High-pressure melting behavior of tin up to 105 GPa

The melting curve of Sn initially rises steeply as a function of pressure but exhibits a decrease in slope (dTm/dP) above 40 GPa to become nearly flat above 50 GPa. Previous studies have argued that a body-centered tetragonal (bct) to cubic (bcc) phase transition occurs in this range at room temperature. However, our investigations have shown that the phase behavior is more complex in this region with orthorhombic (bco) splitting of reflections occurring in the x-ray diffraction pattern above 32 GPa and coexisting diffraction signatures of bco and bcc structures are observed between 40 and 70 GPa. Here we have documented the simultaneous presence of bco and bcc reflections up to the melting point, negating the possibility that their coexistence might indicate a kinetically hindered first-order phase transformation. In this paper we have extended the observation of Sn melting relations into the megabar (P>100 GPa) range using the appearance of liquid diffuse scattering in x-ray diffraction patterns and discontinuities during thermal signal processing to diagnose the occurrence of melting. Both techniques yield consistent results that indicate the melting line maintains the same low slope up to the highest pressure examined and does not flatten. The results below approximately 40 GPa agree well with the melting relations produced recently using a multiphase equation of state fitted to available or assumed data. Above this pressure the experimental melting points lie increasingly below the predicted crystal-liquid phase boundary, but above the flat melting from past studies, indicating that the thermodynamic properties of the body-centered “γ”-Sn structure remain to be clarified.