US20030047462A1 - Method of manufacture for ferro-titanium and other metal alloys electrolytic reduction - Google Patents

Method of manufacture for ferro-titanium and other metal alloys electrolytic reduction Download PDF

Info

Publication number
US20030047462A1
US20030047462A1 US10/204,465 US20446502A US2003047462A1 US 20030047462 A1 US20030047462 A1 US 20030047462A1 US 20446502 A US20446502 A US 20446502A US 2003047462 A1 US2003047462 A1 US 2003047462A1
Authority
US
United States
Prior art keywords
ores
titanium
alloy
mixed
ferro
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.)
Abandoned
Application number
US10/204,465
Other languages
English (en)
Inventor
Charles Ward-Close
Alastair Godfrey
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.)
QINTETIQ Ltd
Original Assignee
QINTETIQ Ltd
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 GB0003971A external-priority patent/GB2359564B/en
Priority claimed from GB0010873A external-priority patent/GB2362164B/en
Application filed by QINTETIQ Ltd filed Critical QINTETIQ Ltd
Assigned to QINTETIQ LIMITED reassignment QINTETIQ LIMITED ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: GODFREY, ALASTAIR B., WARD-CLOSE, CHARLES M.
Publication of US20030047462A1 publication Critical patent/US20030047462A1/en
Priority to US11/066,545 priority Critical patent/US20050175496A1/en
Abandoned legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/04—Electrolytic production, recovery or refining of metal powders or porous metal masses from melts
    • 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
    • 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
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/1263—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds, e.g. by reduction
    • 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
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/12—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08
    • C22B34/129—Obtaining titanium or titanium compounds from ores or scrap by metallurgical processing; preparation of titanium compounds from other titanium compounds see C01G23/00 - C01G23/08 obtaining metallic titanium from titanium compounds by dissociation, e.g. thermic dissociation of titanium tetraiodide, or by electrolysis or with the use of an electric arc
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/02—Pretreatment of the fibres or filaments
    • C22C47/04—Pretreatment of the fibres or filaments by coating, e.g. with a protective or activated covering
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C47/00—Making alloys containing metallic or non-metallic fibres or filaments
    • C22C47/14—Making alloys containing metallic or non-metallic fibres or filaments by powder metallurgy, i.e. by processing mixtures of metal powder and fibres or filaments
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C3/00—Electrolytic production, recovery or refining of metals by electrolysis of melts
    • C25C3/26—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium
    • C25C3/28—Electrolytic production, recovery or refining of metals by electrolysis of melts of titanium, zirconium, hafnium, tantalum or vanadium of titanium
    • 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
    • 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
    • C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
    • C22B4/06—Alloys

