Updated on 2024/09/06

写真a

 
TAKENAKA,Toshihide
 
Organization
Faculty of Chemistry, Materials and Bioengineering Professor
Title
Professor
Contact information
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Degree

  • 工学博士 ( 1986.9 )

Research Areas

  • Manufacturing Technology (Mechanical Engineering, Electrical and Electronic Engineering, Chemical Engineering) / Manufacturing and production engineering

  • Nanotechnology/Materials / Metallic material properties

  • Nanotechnology/Materials / Metals production and resources production

Education

  • Kyoto University   Graduate School, Division of Engineering

    1986

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  • Kyoto University   Faculty of Engineering

    - 1981

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    Country: Japan

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  • Kyoto University   Graduate School, Division of Engineering

    1986

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    Country: Japan

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Professional Memberships

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Committee Memberships

Papers

  • Effects of MgCl2 and NaCl on Si-Thermic Reduction of MgO in Recycle of Mg-air Battery

    Atsushi Hayashida, Toshihide Takenaka, Taiki Morishige

    Minerals, Metals and Materials Series   267 - 273   2021

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    Language:English   Publishing type:Research paper (international conference proceedings)   Publisher:Springer Science and Business Media Deutschland GmbH  

    The effects of the chlorine content used as electrolyte should be controlled in the recycle process of Mg-air battery. The influence of MgCl2 and NaCl in Si-thermic reduction of MgO has been studied in this study. The mixture of MgO with MgCl2 or NaCl was reduced by metallic Si at 1150 °C for 3 h, and the reduction rate was estimated. The reduction rate without MgCl2 or NaCl addition was about 55% under our reduction condition, and 1 mol% addition of MgCl2 rarely affected the reduction rate. However, the reduction rate decreased with added amount of MgCl2, and became about 15% in 10 mol% addition. Even 1 mol% addition of NaCl worsened the reduction rate, and the reduction rate decreased with the addition amount. It is confirmed that the chlorine should be removed before Si-thermic reduction in the recycle of Mg-air battery.

    DOI: 10.1007/978-3-030-72432-0_26

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  • Effect of Pre-sintering in Silicothermic Reduction of MgO and Reduction Using Ca2SiO4 Instead of CaO

    Takeru Saimura, Taiki Morishige, Toshihide Takenaka

    Minerals, Metals and Materials Series   13 - 17   2021

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    Language:English   Publishing type:Research paper (international conference proceedings)   Publisher:Springer Science and Business Media Deutschland GmbH  

    It was shown in our previous study that the contact condition between MgO, CaO, and Si strongly affected Mg metal production by silicothermic reduction of magnesium oxide derived from salt evaporation ponds. In this study, the influence of the contact condition of MgO, CaO, and Si in the reduction was studied
    the dependence of the reduction rate on the preparation procedure of MgO–CaO mixture and pre-sintering before the reduction was examined. A short-term sintering improved the reduction rate, but a longer sintering worsened the rate. Sintering seems effective in the improvement of contact condition, but causes the surface oxidation on Si. In this study, Si reduction with Ca2SiO4 instead of CaO was also attempted to reduce CaO consumption, but it was shown that MgO was lost by CaMgSiO4 formation.

    DOI: 10.1007/978-3-030-72432-0_2

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  • Effect of Microstructure on Corrosion Behavior of Cold-Rolled Mg–Li–Al Alloy

    Taiki Morishige, Hayato Ikoma, Toshihide Takenaka

    Minerals, Metals and Materials Series   189 - 193   2021

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    Language:English   Publishing type:Research paper (international conference proceedings)   Publisher:Springer Science and Business Media Deutschland GmbH  

    Mg–Li system alloy has excellent formability at room temperature due to its crystal structure. However, exfoliation corrosion appears during the progress of corrosion. Therefore, it is difficult to apply for the actual metallic products without corrosion protection. Previously, the suppression of exfoliation could be attained by recrystallization of cold-rolled alloy. The microstructural characteristics were completely changed by recrystallization, so a detailed investigation is required for the explanation of exfoliation corrosion origination. In this study, the origination of exfoliation corrosion of Mg–14 mass%Li–1 mass%Al alloy with various microstructures such as as-rolled, only recovered and recrystallized state. As the results, the induced strain during severe deformation is a major factor of expression of exfoliation corrosion.

    DOI: 10.1007/978-3-030-72432-0_19

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  • Oxide Films Formed on MoSi2 Anode in Molten MgCl2–NaCl–CaCl2 and Molten LiCl–KCl

    Takamasa Miyoshi, Taiki Morishige, Toshihide Takenaka

    Minerals, Metals and Materials Series   19 - 25   2021

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    Language:English   Publishing type:Research paper (international conference proceedings)   Publisher:Springer Science and Business Media Deutschland GmbH  

    The anodic formation of an oxide film on MoSi2 in molten MgCl2–NaCl–CaCl2 containing oxide ions has been investigated based on our former study, and the compatibility as an inert anode in the melt is discussed in contradistinction in molten LiCl–KCl. A small anodic current flew continuously during potentio-static electrolysis, and gas bubble generation was seen. The weight of MoSi2 was changed by the electrolysis, and an oxide film consisting of SiO2 and MgSiO3 was formed by the electrolysis above 1.9 V (vs. Mg/Mg2+). The current contributions estimated from the weight change and the film thickness indicate that the reaction other than the Mo dissolution and the oxide film formation enlarged with the increase in the electrolysis duration and the raise in the electrolysis potential. The current contribution other than the Mo dissolution and the oxide film formation became above 90%, which suggests MoSi2 is promising as an inert anode. A SiO2 film was formed on MoSi2 in molten LiCl–KCl containing oxide ions, but most of the current was consumed for the Mo dissolution and the oxide film formation. It is considered that the formation of MgSiO3 influences the anodic behavior of MoSi2.

    DOI: 10.1007/978-3-030-72432-0_3

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  • The influence of introduced strains on the exfoliation corrosion behavior of Mg-14mass%Li-1mass%Al alloy

    Hayato Ikoma, Taiki Morishige, Toshihide Takenaka

    Materials Science Forum   1016   587 - 591   2021

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    Language:English   Publishing type:Research paper (international conference proceedings)   Publisher:Trans Tech Publications Ltd  

    Mg-Li alloys have much better formability than traditional Mg alloys. However, the corrosion resistance of Mg-Li alloys are low due to Li addition and cold-worked Mg-Li alloys sustain exfoliation corrosion, which is serious problem for practical use of Mg-Li alloys [1]. According to our previous report, the elongated grains may be the cause of the exfoliation corrosion. In this study, the exfoliation corrosion behavior of Mg-14mass%Li-1mass%Al (LA141) alloy processed by equal channel angular extrusion (ECAE) is characterized to see the corrosion morphology of the samples introduced more grains than rolling. The specimens processed by rolling showed only elongated grains and the ones processed by ECAE (Route A) at 2 and 4 times showed elongated grains and partially equiaxial grains and in the samples fabricated by ECAE (Route Bc) at 2 and 4 times, equiaxial grains were found by optical microscopy. In corrosion examination, the specimens of rolling and ECAE (Route A) developed exfoliation corrosions and the samples of ECAE (Route Bc) didn’t sustain exfoliation corrosion. This results were consistent with our previous report. Then the corrosion behavior of rolled and ECAEed samples were focused. The evaluation of the time until crack initiation and the number of cracks were employed to see the corrosion morphology of the samples.

    DOI: 10.4028/www.scientific.net/MSF.1016.587

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  • Effect of Cation Species in the Electrolyte on the Oxidized Film on the Anodizing of Mg–Li–Al Alloys

    Yuka Ichigi, Taiki Morishige, Toshihide Takenaka

    Minerals, Metals and Materials Series   179 - 187   2021

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    Language:English   Publishing type:Research paper (international conference proceedings)   Publisher:Springer Science and Business Media Deutschland GmbH  

    Mg–14mass%Li–3mass%Al (LA143) alloy has higher corrosion resistance than previous Mg-Li alloys such as Mg–14mass%Li–1mass%Al (LA141). However, the corrosion properties of the alloy are not enough to apply for practical use without corrosion protection coatings. The anodization for Mg alloys is an effective technique to prevent metal surface from exposure to corrosion environment. Phosphoric acid-based solutions containing metal cation are useful electrolytes to form a thick oxide layer on the Mg surface. In this study, the effect of cation species on the oxidized film was investigated. The film formed by each electrolytic solution was mainly composed of Mg3(PO4)2, AlPO4, MgAl2O4, and the phosphate and oxide-containing each additive element were slightly present. Particularly, in the electrolyte containing Ca, the dissolution of LA143 was suppressed about twice as much as other electrolytes, and the most uniform and thick film was formed.

    DOI: 10.1007/978-3-030-72432-0_18

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  • Extra-hardening of SPD-processed Al-Mg alloy with minimum grain sizes

    Taiki Morishige, Yuto Suzuki, Toshihide Takenaka

    Materials Science Forum   1016   952 - 956   2021

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    Language:English   Publishing type:Research paper (international conference proceedings)   Publisher:Trans Tech Publications Ltd  

    Severe plastic deformation (SPD) processing of Al alloys could obtain high strength by grain refinement mechanism. The minimum grain size of Al alloy, obtained at higher strain rate at low temperature, is determined the stacking fault energy of the alloy. SPD-processed pure Al metal, has high stacking fault energy, has relatively large grain size. During SPD processing, large strain is introduced, and the dislocation is rearranged in the specimen. The re-arrangement of dislocation in SPD-processed Al alloy with intermediate stacking fault energy significantly delayed, thus the strain remains in the grain interior. The extra-hardening, a kind of strain hardening, results from an incomplete of dynamic recrystallization during SPD processing. Al-Mg solid solution alloy has intermediate stacking fault energy and the minimum grain size of this alloy approaches about 200 nm after SPD. The mechanical property of this alloy is remarkably higher than the predictable strength by Hall-Petch relationship due to the extra-hardening. In addition, the increase in strength by the extra-hardening varies with the Mg content of Al-Mg alloy. In this study, the effect of Mg content, i.e. the stacking fault energy of the alloy, on the degree of the extra-hardening of SPD-processed Al- Mg alloy was investigated in terms of the dislocation density and low-angle grain boundary of the alloy.

    DOI: 10.4028/www.scientific.net/MSF.1016.952

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  • Anodic behavior of MoSi2 in molten MgCl2-NaCl-CaCl2 containing oxide ions

    Takamasa Miyoshi, Taiki Morishige, Toshihide Takenaka

    ECS Transactions   98 ( 10 )   253 - 260   2020

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    Language:English   Publishing type:Research paper (international conference proceedings)   Publisher:IOP Publishing Ltd  

    The anodic behavior of MoSi2 in molten MgCl2-NaCl-CaCl2 containing oxide ions has been investigated in this study to aim at developing an inert anode in this melt. A sharp anodic current peak appeared around 1.8V (vs. Mg / Mg2+) in a cyclic voltammogram, which suggested that MoSi2 was passivated in the melt with oxide ions. An oxide film consisting of SiO2 and MgSiO3 was formed on MoSi2 by potentio-static electrolysis more positively than 1.6V (vs. Mg / Mg2+), and gas bubbles kept generating during the electrolysis. The current contributions assuming that the dissolution of Mo and the formation of MgSiO3 were estimated from the weight change and the film thickness after potentio-static electrolysis. The current contribution other than the Mo dissolution and the oxide film formation enlarged with the increase in the electrolysis duration and the raise in the electrolysis potential, and became above 90%. These results imply that MoSi2 is potential as an inert anode in molten MgCl2-NaCl-CaCl2 containing oxide ions.

    DOI: 10.1149/09810.0253ecst

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  • Al electrodeposition in molten CaCl2 with various calcium aluminates

    Yuta Iwai, Taiki Morishige, Toshihide Takenaka

    ECS Transactions   98 ( 10 )   333 - 340   2020

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    Language:English   Publishing type:Research paper (international conference proceedings)   Publisher:IOP Publishing Ltd  

    In this study, direct production of liquid Al metal was attempted in molten CaCl2 with various calcium aluminates, based on our previous studies on Ti and Si electrolysis. Al and Al-Mo alloys were detected on the electrode surface after electrolysis at -1.8V (Mo vs. dissolution) at 1573K, and the molar ratio of CaO to Al2O3 did not affect Al deposited strongly. By using the electrode with a BN receiver, the electrodeposited Al was kept around the cathode and Al was obtained from the cathode surface. It was shown that calcium aluminate was dissolved in molten CaCl2 above 1573 K and liquid Al metal could be obtained electrochemically with little dependence on the molar ratio of CaO to Al2O3.

    DOI: 10.1149/09810.0333ecst

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  • Dependence of reduction behavior of Ti in molten CaCl2 on various calcium titanate

    Haruka Okada, Kakeru Shimokawa, Taiki Morishige, Toshihide Takenaka

    Materials Transactions   59 ( 4 )   690 - 693   2018

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:Japan Institute of Metals (JIM)  

    The change in TiO2 solubility in molten CaCl2 at 1573 K with CaO addition was studied to clarify the influence of CaO on TiO2 dissolution. The solubility of TiO2 in molten CaCl2 remarkably enlarged with CaO addition, which suggests that a titanate ion (TixOy Z1) was preferentially formed in it. The cathodic behavior in molten CaCl2 containing various species of calcium titanate at 13731573 K was investigated by cyclic voltammetry, and electrodeposition of Ti metal was attempted by potentio-static electrolysis. The reduction behavior was affected by the species of calcium titanate, and the components in the deposit changed consequently. These results indicate that the reduction behavior of Ti was strongly influenced by the species of titanate ion, and that the bath consisting of Ca3Ti2O7 is found suitable.

    DOI: 10.2320/matertrans.MBW201702

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  • Electrodeposition of Si in molten CaCl2 above 1300K

    Toshihide Takenaka, Ryoya Shimokawa, Haruka Okada, Taiki Morishige

    ECS Transactions   86(14), pp.29-35   2018

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  • Influence of molar ratio of CaO to TiO2 on Ti electrodeposition in molten CaCl2

    Haruka Okada, Maito Murata, Taiki Morishige, Toshihide Takenaka

    ECS Transactions   86(14), pp.117-122   2018

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  • Unique Metal Fog Generation in LiCl-KCl Melt

    Toshihide Takenaka, Shogo Akimura, Taiki Morishige

    Electrochemistry   86(4), pp.179-183   2018

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  • Relationship between microstructure and exfoliation corrosion in mg-14mass%li-3mass%al cold-rolled alloy

    Yuki Sekiguchi, Taiki Morishige, Takayuki Goto, Eiji Nakamura, Toshihide Takenaka

    Materials Science Forum   941   1743 - 1747   2018

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    Language:English   Publishing type:Research paper (international conference proceedings)   Publisher:Trans Tech Publications Ltd  

    Relationship between microstructure and exfoliation corrosion in Mg-14mass%Li-3mass%Al cold rolled material were investigated by controlling microstructure using heat treatment. The exfoliation corrosion was exhibited on the specimens with elongated microstructure by cold-rolling. Heat treatment at 200 °C only recovery occurred. Recovery and recrystallization were caused by heat treatment at 300 °C However, heat treated at 300 °C decreased precipitate fraction. Corrosion rate of heat-treated at 200 °C decreased by release the residual strain. However, heat treatment at 300 °C has lower corrosion resistance than heat-treated at 200 °C because it has less precipitate density than as-rolled. Exfoliation corrosion was shown in as-rolled and heat-treated at 200 °C. In as-rolled exfoliation corrosion was shown more significant when reduction rate increase. In as-rolled, exfoliation corrosion was shown more significant than heat-treated at 200 °C. After heat treatment to change the grain shape from elongated to equiatial, exfoliation was suppressed by the distribution of AlLi phase.

    DOI: 10.4028/www.scientific.net/MSF.941.1743

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  • Effect of voltage on mg-li-al alloy anodic oxide film

    Naoya Miyakita, Natsuki Tanigaki, Taiki Morishige, Toshihide Takenaka

    Materials Science Forum   941   1194 - 1197   2018

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    Language:English   Publishing type:Research paper (international conference proceedings)   Publisher:Trans Tech Publications Ltd  

    Anodic oxidation of Mg-Li-Al alloys using phosphoric acid-based bath were processed to obtain the corrosion-proof surface coating. The specimen oxidized at low voltage anodically dissolved without the formation of oxidized film. Anodic oxidation film could be formed at higher voltage due to thin layer preferentially formed on tthe active surface, this layer develops to stable thick film. There were no significant differences in film thickness between LA141 and LA143 alloys.

    DOI: 10.4028/www.scientific.net/MSF.941.1194

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  • The relationship between mg content and extra-hardening in ultrafine grained al-mg alloy by spd

    Yuto Suzuki, Yuichi Shiono, Taiki Morishige, Toshihide Takenaka

    Materials Science Forum   941   1173 - 1177   2018

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    Language:English   Publishing type:Research paper (international conference proceedings)   Publisher:Trans Tech Publications Ltd  

    Severe Plastic Deformation (SPD) process is one of methods for obtaining UFG-Al. It was reported in SPD-processed Al alloy that the extra-hardening due to work hardening caused by accumulated dislocation in the grains. In Al-Mg alloy, Mg decreases the stacking fault energy in this alloy, and dislocation tends to accumulate in the grains. In this study, Al-Mg alloy with various Mg contents were processed by Equal-Channel Angular Pressed (ECAP) which was one of SPD. The relationship between Mg content and magnitude of extra-hardening was investigated. In ECAPed Al-3mass%Mg alloy, it was thought that extra-hardening was caused. Magnitude of extra-hardening was increased with increasing Mg content.

