WO1998000256A1 - Procede de sechage par atomisation de melanges de poudres - Google Patents

Procede de sechage par atomisation de melanges de poudres Download PDF

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Publication number
WO1998000256A1
WO1998000256A1 PCT/SE1997/001066 SE9701066W WO9800256A1 WO 1998000256 A1 WO1998000256 A1 WO 1998000256A1 SE 9701066 W SE9701066 W SE 9701066W WO 9800256 A1 WO9800256 A1 WO 9800256A1
Authority
WO
WIPO (PCT)
Prior art keywords
powder
slurry
spray drying
ammonia
hydrofobic
Prior art date
Application number
PCT/SE1997/001066
Other languages
English (en)
Inventor
Bo Nelander
Mats Waldenström
Annika Hansson
Ulf Jutterström
Peter Dahlberg
Styrbjörn AMBERG
Lennart Bergström
Ove Alm
Jenny Johansson
Original Assignee
Sandvik Ab (Publ)
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
Priority claimed from SE9602598A external-priority patent/SE9602598D0/xx
Priority claimed from SE9603626A external-priority patent/SE9603626D0/xx
Application filed by Sandvik Ab (Publ) filed Critical Sandvik Ab (Publ)
Publication of WO1998000256A1 publication Critical patent/WO1998000256A1/fr

Links

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
    • 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
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/14—Treatment of metallic powder
    • B22F1/148—Agglomerating
    • 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 present invention relates to a method of spray drying powder mixtures .
  • Cemented carbide is made by powder metallurgical methods consisting of 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 with good flow properties by means of spray drying, pressing the dried powder to bodies of desired shape and finally sintering.
  • the intensive milling operation is performed in mills of different sizes using cemented carbide milling bodies. Milling is considered necessary in order to ob- tain a uniform distribution of the binder phase in the milled mixture.
  • the milling time is in the order of several hours up to days.
  • the milling operation produces a slurry which is suitable for spray drying. Successful spray drying depends strongly on the slurry properties.
  • the current technology of intensive milling during extended periods of time usually produces a very fine grained powder the sedimentation rate of which is sufficiently slow.
  • a ready- to-pres ⁇ powder i ⁇ obtained essentially consisting of spherical agglomerates of around 0.1 mm average size.
  • An important property of such a powder is its powder density also referred to as apparent density. It is commonly determined by pouring the powder into a cup of well known volume and weighing, see ISO 3923. The hereby measured powder density is both an indication of agglomerate porosity and is related to powder flowability.
  • a high density i ⁇ in the latter case, a measure of the ability of the agglomerates to move relative to one another and form a dense packing. The same property of good relative mobility will result in a good flowability.
  • a high powder density reduces the pressing force i.e.
  • Thickeners represent a group of polymer additives used for adjustment and control of the rheological properties of different technical products such as paints, food products etc. These additives can be divided into a large number of different groups based on the way they work and their chemical composition. A general classification of thickeners can be made based on their function, i.e. if thickeners are non-associative or associative (Associative thickener: Water soluble polymer with hydrophobic groups chemically bonded to the polymer chain) and with a subclassification based on their chemical type. Optimized rheological properties of the thickener solution can be obtained using different pH- increasing/ decreasing additives such as ammonia, hyd- roxides, acids etc.
  • Dispersants represent a group of organic additives preferably added to slurries of fine grained, ⁇ 1 ⁇ m, particles to prevent flocculation of the particles. Flocculation may cause inhomogeneous suspensions. After being added to the slurry, the dispersants generally ad- sorb on the surfaces of the particles, thus inferring an interparticle repulsion. These repelling forces at short distances between two particles prevent them from establishing large aggregates (floes) .
  • Swedish patent application 9702154-7 discloses a method of making a powder mixture containing hard constituents based on carbides, nitrides and/or carboni- trides of Ti , Zr, Hf, V, Nb, Ta, Cr, Mo and/or W in a binder phase essentially based on Co and/or Ni and fur- ther containing coarse particles by spray drying a slurry containing said powder mixture constituents.
  • Such slurries can not be spray dried without particular measures being taken because of sedimentation of the coarse particles.
  • suitable viscosities of the slurries are obtained and sedimentation problems are eliminated.
  • As a result after spray drying a powder with good flow properties and homogeneity is obtained.
  • the object of the present invention is to provide a method for spray drying fine grained, especially sub- micron, cemented carbide slurries with essentially no sedimentation to a powder with increased powder density.
  • Fig. 1 shows in 500X magnification an agglomerate from a powder spray dried according to the invention and Fig. 2 an agglomerate from a corresponding powder spray dried according to prior art.
  • the present invention thus, relates to a method of spray drying cemented carbide slurries consisting of cemented carbide powder containing hard constituents with sizes up to 2 ⁇ m, preferably up to 1 ⁇ m in an alcohol- water solution.
  • the alcohol-water solution shall contain 5-95 weig t-%, preferably 50-90 weight-% alcohol, preferably ethanol.
  • the amount of alcohol-water solution of the slurry shall be 10-50 weight-%.
  • thickeners of type "crossbonded acrylate emulsion", “hydrofobic modified hydroxyethylcellulose (HMHEC) " , “styrene/maleinacid-blockpolymer” , “hydrofobic modified ethylenoxide-uretane (HEUR) " , xanthan polysackaride” and “ethylhydroxyethylcellulose (EHEC) " alone or in combination
  • 0.1-50 g, preferably 1-20 g per litre alcohol-water solution pH- increasing/ decreasing additives such as ammonia, hydroxides, acids etc. are added provided that they do not negatively affect the properties of the sintered final product. For that reason ammonia is preferred.
  • a dispersant can be added.
  • An amount of about 0.1-10 g, preferably 0.5-5 g dispersant/ kg powder is generally satisfactory.
  • the slurries are subsequently dried in a spray dryer producing spherical, homogeneous powder agglomerates with a diameter of about 0.05-0.5 mm with a significantly increased powder density compared to prior art spray dried powder.
  • the additives according to the invention have no negative effects on the cemented carbide structures (impurities, porosity, excessive grain growth etc.) after pressing and sintering according to standard practise.
  • the powder density of the eight powders was deter- rained according to ISO 3929 with the following results: Powder density, g/cm 3 A 3 , 57 (prior art)
  • Fig. 1 shows an agglomerate according to the invention
  • Fig. 2 an agglomerate according to prior art. From the figures it is evident that the agglomerates according to the invention have much smoother surfaces than the agglomerates according to prior art. This is probably the main reason to the higher powder densities of the powders according to the invention.
  • test bars were pressed. The pressing force was measured and found to be 125 MPa for pow- der A and 110-115 MPa for powders B to H.
  • the test bars were sintered according to standard practice for raeta] - lographical evaluation. Satisfactory results with dense sintered structures were obtained in all cases.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Powder Metallurgy (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

