Friedrich, Alexandra; Knorr, Karsten; Lieb, Alexandra; Rath, Stephanie; Hanfland, Michael; Winkler, Bjoern; Schnick, Wolfgang
High-Pressure Phase Transition of the Oxonitridosilicate Chloride Ce4[Si4O3+xN7-x]Cl1-xOx with x = 0.12 and 0.18.
In: Zeitschrift für Kristallographie, Vol. 220: S. 245-249
The high-pressure behaviour of the oxonitridosilicate chlorides Ce4[Si4O3þxN7-x]Cl1-xOx, x = 0.12 and 0.18, is investigated by in situ powder synchrotron X-ray diffraction. Pressures up to 28 GPa are generated using the diamond-anvil cell technique. A reversible phase transition of first order occurs at pressures between 8 and 10 GPa. Within this pressure range the high- and the low-pressure phases are observed concomitantly. At the phase transition the unit cell volume is reduced by about 5%, and the cubic symmetry (space group P213) is reduced to orthorhombic (space group P212121) following a translationengleiche group-subgroup relationship of index 3. A fit of a third-order Birch-Murnaghan equation of state to the p-V data results in a bulk modulus B0 = 124(5) GPa with its pressure derivative B0 = 5(1) at V0 = 1134.3(4) Å3 for the low-pressure phase and in B0 = 153(10) GPa with B0 = 3.0(6) at V0 = 1071(3) Å3 for the high-pressure phase. The orthorhombic phase shows an anisotropic axial compression with the a axis (which is the shortest axis) being more compressible (k(a) = 0.0143(4) 1/GPa) than the b and c axes (k(b) = 0.0045(2), k(c) = 0.0058(2) 1/GPa). The experimental results confirm an earlier prediction of the pressureinduced instability of isotypic Ce4[Si4O4N6]O, and also show that the bulk modulus was predicted reasonably well.