US3415639A - Method for the manufacture of tantalum and/or niobium powder - Google Patents

Method for the manufacture of tantalum and/or niobium powder Download PDF

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Publication number
US3415639A
US3415639A US540179A US54017966A US3415639A US 3415639 A US3415639 A US 3415639A US 540179 A US540179 A US 540179A US 54017966 A US54017966 A US 54017966A US 3415639 A US3415639 A US 3415639A
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United States
Prior art keywords
tantalum
niobium
manufacture
per million
metal
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Expired - Lifetime
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US540179A
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English (en)
Inventor
Daendliker Gustav
Jacob Alex
Scheller Walter
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BASF Schweiz AG
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Ciba AG
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Publication of US3415639A publication Critical patent/US3415639A/en
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Classifications

    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004Details
    • H01G9/04Electrodes or formation of dielectric layers thereon
    • H01G9/042Electrodes or formation of dielectric layers thereon characterised by the material
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/16Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/16Making metallic powder or suspensions thereof using chemical processes
    • B22F9/18Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
    • B22F9/20Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/16Making metallic powder or suspensions thereof using chemical processes
    • B22F9/30Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00Obtaining refractory metals
    • C22B34/20Obtaining niobium, tantalum or vanadium
    • C22B34/24Obtaining niobium or tantalum
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C1/00Making non-ferrous alloys
    • C22C1/04Making non-ferrous alloys by powder metallurgy
    • C22C1/045Alloys based on refractory metals
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01GCAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004Details
    • H01G9/04Electrodes or formation of dielectric layers thereon
    • H01G9/048Electrodes or formation of dielectric layers thereon characterised by their structure
    • H01G9/052Sintered electrodes
    • H01G9/0525Powder therefor

Definitions

  • the present invention therefore relates to a method for the manufacture of tantalum and/or niobium powders which are suitable for the manufacture of sintered anodes for electrolytic condensers, characterised by reducing tantalum chloride and/or niobium chloride and/or tantalum oxide and/ or niobium oxide with magnesium metal and/ or calcium metal, optionally in the presence of alkali chlorides and/or alkaline earth chlorides, mixing the resulting metal powder, after washing out the salts in a manner which is in itself known, with, at most, the stoichiometric amount of carbon and/or carbide necessary for the formation of CO relative to the amount of oxygen present, purifying the mixture by sintering in vacuo at temperatures of 1600 to 2200 C., hydrogenating the sintered powder in a manner which is in itself known, grinding it and dehydrogenating it.
  • the reduction (or ignition) of the tantalum compounds and/or niobium compounds with magnesium metal and/ or calcium metal takes place in the manner which is usual for thermite reactions.
  • the magnesium may be used in the form of filings, grit or powder, and an excess is advantageously employed.
  • the reaction is preferably carried out in an inert gas atmosphere.
  • the thermite composition may, if desired, also be diluted with alkali chloride and/or alkaline earth chlorides.
  • the tantalum compounds and/or niobium compounds may be used in the form of oxychlorides or alternatively in the form of double chlorides with alkali chlorides.
  • tantalum pentachloride is reduced with magnesium.
  • the carbon may be added in the form of carbon 'black or graphite or metal carbide.
  • Suitable sintering temperatures are those from 1600 to 2200 C.
  • the powder is hydrogenated in a manner which is in itself known, ground, and again dehydrogenated.
  • the subject of the present invention also comprises the use of the powders manufactured according to the invention for the manufacture of sintered anodes for electrolytic condensers, as well as the electrolytic condensers containing such sintered anodes.
  • the manufacture of the 3,415,639 Patented Dec. 10, 1968 anodes and their incorporation into the electrolytic condensers takes place in a manner which is in itself known.
  • EXAMPLE 1 360 parts of powdered TaCl and 74 parts of magnesium grit are mixed under argon and poured into an Inconel tube.
  • the Inconel tube is provided with an argon bypass and fixed in a vertical position.
  • the tube wall is now heated to red heat at the level of the end of the charge, by means of a burner, as a result of which the reaction mixture is ignited'and burns in a downward direction.
  • the pipe wall is cooled with water and the product, which is a solidified salt melt pervaded with spongy metal, is taken out and broken up.
  • the metal is isolated by several times leaching out the reaction mass with dilute hydrochloric acid followed by water, and subsequent filtration and drying in a vacuum cabinet.
  • the material still contains the following impurities, in parts per million:
  • the product is hydrogenated in the known manner.
  • the hydrogenated tablets are broken up in a tantalum-lined stamping mill and are then sieved. This material is dehydrogenated in a high vacuum at 700 C.
  • the free flowing powder exhibits the .following characteristics:
  • BET Specific surface Approx. 0.16 m. g. Oxygen content 1660 parts per million. Carbon content 25 parts per million. Nitrogen content 77 parts per million. Iron content 10 parts per million. Nickel content 10 parts per million. Chromium content .-e 10 parts per million. Magnesium content 1 part per million. Manganese content 1 part per million. Aluminum content 10 parts per million. Silicon content 10 parts per million.
  • the two types of anodes are now jointly sintered, with the final sintering temperature being about 2050 C. They are subsequently formed in 0.01% strength phosphoric acid at 200 volt, and their capacity is measured.
  • a specific capacity of 2800;f-v. per g. of tantalum was found for the product manufactured according to the invention, and a specific capacity of 2380 .f-v. per g. of tantalum was found for the comparison powder.
  • EXAMPLE 2 Specific surface Approx. 0.15 mfl/ g. Oxygen content 2140 parts per million. Carbon content 108 parts per million. Nitrogen content 155 parts per million. Iron content 32 parts per million. Nickel content parts per million. Chromium content 10 parts per million.
  • a process for the manufacture of tantalum powders and niobium powders suitable for the manufacture of sintered anodes for electrolytic condensers which oomprises reducing a member selected from the group consisting of tantalum chloride, tantalum oxychloride, niobium chloride, niobium oxychloride, tantalum oxide and niobium oxide with a member selected from the group consisting of magnesium metal and calcium metal, mixing the resulting metal powder, after washing out the salt in a manner which is in itself known, with at most the stoichiometric amount of a member selected from the group consisting of carbon and metal carbide required for the formation of CO relative to the oxygen content present, purifying by sintering in vacuo at temperatures of 1600 to 2200 C., hydrogenating the sintered powder in a manner which is in itself known, grinding it and dehydrogenating it.
  • a process according to claim 1 which comprises reducing TaCl with magnesium.
  • a process according to claim 1 which comprises using graphite.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Powder Metallurgy (AREA)
  • Electrolytic Production Of Metals (AREA)
US540179A 1965-05-25 1966-04-05 Method for the manufacture of tantalum and/or niobium powder Expired - Lifetime US3415639A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CH727965 1965-05-25

