화학공학소재연구정보센터
Thermochimica Acta, Vol.677, 67-78, 2019
Determination of the equilibrium enthalpy of melting of two-phase semi-crystalline polymers by fast scanning calorimetry
The equilibrium enthalpy of melting Delta H-m(0) [J.g(-1)] is an extrapolated thermodynamic quantity attributed to crystallizable macromolecules and widely used to characterize polymers in their semi-crystalline state, for it allows estimating the degree of crystallinity by direct comparison with the enthalpy of melting obtained from differential scanning calorimetry. Delta H-m(0) is typically obtained by cross-comparing the results obtained by at least two techniques. This work proposes a simplified experimental protocol to determine Delta H-m(0) by the use of Fast Scanning Calorimetry (FSC). This approach applies to any crystallizable polymer for which a specific microstructure can be obtained (i.e. a two-phase semi-crystalline microstructure with a negligible amount of rigid amorphous fraction) and that can also be quenched to its fully amorphous state. Such a two-phase microstructure can be obtained on nanoscale samples through an annealing process performed in situ on the FSC sensor at crystallization temperatures as close as possible to the melting temperature. The enthalpy of melting is then evaluated from the two-phase model for different crystallization times (i.e. different crystallinities) and the Delta H-m(0) is obtained by extrapolating the data to the 100% crystalline state. This procedure was applied on samples whose Delta H-m(0) values are already available in the literature, but also on more recent biobased polyesters whose thermal properties are still under investigations.