Definitions

  • This invention relates to a method for the manufacture of alloys from metal ores. More particularly, the invention is directed to the reduction of metal ores to form alloys. Such alloys include but are not limited to Ferro-titanium alloys.
  • Certain embodiments of these methods involve the electrolysis of metal oxides or other compounds (M 1 X) in a cell containing a liquid (fused salt M 2 Y) electrolyte and an anode, the metal oxide or other compound forming the cathode. Conditions are controlled so as to bring about the selective dissolution of the oxygen or other contaminant of the cathode in preference to deposition of the metal cation. Improved efficiency of this process can be achieved by various methods as described in GB 0003971.9 and GB 0010873.8 some of which are summarised below.
  • Sintered granules or powders of metal oxide can be used as the feedstock for the electrolysis described in the above referenced method, as long as appropriate conditions are present.
  • powdered titanium dioxide in the form of granules or a powder is used, the powdered particles preferably have a size in the region of 200 ⁇ m.
  • the manufacture of titanium dioxide from the raw ore (sand mined illemite) comprises a large number of steps in the production of titanium.
  • titanium dioxide in the form of an amorphous slurry undergoes calcining.
  • the titanium dioxide slurry can be used as the principle feedstock in the above described electrolytic method.
  • a small percentage of calcined material is mixed with amorphous material and a binder to obtain the most satisfactory results after sintering.
  • the calcined material should constitute at least about 5% by weight of the mixture.
  • Individual SiC fibres are coated with an oxide/binder slurry (or mixed oxide slurry for an alloy) of the appropriate thickness.
  • the fibres may be combined with an oxide paste or slurry to produce a preformed sheet consisting of parallel fibres in a matrix of oxide powder and binder, or, a complex three dimensional shape containing the fibres in the correct positions could be cast or pressed from oxide slurry or paste.
  • the coated fibres, preform sheet or three dimensional shape can then be made the anode of an electrochemical cell (with or without a pre-sinter step) and the oxide powder may be reduced by the previously described electrolytic process to a metal or alloy.
  • the product may then be washed or vacuum annealed to remove salt and then hot isostatically pressed to give a 100% dense fibre reinforced composite.
  • fine ceramic particles such as titanium diboride are blended with titania powder to give a uniform mixture prior to sintering and electrolytic reduction. After reduction the product is washed or vacuum annealed to remove salt, and then hot pressed to give a 100% dense composite material. Depending on the reaction chemistries, the ceramic particles may either remain unchanged by the electrolysis and hot pressing or may be converted to another ceramic material which would then be the reinforcing element of the MMC. For example, in the case of titanium diboride, the ceramic reacts with the titanium to form titanium monoboride.
  • fine metal powder is mixed with the titania powder in place of a ceramic powder, with the intention of forming a fine distribution of a hard ceramic or intermetallic phase by reaction with titanium or another alloying element or elements.
  • titanium or another alloying element or elements For example, boron powder can be added, and this reacts to form titanium monoboride particles in the alloy.
  • Metal foams are attractive for a number of applications such as filters, medical implants and structural fillers.
  • the fabrication of a sponge-like sintered oxide pre-form from the starting material M 1 X can be converted into a solid metal/alloy foam via the electrolytic method previously described.
  • Various established methods may be used to make the foam like material from the mixture of oxide powders.
  • the foam preform desirably has open porosity that is, porosity which is interconnected and open to the exterior.
  • a natural or synthetic polymeric foam is infiltrated with a metal (eg titanium) oxide slip, then dried and fired to remove the polymeric foam, leaving an open “foam” which is an inversion of the original polymeric foam.
  • the sintered preform is then electrolytically reduced in accordance with the previously described method to convert it into a titanium/titanium alloy foam.
  • the foam is then washed or vacuum distilled to remove the salt.
  • the metal oxide powder may be mixed with organic foaming agents. These materials are typically two liquids which when mixed, react to evolve a foaming gas, and then cure to give a solidified foam with either an open or closed structure.
  • the metal powder is mixed with one or both of the precursor liquids prior to production of the foam.
  • the foam is then fired to remove the organic material, leaving the ceramic foam which is then electrolytically reduced in accordance with the previously described method.
  • a near net shape component may be made using the previously described electrolytic method by reducing a ceramic facsimile of the component made from a mixture of a metal oxide or mixture of metal oxide and the oxides of other alloying elements. Again this method is particularly suited to the manufacture of titanium metal and alloy components.
  • the ceramic facsimile may be produced using any of a variety of well known production methods for ceramic articles which include; pressing, injection moulding, extrusion and slip casting, followed by firing (sintering). Full density of the metallic component can be achieved by sintering with or without the application of pressure, either in the electrochemical cell, or in a subsequent operation. Shrinkage of the component during the conversion to metal or alloy should be allowed for by making the ceramic facsimile proportionally larger than the desired component.
  • the electrolysis is performed on a preformed sintered mass comprising a mixture of metal oxide made up of a proportion of particles of size generally greater than 20 microns and a proportion of finer particles of less than 7 microns.
  • the finer particles make up between 10 and 55% by weight of the sintered block.
  • High density granules of approximately the size required for the powder are manufactured and then are mixed with very fine unsintered metal oxide (e.g., titanium dioxide), binder and water in the appropriate ratios and formed into the required shape of feedstock.
  • This feedstock is then sintered to achieve the required strength for the reduction process.
  • the resulting feedstock after sintering but before reduction, consists of high density granules in a lower density (porous) matrix.
  • the feedstock can be reduced in block form using the previously described electrolytic method and the result is a friable block which can easily be broken up into powder.
  • the calcine discharge used can be replaced by cheaper amorphous TiO 2 .
