N.A.

Janus colloidal particles show remarkable properties in terms of surface activity, self-assembly and wetting. Moreover they can perform autonomous motion if they can chemically react with the liquid in which they are immersed. In order to understand the self-propelled motion of catalytic Janus colloids at the air-water interface, wetting and the orientation of the catalytic surface are important properties to be investigated. Wetting plays a central role in active motion since it determines the contact between fuel and catalytic surface as well as the efficiency of transduction of chemical reaction into motion. Active motion is not expected to occur either when the catalytic face is completely out of the aqueous phase or when the Janus boundaries are parallel to the interfacial plane. The design of a Janus colloid possessing two hydrophilic faces is required to allow the catalytic face to react with the fuel (e.g. H2O2 for Platinum) in water and to permit some rotational freedom of the Janus colloid in order to generate propulsion parallel to the interfacial plane.Here, we discuss some theoretical aspects that should be accounted when studying Janus colloids at the surface of water. The free energy of ideal Janus colloidal particles at the interface is modeled as a function of the immersion depth and the particle orientation. Analytical expressions of the energy profiles are established. Energetic aspects are then discussed in relation to the particle ability to rotate at the interface. By introducing contact angle hysteresis we describe how the effects of contact line pinning modifies the scenario described in the ideal case. Experimental observations of the contact angle hysteresis of Janus colloids at the interface reveal the effect of pinning; and orientations of silica particles half covered with a platinum layer at the interface do not comply with the ideal scenarios. Experimental observations suggest that Janus colloids at the fluid interface behave as kinetically driven system, where the contact line motion over defects decorating the Janus faces rules the orientation and rotational diffusion of the particle.

The interface between two fluids is never flat at the nanoscale, and this is important for transport across interfaces. In absence of any external field, the surface roughness is due to thermally excited capillary waves possessing subnanometric amplitudes in the case of simple liquids. Here, we investigate the effect of ultrasound on the surface roughness of liquid-gas and liquid-liquid interfaces. MHz frequency ultrasound was applied normal to the interface at relatively low ultrasonic pressures (< 0.6 MPa), and the amplitudes of surface fluctuations have been measured by light reflectivity and ellipsometry. We found a dramatic enhancement of surface roughness, roughly linear with intensity, with vertical displacements of the interface as high as 50-100 nm. As a consequence, the effective contact area between two fluids can be increased by ultrasound. This result has a clear impact for enhancing interface based processes such as mass or heat transfer.

Dynamics of anisotropic particles at a fluid interface governs trapping and particles subsequentassembly. Measuring and controlling this viscous dynamics open the way to new materials [1], andapplications [2]. Despite these domains of applications, measurements of the viscous coefficient ofanisotropic particles were mainly restricted to the bulk [3-4] or in quasi-2D confinement between twoglass plates [5]. Here we measure the complete set of viscous coefficients of single micrometricprolate ellipsoids near and trapped at an air-water interface. These coefficients are obtained from theBrownian motion of the particle coupling interferometry and particle tracking. For particles trapped atthe interface we measured anomalously large drags even larger than in the bulk water (ratio of surface/bulk rotational drags rR > 1 in Figure) [6]. Such an intriguing behaviour is discussed in terms ofadditional random forces due to thermally activated fluctuations of the interface and their coupling tothe particle drag through the fluctuation–dissipation theorem.Figure: Rotational viscous-drag ratio rR (surface/bulk) of polystyrene ellipsoidal particles at anair/water interface versus particle’s aspect ratio φ. Inset: mean square angular displacements (MSADs)versus the time lag τ.[1] M. Cavallaro, L. Botto, E. Lewandowski, M. Wang, and K. Stebe, PNAS 108, 20923 (2011).[2] Z. Huang, D. Legendre, and P. Guiraud, Chem. Eng. Sci. 66, 982 (2011).[3] D. Mukhija and M. Solomon, J. Colloid Interface Sci. 314, 98 (2007).[4] T. H. Besseling, M. Hermes, A. Kuijk et al., Journal of Physics: Condensed Matter 27, 194109 (2015).[5] Y. Han, A. Alsayed, M. Nobili, J. Zhang, T. Lubensky, and A. Yodh, Science 314, 626 (2006).[6] G. Boniello, C. Blanc, D. Fedorenko, M. Medfai, N. Ben Mbarek, M. In, M. Gross, A. Stocco, M. Nobili,Nature Materials 14, 908 (2015).

