WO2002040725A2 - Metal and alloy powders and powder fabrication - Google Patents
Metal and alloy powders and powder fabrication Download PDFInfo
- Publication number
- WO2002040725A2 WO2002040725A2 PCT/GB2001/005031 GB0105031W WO0240725A2 WO 2002040725 A2 WO2002040725 A2 WO 2002040725A2 GB 0105031 W GB0105031 W GB 0105031W WO 0240725 A2 WO0240725 A2 WO 0240725A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- electro
- deoxidation
- powder
- metal
- melt
- Prior art date
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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
- C22B34/10—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
- C22B4/00—Electrothermal treatment of ores or metallurgical products for obtaining metals or alloys
-
- 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
- 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
Definitions
- This invention relates to a method and an apparatus for preparing metallic powders of well-defined particle sizes and composition, and to metallic powders so produced. In a further aspect the invention relates to powder fabrication and the production of near net-shaped products.
- Liquid metals can be atomised by impinging a high velocity gas into a stream of molten metal .
- Metal powders can be produced by shock-cooling metallic vapours.
- shock-cooling metallic vapours For some metals with substantial solubility of hydrogen, it is possible to form brittle hydride phases which can subsequently be crushed or decrepitated into fine particles. By heating at elevated temperatures, the hydrides simply decompose to form metallic particles.
- electrochemical deposition of metal from a compound of the metal dissolved in an aqueous or fused salt electrolyte can result in a dendritic deposit that can easily be crushed to a fine powder.
- Metal oxide powders are much easier to obtain by grinding, as oxides are typically highly brittle and crush readily. Being oxides, they do not suffer from oxidation during this process .
- Very fine oxide powders can also be produced by precipitation from an aqueous or fused salt solution. Alternatively, by reacting a volatile compound with oxygen, it can be possible to form a fine oxide powder. For example the reaction of titanium tetrachloride with oxygen results in a very fine oxide powder. Frequently, these particles are of a uniform size, but the problem remains of producing fine metal' powders . Summary of the Invention
- the invention provides a method and an apparatus for producing a metallic powder, and a metallic powder, as defined in the appended independent claims. Preferred or advantageous features of the invention are set out in dependent subclaims .
- a method for producing a metallic powder in which a precursor powder comprising a compound ⁇ M X) between a metal (M 1 ) and a non-metal species (X) is treated by electro-deoxidation.
- the precursor powder forms a cathode contacting a melt comprising a fused salt (M 2 Y) , under conditions such that the non-metal species dissolves in the melt.
- M 2 Y fused salt
- the metal powders produced according to embodiments of the invention have been found to have a uniform microscopic structure, both in terms of the particle size of the metal powder and the microstructure of individual particles.
- particles of similar shapes may be produced.
- the powders may form a cube structure.
- the small, consistent particle sizes, and the metal purity, produced by this method may be particularly advantageous as the production of metal powders by prior art methods has failed to produce high yields of such materials; in prior art methods, sieving is generally required to produce consistent particle sizes and entails very significant wastage.
- electro-deoxidation is used herein to describe the process of removing the non-metal species (X) from a compound in the solid state by contacting the compound with the melt and applying a cathodic voltage to it such that the non-metal species, or anionic species, dissolves.
- oxidation implies a change in oxidation state and not necessarily a reaction with oxygen. It should not, however, be inferred that electro-deoxidation always involves a change in the oxidation states of both (or all) of the components of the compound; this is believed to depend on the nature of the compound, such as whether it is primarily ionic or covalent.
- electro-deoxidation can only be applied to an oxide; any compound may be processed in this way.
- Other terms to describe the electro-deoxidation process in particular instances may be electro-decomposition, electro-reduction or solid-state electrolysis.
- the cathodic voltage applied to the metal compound is less than the voltage for deposition of cations from the fused salt at the cathode surface. This may advantageously reduce contamination of the intermetallic compound involving the cations . It is believed that this may be achieved under the conditions of an embodiment in which the decomposition potential of the salt, or electrolyte, is not exceeded during electro-deoxidation, or electro-reduction, or under the conditions of an embodiment providing a method for producing a metallic powder by treating a powder of a metal compound (M'-X) by electrolysis in a fused salt M 2 Y or a mixture of salts, under conditions whereby reaction, or ionisation, of X rather than M 2 deposition occurs at an electrode surface, and X dissolves in the electrolyte M 2 Y.
- M'-X metal compound
- the metal produced has a higher melting point than that of the melt, or salt.
