The structural behaviour of the nepheline family: (1) Sr and Ba aluminates (MAl2O4)

Abstract

AbstractThe structural relations of solid solutions in the series (Sr1−xBax)Al2O4 were studied using room- and high-temperature X-ray methods, infra-red spectroscopy, and DTA. At room temperature, SrAl2O4 and solid solutions with x up to 0.31 are monoclinic, between x = 0.31 and 0.43 monoclinic and hexagonal forms coexist, and between x = 0.43 and 1.0 only hexagonal forms occur. On heating, a member of the monoclinic series of solid solutions transforms to hexagonal symmetry over a range of temperature within which both monoclinic and hexagonal forms coexist. The proportion of the hexagonal form increases instantaneously as the temperature is raised. The transformation temperature decreases with increasing BaAl2O4 in solid solution and, in addition, the temperature width of the region of coexistence is markedly enlarged. SrAl2O4 transforms over the range 665–705 °C and (Sr0.7Ba0.3)Al2O4 over 170–405 °C. The DTA trace for SrAl2O4 shows a peak at 677 °C. On cooling, the transformations show hysteresis of 15 to 25 °C.The coexisting monoclinic and hexagonal forms are believed to be isochemical, and discontinuities in cell parameters occur within the region of coexistence both in the compositional series at room temperature and in the elevated temperature transformation experiments. The low-to-high transformation is accompanied by a volume change of −0.2 to −0.3 %, and is believed to be first-order displacive with additional characteristics similar to those of martensitic transformations.The thermal expansion behaviour of structures in the (Sr,Ba)Al2O4, series indicates that two tilt systems are operative: co-operative rotation of tetrahedra about the c-axis, and tilting of tetrahedra relative to the 0001 plane.The results for the (Sr,Ba)Al2O4 series are shown to be invaluable in reinterpreting the structural behaviour of members of the nepheline and leucite groups of minerals.