    DOI: 10.4028/www.scientific.net/MSF.941.1173

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  • The effect of vibration condition for magnesium dry gravity sorting by vibrating particulate bed

    Shingo Itoh, Keigo Tsujita, Taiki Morishige, Toshihide Takenaka

    Materials Science Forum   941   1535 - 1539   2018

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    Language:English   Publishing type:Research paper (international conference proceedings)   Publisher:Trans Tech Publications Ltd  

    Recycling Mg alloys has been demanded as the demand of Mg alloys has been increased. It is difficult to separate Mg with Al because the properties are similar except for the density. In this study, gravity sorting by vibrating particulate bed ajusted the density to intermediate between Mg and Al was applied for Mg separation with Al. The relationship the vibrating condition and the sorting accuracy was investigated by applying different vibration acceleration and by applying the vertical and horizontal vibration. Turbulent flow was observed and the recovery rate was improved when vertical vibration with high acceleration was applied to the bed. Higher recovery rate was achieved when horizontal vibration was applied to the bed. This result suggested that the horizontal movement of particle affected the behavior of sorting materials and high recovery ratio was achieved by optimizing vibrational condition such as vibration acceleration and the direction of vibration.

    DOI: 10.4028/www.scientific.net/MSF.941.1535

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  • Effect of Zn existence on Mg corrosion due to Cu

    Hiroaki Ishimaru, Taiki Morishige, Toshihide Takenaka

    ECS Transactions   75(26), pp.1-5   2017

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  • Dissolution of Calcium Titanate in Calcium Chloride Melt and Its Application to Titanium Electrolysis

    Toshihide Takenaka, Kakeru Shimokawa, Kazuyoshi Nishikawa, Haruka Okada, Taiki Morishige

    MATERIALS TRANSACTIONS   58 ( 3 )   350 - 354   2017

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:JAPAN INST METALS  

    The solubility of calcium titanate in CaCl2 melt was investigated above 1373 K, and electrodeposition of Ti metal in the melt was attempted. Many pits were formed on the surface of sintered CaTiO3 compact by the immersion in CaCl2 melt above 1373 K. The weight of the compact decreased with the increase in the immersion time, and the decrease got faster with the increase in temperature. Cathodic current in cyclic voltammetry increased with the addition of CaTiO3 powder in the bath, and the increase in the cathodic currents depended on the bath temperature and the added amount of CaTiO3. From the results by the electrochemical measurement, the solubilities of CaTiO3 in CaCl2 melt were estimated about 7 mol% at 1573 K, and less than 1 mol% at 1373 K. Metallic Ti was detected by XRD analysis in the electrodeposit obtained by potentio-static electrolysis in the bath containing CaTiO3 above 1373 K, but the amount of Ti metal seemed a little. The similar results were obtained in CaCl2 melt containing Ca3Ti2O7 though the detailed study has not been completed. It was concluded that calcium titanate was soluble in molten CaCl2 above 1373 K, and that the CaCl2 bath containing calcium titanate could be applied to Ti electrolysis.

    DOI: 10.2320/matertrans.MK201615

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  • マグネシウム材料の乾式リサイクル法に関する基礎的研究

    竹中俊英, 森重大樹

    溶融塩および高温化学   59, pp.114-123   2016

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  • Effect of Al Composition on the Corrosion Resistance of Mg-14 mass% Li System Alloy

    Taiki Morishige, Yutaro Obata, Takayuki Goto, Tomoki Fukagawa, Eiji Nakamura, Toshihide Takenaka

    MATERIALS TRANSACTIONS   57 ( 10 )   1853 - 1856   2016

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:JAPAN INST METALS  

    Mg-Li system alloys have poor corrosion properties, especially cold-rolled sheet leads to exfoliation corrosion as a result of long-term immersion test. Addition of aluminum element to Mg-14 mass% Li alloy could be suppressed the occurrence of exfoliation corrosion. However, excess addition of aluminum to Mg-14 mass% Li alloy causes the degradation of corrosion resistance. In this study, the composition of aluminum in Mg-14 mass% Li was optimized to improve the corrosion property. 3 mass% of Al addition could be suppressed the corrosion rate because enough aluminum element dissolved into matrix and precipitation of the second phase was inhibited.

    DOI: 10.2320/matertrans.M2016247

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  • Influence of cathode potential on Ti electrodeposition in molten fluoride

    Kazuyoshi Nishikawa, Sawada Humiya, Taiki Morishige, Toshihide Takenaka

    MOLTEN SALTS AND IONIC LIQUIDS 20   75 ( 15 )   199 - 206   2016

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    Language:English   Publishing type:Research paper (international conference proceedings)   Publisher:ELECTROCHEMICAL SOC INC  

    The electrolysis condition to obtain Ti metal in a CaF2-MgF2 with CaO and TiO2 has been studied at 1573K. It was shown by cyclic voltammetry that cathodic current increased below 0.8V ( vs. Mg/Mg2+) with CaO and TiO2 addition and that three reduction steps of Ti was suggested. The particles containing Ti were obtained by potentio-static electrolysis; only Ti oxide particles were detected by the electrolysis above 0.5V, while Ti metal particles did by the electrolysis below 0.4V. This result indicates that Ti metal can be electrodeposited below 0.4V (vs. Mg/Mg2+).

    DOI: 10.1149/07515.0199ecst

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  • Availability evaluation of SiC anode in chloride molten salt electrolysis

    Yoshihiro Takahashi, Toshihide Takenaka

    MOLTEN SALTS AND IONIC LIQUIDS 20   75 ( 15 )   207 - 214   2016

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    Language:English   Publishing type:Research paper (international conference proceedings)   Publisher:ELECTROCHEMICAL SOC INC  

    Carbon or graphite is commonly used to anode material in molten salt electrolysis, but they are consumed by a electrochemical reaction with a residual O(2-)in the bath. In this study, the dependence of anodic behavior in molten chloride containing O2- on some carbon materials with different structure has been investigated in LiCl-KCl-ClO melts at 723K. The anodic behavior of SiC was also investigated in the bath. In all materials, reactions of CO2 and CO32- occurred, and electrodes were consumed; a graphitization degree slightly influenced the consumption at graphite material, and the consumption of GC seemed the lowest. Although SiO2 was formed on SiC material, the consumption of SiC was not prevented completely. The unevenness of SiO2 layer on SiC might cause the consumption of SiC.

    DOI: 10.1149/07515.0207ecst

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  • Effect of electrode shape on lithium metal fog in LiCl-KCl

    Shogo Akimura, Taiki Morishige, Toshihide Takenaka

    MOLTEN SALTS AND IONIC LIQUIDS 20   75 ( 15 )   233 - 237   2016

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    Language:English   Publishing type:Research paper (international conference proceedings)   Publisher:ELECTROCHEMICAL SOC INC  

    The so-called metal fog sometimes formed during the molten salt electrolysis. In this paper, the effect of the surface shape of electrode on the metal fog formation was investigated in LiCl-KCl. Cyclic voltammetry and potentiostatic electrolysis were carried out at Mo wire electrode with/without screw cutting. The dark blue metal fog was formed at both types of electrodes, while the gray metal fog was generated only at the screw-cut electrode. The gray fog formation also depended on the diameter of the electrode; the formation was intenser at a small electrode than at a large electrode. It is concluded that the shape of electrode strongly affects the gray metal fog formation, and it is suggested that the current concentration at the edge causes the formation.

    DOI: 10.1149/07515.0233ecst

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  • Magnesium Sorting by Vibrating Particulate Bed from Mixed Metal Scrap

    Taiki Morishige, Keigo Tsujita, Soshiro Murasa, Toshihide Takenaka

    MATERIALS TRANSACTIONS   56 ( 10 )   146 - 148   2015.10

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:JAPAN INST METALS  

    As increasing the demand of Mg alloys, recycling of these alloys require for securing a metallic resource and energy conservation. A commercial metal scrap includes other structural materials such as iron, copper and aluminum alloys. These metal elements deteriorate mechanical properties or corrosion properties of Mg alloys. Therefore, these different materials were possibly removed from Mg scrap during recycling process. The separation of Al and Mg materials has difficulty except for the gravity separation. However, there is a limited difference in density between Mg and Al. In this study, Mg recovery from mixed metal scrap was attempted by dry gravity separation using solid particulate vibrating bed. Mg separation with high recovery ratio was achieved by adjusting the density of the particulate bed. It was suggested that the bulk density of the particulate bed affected the behavior of separation materials for the favorable recovery.

    DOI: 10.2320/matertrans.M2015226

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  • Removal of Impurity Fe from Mg-3 mass% Al Alloy Melt by CO2 Injection

    Taiki Morishige, Kazuchika Kurino, Toshihide Takenaka

    MATERIALS TRANSACTIONS   56 ( 3 )   454 - 456   2015

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:JAPAN INST METALS  

    The purification process is required for recycling Mg process. Selective impurity removal has an efficient purification process in the purity level of commercial Mg metal and alloys. Especially, iron impurity deteriorates the corrosion resistance of Mg alloys. Carbon addition to Mg-3 mass% Al alloy melt is an effective method for the removal of iron impurity by the formation of Fe-Al-C compounds. In this study, gas injection of carbon dioxide (CO2) into Mg alloy melt as the method of carbon addition was investigated for the separation of iron compounds. Carbon dioxide was decomposed by Mg melt and carbon substance affected the formation of iron carbide in the melt. Magnesium oxide and Fe-Al-C compound were formed in the melt slag and floated to the top of the solidified Mg-3 mass% Al alloy.

    DOI: 10.2320/matertrans.MBW201407

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  • Mg-Li合金の腐食挙動と防食法

    竹中俊英, 森重大樹

    めっき技術   28巻5号,15-20頁   2015

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  • マグネシウムリサイクルへの種々の乾式分離法の適用

    竹中俊英, 森重大樹

    環境資源工学   62, pp.123-127   2015

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  • Effect of Impurity Fe Concentration on the Corrosion Behavior of Mg-14 mass%Li-1 mass%Al Alloy

    Taiki Morishige, Kumiko Ueno, Masahiro Okano, Takayuki Goto, Eiji Nakamura, Toshihide Takenaka

    MATERIALS TRANSACTIONS   55 ( 9 )   1506 - 1509   2014.9

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:JAPAN INST METALS  

    Mg-Li system alloys with over 11 mass% Li have an excellent cold-workability in Mg alloys due to the bcc-structured crystal system. However this system alloys have poor corrosion resistance caused by Li solid-solution alloy. The corrosion resistance of conventional hcp-Mg alloys is influenced by the composition of impurity elements. Particularly, minute iron element deteriorates the corrosion resistance of Mg alloy and there is a threshold concentration on the corrosion rate in Mg alloys. In this study, the effect of iron element on the corrosion resistance of Mg-Li alloy was investigated by addition of iron. The corrosion resistance of Mg-Li with no Fe addition was higher than conventional Mg alloy. The corrosion rate of Mg-Li alloy increased with increasing iron concentration. However, there is no threshold iron concentration affected to the corrosion resistance on Mg-Li alloy.

    DOI: 10.2320/matertrans.MAW201405

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  • Effect of Cooling Rate and Dissolved Oxygen Content on Sulfide Morphology in Cu-Sn-Zn-S Alloy Castings

    Ryoko Yoshida, Toru Maruyama, Hiroyuki Abe, Ryozo Matsubayashi, Masakazu Teramura, Takeshi Kobayashi, Toshihide Takenaka

    Journal of Japan Foundry Engineering Society   86巻, 1号, 26-30頁 ( 1 )   26 - 30   2014.1

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    Language:Japanese   Publisher:Japan Foundry Engineering Society  

    <p>  The sulfide morphology in Cu-Sn-Zn-S alloy castings was investigated to understand the transition from eutectic solidification to monotectic solidification. The sulfide morphology was observed to clarify whether sulfides were formed by eutectic reaction or monotectic reaction. The cooling rate during solidification was changed by changing mold materials, mold shapes, and mold sizes. The holding time from deoxidation of melt to casting was changed to understand the effect of deoxidation on the sulfide morphology. Eutectic sulfides were formed when the melt was cooled slowly, and the amount of monotectic sulfide increased with increasing cooling rate. The transition from eutectic morphology to monotectic morphology occurred at cooling rates of 0.5K/s to 1.0K/s. Just after deoxidation with Cu-P alloys, sulfides were formed by monotectic reaction. However, with increasing holding time of the melt after deoxidation, the amount of the sulfides formed by eutectic reaction increased.</p>

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  • Electrochemical Behavior of Ti in Molten Fluoride-Oxide System

    Y. Yamanaka, T. Morishige, T. Takenaka

    MOLTEN SALTS AND IONIC LIQUIDS 19   64 ( 4 )   275 - 283   2014

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    The cathodic reaction of Ti has been studied in a CaF2-MgF2 bath with CaO and TiO2 at 1373K. Cyclic voltammograms were measured in the baths of various compositions, and the dependence of the cathodic reaction of Ti on the bath composition was discussed. With reference to the results of the cyclic voltammetry, Ti metal deposition by potentio-static electrolysis was attempted. It was shown that the reduction sequence of Ti consisted of three steps, and Ti metal was deposited under the suitable condition. The cathodic behavior of Ti was influenced by the molar ratio of TiO2 to CaO in the melt. Considering the previous results of Ti electrolysis by using DC-ESR unit, it is strongly suggested that a binuclear complex ion of Ti with O, such as Ti2O76-, affects the reduction sequence of Ti in CaF2-CaO-TiO2 and CaF2-MgF2-CaO-TiO2 baths.

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  • Exfoliation Corrosion Behavior of Cold-Rolled Mg-14 mass% Li-1 mass% Al Alloy in NaCl Solution

    Taiki Morishige, Hirokazu Doi, Takayuki Goto, Eiji Nakamura, Toshihide Takenaka

    MATERIALS TRANSACTIONS   54 ( 9 )   1863 - 1866   2013

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    Cold-rolled Mg-Li system alloys represent the exfoliation corrosion on the surface of the longitudinal and the transverse sections. In this study, the origination of the exfoliation corrosion of the cold-rolled Mg-Li alloy was clarified. In the initial stage of the corrosion, the oxide film formed immediately on the surface of each section, and then the film destruction with a remarkable bubble generation was observed in a certain spot. There were microcracks on the trace of the film destruction along the grain boundary. The corrosion resistance in the annealed specimen was more than that in the as-rolled specimen because the microstructure of the as-rolled specimen has elongated and thinned grains by severe cold rolling. The exfoliation corrosion was not observed in the annealed specimen, because the annealed specimen has homogeneous equiaxial grains. The successive film destruction in annealed specimen progressed along the grain boundary to random direction. Moreover, the initiation time of the bubble generation was delayed in the annealed specimen.

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  • Fe elimination from Mg by carbide formation

    Toshihide Takenaka, Ryunosuke Morikawa, Taiki Morishige

    Materials Science and Technology Conference and Exhibition 2013, MS and T 2013   3   1550 - 1554   2013

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    Iron should be removed in the Mg recycling flow because of its ill effect to the corrosion property. In this study, the Fe elimination from Mg and its alloys has been investigated by carbon addition in liquid Mg metal containing Fe. Iron in liquid Mg metal was hardly removed by only the carbon addition. The existence of Ca in Mg melt was helpful for the Fe removal, but the excess Ca addition resulted in an adverse effect. In Mg metal containing Al, Fe was removed by C addition, and AlFe3C was detected. In all the cases, Fe and its compound tended to concentrate around the bottom and the shrinkage cavity, but the Fe compounds still remained even in the purified ingot. The control of Fe precipitation should lead to the better Fe elimination. Copyright © 2013 MS&amp
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  • Solidification Cracking Resistance in Permanent Mold Casting Process for Sulfide Dispersed Lead Free Bronze Castings

    Ryoko Yoshida, Toru Maruyama, Hiroyuki Abe, Ryozo Matsubayashi, Masakazu Teramura, Takeshi Kobayashi, Toshihide Takenaka

    Journal of Japan Foundry Engineering Society   84巻, 7号, 383-388頁 ( 7 )   383 - 388   2012.7

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    The applicability of the permanent mold casting process for the new type of lead-free bronze with dispersed sulfide was evaluated by comparison with other conventional copper alloys, such as leaded bronze, leaded brass, and lead-free bronze containing bismuth. The copper alloys were cast into the permanent mold for the solidification cracking test. The relationship between the degree of cracking and solidification temperature range was examined. <br>&nbsp;&nbsp;The new lead-free bronze with dispersed sulfide was more unbreakable than the other copper alloys. The smaller the solidification temperature range, the harder it was for solidification cracking to occur. Comparison of the new lead-free bronze with the leaded bronze and lead-free bronze containing bismuth indicated differences in the dendrite shape near the fracture and distribution of the residual melt segregated to one area towards the end of the solidification. The new lead-free bronze may also have a solidification morphology that makes it more difficult to crack, allowing it to be applied to permanent mold casting compared to other copper alloys. Its level of applicability is more or less the same as brass castings.

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  • Electrodeposition of Ti in Molten Salt at High Temperature

    Toshihide Takenaka, Hidetaka Matsuo, Masahiro Kawakami

    TI-2011: PROCEEDINGS OF THE 12TH WORLD CONFERENCE ON TITANIUM, VOL I   vol.1, pp.75-78   75 - 78   2012

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    Direct electrolysis of Ti-Fe alloy has been attempted in a CaF2-CaO-TiO2-FeO bath by the process using a direct -current electro-slag remelting unit. The electrolysis strongly depended on the electrolysis conditions, and Ti -Fe alloy was successfully obtained in the bath of a particular composition. The strong influence of the bath composition was also seen in the Ti and Ti -Al electrolysis in the previous, and suggested that the cathodic reaction of Ti was affected by the change in the bath composition. To clarify the influence of the bath composition, electrochemical measurement was carried out in a CaF2-MgF2-CaO-TiO2 bath. The cathodic current due to Ti reduction was observed by cyclic voltammetry, and the change in the shape of cyclic voltammogram with the bath composition was found. This result indicated the change in the electrode reaction of Ti, and explained the results of the Ti electrolysis with a direct -current electro-slag remelting unit.

