Lydéric Bocquet

Molecular Origin of Fast Water Transport in Carbon Nanotube Membranes: Superlubricity versus Curvature Dependent Friction

In this paper, we study the interfacial friction of water at graphitic interfaces with various topologies, water between planar graphene sheets, inside and outside carbon nanotubes, with the goal to disentangle confinement and curvature effects on friction. We show that the friction coefficient exhibits a strong curvature dependence; while friction is independent of confinement for the graphene slab, it decreases with carbon nanotube radius for water inside, but increases for water outside. As a paradigm the friction coefficient is found to vanish below a threshold diameter for armchair nanotubes. Using a statistical description of the interfacial friction, we highlight here a structural origin of this curvature dependence, mainly associated with a curvature-induced incommensurability between the water and carbon structures. These results support the recent experiments reporting fast transport of water in nanometric carbon nanotube membranes.

Slippage of water past superhydrophobic carbon nanotube forests in microchannels.

We present in this Letter an experimental characterization of liquid flow slippage over superhydrophobic surfaces made of carbon nanotube forests, incorporated in microchannels. We make use of a particle image velocimetry technique to achieve the submicrometric resolution on the flow profile necessary for accurate measurement of the surface hydrodynamic properties. We demonstrate boundary slippage on the Cassie superhydrophobic state, associated with slip lengths of a few microns, while a vanishing slip length is found in the Wenzel state when the liquid impregnates the surface. Varying the lateral roughness scale L of our carbon nanotube forest-based superhydrophobic surfaces, we demonstrate that the slip length varies linearly with L in line with theoretical predictions for slippage on patterned surfaces.

Giant osmotic energy conversion measured in a single transmembrane boron nitride nanotube

New models of fluid transport are expected to emerge from the confinement of liquids at the nanoscale, with potential applications in ultrafiltration, desalination and energy conversion. Nevertheless, advancing our fundamental understanding of fluid transport on the smallest scales requires mass and ion dynamics to be ultimately characterized across an individual channel to avoid averaging over many pores. A major challenge for nanofluidics thus lies in building distinct and well-controlled nanochannels, amenable to the systematic exploration of their properties. Here we describe the fabrication and use of a hierarchical nanofluidic device made of a boron nitride nanotube that pierces an ultrathin membrane and connects two fluid reservoirs. Such a transmembrane geometry allows the detailed study of fluidic transport through a single nanotube under diverse forces, including electric fields, pressure drops and chemical gradients. Using this device, we discover very large, osmotically induced electric currents generated by salinity gradients, exceeding by two orders of magnitude their pressure-driven counterpart. We show that this result originates in the anomalously high surface charge carried by the nanotube’s internal surface in water at large pH, which we independently quantify in conductance measurements. The nano-assembly route using nanostructures as building blocks opens the way to studying fluid, ionic and molecule transport on the nanoscale, and may lead to biomimetic functionalities. Our results furthermore suggest that boron nitride nanotubes could be used as membranes for osmotic power harvesting under salinity gradients.

Achieving large slip with superhydrophobic surfaces: Scaling laws for generic geometries

We investigate the hydrodynamic friction properties of superhydrophobic surfaces and quantify their superlubricating potential. On such surfaces, the contact of the liquid with the solid roughness is minimal, while most of the interface is a liquid-gas one, resulting in strongly reduced friction. We obtain scaling laws for the effective slip length at the surface in terms of the generic surface characteristics (roughness length scale, depth, solid fraction of the interface, etc.). These predictions are successfully compared to numerical results in various geometries (grooves, posts or holes). This approach provides a versatile framework for the description of slip on these composite surfaces. Slip lengths up to 100μm are predicted for an optimized patterned surface.

Dynamic clustering in active colloidal suspensions with chemical signaling.

In this Letter, we explore experimentally the phase behavior of a dense active suspension of self-propelled colloids. In addition to a solidlike and gaslike phase observed for high and low densities, a novel cluster phase is reported at intermediate densities. This takes the form of a stationary assembly of dense aggregates-resulting from a permanent dynamical merging and separation of active colloids-whose average size grows with activity as a linear function of the self-propelling velocity. While different possible scenarios can be considered to account for these observations-such as a generic velocity weakening instability recently put forward-we show that the experimental results are reproduced mathematically by a chemotactic aggregation mechanism, originally introduced to account for bacterial aggregation and accounting here for diffusiophoretic chemical interaction between colloidal swimmers.

