Langmuir, Vol.19, No.18, 7164-7172, 2003
Manifestation of polyacrylamide inverse-emulsion instabilities through oscillatory shear
The stability of polyacrylamide-based inverse emulsions, prepared with surfactant blends consisting of mixtures of fatty acid esters, ethoxylated fatty acid esters, and ABA triblock copolymeric stabilizers, was investigated by means of oscillatory shear measurements. "Milky-like" inverse lattices were obtained from inverse-emulsion polymerization of acrylamide. The surfactant blend composition and type were varied at a fixed concentration of 3 wt %, with the elastic modulus followed as a function of time for a period not exceeding 30 days. The data indicated that the logarithm of G' as a function of time was linear for at least 15 days. The slope of log G' versus time was validated as an index of stability, such that the higher the slope, the less stable the system. A threshold with regard to this indicator was also established at 0.02. As two surfactant types (fatty acid esters and block copolymers) were used to stabilize the emulsion, a threshold stability was also observed as a function of the stabilizer ratio, with emulsions reported to be stable below 40% fatty acid ester levels. In contrast, for emulsions stabilized with three types of surfactants (the aforementioned two plus ethoxylated fatty acid esters), nonsettling emulsions were obtained, regardless of the blend composition. Oscillatory shear measurements were further compared with the level of separated oil phase obtained from accelerated settling tests and shelf life. The results were found to be in close accordance and to indicate the efficiency of long-range interparticle interaction toward emulsion stability. Similarly to the range and magnitude of the interaction forces, the dispersed-phase volume fraction was observed to influence emulsion stability. For volume fractions less than 0.55, all inverse emulsions were unstable.