The thermally stimulated current (TSC) technique has been used to investigate three anionic polystyrenes of M̄n 17,000, 71,700, and 1.55 × 106, i.e., M < Mc, M > Mc, and M ≫ Mc, where Mc is the entanglement molecular weight. A current maximum near Tg designated TMg, has relaxation times which follow an Arrhenius equation. A second current maximum at T > Tg appears to be the Tll process and is designated TMll. Relaxation times for it follow a Vogel equation. TMg and TMll vary with molecular weight, increasing below Mc and leveling off above Mc at a temperature of about 170°C. Values of TMg and TMll are compared with values of Tg and Tll obtained from torsional braid analysis, which involves melt flow; and with differential‐scanning‐calorimetric values on fused films, where there is no transport of polymer. It is concluded from such cross‐comparisons that TSC, at least for polystyrene, is a quasistatic test which may involve microscopic viscosity. Macroscopic viscosity does not play a role. The ratio TMll/TMg is in the range 1.10–1.16, similar to Tll/Tg values by other methods. A few comments about Tll in atactic poly(methyl methacrylate) by the TSC method are given.
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Lacabanne et al. (1980) studied this question.
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