| 大上 悟（おおうえ さとし） | データ更新日：2024.04.25 |
助教 ／
工学研究院
材料工学部門
材料反応工学
| 1. | 今谷 智貴, 大上 悟, 谷ノ内勇樹, 青木泰紀, 中野博昭, アルカリジンケート浴からの亜鉛の電析挙動とその結晶形態に 及ぼす有機添加剤の構造の影響, 日本金属学会誌, doi:10.2320/jinstmet.J2023018, 68, 3, 58-67, 2024.03, The effect of structure of organic additives on the electrodeposition behavior of Zn from alkaline zincate solution and its crystal morphology was investigated. Zn was electrodeposited on an Fe electrode at 20–1000 A·m−2, 2.4 × 104 C·m−2, 300 K from unagitated zincate solutions containing the various organic additives as a leveling agent. The suppression effect of additives on the charge transfer and diffusion of ZnO22− ions in Zn electrodeposition corresponded to the number of adsorption site per a straight chain molecule of polymer. The effect of polymer alone on the decrease in size of Zn platelets crystals was small, but the crystal size significantly decreased with coexistence of low molecular additive. The crystal size of deposited Zn decreased in spite of small suppression effect on Zn deposition, showing that the crystal size of deposited Zn doesn’t depend on the overpotential for deposition. With coexistence of low molecular additive with polymer, the crystal of deposited Zn was fine regardless of kind of polymer even though Zn deposited at the diffusion control of ZnO22− ions. . |
| 2. | Sota TOYOKUNI, Satoshi OUE, Yu-ki TANINOUCHI and Hiroaki NAKANO, Micro Structure and Corrosion Resistance of Zn Composites Films Produced by Pulse Electrolysis from a Insoluble Particle-free Solution Containing Zr Ions, ISIJ International, https://doi.org/10.2355/isijinternational.ISIJINT-2023-270, 63, 11, 1908-1918, 2023.11, The electrodeposition of an Zn–Zr compound composite is performed under pulsed and double-pulsed current conditions at 313 K in unagitated pH 2 sulfate solutions containing Zn2+ and ZrO2+ ions and poly- ethylene glycol. Under constant-current electrolysis at 5 000 A·m − 2, coarse granular partial deposits con- taining Zr compounds are observed. Under pulse electrolysis, such coarse deposits are observed rarely; however, both deposited films containing Zr compounds and exfoliated films are observed. On the con- trary, in double-pulse electrolysis at high (5 000 A·m−2) and low (500 A·m−2) current densities, coarse deposits are not observed while fine-particle deposits containing Zr compounds are observed. In double- pulse electrolysis at low current densities, the rate of hydrogen evolution decreases and Zn is deposited without the codeposition of Zr compounds; therefore, the continuous hydrogen evolution is suspended in some areas. That is, the area of hydrogen evolution appears to be random. Although Zr compounds are usually concentrated at the upper regions of the deposited films, regardless of the electrolysis method, it is found to have been codeposited even in the inner regions under double-pulse electrolysis. The corrosion current density in 3 mass% NaCl solution is the smallest for the films produced by double-pulse elec- trolysis, when comparing with the films obtained by pulse electrolysis and constant-current electrolysis. This can be attributed to the suppression of the reduction reaction of dissolved oxygen.. |
| 3. | Sung Hwa BAE, Satoshi OUE, Yu-ki TANINOUCHI, Injoon SON and Hiroaki NAKANO, Corrosion Resistance of Zn–Ni Alloy Films Electroplated in Alkaline Zincate Solutions Containing a Brightener, ISIJ International, https://doi.org/10.2355/isijinternational.ISIJINT-2023-236, 63, 11, 1897-1907, 2023.11, Zn–Ni alloys were electroplated on a Fe plate with a thickness of 40 μm at 500 A·m−2 and 293 K in unagitated zincate solutions. The reaction product of epichlorohydrin and imidazole (IME) was added to the solution as a brightener at concentrations of 0–5 mL dm–3. The corrosion resistance of the obtained Zn–Ni alloy films was investigated from the polarization curve in 3 mass% NaCl solution before and after the corrosion treatment (formation of corrosion products) for 48 hours. Before the corrosion treatment, the corrosion current density of plated films rarely changed, regardless of the addition of IME into the zincate solution, because the reduction reaction of dissolved oxygen rarely changed. However, in films plated from the solution containing IME, the anode reaction was suppressed, and the corrosion potential shifted toward the noble direction. The suppression of the anode reaction with an addition of IME into the plating solution is attributed to the increase in γ-phase in the plated films. After the corrosion treatment, Zn chlo- ride hydroxide of the corrosion product uniformly formed on the surface when increasing the concentra- tion of IME. The reduction reaction of dissolved oxygen was suppressed by increasing the concentration of IME, resulting in a decrease in corrosion current density.. |
| 4. | 豊國 想太, 大上 悟, 谷ノ内 勇樹, 中野 博昭, Zrイオンを含む非懸濁溶液からパルス電解法により作製したZn系複合電析膜の微細構造と耐食性, 鉄と鋼, https://doi.org/10.2355/tetsutohagane.TETSU-2023-013, 109, 8, 684-694, 2023.08, Electrodeposition of Zn–Zr compound composite was performed under pulsed and double pulsed current conditions at 313 K on unagitated pH 2 sulfate solutions containing Zn2+, ZrO2+ ions and a polyethylene glycol (PEG). At constant current density of 5000 A∙m−2 , the coarse granular deposits containing Zr compound existed partially. Meanwhile, in pulse electrolysis, the coarse deposits were rarely seen and the both areas of deposited films containing Zr compound and its films being exfoliated were observed. On the contrary, in double pulse electrolysis of high current density (5000 A∙m−2) and low current density (500 A∙m−2), the coarse deposits were not observed and the fine particle deposits containing Zr compound were present. In double pulse electrolysis, since at low current density, the rate of hydrogen evolution decreases and Zn deposits without co-deposition of Zr compound, the continuous hydrogen evolution is suspended in some areas and the area of hydrogen evolution seems to become random. Although Zr com- pound concentrated at upper area of deposited films regardless of electrolytic method, it codeposited even at inner part with double pulse electrolysis. The corrosion current density in 3 mass% NaCl solution was the smallest for the films produced by double pulse electrolysis, comparing with films obtained by pulse electrolysis and constant current electrolysis. This is attributed to reduction reaction of dissolved oxygen being suppressed.. |
| 5. | Wataru MURAKAMI, Satoshi OUE, Yu-ki TANINOUCHI, Shinya Akamatsu, Hiroaki NAKANO, Electrodeposition Behavior of Zn-Ni Alloy from Alkaline Zincate Solutions Containing Various Brighteners and its Microstructure, 鉄と鋼, https://doi.org/10.2355/tetsutohagane.TETSU-2022-110, 109, 4, 277-288, 2023.04, The effect of brighteners on the deposition behavior of Zn–Ni alloys ant its microstructure was investigat- ed. Zn–Ni alloys were electrodeposited on Cu electrode at 10–5000 A·m−2, 105 C·m−2, 308 K in unagitated zincate solutions containing various brighteners. Although the degree of suppression of hydrogen evolu- tion was different depending on the kind of brightener, the transition current density at which the depo- sition behavior shifted from normal to anomalous was almost same in solutions containing brighteners. The current efficiency for alloy deposition significantly decreased with an addition of brighteners which had suppression effect on the Zn deposition. Since the brighteners more suppressed the Ni deposition than Zn deposition, the Ni content in deposited films decreased with an addition of brighteners. When the brightener of a straight-chain polymer composed of a quaternary ammonium cation (PQ) which can suppress the diffusion of ZnO22− and Ni ions in solution was added, the Ni content in deposited films in- creased with increasing current density at high current density region. This is attributed to that Zn which is preferentially deposited over Ni earlier reached the diffusion limitation of ZnO22− ions and Ni deposi- tion didn’t reach the diffusion-limited current density. When both PQ and a quaternary ammonium salt with a benzene ring were added in solution, the films obtained at the diffusion-limited current density of ZnO22− ions exhibited the smooth surfaces composed of fine crystals. With an addition of brighteners to increase the overpotential for deposition, the γ-phase (intermetallic compound of Ni2Zn11) of the deposit- ed films was formed easily.. |
| 6. | Sung Hwa BAE, Satoshi OUE, Yu-ki TANINOUCHI, Injoon SON, Hiroaki NAKANO, Corrosion Resistance of Zn-Ni Alloy FilmsElectroplated from Alkaline Zincate SolutionContaining Brightener, 鉄と鋼, https://doi.org/10.2355/tetsutohagane.TETSU-2022-110, 109, 4, 289-300, 2023.04, Zn–Ni alloys were electroplated on an Fe plate with thicknesses of 40 μm at 500 A·m−2 and 293 K in un- agitated zincate solutions. The reaction product of epichlorohydrin and imidazole (IME) was added in the solution as a brightener at the concentration of 0-5 ml/dm−3. The corrosion resistance of the obtained Zn– Ni alloys films was investigated from the polarization curve in 3 mass% NaCl solution before and after the corrosion treatment (formation of corrosion products) in NaCl solution for 48 h. Before the corrosion treatment, the corrosion current density of plated films rarely changed regardless of addition of IME into the zincate solution because the reduction reaction of dissolved oxygen rarely changed. However, in films plated from the solution containing IME, the anode reaction was suppressed and the corrosion potential shifted to noble direction. The suppression of anode reaction with an addition of IME in plating solution is attributed to the increase in γ-phase in plated films. On the other hand, after the corrosion treatment, the morphology of Zn chloride hydroxide of corrosion product was uniformly formed on the surface with increasing the concentration of IME. The reduction reaction of dissolved oxygen was suppressed with increasing the concentration of IME, resulting in decrease in corrosion current density.. |
| 7. | Kohei Mori, Yuta Yamakawa , Satoshi Oue , Yu-ki Taninouchi and Hiroaki Nakano, Effect of Impurity Ions and Additives in Solution of Copper Electrorefining on the Passivation Behavior of Low-Grade Copper Anode, Materials Transactions, doi:10.2320/matertrans.MT-M2022087, 64, 1, 242-251, 2023.01, Cu electrorefining using a low-grade copper anode is desirable from the standpoint of electric power savings. Cu electrolysis was carried out in an unagitated sulfate solution with a low-grade copper anode, and the effect of impurity ions and additives in the solution on the passivation of the anode was investigated. The time when anode passivation firstly occurs shortened significantly in a solution containing 0.596 mol·dm13 of Ni2+ ions as impurity and shortened somewhat in a solution containing As5+(0.053 mol·dm13) or Bi3+(0.0005 mol·dm13) ions. Sn2+(0.0004 mol·dm13) and As3+(0.053 mol·dm13) ions slightly decreased the time to passivation, but Sb3+(0.004 mol·dm13) ions did not. The viscosity coefficient of the solution increased when the 0.596mol·dm13 of Ni2+ ions were added to the solution, while the diffusion coefficient of Cu2+ ions decreased. The compound of the AsSbO or AsBiO system was formed in anode slime when the As5+(0.053 mol·dm13) or Bi3+(0.0005 mol·dm13) ions were added to the solution, which seemed to increase the compactness of slime. The time to passivation was slightly longer in thiourea-free solution but shortened when the concentration of thiourea was increased from 0.525 to 2.24 mmol·dm13. The time to passivation was constant in solutions containing 0 to 1.13 mmol·dm13 of Cl1 ions, but significantly decreased as the concentration of Cl1 ions increased above 1.13 mmol·dm13. Cl1 ions formed CuCl at the upper area of anode slime, which increased the compactness of slime and promoted the passivation.. |
| 8. | Sung Hwa BAE, Satoshi OUE, Yu-ki TANINOUCHI, Injoon SON, Hiroaki NAKANO, Synergistic Effect of Brightener and Solution Temperature on the Electrodeposition Behavior of Zn–Ni Alloy from Alkaline Zincate Solution, ISIJ International, https://doi.org/10.2355/isijinternational.ISIJINT-2022-160, 62, 9, 1918-1929, 2022.09, Zn–Ni alloys were electrodeposited on a Cu electrode at 10–5 000 A·m−2, 5 × 104 C·m−2, 293 K, 313 K, and 333 K in unagitated zincate solutions containing the reaction product of epichlorohydrin and imid- azole (IME) as a brightener. The synergistic effect of IEM and solution temperature on the deposition behavior of Zn–Ni alloys was investigated. The transition current density at which the deposition behavior shifted from normal to anomalous one decreased with IME at 293 K, but did not change regardless of IME addition at 313 K and 333 K. The suppression effect of IME on the Zn and Ni depositions during alloy deposition was observed at 293 K while at 313 K and 333 K, the suppression effect decreased on the Zn deposition but was maintained on the Ni deposition. Therefore, Ni content in deposits significantly decreased with IME as the temperature increased. The current efficiency of Zn deposition significantly decreased with IME at 293 K, with a small degree of decrease at 313 K and 333 K. The C content in deposits was the highest at 293 K and decreased with increasing solution temperature, indicating that the adsorption ability of IME on the cathode decreases with the increasing temperature. As a result, the sup- pression effect of IME on the Zn deposition decreases with the increasing temperature. The gloss of deposited films was the highest at 293 K, attributed to the IME adsorption ability being large at 293 K and deposited films with fine crystals becoming smooth.. |
