First-principles investigation of oxygen interaction with hydrogen/helium/vacancy irradiation defects in Ti3AlC2

Abstract

First-principles calculations have been performed to investigate the interaction between solute impurity O and H/He/vacancy irradiation defects in Ti₃AlC₂. The formation energy and occupation of O atoms within different defects as well as the trapping progress of O/H clusters are discussed. It is found that the O atom preferentially occupies the hexahedral interstitial site (I_hex-1) in bulk Ti₃AlC₂, whereas it prefers to occupy the neighbouring tetrahedral interstitial site (I_tetr-2) within pre-exisiting Al monovacancy (V_Al), Al divacancy (2V_Al–Al) and the 2V_Al–C divacancy composed of Al and C vacancies. The appearance of C vacancy could greatly reduce the oxygen formation energy and make an O atom more inclined to occupy the center of C vacancy. Vacancy could capture more O atoms than H/He atoms, where V_Al and 2V_Al–Al could hold up to fifteen and eighteen O atoms, respectively. Meanwhile, the O could also promote the formation of Al vacancy. On the other hand, O atoms tend to occupy the interstitial sites near the Al atomic layer and have attraction to Al atoms, which is likely to enable the O atoms to combine with the Al atoms to form a Al₂O₃ protective layer, thus effectively inhibiting further oxidation inside the Ti₃AlC₂. In addition, the H–O exhibits repulsion interaction, but strong attraction occurs in the He–O interaction. Therefore, the O atom has an inhibitory effect on the formation of the H cluster, while it could bind more He atoms to form a large number of He bubbles. Besides, the O impurity greatly reduces the trapping ability of vacancy to H atoms, and O and He have a synergistic interaction for inhibiting the aggregation of H clusters. The present results are expected to provide a new insight into the behaviour of Ti₃AlC₂ under irradiation and oxidation conditions so that structural materials could be better designed.