EP1666616A1 - Liquide et son usage pour la production de métaux durs - Google Patents

Liquide et son usage pour la production de métaux durs Download PDF

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Publication number
EP1666616A1
EP1666616A1 EP05018858A EP05018858A EP1666616A1 EP 1666616 A1 EP1666616 A1 EP 1666616A1 EP 05018858 A EP05018858 A EP 05018858A EP 05018858 A EP05018858 A EP 05018858A EP 1666616 A1 EP1666616 A1 EP 1666616A1
Authority
EP
European Patent Office
Prior art keywords
liquid
inhibitor
weight
gew
powder
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP05018858A
Other languages
German (de)
English (en)
Other versions
EP1666616B1 (fr
Inventor
Peter Dr. Quirmbach
Michael Dipl.-Ing. Hölzgen
Alfred Dipl.-Ing. Vuin
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zschimmer and Schwarz GmbH and Co KG
Original Assignee
Zschimmer and Schwarz GmbH and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zschimmer and Schwarz GmbH and Co KG filed Critical Zschimmer and Schwarz GmbH and Co KG
Publication of EP1666616A1 publication Critical patent/EP1666616A1/fr
Application granted granted Critical
Publication of EP1666616B1 publication Critical patent/EP1666616B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • 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
    • 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
    • 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
    • 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
    • B22F2009/042—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling using a particular milling fluid
    • 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
    • B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling

Definitions

  • the invention relates to the composition of a liquid and its use for the preparation of powder mixtures based on hard metal.
  • hard metal or WC powder are treated with other metal powders, in particular cobalt powder to form a powder mixture, pressed the prepared powder mixture by pressing to form parts and then by sintering the moldings below the melting temperature of the hardmetal sintered to the desired product.
  • the intimate mixture of the WC powder with the co-powder is in the foreground.
  • segregations occur, in particular due to the different densities of the two powders.
  • the powder mixture in order to produce as homogeneous and hard a material as possible from the cemented carbide, the powder mixture must be as homogeneous as possible.
  • the WC / Co powder mixture is therefore mixed with the aid of liquids.
  • This mixing process in a liquid is usually carried out today in so-called attritors, a type of ball mill, with the mixing of WC / Co powder mixture, grinding balls, liquid and Paraffin are filled.
  • the mixing of the powders in the attritors presents itself as a combination of a mixing and a grinding process, so that the liquid, by means of which the powder mixture is mixed in the attritor, is also referred to as grinding liquid.
  • the WC powder particles are comminuted and simultaneously mixed with the cobalt powder particles.
  • liquids or grinding liquids
  • organic liquids especially alcohols, such as hexane, heptane, ethyl alcohol or acetone are used.
  • the paraffin dissolved in the organic liquid settles in the mixing / grinding process in the attritor to the WC and Co particles and acts u.a. as a pressing aid.
  • the use of organic, especially alcoholic grinding liquids is associated with numerous disadvantages.
  • Another disadvantage is the high material costs of the organic milling liquids and the high cost of their disposal or landfill.
  • the object of the invention is to provide a way of using water as the mixing / milling liquid instead of the organic solvent previously used in the attritors for mixing and milling powder mixtures based on hard metal.
  • the invention is based on the finding that the milling liquid previously used in attritors in the form of an organic liquid can then be replaced by water if the water is added to a suitable inhibitor, which surrounds the hard metal powder and prevents their hydrolysis.
  • polyvinyllactam or a wax emulsion or carboxylic acid, amines or their derivatives are suitable inhibitors.
  • the abovementioned substances encase both the hard metal powder particles and the other powder particles of the powder mixture, ie in particular the co-powder particles or regulate the oxygen attachment to the particles such that they do not or hardly hydrolyze in the water or undergo any other reaction with the water.
  • the polyvinyl lactam used may be, for example, a polyvinyl caprolactam.
  • the polyvinyllactam used may be a polyvinylpyrrolidone (PVP) or one or more of its co- or terpolymers, such as groups consisting of vinyl acetate, acrylate, methacrylate, acrylamide, methacrylamide, vinylimidazole, vinylcaprolactam, 3-methyl-1-vinylimidazoniummethylsulfate or other co- or terpolymers of polyvinylpyrrolidone.
  • PVP polyvinylpyrrolidone
  • the co-polymer content may range from 5 to 95% by weight.
  • the polymers may, for example, have a molecular weight of from 1,000 to 5,000,000 daltons, preferably from 5,000 to 500,000 daltons.
  • the wax emulsion may be a wax emulsion based on paraffin, oxidized paraffin, polyethylene, polypropylene, amide wax, e.g. Ethylene-bis-stearylamide, stearylamide, stearate or mixtures thereof.
  • wax can only be used as an inhibitor in a generic liquid or grinding liquid if it is present as an emulsion in the liquid.
  • the addition of wax in non-emulsified form would not result in distribution of the wax in the water. Accordingly, earlier attempts to use water as a liquid for processing hard metals failed the non-emulsified paraffin did not dissolve or disperse in the water.
  • water as a liquid for the treatment of hard metals or as a grinding and mixing liquid in the treatment of hard metals leads to the fact that a complex encapsulation of the treatment units is no longer necessary. Furthermore, the water is much cheaper to buy than an organic liquid and its disposal is less expensive.
  • the liquid according to the application as inhibitor may in particular also contain carboxylic acids and / or amines or their respective derivatives.
  • carboxylic acid derivatives prove to be particularly effective inhibitors in the amine neutralized state.
  • the carboxylic acids used may preferably be dicarboxylic acids and / or triazine derivatives.
  • dicarboxylic acids may be, in particular, 1,8-octanedicarboxylic acid, 1,9-nonanedicarboxylic acid, 1,10-decanedicarboxylic acid (sebacic acid), 1,11-undecanedicarboxylic acid, 1,12-dodecanecarboxylic acid and so on up to and including 1,16-hexadecanedicarboxylic acid.
  • triazine derivatives in particular 1,3,5-triazine derivatives, in particular 1,3,5-triazine-2,4,6-triaminetricarboxylic acid, may be provided, for example.
  • the amines used can preferably be ethanolamines and / or imidazolines.
  • Ethanolamines may be, for example, in particular triethanolamine, diethanolamine, monoethanolamine and / or trishydroxymethylaminomethane.
  • Imidazole units may also be provided with non-polymeric imidazole derivatives such as, for example, 2- (2-hepatadec-8-enyl-2-imidazolin-1-yl) ethanol. It is also possible for these latter to be provided with imidazole compounds, for example imidazoline derivatives, for example hydroxyethyl, aminoethyl and / or amidoethyl imidazole derivatives.
  • alkyl radicals may be present residues of oil and tall oil fatty acids to octanoic acid.
  • the abovementioned inhibitors are particularly effective if they are present in combination of amines and carboxylic acids, in each case in particular those of the abovementioned type.
  • Stabilizers for example a cellulose
  • dispersants for example based on acrylic
  • the liquid according to the application can be used for the preparation of powder mixtures based on hard metals, for example for the preparation of carbides of titanium, of tantalum and of niobium.
  • the liquid according to the application can be used for the preparation of hard metals based on monotungsten carbide and here in particular for the preparation of powder mixtures based on powders of monotungsten carbide and cobalt.
  • the moist Powder mixture removed from the attritor and a drying unit, such as a spray-drying system, are supplied.
  • the moist mixture is atomized to a granulate.
  • the granules are fed to a shaping unit, usually a press, where they are pressed into the molded part.
  • the wax emulsion in addition to its property as an inhibitor, simultaneously acts as an excellent pressing aid, whereby the homogeneity and green density of the pressed molded part at the same compacting pressure (compared to the pressing pressure or the properties of a molded part, according to the prior art Technique was prepared) is increased or only a lower pressing pressure is required to obtain the same properties in the molding that would be obtained without the use of a wax emulsion in the grinding fluid.
  • the molding is finally subjected to a heat treatment and thereby sintered to the cemented carbide product.
  • Inhibitor in the form of polyvinyllactam can be present, for example, in proportions of 0.5-50% by weight, that is to say, for example, in proportions of 1-10% by weight or 1-5% by weight in the liquid.
  • Inhibitor in the form of a wax emulsion can be present for example in proportions of 0.5-66 wt .-%, that is, for example, in proportions of 1-25 wt .-% or 2-15 wt .-% in the liquid.
  • Carboxylic acid for example, in proportions of 0.1 to 5 wt .-%, that is, for example, in proportions of 0.5 to 4 wt .-% in the liquid.
  • Amines may, for example, in proportions of 0.1 to 7 wt .-%, that is, for example, in proportions of 0.5 to 5 wt .-% in the liquid.
  • Dispersant may, for example, in proportions of 0.01-33 wt .-%, that is, for example, in proportions of 0.1-5 wt .-% or 0.5-3 wt .-% in the liquid.
  • Stabilizer can be present for example in proportions of 0.01-33 wt .-%, that is, for example, in proportions of 0.05-6 wt .-% or of 0.1-3 wt .-% in the liquid.
  • the liquid according to the application can be mixed with 3 to 5 times the amount of WC / Co powder particles to form a moist mixture.
  • Inhibitor in the form of polyvinyl lactam in addition to the 100 wt .-% WC and Co-particles, for example, additionally with 0.01-10 wt .-%, that is, for example, also be contained with 0.1-2 wt .-% in the wet mixture.
  • Inhibitor in the form of wax emulsion in addition to the 100 wt .-% WC and Co particles, for example, in addition to 0.1-20 wt .-%, that is, for example, 1-5 wt .-% in the wet mixture.
  • the moist mixture in addition to the 100% by weight of WC and Co particles and the abovementioned components, it is possible for example in the moist mixture to contain 0.01-5% by weight, that is to say also 0.1-0.8% by weight of dispersant and / or or, for example, 0.01-5 wt .-%, that is, for example, 0.05-0.5 wt .-% stabilizer present.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Cosmetics (AREA)
  • Lubricants (AREA)
  • Powder Metallurgy (AREA)
EP05018858A 2004-11-04 2005-08-31 Usage d'un liquide pour la production de métaux durs Active EP1666616B1 (fr)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DE102004053221A DE102004053221B3 (de) 2004-11-04 2004-11-04 Flüssigkeit und deren Verwendung zur Aufbereitung von Hartmetallen