- other metal compounds such as metal oxides, may be present and the electrolysis product may be an alloy powder.
- the method of the invention may advantageously give a product which is of very uniform particle size and free of oxygen or other contaminants.
- electrochemical reduction of metal oxide powders by cathodically ionising the oxygen away from the oxide, results in agglomerates of pure metal powder, the particle size of which depends upon the conditions of pre-forming and sintering of the metal oxide powders and the time and temperature of electro-deoxidation, or electrolysis.
- Other electrolysis parameters such as voltage, current and salt composition may also be varied to control the metal powder morphology. Control of these parameters may advantageously be applicable to precursor powders other than oxides .
- the metal compound or oxide should show at least some electronic conductivity or be used in contact with a conductor .
- Metal alloy powders may advantageously be formed by electro-deoxidation of precursor powders comprising a mixture or solid solution of two or more metal compounds or one or more metals or alloys with one or more metal compounds .
- the invention may advantageously provide a method for forming a near net-shaped product.
- a shaped precursor is formed from a powdered feed material comprising a compound (M X X) between a metal (M 1 ) and a non-metal species (X) .
- the precursor is then treated by electro-deoxidation, the precursor forming a cathode contacting a melt comprising a fused salt (M 2 Y) under conditions such that the non-metal species dissolves in the melt.
- the electro-deoxidation is carried out for a sufficiently long time and/or at a sufficiently high temperature to form interconnections between the metallic powder particles produced by the electro-deoxidation, in order to produce the near net-shaped product strong enough for further processing.
- Figure 1 illustrates an apparatus for the electro- deoxidation of a metal oxide powder according to a first embodiment of the invention
- Figure 2 illustrates an apparatus according to a second embodiment of the invention
- Figure 3 is a photomicrograph of a titanium oxide powder, as used as the starting material in Examples 1 and 2;
- Figure 4 is a photomicrograph of a titanium powder produced from the oxide of Figure 3 in Example 1;
- Figure 5 is a photomicrograph of a titanium powder produced from the oxide of Figure 3 in Example 2;
- Figure 6 is a photomicrograph of a chromium powder as produced in Example 3.
- Figure 7 is a photomicrograph of an AlNi 3 powder as produced in Example 5.
- Figure 8 is an XRD (X-ray diffraction) spectrum for the powder of Figure 7 , overlaid on a spectrum for a reference sample of AlNi 3 ;
- Figure 9 is a photomicrograph of a niobium oxide powder, as used as the starting material in Example 6;
- Figure 10 is a photomicrograph of a niobium powder as produced in Example 6 from the oxide powder of Figure 9;
- Figure 11 is a schematic diagram of an apparatus for electro-deoxidation as used in Example 6;
- Figure 12 is a plot of an XRD analysis of a niobium powder produced as in Example 6.
- Figures 1 and 2 show pellets 2 of metal oxide in contact with a cathode conductor. Each pellet is prepared by powder processing techniques, such as pressing or slip-casting a submicron or micron-sized powder ( Figure 3) such as titanium dioxide. The pellet may then be fired to give it structural strength before being made the cathode in a cell in which a crucible 6 contains a fused salt 8.
- the cell contains chloride salts, being either CaCl 2 or BaCl 2 or their eutectic mixture with each other or with another chloride salt such as NaCl .
- the pellets are annular and are threaded onto a cathodic conductor in the form of a Kanthal wire 4.
- the crucible is an inert crucible of graphite or alumina.
- the crucible 12 is made of a conducting material such as titanium or graphite. The pellets sink in the melt and contact the crucible, to which the cathodic voltage is applied. The crucible itself thus acts as a current collector.
- the electrochemical process is the same, as follows.
- the oxygen ionises, dissolves in the salt and diffuses to a graphite anode 10 where it is discharged.
- the oxygen is thereby removed from the oxide, leaving the metal behind.
- the metal product is a very fine powder of very uniform size, as shown in Figure 4. It should be noted that the metal powder produced has a much larger grain size than the initial grain size of the oxide powder.
- the embodiment described above produces titanium metal powder but it is possible to make alloy powders by the same route simply by mixing the oxide powders together, and preferably firing or sintering them to strengthen the pellet.
- the pellet may also be fired so as to form a solid solution of the oxides. It is preferable that the oxide powders are not greater than microns in particle size and are finer than the metal powder to be produced.
- the electrolyte should consist of salts which are more stable than the equivalent salts of the metal which is being produced and, preferably, the salt should be as stable as possible to remove the oxygen to as low as concentration as possible.
