Oscillating oxygen evolution at Ta anodes

Anodic Ta oxide films are said to inhibit oxygen evolution. In industry, however, large amounts of gas are evolved during the anodization of tantalum anodes for electrolytic capacitor fabrication. We quantified the oxygen by fluorescence quenching in a flow-through cuvette and found that 4% of the anodic charge are consumed for oxygen evolution. In wires or sheets, this oxygen is removed by diffusion without bubble formation and, thus, not recognized. Due to the large inner area of the sintered Ta anodes, the oxygen evolution causes strong oscillations of the current density and bubble formation. The amount of oxygen is proportional to the oxide amount formed in parallel. This is explained by a model where mobile ions during oxide growth form interband states which allow electron tunneling. Accordingly, stationary no oxygen evolution is observed.