Onset temperature, polymer glass formation

The onset of glass formation in a polymer melt is associated with the development of orientational correlations that arise from chain stiffness. At the temperature Ta, there is a balance between the energetic cost of chain bending and the increased chain entropy, and below this temperature orientational correlations are appreciable while the melt still remains a fluid. Such a compensation temperature has been anticipated based on a field theoretic description of semiflexible polymers by Bascle et al. [120]. The temperature 7a is important for describing liquid dynamics since the orientational correlations (and dynamic fluid heterogeneities associated with these correlations) should alter the polymer dynamics for T < Ta from the behavior at higher... 

A close connection exists between the presence of a flexible polymer skeleton and the flexibility of the bulk material. Macromolecular flexibility is often defined in terms of the glass-transition temperature, Tg. Below this temperature, the polymer is a glass, and the backbone bonds have insufficient thermal energy to undergo significant torsional motions. As the temperature is raised above the Y g, an onset of torsional motion occurs, such that individual molecules can now twist and yield to stress and strain. In this state the polymer is a quasi-liquid (an elastomer) unless the bulk material is stiffened by microcrystalfite formation. Thus, a polymer with a high Tt is believed to have a backbone that offers more resistance to bond torsion than a polymer with a low 7 g. 

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