M. N. Popescu

Transport of cargo by catalytic Janus micro-motors

Catalytically active Janus micro-spheres are capable of autonomous motion and can potentially act as carriers for transportation of cargo at the micron-scale. Focusing on the cases in which a single or a pair of Janus micro-motors is used as carrier, we investigate the complex dynamics exhibited by various active carrier–cargo composites.

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.

Capillary Rise with Velocity-Dependent Dynamic Contact Angle

The classic description of the rate of capillary rise given by the Washburn equation, which assumes that the contact angle preserves the equilibrium value at all times, has been recently questioned in the light of the known experimental dependence of the dynamic contact angle on the velocity of the contact line. For a number of such proposed functions of velocity for the dynamic contact angle, we analyze the resulting dependences of the contact angle and of the time of rise, respectively, on the height of the capillary rise. By applying our results to the particular cases of a high-viscosity silicone oil and water, respectively, in a glass capillary, we show that, in general, strong similarities arise between the various approaches and the classic theory in what concerns the time dependence of the capillary rise, which explains the lack of consistent experimental evidence for deviations in the rate of capillary rise from the Washburn equation. However, for a strong dependency of the contact angle on the velocity in the range of small velocities, as in the case of water on glass, one of the models predicts significant deviations even for the time dependence of the capillary rise. Moreover, our results show that the time or height dependence of the contact angle during the capillary rise can clearly discriminate between the various models.

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.

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.

Wetting on structured substrates

Chemically patterned surfaces are of significant interest in the context of microfluidic applications, and miniaturization of such devices aims at generating structures on the nano-scale. Whereas on the micron scale purely macroscopic descriptions of liquid flow are valid, on the nanometre scale long-ranged inter-molecular interactions, thermal fluctuations such as capillary waves, and finally the molecular structure of the liquid become important. We discuss the most important conceptual differences between flow on chemically patterned substrates on the micron scale and on the nanometre scale, and formulate four design issues for nanofluidics related to channel width, channel separation, and channel bending radius. As a specific example of nano-scale transport we present a microscopic model for the dynamics of spreading of monolayers on homogeneous substrates. Kinetic Monte Carlo simulations of this model on a homogeneous substrate reveal a complex spatio-temporal structure of the extracted monolayer, which includes the emergence of interfaces and of scaling properties of density profiles. These features are discussed and rationalized within the corresponding continuum limit derived from the microscopic dynamics. The corresponding spreading behaviour on a patterned substrate is briefly addressed.

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.

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.

Model for spreading of liquid monolayers

Manipulating fluids at the nanoscale within networks of channels or chemical lanes is a crucial challenge in developing small scale devices to be used in microreactors or chemical sensors. In this context, ultrathin (i.e., monolayer) films, experimentally observed in spreading of nanodroplets or upon extraction from reservoirs in capillary rise geometries, represent an extreme limit which is of physical and technological relevance since the dynamics is governed solely by capillary forces. In this work we use kinetic Monte Carlo (KMC) simulations to analyze in detail a simple, but realistic model proposed by Phys. Rev. Lett. 76, 86 (1996)]] for the two-dimensional spreading on homogeneous substrates of a fluid monolayer which is extracted from a reservoir. Our simulations confirm the previously predicted time dependence of the spreading, X ( t--> infinity ) =A square root of t, with X (t) as the average position of the advancing edge at time t, and they reveal a nontrivial dependence of the prefactor A on the strength U0 of interparticle attraction and on the fluid density C0 at the reservoir as well as an U0 -dependent spatial structure of the density profile of the monolayer. The asymptotic density profile at long time and large spatial scale is carefully analyzed within the continuum limit. We show that including the effect of correlations in an effective manner into the standard mean-field description leads to predictions both for the value of the threshold interaction above which phase segregation occurs and for the density profiles in excellent agreement with KMC simulation results.