High-temperature thermal expansion and structural behaviour of stromeyerite, AgCuS
High-temperature thermal expansion and structural behaviour of stromeyerite, AgCuS
Trots, D. M.; Senyshyn, A.; Mikhailova, D. A.; Knapp, M.; Baehtz, C.; Hoelzel, M.; Fuess, H.
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.
Keywords: XRD phase transition AgCuS
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Journal of Physics: Condensed Matter 19(2007), 136204-136217
DOI: 10.1088/0953-8984/19/13/136204
Cited 24 times in Scopus
Permalink: https://www.hzdr.de/publications/Publ-12275