WO2002040725A2 - Poudres metalliques et d'alliages et fabrication de ces poudres - Google Patents

Poudres metalliques et d'alliages et fabrication de ces poudres Download PDF

Info

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
Application number
PCT/GB2001/005031
Other languages
English (en)
Other versions
WO2002040725A3 (fr
Inventor
Derek John Fray
George Zheng Chen
Original Assignee
Cambridge University Technical Services Limited
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 Cambridge University Technical Services Limited filed Critical Cambridge University Technical Services Limited
Priority to US10/416,910 priority Critical patent/US20040052672A1/en
Priority to CA002429024A priority patent/CA2429024A1/fr
Priority to JP2002543034A priority patent/JP2004522851A/ja
Priority to EP01982619A priority patent/EP1339884A2/fr
Priority to AU2002214161A priority patent/AU2002214161A1/en
Priority to BR0115347-1A priority patent/BR0115347A/pt
Publication of WO2002040725A2 publication Critical patent/WO2002040725A2/fr
Publication of WO2002040725A3 publication Critical patent/WO2002040725A3/fr

Links

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.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Electrochemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Preventing Corrosion Or Incrustation Of Metals (AREA)

Abstract

Selon la présente invention, on transforme une poudre précurseur comprenant un composé métallique en un échantillon destiné à l'électroréduction, par exemple par coulage en barbotine. On immerge ensuite l'échantillon dans un bain comprenant un sel fondu et on applique un potentiel cathodique afin d'enlever l'espèce non métallique de la poudre précurseur par électroréduction et dissolution dans le bain. Ceci permet généralement de former un échantillon métallique que l'on peut fragmenter pour former une poudre métallique. Dans un second aspect, l'invention concerne une matière d'alimentation en poudre que l'on transforme en un précurseur formé et l'on procède à une électroréduction plus longue afin d'obtenir un produit formé d'une grande précision dimensionnelle.
PCT/GB2001/005031 2000-11-15 2001-11-15 Poudres metalliques et d'alliages et fabrication de ces poudres WO2002040725A2 (fr)

Priority Applications (6)

Application Number Priority Date Filing Date Title
US10/416,910 US20040052672A1 (en) 2000-11-15 2001-11-15 Metal and alloy powders and powder fabrication
CA002429024A CA2429024A1 (fr) 2000-11-15 2001-11-15 Poudres metalliques et d'alliages et fabrication de ces poudres
JP2002543034A JP2004522851A (ja) 2000-11-15 2001-11-15 金属および合金粉末ならびに粉末製造
EP01982619A EP1339884A2 (fr) 2000-11-15 2001-11-15 Poudres metalliques et d'alliages et fabrication de ces poudres
AU2002214161A AU2002214161A1 (en) 2000-11-15 2001-11-15 Metal and alloy powders and powder fabrication
BR0115347-1A BR0115347A (pt) 2000-11-15 2001-11-15 Pós de metal e de ligas e sua fabricação

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
WO2002040725A2 true WO2002040725A2 (fr) 2002-05-23
WO2002040725A3 WO2002040725A3 (fr) 2002-08-15

Family

ID=9903259

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/GB2001/005031 WO2002040725A2 (fr) 2000-11-15 2001-11-15 Poudres metalliques et d'alliages et fabrication de ces poudres

Country Status (10)

Country Link
US (1) US20040052672A1 (fr)
EP (1) EP1339884A2 (fr)
JP (1) JP2004522851A (fr)
CN (1) CN1479794A (fr)
AU (1) AU2002214161A1 (fr)
BR (1) BR0115347A (fr)
CA (1) CA2429024A1 (fr)
GB (1) GB0027929D0 (fr)
WO (1) WO2002040725A2 (fr)
ZA (1) ZA200303724B (fr)

Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2032727A1 (fr) * 2006-06-14 2009-03-11 Norsk Titanium Metals AS PROCÉDÉ ET APPAREIL DE PRODUCTION DE Ti DANS UN ÉLECTROLYTE À SEL FONDU
AU2003245482B2 (en) * 2002-06-14 2009-03-12 General Electric Company Method for fabricating a metallic article without any melting
EP2133447A1 (fr) * 2001-08-16 2009-12-16 Metalysis Limited Procédé de fabrication de produits en titane et en alliages de titane
WO2010051759A1 (fr) 2008-11-06 2010-05-14 北京有色金属研究总院 Procédé électrochimique de fabrication de nanopoudre, de nanofils et/ou de nanotubes de silicium
EP2281648A1 (fr) * 2002-06-14 2011-02-09 General Electric Company Procede permettant de fabriquer un article metallique en alliage sans fusion
RU2615668C1 (ru) * 2015-12-31 2017-04-06 Федеральное государственное бюджетное образовательное учреждение высшего образования "Вятский государственный университет" Способ получения порошков интерметаллидов самария и кобальта
RU2621508C2 (ru) * 2015-10-09 2017-06-06 Федеральное государственное бюджетное образовательное учреждение высшего образования "Кабардино-Балкарский государственный университет им. Х.М. Бербекова" (КБГУ) Электрохимический способ получения наноразмерных порошков интерметаллидов гольмия и никеля в галогенидных расплавах
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

Families Citing this family (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AUPR317201A0 (en) * 2001-02-16 2001-03-15 Bhp Innovation Pty Ltd Extraction of Metals
WO2006010229A1 (fr) * 2004-07-30 2006-02-02 Bhp Billiton Innovation Pty Ltd Reduction electrochimique d'oxydes metalliques
JP5293007B2 (ja) * 2008-08-29 2013-09-18 住友大阪セメント株式会社 タリウム及び硝酸カリウムの回収方法及び回収装置
GB0902486D0 (en) * 2009-02-13 2009-04-01 Metalysis Ltd A method for producing metal powders
CN101967649A (zh) * 2010-09-09 2011-02-09 昆明理工大学 一种复合熔盐电解质制备硅的方法
JP2012186145A (ja) * 2011-02-18 2012-09-27 Sumitomo Electric Ind Ltd 電気化学素子用電極の製造方法
RU2562717C1 (ru) * 2014-02-20 2015-09-10 Ашот Александрович Навасардян Способ получения кремния из оксида кремния
CN104060300B (zh) * 2014-07-15 2017-08-25 攀钢集团攀枝花钢铁研究院有限公司 钛铝钒合金粉末的制备方法
CN104451215B (zh) * 2014-12-12 2016-08-24 东北大学 一种熔盐电脱氧-铸锭冶金制备铝合金的方法
CN105112946A (zh) * 2015-08-31 2015-12-02 攀钢集团攀枝花钢铁研究院有限公司 一种钒铬钛合金粉及其制备方法
CN105780059B (zh) * 2016-03-11 2018-05-04 西安建筑科技大学 一种钒铝合金的电解制备方法
JP6089137B1 (ja) * 2016-06-16 2017-03-01 Ｓｅｃカーボン株式会社 カソード
CN106978612A (zh) * 2017-03-16 2017-07-25 广东省稀有金属研究所 一种金属化合物的冶金方法
CN107059063B (zh) * 2017-06-08 2018-08-24 四川理工学院 一种制备AlFeMnTiZr高熵合金的方法
CN107858709B (zh) * 2017-12-14 2019-08-06 东莞理工学院 一种制备金属混合粉末的熔盐电解装置
US10872705B2 (en) * 2018-02-01 2020-12-22 Battelle Energy Alliance, Llc Electrochemical cells for direct oxide reduction, and related methods
CN108380896B (zh) * 2018-03-26 2019-11-12 北京科技大学 一种用碳镁还原制备超细钼粉的方法
CN109750320B (zh) * 2019-03-04 2019-12-13 海安县鹰球粉末冶金有限公司 雾化电解联合制备金属合金粉末的方法
CN114477260A (zh) * 2022-02-11 2022-05-13 江西思远再生资源有限公司 一种从钛粉中回收氯化钙的方法
CN115632132B (zh) * 2022-10-25 2023-10-24 辽宁金谷炭材料股份有限公司 一种铁铬液流电池的复合电极制备方法
CN115928155A (zh) * 2023-02-17 2023-04-07 昆明理工大学 一种钛硅合金的熔盐电解分离方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999064638A1 (fr) * 1998-06-05 1999-12-16 Cambridge University Technical Services Limited Elimination d'oxygene d'oxydes metalliques et de solutions solides par electrolyse dans un sel fondu
WO2001062994A1 (fr) * 2000-02-22 2001-08-30 Qinetiq Limited Procede de fabrication de ferro-titane et d'autres alliages metalliques par reduction electrolytique

