EP1373586B1 - Procede de production d'un granulat en metal dur - Google Patents

Procede de production d'un granulat en metal dur Download PDF

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Publication number
EP1373586B1
EP1373586B1 EP02703390A EP02703390A EP1373586B1 EP 1373586 B1 EP1373586 B1 EP 1373586B1 EP 02703390 A EP02703390 A EP 02703390A EP 02703390 A EP02703390 A EP 02703390A EP 1373586 B1 EP1373586 B1 EP 1373586B1
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EP
European Patent Office
Prior art keywords
hard metal
producing
spray
wet slurry
spray tower
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Expired - Lifetime
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EP02703390A
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German (de)
English (en)
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EP1373586A2 (fr
Inventor
Gerhard Knünz
Helmut Beirer
Andreas Lackner
Wolfgang GLÄTZLE
Erwin Hartlmayr
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Ceratizit Austria GmbH
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Ceratizit Austria GmbH
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00—Making metallic powder or suspensions thereof
    • B22F9/02—Making metallic powder or suspensions thereof using physical processes
    • B22F9/06—Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • 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
    • B22F9/026—Spray drying of solutions or suspensions
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
    • C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
    • C22C29/06—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds
    • C22C29/08—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides based on carbides, but not containing other metal compounds based on tungsten carbide
    • 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
    • B22F2998/10—Processes characterised by the sequence of their steps
    • 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

