Systematic calorimetric investigation of the effect of silica aerosils on the nematic to isotropic transition in heptylcyanobiphenyl

• Published in: Physical review. E, Statistical, nonlinear, and soft matter physics Vol. 66; no. 2 Pt 1; p. 021707
• Main Authors: Jamée, P, Pitsi, G, Thoen, J
• Format: Journal Article
• Language: English
• Published: United States 01.08.2002
• ISSN: 1539-3755
• DOI: 10.1103/PhysRevE.66.021707

The effect of confinement on liquid crystal phase transitions was investigated in mixtures of the liquid crystal heptylcyanobiphenyl with hydrophilic aerosils. The influence of the aerosil density on the nematic to isotropic transition was studied by adiabatic scanning calorimetry. Mixtures have been investigated with an aerosil content between rho(S)=0.1 and rho(S)=0.7, the latter being substantially higher than that investigated in previous studies with other liquid crystal-aerosil mixtures. The transitions in the examined mixtures exhibited an unusually large broadening, while the transition temperatures showed peculiar behavior. Notwithstanding, the transition (latent) heat behaved as could be expected on the basis of previous studies. The observed behavior can be explained, in the context of the elastic-strain approach usually employed to describe transition temperature shifts, by variations in the distribution of the radius of curvature R of the aerosil voids originating from sample preparation. It is important in this regard to separate the behavior of the transition temperatures and the transition (latent) heats, the former being influenced by the radius of curvature of the voids and the latter by the total void surface per unit volume. Three quantitative models were compared with experimental results. Both the pinned boundary layer and the random field model yield an evolution of transition temperatures not in agreement with experimental observations. More importantly, they predict a decrease of the pretransitional specific heat capacity, not supported by experiment. The difficulties with these models are avoided in a third, mean-field surface-induced order model.