Novel potentials for modelling defect formation and oxygen vacancy migration in Gd2Ti2O7 and Gd2Zr2O7 pyrochlores

• Published in: Journal of materials chemistry 2012-01, Vol.22 (11), p.4675-468
• Main Authors: Gunn, David S. D, Allan, Neil L, Foxhall, Henry, Harding, John H, Purton, John A, Smith, W, Stein, Michael J, Todorov, Ilian T, Travis, Karl P
• Format: Article
• Language: English
• ISSN: 0959-9428; 1364-5501
• DOI: 10.1039/c2jm15264a

Ceramic materials play a critical role in the safe long-term immobilisation of nuclear waste and fundamental understanding of both radiation damage and healing processes are required in order to determine the suitability of proposed storage materials, such as pyrochlores. Here, new interatomic potentials are derived for the pyrochlores Gd 2 Ti 2 O 7 and Gd 2 Zr 2 O 7 . Their accuracy and robustness is demonstrated by calculating and comparing values for a selection of point defects with those calculated using a selection of other published potentials. Frenkel pair defect formation energies are substantially lowered in the presence of a small amount of local cation disorder. The activation energy for oxygen vacancy migration between adjacent O48f sites is calculated for Ti and Zr pyrochlores using an improved tangent nudged elastic band method. This energy is lower for the non-defective Ti than for the Zr pyrochlore by 0.1 eV, consistent with the majority of the potentials tested. The effect of local cation disorder on the V O 48 f V O 48 f migration energy is minimal for Gd 2 Ti 2 O 7 , while in contrast the migration energy is lowered typically by 43% for Gd 2 Zr 2 O 7 . Since the healing mechanisms of these pyrochlores are likely to rely upon the availability of oxygen vacancies, the healing of a defective Zr pyrochlore is predicted to be faster than for the equivalent Ti pyrochlore. Novel interatomic potentials are derived for Gd 2 Ti 2 O 7 and Gd 2 Zr 2 O 7 , used in determining their suitability as storage media for radioactive waste.