Definitions

  • the invention relates to a method for producing a hard metal granules by wet grinding the desired in the finished granules hard material and binder metal and forming a sprayable wet sludge using pure water as a liquid phase, wherein the wet sludge by spray drying in a gas stream with a gas inlet temperature in the range of about 160 to 220 ° C and a gas outlet temperature in the range of about 85 to 130 ° C in a spray tower in granular form, wherein the spray tower consists of a cylindrical portion and a conical portion.
  • Carbide-alloy shaped parts are produced by pressing and sintering the powdery starting materials.
  • the individual hard material and binding metal powders are first brought into the form of a wet sludge by grinding with the addition of liquid in finely disperse mixture.
  • this step is associated with a comminution of the starting powder, while in fine-grained starting powders mainly a homogenization of the wet sludge takes place.
  • the liquid is intended on the one hand to prevent the caking of the powder particles and on the other hand their oxidation during the grinding.
  • Attritors As a suitable grinding units today almost exclusively agitator ball mills so-called attritors are used in which the ground material is mixed in a cylindrical container together with carbide balls by a multi-bladed stirring in motion.
  • a pressing aid eg in the form of paraffin
  • the addition of a pressing aid is particularly necessary when the finished granules are compacted by die pressing and brought into the desired shape.
  • the pressing aid gives the granules in addition to the better compression during the pressing process also a better flowability, which facilitates the filling of the press dies.
  • the wet sludge is usually added no pressing aid.
  • the wet sludge is then brought to a sprayable consistency and dried in a spray drying plant and granulated at the same time.
  • the wet sludge is sprayed through a nozzle, which is located inside a spray tower.
  • a hot gas stream dries the sprayed droplets on the flight path and these are deposited in the lower conical part of the spray tower in the form of small pellets as granules, where it can then be removed.
  • the attritors and the spray-drying plant must be explosion-proof, which entails a high constructive effort and thus high investment costs.
  • the drying in the spray tower under a protective gas atmosphere, usually nitrogen, must be performed.
  • the spray towers of spray drying in the cemented carbide industry are designed with a cylindrical upper portion and a tapered, lower portion and work in countercurrent to the fountain principle, ie located in the lower portion of the spray tower is centrally arranged the spray lance the wet sludge from high pressure about 12 to 24 bar sprayed in the form of a fountain upwards.
  • the gas stream for drying the sprayed droplets is from above against the Spraying the droplets out and leaves the spray tower in the upper third of the tapered section below the spray lance. In this way, the droplets are first pushed upwards and then diverted downwards due to gravity and the oppositely directed gas flow. In the course of running this drying path, the droplets are converted into a compact granules with a low residual moisture, which then trickles after hitting the bottom of the spray tower by its tapered course automatically to the central discharge opening.
  • Spray towers operating countercurrently according to the fountain principle are in practice designed with a cylindrical section having a height in the range of about 2 to 9 meters with a height to diameter number ratio in the range of about 0.9 to 1.7 while Spray towers operating cocurrently with supply from above are designed with a cylindrical section having a height in the range of about 5 - 25 m with a numerical ratio of height to diameter in the range of about 1 to 5.
  • carbide includes, of course, so-called cermets, a special group of hard metals with usually nitrogen-containing hard materials.
  • the US 4,070,184 describes a process for the production of a cemented carbide granulate by milling and spray-drying, in which pure water is used instead of organic solvents for grinding and producing the sprayable wet sludge.
  • pure water as a liquid phase makes it possible to produce the attritors and the spray-drying plant in an open, no longer explosion-proof construction, which brings significant cost savings.
  • spray drying instead of inert gas, air can be used as the dry medium.
  • the complete replacement of organic solvents avoids any health hazard from solvent vapors.
  • a disadvantage is that such polyglycols show an unfavorable evaporation behavior during sintering of the pressed powder. It comes only at temperatures of about 250 to 300 ° C to a complete evaporation, which can cause bursting of the part or to form cracks especially for large parts due to the evaporation over a wide temperature range.
  • the object of the present invention is therefore to provide a method for producing a hard metal granules by grinding and spray drying using pure water as the liquid phase, in which also extremely fine-grained hard metal powder can be ground and sprayed and in which the disadvantages mentioned in the prior art are avoided during sintering.
  • this is inventively achieved in that the wet sludge is sprayed and dried without using a water-soluble, long-chain polyglycol in the spray tower and that the spray tower is designed and operated so that the numerical ratio of the supplied via the wet sludge amount of water in liters per hour , based on the tower volume in m 3 in the range between 0.5 and 1.8 and that a maximum of 0.17 kg wet sludge per m 3 supplied drying gas are atomized, wherein the wet sludge has a solids content in the range of 65 to 85 wt.% ,
  • the essence of the method according to the invention is to keep the amount of water supplied via the wet sludge in relation to the tower volume significantly smaller than is usual in spray towers and adjust the amount of air supplied to the sprayed wet sludge so that at least 1 m 3 air per 0.17 kg wet sludge is available.
  • a solids content of the wet sludge in the range from 70 to 80% by weight has proven to be particularly advantageous.
  • Oxidation of even extremely fine-grained starting powder is largely prevented under the process conditions mentioned, so that the waiver on polyglycols also in the granule production is associated with no disadvantages.
  • the carbon balance taking into account the chemical analysis of the starting powder used and the oxygen uptake during milling and spray drying is adjusted, possibly by adding carbon before milling, that with the hard metal granules the production of a finished sintered carbide without eta-phase and without free carbon is guaranteed.