  • the key requirement for this “matrix” material is that it sinters easily with significant shrinkage during the sintering process. Any oxide or mixture of oxides which fulfil these criteria would be usable. In the case of TiO 2 this means the particle size must be less than about 1 ⁇ m. It is estimated that at least 5% of the matrix material should be present in order to give any significant strength to the sintered product.
  • the starting granules for this method need not be rutile sand but could be manufactured by a sintering and crushing process, and in principle there is no reason to suppose that alloy powders could not be made by this route.
  • X may be a metalloid such as oxygen, sulphur, carbon or nitrogen, preferably, X is oxygen.
  • M 1 may be a Group IVA element such as Ti, SI, Ge, Zr, Hf, Sm, Nd, Mo, Cr, Nb or an alloy of any of the preceding metals, preferably, M 1 comprises titanium.
  • a preferred electrolyte, M 2 Y, is calcium chloride (CaCl 2 ).
  • suitable electrolytes include but are not limited to the molten chlorides of all common alkali and alkaline earth metals.
  • Other preferred metals for M 2 are barium, caesium, lithium, strontium and yttrium.
  • the anode of the cell is preferably of a relatively inert material.
  • One suitable anode material is graphite.
  • Processing conditions suitable for the favourable dissolution of the contaminant X require that the potential of the cell preferably be maintained at a potential which is less than the decomposition potential of the molten electrolyte M 2 Y during the process. Allowing for polarisation and resistive losses in the cell, it will be understood that the cell potential may be maintained at a level equal to, or marginally higher than, the decomposition potential of M 2 Y and still achieve the desired result. Potentiostatic methods may be used to control the potential.
  • the temperature of the cell is maintained at an elevated temperature which is significantly above the melting point of M 2 Y but below the boiling point of M 2 Y.
  • M 2 Y is CaCl 2.
  • suitable processing parameters include a potential of up to about 3.3 V and a processing temperature of between about 825 and 975° C.
  • this more recent method may include an additional step wherein the scrap metal may be processed before being introduced into the electrochemical cell, for example to form small granules, or a powder, or an amorphous slurry of the contaminated material.
  • the scrap metal may be fabricated into a sponge-like sintered oxide preform prior to electrolysis.
  • the scrap material may be sintered in a mixture containing particles of M 1 X greater than 20 microns in size and finer particles of M 1 X less than about 7 microns in size, binder and water to form a friable block.
  • the finer particles are in a proportion of about 10 to about 55% by weight of the sintered block.
  • the scrap metal may be fabricated into a ceramic facsimile of a desired metal or metal alloy component before introduction into the electrochemical cell. This fabrication may be achieved by various known methods including pressing, injection moulding, extrusion and slip casting followed by sintering.
  • the present invention provides a method for the production of a Ferro-titanium master alloy including the steps of:
  • the invention is particularly suited to the manufacture of Ferro-titanium alloys.
  • Preferred ores include ilmenite and rutile, other suitable ores will no doubt occur to the skilled addressee.
  • the ores are mixed in proportions suitable to provide a eutectic Ferro-titanium alloy comprising about 70% Ti to about 30% Fe by weight.
  • the ores can be obtained already crushed into small pieces or powders or may be ground or crushed as a first step of the method.
  • preferred sizes of the crushed pieces are in the order of 100 to 600 microns.
  • the ores are mixed in proportions suitable to provide the constituent alloy metals in correct stoichiometric quantities to form the chosen alloy.
  • the mixed particles of ore are sintered and may be used as a starting material in any of the variations of the electrochemical reduction processes previously described.
  • Ferro-titanium for use in the steel making process, it is not necessary to reduce the contaminant level to the low levels actually obtainable by the reduction process. The process may therefore be applied for a shortened period to reduce the contamination to below a maximum acceptable level.
  • crushed pieces of the order of a few millimeters in size are acceptable.
  • the purification of the mixed ores provided by the electrolytic reduction method described herein may not need to be completed, since the total elimination of contaminants such as oxygen is not essential for these purposes.
  • oxygen levels of up to 2% by weight are considered acceptable.
  • the present invention maybe used to partially purify the mixed ores to a state where the contaminant levels are acceptable but not negligible.
  • the time taken to reduce the level of contaminant oxygen to about 2% in Ferro-titanium made according to this method has been found to be only about 70% of the time taken to reduce the levels to about 0.1% by weight, the preferred level for other commercial applications of the alloy.
  • a preferred electrolyte, M 2 Y is calcium chloride (CaCl 2 ).
  • suitable electrolytes include but are not limited to the molten chlorides of all common alkali and alkaline earth metals.
  • Other preferred metals for M 2 are barium, caesium, lithium, strontium and yttrium.
  • the anode of the cell is preferably of a relatively inert material.
  • One suitable anode material is graphite.
  • Processing conditions suitable for the favourable dissolution of the contaminants require that the potential of the cell preferably be maintained at a potential which is less than the decomposition potential of the molten electrolyte M 2 Y during the process. Allowing for polarisation and resistive losses in the cell, it will be understood that the cell potential may be maintained at a level equal to, or marginally higher than, the decomposition potential of M 2 Y and still achieve the desired result. Potentiostatic methods may be used to control the potential.
  • the temperature of the cell is maintained at an elevated temperature which is significantly above the melting point of M 2 Y but below the boiling point of M 2 Y.
  • M 2 Y is CaCl 2.
  • suitable processing parameters include a potential of up to about 3.3 V and a processing temperature of between about 825 and 1050° C.
  • the Ferro-titanium alloy can be provided in various physical forms, eg, powdered, foamed, sintered plate or 3-dimensional shape as may be required in different applications.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Powder Metallurgy (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)
US10/204,465 2000-02-22 2001-02-19 Method of manufacture for ferro-titanium and other metal alloys electrolytic reduction Abandoned US20030047462A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US11/066,545 US20050175496A1 (en) 2000-02-22 2005-02-28 Method of reclaiming contaminated metal

