Temperature-modulated differential scanning thermodynamics

For many years, the thermodynamic description of macromolecules lagged behind other materials because of the unique tendency of pol5nneric systems to assume nonequilibrium states. Most standard sources of thermodynamic data are, thus, almost devoid of polymer information (1-7). Much of the aversion to include polymer data in standard reference sources can be traced to their nonequilibrium nature. In the meantime, polymer scientists have learned to recognize equilibrium states and utilize nonequilibrium states to explore the history of samples. For a nonequilibrium sample it is possible, for example, to thermally establish how it was transferred into the solid state (determination of the thermal and mechanical history). More recently, it was discovered with the use of temperature-modulated differential scanning calorimetry (TMDSC) that within the global, nonequilibrium structure of semicrystalline polymers, locally reversible melting and crystallization processes are possible on a nanophase level (8). 

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