Anomalous Codepositon Behavior of Fe-Ni and Zn-Ni Alloys from Methanol Baths

"Electrodeposition of Fe-Ni and Zn-Ni alloys from aqueous solutions is one of the well-known examples of anomalous codeposition in which less noble metal deposits preferentially. In this paper, the electrodeposition behavior of these alloy systems was compared between the methanol and aqueous baths. In Fe-Ni system, the significant suppression of the deposition rate of more noble Ni was observed over a wide range of electrolysis conditions in both methanol and aqueous baths. However, the electrodeposition of Zn-Ni alloys showed the typical feature of normal type codeposition in the methanol baths, which was completely different from that in aqueous sulfate baths. The difference in the electrodeposition mechanism between Fe-Ni and Zn-Ni alloys was discussed on the basis of the alloy deposition behavior in the baths in which the activity of water was varied:INTRODUCTION'It has been well known that Fe-Ni alloys show an excellent soft magnetic property. Therefore, thin films of this alloy have been used to fabricate the'-various magnetic devices. For the production of Fe-Ni thin films, dry processes such as sputtering, PVD and CVD are 'employed frequently and the resulting films showed a preferable property as a magnetic material. Electrolyses as a production technique of thin films, on the other hand, has the advantage over other processes in its cheaper production cost due to the simplicity of the production unit The Zn-iron-group metal alloys such as Zn-Ni and Zn-Fe electrodeposited on a steel sheet ale known to exhibit excellent corrosion resistance and therefore the electrodeposition of these, alloys has been applied to the production of surface treated steel sheets mainly for automotive body panels.According to Brenner (1), the electrodeposition behavior of Fe-Ni and Zn-Ni alloys was' classified into the' 'anomalous type. In this type of codeposition, less noble metal, i.e. Fe for Fe-Ni and Zn for Zn-Ni system, deposits preferentially and the change in -the alloy composition- with the variation of electrolysis conditions was unpredictable because of their obscure deposition mechanism. Since most properties of the alloys mainly depend on their composition, the composition of the deposited' alloys must be controlled strictly. Therefore, it is neces5al)' to clarify the mechanism of anomalous codepasition in Fe-Ni and Zn-Ni systems: Several mechanisms have been proposed so fur, and among them the hydroxide .suppression mechanism (2), (3) has been regarded most plauslble depend on their composition, the composition of the deposited' alloys must be controlled strictly. Therefore, it is necessary to clarify the mechanism of anomalous codeposition in Fe-Ni and Zn-Ni systems: Several mechanisms have been proposed so far, and among them the hydroxide suppression mechanism (2), (3) has been regarded most plausible. According to this mechanism, it can be predicted that the codeposition behavior depends greatly on the characteristic of water solvent in this study, using methanol as a solvent, the electrodeposition behavior of the anomalous codeposition was investigated to discuss the validity of the hydroxide suppression mechanism."