstufe treten sowohl das reagierte Gut, das ist hochreines Wolframpulver, als auch die Abgase, am unteren Ende der senkrecht ausgerichteten rohrförmigen Kammer aus. Das Wolframpulver wird in einem Behälter (5) gesammelt.
Die Temperatursteuerung des gesamten zweistufigen Prozesses erfolgt mittels eines Thermoelementes (9) am Abgasauslaß der ersten Reaktionskammer.In the first stage, powdered W 4 O 11 is blown in via a feed device (1) together with reaction and / or carrier gas into the head part of a reaction chamber (2) which is approximately rotationally symmetrical with respect to the direction of fall. The amount of gas is metered by means of a flow meter (7). The reaction chamber is brought to a reaction temperature of 1100 ° C. by means of an electrical heating device (6). The pulverulent reaction product leaves the chamber at the lower end, falls into a storage room with screw conveyor (3) and is introduced into the second reaction chamber (4) with heating device (6). The exhaust gas (8), reaction and / or carrier gas and H 2 O vapor as the end product of the reaction leave the first chamber at the top.
In the second process stage, both the reacted material, that is high-purity tungsten powder, and the exhaust gases emerge at the lower end of the vertically aligned tubular chamber. The tungsten powder is collected in a container (5).
The temperature of the entire two-stage process is controlled by means of a thermocouple (9) at the exhaust outlet of the first reaction chamber.

Bei einer kontinuierlich zugegebenen Pulverdurchsatzmenge von 1000 g W4O11 (Wolframoxid blau) pro Stunde wird eine Gasmenge von 4000 l H2-Gas eingesetzt, das heißt ein großer Gasüberschuß bezogen auf die stöchiometrischen Reaktionsmengen. Wolframoxid als zu reduzierendes Gut und H2 als Träger- bzw. Reduktionsgas werden dem Zyklon getrennt zugeführt. Das Träger- bzw. Reduktionsgas wird am oberen Ende mit hoher Strömungsgeschwindigkeit vorzugsweise horizontal in die Kammer eingeleitet. Das pulverförmige zu reduzierende Gut wird so an die Gaseinlaßdüse herangeführt, daß es beim Eintritt in die Kammer vom Gasstrahl mitgerissen, mit diesem intensiv verwirbelt und vermischt wird und die Kammer entsprechend der Führung des Gasstromes auf vorbestimmten Flugbahnen durchläuft. Das zu Wolframpulver reduzierte Gut verläßt die Reduktionskammer nach 1 - 2 s Durchlaufzeit und besitzt beim Austritt einen Restsauerstoff-Gehalt von 10.500 µg/g. Das austretende Wolframpulver hat eine dem eingelassenen Pulver vergleichbare Korngröße von größenordnungsmäßig 20 um Durchmesser, wobei jedoch die einzelnen Pulverteilchen, bzw. -körner in ihrem gesamten Volumen durchgehend eine große Porigkeit aufweisen. Die räumliche Ausdehnung der Substruktur im Wolframpartikel liegt bei 0,1 µm.With a continuously added powder throughput of 1000 g W 4 O 11 (tungsten oxide blue) per hour, a gas amount of 4000 l H 2 gas is used, ie a large excess of gas based on the stoichiometric reaction amounts. Tungsten oxide as the material to be reduced and H 2 as the carrier or reducing gas are fed to the cyclone separately. The carrier or reducing gas is preferably introduced horizontally into the chamber at the upper end at a high flow rate. The pulverulent material to be reduced is brought up to the gas inlet nozzle in such a way that it is entrained by the gas jet as it enters the chamber, is swirled and mixed intensively with it, and passes through the chamber in accordance with the guidance of the gas flow on predetermined trajectories. The material reduced to tungsten powder leaves the reduction chamber after a passage time of 1-2 s and has a residual oxygen content of 10,500 µg / g at the outlet. The emerging tungsten powder has a grain size comparable to that of the powder taken in, of the order of 20 µm in diameter, but the individual powder particles or grains have a large porosity throughout their entire volume. The spatial expansion of the substructure in the tungsten particle is 0.1 µm.

Für die Herstellung hochreiner Wolframpulver mit sehr niedrigem SauerstoffRestgehalt wird der Reduktionsprozeß im Zyklon einmal wiederholt. For the production of high-purity tungsten powder with a very low residual oxygen content the reduction process in the cyclone is repeated once.

