Clarifying the mechanism of reverse structuring during electrodeposition in magnetic gradient fields.

Deviating from the common expectation, magnetoelectrochemical structuring during deposition of diamagnetic ions was demonstrated, very recently. To achieve this, electrochemically inert paramagnetic ions have to be added to the electrolyte and the deposition has to be performed in a magnetic gradient field. A reverse structuring occurs, yielding thinner deposits near high gradient regions. In this paper we aim to clarify the mechanism of this reverse structuring. Potentiodynamic and potentiostatic investigations were performed, including measurements of the deposited mass with an electrochemical quartz crystal microbalance (EQCM). The convection of the electrolyte was studied in situ by astigmatism particle tracking velocimetry (APTV). It was revealed that during the reverse structuring a convection is induced in the electrolyte, which is directed away from the working electrode in regions of high magnetic gradients. Due to this additional convection, the overall deposition rate is increased, whereby it is locally reduced in regions of high magnetic gradients. The mechanism for reverse structuring is discussed in detail. Also, the influence of all relevant magnetic forces is addressed.