EP0667200A1 - Préparation de poudre de métal de haute pureté à partir d'alkoxydes de métal - Google Patents

Préparation de poudre de métal de haute pureté à partir d'alkoxydes de métal Download PDF

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Publication number
EP0667200A1
EP0667200A1 EP95101419A EP95101419A EP0667200A1 EP 0667200 A1 EP0667200 A1 EP 0667200A1 EP 95101419 A EP95101419 A EP 95101419A EP 95101419 A EP95101419 A EP 95101419A EP 0667200 A1 EP0667200 A1 EP 0667200A1
Authority
EP
European Patent Office
Prior art keywords
alkoxide
tungsten
methoxide
metal
pref
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
EP95101419A
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German (de)
English (en)
Other versions
EP0667200B1 (fr
Inventor
Dr. Martin Schloh
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.)
HC Starck GmbH
Original Assignee
HC Starck GmbH
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 HC Starck GmbH filed Critical HC Starck GmbH
Publication of EP0667200A1 publication Critical patent/EP0667200A1/fr
Application granted granted Critical
Publication of EP0667200B1 publication Critical patent/EP0667200B1/fr
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
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/24—Obtaining niobium or tantalum
    • 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
    • B22F9/28—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from gaseous metal compounds
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/30—Obtaining chromium, molybdenum or tungsten
    • C22B34/36—Obtaining tungsten
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B5/00—General methods of reducing to metals
    • C22B5/02—Dry methods smelting of sulfides or formation of mattes
    • C22B5/12—Dry methods smelting of sulfides or formation of mattes by gases
    • 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
    • B22F2201/00—Treatment under specific atmosphere
    • B22F2201/01—Reducing atmosphere
    • B22F2201/013—Hydrogen
    • 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
    • B22F2203/00—Controlling
    • B22F2203/11—Controlling temperature, temperature profile

Definitions

  • the present invention relates to a method for producing high-purity metal powder.
  • the microfabrication of highly integrated electronic components places increasing demands on the purity of the interconnect metals, e.g. Titanium, niobium, tantalum, molybdenum or tungsten.
  • the radioactive elements thorium and uranium can cause serious errors in highly integrated memory chips as a-emitters.
  • the van Arkel and de Boer process for producing high-purity titanium is known.
  • the raw titanium to be cleaned is heated together with iodine in an evacuated vessel to -500 ° C, whereby gaseous titanium iodide is formed, which in turn is highly purified at another point in the apparatus on a tungsten wire which is electrically heated to -1200 ° C Titan decomposes.
  • a disadvantage of the process is that only small amounts can be produced in this way and a number of other elements such as zirconium, hafnium and especially also thorium can also be transferred.
  • the desired metal species can also be separated and purified using ion exchange resins, as described in Metallurgy of the Rarer Metals, Volume 6, Tantalum and Niobium, pages 129-133.
  • a separation by distillation via the metal halides for example tungsten hexafluoride, is in principle also possible.
  • This method is the subject of JP-A 02 30,706.
  • Tungsten hexafluoride is reduced with hydrogen at 650-1400 ° C to tungsten powder, which is suitable for the production of sputtering targets.
  • the disadvantage of this process is that a large amount of hydrogen fluoride is produced during the reduction with hydrogen.
  • the object of this invention was therefore to provide a process for the production of high-purity metal powder which can be carried out simply and inexpensively. This object is achieved by reacting volatile, that is sublimable or distillable, metal alkoxides with a reaction gas.
  • This method is the subject of this invention.
