Shear and dilational interfacial rheology of surfactant-stabilized droplets.

A new measurement method is suggested that is capable of probing the shear and dilational interfacial rheological responses of small droplets, those of size comparable to real emulsion applications. Freely suspended aqueous droplets containing surfactant and non-surface-active tracer particles are transported through a rectangular microchannel by the plane Poiseuille flow of the continuous oil phase. Optical microscopy and high-speed imaging record the shape and internal circulation dynamics of the droplets. Measured circulation velocities are coupled with theoretical descriptions of the droplet dynamics in order to determine the viscous (Boussinesq) and elastic (Marangoni) interfacial effects. A new Marangoni-induced stagnation point is identified theoretically and observed experimentally. Particle velocimetry at only two points (including gradients) in the droplet is sufficient to determine the amplitudes of the dilational and shear responses. We investigate the sensitivity for measuring interfacial properties and compare results from droplets stabilized by a small-molecule surfactant (butanol) and those stabilized by relatively large block copolymer molecules. Future increased availability of shear and dilational interfacial rheological properties is anticipated to lead to improved rules of thumb for emulsion preparation, stabilization, and general practice.