Publications (2)

Publication Number Publication Date
EP1666616A1 true EP1666616A1 (fr) 2006-06-07
EP1666616B1 EP1666616B1 (fr) 2007-11-21

Family

ID=35480131

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05018858A Active EP1666616B1 (fr) 2004-11-04 2005-08-31 Usage d'un liquide pour la production de métaux durs

Country Status (3)

Country Link
US (1) US7531022B2 (fr)
EP (1) EP1666616B1 (fr)
DE (2) DE102004053221B3 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102006043498A1 (de) * 2006-09-12 2008-03-27 Artur Wiegand Dispergiermaschine und deren Verwendung für die Herstellung von Pulvermischungen
DE102006043581B4 (de) * 2006-09-12 2011-11-03 Artur Wiegand Verfahren und Vorrichtung zur Herstellung einer Hartmetall- oder Cermetmischung
US9475945B2 (en) * 2013-10-03 2016-10-25 Kennametal Inc. Aqueous slurry for making a powder of hard material
IN2013CH04500A (fr) 2013-10-04 2015-04-10 Kennametal India Ltd
WO2016049257A1 (fr) 2014-09-26 2016-03-31 Henry Company, Llc Poudres obtenues à partir de dispersions colloïdales à base de cire et leur procédé de fabrication
WO2016070012A1 (fr) 2014-10-30 2016-05-06 Henry Company, Llc Matériaux à changement de phase à partir de dispersions colloïdales à base de cire et leur procédé de fabrication
WO2016094719A1 (fr) 2014-12-11 2016-06-16 Henry Company, Llc Matériaux à changement de phase obtenus à partir de dispersions colloïdales à base de cire et leur procédé de fabrication

Citations (4)

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US5590387A (en) * 1993-10-27 1996-12-31 H. C. Starck, Gmbh & Co, Kg Method for producing metal and ceramic sintered bodies and coatings
US5922978A (en) * 1998-03-27 1999-07-13 Omg Americas, Inc. Method of preparing pressable powders of a transition metal carbide, iron group metal or mixtures thereof
US20030075012A1 (en) * 2001-03-29 2003-04-24 Gerhard Knunz Method of producing hard metal grade powder
EP1375035A1 (fr) * 2001-03-30 2004-01-02 Catalysts & Chemicals Industries Co., Ltd. Fines particules de metal, procede d'elaboration, liquide de revetement renfermant ces particules pour la realisation de film electro-conducteur transparent, substrat equipe de ce film, et visuel

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US5590387A (en) * 1993-10-27 1996-12-31 H. C. Starck, Gmbh & Co, Kg Method for producing metal and ceramic sintered bodies and coatings
US5922978A (en) * 1998-03-27 1999-07-13 Omg Americas, Inc. Method of preparing pressable powders of a transition metal carbide, iron group metal or mixtures thereof
US20030075012A1 (en) * 2001-03-29 2003-04-24 Gerhard Knunz Method of producing hard metal grade powder
EP1375035A1 (fr) * 2001-03-30 2004-01-02 Catalysts & Chemicals Industries Co., Ltd. Fines particules de metal, procede d'elaboration, liquide de revetement renfermant ces particules pour la realisation de film electro-conducteur transparent, substrat equipe de ce film, et visuel

Also Published As

Publication number Publication date
US7531022B2 (en) 2009-05-12
DE102004053221B3 (de) 2006-02-02
DE502005002035D1 (de) 2008-01-03
EP1666616B1 (fr) 2007-11-21
US20060091579A1 (en) 2006-05-04

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