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999064638A1 (fr) * 1998-06-05 1999-12-16 Cambridge University Technical Services Limited Elimination d'oxygene d'oxydes metalliques et de solutions solides par electrolyse dans un sel fondu
WO2001062994A1 (fr) * 2000-02-22 2001-08-30 Qinetiq Limited Procede de fabrication de ferro-titane et d'autres alliages metalliques par reduction electrolytique

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
HIROTA K ET AL: "Electrochemical deoxidation of RE-O (RE=Gd, Tb, Dy, Er) solid solutions" JOURNAL OF ALLOYS AND COMPOUNDS, ELSEVIER SEQUOIA, LAUSANNE, CH, vol. 282, no. 1-2, 15 January 1999 (1999-01-15), pages 101-108, XP004182360 ISSN: 0925-8388 *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2133447A1 (fr) * 2001-08-16 2009-12-16 Metalysis Limited Procédé de fabrication de produits en titane et en alliages de titane
CN103801687B (zh) * 2002-06-14 2017-09-29 通用电气公司 不熔化制备金属性合金制品的方法
AU2003245482B2 (en) * 2002-06-14 2009-03-12 General Electric Company Method for fabricating a metallic article without any melting
EP2281647A1 (fr) * 2002-06-14 2011-02-09 General Electric Company Procede permettant de fabriquer un article metallique sans fusion
EP2281648A1 (fr) * 2002-06-14 2011-02-09 General Electric Company Procede permettant de fabriquer un article metallique en alliage sans fusion
CN103801687A (zh) * 2002-06-14 2014-05-21 通用电气公司 不熔化制备金属性合金制品的方法
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
EP2032727A1 (fr) * 2006-06-14 2009-03-11 Norsk Titanium Metals AS PROCÉDÉ ET APPAREIL DE PRODUCTION DE Ti DANS UN ÉLECTROLYTE À SEL FONDU
EP2032727A4 (fr) * 2006-06-14 2012-09-12 Norsk Titanium Technology As PROCÉDÉ ET APPAREIL DE PRODUCTION DE Ti DANS UN ÉLECTROLYTE À SEL FONDU
WO2010051759A1 (fr) 2008-11-06 2010-05-14 北京有色金属研究总院 Procédé électrochimique de fabrication de nanopoudre, de nanofils et/ou de nanotubes de silicium
US8771498B2 (en) 2008-11-06 2014-07-08 General Research Institute For Nonferrous Metals Electrochemical methods for making silicon nanopowder, silicon nanowires and silicon nanotubes
RU2621508C2 (ru) * 2015-10-09 2017-06-06 Федеральное государственное бюджетное образовательное учреждение высшего образования "Кабардино-Балкарский государственный университет им. Х.М. Бербекова" (КБГУ) Электрохимический способ получения наноразмерных порошков интерметаллидов гольмия и никеля в галогенидных расплавах
RU2615668C1 (ru) * 2015-12-31 2017-04-06 Федеральное государственное бюджетное образовательное учреждение высшего образования "Вятский государственный университет" Способ получения порошков интерметаллидов самария и кобальта

