研究者詳細 - 高須　登実男

その他リンク： https://ci.nii.ac.jp/naid/130007999494

Removal of boron from aqueous solution using zero-Valent magnesium granules 査読有り国際誌

Kasahara S., Takasu T., Nagano N., Mikoshi Y., Itou H., Sakamoto N.

Materials Transactions ( 公益社団法人日本金属学会 ) 61 ( 10 ) 1930 - 1939 2020年10月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）

© 2020 The Mining and Materials Processing Institute of Japan. In order to understand the characteristics of the wastewater treatment method using zero-valent magnesium granules, the reaction between an aqueous solution containing boron and zero-valent magnesium granules was investigated by experiments and a reaction rate model. Particular attention was paid to the effect of adding hydrochloric acid before adding zero-valent magnesium and to the effect of adding sodium hydroxide to adjust the pH to 10.5 after 110 minutes. The following findings were obtained. The relationship between the pH and the dissolved magnesium concentration over time is determined by a reaction formula in which zero-valent magnesium granules react with an aqueous solution to generate Mg2+ ions while generating hydrogen. When magnesium hydroxide is produced, the pH becomes constant over time. Increasing the concentration of hydrochloric acid lowers the pH value reached. This relationship is determined in equilibrium with magnesium hydroxide. The reaction rate of the zero-valent magnesium granules is determined as the first-order reaction of the hydrogen ion activity when the pH was lower than 2.3 or higher than 8.5, and as the zero-order reaction of the hydrogen ion activity at pH from 2.3 to 8.5. The amount of magnesium hydroxide produced without the addition of sodium hydroxide is determined by the above-described reaction rate model of zero-valent magnesium granules. The boron concentration of the solution when the pH is adjusted to 10.5 by adding sodium hydroxide is determined by the Langmuir-type sorption isotherm of boron to the magnesium hydroxide produced. As described above, the behavior of removing boron from an aqueous solution using zero-valent magnesium granules can be well reproduced by the simple reaction rate model used in this study, and it can be said that it is useful for process design. [doi:10.2320/matertrans.M-M2020842]

DOI： 10.2320/matertrans.M-M2020842

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Effect of polyethylene glycol on electrodeposition of zn active metal oxide composites from a particle-free solution 査読有り国際誌

Ueda D., Oue S., Takasu T., Nakano H.

Materials Transactions ( 公益社団法人日本金属学会 ) 61 ( 11 ) 2170 - 2177 2020年09月

記述言語：英語掲載種別：研究論文（学術雑誌）

©2020 The Japan Institute of Metals and Materials. Electrodeposition of ZnZr and ZnVoxide composites was performed under galvanostatic conditions at 313K on unagitated pH 2 sulfate solutions containing Zn2+ and Zr4+ or VO2+ ions and an additive such as polyethylene glycol (PEG). The effects of PEG addition on the codeposition of Zr and V oxides and their polarization behavior, and on the microstructure of the deposits, were investigated. Although the Zr content in the deposits obtained from the ZnZr solution in the absence of PEG was approximately zero, it increased significantly at a current density of above 1000 A m 2 following the addition of PEG. In the ZnV solution, the V content in the deposits obtained from 100 to 2000 A m 2 was higher with PEG than without it. In the presence of PEG, the cathode potential polarized, the rate of hydrogen evolution increased, and the hydrolysis reaction of Zr4+ and VO2+ ions proceeded smoothly, resulting in an increase in the Zr and V content in the deposits. Additionally, the crystal platelets of Zn in the ZnZr and the ZnVoxide films became fine, and the surface coverage of the spongiform Zr and film-like Voxides increased. Furthermore, the corrosion current densities of the ZnZr and ZnVoxide films obtained from the solution with PEG were lower than those from the solution without it. The reduction rate of dissolved oxygen decreased in the films in the presence of PEG, thereby leading to a decrease in the corrosion current density

DOI： 10.2320/matertrans.MT-M2020164

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Effect of Organic Additives on the Electrodeposition Behavior of Zn from an Alkaline Zincate Solution and Its Microstructure 査読有り国際誌

Kenta Fukumoto, Satoshi Oue, Yoshiharu Kikuchi, Shinya Akamatsu, Tomio Takasu, Hiroaki Nakano

