Book Description

This thesis is mainly concerned with some important properties of complex fluids, and how these properties are influenced by structures in the nano/mesoscopic scale. Short-range assembly of the constituent molecules results in an amazing variety of phase behavior in these systems. Liquid-liquid phase transitions, or transitions from a homogeneous(mixed) phase to an immiscible phase (two-phase coexistence), are the outcome of a competition between entropy and short-ranged attractive forces, and form an important part of this thesis. A rich phase behavior is uncovered by a detailed study of liquid-liquid phase transitions in a mixture of ethanol(E) and water(W), induced by the addition of ammonium sulfate(AS) ions (E and W are otherwise completely soluble in each other). This is the main motivation for choosing this system. Furthermore, experimental evidence of the presence of supramolecular association in alcohol-water mixtures [J.-H. Guo et al., Phys. Rev Lett, 91, 15401(2003)] enhances our interest to study the phase behavior in more detail. The presence of a critical point, at which there is a second order phase transition, is quite common in complex fluids. An issue which has been the subject of extensive scientific research in recent years is the influence of nano/mesoscopic structure on the critical behavior of these fluids corresponds to the Ising universality class. However, the approach to the asymptotic regime is governed by a competition between the correlation length of critical concentration fluctuations and the additional length scale arising due to structuring., which results in a crossover from the universal Ising behavior to the mean-field behavior, sometimes within the critical domain. This phenomenon of crossover criticality is presently explored in the E + W + AS system. A significant portion of the thesis presents explorations on the critical behavior in the vicinity of special critical points (SCP), which are formed by the coalescence of two or.