Calorimetric study of phase transitions in ocylcyanobiphenyl-barium titanate nanoparticle dispersions

High-resolution ac-calorimetry is reported on the weakly first-order isotropic to nematic (I-N) and the continuous nematic to smectic-A (N-SmA) phase transitions in the liquid crystal octylcyanobiphenyl (8CB) doped with a ferroelectric nanoparticle barium titanate, BaTiO3 (BT). Measurements were performed as a function of BT concentration and over a wide temperature range well above and below the two transitions. From the thermal scans of all samples (having BT mass fraction φ(m) = 0.001 to 0.014 and pure 8CB), both the I-N and the N-SmA transitions evolve in character. Specifically, there appears an unusual change of the I-N specific heat peak shape on heating as φ(m) increases. Both the transitions shift to lower temperature at a different rate for φ(m)<φ(m)(c)=0.002 as compared to that for φ(m)>φ(m)(c). The effective transition enthalpies are essentially constant and similar to that seen in the bulk. Using a simple geometric model, the mean distance between the BT particles at the cross-over φ(m)(c) is found to be x(c)~3 μm, which is consistent with an estimated surface extrapolation length b for the nematic director. This suggests that the low φ(m) regime is dominated by an impurity/disorder effect while for φ(m)>φ(m)(c) the mean distance is small enough for the LC to mediate coupling between the BT ferroelectric nanoparticles.