Abstract
The crystallization of higher polymers is a phenomenon which is not yet fully understood, one of the main difficulties being to explain how the spherulites arise. An attempt will be made in this paper to draw a clearer picture of the mechanism of crystallization and thus to account for the origin of spherulites. It will then be seen how several other phenomena involved in the crystallization of natural rubber can be shown to be logically interrelated. The current view is that a crystalline polymer consists of a continuous amorphous phase containing small crystalline regions, the crystallites. The evidence as to the size of these crystallites, however, is at present inconclusive, because only the lower limit of their size can be measured by means of x-ray examination. The reason is that, owing to the absence of reflections of a higher order, the effect of irregularities in the crystallites and of the heat motion of the molecules cannot be measured separately. Another doubtful question is whether the small angle interference maxima are to be interpreted as a measure of mean distances between the crystallites. To do this, Wallner has to resort to the assumption that the crystallites are unstable, whereas it is presumed, on the evidence of the mechanical properties of the high polymers, that a crystallite is stable and permanent. Hoffmann found 82 ± 7 per cent of crystalline material in polychlorotrifluoroethylene and Buckley, Cross, and Ray found as much as 95 per cent in polymethylene. Such high percentages make it doubtful whether the crystalline phase can be discontinuous at all. In this article any volume of material in which the molecules lie parallel is called a crystallite. The direction in which the molecules are oriented is termed the longitudinal direction of the crystallite. It is immaterial to the argument whether a crystallite consists of several crystallites, aligned in parallel separated by a small amount of amorphous material, or of a single crystallite containing large irregularities.