EP0963454B1 - Verfahren zum herstellen von zementiertem carbid durch spritzgiessen von pulver - Google Patents

Verfahren zum herstellen von zementiertem carbid durch spritzgiessen von pulver Download PDF

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Publication number
EP0963454B1
EP0963454B1 EP97910662A EP97910662A EP0963454B1 EP 0963454 B1 EP0963454 B1 EP 0963454B1 EP 97910662 A EP97910662 A EP 97910662A EP 97910662 A EP97910662 A EP 97910662A EP 0963454 B1 EP0963454 B1 EP 0963454B1
Authority
EP
European Patent Office
Prior art keywords
binder
powder
surfactant
injection molding
mixing
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.)
Expired - Lifetime
Application number
EP97910662A
Other languages
English (en)
French (fr)
Other versions
EP0963454A1 (de
Inventor
Ingrid C/O Eriksson Hurme
Peter Samuelson
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.)
Sandvik AB
Original Assignee
Sandvik AB
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 Sandvik AB filed Critical Sandvik AB
Publication of EP0963454A1 publication Critical patent/EP0963454A1/de
Application granted granted Critical
Publication of EP0963454B1 publication Critical patent/EP0963454B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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Classifications

    • 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
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/22—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip
    • B22F3/225—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces for producing castings from a slip by injection molding
    • 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

Definitions

  • the present invention relates to a method of making cemented carbide by powder injection molding.
  • Cemented carbide is generally made by powder metallurgical methods comprising wet milling in an alcohol-water solution of a powder mixture containing powders forming the hard constituents and binder phase, drying the milled mixture to a powder consisting of agglomerates about 0.1 mm in diameter with good flow properties by means of spray drying, pressing the dried powder to bodies of desired shape and finally sintering.
  • An alternative method of making cemented carbide parts is by injection molding.
  • Injection molding is a common production method in the plastics industry for the production of 'net-shape' or 'near net-shape' parts.
  • a paste consisting of or containing thermoplastics or thermosetting polymers is heated to a suitable temperature and forced through a nozzle into a form with desired geometry.
  • injection molding is generally referred to as Powder Injection Molding (PIM). Because PIM is a more expensive method of making parts than conventional powder metallurgical technique, tool pressing, it is preferably applied to parts of complex shape in small or large series.
  • the surfactant is dryblended with the powder and the same or another surfactant is mixed with a part of or the rest of the binder constituents before mixing in molten state as in I and II.
  • cemented carbide powders are milled. Milling is considered necessary in order to obtain a uniform distribution of the binder phase in the milled mixture.
  • the milling operation is performed in mills of different sizes using cemented carbide milling bodies.
  • the milling time is in the order of several hours up to days.
  • the milling operation produces a slurry which subsequently is spray dried. As a result of the spray drying a powder is obtained essentially consisting of spherical agglomerates of around 0.1 mm size.
  • the binder adheres to the powder agglomerates and in that way helps to keep the agglomerates together. If agglomerates are broken up into particles during the mixing step there will be homogenizing problems due to poor wetting of the binder on the powder.
  • EP-A-443048 discloses a process wherein a carbide and a metal binder phase are wet milled and dried. Subsequently organic binder and surfactants are added and mixed and the mixture is injection moulded.
  • the object of the present invention is to provide a method of enhancing dispersion of the surfactant to ensure that the surfactant is adhering to particles and smaller agglomerates, rather than just to larger agglomerates.
  • powders forming the hard constituents( ⁇ 0.5 ⁇ m-10 ⁇ m) and powders forming the binder phase (3-20 percent by weight of the hard constituents) are milled together with the surfactant instead of the lubricating agent that is added to powders used for conventional tool pressing.
  • the milling liquid shall in this case be able to dissolve or at least partially dissolve the surfactant.
  • the amount of surfactant should be sufficient to cover all powder surfaces and the excess should preferably not be larger than what is soluble in or miscible with the rest of the binder components.
  • the surfactant can be a single fatty acid like hexadecanoic acid, tetradecanoic acid, 9,10 Octadecanoic acid, 9,12 Octadienoic acid or 9,12,5 Octadecatrienoic acid mixed with the powder in ethanol, acetone, benzene.
  • the surfactant can be some kind of organometallic compound, Zn-stearate, or corresponding alcohol to a fatty acid such as 1-hexadecanol. It can also be an amine such as octadecylamine. All these surfactants can be milled in ethanol.
  • Zn-salts of higher molecular nonsaturated fatty acids with melting point at 75-95 °C can be used or Zn-salts of high molecular mostly unsaturated fatty acids with a melting point of 97-105 °C, which can be milled together with benzene, ethanol, xylol.
  • the surfactant is Zn salts of high molecular mostly unsaturated fatty acids or hexadecanol.
  • the binder components composition can be a wax mixed with a polyolefine i.e. paraffin wax or a microcrystalline wax mixed with EVA(Ethene Vinyl Acetate), EBA(Ethene Butyl Acrylate), EAA (Ethene Acrylic Acid), PE(Polyethylene), PP(Polypropylene) alone or in combination or solely mixed with the wax.
  • Preferred binders are paraffine wax mixed with PP.
  • the binder is removed from the molded part preferably by extraction in a bath with para menta 1,8-dien or Methyl-Ethyl-Ketone and 2 propanole and after that by drying in vacuum or heating. Finally, sintering is performed essentially in the same way as for tool pressed parts.
  • the reason for the improvement observed is probably that a homogeneous coating of the powder particles with the surfactant is obtained.
  • Wet mixing of powder and surfactant while milling the powder allows the surfactant to coat the powder particles and most of the agglomerates are breakable in this operation. This allows the surfactant to coat each particle rather than each agglomerate.
  • the risk of having agglomerates of the powder is minimized.
  • Example 1 was repeated with the exception that 0.7 kg stearic acid was milled with the powder in an ethanol solution and then spray dried and mixed as in Example 1. The sintered parts were found to have a porosity level of A00+B00+C00 and 1-2 macropores/cm 2 .
  • Example 1 was repeated with the exception that the cetylalcohol was added together with the powder during the mixing step.
  • the molded parts were sintered together with those from Example 1.
  • the sintered parts were found to have a porosity level of A00+B02+C00 and 8-10 macropores/cm 2 .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Powder Metallurgy (AREA)

