The mechanisms for the growth of the anodic Pb(II) oxides films formed on Pb–Sb and Pb–Sn alloys in sulfuric acid solution

Abstract

The anodic Pb(II) films formed on Pb, Pb–Sb and Pb–Sn alloys at 0.9 V (versus Hg/Hg 2SO 4) in 4.5 mol/l H 2SO 4 solution for 1 h were studied using alternating current (ac) impedance, open circuit decay curve and linear sweep voltammetry methods. Our research group has obtained the thickness of the anodic PbO film on Pb from the photocurrent measurement and proved that the resistance of the anodic PbO film is close to that of the interstitial liquid among the PbO particles in the film, from which it was inferred that the anodic PbO film grows via the dissolution–precipitation mechanism. It was concluded from the experimental results that (1) the films on Pb–Sb and Pb–Sn alloys also grow via the dissolution–precipitation mechanism, and the interstitial liquid may serve as the major passage for ion transportation during the film growth, (2) Sn facilitates the mechanism of oxidation of the surface layer of PbO particles to PbO 1+ x (0< x<1), (3) the influence of Sb to facilitate the growth of PbO 1+ x is smaller than that of Sn, but the doping effect of Sb(III) in the PbO crystals is more remarkable, (4) Sn increases the porosity of the anodic PbO film remarkably. All of the above effects decrease the specific resistance of the films.