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  • Anodic Reactions on Some Materials in LiCl-KCl Melt

    T. Takenaka, M. Umehara, D. Araki, T. Morishige

    MOLTEN SALTS AND IONIC LIQUIDS 18   50 ( 11 )   127 - 134   2012

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    The anodic reactions on some materials in LiCl-KCl eutectic melt have been investigated. Palladium and Mo were dissolved though Mo showed passivation behavior. In the melt including Li2O, O-2 gas generation occurred at both metal anodes along with their anodic dissolution. At the graphite anode, some anodic reactions besides the Cl-2 gas generation reaction were observed in the melt with Li2O. The visual observation and the weight change of the anode indicated that the anodic reaction without gas generation and the electrode consumption preceded the CO2 gas generation. The potential of the CO2 gas generation reaction on graphite looked more positive than that of the O-2 gas generation on Pd and Mo, which suggested the overpotential of the CO2 generation reaction on graphite was rather large in the melt.

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  • Removal of Impurities in Steel by DC-ESR Operation Reviewed

    Toshihide Takenaka, Masatoshi IIZUKA

    J. Rare Earth   vol.29(sp), pp.51-54   2011.12

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  • 高温溶融塩化物中での電極反応 ~電気化学挙動と実現象~

    竹中俊英

    溶融塩および高温化学   vol.54(1), pp.5-11   2011

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  • Direct Production of Ti-Fe Alloy in Liquid by Electrowinning in Molten Slag

    Toshihide Takenaka, Hidetaka Matsuo, Masahiro Kawakami

    ISIJ INTERNATIONAL   51 ( 11 )   1762 - 1765   2011

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    Aiming at the direct production of Ti-Fe alloy, its direct electrowinning has been attempted in a CaF(2)-CaO-TiO(2)-FeO bath by using a direct-current electro-slag remelting unit. The experiments were carried out in the slag where the molar ratio of CaO to TiO(2) was fixed as 1.5, and the influence of the molar ratio of FeO to TiO(2) was mainly investigated. The experimental results proved that Ti-Fe alloy in liquid could be obtained at the limiting bath compositional range. At the molar ratio of FeO to TiO(2) was 0.90, both the Ti content in the deposit and the cathodic current efficiency were the best under the conditions in this study; the Ti content reached about 50 wt%, and the cathodic current efficiency also did about 50% at best.

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  • Evaluation of joint interface of friction stir welding between dissimilar metals using HTS-SQUID gradiometer

    Y. Mashiko, Y. Hatsukade, T. Yasui, H. Takenaka, Y. Todaka, M. Fukumoto, S. Tanaka

    PHYSICA C-SUPERCONDUCTIVITY AND ITS APPLICATIONS   470 ( 20 )   1524 - 1528   2010.11

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    In this study, we investigated conductive properties of joint interfaces of friction stir welding (FSW) between dissimilar metals, stainless steel SUS304 and aluminum A6063, using a SQUID nondestructive evaluation (NDE) system. With current injection method, the current maps above the FSW specimens jointed under various conditions were measured by a HTS-SQUID gradiometer. The conductivities of the joint interfaces, which were estimated from the current maps, differed between the joint conditions. By destructive tests using optical microscope, large voids were observed on the joint interfaces with low welding speed that generated excess heating. In case of one specimen, which was welded with welding speed of 500 and 200 mm/min, the conductivity of the former was higher than that of the latter, although the inside voids in the respective regions were not much different. From these results, it is suggested that the current maps were influenced not only by the conductivity of the joint interface but also by inside voids. By hardness test on the SUS boards near the interfaces, only the SUS jointed with 200 mm/min was about half softer than its matrix. (C) 2010 Elsevier B.V. All rights reserved.

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  • High Temperature Electrolysis of Ti and Its Alloys with a DC-ESR Unit

    Toshihide Takenaka, Hidetaka Matsuo, Mitsuru Sugawara, Masahiro Kawakami

    COST-AFFORDABLE TITANIUM III   436   85 - 91   2010

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    Direct electrolysis of Ti and its alloys has been attempted by the process using a DC-ESR unit. The concept of the process is explained in detail, and the expected key issues are commented. Liquid Ti metal was obtained in a CaF(2)-CaO-TiO(2) bath, and electrolysis by using a new type of the electrolytic cell was also tried. Ti-Al alloy was successfully deposited in a CaF(2)-CaO-TiO(2)-Al(2)O(3) bath, whereas Ti-Si alloy was not obtained in a CaF(2)-CaO-TiO(2)-SiO(2) bath yet. Ti-Fe alloy was extracted in CaF(2)-CaO-TiO(2)-FeO bath of a particular composition. A common correlation between the cathodic current efficiency and the average consumed electric power seen in the Ti, Ti-Al and Ti-Fe electrolysis suggested the importance of sufficient temperature in the process. The bath composition also affected the temperature through the change in the electric conductivity of the bath.

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  • Anodic Dissolution and Chemical Reduction of Noble Metals in LiCl-KCl Melt

    Toshihide Takenaka, Keisuke Iwasa, Yoshifumi Hashigaya, Masanobu Izaki

    ELECTROCHEMISTRY   77 ( 8 )   633 - 635   2009.8

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    The anodic behaviors of Pd, Pt and Au have been investigated in LiCl-KCl eutectic melt at 683 K. Chemical reduction of the dissolved noble metal ions by H-2 and CH4 has been also carried out. It was shown that I'd and ALL could be dissolved anodically with a large dissolution rate, and that the dissolution rate of Pt was limited because of its passivation behavior. Fine particles of these noble metals were obtained by H-2 or CH4 reduction though they combined together.

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  • チタン、チタン合金の直接電解製造~液体金属の電析は可能か?~

    竹中俊英, 川上正博

    溶融塩および高温化学   52巻3号,109-116頁   2009

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  • Influence of conversion coating conditions with rare earth elements on corrosion resistance of Mg alloys

    Nobuo Uesaka, Yuichi Shikai, Toshihide Takenaka

    ECS Transactions   16 ( 43 )   39 - 46   2009

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    Influence of the conversion coating with some rare-earth elements, such as La, Y, Sm, Nd and Ce, on corrosion resistance of Mg alloy has been studied. Effect of pretreatment, such as alkaline degrease, acid pickling and surface activation, has been also investigated. The surface of Mg alloy was covered with the so-called dry mad structure by the coating. The coating layer was a thin oxide film containing Mg, Al and rare earth element. F and P were detected in the coating with the pretreatment in addition. The corrosion resistance of Mg alloy against salt water was significantly improved by the conversion coating by immersion in the solution including both Mg(NO3)2 and rare earth nitrate. The corrosion resistance was improved by applying the pretreatment, further. ©The Electrochemical Society.

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  • Direct electrodeposition of Ti and Ti alloys in high temperature melt

    Toshihide Takenaka, Hidetaka Matsuo, Mitsuru Sugawara, Akihiro Matsuyama, Masahiro Kawakami

    pp.721-730   2009

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  • Desiliconization and Decarburization of Molten Pig Iron by Injection of Weakly Oxidizing Gas Reviewed

    Toshihide Takenaka, Tatsuya Aihara, Masahiro Kawakami, Tomohiro Kojima

    TETSU TO HAGANE-JOURNAL OF THE IRON AND STEEL INSTITUTE OF JAPAN   94 ( 11 )   483 - 490   2008.11

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    Water vapor or carbon dioxide gas was injected into molten pig iron in order to oxidize silicon without oxidizing iron. When water vapor was injected, decarburization was predominant at high temperature. The oxidation of silicon occurred at low temperature of 1473 K. When carbon dioxide gas was injected, both of silicon oxidation and decarburization occurred simultaneously. But the former was predominant at lower temperature, while the latter at higher temperature, At 1523 K, the silicon content was lowered at 0.16 mass %. The oxidation of iron was not observed at all. The rate controlling step of silicon oxidation and decarburization are judged the mass transfer in the gas phase. With the increase in gas injection rate, the reaction rates decreased, because of bubble integration. The slag addition decreased the reaction rates, because the reactions were blocked on the melt surface.

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  • Improvement of corrosion resistance of magnesium alloys by surface film with rare earth element

    Toshihide Takenaka, Yuji Narazaki, Nobuo Uesaka, Masahiro Kawakami

    MATERIALS TRANSACTIONS   49 ( 5 )   1071 - 1076   2008.5

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    Conversion coating by immersion in solution including Mg(NO3)(2) and/or La(NO3)(3) was applied to commercial Mg alloys: AZ31, AZ61, AZ91 and AM60. The formed layer was analyzed, and the corrosion resistance of the specimen against salt water was investigated. The influences of the coating conditions on the characteristics of the layer and on the corrosion behavior were discussed. A thin oxide layer was formed on the surface of the specimen by the conversion coating, and La was contained in the layer obtained in the solution including La(NO3)(3). The corrosion resistance of Mg alloys wasn't remarkably improved by the conversion coating using either Mg(NO3)(2) solution or La(NO3)(3) solution, while it was particularly bettered by the coating using the solution including both Mg(NO3)(2) and La(NO3)(3). The good corrosion resistance was obtained under the wide concentration ratio of La(NO3)(3) to Mg(NO3)(2), and the optimum coating conditions for each alloy was specified. The pretreatment, such as the alkaline degrease, the acid pickling and the surface activation, was effective for the uniform coating on large specimen.

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  • 弱酸化成ガス吹き込みによる溶鉄の脱珪と脱炭 Reviewed

    竹中俊英, 粟飯原達也, 川上正博, 小嶋智宏

    鉄と鋼   94巻11号,23-30頁   2008

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  • Influence of some factors upon electrodeposition of liquid Li and Mg

    Toshihide Takenaka, Kouji Shigeta, Hiroshi Masuhama, Kazushi Kubota

    ECS Transactions   16 ( 49 )   441 - 448   2008

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    Change in the morphology of electrodeposited Mg with codeposition of La has been investigated in a MgCl2-NaCl-CaCl2 bath containing LaCl3. The morphology of Mg electrodeposit remarkably changed with the codeposition of a small amount of La, and the electrochemical behaviors were influenced consequently. These results suggested the possibility that the efficiency of electrolysis could be improved by the codeposition. In this study, metal fog formation of Li has been also studied in a LiCl-KCl bath with reference to the formation in pure LiCl melt or in equi-molar NaCl-KCl melt. The results suggested that the mechanism of the metal fog formation in the Li electrolysis and the Na electrolysis was different. Based on the consideration of the formation mechanism, the ways to control the metal fog formation were discussed. ©The Electrochemical Society.

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  • Influence of bath composition on Ti electrolysis in CaF2-CaO- TiO2 melt

    Toshihide Takenaka, Mitsuru Sugawara, Hidetaka Matsuo, Akihiro Matsuyama, Masahiro Kawakami

    ECS Transactions   16 ( 49 )   221 - 228   2008

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    Ti electrolysis by using a DC-ESR unit was performed in a CaF 2-CaO-TiO2 bath, and the influence of the bath composition was discussed. Ti metal in liquid was electrodeposited though some impurity elements were contained. The cathodic current efficiency strongly depended on the bath composition, and reached about 25% in the bath where the molar ratio of CaO to TiO2 was 1.5. The consumed electric power was also affected by the bath composition so that the close relationship between the cathodic current efficiency and the electric power was seen. The influence of the bath composition was considered due to the change in the species in the bath, and Ca3Ti2O7 seemed suitable for Ti deposition. ©The Electrochemical Society.

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  • Improvement of corrosion resistance of magnesium metal by rare earth elements

    Toshihide Takenaka, Takami Ono, Yuji Narazaki, Yusuke Naka, Masahiro Kawakami

    ELECTROCHIMICA ACTA   53 ( 1 )   117 - 121   2007.11

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    Mg metal containing rare earth metals (REs) can be electrowon directly by molten salt electrolysis. The clarification of the optimum RE content in Mg is necessary to fix the electrolytic conditions in the direct electrowinning of Mg with RE. From this point of view, effect of RE addition in Mg metal on its corrosion property was studied in detail in this study. The specimen was prepared by adding La, Nd, or Cc in melted Mg metal, and its corrosion resistance was examined by an immersion test in 3 mass%-NaCl solution at room temperature. The corrosion resistance of Mg was improved greatly by adding a small amount of RE, whereas the excess addition of RE deteriorated the corrosion resistance. The optimum RE content was about 0.5 mass%. In this study, the corrosion property of Mg with an artificial surface oxide layer was also studied to clarify the effect of surface oxide. The corrosion resistance of Mg was particularly strengthened by conversion coating in a solution including La(NO3)(3), Nd(NO3)(3), or Ce(NO3)(3), with Mg(NO3)(2). This result suggests that the surface oxide film consisting of both Mg and RE gives ideal corrosion resistance to Mg metal. Mg metal with conversion coating including RE should also be of use as a corrosion-resistant material. (C) 2007 Elsevier Ltd. All rights reserved.

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  • Anodic behaviors of noble metals in eutectic LiCl-KCl melt

    Toshihide Takenaka, Masahiro Kawakami

    ECS Transactions   3 ( 35 )   385 - 393   2007

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    The anodic behaviors of some noble metals and their alloys in dehydrated LiCl-KCl eutectic melt have been studied as a basic study on a new reprocessing process of spent UO2 nuclear fuel by an electrorefining technique. Palladium and Ru dissolved anodically as Pd2+ and Ru3+, respectively. Rhodium dissolved as Rh3+, and was passivated by surface film formation. The potentials where the steady dissolution current density was 10-3 A/cm2 were 3.02V for Pd, 3.08V for Rh and 3.12V for Ru, These values were more positive than the reported value of UO2. The anodic behaviors of Pt-Rh and Pd-Ru alloys were explained from those of each component, and no peculiar influence by alloying was seen. These results indicate that the noble metals and alloys can be separated from UO2 by leaving them in the anode by the control of the anode potential. copyright The Electrochemical Society.

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  • Effect of Al2O3 content on tile electro-winning of Ti in DC-ESR operation

    M. Kawakami, T. Takenaka, T. Kawabata, A. Matsuyama, S. Yokoyama

    INNOVATIONS IN TITANIUM TECHNOLOGY   pp.145-153   137 - +   2007

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    In order to make titanium ingot directly from molten slag, the metal pool was tried to form and used as the cathode. The electro-slag remelting (ESR) unit was used for the purpose. The unit is composed of water-cooled copper mold and the DC power source of 2000 A and 100V. The graphite electrode was used for anode and the base plate was used for cathode. The slag was composed of the CaF2-CaO-Al2O3 system. By the addition of Al2O3 to the slag, the electro-deposit of Ti-Al was obtained. The current efficiency increased with the supplied electric power. It is concluded that the mechanism of high current efficiency should be the formation of liquid metal deposit due to high heat generation and the suppression of metal fog formation and suboxide formation of titanium.

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  • Extraction of titanium in a liquid state from molten slag with a DC-ESR unit Reviewed

    Akihiro Matsuyama, Takuya Kawabata, Mitsuru Sugawara, Toshihide Takenaka, Masahiro Kawakami

    pp.177-180,   2007

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  • Titanium Coating on Steel by Disproportionation Reaction in Molten Salt Reviewed

    Toshihide Takenaka, Masataka Muro, Masahiro Kawakami

    pp.1683-1686   2007

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  • Development of New Titanium Production Process Reviewed

    Masanori Yamaguchi, Yuichi Ono, Susumu Kosemura, Wataru Kagohashi, Toshihide Takenaka

    pp.143-146   2007

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  • Coating of titanium alloy by using disproportionation reaction in molten chloride Reviewed

    Masataka Muro, Shunsuke Miyazawa, Toshihide Takenaka, Masahiro Kawakami

    Nippon Kinzoku Gakkaishi/Journal of the Japan Institute of Metals   70 ( 2 )   126 - 129   2006.2

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    The dependence of Ti alloy coating by using a disproportionation reaction in molten chloride upon the coating conditions has been investigated. The corrosion resistance of the coated specimen was also examined. An equimolar NaCl-KCl mixture was melted in a quartz crucible under the atmosphere of high-purity Ar, and TiCl3 was added with Ti sponge into the mixture. Iron, carbon steel, Ni and stainless steel plates were immersed in the bath at 1100∼1250 K for a scheduled period. After the immersion, the Fe plate was covered with a dense layer of Ti-Fe alloy of which thickness was more than 10 μm. The layer adhered to the surface, and mainly consisted of Fe2Ti. Carbon steel was covered with a similar Ti-Fe layer to that on the Fe plate, and carbides were not found. The surface of the Ni plate was fully covered with NiTi2, and a dense layer of Ni3Ti was formed under the NiTi2 layer. The Ti alloy layer on Ni was thicker than those on Fe and carbon steel under the same condition. A dense layer of a few μm, where Ti content was about 90 mass%, was observed on the surface of the stainless steel plate after the immersion. The thickness of the Ti alloy layer was in proportion to the square root of the immersion time, and its formation rate was not affected very much by the initial TiCl3 concentration. These results indicated that the formation rate of Ti alloy layer was mainly controlled by the diffusion of elements in the formed layer. The corrosion resistance of Fe and carbon steel against salt water was significantly improved by the Ti alloy coating on the surface. © 2006 The Japan Institute of Metals.

