Relationship between self‐seeded and epitaxial crystallization from polymer solutions: A potentially new method for molecular weight separation and a new decoration method for alkali halides

Abstract

AbstractIt was established that polyethylene and polyoxymethylene crystallize epitaxially on NaCl cleavage faces over a temperature range in which the usual polymer single crystals dissolve but a crystallization memory remains due to very small quantities of self‐seeding nuclei persisting in the solution. By performing this epitaxial crystallization in the presence of self‐seeding nuclei, it could be established that epitaxial crystallization at these elevated temperatures involves only the very largest molecules in the distribution. Further, the self‐seeding nuclei themselves could be isolated for observation, and these results were found consistent with previous predictions. By utilizing both the adhesion of these nuclei to NaCl and the selective nature of the epitaxial crystallization, the largest molecules could be extracted and reintroduced again to the same or different solutions. This opens up the possibility of a novel kind of chromatography for the separation and characterization of the highest molecular weight end of a distribution to a sensitivity which cannot be approached by other methods. The epitaxy phenomenon itself, under the circumstances involved, provides a new decoration method for the study of the surface topography of alkali halides. The origin of such as epitaxy occurring at low supercoolings and terminating at a limiting thickness raises important questions regarding long‐range forces and some unsettled features in the theory of chain‐folded crystal growth in polymers.