Monoclinic–orthorhombic first-order phase transition in K2ZnSi5O12 leucite analogue; transition mechanism and spontaneous strain analysis

Abstract

AbstractHydrothermally synthesised K2ZnSi5O12 has a polymerised framework structure with the same topology as leucite (KAlSi2O6, tetragonal I41/a), which has two tetrahedrally coordinated Al3+ cations replaced by Zn2+ and Si4+. At 293 K it has a cation-ordered framework P21/c monoclinic structure with lattice parameters a = 13.1773(2) Å, b = 13.6106(2) Å, c = 13.0248(2) Å and β = 91.6981(9)°. This structure is isostructural with K2MgSi5O12, the first cation-ordered leucite analogue characterised. With increasing temperature, the P21/c structure transforms reversibly to cation-ordered framework orthorhombic Pbca. This transition takes place over the temperature range 848−863 K where both phases coexist; there is an ~1.2% increase in unit cell volume between 843 K (P21/c) and 868 K (Pbca), characteristic of a first-order, displacive, ferroelastic phase transition. Spontaneous strain analysis defines the symmetry- and non-symmetry related changes and shows that the mechanism is weakly first order; the two-phase region is consistent with the mechanism being a strain-related martensitic transition.