Abstract:

Sub-zero temp. DSC measurements were conducted to evaluate the behavior of water in non-ionic microemulsions. Two surfactant systems were studied. The first, based on ethoxylated fatty alc., octaethylene glycol mono n-dodecylether and also contg. water, pentanol and dodecane at a fixed wt. ratio of 1:1. The second system, based on oligomeric ethoxylated siloxanes, water and dodecanol as oil phase. In both systems it was found that in up to 30 wt.% of the total water content, all water mols. solubilize in the amphiphilic phase and are bound to the ethylene oxide (hereafter referred to as EO) head-groups. No free water exists in the surfactant aggregates' core. Up to three mols. of water are bound to each EO group. In the first system, the behavior changes significantly upon adding more water. The added pentanol allows further swelling and the water penetrates into the amphiphile structures and forms a reservoir of free water. Structures are deformed and grow from elongated channels (up to 15-20 wt.% water), via ill-defined (one-dimensional growth) local lamellar structures (up to ca. 60 wt.% water) to spherical normal, O/W micelles (at ≥85 wt.% water). In contrast, the oligomeric systems, due to geometrical restrictions of the amphiphiles and the nature of their curvature that prevents inversion, cannot further solubilize water in the surfactant aggregates' core, causing phase sepn. to occur. [on SciFinder(R)]