  • the metal alkoxide compounds which are used according to the invention have the general formula M (OR) x , where M is a metal from Group 3-14 (according to IUPAC 1985), R is an alkyl, aryl, cycloalkyl or aralkyl radical and M (OR ) x is a sublimable or distillable compound.
  • M is a metal from Group 3-14 (according to IUPAC 1985)
  • R is an alkyl, aryl, cycloalkyl or aralkyl radical
  • M (OR ) x is a sublimable or distillable compound.
  • some alkoxide compounds that are suitable according to the invention are listed as examples.
  • Chromium tert-butoxide, niobium methoxide, niobium ethoxide, tantalum methoxide, tantalum ethoxide, tungsten methoxide and tungsten methoxide are particularly preferred according to the invention.
  • the reaction gas in the reaction according to the invention is preferably hydrogen.
  • the reaction gas can also be diluted with an inert carrier gas, in particular argon.
  • the process according to the invention is preferably carried out at a temperature between 400 ° C. and 1400 ° C.
  • the particularly preferred reaction temperature is between 600 ° C and 1200 ° C.
  • WF 6 is converted into W (OCH 3 ) 6 in an equilibrium reaction with volatile Si (OCH 3 ) 4 as ligand transfer agent.
  • OCH 3 volatile Si
  • Complete methoxylation is only possible by treating the partially fluorinated product with a methanolic NaOCH 3 solution.
  • tungsten (VI) alkoxides can be prepared from the reaction of tungsten (VI) hexakis (dimethylamide) and the corresponding alcohol.
  • the synthesis of the tungsten amide compound is according to Inorg. Chem. 1977, 16, 1791-1794 very complex and is therefore ruled out for an industrial process.
  • Suitable reactors for carrying out the process according to the invention can be furnaces with an adjustable atmosphere or else gas phase reactors. Since the metal alkoxide compounds according to the invention can all be brought into the gas phase in a simple manner, a gas phase reactor according to DE-A 4 214 720 is also suitable. The choice of the reactor is determined by the requirements with regard to fine particle size and particle size distribution of the metal powder.
  • a 0.5 molar solution of LiCl in methanol was electrolysed under argon protective gas in a flat ground reaction vessel which was provided with a steel cathode, an anode made of tungsten and a reflux condenser. It was electrolyzed with direct current and a current density of 200 mA / cm 2 . The electrolyte solution turned yellow-orange and began to boil shortly after the start of electrolysis.
  • a solution of 50 g of NH 4 CI in 2000 ml of methanol was electrolysed under argon protective gas in a flat-ended reaction vessel which was provided with a steel cathode, an anode made of tantalum and a reflux condenser. It was electrolyzed with direct current and a current density of 200 mA / cm 2 .
  • the electrolytic solution turned yellowish and began to boil shortly after the start of the electrolysis.
  • Electrochemically produced tungsten ethoxide is purified by sublimation in a glass apparatus and then reacted with hydrogen in a tube furnace at 1000 ° C., equation (2).
  • the tungsten metal powder was analyzed for impurities using GDMS (glow-discharge mass spectroscopy).
  • Electrochemically produced tantalum methoxide is purified by distillation at 130 ° C. in a vacuum (0.3 mbar) in a glass apparatus and then reacted with hydrogen in a tube furnace at 1000 ° C., equation (3).
  • the tantalum metal powder was analyzed for impurities using GDMS (glow-discharge mass spectroscopy).
  • Electrochemically produced titanium ethoxide is purified by distillation at 104 ° C. in a vacuum (0.3 mbar) in a glass apparatus and then reacted with hydrogen in a tube furnace at 1000 ° C., equation (4).
  • the titanium metal powder was analyzed for impurities using GDMS (glow-discharge mass sprectroscopy).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP95101419A 1994-02-15 1995-02-02 Préparation de poudre de métal de haute pureté à partir d'alkoxydes de métal Expired - Lifetime EP0667200B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4404747 1994-02-15
DE4404747A DE4404747C2 (de) 1994-02-15 1994-02-15 Herstellung von Reinstmetallpulver aus Metallalkoxiden

