Investigations on the polymorphism of K4CaSi6O15 at elevated temperatures

Abstract

AbstractIn the present study, single crystals and polycrystalline material of K4CaSi6O15 were prepared from solid‐state reactions between stoichiometric mixtures of the corresponding oxides/carbonates. Heat capacity (Cp) measurements above room temperature using a differential scanning calorimeter indicated that two thermal effects occurred at approximately T1 = 462 K and T2 = 667 K, indicating the presence of structural phase transitions. The standard third‐law entropy of K4CaSi6O15 was determined from low‐temperature Cp’s measured by relaxation calorimetry using a Physical Properties Measurement System and amounts to S°(298K) = 524.3 ± 3.7 J·mol−1·K−1. For the 1st transition, the enthalpy change ΔHtr1 = 1.48 kJ·mol and the entropy change ΔStr1 = 3.25 J·mol−1·K−1, whereas ΔHtr2 = 3.33 kJ·mol−1 and ΔStr2 = 5.23 J·mol−1·K−1 were determined for the 2nd transition. The compound was further characterized by in‐situ single‐crystal X‐ray diffraction between ambient temperature and 1063 K. At 773 K, the high‐temperature phase stable above T2 has the following basic crystallographic data: monoclinic symmetry, space group P21/c, a = 6.9469(4) Å, b = 9.2340(5) Å, c = 12.2954(6) Å, β = 93.639(3)°, V = 787.13(7) Å3, Z = 2. It belongs to the group of interrupted framework silicates and is based on tertiary (Q3‐type) [SiO4]‐tetrahedra. Together with the octahedrally coordinated Ca‐cations, a three‐dimensional mixed polyhedral network structure is formed, in which the remaining K‐ions provide charge balance by occupying voids within the net. The intermediate temperature modification stable between T1 and T2 shows a (3+2)‐dimensional incommensurately modulated structure that is characterized by the following q‐vectors: q1 = (0.057, 0.172, 0.379), q2 = (‐0.057, 0.172, ‐0.379). The crystal structures of the high‐ and the previously studied ambient temperature polymorph (space group Pc) are topologically equivalent and show a group‐subgroup relationship. The index of the low‐ in the high‐symmetry group is six and involves both, losses in translation as well as point group symmetry. The distortion is based on shifts of the different atom species and tilts of the 4‐ and 6‐fold coordination polyhedra. Actually, for some of the oxygen atoms, the displacements exceed 0.5 Å. A more detailed analysis of the distortions relating to both structures has been performed using mode analysis, which revealed that the primary distortion mode transforms according to the Λ1 irreducible representation of P21/c. However, other modes with smaller distortion amplitudes are also involved.