| 9. | 森 康平,山川裕太,大上悟, 谷ノ内勇樹, 中野博昭, 低品位銅アノードの不動態化挙動に及ぼす銅電解精製浴中の不純物イオンと添加剤の影響, 日本金属学会誌, [doi:10.2320/jinstmet.J2022001], 86, 6, 97-106, 2022.06, he Cu electrorefining using low–grade copper anode is desired from the view point of reduction of electric power. Cu electrolysis was performed using a low–grade copper anode in an unagitated sulfate solution, and the effect of impurity ions and additives in solution on the passivation of anode was investigated. The time when anode passivation firstly occurs shortened significantly in solution containing 0.596 mol·dm−3 of Ni2+ ions as impurity, and shortened somewhat in solution containing As5+(0.053 mol·dm−3) or Bi3+(0.0005 mol·dm−3) ions. Sn2+(0.0004mol·dm−3) and As3+(0.053mol·dm−3) ions slightly decreased the time to passivation, but Sb3+ (0.004mol·dm−3) ions rarely decreased the time. When the 0.596mol·dm−3 of Ni2+ ions were added in solution, the viscosity coefficient of solution increased and the diffusion coefficient of Cu2+ ions decreased. When the As5+(0.053mol·dm−3) or Bi3+(0.0005mol·dm−3) ions were added in solution, the compound of As–Sb–O or As–Bi–O system was formed in anode slime, which seemed to increase the compactness of slime. The time to passivation was slightly longer in thiourea–free solution, but shortened with increasing the concentration of thiourea from 0.525 to 2.24 mmol·dm−3. In the solutions containing 0 to 1.13 mmol·dm−3 of Cl− ions, the time to passivation was constant, but significantly shortened with increasing the concentration of Cl− ions at the region above 1.13 mmol·dm−3. Cl− ions formed CuCl at the upper area of anode slime, as a result, increased the compactness of slime and promoted the passivation. . |
| 10. | 裵 聖和, 大上 悟, 谷ノ内 勇樹, 孫 仁俊, 中野 博昭, ジンケート浴からの Zn-Ni 合金電析挙動に及ぼす 光沢剤と浴温の相乗作用, 鉄と鋼, https://doi.org/10.2355/tetsutohagane.TETSU-2021-105, 108, 4, 268-281, 2022.04, Zn–Ni alloys were electrodeposited on a Cu electrode at 10–5000 A·m−2, 5 × 104 C·m−2, and 293, 313 and 333 K in unagitated zincate solutions containing the reaction product of epichlorohydrin and imidazole (IME) as a brightener. The synergistic effect of IEM and solution temperature on the deposition behavior of Zn–Ni alloy was investigated. The transition current density, at which the deposition behavior shifted from the normal type to anomalous ones, decreased with IME at 293 K, but didn’t change regardless of IME addition at 313 and 333 K. The suppression effect of IME on the Zn and Ni depositions during alloy deposition was observed at 293 K, while at 313 and 333 K, the suppression effect was decreased on the Zn deposition but was maintained on the Ni deposition. Therefore, Ni content in deposits significantly decreased with IME as temperature increased. The current efficiency for Zn deposition significantly decreased with IME at 293 K, while the degree of decrease was small at 313 and 333 K. The content of C in deposits was highest at 293 K, and decreased with increasing solution temperature, indicating that the adsorption ability of IME on the cathode decreases with increasing temperature. As a result, the sup- pression effect of IME on the Zn deposition seems to decrease with increasing temperature. The gloss of deposited films was highest at 293 K. This is attributed to adsorption ability of IME being large at 293 K and depos- ited films with fine crystals becoming smooth.. |
| 11. | 裵 聖和, 大上 悟, 谷ノ内 勇樹, 孫 仁俊, 中野 博昭 , アルカリジンケート浴からのZn-Ni合金電析挙動に及ぼす浴温の影響, 鉄と鋼, https://www.jstage.jst.go.jp/article/tetsutohagane/108/2/108_TETSU-2021-092/_article/-char/ja/, 108, 2, 120-130, 2022.02, Zn電析は古くから鋼板の腐食防止のために使用されてきたが，電析膜の耐食性を更に向上させるためにZn合金電析が行われている1–8)。合金電析の中でもZn-Ni合金は，熱安定性と耐食性に優れており，自動車部品，建築資材など様々な産業分野で適用されている。Zn-Ni合金電析は，通常，硫酸塩浴，塩化物浴から行われるが，小物部品等に対する均一電着性の観点からは，ジンケート浴からの方が望ましい。硫酸塩浴，塩化物浴からのZn-Ni合金電析については，従来より多数の研究が行われており，実用的な電流密度の領域では，電気化学的に卑なZnが貴なNiより優先析出する変則型共析挙動を示すことが知られている9–15)。ジンケート浴からのZn-Ni合金の電析については，電析膜中のNi含有率に及ぼす電流密度16–19)，全金属塩濃度20)，撹拌19)，Ni錯化剤濃度19)，浴組成の影響17,19–21)，合金電析の電流効率に及ぼす電流密度18,20)の影響が報告されているが硫酸塩浴，塩化物浴からの場合に比べて電析機構22)に関する研究例が少ない。 一方，浴温は，電析過電圧，均一電着性，金属塩の溶解度，浴導電率等に影響を及ぼす23)。浴温を高くすると，浴の導電率が増加する。また，イオンの拡散係数および金属塩の溶解度が増大するため金属析出の拡散限界電流密度を高くすることが出来る。浴温を低下させると，電析過電圧が増加することにより電析物の結晶粒が微細化し，また均一電着性が改善される。このように，浴温は電析において極めて重要な因子であるが，ジンケート浴からのZn-Ni合金の電析挙動に及ぼす浴温の影響についてはほとんど報告されていない19)。そこで，本研究では，ジンケート浴からのZn-Ni合金電析挙動に及ぼす浴温の影響をZn，Ni析出および水素発生の部分分極曲線に基づき考察した。. |
| 12. | Kentaro Ochi, Makoto Sekiguchi, Satoshi Oue, Hiroaki Nakano, Effect of Halide Ions on Electrodeposition Behavior and Morphology of Electrolytic Copper Powder, Materials Transaction, https://doi.org/10.2320/matertrans.MT-M2021126, 62, 11, 1647-1652, 2021.11, To investigate the effect of halide ions on the electrodeposition behavior and morphology of copper powder, polarization curves were measured and constant current electrolysis of 300 and 500 A·m−2 was conducted in an electrolytic solution containing 0.079 mol·dm−3 Cu2+ and 0.5 mol·dm−3 free H2SO4 at 293 and 303 K without stirring. Cl− promoted the deposition of copper powder, while Br− and I− suppressed deposition. The current efficiency for copper deposition increased with the addition of Cl− and decreased with the addition of Br−. The addition of Cl− reduced the average particle size of the copper powder and caused the dendrite-shaped branches and trunks to grow thinner and longer, resulting in a lower tap density. In contrast, the addition of Br− caused the average particle size, average crystallite size, and tap density of the copper powder to decrease. With increasing Cl− concentration, the current efficiency for copper deposition increased, that is, copper deposition was promoted. This even occurred in the region in which Cu2+ ion diffusion was the rate-determining process, indicating that the deposition of copper powder was affected by the charge-transfer process. The change in the morphology of the copper powder with the addition of halide ions is attributed to the change in the charge-transfer process. The deposition of copper powder appears to proceed under a mixed rate-determining process involving the diffusion of Cu2+ ions and charge transfer. This Paper was Originally Published in Japanese in J. Japan Inst. Met. Mater. 85 (2021) 207–212. Captions of all figures and tables are slightly modified.. |
| 13. | 越智 健太郎, 関口 誠, 大上 悟, 中野 博昭, 電解銅粉の析出挙動および銅粉の形態に及ぼす高分子添加剤と塩化物イオンの影響, 日本金属学会誌, https://doi.org/10.2320/jinstmet.J2021018, 85, 7, 264-272, 2021.07, To investigate the effect of polymer additives and chloride ions on the electrodeposition behavior and morphology of copper powder, the polarization curves were measured and constant current electrolysis of 300 A·m−2 and 500 A·m−2 was conducted in an electrolytic solution containing 0.079 mol·dm−3 of Cu2+ and 0.5 mol·dm−3 of free H2SO4 at 293K and 393 K without stirring. Polyethylene glycol (PEG) and polyethyleneimine (PEI) were used as polymer additives. PEG and PEI had a suppressing effect on the electrodeposition of copper powder. The current efficiency for Cu deposition decreased with the addition of PEG and PEI. The addition of PEG decreased the average particle size of the copper powder, while PEI didn’t change the average particle size. When Cl− coexisted with PEG, the suppressing effect on the electrodeposition of copper powder became even greater and the particle size of the copper powder became finer than when Cl− or PEG was added alone. |
| 14. | 越智 健太郎, 関口 誠, 大上 悟, 中野 博昭, 電解銅粉の析出挙動および銅粉の形態に及ぼすハロゲン化物イオンの影響, 日本金属学会誌, https://doi.org/10.2320/jinstmet.J2021008, 85, 6, 207-212, 2021.06, To investigate the effect of halide ions on the electrodeposition behavior and morphology of copper powder, the polarization curves were measured and constant current electrolysis of 300 A·m−2 and 500 A·m−2 was conducted in an electrolytic solution of 0.079 mol·dm−3 of Cu2+ and 0.5 mol·dm−3 of free H2SO4 at 293 K and 303 K without stirring. In the deposition of copper powder, Cl− had a promoting effect on the deposition of copper powder, while Br− and I− had a suppressing effect. The current efficiency for Cu deposition increased with the addition of Cl− and decreased with Br−. The addition of Cl− reduced the average particle size of the copper powder and grown dendrite-shaped branches and trunks, resulting in a lower tap density. On the other hand, when Br− was added, the average particle size and crystallite size of the copper powder became smaller, and the tap density also became smaller. With increasing Cl− concentration in solution, the current efficiency for Cu deposition increased, that is, copper deposition was promoted even in the diffusion rate-determining region of Cu2+ ions, showing that the deposition of copper powder was affected by the charge transfer process for Cu deposition. The change in morphology of Cu powder with halide ions is attributed to change of the charge transfer process. The deposition of Cu powder seems to proceed under a mixed rate-determining process of the diffusion of Cu2+ ions and charge transfer.. |
| 15. | 越智 健太郎, 関口 誠, 大上 悟, 中野 博昭, ポリエチレンイミンを含む溶液からの球状電解銅粉の作製 , 日本金属学会誌, https://doi.org/10.2320/jinstmet.J2021032, 85, 11, 413-419, 2021.11, It was investigated whether the spherical electrolytic copper powder could be electrolyzed by adding polyethyleneimine (PEI) in the electrolytic solution. In order to identify the optimum electrolysis conditions for the electrodeposition of spherical copper powder, we investigated the effect of molecular weight of PEI, the amount of PEI added, the current density, and the cathode material on the morphology of electrolytic copper powder. The electrodeposited copper powder was analyzed with a scanning electron microscope, a laser diffraction scattering particle size distribution measuring device, and an X-ray diffractometer. It was found that the spherical copper powder can be obtained by electrolysis at 3000 A·m−2 scraping copper powder every 10 to 60 s in solution containing 0.126 mol·dm−3 Cu2+, 0.5 mol·dm−3 free H2SO4 and 1.0 g·dm−3 PEI with average molecular weight 10000.. |
| 16. | Sung Hwa BAE, Satoshi OUE,Injoon SON and Hiroaki NAKANO, Effect of Reaction Product of Epichlorohydrin and Imidazole on the Electrodeposition Behavior of Zn–Ni Alloy from Alkaline Zincate Solution, ISIJ International, https://doi.org/10.2355/isijinternational.ISIJINT-2021-080, 61, 8, 2256-2263, 2021.08, A Zn–Ni alloy was electrodeposited on a Cu electrode at a current density of 10–5 000 A·m − 2, a charge of 5 × 104 C·m−2, and temperature of 293 K in an unagitated zincate solution containing the reaction product of epichlorohydrin and imidazole (EI polymer) as a brightener. The effect of the EI polymer on the deposition behavior of the Zn–Ni alloy was investigated. The transition current densities at which the deposition behavior shifted from the normal type to anomalous were 50–100 A·m−2 and 10–20 A·m−2 in the EI polymer-free solution and polymer containing solutions, respectively, indicating that the EI polymer decreased the transition current density. The transition current density corresponded to the current density at which the potential of the total polarization curve significantly shifted from the more noble region than the equilibrium potential of Zn to the less noble region. The decrease in transition current density with EI polymer was attributed to the suppression of hydrogen evolution. In addition, the current efficiency for alloy deposition in the high-current-density region decreased due to the suppression of both Zn and Ni depositions. The Ni content of deposited films decreased with EI polymer, indicating that Ni deposition was more suppressed with the EI polymer addition than Zn deposition. With increasing current density, the crystals of the films deposited from the EI polymer-containing solution smoothened and showed sig- nificant brightness. The oxidation reaction of the films deposited from the EI polymer-containing solution was suppressed, thus causing the corrosion potential to shift to a noble direction.. |
| 17. | Kenta Fukumoto, Satoshi Oue, Tsukasa Niwa, Yoshiharu Kikuchi, Shinya Akamatsu and Hiroaki Nakano, E!ect of Organic Additives on Electrodeposition Behavior of Zn from Zincate Solution Containing Potassium Hydroxide and Its Micro Structure, Materials Transactions, doi:10.2320/matertrans.MT-M2021027, 62, 6, 807-814, 2021.06, Zn was electrodeposited on an Fe electrode at a current density of 50!5000 A·m"2, charge of 4 © 104 C·m"2, and temperature of 313 K in an unagitated zincate solution containing 0.62 mol·dm"3 of ZnO, 4.0 mol·dm"3 of KOH or NaOH, and organic additives. The e!ects of KOH and NaOH on the deposition behavior of Zn in the solution containing the organic additives and on the microstructure of the deposits were investigated. In a solution containing a straight-chain polymer composed of a quaternary ammonium cation (PQ) and a quaternary ammonium salt with a benzene ring (QA), the current e"ciency for Zn deposition in a high-current-density region (1000!5000 A·m"2) to produce glossy #lms was higher with KOH than that with NaOH. At high current densities above 1000 A·m"2, the Zn deposition approached the di!usion limitation of ZnO22" ions. With the addition of PQ and QA, the di!usion of ZnO22" ions was signi#cantly suppressed, and the degree of suppression was smaller with KOH than that with NaOH. The polarization resistance at 200 A·m"2, which was investigated through alternating current impedance, revealed that the adsorption ability of PQ and QA onto the cathode was smaller with KOH than that with NaOH. Since the suppression e!ect of the additives on the Zn deposition was smaller with KOH than that with NaOH, the current e"ciency for Zn deposition in the high-current-density region was larger with KOH. The upper limit of the current density needed to produce glossy #lms was smaller with KOH than that with NaOH, and spongy thin #lms were partially observed on platelet crystals obtained at high current densities in the KOH solution. The C content resulting from the additives in the deposited Zn was smaller with KOH because the adsorption ability of PQ and QA onto the cathode was smaller with KOH than that with NaOH. . |