Das so gewonnene Wolframpulver wird nach üblichen Verfahren in Karbid umgewandelt. Dazu wird das Wolframpulver zunächst mit einem für Wolframkarbid, WC stöchiometrischen Anteil an feinen Rußteilchen in der Kugelmühle intensiv vermischt. Dabei werden einzelne Agglomerate des Wolframpulvers zerkleinert. Der so gewonnene Ansatz wird in einem Graphitofen mit Induktionsheizung unter H2-Atmosphäre bei 1300°C während 3 Stunden karburiert. Es entsteht reines Wolframkarbid mit einem Kohlenstoffgehalt von 6,12 % sowie einem Restsauerstoffgehalt von 1200 µg/g.The tungsten powder obtained in this way is converted into carbide by customary methods. For this purpose, the tungsten powder is first intensively mixed in the ball mill with a stoichiometric proportion of fine soot particles for tungsten carbide, WC. Individual agglomerates of the tungsten powder are crushed. The batch obtained in this way is carburized in a graphite furnace with induction heating under an H 2 atmosphere at 1300 ° C. for 3 hours. Pure tungsten carbide with a carbon content of 6.12% and a residual oxygen content of 1200 µg / g is formed.

Das Karbid wird mit Bindermetall und üblichen Mengen an Mischkarbiden (Niobkarbid, Tantalkarbid) vermischt und wahlweise über Attritormahlung und Sprühtrockung zu rieselfähigem Granulat verarbeitet.The carbide is made with binder metal and usual amounts of mixed carbides (Niobium carbide, tantalum carbide) mixed and optionally via attritor grinding and Spray drying processed into free-flowing granules.

Aus derartigen Pulveransätzen mittels Pressen und Sintern nach üblichen Verfahren hergestellte Hartmetallproben besitzen außergewöhnlich große Feinkömigkeit bei sehr homogener Hartmetallstruktur.From such powder batches by means of pressing and sintering according to the usual Processed carbide samples have exceptionally large Fine grain with a very homogeneous carbide structure.

BEISPIEL 2:EXAMPLE 2:

Die verwendete Vorrichtung entspricht derjenigen von Beispiel 1, ohne daß dem Zyklon ein Fallrohr nachgeschaltet ist.
Wolframoxid, blau, wird entsprechend der in Beispiel 1 genannten Verfahrensbedingungen im Zyklon zu Wolframpulver reduziert.
Abweichend von Beispiel 1 wird das Wolframpulver anschließend ebenfalls in einem mit Graphit ausgekleideten Zyklonreaktor mit Hilfe von kohlenstoffhaltigen Gasen plus Trägergas (CH4/H2-Gemisch) zu Wolframkarbid weiterverarbeitet. Die Karburierung erfolgt einstufig bei einer Zyklon-Temperatur von 1100°C.
Für einen Wolframpulver-Durchsatz von 1000g/h wird ein Gasdurchsatz von 6000 l/h einreguliert. Die Methankonzentration im CH4/H2-Gemisch beträgt 1,1 Vol.%. Das entspricht einer C-Aktivität von 0,8 g/mol bei 1100°C. Das eingeblasene Wolframpulver verläßt den Zyklon nach 4 s als Mischung aus W2C und WC, jedoch ohne Anteile an freiem Kohlenstoff. Der KohlenstoffGehalt im Karbid beträgt 4,5 Gew.%, der Restsauerstoff-Gehalt 2390 µg/g. Dabei ist ein unverzichtbarer, entscheidender Vorteil, daß Reaktionsgas durch die Mikroporosität des Ausgangspulvers unmittelbar an den Ort der Reaktion gelangt und dadurch die Reduktionsgeschwindigkeit hoch ist.
Das so erhaltene Gemisch W2C / WC wird in einem zweiten Durchlauf durch den Zyklonreaktor unter etwa gleichen Bedingungen wie oben zu reinem Wolframkarbid WC (C-Gehalt = 6,12 %) umgewandelt.The device used corresponds to that of Example 1 without a downpipe being connected downstream of the cyclone.
Tungsten oxide, blue, is reduced to tungsten powder in the cyclone in accordance with the process conditions mentioned in Example 1.
In a departure from example 1, the tungsten powder is then further processed into tungsten carbide in a cyclone reactor lined with graphite using carbon-containing gases plus carrier gas (CH 4 / H 2 mixture). Carburization takes place in one step at a cyclone temperature of 1100 ° C.
A gas throughput of 6000 l / h is regulated for a tungsten powder throughput of 1000 g / h. The methane concentration in the CH 4 / H 2 mixture is 1.1% by volume. This corresponds to a C activity of 0.8 g / mol at 1100 ° C. The injected tungsten powder leaves the cyclone after 4 s as a mixture of W 2 C and WC, but without free carbon. The carbon content in the carbide is 4.5% by weight, the residual oxygen content is 2390 µg / g. It is an indispensable, decisive advantage that reaction gas reaches the site of the reaction directly through the microporosity of the starting powder and the rate of reduction is high as a result.
The mixture W 2 C / WC thus obtained is converted in a second pass through the cyclone reactor under approximately the same conditions as above to pure tungsten carbide WC (C content = 6.12%).

