Electron crystallography of the polymethylene chain. 4. Defect distribution in lamellar interfaces of paraffin solid solutions

Abstract

As is also found for paraffin lamellar crystals heated near the rotator or melt transition, the major change in electron diffraction patterns imposed by lamellar disorder in binary or multicomponent solid solutions is the attenuation and intensity modification of low-angle (00l) reflections. Using a Gaussian model for atomic occupancies near the interface, a systematic basis is found for the interfacial disorder thickness, describing the phenomenological ‘void’ distribution at the lamellar interface. (Vibrational spectroscopy has shown that this is actually a distribution of non-planar chain conformations.) Single crystal electron diffraction data from various co-soluble paraffin chain assemblies, used previously to determine their crystal structures (but also including a new determination for n-C36H74/ n-C38H78/ n-C40H82 1: 1: 1), are re-analyzed so that further distinctions can be made among simple binary and ternary solid solutions, multicomponent waxes, and low molecular weight polyethylene. Expressions of the latter polyethylene structure, involving ‘bridging molecules’ can be found in certain natural insect and plant waxes.