EP1373585B2 - Procede de production d'un element saillant en metal dur - Google Patents

Procede de production d'un element saillant en metal dur Download PDF

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Publication number
EP1373585B2
EP1373585B2 EP02703388A EP02703388A EP1373585B2 EP 1373585 B2 EP1373585 B2 EP 1373585B2 EP 02703388 A EP02703388 A EP 02703388A EP 02703388 A EP02703388 A EP 02703388A EP 1373585 B2 EP1373585 B2 EP 1373585B2
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EP
European Patent Office
Prior art keywords
hard metal
drying
slurry
producing
spray
Prior art date
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Expired - Lifetime
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EP02703388A
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German (de)
English (en)
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EP1373585B1 (fr
EP1373585A2 (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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Application filed by Ceratizit Austria GmbH filed Critical Ceratizit Austria GmbH
Priority to DK02703388T priority Critical patent/DK1373585T4/da
Priority to AT02703388T priority patent/ATE295903T1/de
Publication of EP1373585A2 publication Critical patent/EP1373585A2/fr
Publication of EP1373585B1 publication Critical patent/EP1373585B1/fr
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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
    • B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
    • 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
    • C22C1/10—Alloys containing non-metals
    • C22C1/1084—Alloys containing non-metals by mechanical alloying (blending, milling)
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic 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
    • C22C1/00—Making non-ferrous alloys
    • C22C1/04—Making non-ferrous alloys by powder metallurgy
    • C22C1/05—Mixtures of metal powder with non-metallic powder
    • C22C1/051—Making hard metals based on borides, carbides, nitrides, oxides or silicides; Preparation of the powder mixture used as the starting material therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • the invention relates to a process for producing a hard metal batch from hard material fractions, binder metal fractions and water-insoluble compression assistant fractions by drying a wet sludge containing the constituents with pure water as the liquid phase.
  • Carbide-alloy shaped parts are produced by pressing and sintering a mixture of the powdery starting materials, the so-called hard metal batch.
  • the individual hard and binder metal powders are first brought by grinding with the addition of liquid in finely disperse mixture in the form of a wet sludge.
  • this step is associated with comminution of the starting powders, while with fine-grained starting bulbs, mainly homogenisation 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 Mahtaggregate 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 facilitates the compression of the hard metal approach during the pressing process and results in a better green strength and thus improved handling of the pressed moldings.
  • the wet sludge is then dried to form the finished hard metal batch which is further processed by pressing and sintering.
  • a commonly used method of drying is spray drying.
  • the wet slurry brought to a sprayable consistency 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 separate in the lower conical part of the spray tower in the form of small beads as so-called hard metal granules, where it can then be removed.
  • the cemented carbide approach is in granular form, this has the great advantage that the flowability of the hard metal approach is significantly improved, whereby the filling of the press dies is facilitated.
  • 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 located 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 directed from above against the spray direction of the droplets and leaves the spray tower in the upper third of the tapered portion 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.
  • 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 made with a cylindrical section having a height in the range of about 5 to 25 meters with a height to diameter number ratio 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.
  • US-A-5922978 discloses a process in which hard material components, binder metal components and pressing assistant components in the water are mixed to form a wet sludge, e.g. B. by grinding.
  • the auxiliary ingredients are preferably added as a paraffin water emulsion.