| 18. | Keisuke FUKUDA, Yuki KASHIWA, Satoshi OUE, Tomio TAKASU, Hiroaki NAKANO, Effect of Additives on the Deposition Behavior and Micro Structure of Invar Fe–Ni Alloys with Low Thermal Expansion Electrodeposited from Watt’s Solution, ISIJ International, https://doi.org/10.2355/isijinternational.ISIJINT-2020-105, 1, 3, 919-928, 2021.03, The electrodeposition of Invar Fe–Ni alloy with low thermal expansion was performed at 100–5 000 A·m and 105 C·m in agitated Watt’s solutions containing NiSO4, NiCl2, FeSO4, malonic acid (C3H4O4), saccharin sodium (C7H4NNaO3S), and H3BO3 at 50°C. With increasing concentration of malonic acid, the Ni content in deposits formed at current densities greater than 2 000 A·m decreased, whereas the Ni content increased in deposits formed at current densities less than 1 000 A·m . The current efficiency for alloy deposition decreased with increasing concentration of malonic acid. The deposits were com- posed of granular crystals whose size decreased with increasing concentration of malonic acid. With the addition of saccharin, the Ni content in the deposits decreased substantially, and the current efficiency for alloy deposition increased. With the addition of boric acid, the Ni content in the deposits somewhat decreased, and the current efficiency for alloy deposition increased. The surface morphology of deposits changed as the current density was varied and with the addition of saccharin, whereas it rarely changed with the addition of boric acid. The morphology was found to depend on the Ni content in the deposits. The deposits with a Ni content of 29–38 mass% were composed of granular crystals approximately 300 nm in size, whereas the deposits with a Ni content of 41–52 mass% exhibited a smooth surface that consisted of fine crystals. The effects of additives on the Ni content in deposits and current efficiency can be explained by the changes in the partial polarization curves for Fe and Ni depositions and H2 evolution during Fe–Ni alloy deposition.. |
| 19. | 裵 聖和, 大上 悟, 孫 仁俊, 中野 博昭, アルカリジンケート浴からの Zn − Ni 合金電析挙動に 及ぼすエピクロルヒドリン−イミダゾール反応物の影響, 鉄と鋼, https://doi.org/10.2355/tetsutohagane.TETSU-2020-108, 107, 3, 229-236, 2021.03, Electrodeposition of Zn-Ni alloy was performed on a Cu electrode at a current density of 10–5000 A·m−2 and a charge of 5 × 104 C·m−2 in an unagitated zincate solution at 293 K containing the reaction product of epichlorohydrin and imidazole as brightener. The effect of brightener on the deposition behavior of Zn-Ni alloy was investigated. The transfer current density at which the deposition behavior shifts from the normal type to anomalous was 50 to 100 A·m−2 in brightener-free solution, while it became 10 to 20 A·m−2 with an addition of brightener, indicating that the brightener greatly decreased the transfer current density. The transfer current density corresponded to the current density at which the potential of total polarization curve significantly shifted from the more noble region than the equilibrium potential of Zn to less noble region. With an addition of brightener, the decrease in transfer current density is attribut- ed to suppression of hydrogen evolution, and the current efficiency for alloy deposition at high current density region decreased due to suppression of both Zn and Ni deposition. The Ni content of deposited films decreased with brightener, indicating that Ni deposition was more suppressed with brightener. With increasing current density, the crystals of films deposited from the solution contain- ing brightener became smooth and showed the significant brightness. The oxidation re- action of films deposited from the solution containing brightener is suppressed, as a re- sult, the corrosion potential shifted to noble direction.. |
| 20. | 福元健太, 大上悟, 丹羽司, 菊池義治, 赤松慎也, 中野博昭, 水酸化カリウムを用いた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, 日本金属学会誌, doi:10.2320/jinstmet.J2020043, 85, 2, 59-66, 2021.02, Electrodeposition of Zn was performed on an Fe electrode at a current density of 50–5000 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 KOH or NaOH, and organic additives. The e!ects of KOH and NaOH on the deposition behavior of Zn in solution containing organic additives and the microstructure of the deposits were investigated. In solution containing a quaternary ammonium cation (PQ) and a quaternary ammonium salt with a benzene ring (QA), the current e"ciency for Zn deposition at high current density region of 1000 to 5000 A·m!2 to produce the glossy #lms was higher with KOH than that with NaOH. At high current densities above 1000 A·m!2, Zn deposition approaches the di!usion limitation of ZnO22! ions. With additions of PQ and QA, the di!usion of ZnO22! ions was signi#cantly suppressed, and the degree of suppression was smaller with KOH than that with NaOH. The polarization resistance at 200 A·m!2 investigated by AC impedance revealed that the adsorption ability of PQ and QA onto the cathode was smaller with KOH than that with NaOH. Since the suppression e!ect of additives on the Zn deposition is smaller with KOH than that with NaOH, the current e"ciency for Zn deposition at high current density region is larger with KOH. The upper limit of current density to produce the glossy #lms was smaller with KOH than that with NaOH, and the spongy thin #lms were partially observed on the platelets crystals obtained at high current density in KOH solution. The content of C resulting from the additives in deposited Zn was smaller with KOH. These phenomena are attributed to the adsorption ability of PQ and QA onto the cathode being smaller with KOH. ". |
| 21. | Daiki Ueda , Satoshi Oue , Tomio Takasu and Hiroaki Nakano, Effect of Polyethylene Glycol on Electrodeposition of Zn Active Metal Oxide Composites from a Particle-Free Solution, Materials Transactions, doi:10.2320/matertrans.MT-M2020164, 61, 11, 2170-2177, 2020.11, Electrodeposition of Zn!Zr and Zn!V oxide composites was performed under galvanostatic conditions at 313 K on unagitated pH 2 sulfate solutions containing Zn2+ and Zr4+ or VO2+ ions and an additive such as polyethylene glycol (PEG). The e!ects of PEG addition on the co- deposition 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 Zn!Zr solution in the absence of PEG was approximately zero, it increased signi"cantly at a current density of above 1000A·m"2 following the addition of PEG. In the Zn!V 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 Zn!Zr and the Zn!V oxide "lms became "ne, and the surface coverage of the spongiform Zr and "lm-like V oxides increased. Furthermore, the corrosion current densities of the Zn!Zr and Zn!V oxide "lms obtained from the solution with PEG were lower than those from the solution without it. The reduction rate of dissolved oxygen decreased in the "lms in the presence of PEG, thereby leading to a decrease in the corrosion current density.. |
| 22. | Keita Uchida, Satoshi Oue, Hiroaki Nakano, Effect of Polyethylene Glycol and Glue on Electrodeposition Behavior of Zn from Electrowinning solution and its Crystal Structure, Materials Transactions, https://doi.org/10.2320/matertrans.MT-M2020182, 61, 10, 1958-1966, 2020.10, To elucidate the e!ects of polyethylene glycol (PEG) and glue on the deposition of Zn from electrowinning solution and its resulting crystal structure, Zn electrodeposition was performed at a current density of 600 A·m!2 and a charge of 8.64 © 106 C·m!2 in an agitated sulfate solution containing 1.07 and 1.8 mol·dm!3 of ZnSO4 and H2SO4, respectively, at 45°C. With the additions of PEG and glue, the evolution of hydrogen was suppressed at the current density region less than the critical current density for Zn deposition, decreasing the critical current density of Zn. The degree of decrease in the critical current density of Zn was larger with glue than that with PEG. The current e"ciency for Zn deposition was higher with PEG and glue than that without at the low current density region because the critical current density of Zn decreased with additives. Since the additives suppressed Zn deposition more than the hydrogen evolution at the high current density region, the current e"ciency of Zn decreased by increasing the additive concentration. At the high current density region, little di!erence was observed in the current e"ciency of Zn between PEG and glue. The e!ect of the molecular weight of PEG on the current e"ciency of Zn was rarely observed at the molecular weight above 2000. With the addition of PEG, the deposits became #ne platelets with preferred orientation of f101"1g and layered pyramidally, while f112"0g orientation was obtained, and the platelets grew perpendicularly to the substrate with the addition of glue. The surface roughness of deposited Zn decreased with additives, and it decreased further with PEG compared with that with glue.. |
| 23. | Atsuhiro Suzuki , Satoshi Oue and Hiroaki Nakano, Synergistic Effects of Additives on the Deposition Behavior, Throwing Power and Surface Roughness of Cu Obtained from Electrorefining Solution, Materials Transactions, doi:10.2320/matertrans.M-M2020808, 61, 5, 972-979, 2020.05, To elucidate the synergistic effects of gelatin, thiourea, and chloride ions on the deposition behavior, throwing power, and surface roughness of Cu obtained from electrorefining solutions, Cu electrodeposition was performed at a current density of 200 A·m12 and a charge of 5 © 105 C·m12 in an unagitated sulfate solution containing 0.708 and 2.04 mol·dm13 of CuSO4 and H2SO4, respectively, at a temperature of 60°C. Gelatin and chloride ions have synergistic effects on the polarization for Cu deposition, and the polarization effect increased with each concentration. Thiourea was found to promote Cu deposition and decrease the polarization effects of gelatin and chloride ions as its concentration in the solution were increased. The throwing power and surface roughness of the deposited Cu changed depending on the concentration of the three additives. The throwing power of Cu significantly worsened with increasing concentrations of thiourea and its surface roughness decreased with decreasing concentrations of chloride ions. With increasing concentrations of gelatin, the throwing power of Cu improved and its surface roughness decreased. The correlation between the throwing power and polarization resistance of Cu deposition was observed, and the throwing power of Cu improved as its polarization resistance increased. Since the surface roughness of deposited Cu is a result of its micro deposition properties, it does not depend on polarization resistance alone. Thiourea appeared to promote Cu deposition at the concavity, and therefore, it decreased the surface roughness of the deposited copper.. |
| 24. | Kenta Fukumoto, Satoshi Oue, Yoshiharu Kikuchi, Shinya Akamatsu, Tomio Takasu, Hiroaki Nakano, Effect of Organic Additives on the Electrodeposition Behavior of Zn from an Alkaline Zincate Solution and Its Microstructure, Materials Transactions, doi:10.2320/matertrans.MT-M2019316, 61, 3, 497-505, 2020.03, Electrodeposition of Zn was performed on an Fe electrode at a current density of 205000 A·m12 and a charge of 4 © 104 C·m12 in an unagitated zincate solution at 313 K containing 0.62 mol·dm13 of ZnO, 4.0 mol·dm13 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 1000A·m12 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 ZnO221 ion diffusion increased with the addition of PQ and QA. The increase in overpotential was considerable at potentials less noble than 11.5 V. Zn deposition reached the diffusion limit of ZnO221 ions at potentials less noble than 11.5 V, indicating that the diffusion of ZnO221 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·m12, the crystallite size decreased with the addition of PQ and QA, and the surface of the film was smooth. The orientation index of the f101"0g 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.. |