Publications (1)

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US3415639A true US3415639A (en) 1968-12-10

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US (1) US3415639A (US08088918-20120103-C00476.png)
BE (1) BE681427A (US08088918-20120103-C00476.png)
GB (1) GB1094283A (US08088918-20120103-C00476.png)
NL (1) NL6607155A (US08088918-20120103-C00476.png)

Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3473915A (en) * 1968-08-30 1969-10-21 Fansteel Inc Method of making tantalum metal powder
US3499753A (en) * 1966-02-02 1970-03-10 Starck Hermann C Fa Process for the preparation of tantalum powder
US3635693A (en) * 1969-01-27 1972-01-18 Starck Hermann C Fa Method of producing tantalum or niobium powder from compact bodies
US3647420A (en) * 1968-06-06 1972-03-07 Starck Hermann C Fa Process for producing high-purity niobium and tantalum
US3647415A (en) * 1967-10-25 1972-03-07 Show Denko Kk Tantalum powder for sintered capacitors
US3867129A (en) * 1974-02-05 1975-02-18 Metallurgie Hoboken Anodically oxidizable metal powder
US3914507A (en) * 1970-03-20 1975-10-21 Sherritt Gordon Mines Ltd Method of preparing metal alloy coated composite powders
US4017302A (en) * 1976-02-04 1977-04-12 Fansteel Inc. Tantalum metal powder
US4128421A (en) * 1973-03-29 1978-12-05 Marsh Harold G Tantalum powder for producing an embrittlement-resistant wire
US4445931A (en) * 1980-10-24 1984-05-01 The United States Of America As Represented By The Secretary Of The Interior Production of metal powder
US4508563A (en) * 1984-03-19 1985-04-02 Sprague Electric Company Reducing the oxygen content of tantalum
EP1075884A2 (en) * 1996-11-07 2001-02-14 Cabot Corporation Niobium powders and niobium electrolytic capacitors
US20050039577A1 (en) * 1999-03-19 2005-02-24 Habecker Kurt A. Method of making niobium and other metal powders
US20060107788A1 (en) * 2002-06-13 2006-05-25 Toru Okabe Method for producing metal powder and formed product of raw material for metal
WO2023109170A1 (zh) * 2021-12-15 2023-06-22 宁夏东方钽业股份有限公司 采用碱土金属还原氧化钽生产电容器用钽粉的方法