  • the order of addition of hard material components, binder metal components and compression assistant components is not fixed.
  • the US 4,397,889 describes a method for producing a hard metal batch in which an insoluble in the liquid grinding medium used pressing aid is used.
  • an insoluble in the liquid grinding medium used pressing aid for example, paraffin is also mentioned as a pressing aid and water as a grinding medium.
  • it is proposed according to the US Patent first to heat the hard material powder fractions with or without binding metal content to a temperature above the melting point of the pressing aid and then to mix with the pressing aid. Then the powder mixture is cooled as quickly as possible to keep oxidation of the powder within limits. In order to avoid excessive clumping of the powder mixture during cooling, the powder mixture is kneaded.
  • the binder metal components are added and the powder mixture is ground in water.
  • the resulting wet sludge is then sprayed, for example, in a spray-drying plant and dried.
  • a disadvantage of this method is that the mixing devices in which the mixing of the hard metal powder is carried out with the pressing aids, are heavily contaminated by lumpy, sticking residues of the powder-Pressosffenmischung and must be removed with large, costly cleaning effort before each new production of a hard metal approach.
  • the object of the present invention is therefore to provide a method for producing a carbide approach, in which the disadvantages mentioned in the prior art are avoided. This is achieved by the method according to claim 1 according to the invention.
  • a uniform distribution of the pressing aid in the hard metal approach is achieved in a simple manner.
  • the preparation of the emulsion takes place without problems in a commercially available emulsifier with a heatable double-walled kettle with a stirrer and a high-dispersion machine.
  • the desired amount of water is added after melting the pressing aid and the emulsifier. Only when the temperatures of the two immiscible phases (pressing aids and water) are adjusted, with the aid of an extremely fast-running high dispersing (for example, about 6000 rpm), the pressing aid phase is dispersed in water.
  • emulsifiers usually commercially available emulsifiers, as they are used in the food industry, can be used.
  • the emulsifier must be adapted to the specific composition of the pressing aid to be emulsified. It is important that the emulsifier does not contain any harmful substances for further Hartrnetallher ein, such as alkali, alkaline earth, or sulfur compounds that can form fracture-initiating phases after sintering.
  • no emulsion-stabilizing additives such as pH-increasing agents, should be included, since these additives may not evaporate completely without residue during dewaxing and may cause problems in the subsequent sintering of the carbide approach. Even without such stabilizing additives, the emulsion is stable for at least 5 days when stored at room temperature, which ensures a trouble-free production process in the production of hard metal approach.
  • an emulsifier which allows the preparation of an emulsion with single droplets having an average droplet diameter of less than 1.5 microns.
  • a particularly frequently used pressing aid for the production of a carbide approach is paraffin.
  • the grinding of the hard material and binder metal parts in the attritor with a viscosity of the wet sludge in the range between 2.500 to 8,000 mPas (measured in a rheometer of type RC 20 from Europhysics at a shear rate of 5.2 [1 / s]) is carried out with at least 4 to 8 times the volume exchange per hour.
  • a spray tower with a cylindrical section and a conical section is used, in which the gas stream for drying the wet sludge has an inlet temperature in the range of 130 to 195 ° C and an outlet temperature in the range of 85 to 117 ° C and wherein 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 to the tower volume in m 3 in the range between 0.5 and 1.8 and that atomizes a maximum of 0.17 kg wet sludge per m 3 supplied drying gas wherein the wet sludge has a solids content in the range of 65 to 85 wt.%.
  • 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 granulate produced by the special spray drying 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 special spray-drying is applicable to both co-current and countercurrent spray-drying equipment, it has been found to be particularly effective in countercurrent systems using the fountain principle, which allows the spray-drying plant to be manufactured in a compact design. It is advantageous to carry out the cylindrical, upper section of the spray tower with about 6 m in height and about 4 - 5 m in diameter. For the adjoining, conical lower section, a cone angle of approximately 45 ° - 50 ° has been proven.
