Abstract
Abstract A more realistic, two-phase structural model is proposed for the amorphous solid state of polymers. The model is based on structural evidence reported to date, in particular the evidence from our own electron diffraction and microscopy studies of crystallizable and non-crystallizable amorphous polymers, including near-molten rubbers. This model is different from either Kargin's chain-packet or Hose-mann's paracrystalline model. The two major elements of the model are the grain, which consists of an ordered domain and a distinct grain boundary, and the intergrain region, which consists of molecules that are in a more truly random conformation. In the ordered domain (∼20∼40 A) the molecular chain segments are aligned parallel to one another with a nearly constant spacing. A natural consequence of the present model is the concentration of excess free volume in the intergrain region. The amount of excess free volume has been estimated for typical polymers in their glassy amorphous state and found to ...
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