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104439264B (zh) * 2014-12-19 2017-01-04 九江有色金属冶炼有限公司 一种铌条的制备方法及其制备的铌条
CN106825589B (zh) * 2016-12-30 2018-07-17 西安交通大学青岛研究院 一种铌金属粉的机械合金化制备方法
CN107297497B (zh) * 2017-06-21 2019-04-05 炎陵县今成钽铌有限公司 一种铌条的制备工艺
CN114210973B (zh) * 2021-12-15 2023-03-24 宁夏东方钽业股份有限公司 一种钽粉的生产方法以及由该方法得到的钽粉

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA657781A (en) * 1963-02-12 Schussler Mortimer Tantalum powder and process for making same
US3203793A (en) * 1963-01-28 1965-08-31 Du Pont Porous columbium and tantalum materials
US3295951A (en) * 1965-02-02 1967-01-03 Nat Res Corp Production of metals

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA657781A (en) * 1963-02-12 Schussler Mortimer Tantalum powder and process for making same
US3203793A (en) * 1963-01-28 1965-08-31 Du Pont Porous columbium and tantalum materials
US3295951A (en) * 1965-02-02 1967-01-03 Nat Res Corp Production of metals

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3499753A (en) * 1966-02-02 1970-03-10 Starck Hermann C Fa Process for the preparation of tantalum powder
US3647415A (en) * 1967-10-25 1972-03-07 Show Denko Kk Tantalum powder for sintered capacitors
US3647420A (en) * 1968-06-06 1972-03-07 Starck Hermann C Fa Process for producing high-purity niobium and tantalum
US3473915A (en) * 1968-08-30 1969-10-21 Fansteel Inc Method of making tantalum metal powder
US3635693A (en) * 1969-01-27 1972-01-18 Starck Hermann C Fa Method of producing tantalum or niobium powder from compact bodies
US3914507A (en) * 1970-03-20 1975-10-21 Sherritt Gordon Mines Ltd Method of preparing metal alloy coated composite powders
US4128421A (en) * 1973-03-29 1978-12-05 Marsh Harold G Tantalum powder for producing an embrittlement-resistant wire
US3867129A (en) * 1974-02-05 1975-02-18 Metallurgie Hoboken Anodically oxidizable metal powder
US4017302A (en) * 1976-02-04 1977-04-12 Fansteel Inc. Tantalum metal powder
US4445931A (en) * 1980-10-24 1984-05-01 The United States Of America As Represented By The Secretary Of The Interior Production of metal powder
US4508563A (en) * 1984-03-19 1985-04-02 Sprague Electric Company Reducing the oxygen content of tantalum
FR2561258A1 (fr) * 1984-03-19 1985-09-20 Sprague Electric Co Procede pour reduire la teneur en oxygene du tantale
EP1075884A2 (en) * 1996-11-07 2001-02-14 Cabot Corporation Niobium powders and niobium electrolytic capacitors
EP1075884A3 (en) * 1996-11-07 2005-10-05 Cabot Corporation Niobium powders and niobium electrolytic capacitors
US20050039577A1 (en) * 1999-03-19 2005-02-24 Habecker Kurt A. Method of making niobium and other metal powders
US7156893B2 (en) * 1999-03-19 2007-01-02 Cabot Corporation Method of making niobium and other metal powders
US20060107788A1 (en) * 2002-06-13 2006-05-25 Toru Okabe Method for producing metal powder and formed product of raw material for metal
WO2023109170A1 (zh) * 2021-12-15 2023-06-22 宁夏东方钽业股份有限公司 采用碱土金属还原氧化钽生产电容器用钽粉的方法

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Publication number Publication date
BE681427A (US08088918-20120103-C00476.png) 1966-11-23
NL6607155A (US08088918-20120103-C00476.png) 1966-11-28
GB1094283A (en) 1967-12-06

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