  • the average particle size of the granules produced is generally between 90 and 250 microns and can be adjusted by the size of the spray nozzle opening, the viscosity of the wet sludge to be sprayed and the spray pressure.
  • the amount of wet sludge supplied via the spray nozzle is in turn regulated by the spray pressure and by the size of the swirl chamber and nozzle opening of the spray nozzle.
  • the method according to the invention is applicable both to spray-drying plants operating in the cocurrent principle and those operating in countercurrent flow, it has proven particularly useful in countercurrent systems using the fountain principle, whereby the spray-drying plant can be manufactured in a compact design.
  • a particular advantage of the method according to the invention is that air can be used as the drying gas, which in turn makes the method extremely cost-effective.
  • a single-substance nozzle for spraying the wet sludge.
  • single-substance nozzles in contrast to two-component nozzles where the wet sludge to be atomized is fed simultaneously with a gas stream to the nozzle, only the wet sludge is supplied under pressure, so that contact with a possibly oxidizing gas stream is further shortened.
  • the milling preferably takes place in the attritor with a viscosity of the wet sludge in the range from 2,500 to 8,000 mPas (measured in a rheometer of the RC20 type from Europhysics at a shear rate of 5.2 [1 / s ]) is carried out at least 4 to 8 times volume exchange per hour.
  • an antioxidant for example based on amine compounds, e.g. Add aminoxethylate or resorcinol, whereby even at longer meals and during subsequent spraying excessive oxidation of the particles can be prevented.
  • the process according to the invention is carried out using a countercurrent spray-drying plant according to the fountain principle, it is advantageous to determine the temperature of the incoming drying air at the upper end of the cylindrical section and the temperature of the exiting drying air in the region of the conical section of the spray tower within the stated ranges to agree that sets a temperature between about 70 and 120 ° C in the geometric center of gravity of the spray tower. Under these conditions, the lowest possible oxidation of the hard metal granules is achieved.
  • the cooling of the granules in the outlet region of the cooling tower is most expedient in that the conically tapered portion of the spray tower is double-walled and is cooled by a suitable cooling medium.
  • the rapid cooling to room temperature for example, take place in that the granules after removal from the spray tower passes through a cooling trough.
  • FIG. 1 shows the schematic diagram of a spray tower for carrying out the method according to the invention.
  • the spray tower -1- consists of a cylindrical portion -2- and an adjoining, tapered downwardly tapered section -3-.
  • the spray tower -1- works in countercurrent to the fountain principle, i. the gas stream for drying the granules is fed at the upper end -11- of the cylindrical portion -2- and blown down, while to be atomized wet sludge at the lower end of the cylindrical portion -2- via a spray lance -4- with a nozzle opening -5 - Is sprayed upward against the direction of the gas flow -6- on the principle of a fountain upwards.
  • the sprayed liquid droplets -7- are thus first directed upward and then change due to the opposite gas flow and due to gravity their direction and fall down. Before hitting the bottom of the spray tower -1-, the tapered portion -3-, the liquid droplets -7- must be converted into the dried granules.
  • the gas stream -6- has an inlet temperature in the range of 160 to 220 ° C and an exit temperature when leaving the spray tower through the outlet pipe -9- below the spray lance -4- in the upper third of the conical section -3-, ranging from 85 to 130 ° C.
  • the gas inlet and outlet gas temperature are advantageously coordinated so that sets a temperature between about 70 and 120 ° C in the geometric center of gravity -S- of the spray tower.
  • the amount of energy provided by the temperature conditions and the amount of the supplied drying gas which is sufficient for easy evaporation of the supplied via the wet sludge amount of water.
  • tapered portion -3- of the spray tower is double-walled for passing a cooling liquid, e.g. Water, running.
  • the granules are cooled in this area to at least 75 ° C.
  • tungsten carbide granulate having an average particle size of 135 ⁇ m, consisting of 6% by weight of cobalt, 0.4% by weight of vanadium carbide, remainder tungsten carbide, 36 kg of cobalt powder having an average particle size of about 0.63 ⁇ m FSSS and an oxygen content of 0.56 wt.%, 2.4 kg vanadium carbide powder with an average particle size of about 1.2 ⁇ m FSSS and an oxygen content of 0.25 wt.% And 563.5 kg tungsten carbide powder with a BET surface area of 1.78 m 2 / g, which corresponds to an average grain size of about 0.6 microns and an oxygen content of 0.28 wt.% Milled with 150 liters of water in an attritor for 5 hours.
  • a spray tower -1- was used with a cylindrical portion -2- with a height of 6 m and a diameter of 4 m and with a tapered portion -3- with a cone angle of 50 °, resulting in a Tower volume of 93 m 3 corresponds.
  • the spray tower was designed to operate in countercurrent to the fountain principle.
  • air was used, which was supplied to the spray tower at 4000 m 3 / h.
  • the slurry was fed to the spray tower through a spray lance 4 with a single fluid nozzle -5- with an outlet opening of 1.12 mm diameter at a pressure of 15 bar, resulting in a slurry feed of 0.08 kg wet sludge per m 3 of drying air revealed.
  • the air outlet temperature was set to a constant value of 85 ° C, which was achieved under the given conditions by an air inlet temperature of 145 ° C.
  • the atomization of 0.08 kg of wet sludge per m 3 of supplied drying air means that at an air feed of 4000 m 3 per hour 320 kg of wet sludge were sprayed per hour. Since the wet sludge was adjusted to 75 wt.% Solids content, the 320 kg wet sludge per hour correspond to an hourly supplied amount of water of 80 liters.
  • the ratio of the amount of water supplied in liters per hour, based on the tower volume, was therefore 80 l / h 0.86 1 . 93 m 3 m 3 .h
  • the oxygen content of the granules produced was 0.53 wt.%.
  • FIG. 2 shows an SEM image of the carbide granules produced according to the example with an average particle size of 135 microns in 100-fold magnification.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
  • Glanulating (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)
  • Treatment Of Sludge (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

