US20060191799A1 - Electrochemical reduction of metal oxides - Google Patents

Electrochemical reduction of metal oxides Download PDF

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Publication number
US20060191799A1
US20060191799A1 US10/530,835 US53083503A US2006191799A1 US 20060191799 A1 US20060191799 A1 US 20060191799A1 US 53083503 A US53083503 A US 53083503A US 2006191799 A1 US2006191799 A1 US 2006191799A1
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United States
Prior art keywords
electrolyte
anode
cell
metal
oxygen
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
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US10/530,835
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English (en)
Inventor
Les Strezov
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BHP Billiton Innovation Pty Ltd
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BHP Billiton Innovation Pty Ltd
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Assigned to BHP BILLITON INNOVATION PTY LTD. reassignment BHP BILLITON INNOVATION PTY LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: RATCHEV, IVAN, OSBORN, STEVE, STREZOV, LES
Publication of US20060191799A1 publication Critical patent/US20060191799A1/en
Abandoned legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/02—Electrodes; Connections thereof
    • C25C7/025—Electrodes; Connections thereof used in cells for the electrolysis of melts
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
    • C25C7/04—Diaphragms; Spacing elements

Definitions

  • the present invention relates to electrochemical reduction of metal oxides.
  • the present invention was made during the course of an on-going research project on electrochemical reduction of metal oxides being carried out by the applicant.
  • the research project has focussed on the reduction of titania (TiO 2 ).
  • the CaCl 2 -based electrolyte was a commercially available source of CaCl 2 , namely calcium chloride dihydrate, that decomposed on heating and produced a very small amount of CaO.
  • the applicant operated the electrolytic cells at potentials above the decomposition potential of CaO and below the decomposition potential of CaCl 2 .
  • the cells could electrochemically reduce titania to titanium with low concentrations of oxygen, ie concentrations less than 0.2 wt %.
  • the cell operation is dependent on decomposition of CaO, with Ca ++ cations migrating to the cathode and depositing as Ca metal and O ⁇ anions migrating to the anode and forming CO and/or CO 2 (in a situation in which the anode is a graphite anode) and releasing electrons that facilitate electrolytic deposition of Ca metal on the cathode.
  • the applicant also believes that the O ⁇ anions, once extracted from the titania, migrate to the anode and react with anode carbon and produce CO and/or CO 2 (and in some instances CaO) and release electrons that facilitate electrolytic deposition of Ca metal on the cathode.
  • the applicant carried out experimental work to identify the mechanism for carbon transfer and to determine how to minimise carbon transfer and/or to minimise the adverse effects of carbon transfer.
  • the invention that is described and claimed in the International application provides an electrolytic cell for electrochemical reduction of a metal oxide, such as titania, in a solid state, which electrolytic cell includes (a) a molten electrolyte, (b) a cathode formed at least in part from the metal oxide in contact with the electrolyte, and (c) a molten metal anode in contact with the electrolyte.
  • a metal oxide such as titania
  • the invention that is described and claimed in the International application is a method of electrochemically reducing a metal oxide, such as titania, in a solid state in an electrolytic cell, which electrolytic cell includes (a) a molten electrolyte, (b) a cathode in contact with the electrolyte, the cathode being formed at least in part from the metal oxide, and (c) a molten metal anode in contact with the electrolyte, and which method includes applying a cell potential across the anode.
  • a metal oxide such as titania
  • the present invention is an improvement of the invention described and claimed in the International application.
  • an electrochemical cell for electrochemical reduction of a metal oxide, such as titania, in a solid state which electrochemical cell includes (a) a molten electrolyte, (b) a cathode formed at least in part from the metal oxide in contact with the electrolyte, (c) an anode, and (d) a membrane that separates the electrolyte and the anode and is permeable to oxygen cations and is impermeable to dissolved metal in the electrolyte, and optionally is impermeable to any one or more of (i) electrolyte anions other that oxygen anions, (ii) anode metal cations, and (iii) any other ions and atoms.
  • a metal oxide such as titania
