Rheological evidence for the existence of subphases in the liquid crystalline 4-n-alkoxybenzoic acids

The rheological behaviour of the homologous series, the alkyloxybenzoic acids, has been studied at steady flow and small amplitude oscillatory shear. The temperature dependencies of the viscosity were compared with differential scanning calorimetry data in order to estimate pretransitional phenomena in mesophases. The values of the viscosity and flow activation energy (E) can be indicative of the mesophase state. 4-n-pentyloxybenzoic acid yields a classic nematic (N) phase while the next homologues show a cybotactic nematic phase having a higher E value. The N phase is a Newtonian fluid of lower viscosity than that of the isotropic phase. The cybotactic nematic phase by its rheological properties takes an intermediate position between the N phase and a smectic C (SmC) phase. The SmC phase is a viscoelastic and viscoplastic medium. The SmC phase of 4-n-octyloxy-, 4-n-nonyloxy-, 4-n-decyloxy- and 4-n-dodecyloxybenzoic acid can exist in high- and low-ordered states. The more ordered smectic phase is characterised by higher stiffness, viscosity and yield stress than those of the less ordered. The SmC phase of 4-n-hexadecyloxybenzoic acid is characterised by the only state with unstable value of apparent viscosity. The phase state and the transition temperature can be dependent on the thermal history of the sample and a mechanical shear.