Journal of Physical Chemistry B, Vol.104, No.18, 4448-4456, 2000
Percolation in concentrated water-in-carbon dioxide microemulsions
The phase behavior and electrical conductivity of water-in-carbon dioxide (W/C) microemulsions are reported over a range of temperatures (5-65 degrees C), pressures (100-450 bar), and droplet volume fractions (phi = 0.0347-0.483) at a constant water-to-surfactant molar ratio (W-o) of 12.5. A phi of 0.483 is a 5-fold increase over those reported previously. A critical point is observed at a droplet volume fraction of approximately 0.12, at which the single-phase microemulsion splits into two microemulsion phases of similar volume upon lowering the pressure (upper critical solution pressure). At low temperatures, a lower critical solution pressure is also observed upon increasing the pressure. Both of the critical solution pressures result from an increase in the attractive interdroplet interactions; consequently, pressure has little effect on the conductivity in the one-phase region. The conductivity increases nearly 3 orders of magnitude with changes in the droplet concentration or temperature. Scaling analysis of the conductivity data supports a dynamic percolation model, whereby the attractive interdroplet interactions form clusters of discrete droplets with rapid charge transport.