MATERIALS TRANSACTIONS ( 公益社団法人日本金属学会 ) 61 ( 3 ) 497 - 505 2020年02月

記述言語：英語掲載種別：研究論文（学術雑誌）

Electrodeposition of Zn was performed on an Fe electrode at a current density of 20–5000 A·m−2 and a charge of 4 × 104 C·m−2 in an unagitated zincate solution at 313 K containing 0.62 mol·dm−3 of ZnO, 4.0 mol·dm−3 of NaOH, and organic additives. The effects of organic additives on the deposition behavior of Zn and the microstructure of the deposits were investigated. Glossy films were obtained by depositing at current densities higher than 1000 A·m−2 from the solution containing additives of a straight-chain polymer composed of a quaternary ammonium cation (PQ) and a quaternary ammonium salt with a benzene ring (QA). The polarization curve was separated into partial polarization curves of Zn deposition and hydrogen evolution by using the galvanostatic data of Zn deposition. The overpotentials of the charge transfer of Zn deposition and that of ZnO22− ion diffusion increased with the addition of PQ and QA. The increase in overpotential was considerable at potentials less noble than −1.5 V. Zn deposition reached the diffusion limit of ZnO22− ions at potentials less noble than −1.5 V, indicating that the diffusion of ZnO22− ions was suppressed considerably by PQ and QA. With the addition of PQ and QA, C, N, and H were codeposited with Zn, which demonstrated that the additives of PQ and QA were incorporated into the deposited films. Zn crystallite size decreased with increasing current density. At a high current density of 5000 A·m−2, the crystallite size decreased with the addition of PQ and QA, and the surface of the film was smooth. The orientation index of the {1010} plane of Zn deposited from the solution containing PQ and QA increased with increasing current density. The changes in the crystallite size and crystal orientation of deposited Zn were explained by the deposition overpotential. This Paper was Originally Published in Japanese in J. Japan Inst. Metals 83 (2019) 399–406.

DOI： 10.2320/matertrans.MT-M2019316

その他リンク： https://ci.nii.ac.jp/naid/130007801654

非懸濁溶液からの Zn-活性金属酸化物複合電析に及ぼすポリエチレングリコール添加の影響査読有り

植田大樹, 大上悟, 高須登実男, 中野博昭

日本金属学会誌 ( 公益社団法人日本金属学会 ) 84 ( 2 ) 50 - 57 2019年12月

記述言語：英語掲載種別：研究論文（学術雑誌）

© 2019 The Japan Institute of Metals and Materials Electrodeposition of Zn-Zr oxide and Zn-V oxide composites was performed under galvanostatic conditions from an unagitated sulfate solution containing Zn2+, Zr4+, or VO2+ ions and an additive such as polyethylene glycol (PEG). The sulfate solution had a pH of 2 and the electrodeposition was performed at 313 K. The effects of PEG on the co-deposition of the Zr oxides and V oxides and their polarization behavior were investigated. Additionally, the effects of PEG on the microstructure of the deposits were investigated. Although the Zr content in the deposits obtained from the Zn-Zr solution without PEG was approximately zero, it increased significantly at a current density above 1000 A m- following the addition of PEG. In the Zn-V solution, the V content in the deposits obtained from 100 A m-2 to 2000 A m-2 was higher with PEG than that without PEG. In the presence of PEG, the cathode potential polarized, the rate of hydrogen evolution increased, and the hydrolysis reaction of Zr4+ and VO2+ ions occurred easily. This resulted in the Zr content and V content increasing in the deposits. Additionally, the crystal platelets of Zn in the Zn-Zr oxide film and the Zn-V oxide film became fine, and the surface coverage of the spongiform Zr oxide and the film-like V oxide increased. Furthermore, the corrosion current densities of the Zn-Zr oxide film and the Zn-V oxide film obtained from the solution with PEG were lower than those from the solution without PEG. The reduction reaction of dissolved oxygen decreased in the films with PEG, thereby decreasing the corrosion current density.

