Electrochemical and XPS measurements on thin oxide films on zirconium

• Published in: Journal of electroanalytical chemistry and interfacial electrochemistry 1987-01, Vol.217 (1), p.159-185
• Main Authors: Meisterjahn, P., Hoppe, H.W., Schultze, J.W.
• Format: Article
• Language: English
• Subjects: Applied sciences; Exact sciences and technology; Other techniques and industries
• ISSN: 0022-0728
• DOI: 10.1016/0022-0728(87)85072-6

The potentiodynamic growth of thin oxide films on zirconium electrodes was investigated by coulometric and simultaneous impedance measurements, as a function of the electrode potential (0 V ⩽ E ⩽ 9 V), the pH (0 ⩽ pH ⩽ 14) and the surface preparation (electropolishing, etching and mechanical polishing). The initial film thickness d 0 is at least 4–6 nm; with increasing potential, the oxide grows irreversibly by 2.6 nm/V (pH 0.3) up to 3.2 nm/V (pH 14). In Cl −- and ClO − 4-containing solutions the oxide growth is limited by localized corrosion. The oxide behaves like a typical insulator with a donor concentration N D < 10 19 cm −3 and a dielectric constant D = 31. Below −0.5 V (vs. SHE) only, th film behaves like an n-type semiconductor with N D ≈ 3 × 10 19 cm −3. From photoelectrochemical measurements a direct and an indirect transition with band gap energies of E g = 5 eV and E g = 2.8 eV could be derived. Anodic electron-transfer reactions (ETRs) are blocked at the homogeneous oxide surface, but cathodic ETRs are possible at larger overvoltages. Near the flatband potential E fb ≈ −1.3 ± 0.2 V (vs. SHE) hydrogen evolution takes place with a simultaneous increase of the capacity which may be attributed to hydrogen incorporation. With XPS measurements the stoichiometry of the oxide film was determined as ZrO 2 at all the pH values examined, but a thin outer layer contained some hydroxide. Components of the forming electrolyte could not be detected (sulphate, borate and perchlorate < 1%), but etching in HF caused accumulation of F − at the inner boundary.