Laboratory parallel-beam transmission X-ray powder diffraction investigation of the thermal behavior of nitratine NaNO3: spontaneous strain and structure evolution

Present work provides in-situ structural data at a fine temperature scale from RT to the melting point of nitratine, NaNO3. From the analysis of log e 33 versus log t plots, it is possible to prove that an univocal indication on the R $$ \overline{3} $$ c (low temperature, LT) → R $$ \overline{3} $$ m (high temperature, HT) transition mechanism cannot be obtained because of the relevant role played by the arbitrary assumptions required for defining the c 0 dependence from temperature of the HT phase. This is due to the occurrence of excess thermal expansion for the HT phase. A significantly better fit for an Ising-spin structural model over a non-Ising rigid-body one has been obtained for the LT phase. Moreover, the Ising model led to a smooth variation of the oxygen site x fractional coordinate throughout the transition. The structure of the HT polymorph has been successfully refined considering an oxygen site at x, 0, ½, with 50% occupancy. Such model was the only acceptable one from the crystal chemical point of view as the alternative model (oxygen site at x, y, z with 25% occupancy) led to unrealistically aplanar $$ {\text{NO}}₃ ^- $$ groups.