Ring-shaped colloidal patterns on saline water films.

HYPOTHESIS: Electrostatically stabilised colloidal particles destabilise when brought into contact with cations causing the particles to aggregate in clusters. When a drop with stabilised colloidal partices is deposited on a liquid film containing cations the delicate balance between the fluid-mechanical and physicochemical properties of the system governs the spreading dynamics and formation of colloidal particle clusters. EXPERIMENTS: High-speed imaging and digital holographic microscopy were used to characterise the spreading process. FINDINGS: We reveal that a spreading colloidal drop evolves into a ring-shaped pattern after it is deposited on a thin saline water film. Clustered colloidal particles aggregate into larger trapezoidally-shaped 'supraclusters'. Using a simple model we show that the trapezoidal shape of the supraclusters is determined by the transition from inertial spreading dynamics to Marangoni flow. These results may be of interest to applications such as wet-on-wet inkjet printing, where particle destabilisation and hydrodynamic flow coexist.

Realization of the Brazil-nut effect in charged colloids without external driving.

Sedimentation is a ubiquitous phenomenon across many fields of science, such as geology, astrophysics, and soft matter. Sometimes, sedimentation leads to unusual phenomena, such as the Brazil-nut effect, where heavier (granular) particles reside on top of lighter particles after shaking. We show experimentally that a Brazil-nut effect can be realized in a binary colloidal system of long-range repulsive charged particles driven purely by Brownian motion and electrostatics without the need for activity. Using theory, we argue that not only the mass-per-charge for the heavier particles needs to be smaller than the mass-per-charge for the lighter particles but also that at high overall density, the system can be trapped in a long-lived metastable state, which prevents the occurrence of the equilibrium Brazil-nut effect. Therefore, we envision that our work provides valuable insights into the physics of strongly interacting systems, such as partially glassy and crystalline structures. Finally, our theory, which quantitatively agrees with the experimental data, predicts that the shapes of sedimentation density profiles of multicomponent charged colloids are greatly altered when the particles are charge-regulating with more than one ion species involved. Hence, we hypothesize that sedimentation experiments can aid in revealing the type of ion adsorption processes that determine the particle charge and possibly the value of the corresponding equilibrium constants.

Evaporation of a Sessile Colloidal Water-Glycerol Droplet: Marangoni Ring Formation.

The transport and aggregation of particles in suspensions is an important process in many physicochemical and industrial processes. In this work, we study the transport of particles in an evaporating binary droplet. Surprisingly, the accumulation of particles occurs not only at the contact line (due to the coffee-stain effect) or at the solid substrate (due to sedimentation) but also at a particular radial position near the liquid-air interface, forming a "ring", which we term as the Marangoni ring. The formation of this ring is primarily attributed to the solutal Marangoni flow triggered by the evaporation dynamics of the water-glycerol droplet. Experiments and simulations show fair agreement in the volume evolution and the general structure of the solutal Marangoni flow, that is, the Marangoni vortex. Experiments show that the location of the Marangoni ring is strongly correlated with the Marangoni vortex. However, finite element numerical simulations fail to describe the particle distribution seen in the experiments. Interestingly, the particles not only accumulate to form the Marangoni ring but also assemble as colloidal crystals close to the liquid-air interface, yielding iridescence. The formation of the colloidal crystals in the experiments is strong evidence that non-hydrodynamic interactions, which are not represented in the simulations, also play a significant role in our system.

Speed-dispersion-induced alignment: A one-dimensional model inspired by swimming droplets experiments.

We investigate the collective dynamics of self-propelled droplets, confined in a one-dimensional microfluidic channel. On the one hand, neighboring droplets align and form large trains of droplets moving in the same direction. On the other hand, the droplets condensate, leaving large regions with very low density. A careful examination of the interactions between two "colliding" droplets demonstrates that local alignment takes place as a result of the interplay between the dispersion of their speeds and the absence of Galilean invariance. Inspired by these observations, we propose a minimalistic 1D model of active particles reproducing such dynamical rules and, combining analytical arguments and numerical evidences, we show that the model exhibits a transition to collective motion in 1D for a large range of values of the control parameters. Condensation takes place as a transient phenomena, which tremendously slows down the dynamics, before the system eventually settles into a homogeneous aligned phase.

Multivalent Patchy Colloids for Quantitative 3D Self-Assembly Studies.

We report methods to synthesize sub-micron- and micron-sized patchy silica particles with fluorescently labeled hemispherical titania protrusions, as well as routes to efficiently characterize these particles and self-assemble these particles into non-close-packed structures. The synthesis methods expand upon earlier work in the literature, in which silica particles packed in a colloidal crystal were surface-patterned with a silane coupling agent. Here, hemispherical amorphous titania protrusions were successfully labeled with fluorescent dyes, allowing for imaging by confocal microscopy and super-resolution techniques. Confocal microscopy was exploited to experimentally determine the numbers of protrusions per particle over large numbers of particles for good statistical significance, and these distributions were compared to simulations predicting the number of patches as a function of core particle polydispersity and maximum separation between the particle surfaces. We self-assembled these patchy particles into open percolating gel networks by exploiting solvophobic attractions between the protrusions.

Interrupted Motility Induced Phase Separation in Aligning Active Colloids.

