Polymorphic transformation from body-centered to face-centered cubic vanadium metal during mechanosynthesis of nanostructured vanadium nitride determined by extended x-ray absorption fine structure spectroscopy

The pathway for vanadium nitride VN formation obtained by milling treatment has been traced out. At the initial stages of the process, the reactant, vanadium metal, showing body-centered cubic bcc structure, becomes highly distorted. Simultaneously, the formation of a small nucleus of the product, VN, takes place. X-ray absorption spectroscopy XAS has allowed the quantification of the distortion degree as well as the detection of the VN nucleus in the early stages of their formation, while other standard structural characterization techniques are unable to detect such phenomena. For increasing milling times, apart from the expected increase in the size of the VN nucleus, a polymorphic transformation from bcc to fcc vanadium metal has been recorded. This phase might play a key role in the overall synthesis process and could be a reaction intermediate in other solid state processes involving V metal. The sensitivity of XAS to noncrystalline domains and to highly distorted environments, as well as the use of high resolution x-ray diffraction, has provided the relevant information to understand the whole reaction process.