Investigating the evolution of the phase behavior of AOT-based w/o microemulsions in dodecane as a function of droplet volume fraction

AOT-based water in oil (w/o) microemulsions are one of the most extensively studied reverse micellar systems because of their rich phase behavior and their ability to form in the absence of any co-surfactant. The aggregation characteristics and interaction of the microemulsion droplets in these systems are known to be governed by AOT–oil compatibility and water to AOT molar ratio (w). In this manuscript by using Dynamic Light Scattering (DLS) and viscometry techniques, we show that droplet volume fraction too plays an important role in shaping the phase behavior of these microemulsions in dodecane. The phase separation characteristics and the evolution of the viscosity and the hydrodynamic radius of the microemulsion droplets on approaching the cloud points have thus been found to undergo complete transformation as one goes from low to high droplet volume fraction even at a fixed ‘w’. Modeling of the DLS data attributes this to the weakening of inter droplet attractive interaction caused by the growing dominance of the excluded volume effect with increase in droplet volume fraction. In the literature, the inter droplet attractive interaction driven phase separation in these microemulsions is explained based on gas–liquid type phase transition, conceptualized in the framework of Baxter adhesive hard sphere theory. The modeling of our viscosity data, however, does not support such proposition as the characteristic stickiness parameter (τ−1) of the microemulsion droplets in this system remains much lower than the critical value (τc-1≈10.25) required to enforce such phase transition.

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► AOT-based w/o microemulsions in dodecane were studied by DLS and viscometry.
► Inter-micellar attraction has been found to weaken at high droplet concentration.
► This transforms the phase separation characteristics of these microemulsions.
► It also has significant influence on the droplet aggregation characteristics.