  • a spray-drying plant operating countercurrently according to the fountain principle is used for spray-drying, 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.
  • FIG. 1 shows the schematic diagram of a spray tower for the particularly advantageous production of hard metal granules from a wet sludge according to the invention.
  • the spray tower -1- consists of a cylindrical section -2- and an adjoining, conically tapering down section -3-.
  • the spray tower -1- works in countercurrent to the fountain principle, ie the gas stream for drying the wet sludge is fed at the upper end -11- of the cylindrical portion -2- and blown down, while the wet sludge to be atomized at the lower end of the cylindrical portion - 2- over a spray lance -4- with a nozzle opening -5- on the principle of a fountain up against the direction of the gas stream is sprayed -6.
  • 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.
  • the liquid droplets -7- Before hitting the bottom of the spray tower -1-, the tapered portion -3-, the liquid droplets -7- must be converted into the dried granules. Through the conically tapered portion -3- of the spray tower, the granules to the discharge opening -8- passed.
  • the gas stream -6- has an inlet temperature in the range of 130 to 195 ° C and an exit temperature on 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 117 ° 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. It is advantageous if the conically tapering section -3- of the spray tower is double-walled for passing a cooling liquid, eg water.
  • the granules are cooled in this area to at least 75 ° C. After leaving the spray tower -1- through the outlet opening -8- the granules pass to a cooling channel -10- where it is then cooled to room temperature.
  • a guarded cemented carbide granules with a mean particle size of 125 microns consisting of, apart from the 2% wax content (paraffin), 6 wt.% Cobalt, 0.4 wt.% Vanadium carbide, remainder tungsten carbide, 36 kg of cobalt powder having an average particle size of about 0.8 microns FSSS and an oxygen content of 0.56 wt.%, 2.4 kg of vanadium carbide powder having an average particle size of about 1.2 microns FSSS and an oxygen content of 0.25 wt.% And 561.6 kg tungsten carbide powder with a BET surface area of 1.78 m 2 / g, which corresponds to an average particle size of about 0.6 ⁇ m and an oxygen content of 0.28% by weight, with 148 liters of water in an attritor for 5 hours.
  • the emulsion was prepared in a commercially available emulsifier from IKA, Germany.
  • 40 kg of paraffin wax were mixed with 2 kg of a commercial emulsifier, essentially a mixture of fatty alcohol polyglycol ether and monodiglyceride and melted at 85 ° C.
  • the exact composition of the emulsifier is to be adjusted empirically to the exact composition of the paraffin wax used).
  • 40 kg of water were added and brought to the same temperature.
  • the Hochdispergier réelle was switched on for Emutsionsher ein for 60 minutes. This was followed by a controlled cooling of the emulsion at 2 ° C per minute to room temperature with the aid of a stirrer.
  • a check of the droplet size distribution in a laser granulometer revealed a mean diameter d 50 of 1.16 ⁇ m.
  • FIG. 2 shows a KRYO-SEM image of the finished emulsion in 7.500x magnification.
  • a spray tower -1- having a cylindrical portion -2- with a height of 6 m and a diameter of 4 m and a tapered portion -3- with a cone angle of 50 ° was used, 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 88 ° 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 one Air supply of 4000 m 3 per hour 320 kg of wet sludge were sprayed per hour.
  • the 320 kg of wet sludge per hour correspond to an hourly supplied amount 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 93 ⁇ m 3 0.86 ⁇ l m 3 , H , ,
  • the oxygen content of the granules produced was 0.51% by weight.
  • FIG. 3 shows a recording of the carbide granules produced according to the example with a mean grain size of 125 microns in 50-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)
  • Powder Metallurgy (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
  • Glanulating (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Crushing And Grinding (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Measurement Of The Respiration, Hearing Ability, Form, And Blood Characteristics Of Living Organisms (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Collating Specific Patterns (AREA)
  • Treatment Of Sludge (AREA)

