EP0397877A1 - Procede de fabrication de poudres metalliques dispersees - Google Patents

Procede de fabrication de poudres metalliques dispersees Download PDF

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Publication number
EP0397877A1
EP0397877A1 EP89902701A EP89902701A EP0397877A1 EP 0397877 A1 EP0397877 A1 EP 0397877A1 EP 89902701 A EP89902701 A EP 89902701A EP 89902701 A EP89902701 A EP 89902701A EP 0397877 A1 EP0397877 A1 EP 0397877A1
Authority
EP
European Patent Office
Prior art keywords
reduction
mol
metal
powder
alkali
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.)
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Application number
EP89902701A
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German (de)
English (en)
Other versions
EP0397877A4 (en
Inventor
Olga Nikolaevna Leontieva
Antonina Vasilievna Shoitova
Alexandr Alexandrovich Royanov
Dmitry Ivanovich Ryzhonkov
Igor Dmitrievich Morokhov
Jury Albertovich Bolotov
Julia Mikhailovna Gavrilova
Jury Leonidovich Krasulin
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.)
Institut Metallurgii Imeni Aabaikova Akademii Nauk Sssr
Original Assignee
Institut Metallurgii Imeni Aabaikova Akademii Nauk Sssr
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Application filed by Institut Metallurgii Imeni Aabaikova Akademii Nauk Sssr filed Critical Institut Metallurgii Imeni Aabaikova Akademii Nauk Sssr
Publication of EP0397877A1 publication Critical patent/EP0397877A1/fr
Publication of EP0397877A4 publication Critical patent/EP0397877A4/de
Withdrawn legal-status Critical Current

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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
    • B22F9/16—Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors

Definitions

  • the present invention relates to the field of powder metallurgy and, in particular, relates to processes for producing this metal powder.
  • disperse metal powders are used extensively in various branches of the economy and are particularly promising when developing new materials with predictable properties. They can also be used to intensify various technological processes.
  • disperse metal powders for example made of iron or copper
  • Metal powders dispersed in a ceramic matrix are used in the energy industry, aircraft industry and in cosmic engineering, where high demands are placed on the heat resistance and heat resistance of the connections.
  • the process for the production of disperse metal powders should have sufficient performance and the production of such disperse metal powders, which have practically no admixtures, with certain dimensions and ensure with minimal dispersion in the fraction composition.
  • the process is said to bring about a uniform distribution of the disperse metal powders in a ceramic matrix.
  • a process was developed for the production of highly disperse copper, nickel and cobalt powders by pyrolysis of formates of these metals in argon medium ("Naukova dumka”, “Poroshkovaya metallurgia”, “Powder Metallurgy”, I980, No. 3, NMKhokhlacheva "Svoistva vysokodispersnykh poroshkov metallov, poluchennykh metodom piroliza formiatov "). Average dimensions of the powder particles are from 20 to 80 nm. However, individual particles of the copper powder are distinguished by large dimensions, which means that the fraction composition is inhomogeneous. The process also does not allow the production of disperse powders of other metals. The metal formates are also quite difficult to access.
  • the process makes it possible to distribute the disperse metal powder evenly in a ceramic matrix.
  • the product to be produced according to this process inevitably has additions which are entrained from the solution during the separation.
  • only nitrates can be used as starting compounds.
  • the invention has for its object to develop such a method for the production of disperse metal powder, which makes it possible to powder a number of metals with a particle size of at most 1000 mm with a narrow fraction distribution, which are free of admixtures, it being possible to to produce an even distribution in a ceramic matrix.
  • This object is achieved in that a process of this type for the production of disperse metal powders is proposed which provides for the processing of the hydrates of the mineral metal salts with alkali lyes, the filtration of the metal hydroxides obtained, their drying and reduction by hydrogen, in which, according to the invention, solid hydrates of the metal salts used, the alkali lye with a concentration of 6 to with a 1.5 to 2-fold excess of alkali metal solution contained in this alkali, based on the stoichiometric amount required for the formation of the hydroxide, and the reduction of the hydroxides at a temperature of 200 to 300 ° C.
  • the conversion of the solid starting salt and the alkali lye promotes the formation of zones of the phase-to-contact conversion in the entire powder volume and consequently of reaction centers at the expense of proton removal from the water of hydration.
  • Implementation guaranteed performs the substitution of the azido ligands of the solid salt by hydroxyl groups at the expense of the developing process in microvolumes, which leads to the formation of a low-water hydroxide.
  • the low-water hydroxide is a non-stoichiometric compound that can be exposed to filtration.
  • the alkali lye is taken at a concentration of 6 to 15 mol / l, because at a concentration below 6 mol / l the dissolution of salt passivates the substitution reaction of azido ligands by hydroxyl groups, which is why the solutions are practically reacted, which leads to the formation of a colloidal precipitate .
  • a concentration above 15 mol / l is not expedient because, in addition to the small particles, larger particles are formed, which does not make it possible to maintain a narrow fraction composition.
  • the excess of alkali compared to the stoichiometric content is necessary to achieve an excess of hydroxyl ions, which contribute to the destruction of the bonds. A greater than 2-fold excess is not appropriate in connection with the inevitable increase in the reaction volume.
  • the reduction of the low-water hydroxides obtained is carried out at a temperature around 200 to 300 ° C. higher than the start of the reduction of the hydroxide of a corresponding metal, because the reduction does not occur completely at a temperature close to the start of the reduction.
  • a temperature more than 300 ° C higher than the start of the reduction the growth of the metal powder particles takes place, which is extremely undesirable.
  • the consumption of hydrogen below 2.5 m 3 / mol Me h does not make it possible to completely reduce a compound down to a metal.
  • a further increase in the consumption of hydrogen causes the metal hydro-k-side to be discharged from the reaction zone together with the gas stream and the yield of the end product to be reduced.
  • the disperse metal powders to be produced have a high activity and reactivity and can be easily measured in the air, it is necessary to passivate them with an inert gas that is held on the powder surface by adsorption forces.
  • the proposed method for producing a disperse metal powder makes it possible to remove powder winding, meet the following requirements: very small particle size, at most 1000 nm, their narrow fraction distribution and practical lack of additives: the process also enables the disperse metal powder to be distributed very evenly in a ceramic matrix.
