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Sohn, Seungman The Polymer Society of Korea 2001 Korea polymer journal Vol.9 No.4
The evolution of conformational constraints in bisphenol-A polycarbonate (BAPC) upon quiescent bulk crystallization was quantitatively analyzed from calorimetric study employing a rigid amorphous fraction (RAF) as an indicator of the level of conformational constraints. From the correlation between corrected crystallinity (X$\sub$c/) and total rigid fraction (f$\sub$r/), it was found that, regardless of molar mass distribution and thermal treatment conditions, semicrystalline BAPC always exhibits greater f$\sub$r/ than X$\sub$c/ maintaining a quantitative relationship of f$\sub$r/〓2X$\sub$c/ in the range of 0.0 <X$\sub$c/< 0.4. This directly indicates the evolution of approximately the same amount of RAF as X$\sub$c/, (i.e., RAF〓X$\sub$c/) upon bulk crystallization of BAPC. It was also found that T$\sub$g/ per se and T$\sub$g/ broadening enhance as RAF increases, and there appears to be a critical level of RAF (>0.2) needed to initiate significant changes in both quantities.