Geerite-type structures and the flotation of sphalerite

"Geerite (Cu1.6S) is a rhombohedral copper sulphide which occurs naturally in epitactic replacement of sphalerite; cell dimensions closely approximate those of the host sphalerite.Geerite-type structures can be produced by leaching digenite (Cu1.8S) in ferric sulphate solutions. X -ray diffract ion and electron microprobe studies indicate that eight metastable geeritetype structures can be produced, depending upon the concentration of f erric sulphate solution used and the duration of the each. Although compositions cluster on or near values observed for natural phases, optical properties indicate that we are dealing with polymorphs of these phases. Leaching of chalcocite (CU2Sj in dilute f erric sulphate solutions produces similar results. In contrast, leaching of chalcocite in more concentrated solutions seems to produce true analogues of natural minerals.During froth flotation, sphalerite is activated with a monolayer of floatable copper sulphide with the composition, CuS, of the mineral covellite. However, covellite is not significantly more floatable than sphalerite, and has an incompatible structure because of the presence of covalently-bonded atoms of sulphur. Leaching ofdigenite was used to produce a polymorph of covellite with a geerite-type structure, compatible with that of sphalerite. This polymorph has a flotational behaviour similar to copper-activated sphalerite, suggesting that the monolayer has a geerite-type CuS structure. IntroductionIn an ideal close-packed sulphide structure the distance between sulphur layers, D, is equal to 2R 2/3, where R is the radius of the sulphur atoms. In sulphides with covalently-bonded sulphur layers, such as covellite (Fig. I), D will be an average of the number of covalentl y-bonded and close-packed sulphur layers, weighted as to the relative number of each type of layer. Both D and R are spacings which are readily identifiable structurally and on X-ray diffraction patterns. Goblel has shown that for copper-iron sulphides with metal-to-sulphur ratios between 0 and 2 and copper-to-total metal ratio s between 113 and I there are strong correlations between composition and measured D and R distances (Fig. 2). D can be represented by a single empirical equation relating interlayer spacing to composition; R must be represented by three equations relating the radius of sulphur atoms to composition. One of these equations (R, in Fig. 2) represents ideal close-packed behaviour, the other two represent sulphur radii greater than (R1) or less than (Rh) the ideal."