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  • 溶融塩化物中での不均化反応を用いたチタン合金コーティング Reviewed

    室昌孝, 宮澤俊輔, 竹中俊英, 川上正博

    日本金属学会誌   第70巻2号,126-129頁   2006

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  • Characterization of thermal annealing effects on the evolution of coke carbon structure using Raman spectroscopy and X-ray diffraction

    Masahiro Kawakami, Haruki Kanba, Kazunori Sato, Toshihide Takenaka, Sushil Gupta, R. Chandratilleke, Veena Sahajwalla

    ISIJ INTERNATIONAL   46 ( 8 )   1165 - 1170   2006

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    An experimental study was conducted to monitor the evolution of coke carbon structure during thermal annealing in a temperature range from 1 273 to 2 473 K in a bench-scale reactor. Coke carbon structure was characterized by using Raman Spectroscopy and the X-ray Diffraction. The Raman spectra of most of the cokes displayed two broad peaks G* (11620 cm(-1)) and D* (1360 cm(-1)). Both Raman peaks were deconvoluted into five peaks namely G, D, D', R, and R-2. On the basis of area under the respective band peaks, new structural parameters were obtained to quantify graphitic (G), graphitic defect (D) and random (R) carbon fractions of cokes.
    XRD analysis was used to show that stack height carbon crystallite, Lc, of coke increases with increasing annealing temperature while the impact of annealing duration was not significant particularly up to 1873 K. On the other hand, average carbon crystallite width, La, did not improve significantly up to 1 873 K, and increased rapidly after subsequent rise in the annealing temperature. It appears that during annealing up to 1873 K, modification of coke carbon structure could occur due to loss of basal carbon as a consequence of in-situ gasification.
    The lateral expansion of carbon crystallite, La, was related to relative intensity or shape of Raman band peaks such that both parameters did not change significantly up to an annealing temperature of 1 873 K. At higher annealing temperatures, La values of coke increased with decreasing D/G ratio. Lateral expansion of carbon crystallite was attributed to progressive reduction of defects of graphitic carbon of coke, which can be monitored by D fraction of Raman Analysis. Combined Raman and XRD analysis suggested that rapid graphitization of coke may not occur along all dimensions until the annealing temperature exceeds 1873 K.
    Combining XRD and Raman analysis would provide a comprehensive evaluation of the evolution of coke carbon structure at different temperatures and their subsequent implications on the efficiency of various ironmaking operations.

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  • An attempt at direct ingot making of titanium by the electro-winning from molten slag with DC-ESR unit

    M. Kawakami, T. Takenaka, M. Orisaka, T. Kawabata, A. Matsuyama, S. Yokoyama

    SOHN INTERNATIONAL SYMPOSIUM ADVANCED PROCESSING OF METALS AND MATERIALS, VOL 7   vol.7, pp.373-381   373 - +   2006

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    In order to make titanium ingot directly from molten slag, the metal pool was tried to form and used as the cathode. The electro-slag remelting (ESR) unit was used for the purpose. The unit is composed of water-cooled copper mold and the DC power source of 2000 A and 100V. The graphite electrode was used for anode and the base plate was used for cathode. The commercial and re-melted slag of CaO-CaF2 was melted in the mold with the addition of TiO2. The following reactions are expected to occur.
    Ti4+ + 4e = Ti at cathode
    2O(2-) + 2C = 2CO + 4e at anode
    During the process, large amount of molten slag splashed out from the mold, showing the CO evolution at anode. The metal deposit was obtained but in the form of block and piled upon the baseplate. The metal pool was not obtained perfectly because of shortage of heat supply. The cathodic current efficiency was 60 % at maximum. The metal deposit contained much impurity. In order to reduce the impurity and increase the current efficiency, the effect of electrode distance was examined. The electro-slag re-melting of titanium was tried in order to examine the condition to make metal pool.

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  • Catalytic effect of some inorganic materials on the gasification reaction of graphite and coke

    M. Kawakami, T. Iwabuchi, Y. Takashima, H. Kanba, T. Takenaka, S. Yokoyama

    SOHN INTERNATIONAL SYMPOSIUM ADVANCED PROCESSING OF METALS AND MATERIALS, VOL 2   vol.2, pp.155-162   155 - +   2006

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    In the blast furnace, the reduction of iron oxide and gasification of coke occur simultaneously. It is well accepted that the gasification reaction controls the simultaneous reaction. Therefore, it is important to develop highly reactive carbonaccous materials. It is also known that the reaction is accelerated catalytically with the addition of some materials. In the present work, the catalytic effect of iron, nickel and CaO on the gasification of graphite and coke was examined. The catalytic effect of iron, nickel and CaO on the reaction rate of graphite was noticed The effect was larger at lower temperature. At 1373 K, the effect almost vanished. The effect was larger in the order of CaO, iron and nickel. The reaction rate of de-ashed coke increased by the addition of iron and nickel. The effect of iron was larger than that of nickel. The effect was larger at higher temperature, which was contrary to the case of graphite. The reactive surface area increased also by the addition. Therefore, the catalytic effect on reaction rate might be attributable to the increase in the reactive surface area.

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  • Effect of rare earth metals on corrosion resistance of MG metal

    Toshihide Takenaka, Takami Ono, Yuji Narazaki, Masahiro Kawakami

    SOHN INTERNATIONAL SYMPOSIUM ADVANCED PROCESSING OF METALS AND MATERIALS, VOL 7   vol.7, pp.509-516   509 - +   2006

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    Improvement of corrosion resistance of Mg metal by addition of rare earth metal (RE) was studied, and the effect of surface oxide layer with RE was investigated. The corrosion resistance of Mg was remarkably improved by adding a small amount of RE, and the suitable RE content was clarified. The corrosion resistance of Mg was particularly bettered by conversion coating using a solution including both RE(NO3)(3) and Mg(NO3)(2). This result indicates that the surface oxide layer consisting of both Mg and RE gives good corrosion resistance to Mg metal. In this study, direct electrodeposition of Mg metal containing RE was also tried in molten chloride with RE chloride, and it was shown that electrolysis could be performed stably. The RE content in the deposited Mg metal was depended on the concentration of RE chloride in the bath and the cathode potential, and Mg metal containing the suitable RE content for its corrosion protection was obtained easily by direct electrolysis.

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  • Electrochemical reduction of Ti ion in various molten salt systems

    T Takenaka, M Kawakami

    JOURNAL OF RARE EARTHS   23   21 - 25   2005.10

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    The electrochemical behavior of Ti was investigated in fluoride and chloride-fluoride melts. The electrode reaction of Ti in a fluoride-oxide mixture above 1300 K was also studied. In a eutectic mixture of LiF-NaF-KF with K2TiF6, only one pair of cathodic and anodic current peaks by the reaction of Ti was observed in a cyclic voltammogram at 773 K, while some cathodic and anodic current peaks appeared at higher temperature. Ti metal was obtained by potentiostatic electrolysis in this melt. Some cathodic and anodic current peaks by the reaction of Ti were observed in a KCl-NaCl-KF-NaF melt at 873 K in a cyclic voltammogram, and the shape resembled that in the LiF-NaF-KF melt at the similar temperature. Two pairs of cathodic and anodic current peaks appeared with K2TiF6 addition in a LiCl-KCl-LiF-KF melt at 653 K in a cyclic voltammogram, and Ti metal deposited by potentiostatic electrolysis. These results show that the electrochemical reduction of Ti ion in molten salt systems is strongly affected by the composition of the bath and the operation temperature. A chloride melt including some amount of fluoride and having a lower melting point should be preferable to perform effective Ti electrolysis. In a CaF2-MgF2-CaO melt above 1300 K, some cathodic and anodic current peaks appear with TiO2 addition in a cyclic voltammogram, and the shape of the voltammogram does not change remarkably with temperature. The Ti ion in this melt seemed to be reduced to Ti metal via multi steps. From the experimental results in the CaF2-MgF2-CaO melt, the deviation in the deposition potentials between Ti and Ca is estimated at IV in a CaF2-CaO melt.

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  • Direct electrodeposition of Mg containing La in molten salt and its corrosion property

    T Takenaka, Y Naka, N Narukawa, T Noichi, M Kawakami

    ELECTROCHEMISTRY   73 ( 8 )   706 - 709   2005.8

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    Direct electrodeposition of Mg metal containing La has been investigated in eutectic MgCl2-NaCl-KCl melt including LaCl3. Electrolysis in the salt was performed stably, and Mg metal containing La was electrodeposited. The La content in the deposited Mg strongly depended. on the concentration of LaCl3 in the molten salt and the cathode potential. Conversely, Mg metal containing the demanded amount of La should be produced easily by controlling the LaCl3 concentration and the cathode potential. The corrosion resistivity of the Mg metal containing La in salt water was also measured. The corrosion resistivity changed with the La content in Mg, and was as good as that of AZ31 when the La content was about 0.5 similar to 3 mass%. It is concluded that the Mg metal containing La which shows good corrosion resistivity can be produced directly by the electrolysis in the molten salt.

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  • Electro Winning of Titanium from Molten Salt with ESR Unit Reviewed

    Masahiro Kawakami, Masayuki Orisaka, Takuya Noichi, Tatsuya Hashimoto, Toshihide Takenaka

    pp.135-138   2005

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  • Structure analysis of coke, wood charcoal and bamboo charcoal by Raman spectroscopy and their reaction rate with CO2

    M Kawakami, T Karato, T Takenaka

    ISIJ INTERNATIONAL   45 ( 7 )   1027 - 1034   2005

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    In order to discuss the reactivity of carbonaceous materials with CO2, the Raman spectroscopy analysis was carried out. Nine kinds of materials were examined. The Raman spectra of ordered materials could be assigned to the graphite structure and its defect, but those of disordered materials could not. New parameters were derived to evaluate the structure of the latter. Using the parameters, the structure change was followed during high temperature heat treatment. The disordered material consists of random structure, graphite structure and its defects. The random structure changes to the graphite structure with many defects and the defects decrease with the heat treatment temperature. The reaction rate constant is evaluated. It increases when the structure changes from the random structure to the graphite structure with many defects. After the change, it decreases with decreasing the defects in graphite structure. Thus, the most reactive material should consist of the graphite structure with many defects.

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  • Separation of Elements in Stainless Steel by Chemical and Electrochemical Methods Reviewed

    Toshihide Takenaka, Masahiro Kawakami

    vol.18(1), pp.39-47   2005

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  • Mechanism of simultaneous decarburization and nitrogen removal by blasting iron ore powder on to molten steel surface Reviewed

    Masahiro Kawakami, Masuo Inouye, Jeong Sik Kim, Toshihide Takenaka, Seiji Yokoyama

    Tetsu-To-Hagane/Journal of the Iron and Steel Institute of Japan   90 ( 6 )   414 - 421   2004

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    In order to develop the effective way of nitrogen removal from molten steel in the electric arc furnace steelmaking, an attempt was made to accelerate the reaction by the simultaneous decarburization. The iron ore powder was blasted on to the molten steel surface with Ar carrier ggas under atmospheric pressure. The melt was 20kg. The temperature was 1850 to 1950K. The gas flow rate was 3.33 and 4.17×10-4m3/s (STP). The ore blasting rate was 0.167, 0,417 and 0.500 g/s. The results are summarized as follows
    (1) By the blasting of iron ore, the decaburization occurs resulting in the acceleration of nitrogen removal several times than the mere Ar blasting. (2) Under the hard blasting condition, the nitrogen content decreased from 70 to 28 ppm for 1,000 s, while the carbon content decreased from 0.55 to 0.12 wt%. (3) When the carbon content is larger than 0.09 wt%, the decarburization was controlled by the oxygen transfer and CO bubbles are formed in the melt. When it is less than 0.09 wt%, however, the decarburization was controlled by the carbon transfer and the reaction occurs only on the melt surface. (4) It is concluded that the effective nitrogen removal is possible even under atmospheric pressure, in the ranger where the decarburization reaction is controlled by the oxygen transfer. (5) The effective interfacial area is 7 times at most as much as the cross sectional area of furnace.

    DOI: 10.2355/tetsutohagane1955.90.6_414

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  • Possibility of several steelmaking reactions by the injection of H 2 into molten steel Reviewed

    Masahiro Kawakami, Takahiko Maeda, Toshihide Takenaka, Seiji Yokoyama

    Tetsu-To-Hagane/Journal of the Iron and Steel Institute of Japan   90 ( 6 )   422 - 428   2004

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    An attempt was made to utilize H2 for the secondary refining in steelmaking process, because H2 would react with [O] and [S] without any inclusions and accelerate the nitrogen removal from the molten steel. The 20kg of plain carbon steel was melted in the induction furnace. The gases of Ar, N2 and H2 were injected from the bottom. The temperature was ca. 1880K. The gas flow arte was 2.50 and 3.33 × 10-4m 3/s (stp). The results are summarized as follows. (1) The rate of nitrogen remove by H2 injection was 1.5 to 2.6 times larger than by Ar injection. The mechanism was (i) reduction of poisoning effect of [O], (ii) acceleration of mass transfer in the gas phase and (iii) finer bubble dispersion due to Marangoni effect. (2) The deoxidation proceeded down to 6.0 ppm by H2 injection. But this result was the sum of deoxidation by [C] and H2. Taking into account of oxygen penetration from the outside of furnace, deoxidation by H2 was evaluated. The H2 bubbles leave the molten steel far from water vapor saturation. One reason is that the deoxidation process should be controlled not only by mass transfer in the molten steel but also that in gas phase. The other reason is the shallow molten steel bath. (3) Neither desulfurization nor methane formation occurred by H 2 injection. (4) The [H] content decreased down to less than 1 ppm by Ar injection for 420 s.

    DOI: 10.2355/tetsutohagane1955.90.6_422

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  • Micro pore structure and reaction rate of coke, wood charcoal and graphite with CO2

    M Kawakami, H Taga, T Takenaka, S Yokoyama

    ISIJ INTERNATIONAL   44 ( 12 )   2018 - 2022   2004

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    The reaction rate of coke, wood charcoal and graphite with pure CO, were obtained at 1 173 and 1 373 K. The change in the reaction rate, specific surface area and micro pore size distribution with reaction degree were examined. The results are summarized as follows. (1) The specific surface area changes remarkably with reaction degree, while the reaction rate does not change so much. (2) The change in the specific surface area accords well to the change in the volume of smaller pores than 10(-8)m in diameter. (3) The reaction occurs exclusively on the surface of pores between 10(-8) to 10(-6) m in diameter. (4) The effective surface area for the reaction is from 0.064 to 0.25 of the total surface area.

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  • Dependence of titanium deposition upon its ionic state in molten salt

    T Takenaka, M Kawakami, N Suda

    DESIGNING, PROCESSING AND PROPERTIES OF ADVANCED ENGINEERING MATERIALS, PTS 1 AND 2   449-4   453 - 456   2004

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    The ionic valence of Ti changed with electrorefining process of Ti in a bath equi-molar mixture of NaCl-KCl containing TiCln (n = 2 or 3); The average valence was about 2.3 initially, and became about 2.1 after electrolysis. The cathodic current efficiency was getting better with electrolysis. It should be necessary to maintain the average ionic valence lower for efficient electrolysis in the molten salt. The dominant Ti ion and its electrode reaction changed with the addition of NaF-KF in the molten salt; The average valence shifted from about 2 to about 3, and the total amount of Ti in the bath decreased. The result indicates the disproportionation reaction: 3Ti(2+) = Ti + 2Ti(3+) is induced by the fluoride addition. The quantity of electricity for Ti deposition changed consequently, and the purity of the Ti deposit was also affected.

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  • Direct Electrodeposition of Mg Including La in Molten Salt Reviewed

    Toshihide Takenaka, Yusuke Naka, Nobuo Narukawa, Masahiro Kawakami

    pp.679-785   2004

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  • Direct Electrowinning of Titanium: Combination of Electrolysis and Melting of Titanium Metal by DC ESR Apparatus Reviewed

    Toshihide Takenaka, Masahiro Kawakami

    vol.I, pp.221-228   2004

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  • Reaction Kinetics of Coke and Some Carbonaceous Materials with CO 2 and Coke Strength after Reaction

    Masahiro Kawakami, Yukitaka Mizutani, Takayuki Ohyabu, Kengo Murayama, Tosihide Takenaka, Seiji Yokoyama

    Steel Research International   75 ( 2 )   93 - 98   2004

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    The reaction rate per unit mass of wood char was an order of magnitude larger than that of coke and graphite and that of glassy carbon was an order of magnitude smaller than the latter. However, the reaction rate per unit surface area of wood char was smaller than that of graphite. The reaction of coke proceeded homogeneously at temperatures lower than 1373 K, while the reaction was restricted to the surface layer at higher temperatures. The tensile strength of coke after reaction decreased with the reaction degree at 1273 K, but was not changed or even increased at 1573 K. This is due to the fact that at 1573 K the core of the sample was not attacked by CO2 but strengthened by further crystallization.