DOI： 10.2320/jinstmet.J2019031

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アルカリジンケート浴からの亜鉛の電析挙動とその微細構造に及ぼす有機添加剤の影響査読有り

福元健太, 大上悟, 菊池義治, 赤松慎也, 高須登実男, 中野博昭

日本金属学会誌 ( 公益社団法人日本金属学会 ) 83 ( 11 ) 399 - 406 2019年11月

記述言語：日本語掲載種別：研究論文（学術雑誌）

Electrodeposition of Zn was performed on a Fe electrode at a current density of 20-5000 A·m−2 and a charge of 4 × 104 C·m−2 in an unagitated zincate solution containing 0.62 mol·dm−3 of ZnO, 4.0 mol·dm−3 of NaOH and organic additives at 313 K. The effects of organic additives on the deposition behavior of Zn and the microstructure of the deposits were investigated. The films deposited at current densities higher than 1000 A・m−2 from the solution containing additives of a straight-chain polymer composed of quaternary ammonium cation (PQ) and a quaternary ammonium salt with benzene ring (QA) exhibited the gloss. The polarization curve was separated into a partial polarization curve of Zn deposition and that of hydrogen evolution by using the galvanostatic data of Zn deposition. The overpotentials of charge transfer of Zn deposition and that of ZnO22− ions diffusion increased with additions of PQ and QA. The increase in overpotential was remarkable at potential less noble than −1.5 V. Zn deposition reached the diffusion limit of ZnO22− ions at potential less noble than −1.5 V, indicating that the diffusion of ZnO22− ions was greatly suppressed by PQ and QA. With additions of PQ and QA, the C, N and H were co-deposited with Zn, showing that the additives of PQ and QA were incorporated in deposited films. The size of the Zn crystallite decreased with increasing current density. At a high current density of 5000 A・m−2, the crystallite size decreased furthermore with additions of PQ and QA and the film showed the smooth surface. The orientation index of the {1010} plane of Zn deposited from the solution containing PQ and QA increased with current density. The change of the crystallite size and crystal orientation of deposited Zn were explained related to the deposition overpotential.

DOI： 10.2320/jinstmet.J2019027

その他リンク： https://ci.nii.ac.jp/naid/130007732609

ワット浴からの低熱膨張型Fe-Niインバー合金の電析挙動と微細構造に及ぼす添加剤の影響査読有り

福田圭祐, 柏裕樹, 大上悟, 高須登実男, 中野博昭

鉄と鋼 ( 一般社団法人日本鉄鋼協会 ) 105 ( 10 ) 988 - 997 2019年10月

記述言語：英語掲載種別：研究論文（学術雑誌）

The electrodeposition of invar Fe-Ni alloy with low thermal expansion was performed at 100-5000 A·m–2 and 105 C·m–2 in agitated Watt's solution containing NiSO4, NiCl2, FeSO4, C3H4O4, C7H4NNaO3S and H3BO3 at 50ºC. With increasing the concentration of malonic acid, the Ni content in deposits decreased at higher current density region than 2000 A·m–2, while it increased at lower current density region than 1000 A·m–2. The current efficiency for alloy deposition decreased with increasing the concentration of malonic acid. The deposits were composed of granular crystals whose size decreased with increasing the concentration of malonic acid. With an addition of saccharin, the Ni content in deposits significantly decreased, and the current efficiency for alloy deposition increased. With an addition of boric acid, the Ni content in deposits somewhat decreased, and the current efficiency for alloy deposition increased. The surface morphology of deposits changed with the current density and an addition of saccharin, and rarely changed with an addition of boric acid. It was found that the morphology depended on the Ni content in deposits. The deposits with Ni content of 29-38 mass% were composed of granular crystals approximately 300 nm in size, while the deposits with Ni content of 41-52 mass% showed the smooth surface consisted of fine crystals. The effects of additives on the Ni content in deposits and current efficiency can be explained by the change of partial polarization curve for Fe and Ni deposition and hydrogen evolution in Fe-Ni alloy deposition.

DOI： 10.2355/tetsutohagane.TETSU-2019-045

その他リンク： https://ci.nii.ac.jp/naid/130007719956

Effects of electrolysis conditions on the formation of electrodeposited invar Fe-Ni alloys with low thermal expansion 査読有り国際誌

Fukuda K., Kashiwa Y., Oue S., Takasu T., Nakano H.

