Interface-mediated spontaneous symmetry breaking and mutual communication between drops containing chemically active particles.

Symmetry breaking and the emergence of self-organized patterns is the hallmark of complexity. Here, we demonstrate that a sessile drop, containing titania powder particles with negligible self-propulsion, exhibits a transition to collective motion leading to self-organized flow patterns. This phenomenology emerges through a novel mechanism involving the interplay between the chemical activity of the photocatalytic particles, which induces Marangoni stresses at the liquid-liquid interface, and the geometrical confinement provided by the drop. The response of the interface to the chemical activity of the particles is the source of a significantly amplified hydrodynamic flow within the drop, which moves the particles. Furthermore, in ensembles of such active drops long-ranged ordering of the flow patterns within the drops is observed. We show that the ordering is dictated by a chemical communication between drops, i.e., an alignment of the flow patterns is induced by the gradients of the chemicals emanating from the active particles, rather than by hydrodynamic interactions.

Self-Motility of an Active Particle Induced by Correlations in the Surrounding Solution.

Current models of phoretic transport rely on molecular forces creating a "diffuse" particle-fluid interface. We investigate theoretically an alternative mechanism, in which a diffuse interface emerges solely due to a nonvanishing correlation length of the surrounding solution. This mechanism can drive self-motility of a chemically active particle. Numerical estimates indicate that the velocity can reach micrometers per second. The predicted phenomenology includes a bilinear dependence of the velocity on the activity and a possible double velocity reversal upon varying the correlation length.

Axisymmetric spheroidal squirmers and self-diffusiophoretic particles.

We study, by means of an exact analytical solution, the motion of a spheroidal, axisymmetric squirmer in an unbounded fluid, as well as the low Reynolds number hydrodynamic flow associated to it. In contrast to the case of a spherical squirmer-for which, e.g. the velocity of the squirmer and the magnitude of the stresslet associated with the flow induced by the squirmer are respectively determined by the amplitudes of the first two slip ('squirming') modes-for the spheroidal squirmer each squirming mode either contributes to the velocity, or contributes to the stresslet. The results are straightforwardly extended to the self-phoresis of axisymmetric, spheroidal, chemically active particles in the case when the phoretic slip approximation holds.

Active Janus colloids at chemically structured surfaces.

If catalytically active Janus particles are dispersed in certain liquid solutions, they can create a gradient in the chemical composition of this solution along their surfaces, as well as along any nearby confining surfaces. This gradient drives self-propulsion via a self-phoretic mechanism, while the compositional gradient along a wall gives rise to chemiosmosis, which additionally contributes to self-motility. In this study, we analyze theoretically the dynamics of an active colloid near chemically patterned walls. We use a point-particle approximation combined with a multipole expansion in order to discuss the effects of pattern geometry and chemical contrast on the particle trajectories. In particular, we consider planar walls patterned with chemical steps and stripes. We investigate in detail the changes in the topology of the corresponding phase portraits upon varying the chemical contrast and the stripe width.

Effective squirmer models for self-phoretic chemically active spherical colloids.

Various aspects of self-motility of chemically active colloids in Newtonian fluids can be captured by simple models for their chemical activity plus a phoretic-slip hydrodynamic boundary condition on their surface. For particles of simple shapes (e.g., spheres) --as employed in many experimental studies-- which move at very low Reynolds numbers in an unbounded fluid, such models of chemically active particles effectively map onto the well studied so-called hydrodynamic squirmers (S. Michelin and E. Lauga, J. Fluid Mech. 747, 572 (2014)). Accordingly, intuitively appealing analogies of "pusher/puller/neutral" squirmers arise naturally. Within the framework of self-diffusiophoresis we illustrate the above-mentioned mapping and the corresponding flows in an unbounded fluid for a number of choices of the activity function (i.e., the spatial distribution and the type of chemical reactions across the surface of the particle). We use the central collision of two active particles as a simple, paradigmatic case for demonstrating that in the presence of other particles or boundaries the behavior of chemically active colloids may be qualitatively different, even in the far field, from the one exhibited by the corresponding "effective squirmer", obtained from the mapping in an unbounded fluid. This emphasizes that understanding the collective behavior and the dynamics under geometrical confinement of chemically active particles necessarily requires to explicitly account for the dependence of the hydrodynamic interactions on the distribution of chemical species resulting from the activity of the particles.