    DOI: 10.1002/srin.200405933

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  • Electrorefining of magnesium in molten salt and its application for recycling

    T Takenaka, S Isazawa, M Mishina, Y Kamo, M Kawakami

    MATERIALS TRANSACTIONS   44 ( 4 )   546 - 551   2003.4

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    Electrorefining of Mg has been investigated in a molten salt system, and the electrolysis conditions for the effective purification have been discussed. A purified mixture of MgCl2-NaCl-CaCl2 was used as an electrolytic bath. Magnesium metal was dissolved anodically by potentiostatic electrolysis, and purified Mg was electrodeposited at the cathode. A certain degree of cathodic overpotential was required for the effective electrodeposition of Mg metal, while large anodic overpotential directly caused the deterioration in the purity of Mg electrodeposit; it was necessary for the anodic overpotential to be less than 1.0V for good purification. In addition to the electrode potentials, some factors affected the electrorefining of Mg metal. Under the suitable electrolysis condition, the Fe content in the Mg electrodeposit was less than 10 ppm. A couple of subjects on recycling Mg metal and its alloys have been also studied: purification of Mg alloy by an electrorefining technique and distinction of Mg alloys. It was shown that pure Mg metal was electrodeposited at the cathode by the electrorefining of Mg alloy. X-ray fluorescence analysis was applied to distinction of Mg alloys, and the measuring conditions were discussed. It was concluded that the electrorefining process and X-ray fluorescence analysis were usable for the recycling of Mg metal and alloys.

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  • コークスおよび各種炭材のCO2によるガス化反応速度 Reviewed

    川上正博, 大藪貴之, 水谷行隆, 竹中俊英, 横山誠二

    鉄と鋼   89巻5号,85-90頁   2003

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  • Reaction rate of coke and other carbonaceous materials with CO2 Reviewed

    Masahiro Kawakami, Takayuki Ohyabu, Yukitaka Mizutani, Toshihide Takenaka, Seiji Yokoyama

    Tetsu-To-Hagane/Journal of the Iron and Steel Institute of Japan   89 ( 5 )   581 - 586   2003

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    The reaction rates of Bintyo char, Bamboo char, activated carbon, coke, graphite and glassy carbon with pure CO2 have been obtained by thermo gravimetric method. After the reaction, N2 was introduced to the reaction tube to obtain the amount of adsorbed CO on the active reaction sites. The specific surface area after the reaction was measured by BET method. The results are summarized as follows: The reaction rate per unit mass were in the order of Bintyo char≒Bamboo char≒activated carbon≻graphite≒coke≻glassy carbon. The difference between the maximum and minimum were two orders of magnitude. The activation energy was 180 to 220 kJ/mol. The reaction rate per unit area of graphite, however, was an order of magnitude higher than those of Bintyo char and Bamboo char. The estimated amount of adsorbed CO was positively correlated to the reaction rate. The reaction rate constant which is independent from surface area was obtained using the reaction rate and the amount of CO adsorption, respectively per unit area. They are ranged in the order of 10-4 to 10-3 1/s. The differences among Bintyo char, Bamboo char and graphite became smaller. The enthalpy of CO adsorption was estimated as about 230 kJ/mol for Bintyo char and Bamboo char, and about 280 kJ/mol for graphite.

    DOI: 10.2355/tetsutohagane1955.89.5_581

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  • Reaction kinetics of some carbonaceous materials with oxidizing gas

    M Kawakami, Y Mizutani, T Iwabuchi, T Takenaka, S Yokoyama

    HIGH TEMPERATURE MATERIALS AND PROCESSES   22 ( 3-4 )   171 - 178   2003

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    In order to get a highly reactive carbonaceous material at low temperature, the reaction kinetics of various carbonaceous materials with different structure was investigated. The reaction rate was the largest for Bintyo char and bamboo char on unit mass base, but it was the largest for graphite on unit area base. The rate had a positive relation with the amount of CO adsorption, showing that the rate determining step would be the desorption of CO from the active site on the surface. The rate independent of surface area was derived from the data of the rate and amount of CO adsorption per unit area.

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  • Electrorefining of Mg in molten salt

    T Takenaka, S Isazawa, Y Kamo, M Mishina, M Kawakami

    MAGNESIUM ALLOYS 2003, PTS 1 AND 2   419-4   653 - 657   2003

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    Electrorefining of Mg has been investigated in a molten salt system, and the electrolysis conditions for the effective purification have been discussed. A purified mixture of MgCl2-NaCl-CaCl2 at 943K was used as an electrolytic bath. Magnesium metal was dissolved anodically by potentiostatic electrolysis, and purified Mg was electrodeposited at the cathode. The potential during electrolysis was essential for the electrolysis; large anodic overpotential directly caused the deterioration in purity of Mg electrodeposit. It was necessary for the anodic overpotential to be less than 1.0V for good purification, though a certain degree of cathodic overpotential was required for the effective electrodeposition of Mg. In addition to the electrode potentials, some factors affected the electrorefining of Mg metal. Under the suitable electrolysis condition, the Fe content of the Mg electrodeposit was less than 10ppm. The so-called "three-layer" electrolysis has been also tried in this study by using the similar experimental procedure. Magnesium metal in Mg-Cu alloy at the bottom of an electrolytic bath was dissolved anodically, and Mg metal electrodeposited at the cathode simultaneously. It is concluded that an electrorefining technique is effective for the purification of Mg metal.

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  • Preparation of Mg alloys by using molten salt

    T Takenaka, Y Naka, T Noichi, M Kawakami

    MAGNESIUM ALLOYS 2003, PTS 1 AND 2   419-4   677 - 681   2003

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    Chemical distribution of metallic elements between molten salt and liquid Mg metal has been investigated as a fundamental study on the preparation of Mg alloys by using molten salt. A purified eutectic mixture of MgCl2-NaCl-KCl was melted with Mg metal, and CaCl2, MnCl2 or LaCl3 was added to the molten salt. The contents of Na, K and Ca in Mg metal did not change remarkably even after contact with the molten salt consisting of these elements. Manganese moved from the molten salt with MnCl2 to Mg metal, and La also transferred from the molten salt with LaCl3 chemically. However, the migration of these elements were slow, and some factors should affect their chemical distributions.

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  • Separation of elements in stainless steel by electrorefining process

    T Takenaka, M Kawakami, M Kawaguchi

    METALLURGICAL AND MATERIALS PROCESSING: PRINCIPLES AND TECHNOLOGIES   vol.3, pp.409-415   409 - 415   2003

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    Language:English   Publishing type:Research paper (international conference proceedings)   Publisher:MINERALS, METALS & MATERIALS SOC  

    The management of radiciactivated stainless steel from a terminated nuclear reactor will become an important subject in the near future. The separation of the elements in stainless steel should be effective to reduce the management labor. In this study, the separation of the elements in stainless steel by an electrorefining technique was investigated in an aqueous solution. The electrochemical reactions of the elements in stainless steel were studied by voltammetry and potentio-static electrolysis was carried out. A stainless steel anode was dissolved electrochemically with good anodic current efficiency in a chloride solution. The residue, where Ni was concentrated, was found on the anode after electrolysis. The electrodeposit in a stainless steel cathode consisted mainly of Fe and Cr and the Ni content in it was less than 0.5wt% under suitable condition. It is concluded that an electrorefining technique is effective for the separation of the elements in stainless steel.

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  • Reaction kinetics of some carbonaceous materials with carbon dioxide

    M Kawakami, T Ohyabu, T Takenaka, S Yokoyama

    METALLURGICAL AND MATERIALS PROCESSING: PRINCIPLES AND TECHNOLOGIES, VOL 1   vol. I, pp.75-83   75 - 83   2003

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    In relation to the designing of a new-type blast furnace, the reaction of carbonaceous materials with CO2 is expected to occur at as low temperature as possible, In order to get a highly reactive carbonaceous material at low temperature, the reaction kinetics was investigated by measuring such quantities as the reaction rate from weight loss, the amount of CO adsorption and specific surface area by BET method. The reaction rates were large in the order of the c bar, metallurgical coke, graphite and glassy carbon. If the rate was converted to the rate per unit area, however, those of the Bintyo char was smaller than that of graphite. Thus, it is suggested that the rate of the Bintyo char is influenced by the pore diffusion Of CO2. The rate had a positive relation with the amount of CO adsorption, showing that the rate determining step would be the desorption of CO from the active side on the surface. The rate independent of surface area was derived, combining all the obtained data.

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  • Electrode reactions in dc electroslag remelting of steel rod

    M Kawakami, T Takenaka, M Ishikawa

    IRONMAKING & STEELMAKING   29 ( 4 )   287 - 292   2002.8

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    The non-metallic inclusion content increased significantly when a steel rod of Fe-Ni was remelted by dc electroslag remelting. The silicon content increased slightly. The manganese and sulphur contents did not change. The total aluminium content in the ingot was max. 0.7%, while that in the electrode was only 10 ppm. The aluminium cations Al3+ in the slag are reduced to metallic aluminium at the slag/electrode interface, while O-2(-) anions are oxidised to dissolved (O) under bar in the metal pool. This Al and (O) under bar subsequently recombine to form alumina inclusions in the metal pool. The inclusion content was dependent on the alumina content in the slag. When a rod of plain carbon steel was remelted, however, the increase in nonmetallic inclusion content was as little as one-tenth of that for the remelted Fe-Ni rod. The non-metallic inclusion content was independent of the polarity of the electrode.

    DOI: 10.1179/030192302225005132

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  • Electrorefining of magnesium in chloride melts

    T Takenaka, S Isazawa, Y Naka, M Kawakami

    MOLTEN SALTS XIII   2002 ( 19 )   779 - 788   2002

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    Electrorefining of Mg in molten chloride has been investigated. A mixture of MgCl2, CaCl2 and NaCl was used as molten salt bath. The electrochemical behaviors of Fe, Cr and Ni were examined by voltammetry, because they are typical impurities in Mg and seriously debase Mg metal. The results being referred, the electorefining of Mg was carried out. Magnesium moved electrochemically from anode to cathode with a good cur-rent efficiency. Iron was enriched in the residual Mg metal at anode, whereas the Fe content in the Mg electrodeposit at cathode was less than that in the Mg metal supplied originally. The dependence on some electrolytic conditions being discussed, it was found that the anode potential should be essential for elimination of Fe from Mg. It was concluded that the electrorefining process was promising for purification of Mg metal.

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  • Recycling of Electric Arc Furnace Dust and Smelting Reduction of Chromite Ore with The aid of Powder Injection Technique to Molten Iron

    Masahiro Kawakami, Seiji Yokoyama, Toshihide Takenaka

    pp.155-168   2002

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  • Dissolution and deposition of impurities in Mg electrolysis

    T Takenaka, T Fujita, S Isazawa, M Kawakami

    MATERIALS TRANSACTIONS   42 ( 7 )   1249 - 1253   2001.7

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    Electrochemical behaviors of Fe, Cr and Ni have been investigated in molten salt systems as a basic study on the electrorefining of Mg metal; The electrochemical behaviors of FeCl2, NiCl2 and CrCl3 were examined by voltammetry, and the electrochemical dissolutions of these metals were also studied. A MgCl2-CaCl2-NaCl or MgCl2-NaCl-KCl melt was used as electrolytic bath. The electrode reactions of these elements were discussed on these results, and it was concluded that these elements could be eliminated from Mg metal easily by electrorefining process in molten salts. Magnesium metal was obtained electrochemically not only above the melting point of Mg metal but also below the melting point. However, Mg electrodeposit with good morphology could not be obtained under any electrolytic condition below the melting point of Mg metal.

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  • Dissolution and deposition of impurities in Mg electrolysis

    T Takenaka, T Fujita, S Isazawa, M Kawakami

    MATERIALS TRANSACTIONS   42 ( 7 )   1249 - 1253   2001.7

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    Electrochemical behaviors of Fe, Cr and Ni have been investigated in molten salt systems as a basic study on the electrorefining of Mg metal; The electrochemical behaviors of FeCl2, NiCl2 and CrCl3 were examined by voltammetry, and the electrochemical dissolutions of these metals were also studied. A MgCl2-CaCl2-NaCl or MgCl2-NaCl-KCl melt was used as electrolytic bath. The electrode reactions of these elements were discussed on these results, and it was concluded that these elements could be eliminated from Mg metal easily by electrorefining process in molten salts. Magnesium metal was obtained electrochemically not only above the melting point of Mg metal but also below the melting point. However, Mg electrodeposit with good morphology could not be obtained under any electrolytic condition below the melting point of Mg metal.

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  • コークスのCO2との反応速度と反応後の強度変化

    川上正博, 村山賢悟, 柴田将寛, 竹中俊英, 横山誠二

    溶融塩および高温化学   44巻1号,38-51頁   2001

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  • Electroplating of Al-Ti and Ti in room temperature melt

    T Takenaka, M Kawakami

    INTERNATIONAL JOURNAL OF MATERIALS & PRODUCT TECHNOLOGY   SPM I(2), pp.500-505   500 - 505   2001

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:INDERSCIENCE ENTERPRISES LTD  

    Electroplating of Al-Ti alloy in AlCl3-BPC (n-butylpyridinium-chloride) melts containing TICln (n=2,3,4) has been studied at 300similar to450K. The cathode surface was covered with a smooth and dense metallic layer which consisted of mainly Al and included Ti. The surface became uneven with the increase in Ti content in the deposit. Intermetallic compounds of Al and Ti were not detected even in the deposit containing Ti more than 10 at%. Electrolysis in TiCln (n=2,3,4)-BPC melts has been tested above the melting point of BPC (similar to405K). Metallic electrodeposit was not obtained under any condition in these melts.

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  • Strength and Morphology Change of Coke after Reaction with CO2

    Masahiro Kawakami, Kenji Murayama, Toshihide Takenaka, Seiji Yokoyama

    pp.33-42   2001

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  • Purification of magnesium using molten salt

    T Takenaka, T Fujita, R Uchida, M Kawakami

    PROCEEDINGS OF THE 6TH INTERNATIONAL SYMPOSIUM ON MOLTEN SALT CHEMISTRY AND TECHNOLOGY   pp.318-321   318 - 321   2001

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    Some impurity elements, such as Fe, Cr and Ni are said to debase Mg metal in corrosion resistivity so that their level must keep very low for some purposes. Because primary product of Mg metal does not answer this criterion, the purification procedure of Mg metal are desired. The electrorefining process in molten salt should be promising for this purpose. In this study, electrochemical behaviors of Fe, Cr and Ni have been investigated in molten salt systems as a basic study on electrorefining of Mg metal. The mixture Of MgCl2, CaCl2 and NaCl was mainly used as molten salt bath. The electrochemical behaviors of FeCl2, CrCl3 and NiCl2 were examined by voltammetry, and the electrochemical dissolutions of these metals were examined. Potentio-static electrolysis was carried out at various electrolytic conditions, and the electrodeposit on the cathode and residue of the anode were analyzed. The results indicated that these elements could be eliminated from magnesium metal easily by electrorefining process in molten salts. Chemical distribution of elements between Mg metal and molten salts has been also examined to clarify the interaction between Mg metal and molten salts. The behaviors of main ingredients of molten salts were investigated, and those of some alloying elements were discussed.

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  • Simultaneous Decarburization and Nitrogen Removal of Molten Steel by Blasting of Ito Ore Powder on the Free Surface

    Masahiro Kawakami, Seiji Yokoyama, Toshihide Takenaka, Masuo Inoue, J S. Kim

    vol. 2, pp.555-563   2001

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  • コークスのCO2との反応速度と反応後の強度の評価 Reviewed

    川上正博, 村山賢悟, 柴田将寛, 竹中俊英, 戸田裕之

    鉄と鋼   87巻5号、252-258頁   2001

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  • Electrochemical behavior of impurity elements in magnesium electrolysis

    T Takenaka, T Fujita, M Kawakami

    MAGNESIUM ALLOYS 2000   350-3   291 - 296   2000

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    Electrochemical behavior of some metallic elements in molten salt systems has been investigated as a fundamental study for purification of Mg metal. A mixture of MgCl2, CaCl, and NaCl was mainly used as an electrolytic bath, and a eutectic mixture of LiCl and KCl including MgCl2 was also used. The electrochemical behavior of Li, Cr, Fe and Ni was examined by voltammetry, and their cathodic reactions were discussed. The results indicated that the electrochemical separation of the elements from Mg metal was possible in the molten salt systems. Potentio-static electrolysis was carried out below the melting point of Mg metal, and Mg metal was obtained. However, the deposit consisted of small Mg metal particle, and the surface of the particle was oxidized during rinsing with water.

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  • Electrochemical behavior of impurity elements in magnesium electrolysis

    T Takenaka, T Fujita, M Kawakami

    MAGNESIUM ALLOYS 2000   350-3   291 - 296   2000

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    Electrochemical behavior of some metallic elements in molten salt systems has been investigated as a fundamental study for purification of Mg metal. A mixture of MgCl2, CaCl, and NaCl was mainly used as an electrolytic bath, and a eutectic mixture of LiCl and KCl including MgCl2 was also used. The electrochemical behavior of Li, Cr, Fe and Ni was examined by voltammetry, and their cathodic reactions were discussed. The results indicated that the electrochemical separation of the elements from Mg metal was possible in the molten salt systems. Potentio-static electrolysis was carried out below the melting point of Mg metal, and Mg metal was obtained. However, the deposit consisted of small Mg metal particle, and the surface of the particle was oxidized during rinsing with water.

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  • Electrowinning of titanium in fluoride melt by using hydrogen gas oxidation as anodic reaction

    T Takenaka, N Murakami, T Matsui, M Kawakami

    SECOND INTERNATIONAL CONFERENCE ON PROCESSING MATERIALS FOR PROPERTIES   pp.803-806   803 - 806   2000

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    Electrowinning of Ti have been investigated in a LiF-NaF-KF melt including K2TiF6 at 773-923K by applying electrochemical oxidation of H-2 gas as an anodic reaction. The cathodic behavior of titanium and the anodic behavior of H-2 gas were studied by voltammetry in detail to clarify the electrolytic condition for the process. The electrowinning of Ti was carried out by potentiostatic electrolysis. Steady electrolysis was achieved under the suitable electrolytic condition without breaking out the anode effect. Titanium metal was electrodeposited on a Ti cathode though the deposits were usually powdery. It is concluded that this process is potential if the morphology of the deposit can be improved.