  • the above-described membrane prevents back reaction of dissolved metal in the electrolyte and oxygen atoms generated at the anode that can significantly reduce the current efficiency of the cell. Specifically, the membrane allows oxygen anions to migrate to the anode and give up electrons at the anode and prevents dissolved metal in the electrolyte migrating to the anode and reacting with oxygen atoms generated at the anode.
  • the membrane makes it possible for the cell to operate at high current efficiencies.
  • the membrane makes it possible to operate the cell at higher potentials without the disadvantages that are often associated with operating at such higher cell potentials.
  • the electrolyte includes CaCl 2 it is undesirable to operate at potentials that result in evolution of chlorine gas because of the corrosive and toxic properties of the gas.
  • the membrane prevents the migration of Cl ⁇ anions to the anode and thereby prevents the evolution of chlorine gas. Operating at higher cell potentials is advantageous because it produces higher currents and therefore reduces cycle times.
  • the anode is a molten metal anode.
  • the present invention also extends to other arrangements.
  • the present invention extends to fuel cell arrangements in which there is (a) a coating of a suitable metal/metal oxide system, such as Ni/NiO, on the membrane that forms the anode and conducts electrons released by the oxygen anions and (b) a fuel, such as hydrogen or natural gas, that consumes oxygen that is evolved at the anode.
  • a suitable metal/metal oxide system such as Ni/NiO
  • the anode may be arranged so that oxygen gas is evolved at the anode and is removed from the cell.
  • the anode may be also be arranged so that there is no oxygen gas released from the anode assembly.
  • the anode may include a means for scavenging oxygen that is generated at the anode when oxygen anions migrate to the anode and give up electrons at the anode.
  • the above-described gaseous fuel is one suitable scavenging means.
  • the scavenging means may also be a solid material that is oxidised by oxygen.
  • solid scavenging materials are preferred in situations in which the anode is a molten metal anode.
  • Suitable solid scavenging materials for molten silver anodes include iron, carbon and tungsten.
  • the use of a scavenging means reduces the need to select molten metal anodes that have high solubility of oxygen in anode metal.
  • the solid scavenging materials form the anode electrode for molten metal anodes.
  • the membrane be impermeable to the anode electrode material.
  • the present invention is based on experimental work carried out by the applicant to electrochemically reduce titania.
  • the experimental work was carried out on a cell that included a stainless steel crucible containing molten CaCl 2 -based electrolyte containing at least some CaO, a cathode extending into the electrolyte, the cathode including TiO 2 , and an anode in the form of molten silver contained in a yttria stabilised zirconia crucible extending into the electrolyte.
  • the yttria stabilised zirconia is permeable to oxygen anions and is impermeable to calcium metal dissolved in the electrolyte, chlorine anions, and silver cations.
  • the anode electrical connection was made via a low carbon steel wire extending into the molten silver.
  • the cell was operated initially at a potential around 3V.
  • the cell was also operated at higher potentials, up to 10V. It was found that there was decomposition of CaCl 2 and no evolution of chlorine gas under these conditions. There was also a proportional increase in current with increasing voltage.
  • the experimental work opens up the following possibilities for an electrolytic cell for electrochemically reducing metal oxides, such as titania.
  • the metal is chosen such that its melting point is within the operating temperature range of the electrolyte.
  • the melting point of the metal of the molten metal anode is higher than the melting point of the electrolyte and lower than the vaporisation and/or decomposition temperature of the electrolyte in order to prevent electrolyte consumption and removal through vaporisation.
  • the metal of the molten metal anode is silver or copper.
  • the membrane is formed from a solid electrolyte.
  • the solid electrolyte is an oxide.
  • the solid electrolyte is yttria stabilised zirconia.
  • the membrane includes a body and an outer lining, with the outer lining being in contact with the electrolyte, and the outer lining being formed from a material that is inert with respect to dissolved metal in the electrolyte and is impermeable to the dissolved metal.
  • the electrolyte be a CaCl 2 -based electrolyte that includes CaO as one of the constituents.
  • CaO the electrolyte
  • the body is formed from the solid electrolyte.
  • the outer lining is formed from a rare earth oxide.
  • the rare earth oxide is yttria.
  • the lining is continuous and covers all of the surface of the membrane that is in contact with the electrolyte so that there are no sections of the body that are in contact with the electrolyte.