L'invention concerne un procédé permettant de produire un granulat de métal dur par mouture humide et séchage par pulvérisation dans une tour de pulvérisation 1 à l'aide d'eau pure comme phase liquide. Selon l'invention, la tour de pulvérisation 1 se présente et est actionnée de manière que le rapport de la quantité d'eau, exprimée en litres par seconde, acheminée par l'intermédiaire des boues humides, par rapport au volume de la tour exprimé en m3 se situe entre 0,5 et 1,8, et qu'au maximum 0,17 kg de boues humides par m3 de gaz de séchage soit acheminé. Les boues humides présentent une teneur solide de l'ordre de 65 à 85 % en poids. Ces conditions étant posées, l'adjonction nécessaire habituelle aux boues humides, de polyalcool à chaîne longue, soluble dans l'eau, avant la pulvérisation, afin d'empêcher toute oxydation du granulat de métal dur, n'est plus indispensable.

Claims (9)

  1. Procédé de fabrication d'un granulat de métal dur par broyage humide des parts de substance dure et de métal liant prévues dans le granulat fini et élaboration d'une barbotine humide pulvérisable avec de l'eau pure comme phase liquide, dans lequel on transforme la barbotine en granulat en la séchant par pulvérisation dans un flux de gaz dont la température d'entrée est comprise entre 160 et 220°C environ et la température de sortie entre 85 et 130°C, à l'intérieur d'une tour de pulvérisation (1) constituée d'une partie cylindrique (2) et d'une partie conique (3), caractérisé en ce que la barbotine est pulvérisée et séchée dans la tour (1) sans utilisation d'un polyglycol à chaîne longue soluble dans l'eau, en ce que la tour de pulvérisation (1) est dimensionnée et mise en oeuvre de telle sorte que le rapport entre la quantité d'eau apportée par la barbotine humide, en litres par heure, et le volume en m3 de la tour, est compris entre 0,5 et 1,8, et en ce que la quantité de barbotine pulvérisée est au maximum de 0,17 kg par m3 de gaz de séchage introduit, la teneur en substance dure de la barbotine humide étant comprise entre 65 et 85 % en poids.
  2. Procédé selon selon la revendication 1, caractérisé en ce que la teneur en substance dure de la barbotine humide est comprise entre 70 et 80 % en poids.
  3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le séchage par pulvérisation est effectué à contre-courant, selon le principe des jets ascendants.
  4. Procédé selon la revendication 3, caractérisé en ce que la température du gaz à l'admission et la température du gaz à la sortie sont coordonnées de sorte telle qu'au barycentre géométrique (S) de la tour de pulvérisation (1), la température s'établit entre environ 70 et 120°C.
  5. Procédé selon l'une quelconque des revendications 1 à 4, caractérisé en ce que le gaz employé est de l'air.
  6. Procédé selon l'une quelconque des revendications 1 à 5, caractérisé en ce que l'on utilise une buse à flux unique pour la pulvérisation de la barbotine.
  7. Procédé selon l'une quelconque des revendications 1 à 6, caractérisé en ce que le broyage est effectué, de préférence en attriteur, avec une barbotine humide dont la viscosité est comprise entre 2.500 et 8.000 mPas et avec un échange de volume d'au moins 4 à 8 fois par heure.
  8. Procédé selon l'une quelconque des revendications 1 à 7, caractérisé en ce qu'un antioxydant à base de composés amine est ajouté à l'eau avant le broyage humide et/ou le séchage par pulvérisation.
  9. Procédé selon l'une quelconque des revendications 1 à 8, caractérisé en ce que le granulat est refroidi à une température maximum de 75°C lorsqu'il se trouve dans le secteur de sortie (3) de la tour de pulvérisation (1) et en ce qu'il est rapidement refroidi à la température ambiante aussitôt après son extraction de la tour de refroidissement.
EP02703390A 2001-03-29 2002-03-08 Procede de production d'un granulat en metal dur Expired - Lifetime EP1373586B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AT0023101U AT4929U1 (de) 2001-03-29 2001-03-29 Verfahren zur herstellung von hartmetallgranulat
AT2312001 2001-03-29
PCT/AT2002/000077 WO2002079532A2 (fr) 2001-03-29 2002-03-08 Procede de production d'un granulat en metal dur

Publications (2)

Publication Number Publication Date
EP1373586A2 EP1373586A2 (fr) 2004-01-02
EP1373586B1 true EP1373586B1 (fr) 2010-08-11

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EP02703390A Expired - Lifetime EP1373586B1 (fr) 2001-03-29 2002-03-08 Procede de production d'un granulat en metal dur

Country Status (12)

Country Link
US (1) US6852274B2 (fr)
EP (1) EP1373586B1 (fr)
JP (1) JP3697242B2 (fr)
KR (1) KR100898842B1 (fr)
AT (2) AT4929U1 (fr)
CA (1) CA2406372C (fr)
CZ (1) CZ304422B6 (fr)
DE (1) DE50214577D1 (fr)
ES (1) ES2346190T3 (fr)
IL (1) IL152968A (fr)
RU (1) RU2281835C2 (fr)
WO (1) WO2002079532A2 (fr)

Cited By (3)

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CN102601378A (zh) * 2011-07-18 2012-07-25 厦门虹鹭钨钼工业有限公司 一种低温燃烧法制备超细钨铜复合粉末的方法
EP2857124A1 (fr) 2013-10-03 2015-04-08 Kennametal Inc. Suspension aqueuse permettant de fabriquer une poudre de matériau dur
EP2860274A2 (fr) 2013-10-04 2015-04-15 Kennametal India Limited Matériau dur et son procédé de fabrication à partir d'une boue aqueuse de broyage contenant le matériau dur.