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  • Reaction rate of coke with CO2 and degradation of coke after reaction

    M Kawakami, K Murayama, T Takenaka, S Yokoyama

    SECOND INTERNATIONAL CONFERENCE ON PROCESSING MATERIALS FOR PROPERTIES   pp.547-552   547 - 552   2000

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    Coke plays an important role of spacer in blast furnace. However, they degenerate during Boudouard reaction. Blast furnace cokes are reacted with pure CO2 at 1072 to 1673 K. Reaction rate was obtained by the weight change of spherical specimen. The specimen after reaction was examined by microscopic observation. The reaction rate increased with temperature and was expressed by two Arrhenius type lines. The activation energy was 126 KJ/mol at higher temperature than 1373 K and 202 KJ/mol at lower temperature range. At the higher temperature range, the reaction proceeded from the surface leaving unreacted core, whereas homogeneously whole inside at lower temperature. The porosity increased from the center to surface at higher temperature, whereas it was almost constant at lower temperature.

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  • Electrode Reactions in DC-ESR Process of Steel Rod

    Masahiro Kawakami, Toshihide Takenaka, Masahiro Ishikawa

    \slags\pdf\380.pdf   2000

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  • チタン溶融塩電解採取法への新しい試み

    竹中俊英, 川上正博

    溶融塩および高温化学   43巻2号,149-159頁   2000

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  • Electrode reactions of borides of refractory metals in fluoroborate melt

    T Takenaka, K Nagao, M Kawakami

    MOLTEN SALTS XII, PROCEEDINGS   99 ( 41 )   636 - 644   2000

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    The electrodeposition of titanium boride and zirconium boride in a NaF-NaBF4 eutectic melt have been studied. The voltammetric measurements showed that Ti ions were reduced electrochemically to di-valent by two steps. A flat and adhesive TiB2 layer up to 50 mu m was obtained by potentio-static electrolysis under a proper condition, though no cathodic current peak for TiB2 deposition was detected in the voltammograms. A cathodic current peak corresponding to reduction of Zr ion was observed in a NaF-NaBF4-K2ZrF6 melt, but ZrB2 was not obtained under any electrolytic condition. The electrode behavior of B and Zr ions in a LiF-KF-NaF melt was different from those in a NaF-NaBF4 melt, and ZrB2 was electrodeposited in a LiF-KF-NaF-NaBF4-K2ZrF6 melt. These results indicate that the deposition of TiB2 in a NaF-NaBF4 system was not a simple electrode reaction but a sequence of electrochemical and chemical reactions.

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  • Direct electrowinning of liquid titanium metal by using Direct Current Electro Slag Remelting Apparatus

    T Takenaka, M Ishikawa, M Kawakami

    MOLTEN SALTS XII, PROCEEDINGS   99 ( 41 )   578 - 584   2000

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    Direct electrowinning of liquid titanium metal has been investigated by using a DC-ESR (Direct Current Electro-Slag Remelting) apparatus. A graphite rod was used as anode and a metal base-plate was used as cathode. A metal pool was formed on the base-plate with the small distance between the cathode and the anode, though the current efficiency got worse when the distance was too small. Pure titanium metal pieces were obtained in the solidified slag after the run with the bigger distance. It is concluded that Ti is able to be electrowon by the present process and that the formation of a larger metal pool on the base-plate with the bigger distance between the electrode was essential to efficient electrolysis.

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  • Electrode reactions of borides of refractory metals in fluoroborate melt

    T Takenaka, K Nagao, M Kawakami

    MOLTEN SALTS XII, PROCEEDINGS   99 ( 41 )   636 - 644   2000

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    Language:English   Publishing type:Research paper (international conference proceedings)   Publisher:ELECTROCHEMICAL SOCIETY INC  

    The electrodeposition of titanium boride and zirconium boride in a NaF-NaBF4 eutectic melt have been studied. The voltammetric measurements showed that Ti ions were reduced electrochemically to di-valent by two steps. A flat and adhesive TiB2 layer up to 50 mu m was obtained by potentio-static electrolysis under a proper condition, though no cathodic current peak for TiB2 deposition was detected in the voltammograms. A cathodic current peak corresponding to reduction of Zr ion was observed in a NaF-NaBF4-K2ZrF6 melt, but ZrB2 was not obtained under any electrolytic condition. The electrode behavior of B and Zr ions in a LiF-KF-NaF melt was different from those in a NaF-NaBF4 melt, and ZrB2 was electrodeposited in a LiF-KF-NaF-NaBF4-K2ZrF6 melt. These results indicate that the deposition of TiB2 in a NaF-NaBF4 system was not a simple electrode reaction but a sequence of electrochemical and chemical reactions.

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  • The new concept for electrowinning process of liquid titanium metal in molten salt

    T Takenaka, T Suzuki, M Ishikawa, E Fukasawa, M Kawakami

    ELECTROCHEMISTRY   67 ( 6 )   661 - 668   1999.6

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    Direct electrowinning of liquid titanium metal has been investigated by using a DC-ESR (Direct Current Electro Slag Remelting) apparatus. A small scale DC-ESR unit was operated in a DC reverse polarity mode, where a graphite rod tvas used as anode and a steel or a copper base-plate was used as cathode. The used salt was CaO-CaF2-TiO2 mixture. The distance between the cathode and the anode was essential to the electrolysis. A metal pool was formed on the base-plate and the current efficiency for the reduction was up to 18 % with the proper distance between the electrodes. Some amount of titanium was electrodeposited on the base-plate though its state changed with the electrolytic condition. Pure titanium metal pieces were obtained in the solidified salt after the run with the bigger distance. It is concluded that the electrowinning of liquid titanium metal by the present process is possible if sufficient heat to form a metal pool can be supplied at the bigger distance between the electrodes.

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  • Characterization of relieved non-metallic inclusions in stainless steel by image processing of micrographs

    M Kawakami, T Nishimura, T Takenaka, S Yokoyama

    ISIJ INTERNATIONAL   39 ( 2 )   164 - 170   1999

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    In the previous work, a new method to identify the shape of an inclusion was developed with the aid of image processing equipment. An attempt has been made to characterize inclusions in stainless steel using the method. Classifying areas for circles, triangles, squares, bars and intricates has been determined more accurately on two dimensional chart of y=L-2/(4A pi) and X=pi D-2/(4A). The inclusions were relieved on the surface of specimen by electrolytic etching with the SPEED technique. By these improvements, the inclusions with triangular, square, bar and intricate shape, as well as circular inclusions, were clearly classified. However, it seemed difficult to identify the chemical species of inclusion from its shape in the case of specimen from molten steel and CC slab. In the case of rolled sheet, the inclusions with different shape could be identified respectively. Therefore, the image processing of inclusions coupled with relieving of them by electrolytic etching might be one of the hopeful ways to characterize the inclusions in rolled sheet of stainless steel.

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  • Electrode Behavior of Hydrogen in Alkali Halide Melts Reviewed

    Toshihide Takenaka, Yukiyohi Mitani, Masahiro Kawakami

    vol.5-6, pp.275-278   1998

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  • Nb3Cl8を添加したLiCl−KCl共晶溶融塩浴を用いたニオブの電解精製 Reviewed

    周康根, 竹中俊英, 佐藤修彰, 徳田昌則

    電気化学および工業物理化学   65巻,134-137頁   1997

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  • The Possibility of ElectroWinning of Liquid Titanium Using ESR Apparatus

    Masahiro Kawakami, Masaki Ooishi, Toshihide Takenaka, Takayuki Suzuki

    pp.477-482   1997

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  • LiCl−KCl共晶塩-塩化ニオブ(NbCl5及びNb3Cl8)系溶融塩の導電率測定 Reviewed

    周康根, 竹中俊英, 佐藤修彰, 徳田昌則

    電気化学および工業物理化学   65巻,242-244頁   1997

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  • Electrorefining of niobium in LiCl-KCl eutectic melt with Nb3Cl8

    Kanggen Zhou, Toshihide Takenaka, Nobuaki Sato, Masanori Tokuda

    Denki Kagaku   65 ( 2 )   134 - 137   1997

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    The electrorefining of niobium has been investigated in LiCl-KCl eutectic melt with Nb3Cl8 at the temperature of 550°C by controlled potential electrolysis. The cathode deposits obtained at various cathode potentials were analyzed by XRD and EPMA. Tantalum content in deposits was measured by ICP. The cathode deposit was granular, powdery or dendritic niobium metal, and its morphology strongly depended on the cathode potential. Cathodic current efficiency was about 80% at the cathode potential of -0.8 to -1.2 Vvs. Ag/AgCl [(LiCl-KCl)eut.+ AgCl (5mol%)]. and it deteriorated above and below this potential range. The tantalum removal ability was affected obviously neither by the cathode potential nor by the tantalum content in the anode. The tantalum content in the cathode deposit was reduced to about a half of that in the anode. However, the tantalum removal ability in the chloride melt was inferior to that in the fluoride melt.

    DOI: 10.5796/kogyobutsurikagaku.65.134

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  • Electroplating of TiB2 in NaF-NaBF4 eutectic melt with titanium fluoride

    T Yamamoto, T Takenaka, M Kawakami

    MATERIALS TRANSACTIONS JIM   37 ( 3 )   363 - 366   1996.3

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    TiB2-coated metal should be a very promising material for many purposes. One of the hardest problems on TiB2 coating is to prevent necking or stripping by thermal expansion gap between TiB2 deposit and substrate. In this study, we have investigated the electroplating of TiB2 in NaF-NaBF4 eutectic melt(m.p.657K) with Na2TiF6 or TiF3. The constant-potential electrolysis was carried out at various potentials. The electrodeposit was obtained at more negative potential than that of reduction of Ti(III) to Ti(II). The result of EPMA and XRD showed that the main ingredient of electrodeposit was TiB2. The morphology of electrodeposit changed remarkably at the potential where the cathodic current began to increase sharply in a voltammogram. The flat and adhesive deposit was obtained at more positive potential, while the electrodeposit became powdery at more negative potential. The morphology also changed with time, that is, the protuberant deposit grew with the current increase after a certain time even at the potential where the flat deposit was expected. The monitoring of current was important for depositing the thick and flat layer in this process, and the layer up to 50 mu m was obtained under suitable conditions, The dependence of the morphology on Ti ion concentration or substrate was not critical in this process.

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  • Tiフッ化物を添加した NaF−NaBF4 共晶溶融塩中でのTiB2電析反応 Reviewed

    山本貴史, 竹中俊英, 川上正博

    電気化学および工業物理化学   64巻,132-137頁   1996

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  • 高力アルミニウム合金の剥離腐食の定量評価法 Reviewed

    山本成規, 竹中俊英, 川上正博

    日本金属学会誌   60巻12号,1187-1191頁   1996

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  • Quantitative estimation method of exfoliation corrosion of high strength aluminum alloys Reviewed

    Shigenori Yamamoto, Masahiro Kawakami, Toshihide Takenaka

    Nippon Kinzoku Gakkaishi/Journal of the Japan Institute of Metals   60 ( 12 )   1187 - 1191   1996

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:Japan Institute of Metals (JIM)  

    Exfoliation corrosion proceeds laterally along planes parallel to the surface of high strength aluminum alloys. The ASTM G34 (EXCO) test is widely used to predict exfoliation corrosion susceptibility. The susceptibility is determined by visual examination in which the surface profile is compared with the reference standard photograph. This method is ambiguous, so that it is difficult to distinguish general corrosion (overall corrosion, pitting) from exfoliation. In this study, a quantitative estimation method of exfoliation corrosion susceptibility based on ASTM G34 was developed, and the effect of composition and heat treatment of the alloys on exfoliation corrosion susceptibility were examined by this method. The specimens used were of 7XXX, Al-Li series alloys treated in T6, T7 and T4 modes. The normal procedure of ASTM G34 was carried out. Moreover, as quantitative measurements, the mass losses and quantity of exfoliation were evaluated by the following procedure. The specimens were soaked in nitric acid for 2 min and rinsed in water after being rated. After drying for about 30 min, the mass losses were measured. One week later, piles on the specimens were removed from the surface by a tooth brush. The piles and residues in solution were treated with hydrochloric acid, so that the weight of the metallic component was estimated by the amount of evolved hydrogen gases. The quantity of exfoliation was defined by the weight. The results obtained in this study were as follows
    (1) The quantity of exfoliation was slightly correlated with ASTM G34 rating. The exfoliation corrosion could be distigushed from the overall corrosion and pitting. (2) Exfoliation susceptibility was especially high in the alloys containing from 0.7 to 1.0%Cu. The alloy containing 0.37%Cu was the lowest. (3) The heat treatment in T7 gave high susceptibility of exfoliation corrosion, while that in T4 gave high susceptibility of overall corrosion and pitting.

    DOI: 10.2320/jinstmet1952.60.12_1187

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  • Chloride pyrometallurgy of uranium ore, (II)

    Tomihiro Taki, Shigetoshi Komoto, Keiichiro Otomura, Toshihide Takenaka, Nobuaki Sato, Takeo Fujino

    Journal of Nuclear Science and Technology   33 ( 4 )   327 - 332   1996

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    Selective extraction of uranium from a phosphate ore was studied by using the mixed gas of Cl2 and O2. On heating the ore and carbon mixture in Cl2, the volatilized chloride of uranium is accompanied by iron, aluminum, phosphorus and silicon chlorides. The addition of O2 gas effectively lowered the volatilization ratios of aluminum, phosphorus and silicon. The ratio decreased with increasing oxygen flow rate up to 50ml/min at 1,223 K (Cl2: 100ml/min, O2+N2: 400m//min). The volatilization ratio of uranium was almost unchanged at 90% up to 50 ml/min O2 (carbon amount: 15wt%). The effect of the other parameters, i.e. Cl2 flow rate, carbon amount, reaction temperature and time was examined. © 1996 Taylor and Francis Group, LLC.

    DOI: 10.1080/18811248.1996.9731912

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  • Chloride pyrometallurgy of uranium ore, (II)

    Tomihiro Taki, Shigetoshi Komoto, Keiichiro Otomura, Toshihide Takenaka, Nobuaki Sato, Takeo Fujino

    Journal of Nuclear Science and Technology   33 ( 4 )   327 - 332   1996

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    Selective extraction of uranium from a phosphate ore was studied by using the mixed gas of Cl2 and O2. On heating the ore and carbon mixture in Cl2, the volatilized chloride of uranium is accompanied by iron, aluminum, phosphorus and silicon chlorides. The addition of O2 gas effectively lowered the volatilization ratios of aluminum, phosphorus and silicon. The ratio decreased with increasing oxygen flow rate up to 50ml/min at 1,223 K (Cl2: 100ml/min, O2+N2: 400m//min). The volatilization ratio of uranium was almost unchanged at 90% up to 50 ml/min O2 (carbon amount: 15wt%). The effect of the other parameters, i.e. Cl2 flow rate, carbon amount, reaction temperature and time was examined. © 1996 Taylor and Francis Group, LLC.

    DOI: 10.1080/18811248.1996.9731912

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  • Effect of Additives on Ti Electrorefining in Molten Chloride Reviewed

    Toshihide Takenaka, Akihisa Sugimoto, Yukiyoshi Mitani, Masahiro Kawakami

    pp.171-178   1996

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  • Chloride pyrometallurgy of uranium ore, (I) chlorination of phosphate ore using solid or gas chlorinating agent and carbon Reviewed

    Tomihiro Taki, Shigetoshi Komoto, Keiichiro Otomura, Toshihide Takenaka, Nobuaki Sato, Takeo Fujino

    Journal of Nuclear Science and Technology   32 ( 9 )   880 - 888   1995

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    A thermodynamical and pyrometallurgical study to recover uranium from the phosphate ores was undertaken using the chloride volatilization method. Iron was chlorinated with solid chlorinating agents such as NaC1 and CaCl2 in combination with activated carbon, which will be used for removing this element from the ore, but uranium was not. On the other hand, the chlorination using Cl2 gas and activated carbon gave a good result at 1,223 K. Not only uranium but also iron, phosphorus, aluminum and silicon were found to form volatile chlorides which vaporized out of the ore, while calcium remained in the ore as non-volatile CaCl2. The chlorination condition was studied as functions of temperature, reaction time and carbon content. The volatilization ratio of uranium around 95% was obtained by heating the mixture of the ore and activated carbon (35 wt%) in a mixed gas flow of Cl2 (200 ml/min) and N2 (200 ml/min) at 1,223 K for 120 min. © 1995 Taylor and Francis Group, LLC.