Self-diffusiophoresis induced by fluid interfaces.

The influence of a fluid-fluid interface on self-phoresis of chemically active, axially symmetric, spherical colloids is analyzed. Distinct from the studies of self-phoresis for colloids trapped at fluid interfaces or in the vicinity of hard walls, here we focus on the issue of self-phoresis close to a fluid-fluid interface. In order to provide physically intuitive results highlighting the role played by the interface, the analysis is carried out for the case that the symmetry axis of the colloid is normal to the interface; moreover, thermal fluctuations are not taken into account. Similarly to what has been observed near hard walls, we find that such colloids can be set into motion even if their whole surface is homogeneously active. This is due to the anisotropy along the direction normal to the interface owing to the partitioning by diffusion, among the coexisting fluid phases, of the product of the chemical reaction taking place at the colloid surface. Different from results corresponding to hard walls, in the case of a fluid interface the direction of motion, i.e., towards the interface or away from it, can be controlled by tuning the physical properties of one of the two fluid phases. This effect is analyzed qualitatively and quantitatively, both by resorting to a far-field approximation and via an exact, analytical calculation which provides the means for a critical assessment of the approximate analysis.

Perils of ad hoc approximations for the activity function of chemically powered colloids.

Colloids can achieve motility by promoting at their surfaces chemical reactions in the surrounding solution. A well-studied case is that of self-phoresis, in which motility arises due to the spatial inhomogeneities in the chemical composition of the solution and the distinct interactions of the solvent molecules and of the reaction products with the colloid. For simple models of such chemically active colloids, the steady-state motion in an unbounded solution can be derived analytically in closed form. In contrast, for such chemically active particles moving in the vicinity of walls, the derivation of closed-form and physically intuitive solutions of the equations governing their dynamics turns out to be a severe challenge even for simple models. Therefore, recent studies of these phenomena have employed numerical methods as well as approximate analytical approaches based on multipolar expansions. We discuss and clarify certain conceptual aspects concerning the latter type of approach, which arise due to ad hoc truncations of the underlying so-called activity function, which describes the distribution of chemical reactions across the surface of the particle.

Chemically active colloids near osmotic-responsive walls with surface-chemistry gradients.

Chemically active colloids move by creating gradients in the composition of the surrounding solution and by exploiting the differences in their interactions with the various molecular species in solution. If such particles move near boundaries, e.g. the walls of the container confining the suspension, gradients in the composition of the solution are also created along the wall. This give rise to chemi-osmosis (via the interactions of the wall with the molecular species forming the solution), which drives flows coupling back to the colloid and thus influences its motility. Employing an approximate 'point-particle' analysis, we show analytically that-owing to this kind of induced active response (chemi-osmosis) of the wall-such chemically active colloids can align with, and follow, gradients in the surface chemistry of the wall. In this sense, these artificial 'swimmers' exhibit a primitive form of thigmotaxis with the meaning of sensing the proximity of a (not necessarily discontinuous) physical change in the environment. We show that the alignment with the surface-chemistry gradient is generic for chemically active colloids as long as they exhibit motility in an unbounded fluid, i.e. this phenomenon does not depend on the exact details of the propulsion mechanism. The results are discussed in the context of simple models of chemical activity, corresponding to Janus particles with 'source' chemical reactions on one half of the surface and either 'inert' or 'sink' reactions over the other half.

Collective dynamics of chemically active particles trapped at a fluid interface.