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
GB0003971A GB2359564B (en) 2000-02-22 2000-02-22 Improvements in the electrolytic reduction of metal oxides
GB0003971.9 2000-02-22
GB0010873A GB2362164B (en) 2000-05-08 2000-05-08 Improved feedstock for electrolytic reduction of metal oxide
GB0010873.8 2000-05-08

Related Child Applications (1)

Application Number Title Priority Date Filing Date
US11/066,545 Continuation-In-Part US20050175496A1 (en) 2000-02-22 2005-02-28 Method of reclaiming contaminated metal

Publications (1)

Publication Number Publication Date
US20030047462A1 true US20030047462A1 (en) 2003-03-13

Family

ID=26243686

Family Applications (5)

Application Number Title Priority Date Filing Date
US10/204,465 Abandoned US20030047462A1 (en) 2000-02-22 2001-02-19 Method of manufacture for ferro-titanium and other metal alloys electrolytic reduction
US10/204,460 Abandoned US20030057101A1 (en) 2000-02-22 2001-02-19 Method for the manufacture of metal foams by electrolytic reduction of porous oxidic preforms
US10/204,547 Expired - Fee Related US6921473B2 (en) 2000-02-22 2001-02-20 Electrolytic reduction of metal oxides such as titanium dioxide and process applications
US11/149,588 Abandoned US20060110277A1 (en) 2000-02-22 2005-06-10 Electrolytic reduction of metal oxides such as titanium dioxide and process applications
US12/929,993 Abandoned US20110158843A1 (en) 2000-02-22 2011-03-01 Electrolytic reduction of metal oxides such as titanium dioxide and process applications