Claims (1)

  1. Verfahren zur Herstellung eines gesinterten Körpers, der ein oder mehrere harte Bestandteile in einer Bindephase umfasst, durch Spritzgießtechnik unter Mischen von die harten Bestandteile und Bindephase bildenden Pulvern mit einem Bindemittel, das organische Verbindungen, Wachse und oberflächenaktive Stoffe umfasst, zu einem Beschikkungsmaterial, Formen dieses Beschickungsmaterials zu einem Körper erwünschter Form in einer herkömmlichen Kunststofformmaschine und Entfernung des Bindemittels aus dem Körper und Sintern, wobei das Verfahren ein Nassvermahlen der die harten Bestandteile und Bindephase bildenden Pulver zusammen mit dem oberflächenaktiven Stoff, Trocknen und Zugabe des Restes des Bindemittels enthält.
EP97910662A 1996-10-25 1997-10-14 Verfahren zum herstellen von zementiertem carbid durch spritzgiessen von pulver Expired - Lifetime EP0963454B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
SE9603936 1996-10-25
SE9603936A SE9603936D0 (sv) 1996-10-25 1996-10-25 Method of making cemented carbide by metal injection molding
PCT/SE1997/001715 WO1998018973A1 (en) 1996-10-25 1997-10-14 Method of making cemented carbide by powder injection molding

Publications (2)

Publication Number Publication Date
EP0963454A1 EP0963454A1 (de) 1999-12-15
EP0963454B1 true EP0963454B1 (de) 2002-12-11

Family

ID=20404398

Family Applications (1)

Application Number Title Priority Date Filing Date
EP97910662A Expired - Lifetime EP0963454B1 (de) 1996-10-25 1997-10-14 Verfahren zum herstellen von zementiertem carbid durch spritzgiessen von pulver

Country Status (6)