Chemically active colloids generate changes in the chemical composition of their surrounding solution and thereby induce flows in the ambient fluid which affect their dynamical evolution. Here we study the many-body dynamics of a monolayer of spherically symmetric active particles trapped at a fluid-fluid interface. To this end we consider a model for the large-scale spatial distribution of particles which incorporates the direct pair interaction (including also the capillary interaction which is caused specifically by the interfacial trapping) as well as the effect of hydrodynamic interactions (including the Marangoni flow induced by the response of the interface to the chemical activity). The values of the relevant physical parameters for typical experimental realizations of such systems are estimated and various scenarios, which are predicted by our approach for the dynamics of the monolayer, are discussed. In particular, we show that the chemically-induced Marangoni flow can prevent the clustering instability driven by the capillary attraction.

Erratum: Effective Interaction between Active Colloids and Fluid Interfaces Induced by Marangoni Flows [Phys. Rev. Lett. 116, 078301 (2016)].

This corrects the article DOI: 10.1103/PhysRevLett.116.078301.

Guiding Catalytically Active Particles with Chemically Patterned Surfaces.

Catalytically active Janus particles suspended in solution create gradients in the chemical composition of the solution along their surfaces, as well as along any nearby container walls. The former leads to self-phoresis, while the latter gives rise to chemiosmosis, providing an additional contribution to self-motility. Chemiosmosis strongly depends on the molecular interactions between the diffusing chemical species and the wall. We show analytically, using an approximate "point-particle" approach, that by chemically patterning a planar substrate one can direct the motion of Janus particles: the induced chemiosmotic flows can cause particles to either "dock" at the chemical step between the two materials or follow a chemical stripe. These theoretical predictions are confirmed by full numerical calculations. Generically, docking occurs for particles which tend to move away from their catalytic caps, while stripe following occurs in the opposite case. Our analysis reveals the physical mechanisms governing this behavior.

Active colloids at fluid interfaces.

If an active Janus particle is trapped at the interface between a liquid and a fluid, its self-propelled motion along the interface is affected by a net torque on the particle due to the viscosity contrast between the two adjacent fluid phases. For a simple model of an active, spherical Janus colloid we analyze the conditions under which translation occurs along the interface and we provide estimates of the corresponding persistence length. We show that under certain conditions the persistence length of such a particle is significantly larger than the corresponding one in the bulk liquid, which is in line with the trends observed in recent experimental studies.

Effective Interaction between Active Colloids and Fluid Interfaces Induced by Marangoni Flows.

We show theoretically that near a fluid-fluid interface a single active colloidal particle generating, e.g., chemicals or a temperature gradient experiences an effective force of hydrodynamic origin. This force is due to the fluid flow driven by Marangoni stresses induced by the activity of the particle; it decays very slowly with the distance from the interface, and can be attractive or repulsive depending on how the activity modifies the surface tension. We show that, for typical systems, this interaction can dominate the dynamics of the particle as compared to Brownian motion, dispersion forces, or self-phoretic effects. In the attractive case, the interaction promotes the self-assembly of particles into a crystal-like monolayer at the interface.

Rheotaxis of spherical active particles near a planar wall.

For active particles the interplay between the self-generated hydrodynamic flow and an external shear flow, especially near bounding surfaces, can result in a rich behavior of the particles not easily foreseen from the consideration of the active and external driving mechanisms in isolation. For instance, under certain conditions, the particles exhibit "rheotaxis", i.e., they align their direction of motion with the plane of shear spanned by the direction of the flow and the normal of the bounding surface and move with or against the flow. To date, studies of rheotaxis have focused on elongated particles (e.g., spermatozoa), for which rheotaxis can be understood intuitively in terms of a "weather vane" mechanism. Here we investigate the possibility that spherical active particles, for which the "weather vane" mechanism is excluded due to the symmetry of the shape, may nevertheless exhibit rheotaxis. Combining analytical and numerical calculations, we show that, for a broad class of spherical active particles, rheotactic behavior may emerge via a mechanism which involves "self-trapping" near a hard wall owing to the active propulsion of the particles, combined with their rotation, alignment, and "locking" of the direction of motion into the shear plane. In this state, the particles move solely up- or downstream at a steady height and orientation.

Self-propulsion of a catalytically active particle near a planar wall: from reflection to sliding and hovering.

