Two calorimetric glass transitions in miscible blends containing poly(ethylene oxide)

Miscible blends containing poly(ethylene oxide) (PEO) have been examined over the entire composition range using differential scanning calorimetry to explore further the reported presence of two glass transitions. Three systems, poly(ethylene oxide)-dimethyl ether (PEO-DME)/poly(methyl methacrylate) (PMMA), PEO/poly(lactide) (PLA), and PEO/poly(vinyl acetate) (PVAc), were chosen in order to study the effects of end-group chemistry, annealing time, and crystallinity on the calorimetric behavior of the blends. The molecular weight of PEO was kept low to minimize the interference due to crystallization. Two distinct glass transitions were observed in the mid-composition range for all three systems. The glass transition temperatures varied smoothly with blend composition between the glass transition temperatures of the two homopolymer components. It was found that the self-concentration model describes the composition dependence of these glass transitions well. Further investigation on selected PEO/PVAc blends showed that annealing time and degree of crystallinity had a little effect on the glass transition behavior. These results confirm that the presence of two glass transitions should not necessarily be taken as an indication of immiscibility.