Thermal Stability of Assemblages in the Cu--Fe--S System

The phase relations in the Cu-Fe-S system were determined from700 C to approximately 200 C in most portions of the systemand below 100 C in restricted areas. Approximate solid solutionlimits for bornite, chalcopyrite, and pyrrhotite were determinedat elevated temperatures. At low temperatures emphasis was placedon establishing the stable assemblages and less on determiningthe compositions of coexisting phases. At 700 C two extensiveternary solid solutions dominate the phase relations in thissystem. One of these solid solutions (bornite) includes thecompositions Cu₂S, Cu₁₈S, and Cu₅FeS₄and the other (chalcopyrite)lies with in the area bounded by the compositions CuFeS₂ CuFe₂S₃,and CU₃Fe₄S₄. The two fields are separated by approximately10 weight per cent copper at 700 C. The chalcopyrite volume,as seen in a trigonal prism representing temperature and composition,is intersected by a miscibility gap below approximately 600C.Below this temperature the two one-phase volumes are referredto as chalcopyrite and cubanite. Chalcopyrite is tetragonalat low temperature but isometric above approximately 550C.The temperature of the transformation is a function of composition.Cubanite is isometric above 252C, tetragonal from 252 to atleast 213C, and orthorhombic at lower temperature. The temperatureof the second transformation is unknown because the tetragonal-to-orthorhombictransformation has not been achieved in the laboratory. Borniteand pyrite become stable together at 568C and coexist downto 228C. Covellite appears with lowering temperature at 507C,and idaite at 501C. Idaite—pyrite and idaite—borniteare stable assemblages below 501 C. The composition of bornitecoexisting with idaite changes gradually towards digenite withdecreasing temperature, thus permitting the change from thebornite—pyrite tie-line to the digenite—chalcopyritetie-line at 228C. Other major tie-line changes are bornite—ironto pyrrhotite—copper below 475C and cubanite—pyriteto chalcopyrite—pyrrhotite below 334C. A new syntheticphase, x-bornite, which has a composition close to bornite (Cu₅FeS₄)but contains about 04 weight per cent more sulfur, forms whensulfur-rich bornite synthesized at high temperature is annealedbetween 62 and 140C. Optically this new phase is very similarto bornite, and their X-ray powder diffraction patterns aregiven for comparison. o The determined phase relations are applicable to numerous deposits.The tie-line changes involving bornitepyrite reacting to producedigenitechalcopyrite below 228 C and cubanite (isometric)pyritegoing to chalcopyritepyrrhotite below 334 C are of considerablegeological interest. The rates of these reactions are sufficientlyslow to allow the higher temperature assemblages to be observedin some ores. The cubic—tetragonal inversion in chalcopyriteis often deduced in ores by inversion twins. However, twinningis also commonly produced through deformation. Geological applicationof the inversion therefore depends on correct interpretationof the twinning. Because of the considerable solubility of copperin pyrrhotite the pyrrhotite—pyrite solvus of the pureFe—S system cannot be applied indiscriminately to oresthat also contain chalcopyrite or cubanite, or both. The newx-bornite phase was identified with the natural ‘anomalousbornites’, which when heated exsolve chalcopyrite and,depending on their composition, also digenite. The experimental results indicate that the mineral commonlyidentified as chalcopyrrhotite is in reality tetragonal or evenisometric cubanite. Experimental evidence could not be obtainedfor the existence of a phase of Cu₂Fe₄S₇ or Cu₂Fe₄S₇ composition,the older formulae given foor valleriite. The thermal breakdownof natural material supports the idea that valleriite is a low-temperaturepolymorph of chalcopyrite. The relatively uncommon occurrenceof idaite in comparison to covellite is attributed to the greaterdifficulty in nucleating idaite. The possibility of stable coexistenceof chalcocite and pyrite was investigated but was found to beprohibited by tie-lines between bornite and digenite even aslow as 100 C.