An Experimental Study on Three Quaternary Phases in the Fe-Sn-Sb-S System: Pb-Free Franckeite, Pb-Free Cylindrite and (Fe, Sb)-Ottemannite s.s.

Experimental studies on the two solid solutions franckeite s.s. and cylindrite s.s. yielded among others thePb-free endmembers of franckeite and cylindrite respectively. In these endmembers the lead content of the twomineral phases are completely substituted by bivalent tin. A third phase, ottemannite s.s. with （Fe. Sb）-bearingcompositions, was further identified in the Pb-free 4-component system Fe-Sn-Sb-S. Pb-free franckeite andcylindrite could only be synthesized as homogeneous phases at high temperatures. The ottemannite s.s. was ob-tained at 600℃ but an extensive existing range was also confirmed at temperatures below 500℃. The phase relations were discussed in the pseudoternary subsystem SnS-SnS;-FeSb;S;. The following se-quence of Pb-free phases and phase assemblages were observed under increasing Sn;content at 600℃:herzenhergite （SnS）+franckeite, franckeite, franckeite+cylindrite, cylindrite, cylindrite+（Fe, Sb）-ottemannite.（Fe, Sb）-ottemannite. （Fe. Sb）-ottemannite+berndtite （SnS;）. The assemblage cylindrite+berndtite was identi-fied in synthetic systems involving Pb. The phase Fe. Sb-ottemannite s.s. appears to be stable only under Pb-de-ficient and high sulfur fugacity conditions.