Structural behavior of a stuffed derivative of α-quartz, Mg_0.5AlSiO₄, at high temperature: an in situ synchrotron XRD study

High-temperature structural behavior of a stuffed derivative of α-quartz, Mg_0.5AlSiO₄, has been investigated using in situ synchrotron-based angle-dispersive powder X-ray diffraction (XRD) from 299 to 1273 K. Rietveld analysis of the XRD data indicates that the framework of Mg_0.5AlSiO₄ remains isostructural with α-quartz throughout the temperature range tested. As in α-quartz, unit-cell parameters a and c and cell volume V of Mg_0.5AlSiO₄ increase with increasing temperature, primarily due to progressive tilting of [(Al,Si)O₄] tetrahedra along the a axes. However, the rates of increase in the cell parameters and the rate of decrease in the tetrahedral tilt angle (δ) are much smaller for Mg_0.5AlSiO₄ than for α-quartz. This behavior can be attributed to the occupancy of Mg²⁺ over the octahedral channel sites in the α-quartz-type framework, effectively hindering the [(Al,Si)O₄] tetrahedral tilting. As a result, the α- to β-quartz phase transformation, which exists in silica at 846 K, does not occur in Mg_0.5AlSiO₄ up to 1273 K, and probably beyond, to its melting point.