Polymer, Vol.38, No.16, 4065-4069, 1997
Comments on Compensation Analysis as Applied to Thermally Stimulated Current Thermal Sampling
Compensation of Arrhenius relaxation curves coming to an extrapolated focus point is observed for many materials, especially in thermally stimulated current or related relaxation studies of polymers. Here we compare typical thermally stimulated current thermal sampling (t.s.c.-t.s.) data which exhibit compensation phenomena, with simulated data. The simulations were constructed on the basis of different curves of apparent activation energies, E-a, vs temperature, in an effort to represent a variety of possible experimental systems near a cooperative or high activation energy transition such as a glass transition (T-g). We show that compensation is universally observed for all simulated results, essentially independently of the nature of the cooperative transition, and proof is given that it is simply a result of mathematical manipulation of the Arrhenius equation in an under-determined system. The compensation temperature T-c must be related to T-g because of the steep Arrhenius curves. The difference, T-c - T-g, is indirectly related to the shape of the onset of glass transition as one approaches T-g from the low temperature side, but is not related to the ’breadth’ of the main glass transition which is usually the region of interest, nor is it sensitive to the high temperature side of the transition. Correlating compensation with any physically observable quantity is ill-advised, for a variety of reasons discussed here.
Keywords:GLASS-TRANSITION;ISOTACTIC POLYPROPYLENE;CURRENT SPECTROSCOPY;RELAXATION;POLYMERS;DEPOLARIZATION;BETA