ISIJ International ( 一般社団法人日本鉄鋼協会 ) 59 ( 9 ) 1632 - 1641 2019年09月

記述言語：英語掲載種別：研究論文（学術雑誌）

© 2019 ISIJ. To elucidate the effects of the electrolysis conditions on the formation of electrodeposited invar Fe-Ni alloys with low thermal expansion, Fe-Ni electrodeposition was performed at 10-5 000 A·m−2 and 5 × 105 C·m−2 in an agitated solution containing NiSO4, NiCl2, FeSO4, H3BO3, C7H4NNaO3S, and C3H4O4 at 40°C-60°C. In the low-current-density region, the Ni content in the deposits significantly decreased with increasing current density, reached a minimum, and then increased after reaching the diffusion-limiting current density for Fe deposition. With the increasing concentration of FeSO4 in the solution, the Ni content in the deposits decreased in the lower-current-density region, reached a constant at a moderate current density, and then began to increase at higher current density. As a result, the current density range in which the Ni content in the deposits reached a minimum and remained constant became wider with increasing FeSO4 concentration. With the decreasing pH of the solution, since the partial polarization curve for H2 evolution and the total polarization curve shifted to a higher-current-density region, the curve of the Ni content in the deposits as a function of the current density shifted toward a higher current density. The change in the composition of the Fe-Ni alloy deposits because of the electrolysis conditions can be explained by the changes in the total polarization curve and the partial polarization curves for Fe and Ni deposition and H2 evolution.

DOI： 10.2355/isijinternational.ISIJINT-2019-023

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Effects of electrolyte composition and additives on the formation of invar Fe–Ni alloys with low thermal expansion electrodeposited from sulfate bath 査読有り国際誌

Kashiwa Y., Nagano N., Takasu T., Kobayashi S., Fukuda K., Nakano H.

ISIJ International ( 一般社団法人日本鉄鋼協会 ) 59 ( 3 ) 514 - 523 2019年03月

記述言語：英語掲載種別：研究論文（学術雑誌）

© 2019 ISIJ. The effects of solution composition and additives on the formation of electrodeposited invar Fe–Ni alloys with low thermal expansion were investigated. In all solutions, increasing the current density from 10A·m −2 significantly decreased the Ni content in the deposits and resulted in anomalous codeposition, in which the electrochemically less noble Fe was preferentially deposited. Further increasing the current density increased the Ni content in the deposits as Fe deposition reached the diffusion limitation of the Fe 2+ ions. Increasing the concentration of Fe 2+ ions increased the current density required to initiate an increase in the Ni content in the deposits because of increase in the diffusion-limited current density of Fe. With the increasing concentration of malonic acid, the current density region in which Ni deposition was suppressed was extended, and the potential at which Fe deposition reached the diffusion limitation of the Fe 2+ ions was shifted to a less noble direction. As a result, the relationship between the Ni content in the deposits and the current density shifted to a higher-current-density region with increasing malonic acid concentration. At malonic acid concentrations above 0.05mol·dm −3 , the current efficiency for alloy deposition was greatly reduced owing to the promotion of hydrogen evolution. The Ni content in the deposits was significantly increased with the addition of thiourea. Boric acid somewhat increased the Ni content in the deposits in the lower-current-density region. In solutions containing both boric acid and saccharin, an invar alloy of 36 mass% Ni was obtained in the wider-current-density region.

DOI： 10.2355/isijinternational.ISIJINT-2018-676

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低熱膨張型電析Fe-Niインバー合金の形成に及ぼす電解条件の影響査読有り