| 25. | 内田啓太， 大上 悟， 高須登実男， 中野博昭, 電解採取浴からの亜鉛の電析挙動と結晶組織に及ぼすポリエチレングリコール，ニカワ添加の影響, 日本金属学会誌, doi:10.2320/jinstmet.J2019045, 84, 2, 58-65, 2020.02, To elucidate the effects of polyethylene glycol(PEG)and glue on the deposition behavior of Zn from electrowinning solutions and its crystal structure, Zn electrodeposition was performed at a current density of 600 A·m−2 and a charge of 8.64 × 106 C·m−2 in an agitated sulfate solution containing 1.07 mol·dm−3 and 1.8 mol·dm−3 of ZnSO4 and H2SO4, respectively, at a temperature of 45°C. With the additions of PEG and glue, the evolution of hydrogen was suppressed at current density region less than the critical current density for Zn deposition, resulting in decrease in critical current density of Zn. The degree of decrease in critical current density of Zn was larger with glue than that with PEG. The current efficiency for Zn deposition was higher with PEG and glue than that without at low current density region because the critical current density of Zn decreased with additives. Since the additives suppressed Zn deposition more than the hydrogen evolution at high current density region, the current efficiency of Zn decreased with increasing concentration of additives in solution. At high current density region, there was little difference in current efficiency of Zn between PEG and glue. The effect of molecular weight of PEG on the current efficiency of Zn was rarely observed at molecular weight above 2000. With an addition of PEG, the deposits became fine platelets crystals with preferred orientation of {1011} and layered pyramidally, while the deposits orientated to {1120} preferentially and the platelets crystals grew perpendicu- larly to the substrate with an addition of glue. The surface roughness of deposited Zn decreased with additives and it was smaller with PEG than that with glue. |
| 26. | 植田大樹， 大上 悟， 高須登実男， 中野博昭
, 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, 日本金属学会誌, doi:10.2320/jinstmet.J2019031, 84, 2, 50-57, 2020.02, 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 be- havior 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−2 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. Additional- ly, 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 ox- ide and the film-like V oxide increased. Furthermore, the corrosion current densities of the Zn-Zr oxide film and the Zn-V oxide film ob- tained 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]. |
| 27. | 福元 健太, 大上 悟, 菊池 義治, 赤松 慎也, 高須登実男, 中野 博昭, 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, 日本金属学会誌, doi:10.2320/jinstmet.J2019027, 83, 11, 399-406, 2019.10, 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 un- agitated 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 ad- ditives 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 filmshowedthesmoothsurface.Theorientationindexofthe{101 ̄0}planeofZndepositedfromthesolutioncontainingPQandQAincreased with current density. The change of the crystallite size and crystal orientation of deposited Zn were explained related to the deposition overpo- tential. . |
| 28. | 福田 圭祐, 柏 裕樹, 大上 悟, 高須 登実男, 中野 博昭, 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, 鉄と鋼, https://doi.org/10.2355/tetsutohagane.TETSU-2019-045, 105, 10, 48-57, 2019.09, 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.. |
| 29. | 今谷 祐貴, 大上 悟, 小林 亜暢, 高橋 武寛, 後藤 靖人, 中野 博昭, 電析 Zn 鋼板の Zn と Fe の結晶方位関係に及ぼす鋼板表面性状の影響, 日本金属学会誌, 10.2320/jinstmet.J2019023, 83, 10, 363-371, 2019.10, To investigate the effect of the surface texture of steel on the crystal orientation relation between Fe and Zn, we deposited Zn at 1500 A・ m−2 and 1.48 × 104 C・m−2 onto both Al-killed and IF steel sheets in an agitated sulfate solution at 313 K. Chemically polishing the steel simplifies the deposition of Zn epitaxially because of the decreased strain in the steel surface. For Zn deposited on Al-killed steel, the Burgers’ orientation relation of {110}Fe//{0001}Zn was completed after the chemical polishing of the steel. In this case, because the orientation of {111}Fe increased and Zn was deposited according to the orientation relation of {110}Fe//{0001}Zn, the orientation of {0001}Zn decreased. In contrast, for Zn deposited on IF steel, the preferred relation was {111}Fe//{0001}Zn. The crystal-grain size of IF steel is larger than that of Al-killed steel, which makes the epitaxial growth of Zn easier on IF steel than on Al-killed steel. The orientation of {111}Fe was more promi- nent in IF steel than in Al-killed steel. Because the proportion of {0001}Zn increases under conditions where the epitaxial growth of Zn occurs easily and the orientation {111}Fe was more prominent in IF steel, this appears to be the cause of the relation of {111}Fe//{0001}Zn. The ori- entation relation between the deposited Zn and steel changes based on the strain, crystal orientation, and grain size of the steel. Therefore, the crystal orientation of the deposited Zn changes as well.. |
| 30. | Keisuke FUKUDA, Yuki KASHIWA, Satoshi OUE, Tomio TAKASU, Hiroaki NAKANO , Effects of Electrolysis Conditions on the Formation of Electrodeposited Invar Fe–Ni Alloys with Low Thermal Expansion, ISIJ International, https://doi.org/10.2355/isijinternational.ISIJINT-2019-023, 59, 9, 1632-1641, 2019.09, 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 con- tent in the deposits decreased in the lower-current-density region, reached a constant at a moderate cur- rent 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.. |
| 31. | 福元健太，大上悟，菊池義治，赤松慎也，高須登実男, 中野博昭 , 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, 日本金属学会誌, https://doi.org/10.2320/jinstmet.J2019027, 2019.08, 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 un- agitated 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 ad- ditives 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 {101 ̄0} 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 overpo- tential. [doi:10.2320/jinstmet.J2019027]. |
| 32. | Y. Ozaki, Y. Mugita, M. Aramaki, O. Furukimi, S. Oue, F. Jiang, T. Tsuji, A. Takeuchi, M. Uesugi and K. Ashizuka , Four-dimensional observation of ductile fracture in sintered iron using synchrotron X-ray laminography, Powder Metallurgy, https://doi.org/10.1080/00325899.2019.1585032, 2019.03, [URL], Synchrotron X-ray laminography was used to examine the time-dependent evolution of the three-dimensional (3D) morphology of micropores in sintered iron during the tensile test. 3D snapshots showed that the networked open pores grow wider than 20 μm along the tensile direction, resulting in the internal necking of the specimen. Subsequently, these pores initiated the cracks perpendicular to the tensile direction by coalescing with the surrounding pre-existing microvoids or with the secondary-generated voids immediately before fracture. Topological analysis of the barycentric positions of these microvoids showed that they form the two-dimensional networks within the ∼20 μm of radius area. These observations strongly indicate that the microvoid coalescence could occur on shear planes formed close to the enlarged open pores or between closed pores by strain accumulation and play an important role in the crack initiation.. |
| 33. | 秋山徹也, 福島久哲, 大上 悟, 牧野良則, 塩化物溶融塩からのアルミニウムーマンガン合金の電析, 資源と素材, 110, 2, 103-107, 1994.02, The electrodeposition of Al-Mn alloys from the molten chlorides salts was carried out to discuss the funda- mental codeposition behavior. The effect of a current density on the alloy composition and on the cathode current efficiency was investi- gated. The result shows characteristic feature that the Mn content in the deposits is kept almost constant at relatively lower current densities. At higher current densities, the Mn content in the deposits shifts to reach another constant values which are depended on the bath composition and determined by the limiting current densities of Al and Mn. Then, the polarization curves were measured for Al and Al-Mn deposition. Both depositions of Al and Mn from the alloy plating baths occur at the same potential and no potential region where Mn or Al deposited individually is observed. The partial polarization curves for Al deposition show that the potential of Al deposition shifts to less noble direction by 70 mV due to the codeposition with Mn. Raising temperature promotes the mass transfer of the reactants to increase the limiting current densities of Al and Mn. On the other hand, the Mn content of the deposits increases at higher temperatures.. |
| 34. | Yosuke Hara, Daiki Ueda, Satoshi Oue and Hiroaki Nakano, The Effects of Additives on the Electrodeposition of a Zn-Zr Oxide Composite from Dispersed Particle-Free Solution, Materials Transactions, doi:10.2320/matertrans.M2018353, 60, 2, 297-305, 2019.02, Electrodeposition of a ZnZr oxide composite was performed under galvanostatic conditions from an unagitated sulfate solution containing Zn2+ and Zr ions, as well as additives, such as NO3 1 ions and polyethylene glycol (PEG), at pH 2 and 313 K. The effect of these additives on the codeposition of Zr oxide and its polarization behavior, as well as the microstructure of the deposits, was investigated. The Zr content in the deposits obtained at varying current densities increased significantly with the addition of 2.0 g·dm13 of NaNO3. ZnZr oxide films deposited from the NaNO3-containing solution showed a massive structure composed of fine crystals without crystalline Zn platelets, although large cracks were observed between the large crystals. EDX analysis revealed that Zr codeposited on the massive crystals as a fine concave-convex oxide. The corrosion current density of the ZnZr oxide films deposited from the NaNO3-containing solution was almost the same as that of pure Zn deposits, showing that there is no improvement in corrosion resistance when Zn is codeposited with Zr oxide. Moreover, Zr content in the deposits obtained from the PEG-containing solution increased significantly along with increasing current density above 1000 A·m12 . With the addition of 1000 mg·dm13 of PEG, the crystalline Zn platelets disappeared, and the deposits were instead composed of fine mesh-like crystals with a preferred orientation of the f1010! gZn plane, resulting in a smooth surface. The cathodic current density for the reduction of dissolved oxygen on the ZnZr oxide films deposited from the PEG-containing solution was smaller than that of the pure Zn deposits, and as a result, the corrosion current density of the ZnZr oxide films was smaller than that of the pure Zn deposits. The increase in Zr content in the deposits with NO3 1 ions and PEG is attributed to the acceleration of the hydrolysis of Zr ions. [doi:10.2320/matertrans.M2018353]. |
| 35. | 福田 圭祐 柏 裕樹 大上 悟 高須 登実男 中野 博昭, 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, 鉄と鋼, https://doi.org/10.2355/tetsutohagane.TETSU-2018-101, 105, 1, 55-63, 2019.01, 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 5×105 C·m–2 in agitated solution containing NiSO4, NiCl2, H3BO3, FeSO4, C7H4NNaO3S and C3H4O4 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 FeSO4 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 FeSO4. With decreasing pH in solution, since the partial polarization curve for H2 evolution and total polarization curve sifted to higher current density region, Ni content in deposits-cur- rent 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 densi- ty for Fe deposition. The change of the composition in deposits by electrolysis condition can be explained by the changes of the total polariza- tion curve for Fe-Ni alloy deposition and the partial polarization curves for Fe and Ni depositions and H2 evolution.. |
| 36. | Honami Kawano, Satoshi Oue, Takashi Futaba, Akinobu Kobayashi, Yasuto Goto, Hiroaki Nakano, Effect of Surface Textures of Steel Sheets on the Crystal Orientation of Electrodeposited Zinc, ISIJ International, https://doi.org/10.2355/isijinternational.ISIJINT-2018-429, 58, 11, 2117-2124, 2018.11, Prior to electrodeposition, steel sheets underwent polishing using emery paper, buff, and then electro- lytic polishing. Zn deposition was performed galvanostatically at 1 500 A/m2 in an agitated sulfate solution at 40°C to investigate the effect of the surface textures of steel sheets on the crystal orientation of Zn. The strain of the steel surface and the decrease in Fe grain size due to this strain were largest with emery paper polishing, then with buff polishing, then when unpolished, and were smallest after electrolytic pol- ishing. The preferred orientation of the {0001} Zn basal plane of the hcp structure was largest with elec- trolytic polishing, and decreased in the following order: unpolished, buff polishing, and then with emery paper polishing. Thus, the preference of the {0001} orientation of Zn increased with decreasing the strain of steel sheets and increasing the grain size of Fe. With electrolytic polishing, the strain applied to the steel sheets was decreased, the grain size of Fe increased, and therefore the epitaxial growth of deposited Zn occurred easily. The initial Zn deposits appeared to grow epitaxially as indicated by the orientation relationship of {111}Fe//{0001}Zn because the preferred orientation of the steel substrate used in this study is {111} Fe. The preferred orientation of {0001} Zn seems to be more common under conditions where the epitaxial growth of deposited Zn is easy to occur.. |
| 37. | Kousuke Fuchi, Satoshi Oue, Yoshiharu Kikuchi, Shinya Akamatsu, Yuki Kashiwa, Hiroaki Nakano, Electrodeposition Behavior of Zn-Polyethyleneimine Composite from Sulfate Solution and Its Micro Structure, Materials Transactions, doi:10.2320/matertrans.M2018243, 59, 11, 1767-1776, 2018.11, Electrodeposition of Zn-polyethyleneimine composite was performed at 10012000 A·m12 and 4.8 © 105 C·m12 in agitated sulfate solutions containing 1.84 mol·dm13 of ZnSO4 and 4 g·dm13 of polyethyleneimine at pH 1.8 and at 313 K: the composite’s deposition behavior and the relevant deposits’ micro-structure were investigated. The films obtained at current densities above 4000 A·m12 from solutions containing polyethyleneimine exhibited gloss, and the gloss was highest for solutions containing polyethyleneimine with the highest molecular weight (70000). The preferred orientation of deposited Zn crystals changed from {0001} to {112"0} and {101"0} in the presence of polyethyleneimine, and the size of the platelet-shaped Zn crystals decreased as the polyethyleneimine molecular weight and current density increased. The deposition of Zn was polarized in the presence of polyethyleneimine, and the degree of polarization increased with the current density and with polyethyleneimine’s molecular weight. The C and N contents in deposited films increased as the polyethyleneimine molecular weight and current density increased, indicating an increase in the tendency of polyethyleneimine to be adsorbed onto the cathode. During deposition, polyethyleneimine buffered somewhat the pH increase in the layer of the electrolyte solution in contact with the cathode. At this time, H+ ions are released from polyethyleneimine because of an increase in pH in the cathode’s vicinity, and consequently, the number of electron lone-pairs in N atoms of polyethyleneimine increased, resulting in an increase in the adsorption ability of polyethyleneimine onto the cathode.. |
