First principles study of oxidation behavior of irradiated graphite

Abstract The relationship between nuclear graphite microstructure and its oxidation resistance underlines the importance of comprehensive oxidation characterization studies of the new grades of nuclear graphite. Periodic DFT calculations are performed to model oxidation behavior of irradiated graphite. O 2 molecules adsorbed on perfect and defective graphite surfaces are calculated. The adsorptive energy of O 2 on defective graphite adsorption site with one carbon atom missing is approximately 10 times as strong as that on a defect-free perfect graphite surface. Monovacancy and divacancy on graphite surface can easily chemisorb O 2 molecule compared to perfect surface. Two oxidation processes including CO and CO 2 formation steps are analyzed. For symmetric monovacancy defect, three dangling C atoms are unsaturated and exhibit high adsorption ability, as well as reconstructed monovacancy and divacancy defects. These vacancy defects in irradiated graphite decrease oxidation resistance of nuclear graphite.