Steady-state analysis of the nickel oxide in neutral and weakly alkaline solutions

Thin passive nickel oxides are investigated in neutral and weakly alkaline pH solutions under steady-state conditions. The chemical species considered in the oxide film are nickel interstitials and vacancies, as well as oxygen vacancies. The set of differential equations used in this study is solved using the finite element method (FEM) and is able to reproduce the experimental data present in the literature. Steady-state oxide thickness variation with the applied electrode potential presents a linear behavior with an average slope of 2 nm/V. The role of dominant species in these thin films is investigated in terms of current density produced by the reactions at the interfaces, the reactions involving production and consumption of Ni2+ vacancies playing a major role in the steady-state properties of the oxide. We show that the mass transport of species in the oxide is influenced more by the migration component of the flux than the diffusion component. Our results also show that the flux of Ni2+ vacancies is approximately two orders of magnitude higher than the flux of oxygen vacancies and Ni2+ interstitials, making them the dominant defects in the oxide (thus the p-type electronic character is present). Also, the Ni2+ vacancies were found to have density levels of 1020–1021 cm−3 close to the metal–film interface. Variations of the steady-state thickness and logarithm of the current density with the electrolyte pH, show a linear increase and decrease respectively. Some of these results are compared with data from experiments and simulations done on the iron oxide, showing that Ni forms steady-state passive films that are thinner than the ones formed on Fe under the same environment conditions (pH, temperature, and applied potential).