Micron-sized particles moving through a solution in response to self-generated chemical gradients serve as model systems for studying active matter. Their far-reaching potential applications will require the particles to sense and respond to their local environment in a robust manner. The self-generated hydrodynamic and chemical fields, which induce particle motion, probe and are modified by that very environment, including confining boundaries. Focusing on a catalytically active Janus particle as a paradigmatic example, we predict that near a hard planar wall such a particle exhibits several scenarios of motion: reflection from the wall, motion at a steady-state orientation and height above the wall, or motionless, steady "hovering." Concerning the steady states, the height and the orientation are determined both by the proportion of catalyst coverage and the interactions of the solutes with the different "faces" of the particle. Accordingly, we propose that a desired behavior can be selected by tuning these parameters via a judicious design of the particle surface chemistry.

Capillary rise dynamics of aqueous glycerol solutions in glass capillaries: a critical examination of the Washburn equation.

The classic description of capillary rise given by the Washburn equation was recently questioned in the light of experimental evidence for a velocity dependent dynamic contact angle at a moving contact line. We present a systematic investigation of the capillary rise dynamics of glycerol and aqueous glycerol solutions in vertical glass capillaries of various radii. For pure glycerol, the results of our experiments are in almost perfect agreement with the predictions of the Washburn equation using independently measured values for the liquid and capillary parameters. For aqueous glycerol solutions we observe discrepancies between the theoretical expectations and the experimental results, which are increasing with the water content of the solution. A thorough analysis, combined with scaling arguments, allows us to conclude that dynamic contact angle effects alone cannot provide a consistent explanation for these discrepancies. Rather, they can be perfectly accounted for if the mixture flowing in the capillary would have an effective, increased viscosity (in respect to the nominal value). We suggest and briefly discuss various mechanisms that could contribute to this observed behavior.

Precursor films in wetting phenomena.

The spontaneous spreading of non-volatile liquid droplets on solid substrates poses a classic problem in the context of wetting phenomena. It is well known that the spreading of a macroscopic droplet is in many cases accompanied by a thin film of macroscopic lateral extent, the so-called precursor film, which emanates from the three-phase contact line region and spreads ahead of the latter with a much higher speed. Such films have been usually associated with liquid-on-solid systems, but in the last decade similar films have been reported to occur in solid-on-solid systems. While the situations in which the thickness of such films is of mesoscopic size are fairly well understood, an intriguing and yet to be fully understood aspect is the spreading of microscopic, i.e. molecularly thin, films. Here we review the available experimental observations of such films in various liquid-on-solid and solid-on-solid systems, as well as the corresponding theoretical models and studies aimed at understanding their formation and spreading dynamics. Recent developments and perspectives for future research are discussed.

Phoretic motion of spheroidal particles due to self-generated solute gradients.

We study theoretically the phoretic motion of a spheroidal particle, which generates solute gradients in the surrounding unbounded solvent via chemical reactions active on its surface in a cap-like region centered at one of the poles of the particle. We derive, within the constraints of the mapping to classical diffusio-phoresis, an analytical expression for the phoretic velocity of such an object. This allows us to analyze in detail the dependence of the velocity on the aspect ratio of the polar and the equatorial diameters of the particle and on the fraction of the particle surface contributing to the chemical reaction. The particular cases of a sphere and of an approximation for a needle-like particle, which are the most common shapes employed in experimental realizations of such self-propelled objects, are obtained from the general solution in the limits that the aspect ratio approaches one or becomes very large, respectively.

Confinement effects on diffusiophoretic self-propellers.

We study theoretically the effects of spatial confinement on the phoretic motion of a dissolved particle driven by composition gradients generated by chemical reactions of their solvent, which are active only on certain parts of the particle surface. We show that the presence of confining walls increases in a similar way both the composition gradients and the viscous friction, and the overall result of these competing effects is an increase in the phoretic velocity of the particle. For the case of steric repulsion only between the particle and the product molecules of the chemical reactions, the absolute value of the velocity remains nonetheless rather small.