High temperature oxidation resistance in titanium–niobium alloys

•The conventional explanation for oxidation resistance is disproven, an alternative presented.•A generic analytic diffusion model for oxidation resistance is presented.•We develop a class of oxidation resistant niobium–titanium alloys.•Calculation, microscopy, spectroscopy and diffraction analysis of the alloys.•The theory is verified in oxidation tests. 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.