Switching on high activity in a relatively dense system of active Janus colloids, we observe fast clustering, followed by cluster aggregation towards full phase separation. The phase separation process is however interrupted when large enough clusters start breaking apart. Following the cluster size distribution as a function of time, we identify three successive dynamical regimes. Tracking both the particle positions and orientations, we characterize the structural ordering and alignment in the growing clusters and thereby unveil the mechanisms at play in these regimes. In particular, we identify how alignment between the neighboring particles is responsible for the interruption of the full phase separation. Our large scale quantification of the phase separation kinetics in active colloids points towards the new physics observed when both alignment and short-range repulsions are present.

Repulsive van der Waals forces enable Pickering emulsions with non-touching colloids.

Emulsions stabilized by solid particles, called Pickering emulsions, offer promising applications in drug delivery, cosmetics, food science and the manufacturing of porous materials. This potential stems from their high stability against coalescence and 'surfactant-free' nature. Generally, Pickering emulsions require that the solid particles are wetted by both phases and as a result, the adsorption free energy is often large with respect to the thermal energy (kBT). Here we provide the first experimental proof for an alternative scenario: non-touching (effectively non-wetting), charged, particles that are completely immersed in the oil phase through a balance of charge induced attractions and repulsions caused by van der Waals forces. These particles nonetheless stabilize the emulsion. The main advantage of this novel adsorption mechanism is that these particles can easily be detached from the interface simply by adding salt. This not only makes the finding fundamentally of interest, but also enables a triggered de-emulsification and particle recovery, which is useful in fields like enhanced oil recovery, heterogeneous catalysis, and emulsion polymerization.

Charging of poly(methyl methacrylate) (PMMA) colloids in cyclohexyl bromide: locking, size dependence, and particle mixtures.

We studied suspensions of sterically stabilized poly(methyl methacrylate) (PMMA) particles in the solvent cyclohexyl bromide (CHB; εr = 7.92). We performed microelectrophoresis measurements on suspensions containing a single particle species and on binary mixtures, using confocal microscopy to measure the velocity profiles of the particles. We measured the charge of so-called locked PMMA particles, for which the steric stabilizer, a comb-graft stabilizer of poly(12-hydroxystearic acid) (PHSA) grafted on a backbone of PMMA, was covalently bonded to the particle, and for unlocked particles, for which the stabilizer was adsorbed to the surface of the particle. We observed that locked particles had a significantly higher charge than unlocked particles. We found that the charge increase upon locking was due to chemical coupling of 2-(dimethylamino)ethanol to the PMMA particles, which was used as a catalyst for the locking reaction. For particles of different size we obtained the surface potential and charge from the electrophoretic mobility of the particles. For locked particles we found that the relatively high surface potential (∼ +5.1 kBT/e or +130 mV) was roughly constant for all particle diameters we investigated (1.2 µm < σ < 4.4 µm), and that the particle charge was proportional to the square of the diameter.

Self-propulsion of pure water droplets by spontaneous Marangoni-stress-driven motion.

We report spontaneous motion in a fully biocompatible system consisting of pure water droplets in an oil-surfactant medium of squalane and monoolein. Water from the droplet is solubilized by the reverse micellar solution, creating a concentration gradient of swollen reverse micelles around each droplet. The strong advection and weak diffusion conditions allow for the first experimental realization of spontaneous motion in a system of isotropic particles at sufficiently large Péclet number according to a straightforward generalization of a recently proposed mechanism [S. Michelin, E. Lauga, and D. Bartolo, Phys. Fluids 25, 061701 (2013); S. Michelin and E. Lauga, J. Fluid Mech. 747, 572 (2014)]. Experiments with a highly concentrated solution of salt instead of water, and tetradecane instead of squalane, confirm the above mechanism. The present swimming droplets are able to carry external bodies such as large colloids, salt crystals, and even cells.

Effect of size polydispersity on the crystal-fluid and crystal-glass transition in hard-core repulsive Yukawa systems.

We investigated the effect of size polydispersity on the crystal-fluid transition in hard-core repulsive Yukawa systems by means of Monte Carlo simulations for several state points in the Yukawa parameter space. Size polydispersity was introduced in the system only with respect to the hard particle cores; particles with different diameters had the same surface potential ψ0, but the charge per particle was not varied with packing fraction or distance. We observed a shift to higher packing fraction of the crystal-fluid transition of bulk crystals with a fixed log-normal size distribution upon increasing the polydispersity, which was more pronounced for weakly charged particles (ψ0 ≈ 23 mV) compared to more highly charged particles (ψ0 ≈ 46 mV), and also more pronounced for larger Debye screening length. At high polydispersities (≥0.13) parts of the more highly charged systems that were initially crystalline became amorphous. The amorphous parts had a higher polydispersity than the crystalline parts, indicating the presence of a terminal polydispersity beyond which the homogeneous crystal phase was no longer stable.

Formation of dodecagonal quasicrystals in two-dimensional systems of patchy particles.

The behaviour of two-dimensional patchy particles with five and seven regularly arranged patches is investigated by computer simulation. For higher pressures and wider patch widths, hexagonal crystals have the lowest enthalpy, whereas at lower pressures and for narrower patches, lower density crystals with five nearest neighbours that are based on the (3(2),4,3,4) tiling of squares and triangles become lower in enthalpy. Interestingly, in regions of parameter space near to that where the hexagonal crystals become stable, quasicrystalline structures with dodecagonal symmetry form on cooling from high temperature. These quasicrystals can be considered as tilings of squares and triangles and are probably stabilized by the large configurational entropy associated with all the different possible such tilings. The potential for experimentally realizing such structures using DNA multi-arm motifs is also discussed.