- the choice of salt includes the chloride or other halide salts of alkali and/or alkaline earth metals, particularly barium, calcium, cesium, lithium, strontium and yttrium.
- a mixture of salts can be used, preferably the eutectic composition.
- the reduced compact is withdrawn from the molten salt .
- Some of the salt is contained within the withdrawn pellet, however, and stops the powder oxidising.
- the salt can simply be removed by washing in water or an organic solvent such as ethanol. Generally, the pellets are very brittle and can easily be crushed to reveal the metal powder .
- the following Examples illustrate the invention.
- Three pellets 5 mm in diameter and 1 mm in thickness, prepared by pressing moisturised 0.25 ⁇ m titanium dioxide powder (Figure 3) followed by drying and sintering at 950°C in air for 2 hours, were placed in a titanium crucible filled with molten calcium chloride at 950°C.
- the cell arrangement is as shown in Figure 2.
- a potential of 3 V was applied between a graphite anode and the titanium crucible. After 10 hours, the electro-deoxidation was terminated, the salt allowed to solidify and then dissolved in water to reveal a black/metallic pellet which was then removed from the crucible and dried.
- the Ti0 2 powder as in Example 1 was mixed with water to form a slurry which was then slip cast into small pellets, dried and sintered at 950°C in air for 2 hours.
- the sintered pellets were about 8 mm in diameter and 2 mm in thickness.
- Two of them were threaded onto a Kanthal wire, 1.5 mm in diameter, and then inserted into a molten eutectic mixture of calcium chloride and barium chloride at 950°C.
- An alumina crucible was used to accommodate the salts and the cell arrangement is as shown in Figure 1.
- a potential of 3.1 V was applied between a graphite anode and the Kanthal wire.
- Example 1 it is possible to produce titanium powder of a more consistent particle size than this by appropriate control of process parameters but it should be noted that the particle size range produced in Example 2 may advantageously be substantially more uniform than that produced by prior art methods .
- Example 3 A 1 ⁇ m powder of chromic oxide was mixed with water to form a slurry which was slip cast into small samples, or pellets, about 8-10 mm in diameter and 3-5 mm in thickness, followed by drying and sintering at 950°C in air for 2 hours. After sintering, no significant change was observed on the colour (green) and size of the samples, but the mechanical strength was enhanced significantly.
- Example 4 The particle size range produced in this Example may be reduced through process parameter control but is significantly narrower than the chromium particle size range produced by prior art methods, typically by mechanical grinding.
- Example 4
- Powders of titanium dioxide (0.25 ⁇ m particle size), alumina (0.25 ⁇ m) and vanadium oxide (1 - 2 ⁇ m) were mixed in a ratio such that the ratio of the metal elements was the same as a desired alloy, being in this example the Ti-6A1-4V alloy.
- the mixture was then made into a slurry with water and slip cast into pellets, followed by drying and sintering at 950°C for 2 hours in air. After sintering, the colour of the pellets changed from light green to dark brown.
- the size of the sintered pellets was about 8 mm in diameter and 6 mm in thickness.
- one of the sintered pellets was threaded onto a Kanthal wire, and then inserted into a molten eutectic mixture of barium chloride and calcium chloride at 950°C.
- An alumina crucible was used to accommodate the molten salts and the cell arrangement is shown in Figure 1.
- a potential of 3.1 V was applied between a graphite anode and the Kanthal wire .
- the temperature of the salt was allowed to cool to 700°C and then the electro-deoxidation terminated.
- the pellets on the Kanthal wire were removed from the crucible, cooled in air and then washed/leached in water to reveal the grey/metallic pellets.
- Powders of A1 3 0 3 and NiO were mixed in a molar ratio of 1:6, pressed into small cylindrical pellets (10 mm diameter, 5-10 mm height) , and sintered in air at 980-1000°C for about 2 hours. After sintering, the grey-green colour of the pellets became only slightly paler. Holes of 1.7 mm diameter were drilled into the sintered pellets. Four of the sintered pellets, weighing about 4 grams, were threaded onto a Kanthal wire (1.0 mm diameter) to form an assembled cathode.
- Electro- deoxidation was carried out between the assembled cathode and a graphite anode in argon-protected molten CaCl 2 at 950°C and 3.1 V for about 18 hours, as shown in Figure 1.
- the pellets were removed from the molten salt upon reduction, cooled first in argon and then in air to room temperature. Water was used to wash the reduced pellets which were then dried in air, showing a grey metallic colour.
