EP0667200B1 - Herstellung von Reinstmetallpulver aus Metallalkoxiden - Google Patents

Herstellung von Reinstmetallpulver aus Metallalkoxiden Download PDF

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Publication number
EP0667200B1
EP0667200B1 EP95101419A EP95101419A EP0667200B1 EP 0667200 B1 EP0667200 B1 EP 0667200B1 EP 95101419 A EP95101419 A EP 95101419A EP 95101419 A EP95101419 A EP 95101419A EP 0667200 B1 EP0667200 B1 EP 0667200B1
Authority
EP
European Patent Office
Prior art keywords
tungsten
alkoxide
metal
tantalum
methoxide
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
EP95101419A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0667200A1 (de
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/de
Application granted granted Critical
Publication of EP0667200B1 publication Critical patent/EP0667200B1/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
    • 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 always poses higher requirements for the purity of the interconnect metals, e.g. Titanium, Niobium, tantalum, molybdenum or tungsten.
  • the radioactive elements Thorium and uranium, as ⁇ -emitters can have serious consequences in highly integrated applications Cause memory chips.
  • Ion exchange resins are used, as in Metallurgy of the Rarer Metals, Volume 6, Tantalum and Niobium, page 129-133.
  • Tungsten hexafluoride Distillative separation via the metal halides, e.g. Tungsten hexafluoride in principle also possible.
  • This method is the subject of JP-A 02 30,706.
  • Tungsten hexafluoride is converted to tungsten powder with hydrogen at 650-1400 ° C reduced, which is suitable for the production of sputtering targets.
  • Disadvantage of this The process is that in the reduction with hydrogen, a large amount of hydrogen fluoride attack.
  • the object of this invention was therefore to provide a process for the production of to provide high purity metal powder which is simple and can be carried out inexpensively. This problem is solved by Implementation of volatile, i.e. 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.
  • Metal alkoxide boiling point Aluminum isopropylate 128 ° C / 5 mbar Chromium (IV) tert-butoxide 66 ° C / 3.6 mbar Gallium ethylate 185 ° C / 0.7 mbar Niobium methylate 153 ° C / 0.13 mbar Niobium ethylate 156 ° C / 0.07 mbar Tantalum methylate 130 ° C / 0.3 mbar Tantalum ethylate 146 ° C / 0.2 mbar Titanium ethylate 104 ° C / 1.3 mbar Tungsten methylate 90 ° C / 0.5 mbar
  • the reaction gas in the reaction according to the invention is preferably hydrogen.
  • the reaction gas can also be mixed with an inert carrier gas, in particular argon be diluted.
  • the method according to the invention is preferably at a temperature between 400 ° C and 1400 ° C carried out.
  • the most preferred reaction temperature lies 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.
  • Suitable reactors for carrying out the process according to the invention can Furnaces with an adjustable atmosphere or gas phase reactors. Since the metal alkoxide compounds according to the invention all in a simple manner in the gas phase to be brought is also a gas phase reactor according to DE-A 4 214 720 suitable. The choice of reactor is determined by the particular requirements regarding 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 Cl 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). Analysis of the tungsten metal powder, values in ppm.
  • Al 1 B ⁇ 0.05 Ba 0.09 Bi ⁇ 0.02 Approx 0.34 CD ⁇ 0.05 Co 0.08 Cr 0.26 Cu 0.06 Fe 0.31 K ⁇ 0.05 Mg 5 Mn 0.015 Mon 6 N / A 0.2 Ni 0.12 P 0.19 Pb 0.03 Sb ⁇ 0.05 Si 9 Sn ⁇ 0.05 Sr. ⁇ 0.02 Th ⁇ 0.0005 Ti 0.48 U ⁇ 0.0005 V ⁇ 0.02 Zn ⁇ 0.02 Zr ⁇ 0.05
  • 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).
  • Ta (OCH 3 ) 5 + 21 ⁇ 2 H 2 ⁇ Ta + 5 CH 3 OH The tantalum metal powder was analyzed for impurities using GDMS (glow-discharge mass spectroscopy). Analysis of the tantalum metal powder, values in ppm.
  • 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). Analysis of the titanium metal powder, values in ppm.

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 Herstellung von Reinstmetallpulver aus Metallalkoxiden Expired - Lifetime EP0667200B1 (de)

Applications Claiming Priority (2)

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

Publications (2)

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

Family

ID=6510268

Family Applications (1)

Application Number Title Priority Date Filing Date
EP95101419A Expired - Lifetime EP0667200B1 (de) 1994-02-15 1995-02-02 Herstellung von Reinstmetallpulver aus Metallalkoxiden

Country Status (11)

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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10231777A1 (de) * 2002-07-13 2004-02-05 Diehl Munitionssysteme Gmbh & Co. Kg Verfahren zur Herstellung eines Wolfram-Basismaterials und Verwendung desselben

Families Citing this family (10)

* 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
WO2000067936A1 (en) * 1998-05-06 2000-11-16 H.C. Starck, Inc. Metal powders produced by the reduction of the oxides with gaseous magnesium
US5997612A (en) * 1998-07-24 1999-12-07 The Boc Group, Inc. Pressure swing adsorption process and apparatus
US6375704B1 (en) * 1999-05-12 2002-04-23 Cabot Corporation High capacitance niobium powders and electrolytic capacitor anodes
US7187396B2 (en) 2003-11-07 2007-03-06 Engelhard Corporation Low visibility laser marking additive
MXPA06012366A (es) 2004-09-23 2007-01-31 Element Six Pty Ltd Materiales abrasivos policristalinos y metodos de fabricacion.
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
WO2014008410A1 (en) * 2012-07-03 2014-01-09 Ceramatec, Inc. Apparatus and method of producing metal in a nasicon electrolytic cell
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

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
DE3662916D1 (en) * 1985-03-04 1989-05-24 Toshiba Kk Methods for preparing high-purity molybdenum or tungsten powder and high-purity oxides powder of the same
US4582696A (en) * 1985-04-15 1986-04-15 Ford Motor Company Method of making a special purity silicon nitride powder
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

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10231777A1 (de) * 2002-07-13 2004-02-05 Diehl Munitionssysteme Gmbh & Co. Kg Verfahren zur Herstellung eines Wolfram-Basismaterials und Verwendung desselben

Also Published As

Publication number Publication date
CA2142254A1 (en) 1995-08-16
EP0667200A1 (de) 1995-08-16
ATE170116T1 (de) 1998-09-15
IL112620A0 (en) 1995-05-26
DE4404747C2 (de) 1995-12-14
DE59503295D1 (de) 1998-10-01
JPH07252511A (ja) 1995-10-03
IL112620A (en) 1997-09-30
CN1112467A (zh) 1995-11-29
RU2126735C1 (ru) 1999-02-27
US5711783A (en) 1998-01-27
TW257706B (ru) 1995-09-21
KR950031331A (ko) 1995-12-18
RU95101844A (ru) 1997-03-10
DE4404747A1 (de) 1995-08-17

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