Emulsification failure boundary

At the oil-rich side, the phase behaviour is inverted temperature-wise as can be seen in the T( wA)-section provided in Fig. 1.7(c). Thus, the near-critical phase boundary 2 —1 starts at low temperatures from the lower n-octane-QoEs miscibility gap (below <0°C) and ascends steeply upon the addition of water. With increasing wA, this boundary runs through a maximum and then decreases down to the upper critical endpoint temperature Tu. The emulsification failure boundary 1 —r 2 starts at high temperatures and low values of wA, which means that only small amounts of water can be solubilised in a water-in-oil (w/o) microemulsion at temperatures far above the phase inversion. Increasing amounts of water can be solubilised by decreasing the temperature, i.e. by approaching the phase inversion. At Tu the efb intersects the near-critical phase boundary and the funnel-shaped one-phase region closes. 

From the above considerations, it can be concluded that T(wB)- and T(wA)-sections provide an easy method to determine the location of emulsification failure boundaries which are of particular interest if the optimal formulation for an industrial application has to be found. Furthermore, these sections yield the lower and upper temperature of... 

Figure 1.19 Micrographs of microemulsion droplets of the o/w-type in the system II2O- n-octane-CnEs prepared near the emulsification failure boundary at ya = 0.022, wb = 0.040 and T = 26.1 °C. (a) Freeze-fracture direct imaging (FFDI) picture showing dark spherical oil droplets of a mean diameter = 24 9 nm in front of a grey aqueous background. Note that each oil droplet contains a bright domain of elliptic shape which is interpreted as voids, (b) The freeze-fracture electron microscopy (FFEM) picture supports the FFDI result. Each fracture across droplets which contain bubbles shows a rough fractured surface. (From Ref. [26], reprinted with permission of Elsevier.)...

The phase equilibria at temperatures above To, ((f)-(i)) are essentially mirror images of the behaviour at lower temperatures, with a critical end-point on the oil-rich side at and an emulsification failure boundary, here corresponding to the maximum water solubility, which moves to higher 0s/0w with increasing temperature. 

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