Percolation phenomenon of calcium bis(2-ethylhexyl) sulfosuccinate water-in-oil microemulsions by conductivity and dielectric spectroscopy measurements

The sodium counterion (Na+) of the sodium bis(2-ethylhexyl) sulfosuccinate (AOT) surfactant was exchanged with calcium Ca2+ to investigate the counterion charge effect on the structure of water in normal decane microemulsions. Ohmic conductivity and dielectric permittivity measurements were performed on samples at constant water to surfactant mole ratio [water]/[Ca(AOT)(2)]=26.6. Increasing the volume fraction of the dispersed phase phi, a percolation phenomenon was observed at the constant temperature of 25 degrees C. The percolation threshold was found at phi approximately 15% by Ohmic conductivity and static dielectric permittivity studied as a function of phi, and by the frequency dependence of the complex permittivity. Critical exponents typical of the static percolation mechanism (formation of bicontinuous microemulsions) were found below and above threshold. The comparison of these results obtained for the two different counterions, Ca2+ and Na+, in AOT surfactant water in normal decane microemulsions allows detection of an important difference. The percolation below threshold is dynamic for the sodium-based microemulsions, accounting for the formation of clusters of droplets, whereas calcium-based microemulsions show a static percolation. For this system, the coalescence of droplets begins to occur below threshold at phi approximately 12%.