| 38. | Jiang, K, Nakano, H., Oue, S., Morikawa, T., Li, Z., Tian, W., Interrupted Interrupted in situ EBSD study of texture evolution and mechanism of surface grains in electroformed Ni after annealing with an initially duplex + fiber texture during uniaxial tensile deformation, MATERIALS CHARACTERIZATION, 10.1016/j.matchar.2018.05.004, 141, 238-247, 2018.07, The texture evolution process and mechanism of surface grains in electroformed Ni after annealing with an initially duplex 〈100⟩ + 〈111〉 fiber texture during uniaxial tensile deformation were investigated by using interrupted in situ electron backscattered diffraction. The results showed that the initially duplex 〈100〉 + 〈111〉 fiber texture evolved into the metastable Cube orientation with a weak Cu orientation during the uniaxial tensile deformation. The volume fractions of 〈100〉 and 〈111〉 fiber texture decreased from 54.0% to 29.3% and 16.6% to 6.6%, respectively. The volume of the Cube orientation remained almost stable at 12%, whereas that of the Cu orientation increased from 1% to 2.9%. A simulation of the final preferred orientation based on the Taylor model was a cubic texture, which qualitatively agreed well with the experimental result. The simulated results indicated that the formed Cube and Cu textures evolved from the initial 〈100〉 and 〈111〉 fiber textures, respectively. . |
| 39. | 渕 浩輔，大上悟，菊池義治，赤松慎也，柏裕樹，中野博昭, 硫酸塩浴からの亜鉛—ポリエチレンイミン複合電析挙動とその微細構造, 日本金属学会誌, doi:10.2320/jinstmet.J2018020, 82, 8, 281-288, 2018.08. |
| 40. | 久保 文吾, 大上 悟, 二葉 敬士, 小林 亜暢, 後藤 靖人, 中野 博昭, 電析亜鉛と下地鉄の面方位関係に及ぼす鉄表面性状の影響, 鉄と鋼, https://www.jstage.jst.go.jp/article/tetsutohagane/104/6/104_TETSU-2017-097/_article/-char/ja/, 104, 6, 322-330, 2018.06, : Zn deposition was performed galvanostatically at 1500 A/m2 and a charge of 1.48×104 C/m2 onto both the high purity electrolytic iron and the cold rolled steel sheets in an agitated sulfate solution at 40 °C to investigate the effect of surface textures of Fe on the crystal orientation rela- tionship between Fe and Zn. Zn deposited on the high purity electrolytic iron with large grain size showed the orientation relationship of {110} Fe//{0001}Zn. However, with increasing the angle of inclination of {110} Fe plane from the surface of substrate, the deviation of orientation relationship of {110}Fe//{0001}Zn increased. This result suggests that the orientation relationship of {110}Fe//{0001}Zn is difficult to be completed in the middle of deposition with increasing the angle of inclination of {110} Fe plane from the surface of substrate, as a result, the epitaxial growth of Zn easily changes to random growth. On the other hand, Zn deposited on the cold rolled steel sheets with small grain size showed preferred orientation of {0001} regardless of orientation of Fe, which indicates that the orientation of deposited Zn is more affected by deposition overpotential than by the orientation of Fe substrate. Although the strain was introduced to the high purity electrolytic iron with sandblasting, the orientation relationship of {110}Fe//{0001}Zn hardly changed with sandblasting, showing that the strain of Fe substrate has scarcely effect on the orientation relationship between Fe and deposited Zn.. |
| 41. | 鈴木 敦博, 大上 悟. 小林繁夫, 中野博昭, 電解精製浴からの電析銅の表面粗度および均一電着性に及ぼす添加剤の相乗効果, doi:10.2320/jinstmet.J2017015, 81, 7, 358-365, 2017.07. |
| 42. | 徳重晃大 森康平 大上悟 松島寛 鈴木一成 中野博昭, リサイクルした低品位銅をアノードに用いた銅電解精製におけるアノードの不動態化挙動, 資源・素材学会 Journal of MMIJ, https://doi.org/10.2473/journalofmmij.133.165, 133, 7, 165-172, 2017.07. |
| 43. | 河野ほなみ 大上悟 二葉 敬士 小林亜暢 後藤靖人 中野博昭, 電析亜鉛の結晶配向性に及ぼす鋼板表面性状の影響, DOI : http://dx.doi.org/10.2355/tetsutohagane.TETSU-2017-079, 104, 4, 41-48, 2018.04. |
| 44. | Akinori Nakamura, Satoshi Oue, Hiroki Koga, Hiroaki Nakano, Formation behavior of phosphoric acid-based chemical conversion films containing alkaline earth metals on magnesium alloy, Materials Transactions, 10.2320/matertrans.M2016463, 58, 7, 1007-1013, 2017.07, [URL], The phosphating of Mg alloy was performed in unagitated solutions containing 1 g·dm-3 of Mg, Ca, Sr, and Ba as alkaline earth metals (M) and 50 g·dm-3 of H3PO4 of pH 3 at 40°C for 3 min. The structure and formation behavior of the phosphate films were investigated. The X-ray diffraction patterns of phosphate films broadened irrespective of the type of alkaline earth metal, which was a characteristic of an amorphous structure. XPS analysis revealed that the valence of P in the phosphate films was pentavalent. The pH in the vicinity of the Mg alloy during the phosphating, as measured using an Sb microelectrode, was approximately 10.4, 11.4, 10.7, and 12.0 in the solutions containing Mg, Ca, Sr, and Ba, respectively. This shows that phosphoric acid dissociates to the third stage during the phosphating, and the phosphate films comprising M3(PO4)2 containing an alkaline earth metal are formed. The phosphating was successively performed in two types of solutions containing different alkaline earth metals, and the cross section was analyzed. As a result, it was determined that the new phosphate films were formed at the interface between the Mg alloy substrate and phosphate films, and the previously formed phosphate films were boosted in the films.. |
| 45. | Yuki Sato, Satoshi Oue, Shinichi Heguri, Hiroaki Nakano, Effect of dissolved impurities on the lightness and surface morphology of nickel deposits from chloride electrowinning solutions, Materials Transactions, 10.2320/matertrans.M2016442, 58, 4, 606-612, 2017.04, [URL], This study investigated the effect of dissolved impurities on the lightness, surface morphology, and current efficiency of deposited nickel during electrowinning. Nickel electrodeposition was performed at a current density of 300 A·m-2 and 7.2 × 105 C·m-2 of charge in an unagitated chloride solution containing Mn2+, Cr3+, and SO4 2- ion impurities with a pH from 1 to 3, at a temperature of 333 K. Solutions containing 10 g·dm-3 of Mn2+ resulted in a slight decrease in current efficiency for nickel deposition and smaller crystal sizes in the deposited nickel. The lightness of deposited nickel decreased for Mn2+ concentrations exceeding 1 g·dm-3. When nickel deposition was performed using a soluble nickel anode to prevent the formation of MnO2 at the anode, greater nickel lightness resulted than with an insoluble anode, suggesting that MnO2 produced by the insoluble anode caused decreased lightness of nickel. In solutions containing Cr3+, the current efficiency of nickel gradually decreased with increasing Cr3+ concentrations and significantly decreased at Cr3+ concentrations above 0.1 g·dm-3. The lightness of deposited Ni greatly decreased with increasing concentrations of Cr3+ above 0.001 g·dm-3. Formation of Cr(OH)3 at the cathode layer is presumed to suppress nickel deposition, resulting in some codeposition of NiO and Ni(OH)2 along with Ni, which causes the nickel current efficiency and lightness to decrease. Conversely, solutions containing SO4 2- resulted in a moderate decrease in nickel current efficiency at SO4 -2 concentrations above 50 g·dm-3 and a significant decrease above 100 g·dm-3. The lightness of deposited nickel increased slightly at SO4 -2 concentrations of 20 g·dm-3 and strongly increased above 20 g·dm-3. Because the overpotential for nickel deposition increases with the concentration of SO4 2, the surface of the deposited nickel becomes smooth, resulting in greater lightness.. |
| 46. | Keisuke Kashida, Satoshi Oue, Hiroaki Nakano, Effect of chloride ions in electrowinning solutions on zinc deposition behavior and crystal texture, Materials Transactions, 10.2320/matertrans.M-M2017827, 58, 10, 1418-1426, 2017.10, [URL], To clarify the effect of chloride ions on Zn electrowinning in terms of deposition behavior and crystal texture, the partial polarization curve, current efficiency, and AC impedance for Zn deposition as well as its morphology and crystal orientation were investigated. In solutions containing chloride ions, the partial polarization curve for Zn deposition was evidently depolarized, and the degree of depolarization increased when increasing the concentration of chloride ions from 300 to 6,000 mg/L. The exchange current density i0 for Zn deposition also increased with increasing chloride ion concentration, which indicates that the chloride ions promote the charge-transfer process during Zn deposition. The polarization resistance for Zn deposition measured by AC impedance decreased with increasing chloride ion concentration. Conversely, the capacity of the electric double layer increased with increasing chloride ion concentration from 300 to 1,200 mg/L; however, from 3,000 to 6,000 mg/L, the capacity decreased and approached that obtained from a chloride ion-free solution. On the other hand, the partial polarization curve for hydrogen evolution was almost unchanged by the presence of chloride ions. As a result, the current efficiency of Zn deposition increased by 5–7% and 1.7% in the initial stage of deposition (up until the thickness of Zn reached approximately 2.1 μm) and at 500 A/m2 for 6 hours (482 μm), respectively. With the addition of 300 to 1,200 mg/L of chloride ions, the deposited Zn exhibited a preferred orientation of {0001} plane, and it increased with increasing chloride ion concentration, which is attributed to a decrease in the overpotential for Zn deposition; however, no preferred orientation of a specific plane was shown in the deposits when increasing the concentration of chloride ions above 3,000 mg/L. Some spherical concavities resulting from traces of evolved hydrogen gas were observed on the surface of deposited Zn, and the size of the concavities increased with increasing chloride ion concentration. The size of platelet crystals of the deposited Zn decreased with increasing chloride ion concentration, which indicates that the chloride ions possibly promote the nucleation rate of Zn crystals due to specific adsorption onto the cathode.. |
| 47. | Atsuhiro Suzuki, Satoshi Oue, Shigeo Kobayashi, Hiroaki Nakano, Synergistic effect of additives on the surface roughness and throwing power of copper deposited from electrorefining solution, Nippon Kinzoku Gakkaishi/Journal of the Japan Institute of Metals, 10.2320/jinstmet.J2017015, 81, 7, 358-365, 2017.01, [URL], To elucidate the synergistic effect of gelatin, thiourea and chloride ions on the surface roughness, throwing power and polarization curves for Cu deposition from electrorefining solution, Cu electrodeposition was performed at a current density of 200 A•m-2 and 5×105 C•m-2 of charge in an unagitated sulfate solution containing 0.708 mol•dm-3 of CuSO4 and 2.04 mol•dm-3 of H2SO4 at a temperature of 60°C. In solutions containing three kinds of additives such as gelatin, thiourea and chloride ions, the surface roughness of deposited Cu decreased with increasing the concentration of thiouea and gelatin and decreasing the chloride ions. On the other hand, the throwing power of deposited Cu was improved with decrease in thiourea and increase in gelatin in solutions containing three kinds of additives. The throwing power of deposited Cu was significantly improved in solution containing both gelatin and chloride ions. The polarization resistance dE/di for Cu deposition increased in solution containing both gelatin and chloride ions, which resulting in improvement of throwing power of Cu deposition. As small amounts of thiourea have a depolarization effect on Cu deposition, a leveling effect is expected owing to the promotion of deposition at recesses.. |
| 48. | Atsuhiro Suzuki, Satoshi Oue, Shigeo Kobayashi, Hiroaki Nakano, Effects of additives on the surface roughness and throwing power of copper deposited from electrorefining solutions, Materials Transactions, 10.2320/matertrans.M2017215, 58, 11, 1538-1545, 2017.01, [URL], To elucidate the synergistic effects of gelatin, thiourea, and chloride ions on the surface roughness, throwing power, and polarization curves for Cu deposition from electrorefining solutions, Cu electrodeposition was performed at a current density of 200 A·m−2 and a charge of 5 × 105 C·m−2 in an unagitated sulfate solution containing 0.708 mol·dm−3 of CuSO4 and 2.04 mol·dm−3 of H2SO4 at a temperature of 60C. In solutions containing all three additives (gelatin, thiourea, and chloride ions), the surface roughness of deposited Cu decreased with increasing thiourea and gelatin concentrations and decreasing chloride ions concentration. On the other hand, the throwing power of deposited Cu improved with decreasing thiourea concentration and increasing gelatin concentration in solutions containing all three additives. The throwing power of deposited Cu was significantly improved in solutions containing both gelatin and chloride ions. The polarization resistance dE/di for Cu deposition increased in solutions containing both gelatin and chloride ions, resulting in an improvement in the throwing power of Cu deposition. As small amounts of thiourea have a depolarization effect on Cu deposition, a smoothing effect is expected to result from the promotion of deposition at recesses.. |
