Abstract
The dissolution and passivation of pure Cu and Cu-5 wt pct Ag anodes in H2SO4-CuSO4 electrolyte were investigated by a direct observation method that combined the techniques of optical microscopy and channel flow double electrode. Linear sweep voltammetry of the anodes showed that the dissolution of Cu transited from the charge transfer-controlled reaction to the mass transfer-controlled reaction, followed by the passivation of the electrodes. The direct observation of the pure Cu anode revealed that Cu particles were generated on the surface and the particles fell away during passivation. On the other hand, a slime layer of Ag particles that adhered to the surface was generated during the dissolution of the Cu-5 wt pct Ag anode. The Cu-5 wt pct Ag anode was passivated with a lower current density than the pure Cu anode, which suggested that the morphology and adhesive characteristics of the slime on the anode affected the passivation. The direct observation method described herein is useful for understanding reactions on electrodes that undergo drastic changes in their surface morphology. Information obtained from this method can help with the development of new processes for the effective utilization of limited natural resources and energy, such as the recycling of Cu by electrorefining.
Similar content being viewed by others
References
1. J. Hait, R. K. Jana and S. K. Sanyal: Miner. Process. Extr. Metall., 2009, vol. 118, pp. 240-252.
2. S. Abe, B. W. Burrows and V. A. Ettel: Can. Metall. Quart., 1980, vol. 19, pp. 289-296.
3. F. Noguchi, Y. Iida, T. Nakamura and Y. Ueda: J. Min. Metall. Inst. Jpn., 1991, vol. 107, pp. 569-575.
4. M. Bounounghaz, M. Manzini and E. Ghali: Can. Metall. Quart., 1995, vol. 34, pp. 21-26.
5. Z. H. Gu, J. Chen and T. Z. Fahidy: Hydrometallurgy, 1995, vol. 37, pp. 149-167.
6. C. A. Möller, M. Bayanmunkh and B. Friedrich: World of Metallurgy - ERZMETALL, 2008, vol. 61, pp. 357-367.
7. W. Zeng, S. Wang and M. L. Free: Metall. Mater. Trans. B, 2016, vol. 47B, pp. 3178-3191.
8. S. Abe and S. Goto: J. Min. Metall. Inst. Jpn., 1981, vol. 97, pp. 951-956.
9. S. Abe and S. Goto: J. Min. Metall. Inst. Jpn., 1981, vol. 97, pp. 1193-1198.
10. X. Cheng and J. B. Hiskey: Metall. Mater. Trans. B, 1996, vol. 27B, pp. 610-616.
11. J. B. Hiskey and X. Cheng: Metall. Mater. Trans. B, 1998, vol. 29B, pp. 53-58.
12. M. S. Moats and J. B. Hiskey: Can. Metall. Quart., 2000, vol. 39, pp. 297-306.
13. M. S. Moats, J. B. Hiskey and D. W. Collins: Hydrometallurgy, 2000, vol. 56, pp. 255-268.
14. M. O. Ilkhchi, H. Yoozbashizadeh and M. S. Safarzadeh: Chem. Eng. Process., 2007, vol. 46, pp. 757-763.
15. M. Palaniappa, M. Jayalakshmi, P. M. Prasad and K. Balasubramanian: Int. J. Electrochem. Sci., 2008, vol. 3, pp. 452-461.
16. A.-M. Lafront, F. Safizadeh, E. Ghali and G. Houlachi: Electrochim. Acta, 2010, vol. 55, pp. 2505-2512.
17. F. Safizadeh and E. Ghali: Electrochim. Acta, 2010, vol. 56, pp. 93-101.
18. X. Cheng and J. B. Hiskey: Metall. Mater. Trans. B, 1996, vol. 27B, pp. 393-398.
19. Y. Konishi, Y, Nakamura, Y. Fukunaka, K. Tsukada and K. Hanasaki: Electrochim. Acta, 2003, vol. 48, pp. 2615-2624.
20. E. A. Kucharska-Giziewicz and D. J. Mackinnon: J. Appl. Electrochem., 1996, vol. 26, pp.51-57.
21. G. Jarjoura and G. J. Kipouros: Can. Metall. Quart., 2005, vol. 44, pp. 469-482.
22. G. Jarjoura and G. J. Kipouros: J. Appl. Electrochem., 2006, vol. 36, pp. 691-701.
23. T. T. Chen and J. E. Dutrizac: Metall. Trans. B, 1989, vol. 20, pp. 345-361.
24. S. Northey, S. Mohr, G. M. Mudd, Z. Weng and D. Giurco: Resour. Conserv. Recy., 2014, vol. 83, pp. 190-201.
25. B. H. Robinson: Sci. Total Environ., 2009, vol. 408, pp. 183-191.
26. A. Anindya, D. R. Swinbourne, M. A. Reuter and R. W. Matusewicz: Miner. Process. Extr. Metall., 2013, vol. 122, pp. 165-173.