Procédé de fabrication de pièces par des processus d'agglomération de poudres métalliques, qui consiste à effectuer un broyage humide dans une solution alcool-eau d'un mélange de poudres contenant des constituants durs ayant des tailles jusqu'à 2 νm, de préférence jusqu'à 1 νm, et une phase liante, à sécher le mélange broyé de manière à obtenir une poudre ayant une bonne aptitude à l'écoulement grâce au séchage par atomisation, à comprimer la poudre sèche en pièces de forme désirée et finalement à effectuer une opération de frittage. En ajoutant à ce coulis, après broyage, mais avant séchage par atomisation, de 0,1 à 100 g, de préférence 1 à 50 g par litre de solution d'épaississants du type 'émulsion acrylate réticulée', etc., on obtient une poudre prête à la compression à aptitude à l'écoulement améliorée.
PCT/SE1997/001066 1996-06-28 1997-06-17 Procede de sechage par atomisation de melanges de poudres WO1998000256A1 (fr)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
SE9602598A SE9602598D0 (sv) 1996-06-28 1996-06-28 Method of making powder mixtures
SE9602598-6 1996-06-28
SE9603626A SE9603626D0 (sv) 1996-10-02 1996-10-02 Method of spray drying powder mixtures
SE9603626-4 1996-10-02

Publications (1)

Publication Number Publication Date
WO1998000256A1 true WO1998000256A1 (fr) 1998-01-08

Family

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Family Applications (2)

Application Number Title Priority Date Filing Date
PCT/SE1997/001067 WO1998000257A1 (fr) 1996-06-28 1997-06-17 Procede de preparation de melanges de poudres
PCT/SE1997/001066 WO1998000256A1 (fr) 1996-06-28 1997-06-17 Procede de sechage par atomisation de melanges de poudres

Family Applications Before (1)

Application Number Title Priority Date Filing Date
PCT/SE1997/001067 WO1998000257A1 (fr) 1996-06-28 1997-06-17 Procede de preparation de melanges de poudres

Country Status (1)

Country Link
WO (2) WO1998000257A1 (fr)

