Measuring and modeling oxygen diffusion in niobium-vanadium and niobium-palladium alloys

Date of Completion

January 1999


Engineering, Metallurgy|Engineering, Materials Science




Niobium alloys are under consideration for high-temperature aerospace applications, but they have poor oxidation resistance and need high-temperature coatings for protection in severe environments. Our approach to creating an oxidation-resistant Nb alloy is to identify substitutional solute elements that lower the diffusivity of oxygen in Nb. In theory, this will induce a transition from internal to external oxidation and promote the formation of a desirable, protective oxide scale. The objective of this particular project is to compare the oxygen diffusivity in Nb alloys that contain either trap or repulsive sites. In Nb, oxygen atoms diffuse via an interstitial mechanism, and they can interact with substitutional solute atoms in different ways. The interstitial sites adjacent to a substitutional atom constitute a “zone of influence”. If the sites in this zone have a lower energy than the normal sites, they are called “trap” sites. If these sites have a higher energy, they are called “repulsive” sites. Oxygen diffusion is inhibited in both cases: trap sites hold the oxygen and keep it from diffusing further, while repulsive sites block the path of the oxygen. Two new mathematical models for interstitial diffusion in these systems were derived from probability and statistical thermodynamic theory. The models were verified using a new random-walk computer simulation of oxygen diffusion through Nb alloys. These models were also tested experimentally by measuring oxygen diffusivity in Nb-V and Nb-Pd alloys. These results showed that V atoms create trap sites for oxygen atoms, confirming previous work. However, there was not enough data to prove definitively that Pd atoms create repulsive sites, as expected by theory. ^