  • the metal oxide is a titanium oxide.
  • the metal oxide be titania.
  • a method of electrochemically reducing a metal oxide in a solid state in an electrochemical cell which electrochemical cell includes (a) a molten electrolyte, (b) a cathode in contact with the electrolyte, the cathode being formed at least in part from the metal oxide, (c) an anode, and (d) a membrane that separates the electrolyte and the anode and is permeable to oxygen ions and is impermeable to dissolved metal in the electrolyte, and optionally is impermeable to any one or more of (i) electrolyte anions other that oxygen anions, (ii) anode metal cations, and (iii) any other ions and atoms, and which method includes applying a cell potential across the anode and the cathode and electrochemically reducing the metal oxide.
  • the method includes electrochemically reducing the metal oxide to titanium having an oxygen concentration of less than 0.2 wt. %.
  • the method includes maintaining the cell temperature below the vaporisation and/or decomposition temperatures of the electrolyte.
  • the method includes applying a cell potential above a decomposition potential of at least one constituent of the electrolyte so that there are cations of a metal other than that of the cathode metal oxide in the electrolyte.
  • the membrane is formed from a solid electrolyte.
  • the solid electrolyte is yttria stabilised zirconia.
  • the metal oxide is a titanium oxide.
  • the metal oxide be titania.
  • the electrolyte be a CaCl 2 -based electrolyte that includes CaO as one of the constituents.
  • the method includes maintaining the cell potential above the decomposition potential for CaO.
  • the following example illustrates an application of the invention in the process of reducing titania into substantially pure titanium using an electrochemical cell constructed in accordance with the present invention and as illustrated schematically in FIG. 1 .
  • the electrochemical cell 2 includes a graphite-free crucible 10 made of a suitable refractory material that is essentially inert with respect to the electrolyte and electrode materials described below at cell operating temperatures.
  • the electrochemical cell further includes a pool 18 of molten CaCl 2 electrolyte that contains at least some CaO within the crucible 10 .
  • the electrochemical cell 2 further includes a pool 14 of molten silver or copper contained in a crucible of yttria stabilised zirconia that extends into the cell.
  • the molten Ag or Cu forms the molten metal anode 14 of the cell.
  • the yttria stabilised zirconia crucible 16 forms a membrane that allows migration of oxygen anions and prevents migration of calcium metal dissolved in the molten electrolyte into the molten anode.
  • the crucible has an outer lining of yttria.
  • the electrochemical cell 2 further includes a titania plate 12 positioned within a cage 24 .
  • the cage 24 (and therefore the plate 12 ) is suspended into the crucible 10 by means of a lead 26 .
  • This assembly forms the cathode 20 of the cell.
  • the electrochemical cell 2 further includes a power source 22 and electrical connections between the power source 22 and the anode 14 and the cathode 20 .
  • the connections include the above-described lead 26 and a further electrical lead 28 .
  • the electrical lead 28 is a low carbon steel wire that is consumed during the operation of the cell—as described below.
  • power source 22 provides constant potential (voltage) settings thereby that allow the cell 2 to draw the amount of current required during the electrolytic refining of the metal oxide body at a selected potential.
  • the electrochemical cell 2 further includes thermocouples contained in suitable heat-resistant, inert sheaths (not illustrated) for monitoring temperature in the molten metal anode 14 and the molten electrolyte 18 .
  • the above-described electrochemical 2 is positioned in a suitable furnace to maintain the electrolyte and the anode metal in their respective molten states.
  • the atmosphere around the crucible 10 is preferred to be an inert gas, such as argon, that does not react with the molten electrolyte.
  • the oxygen that passes into the electrolyte 18 by virtue of electrochemical reduction of the metal oxide is subsequently transported into the molten metal anode 14 via the membrane 16 and dissolves in the molten metal.
  • the dissolved oxygen then oxidises the steel electrode 28 , and iron oxides accumulate on the surface of the molten metal anode and are periodically removed.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Conductive Materials (AREA)
US10/530,835 2002-10-09 2003-10-09 Electrochemical reduction of metal oxides Abandoned US20060191799A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
AU2002951962A AU2002951962A0 (en) 2002-10-09 2002-10-09 Electrolytic reduction of metal oxides
AU2002951962 2002-10-09
PCT/AU2003/001330 WO2004033760A2 (en) 2002-10-09 2003-10-09 Electrochemical reduction of metal oxides