| 49. | Osamu Furukimi, Chatcharit Kiattisaksri, Yuji Takeda, Masatoshi Aramaki, Satoshi Oue, Shinji Munetoh, Masaki Tanaka, Void nucleation behavior of single-crystal high-purity iron specimens subjected to tensile deformation, Materials Science & Engineering A: Structural Materials: Properties, Microstructure and Processing, 10.1016/j.msea.2017.06.084, 701, 221-225, 2017.07, [URL], Void nucleation plays an important role for determining local deformation properties of ductile materials. In this study, the void nucleation behavior of single-crystal iron was examined in tensile tests. Two micrometer-size single crystals having a different type of slip extracted from electrodeposited pure iron were used to investigate the fracture mechanics during tensile deformation. Scanning electron microscopy (SEM) and high voltage electron microscopy (HVEM) images verified the existence of only a single slip system in the smaller specimen (cross-sectional area A = 16 µm2) and furthermore, no voids were observed. However, multiple slips and voids were observed in the larger specimen (A = 28 µm2). These findings allowed us to reveal that multiple slips are a necessary criterion for void nucleation in single-crystal iron.. |
| 50. | Yuki Sato, Satoshi Oue, Shinichi Hegri, Hiroaki Nakano, Effect of Dissolved Impurities on the Lightness and Surface Morphology of Nickel Deposits from Chloride Electrowinning Solutions, Materials Transactions, doi:10.2320 matertrans.M2016442, 58, 4, 606-612, 2017.04, This study investigated the effect of dissolved impurities on the lightness, surface morphology, and current ef ciency of deposited nickel during electrowinning. Nickel electrodeposition was performed at a current density of 300 A m 2 and 7.2 105 C m 2 of charge in an unagitat- ed chloride solution containing Mn2+, Cr3+, and SO42 ion impurities with a pH from 1 to 3, at a temperature of 333 K. Solutions containing 10 g dm 3 of Mn2+ resulted in a slight decrease in current ef ciency for nickel deposition and smaller crystal sizes in the deposited nickel. The lightness of deposited nickel decreased for Mn2+ concentrations exceeding 1 g dm 3. When nickel deposition was performed using a soluble nickel anode to prevent the formation of MnO2 at the anode, greater nickel lightness resulted than with an insoluble anode, suggesting that MnO2 produced by the insoluble anode caused decreased lightness of nickel. In solutions containing Cr3+, the current ef ciency of nickel gradually decreased with increasing Cr3+ concentrations and signi cantly decreased at Cr3+ concentrations above 0.1 g dm 3. The lightness of deposited Ni greatly decreased with increasing concentrations of Cr3+ above 0.001 g dm 3. Formation of Cr(OH)3 at the cathode layer is presumed to suppress nickel deposition, resulting in some codeposition of NiO and Ni(OH)2 along with Ni, which causes the nickel current ef ciency and lightness to decrease. Conversely, solutions containing SO42 resulted in a moderate decrease in nickel current ef ciency at SO42 concentra- tions above 50 g dm 3 and a signi cant decrease above 100 g dm 3. The lightness of deposited nickel increased slightly at SO42 concentrations of 20 g dm 3 and strongly increased above 20 g dm 3. Because the overpotential for nickel deposition increases with the concentration of SO42 , the surface of the deposited nickel becomes smooth, resulting in greater lightness.. |
| 51. | 中村章紀, 大上 悟, 古賀弘毅, 中野 博昭, マグネシウム合金へのアルカリ土類金属を含むリン酸系化成処理皮膜の形成挙動, 日本金属学会, doi:10.2320 jinstmet.J2016039 , 80, 11, 684-690, 2016.11, The phosphate coating for Mg alloy was performed in the unagitated solutions containing 1 g dm 3 of Mg, Ca, Sr and Ba as alkali earth metal and 50 g dm 3 of H3PO4 of pH 3 and 40 C for 3 min, and the structure and formation behavior of the phosphate films were investigated. The X ray diffraction patterns of phosphate films broadened regardless of the kinds of alkali earth metal, which was a characteristic of an amorphous structure. XPS analysis revealed that the valence of P in the phosphate films was pentavalent. The pH in the vicinity of the Mg alloy during the phosphate coating, as measured using an Sb microelectrode, was approximately 10.4, 11.4, 10.7, 12.0 in the solutions containing Mg, Ca, Sr and Ba, respectively, which shows that the phos- phoric acid dissociates to the third stage during the phosphate coating and the phosphate films composed of M3 PO4 2 containing alkali earth metal M are formed. The phosphate coating were successively performed in the two kinds of solutions containing different alkali earth metals and the cross section was analyzed, as a result, it was suggested that the new phosphate films were formed at the interface between Mg alloy substrate and phosphate films and the previously formed phosphate films were boosted up in films. . |
| 52. | Furukimi Osamu, Hiroki Katafuchi, Masatoshi Aramaki, Muhammad Kozin, Satoshi Oue, Koki Yoshida, I. Narita, Naoya Yamada, Masayuki Yamamoto, Wear resistance of Industrial Pure Iron Treated by Nitriding and Quenching Followed by Aging Process, The Japan Society for Heat Treatment, dos:10.2320/matertrans.H-M2016825, 57, 9, 1587-1592, 2016.09. |
| 53. | Shinichiro Hayata, Satoshi Oue, Takehiro Takahashi, Hiroaki Nakano, Effect of Annealing Duration on the Structure and Hardness of Electrodeposited Ni–W Alloys, ISIJ, http://dx.doi.org/10.2355/isijinternational.ISIJINT-2016-111, 56, 7, 1248-1255, 2016.07. |
| 54. | Hiroaki Nakano, Yosuke Hara, Satoshi Oue, Electrodeposition of Zn–Zr Oxide Composite from Dispersed-Particle-Free Solution, The Japan Institute of Metals and Materials, doi:10.2320 matertrans.M2016084, 57, 7, 1165-1170, 2016.07, Electrodeposition of Zn–Zr oxide composite from an unagitated sulfate solution containing Zn2+ and Zr ions was investigated at pH 1–2 and at 313 K under galvanostatic conditions. The Zr content was higher in deposits formed from the solution at pH 2 than . |
| 55. | Shinichiro HAYATA, Satoshi Oue, Takehiro TAKAHASHI, Hiroaki Nakano, Effect of Initial Ni Plating on the Structure and Hardness of Electrodeposited Ni–W Alloys with and without Annealing, ISIJ International, http://dx.doi.org/10.2355/isijinternational.ISIJINT-2016-110, 56, 6, 1048-1056, 2016.06. |
| 56. | Hiroaki NAKANO, Shingo Arakawa, Satoshi Oue, Shigeo Kobayashi, Electrodeposition Behavior of Zn–Fe Alloy from Zincate Solution Containing Triethanolamine, doi:10.2320/matertrans.M2015230, 56, 10, 1664-1669, 2015.10, The electrodeposition behavior of ZnFe alloys has been investigated at 308K at current densities of 10500A·m12 and a charge of 5 © 104 C·m12 in an unagitated zincate solution containing triethanolamine, which forms a stable complex with Fe2+ ions. The content of Fe in the deposit changed significantly depending on the current density. At current densities lower than 20A·m12, the content of Fe was approximately 90mass%, that is, the ZnFe alloy exhibited normal co-deposition, whereby the electrochemically more noble Fe deposited preferentially. At current densities higher than 100A·m12, however, anomalous co-deposition was observed, whereby the less noble Zn deposited preferentially. The current density at which the Fe content in the deposit changed significantly corresponded to that at which the cathode potential in the total polarization curve abruptly shifted to a less noble region than the equilibrium potential for Zn deposition. Iron deposition and H2 evolution were significantly suppressed by the co-existence of Zn2+ ions in the region of anomalous co-deposition at higher current densities, showing the formation of an inhibitor to deposition arising from Zn2+ ions in the cathode layer. The current efficiency for alloy deposition was not close to zero even in the region of normal co-deposition, and the Fe content in the region of anomalous co-deposition was close to the composition reference line, which shows deposition behavior different from that in sulfate solutions. In the region of normal co- deposition at lower current densities, underpotential deposition of Zn occurred with Fe. TEM analysis revealed that ZnFe alloys deposited at lower current densities comprised the stable intermetallic compound Fe5Zn21. The activity coefficient of Zn in the deposit appears to remarkably decrease because of this formation of stable Fe5Zn21.. |
| 57. | 早田慎一朗, 大上 悟, 高橋武寛, 中野 博昭, Ni-W 合金電析膜の熱処理前後の構造と硬度に及ぼす下地 Ni めっきの影響, 鉄と鋼, http://dx.doi.org/10.2355/tetsutohagane.TETSU-2015-050, 101, 11, 590-597, 2015.11, Electrodeposition of Ni-W alloys was conducted from an unagitated sulfate solution containing citric acid at pH 5 and 60 °C under coulo- static (9.0×105) and galvanostatic (100-5000 A·m–2) conditions onto steel sheets with an initial Ni plating, and the effect of initial Ni plating on the structure and hardness of deposited Ni-W alloys was investigated before and after annealing. The precipitates of Ni4W and NiW were observed in deposits obtained at all the current densities after annealing, irrespective of having undergone initial Ni plating or not. Without initial Ni plating, a lot of large precipitates occurred in the vicinity of steel substrate, while the fine precipitates occurred with initial Ni plat- ing. Without initial Ni plating, the W content in deposits increased in the vicinity of steel substrate due to diffusion of Ni in deposits into steel substrate during annealing. With initial Ni plating, the W content in deposits in the vicinity of Ni plating decreased due to diffusion of Ni in Ni plating into deposits during annealing. Before annealing, W content in deposits was lower with initial Ni plating than that without Ni plating. With initial Ni plating, W content in deposits was lower and Ni diffused from Ni plating to deposits during annealing, as a result, the forma- tion of large precipitates of Ni4W and NiW seems to be suppressed. The hardness of deposited Ni-W alloys after annealing increased when the precipitates of Ni4W and NiW became uniform and fine.. |
| 58. | 早田慎一朗, 大上 悟, 高橋武寛, 中野 博昭, Ni−W合金電析膜の構造と硬度に及ぼす熱処理時間の影響, 鉄と鋼, http://dx.doi.org/10.2355/tetsutohagane.TETSU-2015-051, 101, 11, 598-604, 2015.11, Electrodeposition of Ni-W alloys was conducted from an unagitated sulfate solution containing citric acid at pH 5 and 60 °C under coulostatic (9.0×105) and galvanostatic (100-3000 A·m–2) conditions onto steel sheets with an initial Ni plating to investigate the effect of annealing dura- tion on the structure and hardness of deposited Ni-W alloys. The crystallite size of Ni in deposits with several seconds annealing increased significantly compared to without annealing, and gradually increased with annealing duration. With increasing the holding time at 700 °C to 100 and 1000 s, the precipitates of Ni4W and NiW were increased and became coarse at upper layers of deposits. The hardness of all the de- posits increased with annealing, and the degree of increase became significantly large with increasing W content in deposit by increasing cur- rent density. The hardness of deposit with W content 45 mass% was maximum at holding time of 10 s at 700 °C, and gradually decreased with increasing annealing duration. The hardness of deposits increased when the precipitates of Ni4W and NiW were uniformly distributed in a fine size, which showing the optimum precipitation state at holding time of 10 s at 700 °C.. |
| 59. | Ryo Takahashi, Yuki Sato, Satoshi Oue, Shinichi Heguri, Hiroaki NAKANO, Effect of Electrolysis Condition on the Lightness and Surface Morphology of Ni Deposit from Chloride Electro-winning Solutions, Materials Transactions, doi:10.2320/matertrans.M2014432, 56, 8, 1199-1206, 2015.08, To investigate the effects of current density and pH of the solution on the lightness and surface morphology of Ni deposit, Ni electrodeposition was performed at a current density of 100 to 500 A·m12 and 7.2 © 105 C·m12 of charge, in an unagitated chloride solution with pH 1 to 3, at 333 K. The composition and structure of the surface of deposits were analyzed by radio frequency glow discharge optical emission spectroscopy and three-dimensional scanning electron microscope (3D-SEM). The lightness of the Ni deposit decreased with increasing pH, and was also related to the current density with the minimum reached at 300A·m12. The concentration of the surface oxygen in the deposits increased with pH, with the highest value obtained at 300 A·m12, which shows that the concentration of surface oxygen possibly affects the lightness. On the other hand, the surface of the Ni deposit was composed of several micrometers of pyramidal microcrystals and the mound formed by the aggregation of pyramidal microcrystals. To separate the two types of structural units, the deposits were cut every 200 nm from the top in the thickness direction using 3D SEM. The number and area of the deposits in the cutting plane were measured and it was found that the lightness of the Ni deposit depended on the surface structure. Therefore, the lightness of the Ni deposit seems to depend on both the surface oxygen content and the microstructure of the deposits.. |
