Broadband dielectric spectroscopy study of molecular dynamics in the glass-forming liquid crystal isopentylcyanobiphenyl dispersed with aerosils.

Abstract

The glass-forming liquid crystal isopentylcyanobiphenyl (CB15) filled with different concentrations of hydrophilic and hydrophobic aerosils has been investigated by broadband dielectric spectroscopy in the frequency range from 10(-2) Hz to 10(7) Hz over a temperature range of 173 K-300 K. CB15 that consists of chiral molecules has a monotropic system of phases nematic (N*) and smectic-A upon supercooling and forms a glass further on. In the isotropic phase a single Davidson-Cole process exists in the substance, which is due to the rotation of the molecules around their short axes. In the supercooled N* phase a Cole-Cole process that is an order of magnitude faster is additionally present and is due to the rotation in a cone around the local director. The relaxation times of the process due to rotation around short axes obey the empirical Vogel-Fulcher-Tamman behavior typical for glass-forming systems. Filling of the liquid crystal (LC) with different concentrations of hydrophilic aerosils leads to the emergence of a slow relaxation process that grows with the increasing concentration of the aerosils. The aerosil particles, which form a three-dimensional network dividing the LC phase into domains, have little effect on the relaxation times of the bulk processes. As a consequence the glass transition temperature is merely affected. On the other hand, in LCs dispersed with hydrophobic aerosils the slow process is quite weak. The slow process is attributed to the relaxation of the molecules that are homeotropically attached at the surfaces of the aerosil particles. The LC-aerosil surface interaction leads to a considerable slowing down of the molecular rotation around their short axis. The process has an Arrhenius-like temperature dependence of the relaxation times with an activated type of dynamics, which can be explained by considering a nonincreasing rearranging region of cooperativity in surface layers.