    DOI: 10.1080/18811248.1995.9731789

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  • 水素ガス流通下における炭化カルシウムからの水素化カルシウムの製造 Reviewed

    藤重昌生, 田部井康一, 井野一, 竹中俊英, 川上正博

    日本金属学会誌   58巻3号, 284-290頁   1994

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  • ELECTROPLATING OF TI AND TI COMPOUND IN MOLTEN-SALTS

    T TAKENAKA, T YAMAMOTO, M KAWAKAMI

    FIRST INTERNATIONAL CONFERENCE ON PROCESSING MATERIALS FOR PROPERTIES   pp.425-428   425 - 428   1993

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    Language:English   Publishing type:Research paper (international conference proceedings)   Publisher:MINERALS, METALS & MATERIALS SOC  

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  • Electroplating of Al-Ti in AlCl3-BPC Melt at Room Temperature Reviewed

    Toshihide Takenaka, Akihiro Hoshikawa, Masahiro Kawakami

    pp.184-192   1993

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  • THERMODYNAMIC PROPERTIES AND PHASE-EQUILIBRIA OF THE POTASSIUM INDIUM SYSTEM BY ELECTROMOTIVE-FORCE MEASUREMENTS

    T TAKENAKA, A PETRIC, ML SABOUNGI

    JOURNAL OF PHYSICS-CONDENSED MATTER   3 ( 11 )   1603 - 1612   1991.3

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    The potassium-indium system has been studied using galvanic cells with potassium beta alumina as the electrolyte. The thermodynamic properties of the liquid solution have been determined between 0 and 52 at.% potassium. There is some evidence for a very weak liquid compound near 35 at.% K, but not at 50 at.% K. Changes are proposed for the potassium-indium phase diagram, including the liquidus temperature and the existence of new compounds.

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  • 溶融LiCl−KCl共晶塩中のニオブの電気化学的挙動 Reviewed

    周康根, 竹中俊英, 佐藤修彰, 南條道夫

    電気化学及び工業物理化学   59巻11号,981-989頁   1991

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  • LiCl−KCl−NbCl5三元系の状態図 Reviewed

    周康根, 竹中俊英, 佐藤修彰, 南條道夫

    資源と素材   107巻4号,227-230頁   1991

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  • 溶融塩化リチウム-塩化カリウム中でのデューテライドイオンの電極反応 Reviewed

    竹中俊英, 伊藤靖彦

    電気化学及び工業物理化学   59巻9号,796-797頁   1991

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  • 溶融塩化リチウム-塩化カリウム中でのハイドライドイオンの電極反応 Reviewed

    竹中俊英, 伊藤靖彦

    電気化学及び工業物理化学   59巻9号,759-765頁   1991

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  • 硝酸マンガン六水和物融液中での電極反応 Reviewed

    竹中俊英, 藤井秀司, 南條道夫

    東北大学選鉱製錬研究所彙報   46巻2号,87-95頁   1990

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  • タンタルコンデンサスクラップの塩化処理 Reviewed

    佐藤修彰, 竹中俊英, 韋悦周, 南條道夫

    東北大学選鉱製錬研究所彙報   46巻2号,96-104頁   1990

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  • Taコンデンサスクラップからの脱Mn浸出反応 Reviewed

    韋悦周, 佐藤修彰, 竹中俊英, 南條道夫

    資源と素材   105巻2号, 181-187頁   1989

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  • RELATION BETWEEN POTENTIALS OF LI,K/LI+,K+ DYNAMIC REFERENCE ELECTRODE AND HF/H2 GAS ELECTRODE IN A MOLTEN LIF-KF SYSTEM

    K EMA, Y ITO, T TAKENAKA, J OISHI

    ELECTROCHIMICA ACTA   32 ( 10 )   1537 - 1540   1987.10

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:PERGAMON-ELSEVIER SCIENCE LTD  

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  • BEHAVIOR OF HF/H2 ELECTRODE IN A MOLTEN LIF-KF SYSTEM

    K EMA, Y ITO, T TAKENAKA, J OISHI

    JOURNAL OF THE ELECTROCHEMICAL SOCIETY   134 ( 8B )   C515 - C515   1987.8

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    Language:English   Publisher:ELECTROCHEMICAL SOC INC  

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  • 溶融アルカリハライド中での金電極の電気化学挙動 Reviewed

    竹中俊英, 伊藤靖彦, 大石純

    電気化学及び工業物理化学   53巻7号, 476-480頁   1985

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  • 溶融フッ化物-水系の電気化学挙動 Reviewed

    竹中俊英, 伊藤靖彦, 石川孝康, 大石純

    電気化学及び工業物理化学   52巻11号, 758-762頁   1984

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  • THE ANODIC BEHAVIOR OF OXIDE ION AT GLASSY-CARBON ELECTRODE IN LIF-KF EUTECTIC MELT

    Y ITO, T TAKENAKA, K EMA, J OISHI

    DENKI KAGAKU   51 ( 11 )   864 - 868   1983

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:ELECTROCHEMICAL SOC JAPAN  

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Books

  • 電気化学便覧・第6版(電気化学会編)6.3.1溶融塩の電気化学プロセスへの応用,12.4.4溶融塩電解

    竹中俊英, 上田幹人

    丸善  2013.1 

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  • チタンの新しい製造法をめざして

    竹中俊英

    チタン  2012 

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  • レアメタル便覧(足立吟也監修), 15.3 レアメタル化合物の融点と沸点

    Toshihide Takenaka

    丸善  2011 

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  • 新製錬法の動向~2008年末~

    竹中俊英

    チタン  2009 

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  • 最近の研究:Mg 材料の耐食性向上をめざした最近の研究 Reviewed

    竹中俊英

    マテリア  2007 

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  • 溶融塩電解によるニオブの精製技術 Reviewed

    周康根, 竹中俊英, 南條道夫

    東北大学選鉱製錬研究所彙報  1988 

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  • 金属核燃料の乾式再処理 Reviewed

    竹中俊英, 南條道夫

    東北大学選鉱製錬研究所彙報  1987 

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  • 都市鉱山の魔法のエネルギー源~核燃料のリサイクル~

    竹中俊英

    Boundary  1987 

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MISC

Presentations

  • マグネシウムの製錬・リサイクルの研究動向

    竹中俊英

    (日本マグネシウム協会平成25年度第4回技術講演会)  2014.1 

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    Event date: 2014.1

    Venue:日本大学理工学部駿河台キャンパス  

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  • 新しいチタン金属製造法をめざした動き

    竹中俊英

    (腐食防食学会関西支部特別講演会)  2014.1 

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    Event date: 2014.1

    Venue:関西大学  

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  • Fe Elimination From Mg By Carbide Formation

    Toshihide Takenaka, Ryunosuke Morikawa, Taiki Morishige

    Proceedings of Materials Science & Technology 2013  2013.10 

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    Event date: 2013.10

    Venue:Montreaur, Canada  

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  • Composition of the metal fog in the Li electrowinning in LiCl-KCl eutectic melt

    Soshiro Murasa, Toshiki Hata, Ryosuke Takayanagi, Taiki Morishige, Toshihide Takenaka

    (8th International Symposium in Science and Technology)  2013.8 

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    Event date: 2013.8

    Venue:Kansai University  

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  • Our Recent Researches on Mg recycling

    Toshihide Takenaka, Asato Shimomura, Ryunosuke Morikawa, Taiki Morishige

    (11th Japan/Korea International Symposium on Resource Recycling and Materials Science)  2013.6 

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    Event date: 2013.6

    Venue:Kansai University  

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  • The inspection of the iron removal method from the magnesium dissolution by carbon addition

    Ryunosuke Morikawa, Taiki Morishige, Taiki Morishige

    (11th Japan/Korea International Symposium on Resource Recycling and Materials Science)  2013.6 

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    Event date: 2013.6

    Venue:Kansai University  

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  • マグネシウム合金の腐食特性について

    竹中俊英

    産総研コンソーシアム名古屋工業技術協会 平成24年度特別講演会「自動車関連技術講演会」  2013.1 

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    Event date: 2013.1

    Venue:名古屋駅前イノベーションハブ会議室  

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  • Diffusion of Cu to Ti in Magnesium Melt for Purification Process

    Taiki Morishige, Yuki Konishi, Asato Shimomura, Toshihide Takenaka

    Proceedings of The 8th Pacific Rim International Congress on Advanced Materials and Processing  2013 

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    Event date: 2013

    Venue:Hawaii, USA  

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  • Exfoliation Corrosion Behavior of cold-rolled Mg-Li-Al alloy sheet

    Taiki Morishige, Takayuki Goto, Eiji Nakamura, Toshihide Takenaka

    Proceedings of International Conference on Processing and Manufacturing of Advanced Materials (THERMEC' 2013)  2013 

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    Event date: 2013

    Venue:Las Vegas, USA  

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  • Conditions for Electrowinning of Liquid Ti Metal

    Toshihide Takenaka, Taiki Morishige

    4th Asian Conf. on Molten Salt Chem. and Tech.  2012.9 

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    Event date: 2012.9

    Venue:Matsushima, Japan  

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  • Anodic Behavior of Ti Electrode in Eutectic LiCl-KCl Melt

    Daichi Araki, Taiki Morishige, Toshihide Takenaka

    4th Asian Conf. on Molten Salt Chem. and Tech.  2012.9 

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    Event date: 2012.9

    Venue:Matsushima, Japan  

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  • Anodic Reaction on Carbon Materials in LiCl-KCl Melt

    Masaki Umehara, Taiki Morishige, Toshihide Takenaka

    4th Asian Conf. on Molten Salt Chem. and Tech.  2012.9 

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    Event date: 2012.9

    Venue:Matsushima, Japan  

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  • Condition of Metal Fog Formation in LiCl-KCl Melt and Its Prevention by Li2O Addition

    Ryosuke Takayanagi, Taiki Morishige, Toshihide Takenaka

    4th Asian Conf. on Molten Salt Chem. and Tech.  2012.9 

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    Event date: 2012.9

    Venue:Matsushima, Japan  

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  • Removals of Fe in Mg melt by graphite and Ca addition

    Yuki Konishi, Taiki Morishige, Toshihide Takenaka

    7th International Symposium in Science and Technology  2012.8 

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    Event date: 2012.8

    Venue:Penang, Malaysia  

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  • Investigation of corrosion behavior in cold-rolled Mg-14wt.%Li-1wt.%Al alloy in NaCl solution

    Hirokazu Doi, Taiki Morishige, Takayuki Goto, Eiji Nakamura, Toshihide Takenaka

    7th International Symposium in Science and Technology  2012.8 

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    Event date: 2012.8

    Venue:Penang, Malaysia  

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  • Evaluation for metal based anode in LiCl-KCl molten salt electrolysis

    Taiki Morishige, Daichi Araki, Masaki Umehara, Toshihide Takenaka

    7th International Symposium in Science and Technology  2012.8 

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    Event date: 2012.8

    Venue:Penang, Malaysia  

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  • マグネシウム金属からの不純物除去~マグネシウム材料の実用的リサイクル法の検討~

    竹中俊英

    大阪ベイエリア金属系新素材コンソーシアム第1回セミナー  2011.12 

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    Event date: 2011.12

    Venue:関西大学  

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  • 溶融塩中での電極反応のその場観察技術

    竹中俊英

    第42回溶融塩化学講習会  2011.12 

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    Event date: 2011.12

    Venue:同志社大学  

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  • チタンの新しい製造法をめざして

    竹中俊英

    日本チタン協会平成23年度表彰式・記念講演会  2011.11 

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    Event date: 2011.11

    Venue:学士会館  

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  • 高温溶融塩化物中での電極反応~電気化学挙動と実現象~

    竹中俊英

    第104回黒鉛化合物研究会  2011.10 

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    Event date: 2011.10

    Venue:京都テルサ  

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  • Electrochemical Behavior of Ti in Molten TiO2-CaO-CaF2-MgF2

    Toshihide Takenaka, Taiki Morishige, Hidetaka Matsuo, Masahiro Kawakami

    2011.9 

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    Event date: 2011.9

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  • Corrosion Behavior of Cold-Rolled Mg-14 wt. %Li-1 wt. %Al Alloy in NaCl Solution

    Hirokazu Doi, Taiki Morishige, Toshihide Takenaka, Takayuki Goto, Eiji Nakamura

    2011.9 

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  • Explanation of Anodic Behaviors in LiCl-KCl Melt by Electrochemical Response and in Situ Observation

    Masaki Umehara, Taiki Morishige, Toshihide Takenaka

    2011.9 

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    Event date: 2011.9

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  • マグネシウム, チタンの溶融塩電解と炭素劣化

    竹中俊英

    炭素材料学会先端科学技術講習会2011  2011.6 

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    Event date: 2011.6

    Venue:京都テルサ  

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  • Cathodic Phenomena in Li Electrolysis in LiCl-KCl Melt

    Toshihide Takenaka, Taiki Morishige, Masaki Umehara

    2011.6 

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    Event date: 2011.6

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  • 溶融塩電解プロセスのin-situ計測

    竹中俊英

    第59回マテリアルズ・テーラリング研究会  2011.4 

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    Event date: 2011.4

    Venue:京大桂キャンパス  

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  • Molten salt electrolysis of liquid metals -in-situ observation linked with electrochemical measurements-

    Toshihide Takenaka

    2011.3 

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    Event date: 2011.3

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  • Tiの連続的な製造を目指して~JTS法の上工程の概要~

    竹中俊英

    日本鉄鋼協会チタンフォーラム第1回研究発表会  2010.12 

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    Event date: 2010.12

    Venue:関西大学  

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  • Ti新製錬法に関する最近の研究

    竹中俊英

    材料化学研究会平成22年度第2回講演会・見学会  2010.11 

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    Event date: 2010.11

    Venue:大阪チタニウムテクノロジーズ  

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  • 高温イオン融体(溶融塩)中での電極反応~電気化学応答と実現象の関連~

    竹中俊英

    界面現象研究センター第12回研究講演会  2010.11 

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    Event date: 2010.11

    Venue:同志社大学  

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  • チタン素材製造の刷新をめざして

    竹中俊英

    平成22年度合同研究部門別発表会  2010.11 

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    Event date: 2010.11

    Venue:関西大学100周年記念会館  

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  • マグネシウムの精錬(リサイクル関係)の現状報告

    竹中俊英

    超塑性加工ものづくり研究会第57回勉強会  2010.7 

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    Event date: 2010.7

    Venue:大阪府立大学中之島サテライト  

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  • チタン・チタン合金の直接電解製造の試み

    竹中俊英, 松尾英崇, 川上正博

    第2回機能性チタン合金研究会講演会  2009.11 

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    Event date: 2009.11

    Venue:関西大学  

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  • リサイクルを考慮したマグネシウムの材料・プロセス開発

    竹中俊英

    循環ビジネス創出会議  2009.11 

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    Event date: 2009.11

    Venue:愛知県産業労働センター  

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  • 環境負荷を考慮したマグネシウム材料の表面処理法

    竹中俊英

    東海iNET新技術説明会  2009.10 

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    Event date: 2009.10

    Venue:JSTホール  

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  • Corrosion Analysis of Magnesium Alloys with High Corrosion-Resistance

    Ilhamdi, T. Takenaka, M. Izaki, J. Sasano

    2009.9 

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  • Preparation of 1.45-eV-Bandgap CuO Thin-films by Solution Electrochemical Reaction

    K. Toyoda, J. Sasano, T. Takenaka, M. Izaki, M. Inoue

    2008.10 

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    Event date: 2008.10

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  • Characterization of Cu Oxide Layers Prepared by Chemical Bath Deposition (CBD)

    Y. Yamane, J. Sasano, T. Takenaka, M. Izaki

    2008.10 

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  • マグネシウム材料の耐食性向上をめざした最近の研究

    竹中俊英

    平成20年度第2回素材専門委員会  2008.9 

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    Event date: 2008.9

    Venue:東京・日本航空宇宙工業会  

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  • チタンの新製錬法 ~高温電解や気相還元~

    竹中俊英

    日本金属学会2008年秋季大会  2008.9 

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    Event date: 2008.9

    Venue:熊本・熊本大学  

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  • チタン新製錬法

    竹中俊英

    チタン合金の研究・開発最前線  2008.8 

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    Event date: 2008.8

    Venue:東京,キャンパスイノベーションセンター  

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  • Ti金属素材製造の現状と動向

    竹中俊英

    第1回チタン元素戦略研究会  2008.3 

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    Event date: 2008.3

    Venue:東京,虎ノ門パストラルホテル  

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  • Ti素材製造の現状とDC-ESR装置を用いた研究事例

    竹中俊英, 川上正博

    「体心立方系チタン合金の新しい展開」研究会  2007.3 

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    Event date: 2007.3

    Venue:千葉,千葉工大  

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  • Resent researches on Ti processing in molten salt

    Toshihide TAKENAKA

    2006.3 

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  • Reaction Rate and Structure Analysis of Some Carbonaceous Materials

    Masahiro Kawakami, Tosihide Takenaka

    2006 

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    Event date: 2006

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  • Coating of Ti and Ti Alloys by Disproportionation Reaction in Molten Salt

    Toshihide Takenaka, Shunsuke Miyazawa, Masataka Muro, Masahiro Kawakami

    2005 

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  • Difference in electrochemical reduction of Ti ion in various molten salt systems

    Toshihide Takenaka, Masahiro Kawakami

    2005 

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    Event date: 2005

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  • Coating of Ti alloys by Disproportionation reaction in molten salt

    Masataka Muro, Shunsuke Miyazawa, Toshihide Takenaka, Masahiro Kawakami

    2005 

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  • Dependence of DC ESR operation upon TiO2 concentration in molten fluoride oxide mixture

    Takuya Hashimoto, Takuya Noichi, Masayuki Orisaka, Takahiro Kawabata, Hiroaki Tanigawa, Toshihide Takenaka, Masahiro Kawakami

    2005 

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  • Reaction Rate of Various Carbonaceous Materials with CO2 and Structure Evaluation of Them

    Masahiro Kawakami, Takahiro Karato, Hiromitu Taga, Toshihide Takenaka, Seiji Yokoyama

    2003 

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    Event date: 2003

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  • Reaction Rate of Several Carbonaceous Materials with CO2

    Masahiro Kawakami, Takayuki Ohyabu, Yukitaka Mizutani, Toshihide Takenaka, Seiji Yokoyama

    2003 

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    Event date: 2003

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  • Electrorefining of Mg in molten salt

    ToshihideTakenaka, Satoshi Isazawa, Yusuke Naka, Masahiro Kawakami

    2001 

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    Event date: 2001

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  • Behavior of Impurities in Mg Metal in Molten Salt Treatment

    ToshihideTakenaka, Satoshi Isazawa, Yusuke Naka

    2000 

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    Event date: 2000

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  • Behavior of Electrodeposition of Al-Ti Alloy in the Room Temperature Molten Salt

    Kazuo Yoneda, Toshihide Takenaka, Masahiro Kawakami

    1996 

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    Event date: 1996

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  • Electrode Reaction of Niobium in Molten Chlorides

    Kang-gen Zhou, Toshihide Takenaka, Michio Nanjo

    1988 

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    Event date: 1988

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Awards

  • 平成30年度(第22回)功績賞

    2019.6   一般社団法人日本マグネシウム協会  

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  • 平成23年度技術賞

    2011.11   社団法人日本チタン協会  

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  • 2011年度溶融塩賞

    2011.1   電気化学会溶融塩委員会  

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  • 日本鉄鋼協会学術記念賞(西山記念賞)

    2005.3   日本鉄鋼協会  

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  • 第13回永井学術賞

    1998.3   永井科学技術財団  

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Research Projects

  • Innovative production process of Ti and Si by electrolysis in molten CaCl2 at high temperature

    Grant number:18H01763  2018.4 - 2022.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (B)

    Takenaka Toshihide

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    Grant amount:\17160000 ( Direct Cost: \13200000 、 Indirect Cost:\3960000 )

    Electrolytic production of Ti metal and Si metal in molten CaCl2 with their oxides was investigated in this study.
    TiO2 dissolved in molten CaCl2 with CaO, and Ti metal electrodeposited. The molar ratio of CaO to TiO2 strongly affected the Ti metal deposition. Ti metal was obtained only in the bath where CaO:TiO2 = 3:2., but the obtained Ti was a little even under this condition. It was suggested that the so-called shuttle reaction hindered the Ti deposition.Calcium silicate dissolved in molten CaCl2, and Si metal was obtained. The influence of the molar ratio of CaO to SiO2 on the Si deposition was seen, but Si metal electrodeposited effectively under the suitable condition.

