Fast ion conduction character and ionic phase-transitions in disordered crystals: the complex case of the minerals of the pearceite–polybasite group

Abstract

The minerals of the pearceite–polybasite group, general formula (Ag,Cu)₁₆ M ₂S₁₁ with M = Sb, As, have been recently structurally characterized. On the whole, all the structures can be described as a regular succession of two module layers stacked along the c axis: a first module layer (labeled A), with general composition [(Ag,Cu)₆(As,Sb)₂S₇]²⁻, and a second module layer (labeled B), with general composition [Ag₉CuS₄]²⁺. In detail, in the B layer of the pearceite structure silver cations are found in various sites corresponding to the most pronounced probability density function locations of diffusion-like paths. We have shown for the first time that the observed structural disorder in the B layer is strongly related to the fast ion conduction character exhibited by these minerals. This paper reports an integrated XREF, DSC, CIS and EPMA study on all the members of the pearceite–polybasite group. DSC and conductivity measurements pointed out that the 222 members show ionic-transitions at 340 K (arsenpolybasite-222) and 350 K (polybasite-222), whereas the 221 members have transitions at lower temperature, that is, 310–330 K (arsenpolybasite-221) and 335 K (polybasite-221). For the 111 members (pearceite and antimonpearceite), the transition occurs below room temperature at 273 K. In situ single-crystal X-ray diffraction experiments showed that these minerals present the same high temperature structure and are observed at room temperature either in their high temperature (HT) fast ion conductivity form or in one of the low temperature (LT) fully ordered (222), partially ordered (221) or still disordered (111) forms, with transition temperatures slightly above or below room temperature. The pearceite–polybasite group of minerals can be considered as a homogeneous series with the same aristotype, fast ion conducting form at high temperature. Depending upon the Cu content, an ordering occurs with transition temperatures related to that content: the lower the Cu content, the higher the transition temperature from the fast ion conducting HT form to the non-ion conducting form.