On the relationship between local voltage maxima and efficiency changes during galvanostatic Ti anodising

The evolution of the voltage signal with time during galvanostatic anodising of bulk Ti has been repeatedly reported in the literature to exhibit a striking local maximum, followed by a decrease in the slope of the V-t curve. While the slope change is well-known to be the result of changes in the anodic growth efficiency, the presence of an associated local voltage maximum has received much less attention. In the first part of this paper, we investigate the fundamental origin of the local V-maximum, which to the best of our knowledge, is as yet still unexplained. We have first of all reproducibly observed this behaviour during anodising of sputtered Ti thin films in 1.0 M H2SO4 at a current density of 4 mA/cm(2). Quantifying the evolution of both the thickness and the density of the anodic oxide films with time led to the conclusion that the observed local V-maximum results from an increase of the anodising ratio. It is then demonstrated that, according to the classical high-field theory for ionic migration, such increase in anodising ratio is to be expected when the growth efficiency decreases to such an extent that the ionic current density falls below the mA/cm(2) level. We also show that, once the high-field rate constants for the anodic oxide film have been accurately determined, the local V-maximum can be quantitatively reproduced based only on the evolution of the growth efficiency. In the second part, we discuss the physical origin of the changes in the anodic growth efficiency, based on TEM investigations of the microstructural evolution taking place in the film around the transition region. Our results convincingly demonstrate that anatase crystallites are already present in an amorphous film matrix well before the transition region. Instead, a significant increase in electron diffraction intensity was observed for the rutile phase before and after the local voltage maximum. (C) 2008 Elsevier Ltd. All rights reserved.