Family Applications After (4)

Application Number Title Priority Date Filing Date
US10/204,460 Abandoned US20030057101A1 (en) 2000-02-22 2001-02-19 Method for the manufacture of metal foams by electrolytic reduction of porous oxidic preforms
US10/204,547 Expired - Fee Related US6921473B2 (en) 2000-02-22 2001-02-20 Electrolytic reduction of metal oxides such as titanium dioxide and process applications
US11/149,588 Abandoned US20060110277A1 (en) 2000-02-22 2005-06-10 Electrolytic reduction of metal oxides such as titanium dioxide and process applications
US12/929,993 Abandoned US20110158843A1 (en) 2000-02-22 2011-03-01 Electrolytic reduction of metal oxides such as titanium dioxide and process applications

Country Status (15)

Country Link
US (5) US20030047462A1 (ja)
EP (5) EP1257678B1 (ja)
JP (2) JP4703931B2 (ja)
KR (1) KR100767981B1 (ja)
CN (1) CN1279194C (ja)
AT (2) ATE372395T1 (ja)
AU (5) AU3387601A (ja)
CA (1) CA2401034C (ja)
DE (2) DE60130322T2 (ja)
DK (1) DK1956102T3 (ja)
EA (3) EA013138B1 (ja)
ES (1) ES2231443T3 (ja)
GB (1) GB2376241B (ja)
UA (1) UA74179C2 (ja)
WO (3) WO2001062995A1 (ja)

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040247478A1 (en) * 2001-08-16 2004-12-09 Les Strezov Method of manufacturing titanium and titanium alloy products
US20050050989A1 (en) * 2002-12-12 2005-03-10 Steve Osborn Electrochemical reduction of metal oxides
US20050092129A1 (en) * 2002-03-13 2005-05-05 Bhp Billiton Innovation Pty. Ltd. Minimising carbon transfer in an electrolytic cell
US20060226027A1 (en) * 2003-06-20 2006-10-12 Shook Andrew A Electrochemical reduction of metal oxides
US20070131560A1 (en) * 2004-03-22 2007-06-14 Ivan Ratchev Electrochemical reduction of metal oxides
US20070181438A1 (en) * 2004-06-22 2007-08-09 Olivares Rene I Electrochemical Reduction of Metal Oxides
US20070193877A1 (en) * 2003-09-26 2007-08-23 Rigby Gregory D Electrochemical reduction of metal oxides
US20070251833A1 (en) * 2004-07-30 2007-11-01 Ivan Ratchev Electrochemical Reduction of Metal Oxides
US20080047845A1 (en) * 2003-10-14 2008-02-28 Gregory David Rigby Electrochemical Reduction of Metal Oxides
US20140231262A1 (en) * 2011-10-04 2014-08-21 Metalysis Limited Electrolytic production of powder
WO2016176732A1 (en) * 2015-05-05 2016-11-10 Iluka Resources Limited Novel synthetic rutile products and processes for their production
US9562296B2 (en) 2010-11-02 2017-02-07 I'msep Co., Ltd. Production method for silicon nanoparticles

