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Second-order Phase Transition Behavior behind Polymer Glass Transition

Glass transition has similarity to the second-order phase transition in temperature dependent changes in entropy, non-Arrhenius viscosity, and heat capacity of glass forming materials. However, it has primarily been considered to be not phase transition. Recent single-molecule spectroscopy developments prompted re-investigating glass transition at the nanometer scale probing resolution, showing that glass transition includes phenomena similar to the second-order phase transition. They are characterized by microscopic collective polymer motion and discontinuous changes in temperature dependent relaxation times, the latter of which resembles the critical slowing down of second-order phase transitions, within a temperature window above the polymer calorimetric glass transition temperature. Simultaneous collective motion and critical slowing down occurrences disclose that the second-order phase transition hides behind polymer glass transition.