Crystalline state folded chains

During crystallization, the molecules change their conformation from the random coil to chain folded. The chain conformation in the crystalline state has been the subject of great discussion, since it reflects the path that molecules have followed during crystallization. In the case of sufficiently long... 

In polymer crystallization the challenge is to identify and clarify the transformations by which chain molecules pass from a disordered, molten state to the ordered supra-molecular organization known as the semi-crystalline state. The subject is highly relevant in terms of both basic science and technology it is indeed clear that many modern applications require complete control of the structure and the morphology of polymers from macroscopic dimensions down to below the nanoscale. As a simple example, making the crystallites in a polymer liber equally oriented and reducing the number of chain folds (or hairpins) therein, usually turn out to be very favorable requisites for mechanical performance. 

It is now generally accepted that folding is universal for spontaneous, free crystallisation of flexible polymer chains. It was first of all found in crystallisation from very dilute solutions, but it is beyond doubt now, that also spherulites, the normal mode of crystallisation from the melt, are aggregates of platelike crystallites with folded chains, pervaded with amorphous material. "Extended chain crystallisation" only occurs under very special conditions in the case of flexible chains for rigid polymer chains it is the natural mode ("rigid rod-crystallisation" from the melt in case of thermotropic polymers, and from solution in case of the lyotropic liquid-crystalline polymers both of them show nematic ordering in the liquid state). 

Morphology Some polymers, like PETP, are spun in a nearly amorphous state or show a low degree of crystallinity. In other polymers, such as nylon, the undrawn material is already semi-crystalline. In the latter case the impact of extension energy must be sufficient to (partly) "melt" the folded chain blocks (lamellae) in all cases non-oriented material has to be converted into oriented crystalline material. In order to obtain high-tenacity yarns, the draw ratio must be high enough to transform a fraction of the chains in more or less extended state. 

In Sect. 3 a set of experimental data on cyclic molecules is described supporting the basic discussions of Sects. I and 2. Central are the cycloalkanes that ultimately serve as a model for adjacent reentry, sharply folded polyethylene crystals. Chain-folded polyethylene was shown in the early 1960 s to thicken in the crystalline state by straightening as many as 100 to 1000 folds when brought to elevated pressure and temperature. This surprising observation found its explanation in the fast reptation possible in the condis-crystal state. 

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