  • the developed process is characterized by a simple technology and apparatus design of the process control, in this process standardized equipment can be used.
  • the process also makes it possible to produce disperse metal powders with a comprehensive nomenclature.
  • the process according to the invention is quite economical because the heat absorption is reduced fourfold when the water-poor hydroxide is reduced.
  • the process developed is environmentally friendly because all the used solutions can be easily neutralized and the technological water can circulate in a closed circulation system.
  • the proposed method is characterized by simple technological process control and apparatus design as well as by economy and universal application possibilities, because it is suitable for the production of disperse metal powders of different metals and is ecologically pure.
  • the process for producing disperse metal powder is simple in technological design and is carried out as follows.
  • the starting components are placed in containers for liquid and bulk goods, whereby solid hydrates of the metal salts and alkali lye or a concentrated ammonia solution are poured separately. about a dose
  • the device is first supplied to a reactor with an alkali solution with a predetermined concentration and then a solid metal salt hydrate is added to the same.
  • the reaction proceeds for 1 to 15 hours at room temperature.
  • the reaction mass is fed to a container vacuum filter, then a washing device is switched on.
  • the bulk of the low-water metal hydroxide enters an infrared dryer in which the hydroxide is dried at a temperature of 100 ° C. and then it enters a measuring vessel for bulk goods.
  • the water-poor hydroxide is fed in certain portions to a vortex furnace for reduction with hydrogen, in which the reduction process is carried out at a temperature 200 to 300 ° C higher than the start of reduction of hydroxides of corresponding metals and with a hydrogen consumption of 2.5 to 6 m 3 / Mol Me • h occurs during a certain time.
  • a stream of intergas is fed to it and the dispersed metal powder is passivated. The finished product is then removed from the oven and weighed.
  • the aqueous solution of this salt is fed to an additional container via a measuring vessel, into which the metal hydroxide enters after filtration and washing.
  • the metal hydroxide processed with the solution of the salt of another metal is filtered off again, washed, and then the mass obtained is fed to the infrared dryer.
  • the disperse nickel powder has a particle size of 3 to 30 nm. No admixtures have been proven. The yield of the final product is 92%.
  • the disperse iron powder has a particle size of 3 to 30 nm.
  • the sulfur content is 0.0001%.
  • the yield of the final product is 85%.
  • the disperse copper powder has a particle size of 300 to 500 nm and a scattering power of 10%, the sulfur content is 0.0001%.
  • the yield of the final product is 90%.
  • NiSO 4 .7H 2 O salt 140 g are treated with 250 ml of aqueous alcoholic NaOH solution with a concentration of 6 mol / l at room temperature, the excess of alkali is 1.5.
  • the mother liquor is filtered off in 1.5 hours and the solid phase is washed carefully.
  • the powder of nickel hydroxide is dried in air at a temperature of 100 ° C for 1 hour.
  • the reduction is carried out at a temperature of 500.degree. C., which is 300.degree. C. higher than the start of reduction of nickel hydroxide, with a consumption of hydrogen of 6 m 3 / mol Ni.h in a gas stream.
  • the nickel powder produced is passivated with nitrogen.
  • the disperse nickel powder has a particle size of 3 to 30 nm.
  • the sulfur content is 0.0001%.
  • the yield of the final product is 90%.
  • the disperse nickel powder has a particle size of 3 to 30 nm. No admixtures have been detected.
  • the iron powder obtained has a particle size of 3 to 30 nm. No admixtures have been detected. The yield of the final product is 90%.
  • Powder of the following composition is obtained: 20% Ni and 80% Al 2 O 3 with an even distribution of nickel in a ceramic matrix.
  • the chlorine content is less than 0.01%.
  • the powder obtained has the following composition: 35% Mo and 65% Al 2 O 3 with a uniform distribution of the molybdenum in a ceramic matrix. No sodium was detected.
  • 1 kg of salt ZrOCl 2 .8H 2 O is treated with 2 liters of aqueous NH 4 OH solution at a concentration of 13.4 mol / l at room temperature, the excess of alkali is 2.
  • the mother liquor is filtered off in 1 hour, the solid Phase treated with 68.2 g of the Na 2 WO 4 solution in 300 ml of water (0, d mol / l) with mixing.
  • the mother liquor is carefully filtered off and washed in 1 hour.
  • the powder produced is dried in a drying cabinet at a temperature of 100 ° C.
  • the reduction is carried out at a temperature of 800.degree. C., which is 300.degree. C.
  • Powder of the following composition is obtained: W 10% and ZrO 2 90% with an even distribution of the tungsten in a ceramic matrix. No admixtures have been detected.
  • Powder of the following composition is obtained: 10% Ni and 90% ZrO 2 with a uniform distribution of the nickel in a ceramic matrix.
  • the chlorine content is 0.01%.
  • a powder of the following composition is obtained: 15% Fe and 85% Al 2 O 3 with an even distribution of iron in a ceramic matrix.
  • the chlorine content is less than 0.01%.
  • Disperse metal powders can be used in agriculture, as growth stimulators and in industry to create substances with predetermined properties.