| 60. | 古君 修, 片渕 紘希, 荒牧 正俊, Muhammad Kozin, 大上 悟, 吉田 幸樹, 成田 一人, 山田直矢, 浸窒焼入れ-時効処理した工業用純鉄の耐摩耗特性 , 熱処理, 2015.06. |
| 61. | Hiroaki NAKANO, Syota Kataoka, Satoshi Oue, Shigeo Kobayashi, Coloration by Zinc–Nickel Composite Films Electrodeposited from a Chloride Solution, DOI: http://dx.doi.org/10.2355/isijinternational.54.1661, 54, 7, 1661-1666, 2014.07, Zn–Ni composite films were electrodeposited under coulostatic (515–5145 C⋅m−2) and galvanostatic (5 A⋅m−2) conditions onto brass plates with a Ni precoating in an unagitated chloride solution at 23°C to investigate the color and structure of the deposited films. The chromaticity of the deposited Zn–Ni com- posite films changed in a clockwise direction in each quadrant of the a*b* diagram of the L*a*b* color space with increasing amount of charge. The deposited films contained S, Zn, and Ni, and their content decreased in the order of S > Zn > Ni. X-ray photoelectron spectroscopy revealed that the deposited films were primarily composed of ZnS, ZnO, and Ni and contained small amounts of Zn(OH)2 and Zn. The color of the deposited films is attributed to interference of light, and the index of refraction of the depos- ited films composed of ZnS, ZnO, and Ni is assumed to be large. When Ni was excluded from the elec- trolytic solution, ZnS did not codeposit and the amount of Zn deposited in the metallic state increased. This result suggests that the Ni deposition induces the codeposition of ZnS.. |
| 62. | 早田慎一朗, 大上 悟, 中野 博昭, 高橋武寛容, Ni−W合金電析膜の構造と硬度に及ぼす熱処理の影響, 日本鉄鋼協会, DOI : http://dx.doi.org/10.2355/tetsutohagane.100.1391, 100, 11, 1391-1397, 2014.11. |
| 63. | 高橋 崚, 佐藤祐樹, 大上 悟, 平郡慎一, 中野 博昭, 塩化物系電解採取浴からの電析Niの明度，表面性状に及ぼす電解条件の影響, 日本金属学会誌, doi:10.2320/jinstmet.J2014033, 78, 12, 427-433, 2014.12. |
| 64. | 古賀弘毅, 中村章紀, 大上 悟, 中野 博昭, マグネシウム合金上でのアルカリ土類金属成分を含む化成皮膜の形成挙動とその構造, 表面技術, 66, 3, 34-39, 2015.03. |
| 65. | 中野 博昭, 大上 悟, 案浦 康徳, 永井 啓明, 大穂 元人, 福島 久哲, Electrodeposition of Zn–V Oxide Composites from a Strongly Agitated Solution without Dispersed Particles, ISIJ International, http://dx.doi.org/10.2355/isijinternational.54.1906, 54, 8, 1906-1912, 2014.08, The electrodeposition of a Zn–V oxide composite under galvanostatic conditions from an agitated sul- fate solution without dispersed particles and containing Zn2+ and VO2+ at pH 2 and 313 K was investi- gated. Although the V content in the deposits initially decreased with increasing current density, irrespective of the flow rate of electrolyte, a further increase in the current density resulted in an increase in the V content of the deposits. The curves, which show the relationship between the V content in the deposits and the current density, shifted to the higher-current-density region with increasing flow rate of the electrolyte. Agitation of the electrolyte decreased the V content of the deposits but reduced the seg- regation of V oxide. EDX point analysis of the cross-section of the deposits revealed that the V oxide con- centrated at the surface of the deposits. The polarization curves in 3% NaCl solution revealed that the corrosion potential of the deposited Zn–V oxide films depended on the V content in the deposits, irrespec- tive of the flow rate of electrolyte, and that the corrosion potential shifted toward the more noble direction with the codeposition of V oxide when the V content in the deposits was less than 2 mass%. At V con- tents of . |
| 66. | 山下浩充, 大上 悟, 中野 博昭, 曽我部信義, 電解採取浴からの亜鉛の電析挙動と結晶組織に及ぼすゼラチンとアンチモンの相乗効果事, 資源・素材学会, 130, 4, 125-131, 2014.04. |
| 67. | 中野 博昭, 大上 悟, 案浦康徳, 永井啓明, 大穂元人, 福島 久哲, 分散粒子を含まない溶液からの高流速撹拌下におけるZn-V酸化物複合電析, 日本鉄鋼協会, 100, 3, 376-382, 2014.03, Electrodeposition of Zn-V oxide composite was examined from an agitated sulfate solution without dispersed particles containing Zn2+ and VO2+ at pH 2 and 40 oC under galvanostatic conditions. Although V content in deposits decreased for the moment with increasing current density regardless of flow rate of electrolyte, the further increase in current density brought about the increase in V content in deposits. The curves, which shows the relationship between the V content in deposits and current density, shifted to the higher current density region with increasing flow rate of electrolyte. Agitation of the electrolyte decreased the V content of the deposits but reduced the segregation of V ox- ide. EDX point analysis of cross section of deposits revealed that the V oxide concentrated at the surface of deposits. It was found from the polarization curves in 3% NaCl solution that the corrosion potential of deposited Zn-V oxide films depended on the V content in deposits regardless of the flow rate of electrolyte and it shifted to more noble direction with codeposition of V oxide at V contents in deposits below 2 mass%. At V contents of |
| 68. | 中野 博昭, 浦 高志, 大上 悟, 小林繁夫, 電気亜鉛めっき鋼板の外観, 結晶形態に及ぼす有機添加剤予備吸着の影響, 鉄と鋼, 99, 12, 700-708, 2013.12, Zn electrodeposition was performed galvanostatically on a steel sheet at 1500 A/m2 in an agitated sulfate solution at 40oC to investigate the effect of preadsorption of organic additives on the lightness and morphology of Zn. The organic additives preadsorbed were classified into two types: 1) polyethylene glycol (PEG), gelatin and stearyl dimethyl benzyl ammonium chloride (SDBAC) (type I), which exhibit the po- larization effect on Zn deposition ; 2) saccharin and sodium lauryl sulfate (type II) , which exhibit no polarization effect on Zn deposition. The platelet crystals of deposited Zn became small by preadsorption of all kinds of organic additives. The decrease in size of platelet crystals of Zn with the preadsorption is attributed to both the increase in overpotential for Zn deposition and the decrease in epitaxial growth of Zn. The orientation of {0001} Zn basal plane decreased significantly because of an increase in overpotential for Zn deposition by the preadsorp- tion of PEG and gelatin, and the orientation decreased slightly by saccharin and sodium lauryl sulfate in spite of no polarization effect on Zn deposition. The surface roughness of deposited Zn decreased by the preadsorption of organic additives with the exception of SDBAC. This is due to decrease in size of platelet crystals of Zn. The lightness of deposited Zn was increased by the preadsorption of organic additives with the exception of SDBAC. Because Zn deposited ununiformly by the preadsorption of SDBAC, the surface roughness of Zn increased and the lightness decreased.. |
| 69. | 中野 博昭, 片岡 翔太, 大上 悟, 小林繁夫, 塩化物浴からの Zn-Ni 複合電析による色彩の発現, 鉄と鋼, 99, 12, 709-715, 2013.12, Zn-Ni composite electrodeposition was performed under coulostatic (515-5145C·m–2) and galvanostatic (5A·m–2) conditions on a brass with Ni precoating in an unagitated chloride solution at 23oC to investigate the color and structure of the deposited films. The chromaticity of deposited Zn-Ni composite films changed in a clockwise direction in each quadrant of a*b* diagram of La*b* color space with increasing the amount of charge. The deposited films contained S, Zn and Ni, and the content was in the order of S > Zn > Ni. XPS revealed that the deposited films were composed of ZnS, ZnO and Ni mainly and contained Zn(OH)2 and Zn slightly. The color of deposited films is attributed to interference of light, and the index of refraction of deposited films composed of ZnS, ZnO and Ni is assumed to be large. When the Ni was excluded from the electrolytic solution, ZnS did not codeposit and the deposition of Zn in metallic state increased. This suggests that the Ni deposition induces the codeposition of ZnS.. |
| 70. | 中野 博昭, 山口拓人, 山田遥平, 大上 悟, 孫仁俊, 堀田 善治, 古賀弘毅, Al-Fe合金の耐孔食性に及ぼす巨大ひずみ加工HPT処理の影響, 日本金属学会誌, 77, 11, 489-496, 2013.11. |
| 71. | Hiroaki NAKANO, Hiroto Yamaguchi, Youhei Yamada, Satoshi Oue, In-Joon Son, Zenji Horita, Hiroki Koga, Effects of High-Pressure Torsion on the Pitting Corrosion Resistance of Aluminum-Iron Alloys, JOURNAL OF THE JAPAN INSTITUTE OF METALS, 10.2320/jinstmet.J20130401, 77, 11, 489-496, 2013.11. |
| 72. | Hiroaki NAKANO, Hiroto Yamaguchi, Youhei Yamada, Satoshi Oue, In-Joon Son, Zenji Horita, Hiroki Koga, Effects of High-Pressure Torsion on the Pitting Corrosion Resistance of Aluminum-Iron Alloys, JOURNAL OF THE JAPAN INSTITUTE OF METALS, 10.2320/jinstmet.J20130401, 77, 11, 489-496, 2013.11. |
| 73. | Hiroaki NAKANO, Shingo Arakawa, Satoshi Oue, Shigeo Kobayashi, Electrodeposition Behavior of Zn–Ni alloys from an Alkaline Zincate Solution Containing Ethylenediamine, ISIJ international, 53, 10, 1869-1875, 2013.10. |
| 74. | Hiroaki NAKANO, Shitoku Shibata, Shingo Arakawa, Satoshi Oue, Shigeo Kobayashi, Electrodeposition Behavior of Zn–Co Alloys from an Alkaline Zincate Solution Containing Triethanolamine, ISIJ international, 53, 10, 1863-1868, 2013.10. |
| 75. | Hiroaki NAKANO, Satoshi Oue, Hisaaki FUKUSHIMA, Shigeo Kobayashi, Nobuyoshi Sogabe, Evaluation of harmful effects of impurities in Zn electrowinning solution using cyclic voltammetry, Proc. of European Metallurgical Conference 2013 (EMC2013), 2013.06. |
| 76. | 中野 博昭, 荒川真吾, 大上 悟, 小林繁夫, エチレンジアミンを含むアルカリジンケート浴からのZn-Ni合金電析挙動, 鉄 と 鋼, 99, 6, 425-431, 2013.06. |
| 77. | 中野 博昭, 柴田至徳, 荒川真吾, 大上 悟, 小林繁夫, トリエタノールアミンを含むアルカリジンケート浴からのZn-Co合金電析挙動, 鉄 と 鋼, 99, 5, 346-351, 2013.05. |
| 78. | 古君 修, 新垣翔, 山田直矢, 荒牧 正俊, 大上 悟, 船川 義正, 16%Crフェライト単相鋼の局部変形エネルギーとボイド生成挙動, 鉄と鋼, http://dx.doi.org/10.2355/tetsutohagane.99.60, 99, 1, 60-69, 2013.01, Tensile tests of 16mass%Cr bearing ferritic steels were performed in order to investigate the effect of the mean interparticle spacing (λ) on the local deformation energy. λ of Cr precipitates was changed from 3. 3 to 5. 1 μm. The amounts of Cr precipitates in the specimens tested were controlled to be the same level. The local deformation energy was increased with increasing λ in the specimens without a notch, while the local deformation energy does not depend on λ for the notched specimens. AsB (Angle selective Backscattered Electron Detector) images of voids beneath the fracture surface showed that the difference of the local deformation energy dependence on λ between notchless and notched specimens was due to the void coalescence processes. This finding reveals that the local deformation energy is influenced by the stress triaxiality through the void coalescence behavior.. |
| 79. | Hiroaki Nakano, Shingo Arakawa, Yuya Takada, Satoshi Oue and Shigeo Kobayashi, Electrodeposition Behavior of a ZnNi Alloy in an Alkaline Zincate Solution, Materials Transactions, 10.2320/matertrans.M2012241, 53, 11, 1946-1951, 2012.11, Electrodeposition behavior of ZnNi alloys was investigated at current densities of 10500 A·m12 and a charge of 5 © 104 C·m12 in an unagitated zincate solution containing triethanolamine, which forms a stable complex with Ni2+ ions at 308 K. At low current densities, the Zn Ni alloy exhibited normal codeposition, wherein electrochemically more noble Ni deposited preferentially, while at high current densities, it exhibited anomalous codeposition, wherein less noble Zn deposited preferentially. Ni deposition and H2 evolution were significantly suppressed in the region of anomalous codeposition at higher current densities, showing the formation of an inhibitor for deposition, which results from Zn2+ ions in the cathode layer. In contrast, in the region of normal codeposition at lower current densities, the underpotential deposition of Zn apparently occurred with Ni. Because ZnNi alloys are composed of a stable intermetallic compound of Ni5Zn21, the activity coefficient of Zn in the deposit appears to decrease remarkably.. |
| 80. | 中野 博昭, 大上 悟, 成清久純, 曽我部信義, 仁科一彦, 亜鉛電解採取におけるゼラチンの分解に及ぼす各種因子の影響, Journal of MMIJ, 128, 10,11, 584-589, 2012.10. |
| 81. | 中野 博昭, 大上 悟, 西野友朗, 福島 久哲, 小林繁夫, 電解精製浴からの銅電析初期の表面形態および結晶組織に及ぼす添加剤の相乗効果, Journal of MMIJ, 590-595, 2012.10. |
| 82. | 中野 博昭, 荒川真吾, 高田裕也, 大上 悟, 小林繁夫, アルカリジンケート浴からのZn-Ni合金電析挙動, 日本金属学会誌, 76, 7, 443-448, 2012.07. |
| 83. | Shingo Arakawa, Satoshi Oue, Hiroaki Nakano and Shigeo Kobayashi, Structure of Deposits Obtained from Urea-Based Melt Bath Containing Co and La, Materials Transactions, 10.2320/matertrans.M2011379, 53, 4, 770-772, 2012.04, Electrodeposition was performed in an unagitated solution from a urea-based melt bath containing Co and La under galvanostatic (10 40 mA·cm12) and coulostatic (10 C·cm12) conditions at 403 K, and the structure of the deposits was investigated. Co deposited in a metallic state at 10 mA·cm12, whereas it was incorporated into deposits mainly as an oxide at high current densities of 30 and 40 mA·cm12. La codeposited with Co as an oxide irrespective of current density. The content of La2O3 increased with current density. The deposits showed a granular crystal structure and became nonuniform crystals comprising large localized granules at high current densities.. |
| 84. | 中野博昭, 大上悟, 津山裕史. 福島久哲, 小林繁夫, 富岡賢史, 電解精製浴からの電析銅の表面形態及び結晶組織に及ぼす添加剤の相乗効果, Journal of MMIJ, 127, 10, 11, 662-666, 2011.10. |
| 85. | 中野博昭, 辻 英昭, 大上 悟, 福島久哲, 楊 峰,田 文懐, スルファミン酸浴およびワット浴からの 電析 Ni の硬度に及ぼす有機添加剤の影響, 日本金属学会誌, 75, 7, 406-411, 2011.07. |
| 86. | Hiroaki Nakano, Satoshi Oue, Daisuke Yoshihara, Hisaaki Fukushima, Yoshifumi Saka, Shigeru Sawada and Yasuhiro Hattori, Sn–Cu Alloy Electrodeposition and Its Connecting Reliability for Automotive Connectors, Materials Transactions, 52, 6, 1237-1243, 2011.06. |
| 87. | 中野博昭, 大上 悟, 吉原大介, 福島久哲, 坂 喜文, 澤田 滋, 服部康弘, 自動車接点材料用の Sn-Cu 合金電析とその電気的接続性, 日本金属学会誌, 75, 1, 61-68, 2011.01. |
| 88. | 楊 峰, 田 文懐, 中野博昭, 辻 英昭, 大上 悟, 福島久哲, スルファミン酸とワット浴からの電析Niの組織・硬度に及ぼす電流密度と有機添加剤の影響, 日本金属学会誌, 74, 11, 724-732, 2010.11. |