- the surfaces and cross sections of the reduced pellets consisted of nodular particles of 2-20 microns in size (see Figure 7) and which contained Al and Ni in the atomic ratio of 1:3. No oxygen was detected.
- the pellets were then manually ground into powder in an agate mortar.
- the powders were pressed into porous compacts that were then strengthened by sintering.
- the sintered pellets were attached onto a cathodic current collector to form an assembled oxide cathode .
- the CaCl 2 2H 2 0 and NaCl employed for the melt were analytical reagents. All the chemicals were supplied by Aldrich Chemical .
- the CaCl 2 2H 2 0 was dehydrated in air at 373 K for 1 hour, heated up slowly to 573 K and then was held at 573 K for 12 hours. The dehydrated CaCl 2 and dried NaCl were mixed thoroughly and the mixture was then dried at 473 K before use.
- High-density graphite rods of 10 mm in diameter and 100 mm long were purchased from Graphite Technologies and were used as the anodes.
- the electrolytic cell for electrolysis is schematically shown in Figure 11.
- Two Farnell LS30-10 Autoranging Power Supplies were used for conducting the electrolysis under constant voltages.
- a first wire 50 for connecting the pellets of Nb 2 0 5 60 was led to the negative end of one power supply.
- the stainless steel crucible 56 for holding the molten electrolyte 58 was connected by a second wire 62 to the negative end of the other power supply. Two positive ends of the two power supplies were both connected to the graphite rod anode 52.
- the electrolytic cell was flushed with high purity argon while it was heated to the required temperatures.
- the oxide cathode was immersed in the melt.
- the electrolysis was carried out under constant voltages ⁇ U 1 and U 2 ) applied respectively to the cell as shown in Figure 11.
- the applied voltage (U. , along with the resulting currents, were displayed and logged by a PC with Serial RS232 plus ADAMS 4017-8 Channel Analogue-to-Digital Convertor during the course of electrolysis.
- the samples as-reduced were removed quickly from the melt under a flow of the argon at 873 K and quenched and washed in cold water, followed by acid leaching, water rinse, and acetone wash.
- the resulting porous pellets were made into powders by grinding manually.
- the obtained niobium metal powders were then cleaned with acetone again and dried under vacuum at 'room temperature .
- Morphology of the sintered or reduced pellets was observed using a Jeol JSM-5800LV scanning electron microscope (SEM) with an energy dispersive X-ray analysis (EDXA) attachment . Concentrations of impurities were determined by EDXA.
- Various phases present in the prepared powders were examined by powder X-ray diffractometry (XRD) using a Philips diffractometer PW1710 with Cu K « x radiation. Contents of oxygen were also determined by weighing the prepared niobium metal powders before and after re-oxidation in air, where a complete re-oxidation of the metal powders to the Nb 2 0 5 was confirmed by XRD analysis. A level of chlorine in the off-gasses was monitored using a Drager QuadGard Chlorine Detector.
- a typical measured XRD (X-ray diffraction) pattern is shown in Figure 12 for the niobium metal powders reduced at 1173 K for 48 hours, from which one can see that the powder is pure niobium, free of any oxide phases.
