Structure and Rheology of Monodisperse and Bimodal Emulsions

Emulsions are the basis for many commercial products such as foodstuffs and paint due in part to their highly tunable flow properties. It is qualitatively understood that factors such as the dispersed phase droplet size and size distribution should affect how an emulsion flows because they influence how droplets can deform or pack. Since standard emulsification techniques such as blending and homogenization cannot produce emulsions with well-defined size distributions, little work has been done to, in particular, quantitatively determine the influence of droplet size distribution on emulsion flow properties. Consequently, in this investigation we have probed how the droplet size distribution affects emulsion flow properties by using model monodisperse emulsion systems with narrow, controllable droplet size distributions. Using a microfluidic flow focusing device, dodecane-in-water emulsions with diameters between 50 to 100 m with polydispersities less than 5% were produced, as characterized by pulsed field gradient nuclear magnetic resonance and optical microscopy. Due to the relatively large size of the droplets, it was only possible to examine the creamed phase of the emulsion. Samples of known polydispersity were made by mixing known quantities of two monodisperse emulsions. The monodisperse and bimodal emulsions were then subjected to rotational and oscillatory shear flow using a controlled stress rheometer to determine the effects of droplet size and size distribution on emulsion flow properties. Rotational and oscillatory rheological experiments showed that the monodisperse emulsions had two distinct behaviours: foam-like with appreciable thixotropy and yield stresses as well as emulsion-like with no evident thixotropy. The transition between these two behaviours appears to happen at a critical droplet radius between 33 and 37 micrometres. The rheological properties of the bimodal emulsions was split into three distinct behaviours. In samples that could be considered a matrix of large droplets perturbed by smaller droplets, the flow properties were similar to those of the constituent emulsion with the larger droplets. Increasing the number fraction of smaller droplets to a 1:1 ratio creates an entirely new phase with significantly reduced elastic properties. Surprisingly, when the emulsion primarily consists of small droplets, the flow properties are most similar to that of the large droplets. Additionally, despite the microstructural differences, all emulsions showed flow characteristics typical of soft glassy materials above the glass transition temperature. These results demonstrate the significant influence of microstructure on emulsion rheology, where altering the droplet size or polydispersity essentially creates a new phase with its own unique flow properties that is not simply a combination of the properties of the individual monodisperse components that make up the sampl