Abstract
The thermodynamic description of polymeric systems is summarized based on 50 years of gathering experimental information with adiabatic, differential-scanning, and temperature-modulated calorimetry. This experience has led to a description of macro- to micro- to nano-phases with macromolecules able to traverse the phase boundaries and decouple at the surfaces, resulting in different thermodynamic properties for the separated parts of the molecule. A typical thermodynamic characterization of semicystalline polymers is that of a globally metastable system with locally reversible processes. Unique phenomena in polymers include the ability of semicrystalline polymers to undergo cold crystallization and molecular nucleation, possess thermally generated point defects and rigid-amorphous fractions, and have amorphous to mesophasic to crystalline macroconformations with glass, ordering, and disordering transitions in all three structures. To describe such multifaceted systems, special combinations of equilibrium, and irreversible thermodynamics as well as statistical and quantum mechanics are necessary. Only then is it possible to handle violations of phase rules, changes of properties when approaching nanophase dimensions, local reversibility, and enthalpy relaxation. The enthalpy relaxation in polymers originates in the cooperativeness of conformational motion and the interferences of processes of different time scales. The experiments to identify the effects of the different molecular motions from typical vibrational time scales of picoseconds to cooperative, large-amplitude rearrangements of up to megaseconds span heating rates of thousands of K·s−1 with superfast chip calorimeters to many hours for slow, quasi-isothermal analysis by temperature-modulated differential scanning calorimetry (TMDSC). Selected examples of this far-reaching thermal characterization will be presented.
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Wunderlich, B. Calorimetry of Nanophases of Macromolecules. Int J Thermophys 28, 958–967 (2007). https://doi.org/10.1007/s10765-007-0227-6
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DOI: https://doi.org/10.1007/s10765-007-0227-6