LAUSR

The bulk enthalpy of melting of α-crystals of poly (l-lactic acid) (PLLA) has been evaluated by fast scanning chip calorimetry (FSC), by analysis of the correlation between the measured enthalpy of melting of sets of samples of different crystallinity and the corresponding heat capacity at 90°C, that is at a temperature higher than the glass transition temperature of the bulk amorphous phase and lower than the melting temperature. Extrapolation of this relationship for crystals formed at 140°C towards the heat capacity of fully solid PLLA yields a value of about 104.5±6 J/g when melting occurs at 180-200°C. The analysis is based on the presence of a two-phase structure, that is, absence of a vitrified rigid amorphous fraction (RAF) at the temperature of analysis of the solid fraction of the material (90°C). Formation and vitrification of an RAF was suppressed by avoiding both continuation of primary crystallization and secondary crystallization during cooling the system from the crystallization temperature of 140°C to 90°C, making use of the high cooling capacity of FSC. Small-angle X-ray scattering (SAXS) confirmed distinct thickening of initially grown lamellae which only is possible if these lamellae are not surrounded by a glassy RAF. Linear crystallinity values obtained by SAXS and calorimetrically determined enthalpy-based crystallinities agree close to each other. This article is protected by copyright. All rights reserved.