Low-temperature experiments in the ‘dry’ ternary Cu-Bi-S system, conducted by using sulphidation methods down to 120°C produced a new metastable solid solution series Cu10Bi2S13-Cu5Bi2S8 at 178°C coexisting with CuS. This transformed slowly at 190–200°C to an assemblage of either CuS-(Cu,Bi)8S9 or CuS-Bi2S3 or both, depending on available sulphur. Sulphidation experiments on Cu3BiS3 similarly revealed a solid solution range for the phase (Cu,Bi)8S9 of up to Cu/Bi = 3/2 at 178–190°C, and a lower stability limit of 138°C Isothermal sections of the system were constructed at 200 and 300°C, based on the new information collected but excluding the metastable series.

Sulphosalts in the system CuSbS2-CuBiS2 (chalcostibite-emplectite) form a complete solid solution series. Seven compositions with the general formula Cu(SbxBi1–x)S2 have been synthesized using dry methods at 310°C. All members of the series are orthorhombic (space group Pnma) and show smoothly increasing a and b cell parameters with substitution of Bi for Sb; the c cell parameter increases up to 50% CuBiS2 substitution and then becomes constant. DSC experiments on CuBiS2 show an endothermic heat effect (2.45 kJ/mol.) at 472°C due to the breakdown reaction to Cu3BiS3 (wittichenite) plus Bi2S3 (bismuthinite). With the addition of 10% CuSbS2 to CuBiS2, the decomposition temperature increases and the endothermic peak is broadened but the energy remains essentially the same (2.53 kJ/mol.). No evidence of this decomposition was observed when the amount of the CuSbS2 component was >30%. The local structure and co-ordination of Cu in the samples were studied by EXAFS analysis of the Cu-K edge but no significant variation occurs in the local Cu environment. The Debye-Waller factor for the first shell of S atoms surrounding Cu in end member CuSbS2 tends to be slightly smaller than for the intermediate solid solutions, suggesting that the tetrahedral Cu environments in the intermediate composition samples is somewhat more disordered than in the end-member. The low expansion characteristics along c appear to be controlled by the linkages between the (CuS3 + BiS2) sheets perpendicular to c being relatively inflexible.