Crystal structures of iron bearing tetrahedrite and tennantite at 25 and 250°C by means of Rietveld refinement of synchrotron data

Abstract

Rietveld refinement of X-ray synchrotron data was performed for two synthetic tetrahedrite samples, with 0.61 and 1.83 Fe atoms, and two synthetic tennantite samples with 0.10 and 1.23 Fe atoms p.f.u. M12(Sb,As)4S13. Measurements were performed at 25 and 250°C. For both the phases, increased Fe substitution is reflected in the increased tetrahedral ‘Cu1’–S distance (‘Cu1’ is a site of Fe substitution) and Cu2–S distances. Cu2 was refined as a split position; the Cu2–Cu2 split about the plane of the S12S2 triangle is about 0.56 and 0.65 A for tetrahedrite and tennantite, respectively. Cu2–Cu2 distances in the structure cavity are 2.8–2.9 A. Between 25 and 250°C, the lattice parameter a increased by 0.02–0.04 A and the interatomic distances by 0.01 A on an average. Thermal expansion coefficients of little-substituted samples are similar to those of unsubstituted samples, whereas thermal expansion appears to decrease with increasing substitution by Fe. The Cu2–Cu2 split increases at 250°C by about 0.1 A for tetrahedrite and by more than 0.15 A for tennantite but the cage expansion is minimal so that the Cu2–Cu2 distances in the cavity decrease with temperature. Difference Fourier maps indicate that there is little residual electron density left between the two Cu2 half-sites in tetrahedrite but this inter-site density is substantially higher in tennantite. It increases with temperature, especially in the little-substituted tennantite sample.