Thermal analysis of macromolecules

This review traces the development of thermal analysis over the last 50 years as it was experienced and contributed to by the author. The article touches upon the beginning of calorimetry and thermal analysis of polymers, the development of differential scanning calorimetry (DSC), single-run DSC, and other special instrumentations, up to the recent addition of modulation to calorimetry and superfast calorimetry. Many new words and phrases have been introduced to the field by the author and his students, leaving a trail of the varied interests over 50 years. It began with cold crystallization and more recently the terms oriented, intermediate phase, glass transitions of crystals, and decoupled chain segments were coined. In-between the following phenomena were named and studied: extended-chain crystals, irreversible thermodynamics of melting of polymer crystals, zero-entropy-production melting, dynamic differential thermal analysis (DDTA), the rule of constant increase of C _p per mobile bead within a molecule at the glass transition temperature, superheating of polymer crystals, melting kinetics, crystallization during polymerization, chin-folding principle, molecular nucleation, rigid amorphous phase, system of classifying molecules, macroconformations, amorphous defects, rules for the entropy of fusion based on molecular shape and flexibility, single-molecule single-crystals, systems for classifying phases and mesophases including condis phases, and the globally metastable semicrystalline polymers with reversible, local subsystems. This review is update of a publication written in 1995 and published under the same title in the J. Thermal Anal., 46 (1996) 643. Parts F and G are fully new, and Part G is the basis for my lecture: ‘The development of the idea of thermodynamic decoupling in macromolecules’.