DSC Techniques and Phase Transition Kinetics

• Kinetics of first-order phase transitions in DSC are reviewed. • A power-law-dependent rate coefficient on Δ T is used in the analysis of kinetics. • Fast-scanning and temperature-modulated DSC for nonequilibrium processes are covered. This review summarizes analysis methods for the kinetics of first-order phase transitions, such as crystallization and melting, studied by differential scanning calorimetry (DSC), and clarifies their conditions of applicability. Phase-transition kinetics are treated as elements that respond nonlinearly to temperature changes within instrumental systems otherwise constructed under the assumption of linear response. Models for the evaluation of DSC instrumental coefficients are outlined, and temperature calibration based on the melting behavior of standard materials is described, with separate attention to temperature gradients within the sample. The kinetics of crystallization and melting in assemblies of crystallites are then discussed on the basis of a first-order rate equation, introducing a rate coefficient dependent on the degree of supercooling or superheating, Δ T . Emphasis is placed on the analysis of scan-rate-dependent peak temperature assuming a power-law dependence of the rate coefficient on Δ T . Kinetic analysis methods using advanced DSC techniques, including chip-sensor fast scanning calorimetry and temperature-modulated DSC, are also reviewed, providing a basis for the analysis of fast and nonequilibrium processes using DSC.