Impedance spectroscopy study of passive layers on the surface of lead-tin and lead-tin-calcium alloys anodically oxidized in 4.8 M sulfuric acid solution

摘要

The nature of passive films, which were formed at various potentials in 4.8 M H_2SO_4 solution on the lead-tin and lead-tin-calcium alloys, is studied by the method of impedance spectroscopy. At the potentials of 1.3 and 1.7 V, the electrode impedance is presented by the equivalent circuit, which corresponds to the formation of a bilayer film consisting of lead(II) sulfate and oxide on the electrode surface. Lead(II) oxide, which forms under the layer of lead sulfate, determines a high resistance of passive layer on the electrodes of lead alloys under investigation. An introduction of tin into the lead alloys significantly decreases the resistance of passive layers. An addition of calcium to the lead-tin alloy raises the impedance of the system. At a potential of 2.05 V, a single-layer compact passive film forms on the electrodes of the test lead alloys. It consists predominantly of lead oxides PbO _x (1 < x ≤ 2), which exhibit a higher electron conductivity. An introduction of tin into the lead alloys decreases the resistance of formed films; calcium has almost no effect on the resistance of passive film under these conditions.