Entsprechend Beispiel 1 werden preßfertige Pulveransätze durch Vermischen des WC mit Bindermaterial und kleinen Anteilen an Mischkarbiden bei wahlweiser Granulierung mittels Sprühtrocknung fertiggestellt.
Das aus diesen Pulveransätzen gewonnene Hartmetall entspricht in seiner feinkörnigen Struktur und Homogenität demjenigen nach Beispiel 1.According to Example 1, ready-to-press powder batches are produced by mixing the WC with binder material and small proportions of mixed carbides with optional granulation by means of spray drying.
The hard metal obtained from these powder batches corresponds in its fine-grained structure and homogeneity to that according to Example 1.

BEISPIEL 3:EXAMPLE 3

Ausgestaltung der Zyklon-Vorrichtung und Reduktionsverfahren des Wolframoxids zu Wolframpulver in zwei aufeinanderfolgenden Durchläufen entsprechen denjenigen von Beispiel 1.Design of the cyclone device and reduction process of Tungsten oxide to tungsten powder in two successive runs correspond to those of Example 1.

Die anschließende Karburierung erfolgt wiederum im Zyklonreaktor, jedoch im Unterschied zu Beispiel 2 unter Verwendung von CO als Karburierungs- und Trägergas. Das aus dem Zyklonreaktor gewonnene Wolframpulver wird dazu bei einer Durchsatzmenge von 1000 g/h mit einer Gasmenge von 6000 l/h (CO-Gas) kontinuierlich in die Kammer eingebracht und bei 1000°C Kammertemperatur in einem einstufigen Prozeß zu W2C und WC (C-Gehalt 4,2 Gew.%) und einem Restsauerstoff-Gehalt von 3240 µg/g reagiert Die Röntgendiffraktometer-Untersuchung ergibt, daß neben W2C geringe Mengen WC, aber kein freier Kohlenstoff im so erhaltenen Endprodukt vorhanden ist. Die Durchlaufzeit für die zu karburierenden Teilchen im Zyklonreaktor beträgt 1 - 2 s. The subsequent carburization is again carried out in the cyclone reactor, but in contrast to Example 2, using CO as the carburizing and carrier gas. The tungsten powder obtained from the cyclone reactor is continuously introduced into the chamber at a throughput of 1000 g / h with a gas quantity of 6000 l / h (CO gas) and at 1000 ° C. chamber temperature in a one-step process to produce W 2 C and WC (C content 4.2% by weight) and a residual oxygen content of 3240 µg / g reacts. The X-ray diffractometer examination shows that in addition to W 2 C, small amounts of WC but no free carbon are present in the end product thus obtained. The throughput time for the particles to be carburized in the cyclone reactor is 1-2 s.

