Abstract

A detailed analysis of the three-phase structure of poly(L-lactic acid) was performed by temperature-modulated differential scanning calorimetry upon quasi-isothermal and non-isothermal crystallizations. The TMDSC analyses revealed that the relative amounts of the three fractions of poly(L-lactic acid) depend on the temperature at which crystallization occurs. It was found that rigid amorphous fraction grows in parallel with crystalline phase during quasi-isothermal crystallization at 90 °C, whereas at T c = 130 °C it starts to appear approximately in correspondence with secondary crystallization. At T c = 135 °C RAF practically does not develop. The results prove that RAF development during crystallization depends on the mobility of the chains. The temperature of complete devitrification at 10 °C min −1 seems to be 130 °C: this temperature could be the limit for the formation and the disappearance of rigid amorphous fraction in the PLLA sample analyzed in the present study.

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