Publications (2)

Publication Number Publication Date
EP0667200A1 true EP0667200A1 (fr) 1995-08-16
EP0667200B1 EP0667200B1 (fr) 1998-08-26

Family

ID=6510268

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95101419A Expired - Lifetime EP0667200B1 (fr) 1994-02-15 1995-02-02 Préparation de poudre de métal de haute pureté à partir d'alkoxydes de métal

Country Status (11)

Country Link
US (1) US5711783A (fr)
EP (1) EP0667200B1 (fr)
JP (1) JPH07252511A (fr)
KR (1) KR950031331A (fr)
CN (1) CN1112467A (fr)
AT (1) ATE170116T1 (fr)
CA (1) CA2142254A1 (fr)
DE (2) DE4404747C2 (fr)
IL (1) IL112620A (fr)
RU (1) RU2126735C1 (fr)
TW (1) TW257706B (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6100415A (en) * 1998-03-16 2000-08-08 Japan Pionics Co., Ltd. Purified alkoxide and process for purifying crude alkoxide
RU2170647C1 (ru) * 2000-11-02 2001-07-20 Закрытое акционерное общество "ИНВЕСТ-Технологии" Способ получения ультрадисперсного металлического порошка

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000067936A1 (fr) * 1998-05-06 2000-11-16 H.C. Starck, Inc. Poudres metalliques obtenues par reduction d'oxides au moyen de magnesium gazeux
US5997612A (en) * 1998-07-24 1999-12-07 The Boc Group, Inc. Pressure swing adsorption process and apparatus
RU2164194C2 (ru) * 1999-05-11 2001-03-20 Институт химии и технологии редких элементов и минерального сырья им. И.В. Тананаева Кольского научного центра РАН Способ получения порошка вентильного металла
US6375704B1 (en) * 1999-05-12 2002-04-23 Cabot Corporation High capacitance niobium powders and electrolytic capacitor anodes
DE10030387A1 (de) * 2000-06-21 2002-01-03 Starck H C Gmbh Co Kg Kondensatorpulver
DE10231777A1 (de) * 2002-07-13 2004-02-05 Diehl Munitionssysteme Gmbh & Co. Kg Verfahren zur Herstellung eines Wolfram-Basismaterials und Verwendung desselben
US7187396B2 (en) * 2003-11-07 2007-03-06 Engelhard Corporation Low visibility laser marking additive
KR20070083557A (ko) 2004-09-23 2007-08-24 엘리먼트 씩스 (프티) 리미티드 다결정 연마 물질 및 그 제조방법
US7399335B2 (en) * 2005-03-22 2008-07-15 H.C. Starck Inc. Method of preparing primary refractory metal
US7758668B1 (en) 2006-04-18 2010-07-20 Chemnano, Inc. Process of manufacturing metallic nano-scale powders
RU2413011C1 (ru) * 2009-12-01 2011-02-27 Государственное образовательное учреждение высшего профессионального образования "Ангарская государственная техническая академия" (ГОУ ВПО "АГТА") Плазмохимический реактор для обработки минеральных руд
RU2410446C1 (ru) * 2009-12-01 2011-01-27 Государственное образовательное учреждение высшего профессионального образования Ангарская государственная техническая академия (ГОУВПО АГТА) Способ обработки минеральных руд
EP2870277B1 (fr) * 2012-07-03 2021-04-14 Enlighten Innovations Inc. Appareil et procédé de production de métal dans une cellule électrolytique de nasicon
CN109396456B (zh) * 2018-12-28 2024-02-13 西安赛隆金属材料有限责任公司 一种球形钨粉末的制备装置及方法

Citations (2)

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Publication number Priority date Publication date Assignee Title
US4582696A (en) * 1985-04-15 1986-04-15 Ford Motor Company Method of making a special purity silicon nitride powder
EP0197271A1 (fr) * 1985-03-04 1986-10-15 Kabushiki Kaisha Toshiba Procédé de préparation de poudres très pures de molybdène ou de tungstène, ainsi que de leurs oxydes

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US3117833A (en) * 1958-09-25 1964-01-14 Fansteel Metallurgical Corp Process of purifying and separating columbium and tantalum values from each other
US3640093A (en) * 1969-03-10 1972-02-08 Owens Illinois Inc Process of converting metalorganic compounds and high purity products obtained therefrom
GB1307581A (en) * 1970-05-05 1973-02-21 Monsanto Chemicals Production of alkoxides
JPS5785943A (en) * 1980-11-18 1982-05-28 Nishimura Watanabe Chiyuushiyutsu Kenkyusho:Kk Recovering method for metal from fluorine compound
US4615736A (en) * 1985-05-01 1986-10-07 Allied Corporation Preparation of metal powders
US4755369A (en) * 1985-05-22 1988-07-05 Research Development Corporation Of Japan Production of ultrafine particles
JPS61275108A (ja) * 1985-05-30 1986-12-05 Mitsubishi Mining & Cement Co Ltd 誘電体粉末の製造方法
JPS63184306A (ja) * 1986-09-22 1988-07-29 Mitsui Toatsu Chem Inc 強磁性金属粉末の安定化方法
JPH0230706A (ja) * 1988-07-19 1990-02-01 Central Glass Co Ltd β−タングステン粉末の製造法
US5455223A (en) * 1993-02-24 1995-10-03 American Superconductor Corporation Coated precursor powder for oxide superdonductors

Patent Citations (2)

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EP0197271A1 (fr) * 1985-03-04 1986-10-15 Kabushiki Kaisha Toshiba Procédé de préparation de poudres très pures de molybdène ou de tungstène, ainsi que de leurs oxydes
US4582696A (en) * 1985-04-15 1986-04-15 Ford Motor Company Method of making a special purity silicon nitride powder

Non-Patent Citations (2)

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CHEMICAL ABSTRACTS, Columbus, Ohio, US; *
PATENT ABSTRACTS OF JAPAN *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6100415A (en) * 1998-03-16 2000-08-08 Japan Pionics Co., Ltd. Purified alkoxide and process for purifying crude alkoxide
RU2170647C1 (ru) * 2000-11-02 2001-07-20 Закрытое акционерное общество "ИНВЕСТ-Технологии" Способ получения ультрадисперсного металлического порошка

Also Published As

Publication number Publication date
DE59503295D1 (de) 1998-10-01
KR950031331A (ko) 1995-12-18
US5711783A (en) 1998-01-27
IL112620A (en) 1997-09-30
DE4404747C2 (de) 1995-12-14
JPH07252511A (ja) 1995-10-03
RU2126735C1 (ru) 1999-02-27
CN1112467A (zh) 1995-11-29
IL112620A0 (en) 1995-05-26
DE4404747A1 (de) 1995-08-17
EP0667200B1 (fr) 1998-08-26
CA2142254A1 (fr) 1995-08-16
RU95101844A (ru) 1997-03-10
TW257706B (fr) 1995-09-21
ATE170116T1 (de) 1998-09-15

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