福田圭祐,柏裕樹,大上悟,高須登実男,中野博昭

鉄と鋼 ( 一般社団法人日本鉄鋼協会 ) 105 ( 1 ) 55 - 63 2019年01月

記述言語：英語掲載種別：研究論文（学術雑誌）

© 2019 Iron and Steel Institute of Japan. All Rights Reserved. Synopsis: To elucidate the effects of electrolysis conditions on the formation of electrodeposited invar Fe-Ni alloys with low thermal expansion, Fe-Ni electrodeposition was performed at 10-5000 A·m -2 and 5×10 5 C·m -2 in agitated solution containing NiSO 4 , NiCl 2 , H 3 BO 3 , FeSO 4 , C 7 H 4 NNaO 3 S and C 3 H 4 O 4 at 40-60°C. Ni content in deposits significantly decreased in the low current density region with increasing current density, reached a minimum, and then increased due to reaching at diffusion limiting current density for Fe deposition as the current density increased further. With increasing the concentration of FeSO 4 in solution, Ni content in deposits decreased at lower current density region, reached a constant at lower current density, and then began to increase at higher current density. As a result, the current density range where Ni content in deposits was minimum and constant became wider with higher concentration of FeSO 4 . With decreasing pH in solution, since the partial polarization curve for H 2 evolution and total polarization curve sifted to higher current density region, Ni content in deposits-current density curve shifted to higher current density region. With stirring the solution, Ni content in deposits reached a minimum as the current density increased, and then began to increase at higher current density than without stirring due to increase in diffusion limiting current density for Fe deposition. The change of the composition in deposits by electrolysis condition can be explained by the changes of the total polarization curve for Fe-Ni alloy deposition and the partial polarization curves for Fe and Ni depositions and H 2 evolution.

DOI： 10.2355/tetsutohagane.TETSU-2018-101

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硫酸塩浴からの低熱膨張型電析Fe-Niインバー合金の形成に及ぼす液組成と添加剤の影響査読有り

柏裕樹, 長野暢明, 高須登実男, 小林繁夫, 福田圭祐, 中野博昭

鉄と鋼 104 ( 10 ) 585 - 593 2018年10月

記述言語：日本語掲載種別：研究論文（学術雑誌）

The effects of solution composition and additives on the formation of electrodeposited invar Fe-Ni alloys with low thermal expansion was investigated. In all the solutions, with increasing the current density from 10 A·m–2, the Ni content in deposits significantly decreased and showed the anomalous codeposition in which electrochemically less noble Fe deposits preferentially. With increasing current density further, Fe deposition reached the diffusion limitation of Fe2+ ions, as a result, the Ni content in deposits increased with current density. The current density for initiating to increase the Ni content in deposits shifted to higher value with increasing the concentration of Fe2+ ions because of increase in diffusion-limited current density of Fe. With increasing the concentration of malonic acid, the current density region in which the Ni deposition was suppressed, extended and the potential which Fe deposition reached to the diffusion limitation of Fe2+ ions shifted to the less noble direction. As a result, the curve which showed the relationship between the Ni content in deposits and current density, shifted to higher current density region with increasing the malonic acid. The current efficiency for alloy deposition greatly decreased due to promotion of hydrogen evolution with the concentration of malonic acid above 0.05 mol·dm–3. The Ni content in deposits significantly increased with thiourea. With boric acid, the Ni content in deposits somewhat increased in the lower current density region. With both boric acid and saccharin, the invar alloy of Fe-36 mass% Ni was obtained in the wider current density region.

DOI： 10.2355/tetsutohagane.TETSU-2018-051

その他リンク： https://ci.nii.ac.jp/naid/130007491653

Crystallization of the amorphous ferric arsenate in the saturated steam atmosphere 査読有り国際誌

Itou H., Takasu T., Ueno Y.

High Temperature Materials and Processes 30 ( 4 ) 473 - 483 2011年08月

担当区分：責任著者記述言語：英語掲載種別：研究論文（学術雑誌）

Scorodite is an appropriate compound for the immobilization of arsenic generated in the nonferrous smelting and refining industry. To develop processes to produce scorodite, the mechanism of scorodite formation is important. As a part of the mechanism elucidation of the scorodite formation, crystallization of the amorphous ferric arsenate into scorodite was investigated in the gas atmospheres. The amorphous sample was prepared by the precipitation from the solution of Fe(III) and As(V) at 35°C. The sample was composed of the weak agglomerates around 10 μm which consisted of particles of about 1 μm in diameter. In the dry atmosphere, the crystallization did not occur. However, in the saturated steam atmosphere, the crystallization of the amorphous into the scorodite occurred at 95°C. The higher temperature accelerated the crystallization in terms of the incubation period and crystallinity. The crystallinity of the sample formed at 160°C for 3 h was the same as that of the hydrothermally synthesized scorodite. The start of the crystallization was always coincident with the start of the increase in particle size. It suggested that the increase in particle size contributed to the crystallization. Copyright © 2011 De Gruyter.

DOI： 10.1515/HTMP.2011.070