Impedance spectroscopy study of anodic growth of thick zirconium oxide films in H₂SO₄, Na₂SO₄ and NaOH solutions

Abstract

Anodic zirconium oxide films were grown potentiodynamically at a constant sweep rate up to the breakdown potential on rod electrodes made of 99.8% metallic zirconium. Different media of different pH were tested, namely 0.5 M H₂SO₄ (pH 0.3), 0.1 M Na₂SO₄ (pH 9) and 0.1 M NaOH (pH 13). By electrochemical impedance spectroscopy and scanning electron microscopy the oxide film thickness was monitored during the voltage scan. The behaviour was found to be different in the presence and absence of sulphate anions. In the presence of SO ²⁻₄ , the films were dense but breakdown occurred at 300–340 nm. In NaOH, two relaxations appeared above 50 V and were ascribed to a bi-layered coating structure and the maximum layer thickness was 720 nm before breakdown.