Families Citing this family (63)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2362164B (en) * 2000-05-08 2004-01-28 Secr Defence Improved feedstock for electrolytic reduction of metal oxide
GB0027930D0 (en) * 2000-11-15 2001-01-03 Univ Cambridge Tech Intermetallic compounds
GB0027929D0 (en) * 2000-11-15 2001-01-03 Univ Cambridge Tech Metal and alloy powders
AUPR602901A0 (en) * 2001-06-29 2001-07-26 Bhp Innovation Pty Ltd Removal of oxygen from metals oxides and solid metal solutions
US7543523B2 (en) * 2001-10-01 2009-06-09 Lockheed Martin Corporation Antiballistic armor
GB0124303D0 (en) * 2001-10-10 2001-11-28 Univ Cambridge Tech Material fabrication method and apparatus
WO2003046258A2 (en) * 2001-11-22 2003-06-05 Qit - Fer Et Titane Inc. A method for electrowinning of titanium metal or alloy from titanium oxide containing compound in the liquid state
GB0128816D0 (en) * 2001-12-01 2002-01-23 Univ Cambridge Tech Materials processing method and apparatus
GB2387176B (en) * 2002-04-02 2004-03-24 Morgan Crucible Co Manufacture of sub-oxides and other materials
US7416697B2 (en) 2002-06-14 2008-08-26 General Electric Company Method for preparing a metallic article having an other additive constituent, without any melting
US7329381B2 (en) * 2002-06-14 2008-02-12 General Electric Company Method for fabricating a metallic article without any melting
US6737017B2 (en) * 2002-06-14 2004-05-18 General Electric Company Method for preparing metallic alloy articles without melting
US6884279B2 (en) * 2002-07-25 2005-04-26 General Electric Company Producing metallic articles by reduction of nonmetallic precursor compounds and melting
JP2004156130A (ja) * 2002-09-11 2004-06-03 Sumitomo Titanium Corp 直接電解法による金属チタン製造用酸化チタン多孔質焼結体およびその製造方法
WO2004046262A2 (en) * 2002-11-15 2004-06-03 University Of Utah Integral titanium boride coatings on titanium surfaces and associated methods
US7510680B2 (en) * 2002-12-13 2009-03-31 General Electric Company Method for producing a metallic alloy by dissolution, oxidation and chemical reduction
US6968990B2 (en) 2003-01-23 2005-11-29 General Electric Company Fabrication and utilization of metallic powder prepared without melting
WO2004094312A1 (ja) * 2003-04-21 2004-11-04 Sumitomo Titanium Corporation 金属塩の精製方法並びにチタン材の脱酸方法および製造方法
US7169285B1 (en) * 2003-06-24 2007-01-30 The United States Of America As Represented By The Secretary Of The Navy Low temperature refining and formation of refractory metals
US7794580B2 (en) 2004-04-21 2010-09-14 Materials & Electrochemical Research Corp. Thermal and electrochemical process for metal production
US7410562B2 (en) 2003-08-20 2008-08-12 Materials & Electrochemical Research Corp. Thermal and electrochemical process for metal production
DE102004002343B4 (de) * 2004-01-16 2006-08-03 Deutsches Zentrum für Luft- und Raumfahrt e.V. Hybridfaser, Verfahren zu ihrer Herstellung und Verwendung
EP1598324A1 (en) * 2004-05-15 2005-11-23 Osada Giken Co., Ltd. Method for manufacturing shaped titanium oxide
WO2006009700A2 (en) * 2004-06-16 2006-01-26 The Government Of The United States Of America Low temperature refining and formation of refractory metals
JP2008504438A (ja) * 2004-06-28 2008-02-14 ビーエイチピー ビリトン イノベーション プロプライアタリー リミテッド チタンの製造
US7531021B2 (en) 2004-11-12 2009-05-12 General Electric Company Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix
US7700038B2 (en) * 2005-03-21 2010-04-20 Ati Properties, Inc. Formed articles including master alloy, and methods of making and using the same
CN100415940C (zh) * 2005-05-08 2008-09-03 北京科技大学 一氧化钛/碳化钛可溶性固溶体阳极电解生产纯钛的方法
US7459105B2 (en) * 2005-05-10 2008-12-02 University Of Utah Research Foundation Nanostructured titanium monoboride monolithic material and associated methods
DE102005026267A1 (de) 2005-06-08 2006-12-21 Deutsches Zentrum für Luft- und Raumfahrt e.V. Herstellung eines Verbundwerkstoffs
JP2007016293A (ja) * 2005-07-08 2007-01-25 Kyoto Univ 懸濁電解による金属の製造方法
US7901561B2 (en) * 2006-03-10 2011-03-08 Elkem As Method for electrolytic production and refining of metals
JP5226700B2 (ja) * 2007-01-22 2013-07-03 マテリアルズ アンド エレクトロケミカル リサーチ コーポレイション イン・サイチュ生成塩化チタンの金属熱還元法
CN101302630B (zh) * 2008-01-17 2010-11-10 上海交通大学 固体氧化物电解槽制备金属的方法
CN101302631B (zh) * 2008-01-17 2010-06-23 上海交通大学 固体氧化物电解槽的制作方法
ES2338847B8 (es) * 2008-09-15 2011-08-05 Fundacion Investigacion E Innovacion Para El Desarrollo Social Proceso para la produccion de titanio a partir de la ilmenita con recuperacion de los reactivos empleados en el proceso.
US20100176339A1 (en) * 2009-01-12 2010-07-15 Chandran K S Ravi Jewelry having titanium boride compounds and methods of making the same
WO2011040979A1 (en) * 2009-10-02 2011-04-07 Metal Oxygen Separation Technologies, Inc. (Moxst) Method and apparatus for producing magnesium with a solid oxide membrane elelctrolysis system
US8764962B2 (en) * 2010-08-23 2014-07-01 Massachusetts Institute Of Technology Extraction of liquid elements by electrolysis of oxides
WO2013096893A1 (en) 2011-12-22 2013-06-27 Universal Technical Resource Services, Inc. A system and method for extraction and refining of titanium
CN102505128A (zh) * 2011-12-23 2012-06-20 西北有色金属研究院 一种熔盐电解直接制备多孔金属制品的方法
GB201207997D0 (en) 2012-05-04 2012-06-20 Imp Innovations Ltd Process
GB201208698D0 (en) * 2012-05-16 2012-06-27 Metalysis Ltd Electrolytic method,apparatus and product
KR101385528B1 (ko) 2013-05-07 2014-04-15 충북대학교 산학협력단 혼합금속산화물로부터 고온 용융염 전해환원에 의한 니켈네오디뮴 합금 제조방법
DE102013211922A1 (de) * 2013-06-24 2014-12-24 Siemens Aktiengesellschaft Vorrichtung zur Reduktion eines Metallions aus einer Salzschmelze
US11971193B1 (en) * 2013-11-15 2024-04-30 JEA Holdings, Inc. Humidity and/or hydrogen control products, and production
JP6242182B2 (ja) * 2013-11-21 2017-12-06 Ｊｘ金属株式会社 スクラップからの金属の回収方法
GB2527267A (en) * 2014-02-21 2015-12-23 Metalysis Ltd Method of producing metal
NL2015759B1 (en) 2015-11-10 2017-05-26 Stichting Energieonderzoek Centrum Nederland Additive manufacturing of metal objects.
US10254068B2 (en) * 2015-12-07 2019-04-09 Praxis Powder Technology, Inc. Baffles, suppressors, and powder forming methods
KR101774319B1 (ko) 2016-06-21 2017-09-04 한국생산기술연구원 티타늄 분말 제조방법
GB201615659D0 (en) 2016-09-14 2016-10-26 Metalysis Ltd Method of producing a powder
GB201615658D0 (en) 2016-09-14 2016-10-26 Metalysis Ltd Method of producing a composite material
JP7096235B2 (ja) 2016-09-14 2022-07-05 ユニバーサル アケメタル タイタニウム リミテッド ライアビリティ カンパニー チタン－アルミニウム－バナジウム合金の製造方法
GB201615660D0 (en) 2016-09-14 2016-10-26 Metalysis Ltd Method of producing a powder
WO2018186922A2 (en) 2017-01-13 2018-10-11 Universal Technical Resource Services, Inc. Titanium master alloy for titanium-aluminum based alloys
DK3354337T3 (da) * 2017-01-31 2021-05-10 Alantum Europe Gmbh Fremgangsmåde til at fremstille en metalskumspellet, metalskumpellet, katalysatorfyld og statisk mixer
NL2018890B1 (en) 2017-05-10 2018-11-15 Admatec Europe B V Additive manufacturing of metal objects
CN108444975B (zh) * 2018-04-24 2020-11-24 华南师范大学 一种多区域表面增强拉曼散射基底的制备方法
KR102123509B1 (ko) * 2018-08-02 2020-06-17 한국원자력연구원 미환원 산화물 분리 장치 및 방법
NL2021611B1 (en) 2018-09-12 2020-05-06 Admatec Europe B V Three-dimensional object and manufacturing method thereof
CN110295303A (zh) * 2019-06-24 2019-10-01 中国石油天然气股份有限公司 一种室温超塑性可溶金属及其制作方法
US11181325B2 (en) * 2019-12-23 2021-11-23 Valgroup S.A. System for the production of molten salt used as a heat transfer medium for a pyrolysis system

