Oxygen-17 magnetic resonance, in conjunction with high-temperature X-r
ay diffraction (XRD) and differential thermal analysis (DTA), were use
d to investigate the structure of Ba2In2O5 and the dynamics of oxygen
ion motion between room temperature and 1200-degrees-C. NMR and therma
l analysis demonstrate that at 925-degrees-C there is an order-disorde
r transition which involves oxygen atoms between layers of octahedrall
y coordinated indium atoms. Both NMR and X-ray diffraction show that t
he material retains an orthorhombic (layered) structure until approxim
ately 1075-degrees-C, at which point the material becomes cubic. The n
umber of mobile oxygen atoms in the structure increases continuously b
etween 925 and 1075-degrees-C, and only above 1075-degrees-C does the
full population of anions become mobile. These results imply that vaca
ncies contribute to transport two-dimensionally within the tetrahedral
layers at the order-disorder transition.