Abstract

Un procédé de fabrication de poudres métalliques dispersées consiste à traiter des hydrates solides de sels minéraux métalliques avec des solutions alcalines d'une concentration égale à 6-15 mol/l, cette solution contenant 1,5 à 2 fois plus d'alcalis par rapport à sa quantité stoechiométriquement nécessaire pour obtenir l'hydroxyde. On procède au filtrage, au séchage et à la réduction des hydroxydes métalliques obtenus à l'aide d'hydrogène. On effectue ladite réduction à une température de 200 à 300°C supérieure à celle du début de la réduction des hydroxydes des métaux correspondants, avec une consommation d'hydrogène de 2,5 à 6 m3/mol Mexh sur la base du sel initial. Après réduction, on procède à la passivation des poudres obtenues à l'aide d'un gaz inerte.
EP19890902701 1988-11-25 1988-11-25 Method for making dispersed metal powders Withdrawn EP0397877A4 (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/SU1988/000242 WO1990006200A1 (fr) 1988-11-25 1988-11-25 Procede de fabrication de poudres metalliques dispersees

Publications (2)

Publication Number Publication Date
EP0397877A1 true EP0397877A1 (fr) 1990-11-22
EP0397877A4 EP0397877A4 (en) 1991-05-08

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Family Applications (1)

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EP19890902701 Withdrawn EP0397877A4 (en) 1988-11-25 1988-11-25 Method for making dispersed metal powders

Country Status (5)

Country Link
EP (1) EP0397877A4 (fr)
JP (1) JPH03502345A (fr)
DD (1) DD284826A5 (fr)
FI (1) FI903712A0 (fr)
WO (1) WO1990006200A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6857321B2 (ja) * 2016-10-27 2021-04-14 住友金属鉱山株式会社 ニッケル粉末の製造方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3833351A (en) * 1973-02-15 1974-09-03 Univ Eng Inc Continuous preparation of pure metals by hydrogen reduction
US3877931A (en) * 1973-07-20 1975-04-15 Daniel R Neskora Continuous preparation of pure metals by gaseous reduction
GB2023112A (en) * 1978-05-31 1979-12-28 Gte Sylvania Inc Method for producing extra fine cobalt metal powdwe
US4214896A (en) * 1979-05-14 1980-07-29 Gte Products Corporation Process for producing cobalt metal powder
EP0080996A2 (fr) * 1981-12-02 1983-06-08 VOEST-ALPINE Aktiengesellschaft Procédé de récupération de métaux à partir de solutions acides de leurs sels
US4414021A (en) * 1982-05-06 1983-11-08 Welbon William W Process for the synthesis of iron powder
JPS62139803A (ja) * 1985-12-12 1987-06-23 Okamura Seiyu Kk 強磁性金属粉の製造方法
US4798623A (en) * 1988-02-19 1989-01-17 Gte Products Corporation Method for producing fine cobalt metal powder

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3427159A (en) * 1963-07-25 1969-02-11 Polaroid Corp Diffusion transfer process utilizing heat transfer
IL34081A (en) * 1970-03-16 1972-11-28 Gorin C Production of solid material in a state of thin division
US3940261A (en) * 1974-07-24 1976-02-24 Eastman Kodak Company Process for preparing crystalline silver particles having electrically conductive surfaces and product

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3833351A (en) * 1973-02-15 1974-09-03 Univ Eng Inc Continuous preparation of pure metals by hydrogen reduction
US3877931A (en) * 1973-07-20 1975-04-15 Daniel R Neskora Continuous preparation of pure metals by gaseous reduction
GB2023112A (en) * 1978-05-31 1979-12-28 Gte Sylvania Inc Method for producing extra fine cobalt metal powdwe
US4214896A (en) * 1979-05-14 1980-07-29 Gte Products Corporation Process for producing cobalt metal powder
EP0080996A2 (fr) * 1981-12-02 1983-06-08 VOEST-ALPINE Aktiengesellschaft Procédé de récupération de métaux à partir de solutions acides de leurs sels
US4414021A (en) * 1982-05-06 1983-11-08 Welbon William W Process for the synthesis of iron powder
JPS62139803A (ja) * 1985-12-12 1987-06-23 Okamura Seiyu Kk 強磁性金属粉の製造方法
US4798623A (en) * 1988-02-19 1989-01-17 Gte Products Corporation Method for producing fine cobalt metal powder

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN, Band 11, Nr. 364 (M-646), 27. November 1987; & JP-A-62 139 803 (OKAMURA SEIYU K.K.) 23-06-1987 *
See also references of WO9006200A1 *

Also Published As

Publication number Publication date
FI903712A0 (fi) 1990-07-24
DD284826A5 (de) 1990-11-28
EP0397877A4 (en) 1991-05-08
WO1990006200A1 (fr) 1990-06-14
JPH03502345A (ja) 1991-05-30

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