Atomistic scale investigation of cation ordering and phase stability in Cs-substituted Ba1.33Zn1.33Ti6.67O16, Ba1.33Ga2.66Ti5.67O16 and Ba1.33Al2.66Ti5.33O16 hollandite

Abstract The titanate-based hollandite structure is proposed as an effective ceramic waste form for Cs-immobilization. In this study, quantum-mechanical calculations were used to quantify the impact of A-site and B-site ordering on the structural stability of hollandite with compositions Ba x Cs y (M z Ti 8-z )O 16 , where M = Zn 2+ , Ga 3+ , and Al 3+ . The calculated enthalpy of formation agrees with experimental measurements of related hollandite phases from melt solution calorimetry. Ground state geometry optimizations show that, for intermediate compositions ( e.g ., CsBaGa 6 Ti 18 O 48 )... Mehr ...