Second-order Phase Transition Behavior in a Polymer above the Glass Transition Temperature

Abstract

Glass transition was primarily considered to be not phase transition; instead, regarded as pseudo secondorder phase transition due to its similarity to the ordinary second-order phase transition. Recent single-molecule spectroscopy developments have prompted re-investigating glass transition at the microscopic scale, confirming that the initial classification is correct and revealing that glass transition includes phenomena similar to second-order phase transition. They are characterized by microscopic collective polymer motion and discontinuous changes in temperature dependent relaxation times within a temperature window that includes the polymer calorimetric glass transition temperature. Generally, atom or molecule collective motion and discontinuous changes in physical quantities including relaxation times characterize critical phenomena associated with second-order phase transitions near specific temperatures. Thus, second-order phase transition phenomena are involved in polymer glass transition.