High-temperature thermal expansion and structural behaviour of stromeyerite, AgCuS

Results of simultaneous thermal analysis, synchrotron and neutron powder diffraction in the range from room temperature up to the melting point at 936 K on non-superionic orthorhombic β-AgCuS as well as on superionic hexagonal α- and cubic δ-AgCuS are reported. On heating the sample is only stable in argon. The following phase transitions occur in AgCuS at elevated temperatures: β 361 K −→ α 399 K −→ α + δ 439 K −→ δ. The volume changes at the superionic β −→ α and α −→ δ phase transitions are about 2.3 and 0.6%. The volume thermal expansion coefficients are 26 × 10−6, 130 × 10−6 and 85 × 10−6 K−1 for the pure β-, α-and δ-phases, respectively. Models forthe average structures of α-and δ-AgCuS are proposed and discussed. Ionic conductivity in δ-AgCuS may originate from cation jumps in ‘skewed’ (100) directions between nearest-neighbour tetrahedral sites via the peripheries of the octahedral cavities. A correlation between the temperature dependence of the cation redistribution in δ-AgCuS and the temperature dependence of the ionic conductivity is assumed. A two-dimensional nature of the ionic conductivity due to cation jumps in slabs perpendicular to the c-direction is supposed for α-AgCuS. There is no evidence for ionic diffusion through the (1/2, 1/2, 1/2) site in (111) directions in either superionic α-or δ-phases.