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DE102004053221B3 (de) * 2004-11-04 2006-02-02 Zschimmer & Schwarz Gmbh & Co. Kg Chemische Fabriken Flüssigkeit und deren Verwendung zur Aufbereitung von Hartmetallen
DE102006043581B4 (de) * 2006-09-12 2011-11-03 Artur Wiegand Verfahren und Vorrichtung zur Herstellung einer Hartmetall- oder Cermetmischung
US8500857B2 (en) 2007-05-21 2013-08-06 Peter Eisenberger Carbon dioxide capture/regeneration method using gas mixture
US8163066B2 (en) 2007-05-21 2012-04-24 Peter Eisenberger Carbon dioxide capture/regeneration structures and techniques
US20080289495A1 (en) * 2007-05-21 2008-11-27 Peter Eisenberger System and Method for Removing Carbon Dioxide From an Atmosphere and Global Thermostat Using the Same
US20140130670A1 (en) 2012-11-14 2014-05-15 Peter Eisenberger System and method for removing carbon dioxide from an atmosphere and global thermostat using the same
DE102007024818A1 (de) * 2007-05-29 2008-12-04 Dorst Technologies Gmbh & Co. Kg Verfahren und Anordnung zum Herstellen eines Metallgranulats
EP3653282A1 (fr) 2010-04-30 2020-05-20 Peter Eisenberger Système et procédé pour la capture et la séquestration de dioxyde de carbone
US9028592B2 (en) 2010-04-30 2015-05-12 Peter Eisenberger System and method for carbon dioxide capture and sequestration from relatively high concentration CO2 mixtures
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US11059024B2 (en) 2012-10-25 2021-07-13 Georgia Tech Research Corporation Supported poly(allyl)amine and derivatives for CO2 capture from flue gas or ultra-dilute gas streams such as ambient air or admixtures thereof
EP3089809A4 (fr) 2013-12-31 2017-10-25 Chichilnisky, Graciela Système de mouvement de lit multi-monolithe rotatif pour retirer le co2 de l'atmosphère
CZ305703B6 (cs) * 2014-11-07 2016-02-10 Vysoká škola chemicko- technologická v Praze Výroba nanostrukturovaných prášků slitin kobaltu dvoustupňovým mechanickým legováním
CN107699283B (zh) * 2017-11-03 2020-11-06 河源富马硬质合金股份有限公司 一种高蜡比硬质合金石蜡原料的制备方法
CN112692294B (zh) * 2020-12-22 2022-12-09 厦门钨业股份有限公司 一种高比重钨合金粉末及其制备方法

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102601378A (zh) * 2011-07-18 2012-07-25 厦门虹鹭钨钼工业有限公司 一种低温燃烧法制备超细钨铜复合粉末的方法
EP2857124A1 (fr) 2013-10-03 2015-04-08 Kennametal Inc. Suspension aqueuse permettant de fabriquer une poudre de matériau dur
US9475945B2 (en) 2013-10-03 2016-10-25 Kennametal Inc. Aqueous slurry for making a powder of hard material
US9796633B2 (en) 2013-10-03 2017-10-24 Kennametal Inc. Aqueous slurry for making a powder of hard material
EP2860274A2 (fr) 2013-10-04 2015-04-15 Kennametal India Limited Matériau dur et son procédé de fabrication à partir d'une boue aqueuse de broyage contenant le matériau dur.
US10538829B2 (en) 2013-10-04 2020-01-21 Kennametal India Limited Hard material and method of making the same from an aqueous hard material milling slurry

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KR20030007549A (ko) 2003-01-23
CA2406372C (fr) 2010-09-14
ATE477342T1 (de) 2010-08-15
IL152968A (en) 2007-10-31
ES2346190T3 (es) 2010-10-13
US6852274B2 (en) 2005-02-08
AT4929U1 (de) 2002-01-25
RU2003131683A (ru) 2005-02-10
CZ304422B6 (cs) 2014-04-30
JP2004518825A (ja) 2004-06-24
DE50214577D1 (de) 2010-09-23
RU2281835C2 (ru) 2006-08-20
KR100898842B1 (ko) 2009-05-21
JP3697242B2 (ja) 2005-09-21
EP1373586A2 (fr) 2004-01-02
US20030061906A1 (en) 2003-04-03
CA2406372A1 (fr) 2002-10-16
IL152968A0 (en) 2003-06-24
WO2002079532A3 (fr) 2003-02-27
WO2002079532A2 (fr) 2002-10-10

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