An investigation of the long-range and local structure of sub-stoichiometric zirconium carbide sintered at different temperatures

ZrC(1−x) (sub-stoichiometric zirconium carbide), a group IV transition metal carbide, is being considered for various high temperature applications. Departure from stoichiometry changes the thermo-physical response of the material. Reported thermo-physical properties exhibit, in some cases, a degree of scatter with one likely contributor to this being the uncertainty in the C/Zr ratio of the samples produced. Conventional, methods for assigning C/Zr to samples are determined either by nominal stochiometric ratios or combustion carbon analysis. In this study, a range of stoichiometries of hot-pressed ZrC(1−x) were examined by SEM, XRD, Raman spectroscopy and static (13)C NMR spectroscopy and used as a basis to correct the C/Zr. Graphite, amorphous, and ZrC(1−x) carbon signatures are observed in the (13)C NMR spectra of samples and are determined to vary in intensity with sintering temperature and stoichiometry. In this study a method is outlined to quantify the stoichiometry of ZrC(1−x) and free carbon phases, providing an improvement over the sole use and reliance of widely adopted bulk carbon combustion analysis. We report significantly lower C/Zr values determined by (13)C NMR analysis compared with carbon analyser and nominal methods. Furthermore, the location of carbon disassociated from the ZrC(1−x) structure is analysed using SEM and Raman spectroscopy.