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  • Progressive research on innert anode for Li and Mg electrolysis in molten chloride

    Grant number:26289282  2014.4 - 2017.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (B)

    Takenaka Toshihide

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    Grant amount:\16250000 ( Direct Cost: \12500000 、 Indirect Cost:\3750000 )

    Innovative material of inert anode for Li and Mg electrolysis in molten chloride containing oxide ions of impurity-level was studied. The anodic dissolution of carbon/graphite was hardly prevented, and nickel ferrite was dissolved by immersion. A TiO2 layer was not formed on Mo-Ti or Mo-Ti-Ru alloy, and their dissolution was rarely inhibited. The anodic behaviors of SiC strongly depended on the existence of oxide ions in melt, and a SiO2 layer was formed on its surface by electrolysis. The formed SiO2 seemed stable even under Cl2 gas generation, and its anodic dissolution was considerably lessened. The anodic behavior of MoSi2 resembled that of SiC. These results indicate that SiC and MoSi2 are potential as inert anode material in molten chloride containing oxide ions. The formation of a homogeneous and coherent SiO2 layer with better electric conductivity should be studied to apply them as a practical inert anode.

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  • Fundamental Study on the Establishment of Innovative System on Hydrogen Storage and Transportation using Lithium Hydride.

    Grant number:21246113  2009 - 2011

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (A)

    SATO Yuzuru, TAKEDA Osamu, TAKENAKA Toshihide, YAMAGUCHI Katsunori, UEDA Mikito

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    Grant amount:\48880000 ( Direct Cost: \37600000 、 Indirect Cost:\11280000 )

    Hydrogen energy is widely developed recently from the viewpoint of efficient energy utilization and the environmental conservation such as a fuel cell technology. However, efficient methods for the storage and transportation are not yet established due the lower density and extremely low boiling temperature of hydrogen. Therefore, authors made an offer new method for the storage and transportation using lithium hydride, LiH at room temperature. Metallic lithium is let to react with hydrogen to form lithium hydride and is transported to the place on demand. The hydrogen is generated by reacting of LiH with water vapor. Then, LiOH is generated as a by-product of the reaction and must be returned to produce metallic lithium for establishing the whole cycle of hydrogen utilization using LiH. In this study, lithium production from LiOH through the molten salt electrolysis was successfully developed, and the mechanism of the reaction of metallic lithium with hydro- gen was made clear.

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  • Novel Process of Practical Impurity Removal from Magnesium Scrap

    Grant number:21560770  2009 - 2011

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (C)

    TAKENAKA Toshihide, MORISHIGE Taiki

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    Grant amount:\4810000 ( Direct Cost: \3700000 、 Indirect Cost:\1110000 )

    Aiming at the development of the practical recycle process of Mg materials, the removal of Fe and Cu, which seriously deteriorate the properties of Mg materials and are easily contaminated in recycle process, has been investigated. Fe which has a stronger affinity with carbon than Mg was eliminated by simply adding a carbon source and additives in Mg melt. It was also found that Cu could be absorbed to Ti metal immersed in Mg melt.

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  • Improvement of corrosion resistance of Mg by rare earth elements〜Development of low nvironmental-burden material and investigation into mechanism

    Grant number:18560714  2006 - 2007

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (C)

    TAKENAKA Toshihide, KAWAKAMI Masahiro

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    Grant amount:\3780000 ( Direct Cost: \3300000 、 Indirect Cost:\480000 )

    Surface oxide film containing rare earth elements(REs)was formed on Mg materials by chemical conversion and anodization to improve their corrosion resistance. Analysis of the film was carried out and the corrosion resistance against salt water was examined. Co-deposition of REs with magnesium metal in molten salt electrolysis was also studied in this study, and the influence of REs on the electrolysis efficiency was discussed.
    The corrosion resistance of common magnesium alloys, such as AZ31, AZ61, AZ91 and AM60, was particularly improved by chemical conversion coating in solution containing both magnesium nitrate and RE nitrates, and the suitable coating condition for each alloy was clarified. The results from XRD, EPMA and XPS analyses indicated that the surface film consisted of complex oxides of magnesium and RE, and that the improvement of the corrosion resistance was affected by the distribution of the elements in the film.
    Oxide film was formed on Mg alloy by anodization in solution containing RE nitrate. The corrosion resistance was bettered consequently, but particular results by the treatment with both magnesium and REs was hardly seen.
    Magnesium metal containing REs was directly electrodeposited in a molten MgCl_2-NaCl-CaCl_2 bath with RECl_3.The morphology of the deposit strongly depended on the co-deposition of RE, and the electrochemical responses were remarkably changed. These results suggested a possibility that the electrolysis efficiency of magnesium deposition was improved by the co-deposition of REs

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  • Direct Ingot Making of Titanium by Electro-winning from Molten Salt, Using Metal Pool of Titanium

    Grant number:15206084  2003 - 2005

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (A)

    KAWAKAMI Masahiro, TAKENAKA Toshihide

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    Grant amount:\48100000 ( Direct Cost: \37000000 、 Indirect Cost:\11100000 )

    The purpose of the present research project is to develop the direct ingot making process of titanium by electro-winning of titanium, where the metal pool of titanium is used as the cathode. By using ESR unit, the thermo-analysis of process, electrode reaction mechanism and contamination mechanism were examined.
    At first, the electrical conductivity of CaO-CaF_2-TiO_2 slag was measured. The effect of TiO_2 addition was so small that the electronic conduction could be neglected. Thus, the addition of TiO_2 to the slag was possible at relatively large amount.
    By operating ESR unit with steel rod, the relation between shape of metal pool and current-voltage condition was clarified. In the case of ESR, the metal pool could not be obtained at far higher temperature than the melting point of pure titanium. It was seen that the melting point of titanium rose by the absorption of oxygen. Thus, the atmosphere of the whole apparatus, especially, cathode part, must be innert.
    In the single cell operation with CaO-CaF_2-TiO_2 slag, the maximum cathodic current efficiency was 12%, and the anodic current efficiency was far less than 100%. The reasons must be 1) formation of metal fog of Ca and its re-oxidation at the anode, 2) formation of Ti^<2+> by the reaction of Ti with Ti^<4+> and its re-oxidation at the anode, and 3) formation of Ti^<2+> by the insufficient amount of Ca and its re-oxidation at the anode. Thus, it is important to control the electrodes distance properly and to control the TiO_2 content properly.
    On the contrary, by the addition of Al_2O_3 to the slag, c.a. 70 g of electro-deposit and c.a. 60% of cathodic current efficiency were obtained. The reasons must be that the temperature of molten slag should be kept higher temperature by the addition, and that the Al deposit should act as the reductant of Ti^<4+> in the slag. This process is good for producing Ti-Al alloy, but not good for producing pure Ti, because the electro-deposit contained much Al.
    On the base on the above results, the new apparatus was designed. It consists of twin cell, one of which is anode cell and the other, cathode cell, connected with molten salt bridge. By this apparatus, the distance between cathode and anode can be kept long, resulting in the larger current efficiency and better quality of electro-deposit. The apparatus was successfully operated. Thus, the proposed process is very promising. The above results are published in 6 papers.

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  • New Coating & Metallizing Process of Refractory Metals & Compound in Molten Salt Bath

    Grant number:15360401  2003 - 2005

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (B)

    TAKENAKA Toshihide, KAWAKAMI Masahiro

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    Grant amount:\13700000 ( Direct Cost: \13700000 )

    Coating and metallizing of refractory metal or its compound by using a disproportionation reaction in molten salt has been studied. Titanium coating in NaCl-KCl equi-molar melt with Ti chloride or fluoride at 1000-1200K was mainly examined in this study. The results are summarized as follows ;
    1) The effects of some factors on the disproportionation reaction were clarified theoretically and experimentally. Titanium can be deposited by temperature change owing to the shift in the equilibrium. Titanium alloy coating should also be expected in the case that the substrate can form Ti alloy. Addition of fluoride in the bath may improve the rate of Ti deposition.
    2) Titanium metal deposited on alumina substrate by the simple immersion for hours, while Ti compound was seen on quartz glass substrate. These deposits seemed particle-like, and a dense coating layer wasn't obtained. The temperature gradient in the bath seemed effective in the improvement in the deposition rate.
    3) Dense and coherent Ti alloy layers up to 100μm were formed on Fe, Ni and carbon steel. The layer consisted of some layers with different composition, and almost the same Ti alloy layer was obtained in the bath with TiCl_8 and K_2TiF_6. The change in the formation rate indicated that the diffusion of the elements in the formed layer controlled the formation rate of the layer. Corrosion resistance of steel against saline was remarkably improved by our Ti alloy coating. A dense and coherent Ti metal layer of a few μm was obtained on stainless steel, and Cr seemed to influenced the peculiar behavior of stainless steel. Deposition in LiCl-KCl eutectic melt at lower temperature was also tried in this study, but enough Ti deposit wasn't obtained.
    4) MoO_2 was deposited on metal substrates in the melt with K_2MoO_4, while no deposit was obtained on ceramic.

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  • Electrorefining and Recycling of Magnesium

    Grant number:11225208  1999 - 2002

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research on Priority Areas

    TAKENAKA Toshihide, KAWAKAMI Masahiro

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    Grant amount:\23000000 ( Direct Cost: \23000000 )

    The application of electrorefining process for the purification of Mg and for the recycling of Mg scrap has been studied in MgC12-NaCl-CaC12 and MgC12-NaCl-KCl molten salts. The electrochemical behaviors of Mg and impurity elements, such as Fe and Ni, were measured by voltammetry, and the necessary conditions of the electrorefining of Mg were deduced. The electrorefining of Mg was carried out on the basis of the result by the electrochemical measurement. By the process, impurity elements were removed from Mg metal effectively, and the suitable electrolysis condition was revealed. Because Mg alloys were purified by the electrorefining, this process can be applied for the recycling of Mg and its alloys. It was also shown that the more efficient electrolysis can be actualized by the so-caalled three-layer electrolysis where MgCu alloy was used as anode.
    Co-e1ectrodeposition of alloying elements, such as rare earth metal, with Mg has been also studied in the same molten salt system including rare earth metal chlorides. Rare earth metals were electrodeposited with Mg metal, and their contents can be controlled by the electrolysis conditions, such as the concentration of their chloride in the salts. The Mg metal including the same amount of rare earth metals as those by electrolysis showed good corrosion-resistivity. It is concluded that the co-electrodeposition of rare earth metals with Mg can be available for the production of Mg alloy.

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  • New Concept for Electrplysis of Rare Metals-application of hydrogen gas oxidation as anodic reaction=

    Grant number:10650730  1998 - 2000

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (C)

    TAKENAKA Toshihide, KAWAKAMI Masahiro

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    Grant amount:\3500000 ( Direct Cost: \3500000 )

    Electrolysis of rare metal has been studied by using H_2 gas oxidation as anodic reaction. Ti was chosen as a target material because of its wider market. Two other methods were also tried, namely electrowinning of Ti from a fluoride-chloride melt and direct electrolysis of a Ti ingot at high temperature.
    The results are summaized as follows ;
    (1) Ti metal was electrowon in a LiF-NaF-KF melt with K_2TIF_6. Partial electrochemical reduction of Ti ions was not necessary so that the process was simplified in comparison to that in a chloride melt. The electrochemical oxidation of H_2 gas at a carbon gas electrode could be used as an anodic reaction for the process. Stable electrolysis was performed, and the cell voltage kept very low as about 2V.However, the morphology of the deposited Ti was usually powdery. Rinsing of the salt with water was not easy.
    (2) Ti metal was electrowon in a NaCl-KCI-NaF-KF melt with K_2TIF_6. The anode potential could be controlled to lower value under the suitable condition, and stable electrolysis was conducted. Partial electrochemical reduction of Ti ions was not necessary. and a gas electrode was disused. Therefore, the process could be simplified in comparison to not only that in a chloride melt and also that in a fluoride melt by using H_2 gas oxidation as anodic reaction. The NaCl-KCl-NaF-KF salt was removed from the Ti deposit with water more easily than the LiF-NaF-KF salt.
    (3) High DC-current was applied through a CaF_2-CaO mixture containing TiO_2 in an electro-slag remelting apparatus. The mixture was melted by Joule heat. and Ti metal was obtained at the cathode on the bottom of the cell. It is concluded that this process is promising in principal, and that a sufficient heat must be supplied to actualize the process.

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  • Physicochemical Research on Molten Salt Electrolysis of Ti and Ti-Al

    Grant number:06452340  1994 - 1996

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (B)

    KAWAKAMI Masahiro, TAKENAKA Toshihide

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    Grant amount:\7800000 ( Direct Cost: \7800000 )

    The physicochemical research on molten salt electrolysis of Ti and Ti-Al has been carried out. The results is summarized as follows ;
    1.Electrowinning of Ti in molten chloride
    Three electrode reactions have been studied in detail, and the valuable results for the development of more efficient electrowinning process were obtained.
    (1) Electrodeposition of Ti
    The dependence of the morphology and purity of Ti deposit and the cathodic current efficiency upon the electrolysis condition was investigated, and the proper condition was specified. Moreover, the effect of fluoride addition in chloride melt on the electrodeposition of Ti was studied.
    (2) Electro-oxidation of H_2 gas
    It was shown that H_2 gas could be oxidized anodically on carbon electrode, and that the electricity of the electrowinning of Ti could be reduced by the use of H_2 oxidation. The dependence of oxidation rate on the electrolysis condition was investigated, and the behavior of reaction product was studied.
    (3) Partial reduction of TiCl_4
    The electrochemical partial reduction of TiCl_4 was studied in detail, because it was an effective process for the supply of Ti ion in chloride melt. The effect of the electrolysis condition on reduction rate and reaction product was studied.
    2.Electroplating of TiB_2
    The electrode reaction of Ti ion in molten fluoroborate was studied in detail, and it was shown that TiB_2 could be deposited under a suitable condition. The dependence of TiB_2 deposition on electrolysis condition was investigated, and the condition where the good electroplationg layr of TiB_2 was obtained was specified.

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Devising educational methods

  • 2009年度までは、国立大学法人豊橋技術科学大学に在職して、情報処理、電磁気学、応用熱力学、腐食工学、電気化学などに関する授業、および学生実験を、学部・大学院で担当した。一部の授業では、プレゼンテーションソフトなどを多用し、電磁気学の授業についてはWEB教材化して、外部発信した。また、社会人教育として、人材育成事業にも参画して授業を行った。 2010年度からは、学校法人関西大学に在職して、反応速度論、応用熱力学、環境工学、金属生産工学、技術英語などに関する授業、および学生実験を、学部・大学院で担当している。可能な限りミニッツペーパーなどを用いることによって、学生の意見を聞き、授業内容の改善を進めている段階である。また、授業内で簡単な課題を与えて解かせるなど、学生の授業参加も考慮した授業を試みている。

Teaching materials

  • 関西大学での教育に用いた主な教科書等は以下の通りである。なお、参考書は適宜紹介している。 反応速度論:「アトキンス・物理化学」、東京化学同人 応用熱力学:「金属物理化学」、日本金属学会 環境工学:(資料を作成して配布) 材料プロセス工学:(資料を作成して配布) 金属生産工学特論:「大学教材・鉄鋼材料(プロセス編)」JFE21世紀財団 技術英語:(資料を作成して配布) 学生実験:(コース独自の教科書)

Teaching method presentations

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Special notes on other educational activities

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