Das so gewonnene W2C-WC-Pulvergemisch wird in einem zweiten Verfahrensschritt im Zyklon unter etwa den gleichen Versuchsbedingungen wie für die erste Karburierungsstufe zu reinem Wolframkarbid WC bei nur sehr kleinem Sauerstoffrest-Gehalt und ohne nachweisbare Reste an freiem Kohlenstoff weiterreagiert.
Die Fertigstellung der Pulversätze über Mischen und wahlweises Granulieren erfolgt wie in den Beispielen 1 und 2.
Ein aus diesen Pulveransätzen nach üblichen Verfahren hergestelltes Hartmetall weist hohe Feinkörnigkeit und hohe Materialhomogenität auf.The W 2 C-WC powder mixture obtained in this way is reacted in a second process step in the cyclone under approximately the same test conditions as for the first carburization step to pure tungsten carbide WC with only a very small residual oxygen content and without detectable free carbon residues.
The powder sets are completed by mixing and optionally granulating as in Examples 1 and 2.
A hard metal made from these powder batches by customary processes has a high degree of fine grain and a high degree of material homogeneity.

Claims (5)

  1. A process for the production of powder pressing feedstocks for metal carbide based, fine grain hard metal, starting from metal oxide powder or from reducible, pulverulent metal compounds and comprising the process steps
    reduction of the oxide or the metal compound to yield the metal
    carburisation of the metal
    a mechanical-chemical powder grain treatment and/or mixing process
    characterised in that,
    in at least one of the two chemical process steps, reduction and carburisation, a cyclone apparatus and the cyclone process are used, which exhibit the sum of the following features
    the apparatus is a temperature-controllable reaction chamber, at least a portion of which is approximately rotationally symmetrical around the longitudinal axis of the apparatus, with inlet and outlet openings both for the pulverulent material to be reduced and/or to be carburised and for substances reacting with the material and for carrier gas,
    the continuously introduced pulverulent material, while retaining the solid phase state, passes through the reaction chamber at elevated powder velocities on predetermined flight paths which are at least in part tangential to the chamber wall
    the flight paths are controlled by means of the flight direction and velocity of the pulverulent material on introduction and by means of the flow parameters of the carrier and/or reaction gas at the inlet
    the pulverulent material leaves the apparatus, having reacted chemically at least to an extent of 90 vol.%, on average 0.1-60 s after being introduced.
  2. A process for the production of powder pressing feedstocks according to claim 1, characterised in that the pulverulent material is converted into the predetermined reaction state during a transit time of 0.2-10 s.
  3. A process for the production of powder pressing feedstock according to claims 1 to 2, characterised in that elevated relative velocities between solid and gaseous substances arise in the apparatus.
  4. A process for the production of powder pressing feedstocks according to claims 1 to 3, characterised in that at least one of the two process steps, reduction and carburisation, is repeated at least once.
  5. A process for the production of powder pressing feedstocks according to claims 1 to 4, characterised in that, prior to reduction, metallic additional materials are added to the metal oxide powder or to the pulverulent metal compound in the form of a separate powder or by prior formation of a solid solution in the material to be reduced.
EP97203354A 1996-11-04 1997-10-29 Process for preparing a starting powder material for fine grained hard metal Expired - Lifetime EP0839920B1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AT0191296A AT404912B (en) 1996-11-04 1996-11-04 METHOD FOR PRODUCING POWDER PRESSING APPARATUS FOR FINE-GRAINED HARD METAL
AT1912/96 1996-11-04
AT191296 1996-11-04

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EP0839920A3 EP0839920A3 (en) 2000-03-29
EP0839920B1 true EP0839920B1 (en) 2002-12-18

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JP4619907B2 (en) * 2005-09-20 2011-01-26 中外炉工業株式会社 Powder production equipment
US20130209308A1 (en) * 2012-02-15 2013-08-15 Baker Hughes Incorporated Method of making a metallic powder and powder compact and powder and powder compact made thereby
JP2013222497A (en) * 2012-04-12 2013-10-28 Toshiba Corp Contact material for vacuum valve
CN112390261A (en) * 2019-08-13 2021-02-23 斯特里特技术有限公司 System and method for separation and dehydrogenation of fumed silica particles
CN114853021A (en) * 2022-05-23 2022-08-05 赣州海盛钨业股份有限公司 Nano tungsten carbide powder and preparation method thereof

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EP0839920A2 (en) 1998-05-06
DE59709001D1 (en) 2003-01-30
JPH10140216A (en) 1998-05-26
AT404912B (en) 1999-03-25
ATE230038T1 (en) 2003-01-15
ATA191296A (en) 1998-08-15
ES2186840T3 (en) 2003-05-16
EP0839920A3 (en) 2000-03-29

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