27. M. Ghodrat, M. A. Rhamdhani, G. Brooks, S. Masood and G. Corder: J. Clean. Prod., 2016, vol. 126, pp. 178-190.
H. Matsushima, H. Yatsuhashi, S. Kato, H. Nakano, S. Oue, T. Kamiya, H. Metsugi, H. Takiguchi and Y. Abe: Proceedings of the 9th International Copper Conference, 2016, Vol. 4 Electrowinning and Electrorefining, pp. 115–26.
29. W. Zeng, S. Wang and M. L. Free: J. Electrochem. Soc., 2017, vol. 164, pp. E233-241.
30. T. Tsuru: Mat. Sci. Eng. A, 1991, vol. 146, pp. 1-14.
31. E. O. Barnes, G. E. M. Lewis, S. E. C. Dale, F. Marken and R. G. Compton: Analyst, 2012, vol. 137, pp. 1068-1081.
32. A. Nishikata, M. Itagaki, T. Tsuru and S. Haruyama: Corr. Sci., 1990, vol. 31, pp. 287-292.
33. M. Itagaki, M. Tagaki, T. Mori and K. Watanabe: Corr. Sci., 1996, vol. 38, pp. 601-610.
34. M. Itagaki, M. Tagaki, T. Mori and K. Watanabe: Corr. Sci., 1996, vol. 38, pp. 1109-1125.
35. M. Itagaki, T. Mori and K. Watanabe: Corr. Sci., 1999, vol. 41, pp. 1955-1970.
36. Y. Ninomiya, H. Sasaki and M. Maeda: Proc. MMIJ Annual Meeting, 2015, vol. 2, No. 2, [1802].
37. Y. Hoshi, T. Oda, I. Shitanda and M. Itagaki: J. Electrochem. Soc., 2017, vol. 164, pp. C450-452.
T. Oda, Y. Hoshi, I. Shitanda, and M. Itagaki: Proc. JSCE Materials and Environments 2016, 2016, pp. 347–48.
M. Pourbaix: Atlas of Electrochemical Equilibria in Aqueous Solutions, English ed., Pergamon Press Ltd., London, 1966, pp. 385–87, 394–96.
40. H. Matsuda: J. Electroanal. Chem. Interfacial Electrochem., 1968, vol. 16, pp. 153-164.
E. Mattson and J. O’M. Bockris: Trans. Faraday Soc., 1959, vol. 55, pp. 1586–1601.
42. R. P. Elliott, F. A. Shunk and W. C. Giessen: Bull. of Alloy Phase Diagr., 1980, vol. 1, pp. 41-45.
43. S. Nagakura, S. Toyama and S. Oketani: Acta. Metall., 1966, vol. 14, pp. 73-75.
Acknowledgments
We would like to express our gratitude to Professor T. H. Okabe (Institute of Industrial Science, The University of Tokyo) for his advice on composing the manuscript and Mr. H. Kimura (The University of Tokyo) for technical assistance with the experiments. This study is a part of a research project by the Agency for Natural Resources and Energy. The authors are grateful for the financial support and advice on our experimental design from the Japan Oil, Gas and Metals National Corporation (JOGMEC).
Author information
Authors and Affiliations
Corresponding author
Additional information
Manuscript submitted July 20, 2018.
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Ninomiya, Y., Sasaki, H., Yoshikawa, T. et al. Direct Observation of Pure Cu and Cu-Ag Anode Passivation in H2SO4-CuSO4 Aqueous Solution by Channel Flow Double Electrode and Optical Microscopy. Metall Mater Trans B 50, 407–415 (2019). https://doi.org/10.1007/s11663-018-1447-9
Received:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11663-018-1447-9