Physical kinetics and thermodynamics of phase transitions probed by dynamic nanocalorimetry

A specific ac nanocalorimeter is presented for the study of kinetics in phase transitions. This apparatus designed by means of microfabrication technologies requires a 50-μm-thick solid or liquid sample. The use of the ac calorimetric method allows an operating frequency range around two decades combined with a very high sensitivity. The ability of this apparatus for thermal spectroscopy is illustrated by measuring the thermal behavior of a homopolymer, the polytetrafluoroethylene, which exhibits two phase transitions at room temperature. The variation of the thermal frequency allows the observation of kinetic effects directly seen on the thermodynamic properties (enthalpy and heat capacity). We demonstrate the possibility of extracting a quantitative value of the kinetic time constant occurring at a first-order phase transition and consequently the capabilities offered by highly sensitive ac calorimetry to investigate direct thermal dynamics in macromolecular samples.