Recent advancements in microfluidic technology have allowed for the generation and control of complex chemical gradients; however, few general techniques can measure these spatio-temporal concentration profiles without fluorescent labeling. Here we describe a Fabry-Perot interferometric technique, capable of measuring concentration profiles in situ, without any chemical label, by tracking Fringes of Equal Chromatic Order (FECO). The technique has a sensitivity of 10(-5) RIU, which can be used to track local solute changes of ~0.05% (w/w). The technique is spatially resolved (1 μm) and easily measures evolving concentration fields with ~20 Hz rate. Here, we demonstrate by measuring the binary diffusion coefficients of various solutes and solvents (and their concentration-dependence) in both free solution and in polyethylene glycol diacrylate (PEG-DA) hydrogels.

Using a microfluidic multi-inlet coflow system, we show the Rayleigh-Plateau instability of adjacent, closely spaced fluid threads to be collective. Although droplet size distributions and breakup frequencies are unaffected by cooperativity when fluid threads are identical, breakup frequencies and wavelengths between mismatched fluid threads become locked due to this collective instability. Locking narrows the size distribution of drops that are produced from dissimilar threads, and thus the polydispersity of the emulsion. These observations motivate a hypothesized two-step mechanism for high internal phase emulsification, wherein coarse emulsion drops are elongated into close-packed fluid threads, which break into smaller droplets via a collective Rayleigh Plateau instability. Our results suggest that these elongated fluid threads break cooperatively, whereupon wavelength-locking reduces the ultimate droplet polydispersity of high-internal phase emulsions, consistent with experimental observations.

We describe a microrheological strategy that enables sensitive surface shear rheology measurements of surfactant-laden interfaces, with the capacity to simultaneously visualize deforming interfaces. This technique utilizes a ferromagnetic microbutton probe pinned to a fluid-fluid interface, and actively torqued or forced with externally controlled electromagnets. Various modes of operation are possible: Small-amplitude oscillatory rotations, which provide frequency-dependent viscoelastic shear moduli; controlled torque (analogous to fixing shear stress); controlled rotation rate (analogous to fixing strain rate); and imposed force (analogous to active, translational microrheology). The circular shape of the probe ensures pure shear strains (when driven to rotate). We describe the experimental apparatus, its measurement limits and sources of error. We then highlight its versatility and capabilities with measurements on a variety of qualitatively distinct systems, including purely viscous monolayers, block-copolymer interfaces, aging and evolving interfaces, colloidal monolayers, and bulk rheometry of Newtonian and viscoelastic materials, with sample volumes as small as 2 μl.

Foam and emulsion stability has long been believed to correlate with the surface shear viscosity of the surfactant used to stabilize them. Many subtleties arise in interpreting surface shear viscosity measurements, however, and correlations do not necessarily indicate causation. Using a sensitive technique designed to excite purely surface shear deformations, we make the most sensitive and precise measurements to date of the surface shear viscosity of a variety of soluble surfactants, focusing on SDS in particular. Our measurements reveal the surface shear viscosity of SDS to be below the sensitivity limit of our technique, giving an upper bound of order 0.01 μN·s/m. This conflicts directly with almost all previous studies, which reported values up to 10(3)-10(4) times higher. Multiple control and complementary measurements confirm this result, including direct visualization of monolayer deformation, for SDS and a wide variety of soluble polymeric, ionic, and nonionic surfactants of high- and low-foaming character. No soluble, small-molecule surfactant was found to have a measurable surface shear viscosity, which seriously undermines most support for any correlation between foam stability and surface shear rheology of soluble surfactants.