Early freezing dynamics of an aqueous foam.

Phase-change is an essential and unavoidable process to obtain solid foam. We study experimentally the solidification dynamics of a model aqueous foam in contact with a cold substrate. The substrate temperature, the foam bubble radius and the liquid fraction are changed. We show that the freezing dynamics always starts by following a self-similar square root of time diffusive dynamics. These early dynamics are then predicted as a function of the control parameters using a 1D diffusion model and by treating our foam as a homogeneous fluid with equivalent thermophysical properties. In particular, we build a new expression for the foam conductivity. Finally, experimental and theoretical results are compared and interpreted. This study paves the way towards the understanding of the complex foam freezing dynamics at longer times, when the freezing is then coupled to water migration in the foam.

Contact Line Catch Up by Growing Ice Crystals.

The effect of freezing on contact line motion is a scientific challenge in the understanding of the solidification of capillary flows. In this Letter, we experimentally investigate the spreading and freezing of a water droplet on a cold substrate. We demonstrate that solidification stops the spreading because the ice crystals catch up with the advancing contact line. Indeed, we observe the formation and growth of ice crystals along the substrate during the drop spreading, and show that their velocity equals the contact line velocity when the drop stops. Modeling the growth of the crystals, we predict the shape of the crystal front and show that the substrate thermal properties play a major role on the frozen drop radius.

Nanoparticle-Coated Microbubbles for Combined Ultrasound Imaging and Drug Delivery.

Biomedical microbubbles stabilized by a coating of magnetic or drug-containing nanoparticles show great potential for theranostics applications. Nanoparticle-coated microbubbles can be made to be stable, to be echogenic, and to release the cargo of drug-containing nanoparticles with an ultrasound trigger. This Article reviews the design principles of nanoparticle-coated microbubbles for ultrasound imaging and drug delivery, with a particular focus on the physical chemistry of nanoparticle-coated interfaces; the formation, stability, and dynamics of nanoparticle-coated bubbles; and the conditions for controlled nanoparticle release in ultrasound. The emerging understanding of the modes of nanoparticle expulsion and of the transport of expelled material by microbubble-induced flow is paving the way toward more efficient nanoparticle-mediated drug delivery. This Article highlights the knowledge gap that still remains to be addressed before we can control these phenomena.

Dynamic capillary assembly of colloids at interfaces with 10,000g accelerations.

High-rate deformation of soft matter is an emerging area central to our understanding of far-from-equilibrium phenomena during shock, fracture, and phase change. Monolayers of colloidal particles are a convenient two-dimensional model system to visualise emergent behaviours in soft matter, but previous studies have been limited to slow deformations. Here we probe and visualise the evolution of a monolayer of colloids confined at a bubble surface during high-rate deformation driven by ultrasound. We observe the emergence of a transient network of strings, and use discrete particle simulations to show that it is caused by a delicate interplay of dynamic capillarity and hydrodynamic interactions between particles oscillating at high frequency. Remarkably for a colloidal system, we find evidence of inertial effects, caused by accelerations approaching 10,000g. These results also suggest that extreme deformation of soft matter offers new opportunities for pattern formation and dynamic self-assembly.

Dynamic Organization of Ligand-Grafted Nanoparticles during Adsorption and Surface Compression at Fluid-Fluid Interfaces.

Monolayers of ligand-grafted nanoparticles at fluid interfaces exhibit a complex response to deformation due to an interplay of particle rearrangements within the monolayer, and molecular rearrangements of the ligand brush on the surface of the particles. We use grazing-incidence small-angle X-ray scattering (GISAXS) combined with pendant drop tensiometry to probe in situ the dynamic organization of ligand-grafted nanoparticles upon adsorption at a fluid-fluid interface, and during monolayer compression. Through the simultaneous measurements of interparticle distance, obtained from GISAXS, and of surface pressure, obtained from pendant drop tensiometry, we link the interfacial stress to the monolayer microstructure. The results indicate that, during adsorption, the nanoparticles form rafts that grow while the interparticle distance remains constant. For small-amplitude, slow compression of the monolayer, the evolution of the interparticle distance bears a signature of ligand rearrangements leading to a local decrease in thickness of the ligand brush. For large-amplitude compression, the surface pressure is found to be strongly dependent on the rate of compression. Two-dimensional Brownian dynamics simulations show that the rate-dependent features are not due to jamming of the monolayer, and suggest that they may be due to out-of-plane reorganization of the particles (for instance expulsion or buckling). The corresponding GISAXS patterns are also consistent with out-of-plane reorganization of the nanoparticles.

