arXiv subjects

M. N. Popescu

Publications and source records attributed to M. N. Popescu.

At least 19 recordsLinked to original sources

arXiv2020

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 non-vanishing 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.

cond-mat.soft↗

arXiv2018

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. \textbf{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 \textit{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.

cond-mat.soft↗

arXiv2018

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.

cond-mat.soft↗

arXiv2017

Shape-dependent guidance of active Janus particles by chemically patterned surfaces

Self-phoretic Janus particles move by inducing -- via non-equilibrium chemical reactions occurring on their surfaces -- changes in the chemical composition of the solution in which they are immersed. This process leads to gradients in chemical composition along the surface of the particle, as well as along any nearby boundaries, including solid walls. Chemical gradients along a wall can give rise to chemi-osmosis, i.e., the gradients drive surface flows which, in turn, drive flow in the volume of the solution. This bulk flow couples back to the particle, and thus contributes to its self-motility. Since chemi-osmosis strongly depends on the molecular interactions between the diffusing molecular species and the wall, the response flow induced and experienced by a particle encodes information about any chemical patterning of the wall. Here, we extend previous studies on self-phoresis of a sphere near a chemically patterned wall to the case of particles with elongated shape. We focus our analysis on the new phenomenology potentially emerging from the coupling -- which is inoperative for a spherical shape -- of the elongated particle to the strain rate tensor of the chemi-osmotic flow. Via numerical calculations, we show that the dynamics of a rod-like particle exhibits a novel "edge-following" steady state: the particle translates along the edge of a chemical step at a steady distance from the step and with a steady orientation. Within a certain range of system parameters, the edge-following state co-exists with a "docking" state (the particle stops at the step, oriented perpendicular to the step edge), i.e., a bistable dynamics occurs. These findings are rationalized as a consequence of the competition between fluid vorticity and the rate of strain by using analytical theory based on the point-particle approximation which captures quasi-quantitatively the dynamics of the system.

cond-mat.soft↗

arXiv2017

Active colloids in the context of chemical kinetics

We study a mesoscopic model of a chemically active colloidal particle which on certain parts of its surface promotes chemical reactions in the surrounding solution. For reasons of simplicity and conceptual clarity, we focus on the case in which only electrically neutral species are present in the solution and on chemical reactions which are described by first order kinetics. Within a self-consistent approach we explicitly determine the steady state product and reactant number density fields around the colloid as functionals of the interaction potentials of the various molecular species in solution with the colloid. By using Teubner's reciprocal theorem, this allows us to compute and to interpret -- in a transparent way in terms of the classical Smoluchowski theory of chemical kinetics -- the external force needed to keep such a catalytically active colloid at rest (\textit{stall} force) or, equivalently, the corresponding velocity of the colloid \textit{if} it is free to move. We use the particular case of triangular-well interaction potentials as a benchmark example for applying the general theoretical framework developed here. For this latter case, we derive explicit expressions for the dependences of the quantities of interest on the diffusion coefficients of the chemical species, the reaction rate constant, the coverage by catalyst, the size of the colloid, as well as on the parameters of the interaction potentials. These expressions provide a detailed picture of the phenomenology associated with catalytically-active colloids and self-diffusiophoresis.

cond-mat.soft↗

arXiv2016

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 chemi-osmosis, providing an additional contribution to self-motility. Chemi-osmosis 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 chemi-osmotic flows can cause particles to either "dock" at the chemical step between the two materials, or to 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.

cond-mat.soft↗

arXiv2016

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.

cond-mat.soft↗

arXiv2016

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 active particles trapped at a fluid-fluid interface. To this end we consider a mean-field model 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.

cond-mat.soft↗

arXiv2016

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

Micron-sized particles moving through 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.

cond-mat.soft↗

arXiv2016

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.

cond-mat.soft↗

arXiv2016

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.

cond-mat.soft↗

arXiv2012

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 rather 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.

cond-mat.soft↗

arXiv2011

Pulling and Pushing a Cargo With a Catalytically Active Carrier

Catalytically active particles suspended in a liquid can move due to self-phoresis by generating solute gradients via chemical reactions of the solvent occurring at parts of their surface. Such particles can be used as carriers at the micro-scale. As a simple model for a carrier-cargo system we consider a catalytically active particle connected by a thin rigid rod to a catalytically inert cargo particle. We show that the velocity of the composite strongly depends on the relative orientation of the carrier-cargo link. Accordingly, there is an optimal configuration for the linkage. The subtlety of such carriers is underscored by the observation that a spherical particle completely covered by catalyst, which is motionless when isolated, acts as a carrier once attached to a cargo.

cond-mat.soft↗

arXiv2010

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.

cond-mat.stat-mech↗

arXiv2009

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 its 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.

cond-mat.soft↗

arXiv2007

Confinement-induced enhancement of diffusiophoretic forces on self-propellers

We study the effect of spatial confinement on the strength of propulsive diffusiophoretic forces acting on a particle that generates density gradients by exploiting the chemical free energy of its environment. Using a recently proposed simple model of a self-propelling device driven by chemical reactions taking place on some parts of its surface, we demonstrate that the force significantly increases in the presence of confining walls. We also show that such effects become even more pronounced in two-dimensional systems.

cond-mat.stat-mech↗

arXiv2007

Spreading in narrow channels

We study a lattice model for the spreading of fluid films, which are a few molecular layers thick, in narrow channels with inert lateral walls. We focus on systems connected to two particle reservoirs at different chemical potentials, considering an attractive substrate potential at the bottom, confining side walls, and hard-core repulsive fluid-fluid interactions. Using kinetic Monte Carlo simulations we find a diffusive behavior. The corresponding diffusion coefficient depends on the density and is bounded from below by the free one-dimensional diffusion coefficient, valid for an inert bottom wall. These numerical results are rationalized within the corresponding continuum limit.

cond-mat.stat-mech↗

arXiv2006

Binary Reactive Adsorbate on a Random Catalytic Substrate

We study the equilibrium properties of a model for a binary mixture of catalytically-reactive monomers adsorbed on a two-dimensional substrate decorated by randomly placed catalytic bonds. The interacting $A$ and $B$ monomer species undergo continuous exchanges with particle reservoirs and react ($A + B \to \emptyset$) as soon as a pair of unlike particles appears on sites connected by a catalytic bond. For the case of annealed disorder in the placement of the catalytic bonds this model can be mapped onto a classical spin model with spin values $S = -1,0,+1$, with effective couplings dependent on the temperature and on the mean density $q$ of catalytic bonds. This allows us to exploit the mean-field theory developed for the latter to determine the phase diagram as a function of $q$ in the (symmetric) case in which the chemical potentials of the particle reservoirs, as well as the $A-A$ and $B-B$ interactions are equal.

cond-mat.stat-mech↗