Transient growth and thinning of the barrier oxide layer on iron measured by real-time spectroscopic ellipsometry

The transient growth and thinning of the passive film on iron was investigated in ethylenediaminetetraacetic acid, disodium salt (EDTA) containing borate buffer solutions of pH 8.4 using real-time spectroscopic ellipsometry under potentiostatic control. EDTA effectively suppressed the formation of the outer layer of the passive film, thereby rendering the barrier layer amenable to direct examination. It was shown that the barrier layer growth was completed in about 10 s upon potential stepping in the anodic direction. On the other hand, the thinning of the barrier oxide layer upon potential stepping in the cathodic direction occurred at a rate that was two orders in magnitude lower than the growth rate. The steady-state barrier layer thickness varied linearly with applied potential, whereas the steady-state current density did not depend on the formation potential. These spectroscopic ellipsometric measurements are qualitatively explained by the point defect model (PDM).