Packing of linear molecules: an electron microscope study of disorder in mesophases and binary solids

With the aid of epitaxial orientation techniques originally designed for linear polymer crystallization, it is found that a large assortment of linear chain molecules can be prepared for electron diffraction study in a projection onto the molecular axes. This not only facilitates a study of ordered monodisperse molecular crystal structures but also of the disordered state as well, including thermotropic phase transitions and the structure of binary solids. Representative studies of monodisperse and polydisperse phase behavior based on electron diffraction and differential scanning calorimetry measurements are reviewed for n-paraffins, glycerolipids, and cholesteryl esters. The importance of observing the microcrystalline state is readily apparent from these studies--not only because the symmetry of individual small crystals can be determined, but also because local structural variations not detectable in bulk measurements are readily observed.