Wetting behavior above the liquid-crystal-isotropic transition in a homologous series

An ellipsometric study of the wetting behavior at the free surface above the isotropic to nematic or isotropic to smectic-A transition of nine homologous compounds with even alkyl chain lengths n in the range from four to twenty carbon atoms is presented. All compounds show a pretransitional increase of the nematic or smectic surface coverage as the bulk isotropic to liquid-crystal transition is approached from above. The behavior of the nematic compounds (n=4 to 10) can be interpreted, within the framework of a Landau model, as complete wetting. In short nematic homologs the divergence of the nematic coverage is strongly reduced by a decrease of the nematic susceptibility of the isotropic phase. The elastic coefficient L of the Landau model shows a pronounced increase with increasing n, resulting in the occurrence of a discontinuous prewetting transition in the shortest smectic homolog (n=12) that is still describable by the nematic Landau model. In the longer smectic homologs (n=14 to 20), layering steps appear in the pretransitional increase of the coverage. The results indicate probable partial wetting for the longest homolog, whereas for the other smectic compounds the distinction between complete and partial wetting is difficult on the basis of ellipsometry.