Segmental motion in polyoxymethylene

Abstract

AbstractThe proton spin‐lattice relaxation times (T1) of melt‐crystallized, solution‐crystallized, and solid‐state‐polymerized polyoxymethylene (POM) were measured between −60 and +150°C. The three types of samples each have a pronounced T1 minimum near room temperature which is a high‐frequency manifestation of the γ process. From the quantitative dependence of the relaxation intensity on crystallinity as well as from the absolute magnitude of the relaxation times, it is concluded that the γ process in POM arises from hindered rotation of noncrystalline chain segments. The relation between the relaxation times and the long period indicates that these noncrystalline segments constitute disordered lamellar surface layers, the thickness of which depends on thermal history of the material. The temperature dependence of the motion of the relatively thin surface layers of solution crystallized POM is quite straightforward. The γ process in the bulk‐crystallized material involves cooperative motion, however, leading to temperature‐dependent kinetic parameters.