Mechanism of copper-nickel alloy electrodeposition

The codeposition kinetics of Cu and Ni alloys in complexing citrate ammonia electrolytes has been investigated by means of polarization and electrochemical impedance techniques. It is confirmed that the two-step discharge of the complexed cupric species Cu(II)Cit is diffusion-controlled during the alloy deposition, resulting in an increase in the nickel content of the alloy with electrode polarization. Impedance spectra are also consistent with a two-step discharge of Ni(II) cations involving an intermediate adsorbate, Ni(I) sub ads , origninating from the reversible first step. A reaction model is developed for the parallel discharge of Cu(II)Cit and Ni(II) in which the reactions for nickel deposition are catalysed by active sites permanently renewed at the surface of the growing alloy. The surface density of these sites, slowly nucleated from Ni(I) sub ads and included in the deposit, varies with the electrodes polarization, thus generating a low-frequency feature specific of Cu--Ni codeposition. This reaction model reproduces to a reasonable extent the potential dependence of the particle current densities for nickel and copper discharge, the current dependence of the alloy nickel content and also most of the experimental relaxation processes observed on impedance spectra. 11 ref.--AA