In order to reveal the mechanism of the negative c-axis expansion in cordierite (4 MgO 4 Al2O3 10 SiO2), the thermal expansion of cordierite containing small amounts of Cs, Li, B, Ge, Sc and Ni-cations was investigated by time-of-flight neutron diffraction at temperatures between 22 and 750°C. The samples were prepared by melting the constituent oxides followed by quenching and devitrification to obtain the hexagonal form (Indialite). Using the neutron powder diffraction data, the atom positions in the space group P6/mcc were refined by Rietveld least squares analyses.
The expansion behavior of the cordierite structure could be explained in terms of the various kinds of constraints and the interatomic bond strengths of the structure. It was found that cordierite doped with Cs-cations shows the largest volume expansion, followed by the Li-doped sample. So-doped cordierite has the lowest volume expansion. All cordierite samples show positive expansion along the a-axis and negative expansion along the c-axis, except the Cs-doped sample which has positive expansion in both directions.