Abstract

L'invention concerne un procédé permettant de produire un élément saillant en métal dur, à base de parts d'urée, de parts de métal liant et de parts d'auxiliaires de compression solubles dans l'eau, par séchage de boues humides contenant ces constituants, avec de l'eau pure comme phase liquide. Selon l'invention, les parts d'urée et de métal liant sont d'abord moulues avec de l'eau de manière à former des boues humides. Après mouture, les auxiliaires de compression sont ajoutés sous forme d'émulsion aux boues humides. L'émulsion est obtenue à cet effet, à l'aide d'un émulsifiant, par adjonction d'eau.

Claims (8)

  1. Procédé d'élaboration d'une préparation pour métal dur par séchage d'une barbotine humide qui contient de l'eau pure comme phase liquide et, comme autres ingrédients, des teneurs en substances dures, des teneurs en métaux liants et des teneurs en adjuvants de compression insolubles dans l'eau, caractérisé en ce que les teneurs en substances dures et en métaux liants sont d'abord broyées avec l'eau en formant une barbotine humide, et en ce que les teneurs en adjuvants de compression sont ajoutées à la barbotine humide, après le broyage, sous la forme d'une émulsion, qui est élaborée à l'aide d'un émulsifiant en ajoutant de l'eau, et en ce que le broyage est exécuté dans l'attriteur où la viscosité de barbotine humide est comprise dans une plage de 2500 à 8000 mPas, et l'échange volumique est au moins de 4 à 8 fois par heure.
  2. Procédé d'élaboration d'une préparation pour métal dur selon la revendication 1, caractérisé par l'utilisation d'un émulsifiant qui permet l'élaboration d'une émulsion formée de gouttelettes individuelles d'un diamètre moyen de gouttelette inférieur à 1,5 µm.
  3. Procédé d'élaboration d'une préparation pour métal dur selon l'une des revendications 1 ou 2, caractérisé par l'utilisation de paraffine comme adjuvant de compression.
  4. Procédé d'élaboration d'une préparation pour métal dur selon la revendication 3, caractérisé en ce que l'émulsifiant consiste en un mélange de polyglycoléthers d'alcools gras avec des monodiglycérides
  5. Procédé d'élaboration d'une préparation pour métal dur selon l'une quelconque des revendications 1 à 4, sous la forme d'un granulat de métal dur caractérisé en ce que la barbotine humide est séchée dans une installation de vaporisation.
  6. Procédé d'élaboration d'un granulat de métal dur selon la revendication 5, caractérisé en ce que le séchage par vaporisation est exécuté dans une tour de vaporisation (1) qui inclut une partie cylindrique (2) et une partie conique (3), dans lequel la température d'entrée du flux gazeux de séchage de la barbotine humide est dans une plage de 130 à 195°C et sa température de sortie dans une plage de 85 à 117 °C et dans lequel la tour de vaporisation (1) est construite et mise en oeuvre d'une manière telle que le rapport entre la quantité d'eau amenée par la barbotine humide, en litres par heure, et le volume de la tour, en m3, est dans une plage de 0,5 à 1,8 et que la quantité de barbotine humide vaporisée est au plus de 0,17 kg par m3 de gaz de séchage introduit, la teneur en solides de la barbotine humide étant dans une plage de 65 à 85% en poids.
  7. Procédé d'élaboration d'un granulat de métal dur selon la revendication 6, caractérisé en ce que le séchage par vaporisation est exécuté à contre courant selon le principe des jets ascendants, et en ce que le gaz de séchage utilisé est l'air.
  8. Procédé d'élaboration d'un granulat de métal dur selon la revendication 7, caractérisé en ce que les températures d'entrée de gaz et de sortie de gaz sont adaptées l'une à l'autre de manière à établir une température comprise entre environ 70 et 120°C au centre de gravité géométrique (S) de la tour de vaporisation (1).
EP02703388A 2001-03-29 2002-03-08 Procede de production d'un element saillant en metal dur Expired - Lifetime EP1373585B2 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
DK02703388T DK1373585T4 (da) 2001-03-29 2002-03-08 Fremgangsmåde til fremstilling af en portion af hårdt metal
AT02703388T ATE295903T1 (de) 2001-03-29 2002-03-08 Verfahren zur herstellung eines hartmetallansatzes

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AT2302001 2001-03-29
AT0023001U AT4928U1 (de) 2001-03-29 2001-03-29 Verfahren zur herstellung eines hartmetallansatzes
PCT/AT2002/000075 WO2002079531A2 (fr) 2001-03-29 2002-03-08 Procede de production d'un element saillant en metal dur

Publications (3)

