Phase separation of polymer blends in solution: A case study

[Display omitted] •Phase separation of the quaternary system PLLA/PLA/dioxane/water was investigated.•Demixing temperatures of blends are close to PLLA in the same mixed solvent.•Calculated spinodals confirmed this peculiar phase behavior.•Above PLA cloud point, morphology of blend foams is similar to pure PLLA foams.•Below PLA cloud point, morphology of blend foams resulted highly inhomogeneous. The phase behavior and phase separation features of the quaternary system poly-l-lactide (PLLA)/poly-rac-lactide (PLA)/dioxane/water were investigated. Experiments were performed with fixed total polymer concentration of 6wt%, by varying the PLLA/PLA weight ratio. Blend weight compositions examined were 100/0, 80/20, 50/50, 20/80 and 0/100, at fixed dioxane/water weight ratio (87/13). Cloud point measurements reported that the demixing temperatures of blends are close to PLLA in the same mixed solvent, in line with the calculated spinodals. As regards to foam preparation, above the PLA cloud point, morphology is similar to pure PLLA foams; conversely, below PLA cloud point, the morphology resulted highly inhomogeneous. This behavior could be related to a change in equilibrium conditions occurring close to PLA cloud point. The equilibrium measurements performed gave out results in line with this hypothesis.