The initial transient of natural convection during copper electrolysis in the presence of an opposing Lorentz force: Current dependence

Abstract

Magnetic fields are well-established in electrochemistry as an attractive tool to improve both the quality of the deposit as well as the deposition rate. The key mechanism is a mass transfer enhancement by Lorentz-force-driven convection. However, during electrolysis this convection interacts with buoyancy-driven convection, which arises from concentration differences, in a sometimes intriguing way. In the case of a Lorentz force opposing buoyancy, this is due to the growth of a bubble-like zone of less-concentrated cupric ion solution at the lower part of the vertical cathode when copper electrolysis is performed. If buoyancy is strong enough to compete with the Lorentz force, this zone rises along the cathode and causes surprisingly unsteady initial transient behaviour. We explore this initial transient under galvanostatic conditions by analyzing the development of the concentration and velocity boundary layers obtained by Mach-Zehnder interferometry and particle image velocimetry. Particular attention is also paid to higher current densities above the limiting current, obtained from potentiodynamic measurements, at which a chaotic advection takes place. The results are compared by scaling analysis.