High-frequency linear rheology of hydrogels probed by ultrasound-driven microbubble dynamics.

Ultrasound-driven microbubble dynamics are central to biomedical applications, from diagnostic imaging to drug delivery and therapy. In therapeutic applications, the bubbles are typically embedded in tissue, and their dynamics are strongly affected by the viscoelastic properties of the soft solid medium. While the behaviour of bubbles in Newtonian fluids is well characterised, a fundamental understanding of the effect on ultrasound-driven bubble dynamics of a soft viscoelastic medium is still being developed. We characterised the resonant behaviour in ultrasound of isolated microbubbles embedded in agarose gels, commonly used as tissue-mimicking phantoms. Gels with different viscoelastic properties were obtained by tuning agarose concentration, and were characterised by standard rheological tests. Isolated bubbles (100-200 µm) were excited by ultrasound (10-50 kHz) at small pressure amplitudes (<1 kPa), to ensure that the deformation of the material and the bubble dynamics remained in the linear regime. The radial dynamics of the bubbles were recorded by high-speed video microscopy. Resonance curves were measured experimentally and fitted to a model combining the Rayleigh-Plesset equation governing bubble dynamics, with the Kelvin-Voigt model for the viscoelastic medium. The resonance frequency of the bubbles was found to increase with increasing shear modulus of the medium, with implications for optimisation of imaging and therapeutic ultrasound protocols. In addition, the viscoelastic properties inferred from ultrasound-driven bubble dynamics differ significantly from those measured at low frequency with the rheometer. Hence, rheological characterisation of biomaterials for medical ultrasound applications requires particular attention to the strain rate applied.

Stability of Clay Particle-Coated Microbubbles in Alkanes against Dissolution Induced by Heating.

We investigated the dissolution and morphological dynamics of air bubbles in alkanes stabilized by fluorinated colloidal clay particles when subjected to temperature changes. A model for bubble dissolution with time-dependent temperature reveals that increasing the temperature enhances the bubble dissolution rate in alkanes, opposite to the behavior in water, because of the differing trends in gas solubility. Experimental results for uncoated air bubbles in decane and hexadecane confirm this prediction. Clay-coated bubbles in decane and hexadecane are shown to be stable in air-saturated oil at constant temperature, where dissolution is driven mainly by the Laplace pressure. When the temperature increases from ambient, the particle-coated bubbles are prone to dissolution as the oil phase becomes undersaturated. The interfacial layer of particles is observed to undergo buckling and crumpling, without shedding of clay particles. Increasing the concentration of particles is shown to enhance the bubble stability by providing a higher resistance to dissolution. When subjected to complex temperature cycles, for which the effect of time-dependent temperature is dominant, the clay-coated bubbles can resist long-term dissolution in conditions under which uncoated bubbles dissolve completely. These results underpin the design of ultrastable oil foams stabilized by solid particles with improved shelf life under changing environmental conditions.

Shape oscillations of particle-coated bubbles and directional particle expulsion.

Bubbles stabilised by colloidal particles can find applications in advanced materials, catalysis and drug delivery. For applications in controlled release, it is desirable to remove the particles from the interface in a programmable fashion. We have previously shown that ultrasound waves excite volumetric oscillations of particle-coated bubbles, resulting in precisely timed particle expulsion due to interface compression on a ultrafast timescale [Poulichet et al., Proc. Natl. Acad. Sci. U. S. A., 2015, 112, 5932]. We also observed shape oscillations, which were found to drive directional particle expulsion from the antinodes of the non-spherical deformation. In this paper we investigate the mechanisms leading to directional particle expulsion during shape oscillations of particle-coated bubbles driven by ultrasound at 40 kHz. We perform high-speed visualisation of the interface shape and of the particle distribution during ultrafast deformation at a rate of up to 104 s-1. The mode of shape oscillations is found to not depend on the bubble size, in contrast with what has been reported for uncoated bubbles. A decomposition of the non-spherical shape in spatial Fourier modes reveals that the interplay of different modes determines the locations of particle expulsion. The n-fold symmetry of the dominant mode does not always lead to desorption from all 2n antinodes, but only those where there is favourable alignment with the sub-dominant modes. Desorption from the antinodes of the shape oscillations is due to different, concurrent mechanisms. The radial acceleration of the interface at the antinodes can be up to 105-106 ms-2, hence there is a contribution from the inertia of the particles localised at the antinodes. In addition, we found that particles migrate to the antinodes of the shape oscillation, thereby enhancing the contribution from the surface pressure in the monolayer.

