Structure and oxygen mobility in mayenite (Ca12Al14O33): a high-temperature neutron powder diffraction study

Abstract

The structure of mayenite, Ca12Al14O33, was investigated by neutron powder diffraction up to 1323 K. It has been described previously as a calcium–aluminate framework, in which 32 of the 33 oxygen anions are tightly bound, containing large cages, 1/6 of them being filled randomly by the remaining `free' oxygen. At ambient temperature excess oxygen was found, corresponding to the composition Ca12Al14O33.5 which was attributed to the presence of hydroxide, peroxide and superoxide radicals in the cages. Above 973 K these are lost under vacuum conditions and the composition becomes stoichiometric. From the refined structural parameters it is concluded that the structure is more adequately described as a relatively stable aluminate framework consisting of eightfold rings of AlO4 tetrahedra with disordered Ca and `free' O distributed within. At high temperatures the density of the `free' oxygen is extremely spread out, with the expansion being related to the high ionic conductivity of this material. Since no continuous density distribution between adjacent cages was found and the `free' O forms bonds with part of the Ca, the diffusion proceeds via a jump-like process involving exchange of the `free' oxygen with framework oxygen. The results confirm the recent theoretical predictions of Sushko et al. [(2006), Phys. Rev. B, 73, 014101-1-10].