Country Link
EP (1) EP0963454B1 (de)
JP (1) JP2001507075A (de)
AT (1) ATE229574T1 (de)
DE (1) DE69717861T2 (de)
SE (1) SE9603936D0 (de)
WO (1) WO1998018973A1 (de)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8425652B2 (en) 2005-07-29 2013-04-23 Sandvik Intellectual Property Ab Method of making a submicron cemented carbide powder mixture with low compacting pressure and the resulting powder
EP2857124A1 (de) 2013-10-03 2015-04-08 Kennametal Inc. Wässriger Schlamm zur Herstellung eines Pulvers aus hartem Material
EP2860274A2 (de) 2013-10-04 2015-04-15 Kennametal India Limited Hartmaterial und Verfahren zur Herstellung desselben aus einem Hartmaterialenthaldenen wässrigen Schlamm aus einem Mahlprozess

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19901305A1 (de) 1999-01-15 2000-07-20 Starck H C Gmbh Co Kg Verfahren zur Herstellung von Hartmetallmischungen
US6790252B2 (en) * 2001-04-18 2004-09-14 Hard Metals Partnership Tungsten-carbide articles made by metal injection molding and method
SE526575C2 (sv) 2003-08-27 2005-10-11 Seco Tools Ab Metod att tillverka en sintrad kropp
SE526194C2 (sv) * 2003-08-27 2005-07-26 Seco Tools Ab Metod för att tillverka en sintrad kropp
SE529202C2 (sv) 2005-05-17 2007-05-29 Sandvik Intellectual Property Sätt att tillverka en agglomererad pulverblandning av en slurry och agglomererat pulver
SE529705C2 (sv) * 2005-06-27 2007-10-30 Sandvik Intellectual Property Sätt att tillverka en pulverblandning för hårdmetall
FR2903415B1 (fr) 2006-07-07 2011-06-10 Commissariat Energie Atomique Procede de fabrication d'un melange-maitre pour moulage par injection ou par extrusion
US20110248422A1 (en) * 2008-11-21 2011-10-13 Seco Tools Ab Method for producing cemented carbide or cermet products
SE533922C2 (sv) 2008-12-18 2011-03-01 Seco Tools Ab Sätt att tillverka hårdmetallprodukter
SE534191C2 (sv) * 2009-02-18 2011-05-24 Seco Tools Ab Sätt att tillverka hårdmetallprodukter
US20130064708A1 (en) * 2010-04-20 2013-03-14 Seco Tools Ab Method for producing cemented carbide products
BR112012029592A2 (pt) * 2010-05-26 2017-02-21 Seco Tools Ab método para produção de produtos de metal duro
FR2977251B1 (fr) * 2011-06-30 2013-06-28 Commissariat Energie Atomique Procede de fabrication de pieces colorees en ceramique par pim
CN102642240B (zh) * 2012-04-25 2013-12-25 深圳顺络电子股份有限公司 铁氧体磁芯坯体的制造方法以及铁氧体磁芯的制造方法
US11312766B2 (en) 2016-04-27 2022-04-26 Novartis Ag Antibodies against growth differentiation factor 15 and uses thereof

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4397889A (en) * 1982-04-05 1983-08-09 Gte Products Corporation Process for producing refractory powder
US4478888A (en) * 1982-04-05 1984-10-23 Gte Products Corporation Process for producing refractory powder
WO1991004119A1 (fr) * 1989-09-14 1991-04-04 Sumitomo Electric Industries, Ltd. Procede de production de carbure fritte ou d'alliage de cermet

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8425652B2 (en) 2005-07-29 2013-04-23 Sandvik Intellectual Property Ab Method of making a submicron cemented carbide powder mixture with low compacting pressure and the resulting powder
EP2857124A1 (de) 2013-10-03 2015-04-08 Kennametal Inc. Wässriger Schlamm zur Herstellung eines Pulvers aus hartem Material
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 (de) 2013-10-04 2015-04-15 Kennametal India Limited Hartmaterial und Verfahren zur Herstellung desselben aus einem Hartmaterialenthaldenen wässrigen Schlamm aus einem Mahlprozess
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

Also Published As

Publication number Publication date
DE69717861D1 (de) 2003-01-23
DE69717861T2 (de) 2003-05-08
JP2001507075A (ja) 2001-05-29
WO1998018973A1 (en) 1998-05-07
EP0963454A1 (de) 1999-12-15
SE9603936D0 (sv) 1996-10-25
ATE229574T1 (de) 2002-12-15

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