Publication Number Publication Date
EP1373585A2 EP1373585A2 (fr) 2004-01-02
EP1373585B1 EP1373585B1 (fr) 2005-05-18
EP1373585B2 true EP1373585B2 (fr) 2009-07-29

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EP02703388A Expired - Lifetime EP1373585B2 (fr) 2001-03-29 2002-03-08 Procede de production d'un element saillant en metal dur

Country Status (17)

Country Link
US (1) US6733562B2 (fr)
EP (1) EP1373585B2 (fr)
JP (1) JP4044441B2 (fr)
KR (1) KR100896827B1 (fr)
CN (1) CN1206381C (fr)
AT (2) AT4928U1 (fr)
BG (1) BG65809B1 (fr)
BR (1) BR0204680B1 (fr)
CA (1) CA2409394C (fr)
DE (1) DE50203144D1 (fr)
DK (1) DK1373585T4 (fr)
ES (1) ES2240693T5 (fr)
IL (1) IL152969A (fr)
MX (1) MXPA02011766A (fr)
PL (1) PL201615B1 (fr)
TW (1) TW565482B (fr)
WO (1) WO2002079531A2 (fr)

Cited By (2)

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US9796633B2 (en) 2013-10-03 2017-10-24 Kennametal Inc. Aqueous slurry for making a powder of hard material
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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DE102004053221B3 (de) * 2004-11-04 2006-02-02 Zschimmer & Schwarz Gmbh & Co. Kg Chemische Fabriken Flüssigkeit und deren Verwendung zur Aufbereitung von Hartmetallen
US7470307B2 (en) * 2005-03-29 2008-12-30 Climax Engineered Materials, Llc Metal powders and methods for producing the same
AT9143U1 (de) * 2006-05-02 2007-05-15 Ceratizit Austria Gmbh Verfahren zur herstellung eines hartmetallproduktes
DE102006043581B4 (de) * 2006-09-12 2011-11-03 Artur Wiegand Verfahren und Vorrichtung zur Herstellung einer Hartmetall- oder Cermetmischung
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US8500857B2 (en) 2007-05-21 2013-08-06 Peter Eisenberger Carbon dioxide capture/regeneration method using gas mixture
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
US8163066B2 (en) 2007-05-21 2012-04-24 Peter Eisenberger Carbon dioxide capture/regeneration structures and techniques
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SE533922C2 (sv) * 2008-12-18 2011-03-01 Seco Tools Ab Sätt att tillverka hårdmetallprodukter
EP2246113A1 (fr) * 2009-04-29 2010-11-03 Sandvik Intellectual Property AB Processus pour le broyage de cermet ou mélanges de carbure cimenté
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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MXPA02011766A (es) 2003-04-10
WO2002079531A3 (fr) 2002-11-28
BR0204680A (pt) 2003-06-10
EP1373585A2 (fr) 2004-01-02
ES2240693T5 (es) 2009-10-30
US6733562B2 (en) 2004-05-11
CA2409394C (fr) 2007-06-19
TW565482B (en) 2003-12-11
WO2002079531A2 (fr) 2002-10-10
DE50203144D1 (de) 2005-06-23
JP2004518824A (ja) 2004-06-24
BR0204680B1 (pt) 2010-10-05
CN1206381C (zh) 2005-06-15
CN1460126A (zh) 2003-12-03
DK1373585T3 (da) 2005-09-05
BG107223A (en) 2003-07-31
ATE295903T1 (de) 2005-06-15
CA2409394A1 (fr) 2002-11-19
KR20030007547A (ko) 2003-01-23
IL152969A0 (en) 2003-06-24
DK1373585T4 (da) 2009-11-09
PL359344A1 (en) 2004-08-23
JP4044441B2 (ja) 2008-02-06
PL201615B1 (pl) 2009-04-30
ES2240693T3 (es) 2005-10-16
US20030075012A1 (en) 2003-04-24
AT4928U1 (de) 2002-01-25
KR100896827B1 (ko) 2009-05-12
IL152969A (en) 2006-06-11
BG65809B1 (bg) 2009-12-31

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