High-resolution investigation by Peltier-element-based adiabatic scanning calorimetry of binary liquid crystal mixtures with enhanced nematic ranges

Abstract

High-resolution Peltier-element-based adiabatic scanning calorimetry (pASC) has been used to investigate the temperature dependence of the specific heat capacity and specific enthalpy of two mixture systems of the liquid crystal smectic A1 compound 5-n-nonyl-2-(4′-isothiocyanatophenyl)dioxane-1.3 (9DBT), and one of the smectic Ad compounds 4-n-octyloxy-4′-cyanobiphenyl (8OCB) and 4-nonyloxy-4′cyanobiphenyl (9OCB). For both mixture systems, measurements have been carried out over a large temperature range, from the crystalline solid phase over the smectic and nematic phases into the isotropic liquid phase. Both systems exhibit substantial, mixing-induced, enhanced nematic ranges and large changes in the composition dependence of the transition temperatures between the different phases. In both systems, eutectic melting points have been located and, for the different mixtures, the melting and eutectic transition heats have been obtained. The nematic to isotropic (NI) transitions are weakly first order with latent heat values in the range usually observed for this transition in other liquid crystals. The critical behavior of the specific heat capacity at the NI transition is described by exponent values near the tricritical one of 0.5. Along the smectic A to nematic (AN) transition lines, strong composition dependence was observed for the latent heat, from almost zero to values comparable to those observed at the nematic to isotropic transition. The concentration dependence of these AN latent heats was adequately fitted with a crossover function consistent with a mean-field free-energy expression that has a nonzero cubic term; the latter is induced by the Halperin-Lubensky-Ma coupling between the smectic A order parameter and orientational order director fluctuations. The fitting analysis resulted in the location of a Landau-tricritical point along one branch of the transition line in the system 9DBT-8OCB and one in each branch (for low and high 9OCB mole fractions) of the NA transition line of the 9DBT-9OCB system. The effective critical exponent values for the specific heat capacity of the AN transitions follow the McMillan ratio-dependence observed for other liquid crystal mixtures.