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005107934A1 (fr) 2004-04-27 2005-11-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Procede pour disperser et passiver des poudres a fines particules dans de l'eau et dans des milieux aqueux
EP1724363A1 (fr) * 2005-05-17 2006-11-22 Sandvik Intellectual Property AB Procédé de fabrication de mélanges de poudres de carbure agglomerées
WO2009147428A1 (fr) * 2008-06-03 2009-12-10 The Queen's University Of Belfast Produit doté d’une mouillabilité adaptée
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.
US9103034B2 (en) 2006-09-20 2015-08-11 The Queen's University Of Belfast Method of coating a metallic article with a surface of tailored wettability
CN108010598A (zh) * 2017-12-27 2018-05-08 上海格拉曼国际消防装备有限公司 一种实现低空喷洒多组分压制剂的装置

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SE9802487D0 (sv) 1998-07-09 1998-07-09 Sandvik Ab Cemented carbide insert with binder phase enriched surface zone
SE516324C2 (sv) 2000-05-09 2001-12-17 Sandvik Ab Framställning av väldispergerade suspensioner lämpliga för spraytorkning
US7468413B2 (en) * 2004-01-30 2008-12-23 Khodia Inc. Rare earth aggregate formulation using di-block copolmers
US7867945B2 (en) 2006-02-28 2011-01-11 Fujifilm Corporation Heat-sensitive transfer image-receiving sheet
JP4575889B2 (ja) * 2006-02-28 2010-11-04 富士フイルム株式会社 感熱転写受像シート
GB0608359D0 (en) 2006-04-28 2006-06-07 Johnson Matthey Plc Catalyst additives
CN104942300B (zh) * 2015-06-15 2017-04-26 江苏博迁新材料股份有限公司 空心或实心球形金属粉体的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617358A (en) * 1967-09-29 1971-11-02 Metco Inc Flame spray powder and process
US4070184A (en) * 1976-09-24 1978-01-24 Gte Sylvania Incorporated Process for producing refractory carbide grade powder
US4456484A (en) * 1982-04-05 1984-06-26 Gte Products Corporation Process for producing refractory powder

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617358A (en) * 1967-09-29 1971-11-02 Metco Inc Flame spray powder and process
US4070184A (en) * 1976-09-24 1978-01-24 Gte Sylvania Incorporated Process for producing refractory carbide grade powder
US4456484A (en) * 1982-04-05 1984-06-26 Gte Products Corporation Process for producing refractory powder

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
DIALOG INFORMATION SERVICES, File 351, DERWENT WPI, Dialog Accession No. 010699806, WPI Accession No. 96-196761/199620, (SUMITOMO SPECIAL METALS CO LTD), "Mfg. Sendust Sintered Alloy - by Adding Binder of PVA, Methyl Cellulose and/or Polyacrylamide and Water to Wet Pulverised Metal Powder, Forming Slurry, *
DIALOG INFORMATION SERVICES, File 351, DERWENT WPI, Dialog Accession No. 010747402, WPI Accession No. 96-244357/199625, (SUMITOMO SPECIAL METALS CO LTD), "Powder for Rare-Earth Magnet Used in Motors, Actuator for Computer, Motor Vehicles, etc. Obtd. by Spraying and Drying Slurry Using Spray Drier Device"; & JP,A,08 *
HAHN C. et al., "Effects of Organic Binders on the Compaction Performance of Spray-Dried Granulates, Material Science Monographs", 1987, ELSEVIER, (AMSTERDAM), pages 595-599. *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005107934A1 (fr) 2004-04-27 2005-11-17 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Procede pour disperser et passiver des poudres a fines particules dans de l'eau et dans des milieux aqueux
EP1724363A1 (fr) * 2005-05-17 2006-11-22 Sandvik Intellectual Property AB Procédé de fabrication de mélanges de poudres de carbure agglomerées
US7537637B2 (en) 2005-05-17 2009-05-26 Sandvik Intellectual Property Ab Method of making agglomerated cemented carbide powder mixtures
US9103034B2 (en) 2006-09-20 2015-08-11 The Queen's University Of Belfast Method of coating a metallic article with a surface of tailored wettability
WO2009147428A1 (fr) * 2008-06-03 2009-12-10 The Queen's University Of Belfast Produit doté d’une mouillabilité adaptée
US20110143119A1 (en) * 2008-06-03 2011-06-16 Steven Ernest John Bell Product with tailored wettability
US8734946B2 (en) 2008-06-03 2014-05-27 The Queen's University Of Belfast Product with tailored wettability
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
CN108010598A (zh) * 2017-12-27 2018-05-08 上海格拉曼国际消防装备有限公司 一种实现低空喷洒多组分压制剂的装置
CN108010598B (zh) * 2017-12-27 2023-07-21 上海格拉曼国际消防装备有限公司 一种实现低空喷洒多组分压制剂的装置

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