Also Published As

Publication number Publication date
EP1339884A2 (fr) 2003-09-03
GB0027929D0 (en) 2001-01-03
BR0115347A (pt) 2004-01-27
JP2004522851A (ja) 2004-07-29
US20040052672A1 (en) 2004-03-18
CA2429024A1 (fr) 2002-05-23
AU2002214161A1 (en) 2002-05-27
CN1479794A (zh) 2004-03-03
WO2002040725A3 (fr) 2002-08-15
ZA200303724B (en) 2005-01-17

Similar Documents

Publication Publication Date Title
US20040052672A1 (en) Metal and alloy powders and powder fabrication
AU758931C (en) Removal of oxygen from metal oxides and solid solutions by electrolysis in a fused salt
US6558447B1 (en) Metal powders produced by the reduction of the oxides with gaseous magnesium
AU757790B2 (en) Metal powders produced by the reduction of the oxides with gaseous magnesium
US20160208398A1 (en) Process for recycling waste carbide
WO2000067936A1 (fr) Poudres metalliques obtenues par reduction d'oxides au moyen de magnesium gazeux
US20060037867A1 (en) Method of manufacturing titanium and titanium alloy products
US20100006448A1 (en) Method, apparatus and means for production of metals in a molten salt electrolyte
CA2331707C (fr) Reduction de poudre d'oxyde de nb ou de ta par metal gazeux leger ou l'un de ses hydrures
WO2018052232A1 (fr) Système de préparation de métal à base de zirconium
CA2525259C (fr) Poudres metalliques obtenues par reduction d'oxides au moyen de magnesium gazeux
RU2397279C1 (ru) Способ получения порошков тугоплавких металлов
AU2003206430B2 (en) Removal of substances from metal and semi-metal compounds
KR20220096728A (ko) 지르코늄 회수 공정 및 폐 지르코늄 처리방법
Luidold et al. Processes for Niobium Powder-a Literature Evaluation
AU2006203344A1 (en) Removal of substances from metal and semi-metal compounds
MXPA00011878A (es) Eliminacion de oxigeno de oxidos de metal y soluciones solidas por electrolisis en una sal fusionada
AU2002331406A1 (en) Method of manufacturing titanium and titanium alloy products

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A2

Designated state(s): AE AG AL AM AT AU AZ BA BB BG BR BY BZ CA CH CN CO CR CU CZ DE DK DM DZ EC EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MA MD MG MK MN MW MX MZ NO NZ OM PH PL PT RO RU SD SE SG SI SK SL TJ TM TR TT TZ UA UG US UZ VN YU ZA ZM ZW

AL Designated countries for regional patents

Kind code of ref document: A2

Designated state(s): GH GM KE LS MW MZ SD SL SZ TZ UG ZM ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE TR BF BJ CF CG CI CM GA GN GQ GW ML MR NE SN TD TG

121 Ep: the epo has been informed by wipo that ep was designated in this application
DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
WWE Wipo information: entry into national phase

Ref document number: 2002214161

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 2002543034

Country of ref document: JP

WWE Wipo information: entry into national phase

Ref document number: 2003/03724

Country of ref document: ZA

Ref document number: 2429024

Country of ref document: CA

Ref document number: 200303724

Country of ref document: ZA

WWE Wipo information: entry into national phase

Ref document number: 018201113

Country of ref document: CN

WWE Wipo information: entry into national phase

Ref document number: 2001982619

Country of ref document: EP

WWP Wipo information: published in national office

Ref document number: 2001982619

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 693/DELNP/2003

Country of ref document: IN

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

WWE Wipo information: entry into national phase

Ref document number: 10416910

Country of ref document: US

WWW Wipo information: withdrawn in national office

Ref document number: 2001982619

Country of ref document: EP