Diffusiophoresis in non-adsorbing polymer solutions: the Asakura-Oosawa model and stratification in drying films

A colloidal particle placed in an inhomogeneous solution of smaller non-adsorbing polymers will move towards regions of lower polymer concentration, in order to reduce the free energy of the interface between the surface of the particle and the solution. This phenomenon is known as diffusiophoresis. Treating the polymer as penetrable hard spheres, as in the Asakura-Oosawa model, a simple analytic expression for the diffusiophoretic drift velocity can be obtained. In the context of drying films we show that diffusiophoresis by this mechanism can lead to stratification under easily accessible experimental conditions. By stratification we mean spontaneous formation of a layer of polymer on top of a layer of the colloid. Transposed to the case of binary colloidal mixtures, this offers an explanation for the stratification observed recently in these systems [A. Fortini et al, Phys. Rev. Lett. 116, 118301 (2016)]. Our results emphasise the importance of treating solvent dynamics explicitly in these problems, and caution against the neglect of hydrodynamic interactions or the use of implicit solvent models in which the absence of solvent backflow results in an unbalanced osmotic force which gives rise to large but unphysical effects.Comment: 11 pages, 6 figure

The dynamics of a self-phoretic Janus swimmer near a wall

We study the effect of a nearby planar wall on the propulsion of a phoretic Janus micro-swimmer driven by asymmetric reactions on its surface which absorb reactants and generate products. We show that the behaviour of these swimmers near a wall can be classified ${\bf based \ on \ whether}$ the swimmers are ${\bf mainly}$ absorbing or producing reaction solutes ${\bf and \ whether}$ their swimming directions are such that the inert or active face is at the front. We find that the wall-induced solute gradients always promote swimmer propulsion along the wall while the effect of hydrodynamics leads to re-orientation of the swimming direction away from the wall.Comment: 6 pages, 6 figure

How a "pinch of salt" can tune chaotic mixing of colloidal suspensions

Efficient mixing of colloids, particles or molecules is a central issue in many processes. It results from the complex interplay between flow deformations and molecular diffusion, which is generally assumed to control the homogenization processes. In this work we demonstrate on the contrary that despite fixed flow and self-diffusion conditions, the chaotic mixing of colloidal suspensions can be either boosted or inhibited by the sole addition of trace amount of salt as a co-mixing species. Indeed, this shows that local saline gradients can trigger a chemically-driven transport phenomenon, diffusiophoresis, which controls the rate and direction of molecular transport far more efficiently than usual Brownian diffusion. A simple model combining the elementary ingredients of chaotic mixing with diffusiophoretic transport of the colloids allows to rationalize our observations and highlights how small-scale out-of-equilibrium transport bridges to mixing at much larger scales in a very effective way. Considering chaotic mixing as a prototypal building block for turbulent mixing, this suggests that these phenomena, occurring whenever the chemical environment is inhomogeneous, might bring interesting perspective from micro-systems up to large-scale situations, with examples ranging from ecosystems to industrial contexts.Comment: Submitte

Colloidal motility and pattern formation under rectified diffusiophoresis

In this letter, we characterize experimentally the diffusiophoretic motion of colloids and lambda- DNA toward higher concentration of solutes, using microfluidic technology to build spatially- and temporally-controlled concentration gradients. We then demonstrate that segregation and spatial patterning of the particles can be achieved from temporal variations of the solute concentration profile. This segregation takes the form of a strong trapping potential, stemming from an osmotically induced rectification mechanism of the solute time-dependent variations. Depending on the spatial and temporal symmetry of the solute signal, localization patterns with various shapes can be achieved. These results highlight the role of solute contrasts in out-of-equilibrium processes occuring in soft matter

Particle self-diffusiophoresis near solid walls and interfaces

This paper was presented at the 4th Micro and Nano Flows Conference (MNF2014), which was held at University College, London, UK. The conference was organised by Brunel University and supported by the Italian Union of Thermofluiddynamics, IPEM, the Process Intensification Network, the Institution of Mechanical Engineers, the Heat Transfer Society, HEXAG - the Heat Exchange Action Group, and the Energy Institute, ASME Press, LCN London Centre for Nanotechnology, UCL University College London, UCL Engineering, the International NanoScience Community, www.nanopaprika.eu.The purpose of this paper is to explore, from a theoretical viewpoint, the mechanisms whereby locomotion of low-Reynolds-number organisms and particles is affected by the presence of nearby no-slip surfaces and free capillary surfaces. First, we explore some simple models of the unsteady dynamics of low- Reynolds-number swimmers near a no-slip wall and driven by an arbitrarily imposed tangential surface slip. Next, the self-diffusiophoresis of a class of two-faced Janus particles propelled by the production of gradients in the concentration of a solute diffusing into a surrounding fluid at zero Reynolds and P´eclet numbers is studied, both in free space and near a no-slip wall. The added difficulty now is that the tangential slip is not arbitrarily chosen but is given by the solution of a separate boundary value problem for the solute concentration. Finally, an analysis of a model system is used to identify a mechanism whereby a non-self-propelling swimmer can harness the effects of surface tension and deformability of a nearby free surface to propel itself along it. The challenge here is that it is a free boundary problem requiring determination of the surface shape as part of the solution