In situ monitoring of the internal stress evolution during titanium thin film anodising

Anodisation has been studied for almost eighty years, primarily in the field of corrosion science, as a simple and efficient way of producing thick protective oxide coatings on Al, Ti or Zr alloys. Anodisation is an electrochemical oxidation process which relies on the migration of ions across solid films under the action of a large electric field. From the fundamental point of view, many aspects regarding the growth of anodic films have been studied extensively. However, so far, little interest has been devoted to the mechanical aspects involved in the growth process, in spite of their considerable importance both from an applied as well as from a fundamental point of view. A solid understanding of internal stress development is indeed crucial in order to guarantee the durability of anodic coatings, their structural and functional properties. In addition, the stress evolution directly reflects the motion of the ions in the film and therefore provides a unique means to investigate in situ the growth mechanisms of anodic films. In this thesis, we have studied the evolution of the internal stresses in anodic TiO2 films in situ during their growth. The stresses have been obtained from changes in the curvature of cantilevered anode samples, measured using a high-resolution multibeam optical sensor. We demonstrate, for the first time, the capability of this type of curvature sensor for monitoring processes in liquid environments. Experimental data on the internal stresses developing in anodic TiO2 films is provided, and trends regarding the influence of the experimental conditions on the stress evolution are identified. In particular, the evolution of the internal stresses is shown to be strongly correlated with the evolution of the electrochemical variables, which directly demonstrates the interest of curvature measurements as a fundamental technique for investigating the details of the growth process of anodic oxide films. The reversible and irreversible stress contributions associated, respectively, with electrostriction and with growth-related ionic transport have been separated from one another and quantified. A novel constitutive model for the electrostriction stress is proposed which explicitly takes into account the effect of dielectrostriction.