The effect of oxygen impurities on the stability and structural properties of vacancy-ordered and -disordered ZrCx

Theoretical calculations predict several long-range ordered sub-stoichiometric zirconium carbide phases to be stable at low temperature, rather than a random (disordered solution) distribution of vacancies. However, experimental synthesis of vacancy-ordered phases is extremely challenging and not all predicted phases have been experimentally observed. It has been hypothesised that the inevitable oxygen contamination in experimental samples may affect the vacancy ordering. In this work, the stability and structural properties of the vacancy-ordered and vacancy-disordered phases are investigated as a function of oxygen defect concentration using first-principles calculations. The observed trends are explained in terms of changes to the local bonding in the presence of varying amounts of oxygen and vacancies. It is found that the relative stability of the ordered phases (compared to the disordered phase at the same composition) decreases as oxygen concentration increases, and some vacancy-ordered phases are destabilised by the level of oxygen impurities found in experimental samples. This suggests that oxygen contamination is a contributing factor to the challenge of synthesising ordered zirconium carbides, and gives insight that may assist fabrication in the future. The volume of all ZrC_x (x ≤ 1) phases was found to decrease with increasing oxygen concentration, which can be attributed to the different ionocovalent nature of the C–Zr and O–Zr bonds. The volume of the vacancy-ordered phases within the expected oxygen solubility limit is greater than the disordered phase of the same composition, which is explained in terms of the relative bond strengths surrounding different vacancy distributions.

First-principles calculations are used to explore vacancy ordering in zirconium carbide at various stoichiometries as affected by oxygen impurities. Atomic bonding and electronic charge distribution are linked to stability and volume trends as a function of O concentration.