Equilibrium interactions between particles in aqueous suspensions are limited to distances less than 1 μm. Here, we describe a versatile concept to design and engineer nonequilibrium interactions whose magnitude and direction depends on the surface chemistry of the suspended particles, and whose range may extend over hundreds of microns and last thousands of seconds. The mechanism described here relies on diffusiophoresis, in which suspended particles migrate in response to gradients in solution. Three ingredients are involved: a soluto-inertial "beacon" designed to emit a steady flux of solute over long time scales; suspended particles that migrate in response to the solute flux; and the solute itself, which mediates the interaction. We demonstrate soluto-inertial interactions that extend for nearly half a millimeter and last for tens of minutes, and which are attractive or repulsive, depending on the surface chemistry of the suspended particles. Experiments agree quantitatively with scaling arguments and numerical computations, confirming the basic phenomenon, revealing design strategies, and suggesting a broad set of new possibilities for the manipulation and control of suspended particles.olloidal suspensions and emulsions of 10-nm to 10-μm particles play a central role in a wide variety of industrial, technological, biological, and everyday processes. Everyday goods, including shampoos, inks, vaccines, paints, and foodstuffs as well as industrial products such as drilling muds, ceramics, and pesticides, rely fundamentally on stably suspended microparticles for their creation and/or operation. This incredible versatility derives from the extensive variety of properties (e.g., mechanical, optical, and chemical) attainable in suspension through a generic set of physicochemical strategies (1-4). A proper understanding of the stability and dynamics of suspensions in general thus underpins both fundamental science and technological applications.The properties and performance of suspensions depend preeminently on the effective interactions between particles. The celebrated Derjaguin-Landau-Verwey-Overbeek (DLVO) theory (5-7) balances electrostatic interactions (typically repulsive) between charged colloids-as screened by ions in the surrounding electrolyte-against van der Waals attractions, and successfully predicts the stability, phase behavior, and response of electrostatically stabilized suspensions. Additional (non-DLVO) forces can also be used to stabilize or destabilize colloidal suspensions. Grafted or adsorbed macromolecules provide short-range steric repulsions that stabilize suspended particles against van der Waals-induced flocculation (8-11). By contrast, nonadsorbed macromolecules that remain dispersed in solution introduce entropic depletion attractions whose strength and range is set by the size and concentration of depletants (12, 13). Such depletion interactions scale with thermal energy (k B T), and thus enable tunable and reversible attractions (14, 15). Clever design of shaped or patterned coll...
Surfactants play a ubiquitous role in many areas of science and technology, and gradients often form-either spontaneously or intentionally-in a variety of nonequilibrium situations and processes. We visualize and measure the diffusiophoretic migration of latex colloids in response to gradients of cationic and anionic surfactants, both below and above the critical micelle concentration (cmc). Below the cmc, colloidal migration can be described using classic theories for diffusiophoresis under electrolyte gradients, although subtleties and distinctions do appear. Cationic surfactants adsorb onto anionic colloids, changing the surface charge and thus reversing the direction of diffusiophoretic migration. Above the cmc, diffusiophoretic mobilties decrease by orders of magnitude. We argue this to occur because charged monomers (rather than micelles) dominate colloidal diffusiophoresis. Because monomer concentrations remain essentially constant above the cmc, surfactant gradients imposed above the cmc result in very small monomer gradients-and, therefore, very weak diffusiophoresis. Our findings suggest conceptual strategies to understand diffusiophoresis in the presence of surfactants, as well as strategies to predict and design systems that harness them.
Structures and particles that slowly release solute into solution can attract or repel other particles in suspension via diffusiophoresis, a process we termed “soluto-inertial (SI) interactions.” These SI interactions involve “beacons” that establish and sustain nonequilibrium solute fluxes over long durations. Here, we demonstrate the versatility of the SI concept and introduce distinct strategies to manipulate solute gradients and, hence, suspension behavior using beacons with different physicochemical properties. First, we demonstrate on-demand particle migration using beacons that can be actuated with a trigger. We then show the synergy between multiple, distinct beacons that modify solute fluxes in a way that allows directed, yet selective, colloidal migration to specific target sites. Moreover, this multibeacon harmony enhances migration velocities, and delays the equilibration of the SI effect. The different SI techniques highlighted here suggest previously unidentified possibilities for sorting and separating colloidal mixtures, targeting particle delivery, and enhancing rates of suspension flocculation.
The delivery of small particles into porous environments remains highly challenging because of the low permeability to the fluids that carry these colloids. Even more challenging is that the specific location of targets in the porous environment usually is not known and cannot be determined from the outside. Here, we demonstrate a two-step strategy to deliver suspended colloids to targets that are “hidden” within closed porous media. The first step serves to automatically convert any hidden targets into soluto-inertial “beacons,” capable of sustaining long-lived solute outfluxes. The second step introduces the deliverable objects, which are designed to autonomously migrate against the solute fluxes emitted by the targets, thereby following chemical trails that lead to the target. Experimental and theoretical demonstrations of the strategy lay out the design elements required for the solute and the deliverable objects, suggesting routes to delivering colloidal objects to hidden targets in various environments and technologies.
Two simple model aqueous foams, one made from a perfluoroalkyl surfactant and one from a silicone polyether surfactant, are compared with regard to their stability in contact with heptane as a model fuel oil. The observed foam stabilities are explained in terms of the equilibrium phase behavior of the system water–surfactant–heptane. It is demonstrated that the fundamental enabling factor that makes perfluoroalkyl surfactant perform exceedingly well in stabilizing foams on hydrocarbon fuel oil is its oleophobicity. For hydrocarbon or silicone surfactants, the propensity for the surfactant phase to solubilize hydrocarbon oil and be solubilized in the oil destabilizes the foam. This is particularly so if the surfactant’s phase inversion by temperature (PIT) range falls within the application temperature range.
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