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6712952B1 (en) * 1998-06-05 2004-03-30 Cambridge Univ. Technical Services, Ltd. Removal of substances from metal and semi-metal compounds

Family Cites Families (47)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE150557C (ja)
US2773023A (en) * 1954-04-26 1956-12-04 Horizons Titanium Corp Removal of oxygen from metals
US2986502A (en) * 1954-09-14 1961-05-30 Goldenberg Leo Purification of titanium
US3097930A (en) * 1960-03-09 1963-07-16 Cons Beryllium Ltd Method of making a porous shape of sintered refractory material
BE793982A (fr) * 1972-01-14 1973-05-02 Foseco Int Fabrication de produits ceramiques poreux
US3979267A (en) * 1972-01-24 1976-09-07 Townsend Douglas W Electrolytic method
GB1374832A (en) 1972-04-11 1974-11-20 Magnesium Elektron Ltd Sintered zirconia bodies
GB1362991A (en) 1972-07-20 1974-08-14 Atomic Energy Authority Uk Processes of making nuclear fuel artefacts
JPS51138511A (en) 1975-05-27 1976-11-30 Sony Corp Method for regulating the hardness of metallic tita nium
US4157285A (en) * 1975-05-27 1979-06-05 Universite Libre De Bruxelles Method for preparing manganese chloride and manganese by igneous electrolysis of the manganese chloride obtained
SU577095A1 (ru) * 1976-05-03 1977-10-25 Пермский политехнический институт Способ получени пористого металла
US4187155A (en) * 1977-03-07 1980-02-05 Diamond Shamrock Technologies S.A. Molten salt electrolysis
JPS591232B2 (ja) 1979-09-28 1984-01-11 住友アルミニウム製錬株式会社 ジルコニア焼結体の製造方法
DK156731C (da) 1980-05-07 1990-01-29 Metals Tech & Instr Fremgangsmaade til fremstilling af metal eller metalloid
US4455211A (en) * 1983-04-11 1984-06-19 Aluminum Company Of America Composition suitable for inert electrode
GB8511048D0 (en) * 1985-05-01 1985-06-12 Unilever Plc Inorganic structures
FR2592664B1 (fr) * 1986-01-06 1990-03-30 Pechiney Sa Procede d'elaboration de poudres de metaux de transition par electrolyse en bains de sels fondus
US4948764A (en) * 1986-09-16 1990-08-14 Lanxide Technology Company, Lp Production of ceramic and ceramic-metal composite articles with surface coatings
JPS63130733A (ja) * 1986-11-19 1988-06-02 Toshiba Corp 銅基複合材料の製造方法
US4837230A (en) * 1987-05-07 1989-06-06 Kaiser Aerotech Structural ceramic materials having refractory interface layers
US4935055A (en) * 1988-01-07 1990-06-19 Lanxide Technology Company, Lp Method of making metal matrix composite with the use of a barrier
DE68923268T2 (de) * 1988-08-12 1995-11-16 Ube Industries Karbidfasern mit hoher festigkeit und hohem elastizitätsmodulus und polymerzusammensetzung dafür.
US4875985A (en) * 1988-10-14 1989-10-24 Brunswick Corporation Method and appparatus for producing titanium
US5167271A (en) * 1988-10-20 1992-12-01 Lange Frederick F Method to produce ceramic reinforced or ceramic-metal matrix composite articles
SU1666156A1 (ru) * 1989-08-14 1991-07-30 Белорусское республиканское научно-производственное объединение порошковой металлургии Способ изготовлени керамического фильтрующего материала
FR2680799B1 (fr) * 1991-09-03 1993-10-29 Elf Aquitaine Ste Nale Element de cible pour pulverisation cathodique, procede de preparation dudit element et cibles, notamment de grande surface, realisees a partir de cet element.
CA2073625C (en) 1992-07-10 1998-02-03 Adam Jan Gesing Process and apparatus for melting metals while reducing losses due to oxidation
RU2026394C1 (ru) * 1992-08-25 1995-01-09 Научно-внедренческое, проектно-конструкторское и посредническое предприятие "СИБ-индекс" Способ получения вспененного алюминия
DE4241420C1 (de) 1992-12-09 1993-11-25 Mtu Muenchen Gmbh Verfahren zur Herstellung von Bauteilen oder Substraten mit Verbundbeschichtungen und dessen Anwendung
JP2825005B2 (ja) * 1993-03-19 1998-11-18 日本重化学工業株式会社 多孔金属の製造方法とその製造方法により得られた多孔金属
RU2111935C1 (ru) * 1994-02-15 1998-05-27 Акционерное общество открытого типа "Абразивный завод "Ильич" Шихта для изготовления керамических изделий
RU2103391C1 (ru) * 1994-07-12 1998-01-27 Евгений Михайлович Баранов Способ получения тугоплавких металлов из рудных концентратов
US5656217A (en) * 1994-09-13 1997-08-12 Advanced Composite Materials Corporation Pressureless sintering of whisker reinforced alumina composites
DE69619179T2 (de) * 1995-04-03 2002-08-22 Mitsubishi Materials Corp Poröser metallischer körper mit höher spezifischer oberfläche, verfahren zu dessen herstellung, poröses metallisches material und elektrode für alkalische sekundärbatterie
RU2118394C1 (ru) * 1995-09-08 1998-08-27 Акционерное общество закрытого типа "Стройинжиниринг" Способ получения ферротитана
JP3609182B2 (ja) * 1996-01-08 2005-01-12 日立建機株式会社 建設機械の油圧駆動装置
US5861070A (en) * 1996-02-27 1999-01-19 Oregon Metallurgical Corporation Titanium-aluminum-vanadium alloys and products made using such alloys
US5976454A (en) * 1996-04-01 1999-11-02 Basf Aktiengesellschaft Process for producing open-celled, inorganic sintered foam products
US5733842A (en) * 1996-04-30 1998-03-31 Norton Checmical Process Products Corporation Method of making porous catalyst carrier without the addition of pore forming agents
JP3195753B2 (ja) 1996-11-07 2001-08-06 日本重化学工業株式会社 金属多孔体の製造方法
JPH10251710A (ja) 1997-03-11 1998-09-22 Japan Metals & Chem Co Ltd セラミックス粒子を含有する金属多孔体の製造方法
US6309595B1 (en) 1997-04-30 2001-10-30 The Altalgroup, Inc Titanium crystal and titanium
US6180258B1 (en) * 1997-06-04 2001-01-30 Chesapeake Composites Corporation Metal-matrix composites and method for making such composites
US5865980A (en) * 1997-06-26 1999-02-02 Aluminum Company Of America Electrolysis with a inert electrode containing a ferrite, copper and silver
US6258247B1 (en) 1998-02-11 2001-07-10 Northwest Aluminum Technology Bath for electrolytic reduction of alumina and method therefor
DE29822563U1 (de) * 1998-12-18 1999-02-18 Aesculap AG & Co. KG, 78532 Tuttlingen Implantat
GB9928655D0 (en) * 1999-12-03 2000-02-02 British Nuclear Fuels Plc Actinide production

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6712952B1 (en) * 1998-06-05 2004-03-30 Cambridge Univ. Technical Services, Ltd. Removal of substances from metal and semi-metal compounds

