High temperature oxidation resistance in titanium-niobium alloys

Titanium alloys are ideally suited for use as lightweight structural materials, but their use at high temperature is severely restricted by oxidation. Niobium is known to confer oxidation-resistance, and here we disprove the normal explanation, that Nb⁵⁺ ions trap oxygen vacancies. Using density functional theory calculation, scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) we show that Nb is insoluble in TiO₂. In fact, the Ti-Nb surface has three-layer structure: the oxide itself, an additional Nb-depleted zone below the oxide and a deeper sublayer of enhanced Nb. Microfocussed X-ray diffraction also demonstrates recrystallization in the Nb-depleted zone. We interpret this using a dynamical model: slow Nb-diffusion leads to the build up of a Nb-rich sublayer, which in turn blocks oxygen diffusion. Nb effects contrast with vanadium, where faster diffusion prevents the build up of equivalent structures.