The thermal behavior of stellerite from the Savinskoye deposit (Transbaikalia, Russia), Ca7.69Na0.25K0.06(Si56.24Al15.76)O144·53.39H2O, was investigated by in situ high-temperature X-ray powder diffraction (HTXRPD) and ex situ HT infrared (IR) spectroscopic analysis. Four different HTXRPD experimental procedures were used to study the thermal behavior of the powder samples: (1) RT-750 °C, (2) RT-220 °C -RT, (3) 200-350-RT °C, and (4) 350-700 °C. Electron probe microanalysis and single-crystal X-ray diffraction were preliminary used to determine the chemical composition and crystal structure of stellerite. The A → B phase transition (Fmmm → Amma) starts at ∼110 °C and is completed at about 140 °C (in situ HTXRPD) and 200 °C (ex situ HTIR) depending on the experimental conditions. It involves a cell volume decrease of 5.8% (Experiment 1). The thermal expansion of stellerite is more pronounced along the b and c axes, with αa: αb: αc (× 10-5) = 2.50:-25.52:-6.84 at 100 °C, 0.44:-21.75:-25.64 at 150 °C after the completion of the phase transition, and 3.06:-1.86:-16.94 at 500 °C. The reverse B → A transition occurs at temperatures below 100 °C during slow cooling (Experiment 2), however, it does not occur upon rapid cooling (Experiment 3). The B → D phase transition above 300 °C is not observed (Experiment 4). The temperature barrier of phase transition in the ex situ HTIR spectroscopy experiment is shifted towards high temperatures. The heating above 200 °C leads to an increase of 3430 cm-1 and a decrease of 3600 and 3260 cm-1 bands, which correspond to the stretching vibration of H2O. The heating above 400 °C causes complete dehydration of the stellerite.
Keywords: HTXRPD; IR spectroscopy; Rehydration; Stellerite; Thermal behavior; Zeolite.
© 2022. The Author(s), under exclusive licence to The Japan Society for Analytical Chemistry.