Thermal analysis of macromolecules

This review traces the development of thermal analysis over the last 40 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. Many new words and phrases have been introduced to the field by the author and his students, leaving a trail of the varied interests one can have over 40 years. It began with cold crystallization and most recently the term oriented, intermediate phase was coined, creating in-between: extended chain crystals, the irreversible thermodynamics of melting of polymer crystals, dynamic differential thermal analysis (DDTA), the rule of constant increase ofC _p per mobile bead within a molecule at the glass transition temperature, superheating of polymer crystals, melting kinetics, crystallization during polymerization, the chain-folding principle, molecular nucleation, rigid amorphous phase, a system of classifying molecules, macroconformations, amorphous defects, rules for the entropy of fusion based on molecular shape and flexibility, single-molecule single-crystals, a system of classifying phases and mesophases, and condis phase.First and foremost I would like to acknowledge the unwavering support through my wife, Heidel, without whom many of the projects simply could not have been completed. Similarly, our children had to grow up knowing that often research and teaching had to take precedence. Without coworkers, little could have been accomplished. Of the about 120 postdoctoral fellows, graduate students, and technicians, most of whom contributed to the listed references, and many have participated on their own in this issue, goes my thanks for the bulk of the scientific work. Many friends and colleagues contributed with discussion and constructive criticism, some of them have also contributed in this collection of papers related to thermal analysis. Little work can be done without this interplay of ideas. The limited space has not permitted to give a full appreciation of the importance of the ideas drawn from the literature. These thousands of additional references can be found in the initial papers and reviews of the subjects treated.Material support was received from the three major instrument companies for thermal analysis equipment: TA Instruments, Inc.; Perkin-Elmer Corp.; and Mettler-Toledo, Inc. Without this help we would not always have been able to be at the forefront of instrumentation. Major financial support for the research came from outside the universities. I estimate that over the 40 years about 4 Megadollars were spent by government agencies, companies, and private foundations to support coworkers, myself during the summers, research equipment, expenses, and travel. A large amount of money, but not too much if one compares it to typical expenditures in the field of athletics (about 10 k$ per paper). Major sustained funding came from the Advanced Projects Agency (ARPA), the Office of Naval Research (ONR), the National Aeronautics and Space Agency (NASA), the Department of Energy (DOE), and, most prominently, the National Science Foundation (NSF). At present our work is supported by the Division of Materials Research, National Science Foundation, Polymers Program, Grant # DMR 90-00520 and the Division of Materials Sciences, Office of Basic Energy Sciences, U.S. Department of Energy, under Contract DE-AC05-84OR21400 with Lockheed Martin Energy Systems, Inc. Industrial support is presently given by TA Instruments, Inc; ICI Paints; Exxon Res. and Eng. Co.; Shell Development Co.; Toray Research Center; and Mettler-Toledo, Inc.Last, but by no means least, I would like to thank Dr. E. Turi for the invitation to write this paper and for her untiring effort to entice so many of my students and friends to contribute to this issue of the Journal of Thermal Analysis.