Water in water emulsions: phase separation and rheology of biopolymer solutions

Partially miscible polymers in solution do not separate into two macroscopic phases; in general they behave as viscoelastic fluids containing droplets of the minority phase dispersed into a continuous majority phase (emulsion type systems). Both phases contain two types of polymers and solvent in variable amounts. With time, the smaller droplets tend to merge into larger ones and eventually sediment. Provided the time stability of the emulsion is long enough and the size of the droplets does not exceed a few tens of microns, the emulsion can be characterized by conventional rheological methods as an effective medium, both in the linear regime (viscoelasticity) and under flow. We investigated a ternary system composed by two biopolymers, a protein (caseinate) and a polysaccharide (alginate) in aqueous solution and established an analogy between these phase separated solutions and immiscible blends of polymers. We first characterized the biopolymers and determined the phase diagram at room temperature that we interpreted within the framework of the Edmond and Ogston model. For the rheological investigations, starting with an initial composition of the system, we separated the two phases by centrifugation. The individual phases were then characterized through their viscoelastic and flow behaviors. By recombining variable amounts of these phases, thereby varying only their volume fractions, we were able to prepare stable emulsions with constituents having constant compositions. The effect of shear on these emulsions was investigated. After different shearing protocols, the size of the droplets was derived from the Palierne model and the flow curves were analyzed. The droplet sizes were compared to the critical capillary numbers and coalescence predictions. The flow curves and the dynamic viscosities of the emulsions were interpreted with a model recently proposed by Kroy et al. that extends earlier work of Oldroyd (1953), Schowalter et al. (1968), and Frankel and Acrivos (1970).