Interfacial water at hydrophobic and hydrophilic surfaces: slip, viscosity, and diffusion.

The dynamics and structure of water at hydrophobic and hydrophilic diamond surfaces is examined via non-equilibrium Molecular Dynamics simulations. For hydrophobic surfaces under shearing conditions, the general hydrodynamic boundary condition involves a finite surface slip. The value of the slip length depends sensitively on the surface water interaction strength and the surface roughness; heuristic scaling relations between slip length, contact angle, and depletion layer thickness are proposed. Inert gas in the aqueous phase exhibits pronounced surface activity but only mildly increases the slip length. On polar hydrophilic surfaces, in contrast, slip is absent, but the water viscosity is found to be increased within a thin surface layer. The viscosity and the thickness of this surface layer depend on the density of polar surface groups. The dynamics of single water molecules in the surface layer exhibits a similar distinction: on hydrophobic surfaces the dynamics is purely diffusive, while close to a hydrophilic surface transient binding or trapping of water molecules over times of the order of hundreds of picoseconds occurs. We also discuss in detail the effect of the Lennard-Jones cutoff length on the interfacial properties.

Moisture-induced ageing in granular media and the kinetics of capillary condensation

In 1773 Coulomb recognized that the static properties of granular systems can be discussed in terms of the frictional properties between different layers, leading to his relationship between the angle of repose of a granular pile (θ0) and the coefficient of static friction µ s: tan θ0 =µs. Two centuries later, solid friction and granular media still present many puzzles. One such is that the coefficient of static friction depends on the time during which the solids remain in contact before the measurement. Here we show that this ageing effect is manifested too in the angle of repose of granular media and originates from capillary condensation of water vapour between the packed particles, leading to the formation of water bridges. By assuming that the kinetics of this process are governed by the thermally activated nucleation of bridges, we can reproduce both the time- and humidity-dependence of the ageing behaviour. Our results also clarify the kinetics of adsorption in porous media more generally.

Sedimentation and Effective Temperature of Active Colloidal Suspensions

In this paper, we investigate experimentally the non-equilibrium steady state of an active colloidal suspension under gravity field. The active particles are made of chemically powered colloids, showing self propulsion in the presence of an added fuel, here hydrogen peroxide. The active suspension is studied in a dedicated microfluidic device, made of permeable gel microstructures. Both the microdynamics of individual colloids and the global stationary state of the suspension under gravity – density profiles, number fluctuations – are measured with optical microscopy. This allows to connect the sedimentation length to the individual self-propelled dynamics, suggesting that in the present dilute regime the active colloids behave as ’hot’ particles. Our work is a first step in the experimental exploration of the out-of-equilibrium properties of artificial active systems.

Spatial cooperativity in soft glassy flows.

Amorphous glassy materials of diverse nature—concentrated emulsions, granular materials, pastes, molecular glasses—display complex flow properties, intermediate between solid and liquid, which are at the root of their use in many applications. A general feature of such systems, well documented yet not really understood, is the strongly nonlinear nature of the flow rule relating stresses and strain rates. Here we use a microfluidic velocimetry technique to characterize the flow of thin layers of concentrated emulsions, confined in gaps of different thicknesses by surfaces of different roughnesses. We find evidence for finite-size effects in the flow behaviour and the absence of an intrinsic local flow rule. In contrast to the classical nonlinearities of the rheological behaviour of amorphous materials, we show that a rather simple non-local flow rule can account for all the velocity profiles. This non-locality of the dynamics is quantified by a length, characteristic of cooperativity within the flow at these scales, that is unobservable in the liquid state (lower emulsion concentrations) and that increases with concentration in the jammed state. Beyond its practical importance for applications involving thin layers (for example, coatings), these non-locality and cooperativity effects have parallels in the behaviour of other glassy, jammed and granular systems, suggesting a possible fundamental universality.

A smooth future

Research on superhydrophobic materials has mostly focused on their extreme non-wettability. However, the implications of superhydrophobicity beyond wetting, in particular for transport phenomena, remain largely unexplored.