Cited By (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060037867A1 (en) * 2001-08-16 2006-02-23 Bhp Billiton Innovation Pty Ltd. Method of manufacturing titanium and titanium alloy products
US20040247478A1 (en) * 2001-08-16 2004-12-09 Les Strezov Method of manufacturing titanium and titanium alloy products
US7156974B2 (en) * 2001-08-16 2007-01-02 Bhp Billiton Innovation Pty. Ltd. Method of manufacturing titanium and titanium alloy products
US20050092129A1 (en) * 2002-03-13 2005-05-05 Bhp Billiton Innovation Pty. Ltd. Minimising carbon transfer in an electrolytic cell
US7470355B2 (en) * 2002-12-12 2008-12-30 Bhp Billiton Innovation Pty Ltd Electrochemical reduction of metal oxides
US20050050989A1 (en) * 2002-12-12 2005-03-10 Steve Osborn Electrochemical reduction of metal oxides
US7758740B2 (en) 2003-06-20 2010-07-20 Metalysis Limited Electrochemical reduction of metal oxides
US20060226027A1 (en) * 2003-06-20 2006-10-12 Shook Andrew A Electrochemical reduction of metal oxides
US20070193877A1 (en) * 2003-09-26 2007-08-23 Rigby Gregory D Electrochemical reduction of metal oxides
US20080047845A1 (en) * 2003-10-14 2008-02-28 Gregory David Rigby Electrochemical Reduction of Metal Oxides
US20070131560A1 (en) * 2004-03-22 2007-06-14 Ivan Ratchev Electrochemical reduction of metal oxides
US20070181438A1 (en) * 2004-06-22 2007-08-09 Olivares Rene I Electrochemical Reduction of Metal Oxides
US20070251833A1 (en) * 2004-07-30 2007-11-01 Ivan Ratchev Electrochemical Reduction of Metal Oxides
US9562296B2 (en) 2010-11-02 2017-02-07 I'msep Co., Ltd. Production method for silicon nanoparticles
US20140231262A1 (en) * 2011-10-04 2014-08-21 Metalysis Limited Electrolytic production of powder
US9611558B2 (en) * 2011-10-04 2017-04-04 Metalysis Limited Electrolytic production of powder
WO2016176732A1 (en) * 2015-05-05 2016-11-10 Iluka Resources Limited Novel synthetic rutile products and processes for their production
US10294116B2 (en) 2015-05-05 2019-05-21 Iluka Resources Limited Synthetic rutile products and processes for their production
EP3292233A4 (en) * 2015-05-05 2019-07-31 Iluka Resources Limited NOVEL SYNTHETIC RUTILE PRODUCTS AND METHODS FOR PRODUCING SAME

Also Published As

Publication number Publication date
ATE372395T1 (de) 2007-09-15
DE60130322D1 (de) 2007-10-18
DE60130322T2 (de) 2008-06-12
EP1257678A1 (en) 2002-11-20
EP1956102B1 (en) 2012-10-31
WO2001062996A9 (en) 2001-11-15
US20060110277A1 (en) 2006-05-25
DE60108081T2 (de) 2005-10-13
JP4703931B2 (ja) 2011-06-15
KR100767981B1 (ko) 2007-10-18
DK1956102T3 (da) 2013-02-11
CA2401034A1 (en) 2001-08-30
AU2001233876B2 (en) 2004-09-30
US20030047463A1 (en) 2003-03-13
EA200200895A1 (ru) 2003-02-27
EA200401129A1 (ru) 2005-04-28
US6921473B2 (en) 2005-07-26
US20110158843A1 (en) 2011-06-30
WO2001062995A1 (en) 2001-08-30
CN1404530A (zh) 2003-03-19
EA013138B1 (ru) 2010-02-26
EA008264B1 (ru) 2007-04-27
EP1489192A1 (en) 2004-12-22
EP1257679B1 (en) 2004-12-29
ATE286150T1 (de) 2005-01-15
DE60108081D1 (de) 2005-02-03
KR20020082226A (ko) 2002-10-30
AU2001233871A1 (en) 2001-09-03
GB2376241A (en) 2002-12-11
GB0218516D0 (en) 2002-09-18
EP1956102A2 (en) 2008-08-13
EP1257677A1 (en) 2002-11-20
WO2001062996A1 (en) 2001-08-30
JP4995392B2 (ja) 2012-08-08
JP2003524073A (ja) 2003-08-12
ES2231443T3 (es) 2005-05-16
EA005348B1 (ru) 2005-02-24
AU3387601A (en) 2001-09-03
CN1279194C (zh) 2006-10-11
AU2001233890B2 (en) 2004-07-08
EP1257679A1 (en) 2002-11-20
UA74179C2 (uk) 2005-11-15
EP1257678B1 (en) 2007-09-05
CA2401034C (en) 2013-10-29
US20030057101A1 (en) 2003-03-27
JP2003524072A (ja) 2003-08-12
WO2001062994A1 (en) 2001-08-30
GB2376241B (en) 2004-03-03
EA200601812A1 (ru) 2007-06-29
AU3389001A (en) 2001-09-03
EP1956102A3 (en) 2008-08-20

Similar Documents

Publication Publication Date Title
US20030047462A1 (en) Method of manufacture for ferro-titanium and other metal alloys electrolytic reduction
CN1982506B (zh) 如二氧化钛的金属氧化物的电解还原及其工艺应用
JP2003524073A5 (ja)
AU757790B2 (en) Metal powders produced by the reduction of the oxides with gaseous magnesium
AU2009200027A1 (en) Method of manufacturing titanium and titanium alloy products
US20050175496A1 (en) Method of reclaiming contaminated metal
CA2331707C (en) Reduction of nb or ta oxide powder by a gaseous light metal or a hydride thereof
AU2004216659B2 (en) Electrolytic reduction of metal oxides such as titanium dioxide and process applications
AU2011213888B2 (en) Electrolytic reduction of metal oxides such as titanium dioxide and process applications
AU2007231873B8 (en) Electrolytic reduction of metal oxides such as titanium dioxide and process applications
RO125598B1 (ro) Procedeu de obținere prin proces electrochimic a unor materiale compozite cu matrice metalică

Legal Events

Date Code Title Description
AS Assignment

Owner name: QINTETIQ LIMITED, UNITED KINGDOM

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:WARD-CLOSE, CHARLES M.;GODFREY, ALASTAIR B.;REEL/FRAME:013292/0415

Effective date: 20020904

STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION