Capacitance behaviour of passive films on ferritic and austenitic stainless steel

The electrochemical behaviour of passive films formed on one austenitic stainless steel (AISI 304) and one ferritic stainless steel (AISI 446) in solutions with pH between 0.6 and 8.4 was studied by capacitance measurements and photocurrent spectroscopy. Compositional characterization of the passive films was done by X-ray photoelectron spectroscopy. The capacitance increases with decreasing pH. Doping densities evaluated from Mott-Schottky plots are in the range 2-6 x 10(20) cm(-3) and increased with the pH in the neutral/alkaline range while in pH 0.6, values above 10(21) cm(-3) were found. The bandgap energy indicates two transitions, at 2.5-2.8 and 3.2 eV. The analytical data reveal that, as the pH increased, the films become enriched in Fe(II) and Fe(III), whereas the Cr(III) gradually decreases. The films formed at very low pH had a behaviour that contrasts with that of the films formed in the neutral/alkaline media. The films are described by a bilayer structure, with hydroxides in the outer layer and a spinel type oxide in the inner layer. (C) 2004 Flsevier Ltd. All rights reserved.