ABSTRACT: Yeelimite, Ca4[Al6O12]SO4, is outstanding as an aluminate
sodalite, being the framework of these type of materials flexible and dependent
on ion sizes and anion ordering/disordering. On the other hand, yeelimite is also
important from an applied perspective as it is the most important phase in
calcium sulfoaluminate cements. However, its crystal structure is not well
studied. Here, we characterize the room temperature crystal structure of
stoichiometric yeelimite through joint Rietveld refinement using neutron and Xray
powder diffraction data coupled with chemical soft-constraints. Our structural
study shows that yeelimite has a lower symmetry than that of the previously
reported tetragonal system, which we establish to likely be the acentric
orthorhombic space group Pcc2, with a √2a × √2a × a superstructure based on
the cubic sodalite structure. Final unit cell values were a = 13.0356(7) Å, b =
13.0350(7) Å, and c = 9.1677(2) Å. We determine several structures using
density functional theory calculations, with the lowest energy structure being Pcc2 in agreement with our experimental result.
Yeelimite undergoes a reversible phase transition to a higher-symmetry phase which has been characterized to occur at 470 °C by
thermodiffractometry. The higher-symmetry phase is likely cubic or pseudocubic possessing an incommensurate superstructure,
as suggested by our theoretical calculations which show a phase transition from an orthorhombic to a tetragonal structure. Our
theoretical study also predicts a pressure-induced phase transition to a cubic structure of space group I43m. Finally, we show that
our reported crystal structure of yeelimite enables better mineralogical phase analysis of commercial calcium sulfoaluminate
cements, as shown by RF values for this phase, 6.9% and 4.8% for the previously published orthorhombic structure and for the
one reported in this study, respectively.Universidad de Málaga. Campus de Excelencia Internacional. Andalucía Tech
