Grüneisen functions of polymer polycrystals

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Abstract
The relationship between the bulk Grüneisen function of a polycrystalline polymer and the Grüneisen functions of the individual anisotropic crystallites is examined. The approximations of uniform strain and uniform stress are shown to yield markedly different predictions for the bulk behavior. The role of the internal degrees of freedom in determining the main features of the temperature dependence of γ is discussed and can be understood qualitatively in terms of the behavior of a simple one‐dimensional model. The analysis reveals the similarities and basic assumptions underlying previous theoretical work on simple polymer models. The neeed for single crystal data is emphasized. It is shown to be essential for a more quantitative understanding of the nature of the interactions in polymers.