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- Geochemistry & Mineralogy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
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- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
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Abstract
Description
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Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002543034A JP2004522851A (en) | 2000-11-15 | 2001-11-15 | Metal and alloy powders and powder manufacturing |
EP01982619A EP1339884A2 (en) | 2000-11-15 | 2001-11-15 | Metal and alloy powders and powder fabrication |
US10/416,910 US20040052672A1 (en) | 2000-11-15 | 2001-11-15 | Metal and alloy powders and powder fabrication |
AU2002214161A AU2002214161A1 (en) | 2000-11-15 | 2001-11-15 | Metal and alloy powders and powder fabrication |
CA002429024A CA2429024A1 (en) | 2000-11-15 | 2001-11-15 | Metal and alloy powders and powder fabrication |
BR0115347-1A BR0115347A (en) | 2000-11-15 | 2001-11-15 | Metal and alloy powders and their manufacture |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB0027929.9 | 2000-11-15 | ||
GBGB0027929.9A GB0027929D0 (en) | 2000-11-15 | 2000-11-15 | Metal and alloy powders |
Publications (2)
Publication Number | Publication Date |
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WO2002040725A2 true WO2002040725A2 (en) | 2002-05-23 |
WO2002040725A3 WO2002040725A3 (en) | 2002-08-15 |
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ID=9903259
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB2001/005031 WO2002040725A2 (en) | 2000-11-15 | 2001-11-15 | Metal and alloy powders and powder fabrication |
Country Status (10)
Country | Link |
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US (1) | US20040052672A1 (en) |
EP (1) | EP1339884A2 (en) |
JP (1) | JP2004522851A (en) |
CN (1) | CN1479794A (en) |
AU (1) | AU2002214161A1 (en) |
BR (1) | BR0115347A (en) |
CA (1) | CA2429024A1 (en) |
GB (1) | GB0027929D0 (en) |
WO (1) | WO2002040725A2 (en) |
ZA (1) | ZA200303724B (en) |
Cited By (9)
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EP2032727A1 (en) * | 2006-06-14 | 2009-03-11 | Norsk Titanium Metals AS | Method, apparatus and means for production of metals in a molten salt electrolyte |
AU2003245482B2 (en) * | 2002-06-14 | 2009-03-12 | General Electric Company | Method for fabricating a metallic article without any melting |
EP2133447A1 (en) * | 2001-08-16 | 2009-12-16 | Metalysis Limited | Method of manufacturing titanium and titanium alloy products |
WO2010051759A1 (en) | 2008-11-06 | 2010-05-14 | 北京有色金属研究总院 | Electrochemical method for manufacturing one or more of silicon nanopowder, silicon nanowire and silicon nanotube |
EP2281648A1 (en) * | 2002-06-14 | 2011-02-09 | General Electric Company | Method for preparing metallic alloy articles without melting |
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US10100386B2 (en) | 2002-06-14 | 2018-10-16 | General Electric Company | Method for preparing a metallic article having an other additive constituent, without any melting |
US10604452B2 (en) | 2004-11-12 | 2020-03-31 | General Electric Company | Article having a dispersion of ultrafine titanium boride particles in a titanium-base matrix |
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AUPR317201A0 (en) * | 2001-02-16 | 2001-03-15 | Bhp Innovation Pty Ltd | Extraction of Metals |
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WO2001062994A1 (en) * | 2000-02-22 | 2001-08-30 | Qinetiq Limited | Method of manufacture for ferro-titanium and other metal alloys electrolytic reduction |
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US3330646A (en) * | 1964-02-03 | 1967-07-11 | Harold J Heinen | Method for producing molybdenum from molybdenite |
US5211775A (en) * | 1991-12-03 | 1993-05-18 | Rmi Titanium Company | Removal of oxide layers from titanium castings using an alkaline earth deoxidizing agent |
US6117208A (en) * | 1998-04-23 | 2000-09-12 | Sharma; Ram A. | Molten salt process for producing titanium or zirconium powder |
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2000
- 2000-11-15 GB GBGB0027929.9A patent/GB0027929D0/en not_active Ceased
-
2001
- 2001-11-15 BR BR0115347-1A patent/BR0115347A/en not_active Application Discontinuation
- 2001-11-15 CN CNA018201113A patent/CN1479794A/en active Pending
- 2001-11-15 JP JP2002543034A patent/JP2004522851A/en active Pending
- 2001-11-15 WO PCT/GB2001/005031 patent/WO2002040725A2/en not_active Application Discontinuation
- 2001-11-15 AU AU2002214161A patent/AU2002214161A1/en not_active Abandoned
- 2001-11-15 CA CA002429024A patent/CA2429024A1/en not_active Abandoned
- 2001-11-15 EP EP01982619A patent/EP1339884A2/en not_active Withdrawn
- 2001-11-15 US US10/416,910 patent/US20040052672A1/en not_active Abandoned
-
2003
- 2003-05-14 ZA ZA200303724A patent/ZA200303724B/en unknown
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EP2032727A1 (en) * | 2006-06-14 | 2009-03-11 | Norsk Titanium Metals AS | Method, apparatus and means for production of metals in a molten salt electrolyte |
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Also Published As
Publication number | Publication date |
---|---|
ZA200303724B (en) | 2005-01-17 |
US20040052672A1 (en) | 2004-03-18 |
BR0115347A (en) | 2004-01-27 |
CN1479794A (en) | 2004-03-03 |
WO2002040725A3 (en) | 2002-08-15 |
JP2004522851A (en) | 2004-07-29 |
CA2429024A1 (en) | 2002-05-23 |
AU2002214161A1 (en) | 2002-05-27 |
GB0027929D0 (en) | 2001-01-03 |
EP1339884A2 (en) | 2003-09-03 |
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