"Nothing Can Hide Itself from Thy Heat": Understanding Polymers via Unconventional Applications of Thermal Analysis

This article surveys some exciting possibilities and results offered by less common, yet essential applications of differential scanning calorimetry and thermogravimetric analysis (TGA). The applications are concerned with the most commonly studied processes of the glass transition, crystallization, melting, polymerization, and degradation. Issues related to the glass transition include the non-Arrhenius temperature dependence and fragility, kinetic complexity of physical aging, evaluation of cooperatively rearranging regions, and rigid amorphous fraction. Discussion of crystallization covers separation of heterogeneous and homogeneous nucleation, crystallization controlled by physical aging, and the use of isoconversional methods for determining the Hoffman-Lauritzen parameters. For melting, the role of reorganization and nucleation control is emphasized. For the thermal degradation and polymerization, advanced kinetic treatments as a way of obtaining mechanistic insights are discussed, and the possibility of studying both processes during continuous cooling is stressed. The possibility of using TGA for monitoring polycondensation is also highlighted.