AbstractPolycarbonate blends with the linear aliphatic polyesters poly(ethylene succinate) (PES), poly(ethylene adipate) (PEA), poly(1,4‐butylene adipate) (PBA), and poly(hexamethylene sebacate) (PHS) were prepared by solution casting. Blends containing PES, PEA, and PBA exhibited a singleTgby DSC and thus form a single, miscible amorphous phase with polycarbonate. However, blends containing PHS exhibited only partial miscibility. Crystallinity of the polyesters was reduced by mixing with polycarbonate; however, plasticization by the polyesters induced crystallization of the polycarbonate. Miscibility in these systems is the result of an exothermic heat of mixing stemming from an interaction of the carbonyl dipole of the ester group with the aromatic carbonate. The effect of polyester structure on miscibility with polycarbonate is interpreted by and correlated with heats of mixing obtained by direct calorimetry of low molecular weight liquid analogs of the polymer
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