Tracing locations of new coating material during spark anodizing of titanium

The growth of anodic coatings on titanium, under sparking conditions, is investigated in tracer experiments, using alkaline silicate and phosphate electrolytes. Coatings are formed sequentially in each electrolyte, with phosphorus and silicon located by energy-dispersive X-ray analysis and glow discharge optical emission spectroscopy. The coatings, containing anatase, rutile and amorphous oxide, with incorporated phosphorus and silicon species, are shown to grow by discrete thickening at sites of dielectric breakdown. New material is found near the metal, within the coating bulk and at the coating surface. Approximately 10-30% of the new material is located near to the coating surface and about 40-60% near to the metal. The findings are attributed to the formation of breakdown channels allowing access of electrolyte species to the inner parts of the coating and to subsequent rapid formation of coating material, under high temperatures, associated with increased local current density, and high pressures, associated with volume constraints on oxide growth and gas generation.