Droplets in Microchannels: Dynamical Properties of the Lubrication Film.

We study the motion of droplets in a confined, micrometric geometry, by focusing on the lubrication film between a droplet and a wall. When capillary forces dominate, the lubrication film thickness evolves nonlinearly with the capillary number due to the viscous dissipation between the meniscus and the wall. However, this film may become thin enough (tens of nanometers) that intermolecular forces come into play and affect classical scalings. Our experiments yield highly resolved topographies of the shape of the interface and allow us to bring new insights into droplet dynamics in microfluidics. We report the novel characterization of two dynamical regimes as the capillary number increases: (i) at low capillary numbers, the film thickness is constant and set by the disjoining pressure, while (ii) above a critical capillary number, the interface behavior is well described by a viscous scenario. At a high surfactant concentration, structural effects lead to the formation of patterns on the interface, which can be used to trace the interface velocity, that yield direct confirmation of the boundary condition in the viscous regime.

A versatile technology for droplet-based microfluidics: thermomechanical actuation.

We report on a versatile technique for microfluidic droplet manipulation that proves effective at every step: from droplet generation to propulsion to sorting, rearrangement or break-up. Non-wetting droplets are thermomechanically actuated in a microfluidic chip using local heating resistors. Controlled temperature variation induces local dilation of the PDMS wall above the resistor, which drives the droplet away from the hot (i.e. constricted) region (B. Selva, I. Cantat and M.-C. Jullien, Phys. Fluids, 2011, 23, 052002). Adapted placing and actuation of such resistors thus allow us to push forward, stop, store and release, or even break up droplets, at the price of low electric power consumption (<150 mW). We believe this technically accessible method to provide a useful tool for droplet microfluidics.

Bubbles and foams in microfluidics.

Microfluidics offers great tools to produce highly-controlled dispersions of gas into liquid, from isolated bubbles to organized microfoams. Potential technological applications are manifold, from novel materials to scaffolds for tissue engineering or enhanced oil recovery. More fundamentally, microfluidics makes it possible to investigate the physics of complex systems such as foams at scales where the capillary forces become dominant, in model experiments involving few well-controlled parameters. In this context, this review does not have the ambition to detail in a comprehensive manner all the techniques and applications involving bubbles and foams in microfluidics. Rather, it focuses on particular consequences of working at the microscale, under confinement, and hopes to provide insight into the physics of such systems. The first part of this work focuses on bubbles, and more precisely on (i) bubble generation, where the confinement can suppress capillary instabilities while inertial effects may play a role, and (ii) bubble dynamics, paying special attention to the lubrication film between bubble and wall and the influence of confinement. The second part addresses the formation and dynamics of microfoams, emphasizing structural differences from macroscopic foams and the influence of the confinement.

A Review of Heating and Temperature Control in Microfluidic Systems: Techniques and Applications.

This review presents an overview of the different techniques developed over the last decade to regulate the temperature within microfluidic systems. A variety of different approaches has been adopted, from external heating sources to Joule heating, microwaves or the use of lasers to cite just a few examples. The scope of the technical solutions developed to date is impressive and encompasses for instance temperature ramp rates ranging from 0.1 to 2,000 °C/s leading to homogeneous temperatures from -3 °C to 120 °C, and constant gradients from 6 to 40 °C/mm with a fair degree of accuracy. We also examine some recent strategies developed for applications such as digital microfluidics, where integration of a heating source to generate a temperature gradient offers control of a key parameter, without necessarily requiring great accuracy. Conversely, Temperature Gradient Focusing requires high accuracy in order to control both the concentration and separation of charged species. In addition, the Polymerase Chain Reaction requires both accuracy (homogeneous temperature) and integration to carry out demanding heating cycles. The spectrum of applications requiring temperature regulation is growing rapidly with increasingly important implications for the physical, chemical and biotechnological sectors, depending on the relevant heating technique.