Thermodynamics of pseudo-ternary systems as a tool to predict the morphologies of cellulose acetate/polystyrene blends cast from tetrahydrofuran solutions

The demixing behavior of the ternary system THF/CA/PS (tetrahydrofuran/cellulose acetate/polystyrene) was investigated at 25 °C. Cloud point measurements show that the system exhibits a large miscibility gap caused by the incompatibility of CA and PS. Both ends of the experimentally determined tie lines are located inside the two-phase area of the phase diagram. By means of the measured critical composition of the ternary system and the Flory–Huggins interaction parameters published for two of the binary subsystems (χCA/THF=0.442 and χPS/THF=0.475) the polymer/polymer interaction parameter was adjusted (directly minimizing the Gibbs energy) to χCA/PS=0.057. These thermodynamic data were used to calculate the extension of the metastable and the unstable regions of the phase diagram. This procedure permits a realistic prediction of the morphologies of the (solvent-free) blends from the location of the starting composition of the casting solutions in the Gibbs phase triangle, as demonstrated by means of optical micrographs and field emission scanning electron micrographs.