Lead-free solders: Enthalpies of mixing of liquid Ag–Cu–Ni–Sn alloys

Partial and integral enthalpies of mixing of liquid Ag–Cu–Ni–Sn alloys were determined at 1000 °C by a drop calorimetric technique using a Calvet type microcalorimeter. They were obtained by adding Ni to the ternary Ag–Cu–Sn alloys with different composition. The data were evaluated by means of an extended Redlich–Kister–Muggianu polynomial fit for substitutional solutions. The minimum and maximum in the quaternary system were also calculated. It was found that the maximum integral enthalpy of mixing (13,310 J/mol at 41 at.% Ag) occurs in the binary Ag–Ni system while the minimum integral enthalpy of mixing (−21,390 J/mol at 61 at.% Ni) occurs in the binary Ni–Sn system. Moreover the experimental data were compared to values calculated by different extrapolation models based on binary data.