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US20060191799A1 true US20060191799A1 (en) 2006-08-31

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Country Status (4)

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US (1) US20060191799A1 (zh)
CN (1) CN101166838A (zh)
AU (1) AU2002951962A0 (zh)
WO (1) WO2004033760A2 (zh)

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
US20080149495A1 (en) * 2004-07-30 2008-06-26 Kannapar Mukunthan Electrochemical Reduction of Metal Oxides
WO2008101290A1 (en) * 2007-02-20 2008-08-28 Metalysis Limited Electrochemical reduction of metal oxides
WO2008101283A1 (en) * 2007-02-20 2008-08-28 Metalysis Limited Electrochemical reduction of metal oxides
US20090000955A1 (en) * 2005-07-15 2009-01-01 Trustees Of Boston University Oxygen-Producing Inert Anodes for Som Process
US7628904B2 (en) 2002-10-16 2009-12-08 Metalysis Limited Minimising carbon transfer in an electrolytic cell
WO2012104640A3 (en) * 2011-02-04 2012-10-04 Metalysis Limited Electrolysis method and apparatus
CN103180487A (zh) * 2010-08-23 2013-06-26 麻省理工学院 通过氧化物电解提取液态元素
JP2014019890A (ja) * 2012-07-17 2014-02-03 Furukawa Electric Co Ltd:The 銅微粒子の製造装置、及び銅微粒子の製造方法
US20150050816A1 (en) * 2013-08-19 2015-02-19 Korea Atomic Energy Research Institute Method of electrochemically preparing silicon film
US20150259766A1 (en) * 2014-02-25 2015-09-17 Colorado School Of Mines Decoating of coated materials
JP2016503127A (ja) * 2012-12-24 2016-02-01 メタリシス リミテッド 電解還元による金属を製造するための方法及び装置
KR20200015021A (ko) * 2018-08-02 2020-02-12 한국원자력연구원 미환원 산화물 분리 장치 및 방법

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US20060234098A1 (en) * 2005-04-18 2006-10-19 Clean Coal Energy, Llc Direct carbon fuel cell with molten anode
US20110014526A1 (en) * 2005-05-16 2011-01-20 Guer Turgut M High temperature direct coal fuel cell
WO2006138611A2 (en) 2005-06-16 2006-12-28 Trustees Of Boston University Waste to hydrogen conversion process and related apparatus
CN103422122B (zh) * 2013-08-30 2016-08-10 昆明理工大学 一种二氧化钛直接制备金属钛的方法
CN105040033A (zh) * 2015-07-13 2015-11-11 鄂州汉衍新材料有限公司 一种电解脱氧制备高纯铁粉方法与装置
CN106917113A (zh) * 2015-12-27 2017-07-04 天津赫维科技有限公司 一种电化学法制备金属钛的装置及其方法
EP3427826B1 (en) * 2016-03-08 2020-11-25 Japan Science and Technology Agency Catalyst and use of same
CN108728870B (zh) * 2017-08-07 2021-02-12 南京佑天金属科技有限公司 晶条铪的生产系统及其方法