The interface between a liquid and a fluid affects dramatically both the interactions and the motion of colloidal particles. In this talk, the impact of partial wetting dynamics on the motion of passive and active colloids will be presented. First, experimental results on the Brownian dynamics of micrometric spherical silica colloids andpolymeric ellipsoids trapped at a planar air-water interface will be described. Partial wetting defines a contact angle which sets the immersion depth of the colloid. Particle motion is confined in the interfacial plane. For spherical colloids, the contact angle is finely tuned in the range 30°-140° by surface treatments and measured in situ. Translational and rotational diffusion coefficients of colloids trapped at the water interface are obtained by particle tracking video-microscopy. Counter-intuitively, the friction felt by the colloid increases when the contact angle increases; i.e. when particles are less immersed in water and more in air, which has a negligible viscosity. To explain the slowing down of the translational motion for spheres and rotational diffusion for ellipsoids, an extra friction term originating from contact line fluctuations will be introduced.The second part of the talk deals with the motion of isolated active Janus colloids at the surface of water. Spherical catalytic Janus colloids have been prepared coating half surface of silica particles by a thin platinum layer. Immersion depth of the Janus colloids as well as their orientation with respect to the water surface reveal thecomplex wetting properties of Janus particles. The active motion of Janus colloids at the interface in the presence of various concentration of hydrogen peroxide has been studied. The types of trajectories, directional and circular ones observed revealed the effective force and torque induced by the catalytic decomposition of H2O2. At the water surface, active colloids perform more persistent directional motions as compared to the motions performed in the bulk. This has been interpreted as due to the loss of degrees of freedom resulting from the confinement at interfaceand also to the partial wetting conditions that possibly bring new contributions to the rotational friction at interface.

Janus colloidal particles show remarkable properties in terms of surface activity, self-assembly and wetting. Moreover they can perform autonomous motion if they can chemically react with the liquid in which they are immersed. In order to understand the self-propelled motion of catalytic Janus colloids at the air-water interface, wetting and the orientation of the catalytic surface are important properties to be investigated. Wetting plays a central role in active motion since it determines the contact between fuel and catalytic surface as well as the efficiency of transduction of chemical reaction into motion. Active motion is not expected to occur either when the catalytic face is completely out of the aqueous phase or when the Janus boundaries are parallel to the interfacial plane. The design of a Janus colloid possessing two hydrophilic faces is required to allow the catalytic face to react with the fuel (e.g. H2O2 for Platinum) in water and to permit some rotational freedom of the Janus colloid in order to generate propulsion parallel to the interfacial plane.Here, we discuss some theoretical aspects that should be accounted when studying Janus colloids at the surface of water. The free energy of ideal Janus colloidal particles at the interface is modeled as a function of the immersion depth and the particle orientation. Analytical expressions of the energy profiles are established. Energetic aspects are then discussed in relation to the particle ability to rotate at the interface. By introducing contact angle hysteresis we describe how the effects of contact line pinning modifies the scenario described in the ideal case. Experimental observations of the contact angle hysteresis of Janus colloids at the interface reveal the effect of pinning; and orientations of silica particles half covered with a platinum layer at the interface do not comply with the ideal scenarios. Experimental observations suggest that Janus colloids at the fluid interface behave as kinetically driven system, where the contact line motion over defects decorating the Janus faces rules the orientation and rotational diffusion of the particle.

We study the dynamics of individual polystyrene ellipsoids of different aspect ratios trapped at the air-water interface. Using particle tracking and in situ vertical scanning interferometry techniques we are able to measure translational drags and the protrusion in air of the ellipsoids. We report that translational drags on the ellipsoid are unexpectedly enhanced: despite the fact that a noticeable part of the ellipsoid is in air, drags are found larger than the bulk one in water.