Glass transition and chain flexibility of linear polymers

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Abstract
Dependence of the glass-transition temperature, Tg, on polymer chain flexibility predicted by the Gibbs-DiMarzio theory was empirically tested by studying the relationship between Tg and the stiffness parameter for isolated chains, [sgrave]. It was found that [sgrave] is not a single variable controlling Tg for different polymer series which have different free volume fractions at Tg as a result of intrinsic differences in packing density in the crystalline state. The results obtained suggest that Tg of linear polyethylene lies near 160°K. A functional form of dependence of Tg on chain stiffness parameter and on local chain packing coefficient at Tg is proposed.