Defect formation and its effect on the thermodynamic properties of Pu2Zr2O7 pyrochlore: a first-principles study

In the past decades, pyrochlores, such as Gd₂Zr₂O₇, have demonstrated great potential to immobilize nuclear wastes such as Pu, which results in the production of Pu₂Zr₂O₇. Due to the high radioactivity of Pu, it is difficult to investigate the radiation response behavior of Pu₂Zr₂O₇ and its physical properties of the damaged state experimentally. Consequently, few related data have been reported in the literature thus far. In this study, first-principles calculations have been carried out to investigate the defect formation and its effect on the thermodynamic properties of Pu₂Zr₂O₇. It reveals that Pu_Zr antisite and O_8a interstitial defects are very easy to form in Pu₂Zr₂O₇. In particular, the O_8a interstitial defect can be formed spontaneously, while it is mechanically unstable. When vacancy, interstitial or antisite defects are formed in Pu₂Zr₂O₇, and the elastic moduli and Debye temperature are decreased. Besides, better ductility is resulted. As compared with other zirconate pyrochlores, such as Gd₂Zr₂O₇, the Pu₂Zr₂O₇ is suggested to be less resistant to radiation-induced amorphization. This study demonstrates that the created defects due to self-radiation from actinide decay have remarkable influences on the thermophysical properties of Pu₂Zr₂O₇.