Structural changes in glassy polymers

It has previously been shown that glassy poly(ethylene terephthalate) gives rise to endothermal peaks in DTA when annealed at temperatures near to the glass temperature. The present work describes results obtained from DTA and DSC on annealing a number of glassy polymers which have been rapidly cooled from above the glass temperature and on slowly cooled samples of the same polymers. The polymers which have been studied are: poly(ethylene terephthalate), poly(methyl methacrylate), atactic and isotactic polystyrene, bisphenol‐A polycarbonate, poly(ethyl methacrylate) and poly(vinyl acetate). In every case, evidence of structural reorganization is observed, and the rate at which this takes place is reported. Separate studies on poly(ethylene terephthalate) reflect density changes which also take place upon annealing. These results are discussed in the context of the calorimetric observations.