Miscibility studies of the smectic phases of trans,trans-4'-alkylbicyclohexyl-4-carbonitrile (CCH) liquid crystals

Complete temperature-composition phase diagrams for binary mixtures of 4'-ethyl-, 4'-propyl-, and 4'-butylbicyclohexyl-4-carbonitrile (CCH-2, CCH-3, and CCH-4, respectively) in each of the three possible combinations have been constructed from differential scanning calorimetry and thermal microscopy data. The highest temperature smectic phases of each of the pure mesogens are immiscible with one another, even though CCH-3 and CCH-4 have both been previously assigned the bilayer crystal-B structure on the basis of X-ray diffraction studies. The present studies indicate that the enantiotropic smectic phase of CCH-4 is slightly higher-ordered than is the monotropic smectic phase of CCH-3. The smectic phase of CCH-2, which previously has been found to be characterized by rhombohedral packing on the basis of X-ray diffraction data, is miscible with the second, previously uncharacterized (monotropic) smectic phase (S₂) of CCH-3. Photographs illustrating the subtle differences in the microscopic textures of these smectic phases are also presented.