Droplet clustering in cyclodextrin-based emulsions mediated by methylcellulose

Rapid droplet aggregation in cyclodextrin (CD)-stabilized emulsions limits their practical use as material templates. Herein, we formulate mixtures of submicron CD-based emulsion droplets suspended in aqueous solutions of methylcellulose (MC) with various concentrations and molecular weights. We evaluate the effects of MC on the microstructure and stability of the emulsions using different techniques including optical microscopy, laser particle analysis, confocal laser scanning microscopy and multiple light scattering, explore the rheological behavior of the emulsions through large amplitude oscillatory shear experiments, and study the viscoelastic nonlinearities of the emulsions as a function of strain and strain-rate space through nondimensional elastic and viscous Lissajous-Bowditch plots. It is demonstrated that the emulsion droplets are present in the form of small clusters and their size is almost independent of MC concentration and molecular weight. The clustering pattern is also supported by the changes in viscoelastic properties of the emulsions and the intracycle nonlinear behavior of the Lissajous-Bowditch plots. We propose for the first time that glass-like dynamic arrest takes place with the formation of small equilibrium droplet clusters in the situation where the CD-based emulsion droplets are forced by depletion flocculation and kinetic trapping simultaneously exerted by MC.