Amorphous state residual order

A local order of about 1 nm in length may exist in the amorphous state. Structure and properties are isotropic, in the absence of stress. An anisotropic behaviour is possible, if the amorphous polymer was stretched below Tg even after removing the stress (frozen-in residual stress). 

Fig. 57. From top to bottom experimental spectrum of almost ideally isotactic PMMA (p mm) > 95%), experimental spectrum of preferentially syndiotactic PMMA (p(rr) = 62%, p(mr) = 30%, p mm) — 8%), simulation for ideally isotactic PMMA, simulation of PMMA with the configurational statistics of the experimental preferentially syndiotactic sample. Only the methyl region of the spectra is shown. Compared with aPP (Fig. 16) the agreement between experiment and theory is poor. Especially for the syndiotactic sample the simulated line shape is broader than the experimental one, which is indicative of some residual order in the amorphous glassy state. The fine lines show the contributions of the various conformations and the bold lines the overall simulation with the Gaussian broadening function s, ...

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