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US20040237711A1 (en) * 2001-10-17 2004-12-02 Katsutoshi Ono Method and apparatus for smelting titanium metal
US20050050989A1 (en) * 2002-12-12 2005-03-10 Steve Osborn Electrochemical reduction of metal oxides
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US20070131560A1 (en) * 2004-03-22 2007-06-14 Ivan Ratchev Electrochemical reduction of metal oxides
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US20080047845A1 (en) * 2003-10-14 2008-02-28 Gregory David Rigby Electrochemical Reduction of Metal Oxides
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AUPR443901A0 (en) * 2001-04-10 2001-05-17 Bhp Innovation Pty Ltd Method for reduction of metal oxides to pure metals
AUPR443801A0 (en) * 2001-04-10 2001-05-17 Bhp Innovation Pty Ltd Removal of oxygen from metal oxides and solid metal solutions
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US5089094A (en) * 1989-03-16 1992-02-18 Osaka Titanium Company Limited Process for the electrolytic production of magnesium
US5006209A (en) * 1990-02-13 1991-04-09 Electrochemical Technology Corp. Electrolytic reduction of alumina
US6540902B1 (en) * 2001-09-05 2003-04-01 The United States Of America As Represented By The United States Department Of Energy Direct electrochemical reduction of metal-oxides
US20040237711A1 (en) * 2001-10-17 2004-12-02 Katsutoshi Ono Method and apparatus for smelting titanium metal
US20060180462A1 (en) * 2002-10-16 2006-08-17 Les Strezov Minimising carbon transfer in an electrolytic cell
US20050050989A1 (en) * 2002-12-12 2005-03-10 Steve Osborn 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
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Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7628904B2 (en) 2002-10-16 2009-12-08 Metalysis Limited Minimising carbon transfer in an electrolytic cell
US20060226027A1 (en) * 2003-06-20 2006-10-12 Shook Andrew A Electrochemical reduction of metal oxides
US7758740B2 (en) 2003-06-20 2010-07-20 Metalysis Limited 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
US20080149495A1 (en) * 2004-07-30 2008-06-26 Kannapar Mukunthan Electrochemical Reduction of Metal Oxides
US20070251833A1 (en) * 2004-07-30 2007-11-01 Ivan Ratchev Electrochemical Reduction of Metal Oxides
US20090000955A1 (en) * 2005-07-15 2009-01-01 Trustees Of Boston University Oxygen-Producing Inert Anodes for Som Process
US8658007B2 (en) * 2005-07-15 2014-02-25 The Trustees Of Boston University Oxygen-producing inert anodes for SOM process
WO2008101283A1 (en) * 2007-02-20 2008-08-28 Metalysis Limited Electrochemical reduction of metal oxides
WO2008101290A1 (en) * 2007-02-20 2008-08-28 Metalysis Limited Electrochemical reduction of metal oxides
CN103180487A (zh) * 2010-08-23 2013-06-26 麻省理工学院 通过氧化物电解提取液态元素
WO2012104640A3 (en) * 2011-02-04 2012-10-04 Metalysis Limited Electrolysis method and apparatus
CN103459675A (zh) * 2011-02-04 2013-12-18 金属电解有限公司 电解方法和装置
EA027479B1 (ru) * 2011-02-04 2017-07-31 Металисиз Лимитед Способ электролиза и установка для электролиза
US10066309B2 (en) 2011-02-04 2018-09-04 Metalysis Limited Method and apparatus for electrochemical reduction of a solid feedstock
JP2014019890A (ja) * 2012-07-17 2014-02-03 Furukawa Electric Co Ltd:The 銅微粒子の製造装置、及び銅微粒子の製造方法
JP2016503127A (ja) * 2012-12-24 2016-02-01 メタリシス リミテッド 電解還元による金属を製造するための方法及び装置
US20150050816A1 (en) * 2013-08-19 2015-02-19 Korea Atomic Energy Research Institute Method of electrochemically preparing silicon film
US20150259766A1 (en) * 2014-02-25 2015-09-17 Colorado School Of Mines Decoating of coated materials
US10087502B2 (en) * 2014-02-25 2018-10-02 Colorado School Of Mines Decoating of coated materials
KR20200015021A (ko) * 2018-08-02 2020-02-12 한국원자력연구원 미환원 산화물 분리 장치 및 방법
KR102123509B1 (ko) 2018-08-02 2020-06-17 한국원자력연구원 미환원 산화물 분리 장치 및 방법

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WO2004033760A3 (en) 2007-11-29
AU2002951962A0 (en) 2002-10-24
WO2004033760A2 (en) 2004-04-22
CN101166838A (zh) 2008-04-23

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