| 89. | 中野 博昭 大上 悟 濱口 裕介 小林 繁夫 福島 久哲 , 電気亜鉛めっき鋼板の外観,結晶形態に及ぼす ポリエチレングリコール予備吸着の影響, 鉄と鋼, 96, 6, 371-377, 2010.06. |
| 90. | H. Nakano, S. Oue , H. Fukushima, S. Kobayashi and K. Tomioka, Synergistic Effects of Thiourea, Polymer Additives and Chloride Ions on Copper Electrorefining, Proc. of Copper 2010 conference, Hamburg, 1531-1544, 2010.06. |
| 91. | 中野博昭, 大上 悟, 福島久哲, 硫酸塩水溶液からのZn-活性金属酸化物の複合電析, 防錆管理, 54, 5, 161-168, 2010.05. |
| 92. | Feng Yang, Wenhuan Tian, Hiroaki Nakano, hideaki Tsuji, Satoshi Oue and Hisaaki Fukushima, Effect of Current Density and Organic Additives on the Texture and Hardness of Ni Electrodeposited from Sulfamate and Watt's Solutions, Materials Transactions, 51, 5, 948-956, 2010.05. |
| 93. | Hiroaki Nakano, Satoshi Oue, Masaaki Uranaka, Masataka Masuda, Hisaaki Fukushima, Yoshifumi Saka, Shigeru Sawada and Yasuhiro Hattori, Electrodeposition of Sn-Ag Alloys and Evaluation of Connection Reliability for Automotive Connectors, Materials Transactions, 51, 4, 712-719, 2010.04. |
| 94. | Hiroaki Nakano, In-Joon Son, Satoshi Oue, Shigeo Kobayashi, Hisaaki Fukushima and Zenji Horita , Effect of Equal Channel Angular Pressing on the Pitting Corrosion Resistance on the Aluminum Alloys with/without Anodization, Material Science Forum, 1989-1994, 2010.04. |
| 95. | Hiroaki Nakano, Satoshi Oue, Masaaki Uranaka, Masataka Masuda, Hisaaki Fukushima, Yoshifumi Saka, Shigeru Sawada and Yasuhiro Hattori, Electrodeposition of Sn–Ag Alloys and Evaluation of Connection Reliability for Automotive Connectors, MATERIALS TRANSACTIONS, 51, 4, 712-719, 2010.04. |
| 96. | 孫仁俊, 中野博昭, 大上悟, 小林繁夫, 福島久哲, 堀田善治, Al-Cu合金の耐孔食性に及ぼす強歪み加工ECAP処理の影響, 表面技術, 61, 1, 50-57, 2010.01. |
| 97. | Hiroaki Nakano, Satoshi Oue, Yusuke Hamaguchi, Shigeo Kobayashi and Hisaaki Fukushima, Effect of Preadsorption of Polyethylene Glycol on the Appearance and Morphology of Electrogalvanized Steel Sheets, ISIJ International, 49, 11, 1769-1775, 2009.11. |
| 98. | H. NAKANO, I.J. SON, S. OUE, S. KOBAYASHI, H. FUKUSHIMA and Z. HORITA, Pitting Corrosion Resistance of Aluminum Alloys Processed by Equal-Channel Angular Pressing, Proc. of The 11th International Symposium on Materials Science and Engineering between Chonbuk National University and Kyushu University, 19-24, 2009.11. |
| 99. | H. NAKANO, S. OUE, H. KUBOYAMA, H. FUKUSHIMA and Y. HAYASHIBE, Synergistic effect of Polymer additives and Chloride Ions and the degradation of Polymer Additives in Copper Electrorefining , Proc. of Third International Conference on Processing Materials for Properties (PMP-III), 65-70, 2009.09. |
| 100. | In-Joon SON, Hiroaki NAKANO, Satoshi OUE, Shigeo KOBAYASHI, Hisaaki FUKUSHIMA, Zenji HORITA, Effect of equal-channel angular pressing on pitting corrosion resistance of anodized aluminum-copper alloy, Trans.Nonferrous Met. Soc. China, Vol.19, p.904-908(2009), 2009.08. |
| 101. | 中野博昭, 大上悟, 浦中将明, 増田正孝, 福島久哲, 坂善文, 澤田滋, 服部康弘, 自動車接点材料用のSn-Ag合金電析とその電気的接続性, 日本金属学会誌, No.73 Vol.8, p.622-629(2009), 2009.08. |
| 102. | Satoshi Oue, Hiroaki Nakano, Daisuke Kurai, Katsuaki Nakamura and Hisaaki Fukushima, Effect of Continuous Rotation Evolutional Control on the Pitting Corrosion Resistance of Anodized Al-Mg Alloys, Materials Transactions, Vol. 50,Vol.8, p.1985-1991, 2009.08. |
| 103. | 中野博昭 大上 悟 浦中将明 増田正孝 福島久哲 坂 喜文 澤田 滋 服部康弘, 自動車接点材料用のSn-Ag合金電析とその電気的接続性, 日本金属学会誌, 73, 8, 622-629, 2009.08. |
| 104. | H. NAKANO, I.J. SON, S. OUE, S. KOBAYASHI, H. FUKUSHIMA and Z. HORITA, Effect of Equal Channel Angular Pressing on the Pitting Corrosion Resistance on the Aluminum Alloys with/without Anodization , Proc. of International Conference on Processing & Manufacturing of Advanced Materials (THERMEC’2009), 2009.08. |
| 105. | Satoshi Oue, Hiroaki Nakano, Daisuke Kurai, Hisaaki Fukushima, Katsuaki Nakamura and Masataka Masuda, Effect of Continuous Rotation Evolutional Control on the Surface Color of Anodized Al-Mg Alloys, Materials Transactions, Vol. 50,Vol.7, p.1792-1797 , 2009.07. |
| 106. | Hiroaki Nakano, Satoshi Oue, Hisaaki Fukushima, Shigeo Kobayashi and Kazuhiko Nishina, Degradation of Polymer Additives during Long-Term Zn Electrowinning , European Metallurgical Conference 2009 (EMC2009), 1097-1110, 2009.06. |
| 107. | 中野博昭, 孫仁俊, 大原秀樹, 大上悟, 中村克昭, 福島久哲, 陽極酸化Al-Mg合金の耐孔食性に及ぼす連続強ねじり加工の影響, 日本金属学会誌, Vol.73 No.5 394-400, 2009.05. |
| 108. | 久保山宏, 中野博昭, 大上悟, 福島久哲, 小林繁夫, 銅の電解精製におけるチオ尿素添加の影響, Journal of MMIJ, Vol.125, No.2, pp.62-67, 2009.02. |
| 109. | Satoshi Oue , Hiroaki Nakano, Shigeo Kobayashi and Hisaaki Fukushima, Structure and Codeposition Behavior of Ni-W Alloys Electrodeposited from Ammoniacal Citrate Solutions , Journal of The Electrochemical Society, D17-D22, 2009.01. |
| 110. | In-Joon Son, Hiroaki Nakano, Satoshi Oue, Shigeo Kobayashi, Hisaaki Fukushima and Zenji Horita, Effect of Annealing on the Pitting Corrosion Resistance of Anodized Aluminum-Magnesium Alloy Processed by Severe Plastic Deformation, Materials Transactions, 2008.12. |
| 111. | In-Joon Son, Hiroaki Nakano, Satoshi Oue, Shigeo Kobayashi, Hisaaki Fukushima and Zenji Horita, Pitting Corrosion Resistance of Anodized Aluminum-Copper Alloy Processed by Severe Plastic Deformation, Materials Transactions, Vol.49,Vol.11, p.2648-2655, 2008.11. |
| 112. | 中野博昭, 大上悟, 藤本敦, 久保山宏, 福島久哲 , 林部豊, 銅電解製錬における高分子添加剤の経時劣化の評価, Journal of MMIJ, Vol.124, No.10,11 , pp.626-631, 2008, 2008.10. |
| 113. | 中野博昭，大上悟，清水誠一郎，久保山宏, 福島久哲，林, 亜鉛電解採取における高分子添加剤の経時劣化, Journal of MMIJ, Vol.124,Vol.9, p.583-588 , 2008.09. |
| 114. | 大上 悟, 中野博昭, 倉井大輔, 福島久哲, 中村克昭, 増田正孝, 陽極酸化Al-Mg合金の電解着色後の色調に及ぼす連続ねじり加工の影響, 日本金属学会誌, Vol.72, No.9, p.739-744, 2008.09. |
| 115. | In-Joon Son, Hiroaki Nakano, Satoshi Oue, Shigeo Kobayashi, Hisaaki Fukushima and Zenji Horita, Pitting Corrosion Resistance of Anodized Aluminum-Copper and Aluminum-Magnesium Alloys Processed by Equal-Channel Angular Pressing, 11th International Conference on Aluminum Alloys (ICAA 11), Aachen, 2066-2072, 2008.09. |
| 116. | Hiroaki Nakano Satoshi Oue Shoji Hisano Shigeo Kobayashi and Hisaaki Fukushima, Codeposition Behaviour of Impurities in during Electrogalvanization in Sulfate Baths in the Presence of Fe Ions, ISIJ International, Vol.47 7(2007)pp.1029-1033, 2008.07. |
| 117. | 中野博昭 孫仁俊 大原秀樹 大上悟 中村克昭 福島久哲, 連続ねじり加工を行ったAl-Mg合金の耐孔食性, 表面技術, Vol.59 No.6 pp.295-400, 2008.06. |
| 118. | Hiroaki Nakano Satoshi Oue Shoichi Taniguchi Shigeo Kobayashi Hisaaki Fukushima, Effects of Small Amounts of Molybdenum Tungsten or Tin Additive on the Morphology and Orientation of Electrodeposited Zinc, ISIJ Intertnational, Vol.48 5(2008)pp.634-639, 2008.05. |
| 119. | 孫 仁俊 中野博昭 大上 悟 小林繁夫 福島久哲 堀田善治, 強ひずみ加工を施したAl-Cu合金の陽極酸化膜の耐孔食性, 日本金属学会, 2008.05. |
| 120. | In-Joon Son, Hiroaki Nakano, Satoshi Oue, Shigeo Kobayashi, Hisaaki Fukushima and Horita Zenji, Pitting Corrosion Resistance of Anodized Aluminum-Copper Alloy Processed Bt Severe Plastic Deformation, 日本金属学会誌, Vol.72, No.5, p.354-357, 2008.05. |
| 121. | Hiroaki Nakano Satoshi Oue Daisuke Kozaki Shigeo Kobayashi Hisaaki Fukushima, Electrodeposition of Composites of Zinc with Vanadium Oxide from Sulfate Solutions, ISIJ Intertnationa, Vol.48 4(2008)pp.506-511, 2008.04. |
| 122. | Hiroaki NAKANO, Satoshi OUE, Daisuke KOZAKI, Shigeo KOBAYASHI and Hisaaki FUKUSHIMA, Electrodeposition of Composites of Zinc with Vanadium Oxide from Sulfate Solutions, ISIJ, 506-511, 2008.04. |
| 123. | 中野博昭, 大上悟, 野口智子, 福島久哲, 小林繁夫, 亜鉛電解採取における電析亜鉛の再溶解挙動に及ぼす不純物の相乗作用, Journal of MMIJ, Vol.124 No.3 pp.179-183, 2008.03. |
| 124. | 孫 仁俊, 中野博昭, 大上 悟, 小林繁夫, 福島久哲, 堀田善治, 強ひずみ加工を施したAl-Mg合金の陽極酸化後の耐孔食性に及ぼす熱処理の影響, 日本金属学会誌, 72(2008),pp.27-34, 2008.01. |
| 125. | 中野博昭 大上悟 谷口祥一 小林繁夫 福島久哲, 電析Znの結晶形態，配向性に及ぼす浴中へのMo W Snの微量添加の影響, 鉄と鋼, 2007,12,Vol.93 No.12 pp.763-768, 2007.12. |
| 126. | 中野博昭 大上悟 神崎大輔 小林繁夫 福島久哲, 硫酸塩水溶液からのZn-V酸化物複合電析, 鉄と鋼, Vol.93 11(2007)pp.703-708, 2007.11. |
| 127. | Hiroaki Nakano, Satoshi Oue, Hisaaki Fukushima, Shigeo Kobayashi, EFFECTS OF SMALL AMOUNTS OF VARIOUS INORGANIC ADDITIVES ON THE MORPHOLOGY AND APPEARANCE OF ZINC ELECTRODEPOSITED ON STEEL SHEETS, Proceedings of The 7th International Conference on Zinc and Zinc Alloy Coated Steel Sheet (Galvatech’07), Osaka, 207-212, 2007.11. |
| 128. | H. Kuboyama, H. Nakano, S. Oue and H. Fukushima and S. Kobayashi, SYNERGISTIC EFFECT OF POLYMER ADDITIVES AND CHLORIDE IONS ON COPPER ELECTROREFINING , Copper 2007 conference, 495-506, 2007.08. |
| 129. | H. Nakano, S. Oue and H. Fukushima, S. Kobayashi and Y. Abe, CODEPOSITION BEHAVIOR OF IMPURITIES IN COPPER ELECTROWINNING FROM CUPROUS CHLORIDE SOLUTION, Copper 2007 conference, 507-518, 2007.08. |
| 130. | 中野博昭 大上悟 萩本雅久 福島久哲 小林繁夫, 不純物を含有した亜鉛電解採取浴における電析亜鉛の再溶解挙動に及ぼすポリエチレングリコール添加の影響, Journal of MMIJ, Vol.123 No.6 7 pp.351-356, 2007.07. |
| 131. | Hiroaki NAKANO, Satoshi OUE, Shoji HISANO, Shigeo KOBAYASHI and Hisaaki FUKUSHIMA, Codeposition Behavior of Impurities During Electrogalvanization in Sulfate Baths in the Presence of Fe Ions, ISIJ, 47, 7, 1029-1033, 2007.07. |
| 132. | In-Joon Son, Hiroaki Nakano, Satoshi Oue, Shigeo Kobayashi, Hisaaki Fukushima and Zenji Horita, Effect of Annealing on the Pitting Corrosion Resistance of Anodized Aluminum-Magnesium Alloy Processed by Equal Channel Angular Pressing, CORROSION SCIENCE AND TECHNOLOGY, 6, 6, 275-281, 2007.06. |
| 133. | Hiroaki Nakano, Satoshi Oue, Hisaaki Fukushima and Shigeo Kobayashi, Effect of polymer additives on zinc electrowinning, European metallurgical Conference 2007, 1535-1547, 2007.06. |
| 134. | 中野博昭 大上 悟 青屋健吾 久保山宏 福島久哲 小林繁夫, 銅の電解精製における高分子添加剤と塩化物イオンの相乗効果, Journal of MMIJ, 123, 4,5, 165-170, 2007.04. |
| 135. | 中野博昭 大上悟 山口陽介 前田かおり 木村申平 福島久哲安部吉史, 塩化物系I価銅浴からのCu電析における不純物の共析挙動, 資源素材学会, Vol.123 No.1 pp.33-38, 2007.01. |
| 136. | 大上悟 中野博昭 黒田亮 小林繁夫 福島久哲, TEM-EDXによる電析Ni-Sn合金の微細構造, 日本金属学会誌, Vol.70 No.10 pp.804-808, 2006.10. |
| 137. | Hiroshi Kuboyama Hiroaki Nakano Satoshi Oue Hisaaki Fukushima Masataka Masuda Shunichi Hashimoto, Structure and Polarization Poperties of Zn-Nb Films Formed on Steel Sheet by Sputtering., ISIJ International, Vol.46 No.8 pp.1205-1209, 2006.08. |
| 138. | 中野博昭 大上 悟 三木俊幸 小林繁夫福島久哲, 鋼板上での電析Znの結晶形態に及ぼすポリエチレングリコール添加の影響, 鉄と鋼, Vol.92 No.8 pp.33-38, 2006.08. |
| 139. | 孫 仁俊 中野博昭 大上 悟 小林繁夫 福島久哲堀田善治, 強ひずみ加工を施したアルミニウム合金の陽極酸化後の耐孔食性, 日本金属学会誌, Vol.70 No.7 pp.534-540, 2006.07. |
| 140. | Satoshi Oue Hiroaki Nakano Ryo Kuroda Shigeo Kobayashi Hisaaki Fukushima, TEM-EDX Observations of the Microstructure of Electrodeposited Ni-Sn Alloys, Materials Transactions, Vol.47 No.6 pp.1550-1554, 2006.06. |
| 141. | In-Joon Son Hiroaki Nakano Satoshi Oue Shigeo Kobayashi Hisaaki Fukushima Zenji Horita, Pitting Corrosion Resistance of Ultrafine-Grained Aluminum Processed by Servere Plastic Deformation, Materials Transactions, Vol.47 No.4 pp.1163-1169, 2006.04. |
| 142. | Hiroaki Nakano Satoshi Oue Toshiyuki Miki Shigeo Kobayashi Hisaaki Fukushima, Effect of Polyethylene Glycol on the Morphology of Zn Electrodeposition on Steel Sheet, ISIJ International, Vol.46 No.1 pp.106-110, 2006.01. |
| 143. | 久保山宏 中野博昭 大上悟 福島久哲 増田正孝橋本俊一, スパッタリング法により鋼板上に形成されたZn-Nb膜の構造と分極特性, 鉄と鋼, Vol.92 No.1 pp.16-20, 2006.01. |
| 144. | 孫仁俊 中野博昭 大上悟 小林繁夫 福島久哲堀田善治, 強加工により結晶粒を微細化したアルミニウムの耐孔食性, 日本金属学会誌, Vol.69 No.10 pp.892-898, 2005.10. |
| 145. | 中野博昭 桑原裕樹 大上 悟 小林繁夫 福島久哲尹 正模, 定電流電解重合によるZn上へのポリ2-ビニルピリジン膜の形成, 日本金属学会誌, Vol.69 No.8 pp.780-786, 2005.08. |
| 146. | 中野博昭 松野昌幸 大上 悟 矢野正明 小林繁夫福島久哲, 硫酸塩浴からの変則型Fe-Ni合金電析の機構, 日本金属学会誌, Vol.69 No.7 pp.548-554, 2005.07. |
| 147. | 中野博昭 大上悟 見汐大樹 西畑義則福島久哲 津留豊, 電析膜の密着性の定量的評価方法の検討-スルファミン酸浴からのNi電析膜の密着性-, 表面技術, Vol.56 No.7 pp.421-426, 2005.07. |
| 148. | 中野博昭 大上悟 見汐大樹 西畑義則 福島久哲 津留豊, 電析膜の密着性の定量的評価方法の検討-スルファミン酸浴からのNi電析膜の密着性, 表面技術, Vol.56 No.7 pp.421-426, 2005.07. |
| 149. | 中野博昭，大上悟，小林繁夫，福島久哲，荒賀邦康，奥村和生，茂 博雄, 第4級アンモニウム塩を含む水溶液からのめっき用Mg含有Znの電析, 鉄と鋼, Vol.90 No.10 pp.51-56, 2004.10. |
| 150. | 中野博昭 大上悟 河野俊輔 矢野雅之 小林繁夫 津留壽昭 福島久哲, Fe-Ni合金の変則型電析機構の検討, 表面技術, Vol.55 No.6 pp.428-433, 2004.06. |
| 151. | 中野博昭 大上悟 野口智子 秋山徹也 福島久哲, 亜鉛電析の臨界電流密度に及ぼす不純物の相乗作用, 資源と素材, Vol.120 No.1 pp.39-42, 2004.01. |
| 152. | 大上 悟 中野博昭 福島久哲 小林繁夫 秋山徹也, 電析Ni-Sn合金の微細構造, まてりあ, Vol.42 No.12 pp.909-909, 2003.12. |
| 153. | 中野博昭，大上悟，大貝猛，泉孝平，秋山徹也，福島久哲, 銅電解精製における高分子添加剤の影響, 資源と素材, Vol.119 No.10 11 pp.663-667, 2003.10. |
| 154. | 中野博昭，大上 悟，小林繁夫，秋山徹也，福島久哲，久保田 昭，井上 正, スルファミン酸Ni浴におけるスルファミン酸イオンの陽極酸化とNi電析に及ぼす影響, 表面技術, Vol.54 No.8 pp.-, 2003.08. |
| 155. | 中野博昭，大上悟，吉永文隆，秋山徹也，福島久哲, 直鎖状高分子を含む硫酸塩浴からのZn-Cr合金の電析挙動, 表面技術, Vol.54 No.8 pp.-, 2003.08. |
| 156. | 大上 悟，中野博昭，小林繁夫，秋山徹也，福島久哲，奥村和生, 第4級アンモニウム塩を含む非懸濁溶液からのZn-Al2O3分散めっき, 表面技術, Vol.53 No.12 pp.920-925, 2002.12. |
| 157. | 李 相弼，中野博昭，大上 悟，秋山徹也，福島久哲，尹 正模, Zn板上への2-ビニルピリジン電解重合膜の形成に及ぼす電解因子の影響, 鉄と鋼, Vol.88 No.9 pp.513-519, 2002.09. |
| 158. | H. Nakano K. Nakahara S. Kawano S. Oue T. Akiyama and H. Fukushima, Effect of electrolysis factors on crystal orientation and morphology of electrodeposited cobalt, Journal of Applied Electrochemistry, 10.1023/A:1014219106152, 32, 1, 43-48, Vol.32 No.1 pp.43-48, 2002.01. |
| 159. | 中野博昭，大上悟，岩井正敏，秋山徹也，福島久哲, 電気Znめっき鋼板の白色度，光沢度に及ぼす浴中への微量無機物添加の影響, 鉄と鋼, Vol.86 No.9 pp.584-590, 2000.09. |
| 160. | 久保田 昭，田代康則，山崎和彦，中野博昭，大上 悟，小林繁夫，秋山徹也，福島久哲, アンモニア性クエン酸塩浴からの鉄族金属-Ｗめっきの電析挙動とその皮膜特性, 鉄と鋼, Vol.86 No.2 pp.116-122, 2000.02. |
| 161. | 久保田 昭，高田正人，中尾友則，中野博昭，大上 悟，秋山徹也，福島久哲，小野寺龍太, スルファミン酸浴からのNi電気めっき皮膜の低サイクル疲労特性に及ぼすS共析の影響, 鉄と鋼, Vol.86 No.1 pp.38-44, 2000.01. |
| 162. | 久保田 昭 坪田康彦 中野博昭 大上悟 小林繁夫 秋山徹也 福島久哲, スルファミン酸浴からの連鋳鋳型用Co-Niめっきの電析挙動とその摩耗特性, 鉄と鋼, Vol.85 No.10 pp.728-734, 1999.10. |
| 163. | 久保田昭，中尾友則，大上悟, Ni-アルミナ分散強化めっきによる機械的特性向上, 三島光産技報, Vol.19 No.1 pp.34-39, 1998.01. |
| 164. | 大上悟 秋山徹也 福島久哲 後藤靖人, 塩化物溶融塩浴からの電析Al-Mn合金の構造, 資源と素材, Vol.112 No.10 pp.729-734, 1996.10. |
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