Molecular dynamics simulation of the coalescence of surfactant-laden droplets.

We investigate the coalescence of surfactant-laden water droplets by using several different surfactant types and a wide range of concentrations by means of a coarse-grained model obtained by the statistical associating fluid theory. Our results demonstrate in detail a universal mass transport mechanism of surfactant across many concentrations and several surfactant types during the process. Coalescence initiation is seen to occur via a single pinch due to aggregation of surface surfactant, and its remnants tend to become engulfed in part inside the forming bridge. Across the board we confirm the existence of an initial thermal regime with constant bridge width followed by a later inertial regime with bridge width scaling roughly as the square root of time, but see no evidence of an intermediate viscous regime. Coalescence becomes slower as surfactant concentration grows, and we see evidence of the appearance of a further slowdown of a different nature for several times the critical concentration. We anticipate that our results provide further insights in the mechanisms of coalescence of surfactant-laden droplets.

Role and Effect of Meso-Structuring Surfactants on Properties and Formation Mechanism of Microfluidic-Enabled Mesoporous Silica Microspheres.

We have shown in a previous work that the combination of the emulsion solvent evaporation technique and droplet-based microfluidics allows for the synthesis of well-defined monodisperse mesoporous silica microcapsules (hollow microspheres), whose size, shape and composition may be finely and easily controlled. In this study, we focus on the crucial role played by the popular Pluronic® P123 surfactant, used for controlling the mesoporosity of synthesised silica microparticles. We show in particular, that although both types of initial precursor droplets, prepared with and without P123 meso-structuring agent, namely P123+ and P123- droplets, have a similar diameter (≃30 µm) and a similar TEOS silica precursor concentration (0.34 M), the resulting microparticles exhibit two noticeably different sizes and mass densities. Namely, 10 µm and 0.55 g/cm3 for P123+ microparticles, and 5.2 µm and 1.4 g/cm3 for P123- microparticles. To explain such differences, we used optical and scanning electron microscopies, small-angle X-ray diffraction and BET measurements to analyse structural properties of both types of microparticles and show that in the absence of Pluronic molecules, P123- microdroplets divide during their condensation process, on average, into three smaller droplets before condensing into silica solid microspheres with a smaller size and a higher mass density than those obtained in the presence of P123 surfactant molecules. Based on these results and on condensation kinetics analysis, we also propose an original mechanism for the formation of silica microspheres in the presence and in the absence of the meso-structuring and pore-forming P123 molecules.

Unidirectional Droplet Propulsion onto Gradient Brushes without External Energy Supply.

Using extensive molecular dynamics simulation of a coarse-grained model, we demonstrate the possibility of sustained unidirectional motion (durotaxis) of droplets without external energy supply when placed on a polymer brush substrate with stiffness gradient in a certain direction. The governing key parameters for the specific substrate design studied, which determine the durotaxis efficiency, are found to be the grafting density of the brush and the droplet adhesion to the brush surface, whereas the strength of the stiffness gradient, the viscosity of the droplet, or the length of the polymer chains of the brush have only a minor effect on the process. It is shown that this durotaxial motion is driven by the steady increase of the interfacial energy between droplet and brush as the droplet moves from softer to stiffer parts of the substrate whereby the mean driving force gradually declines with decreasing roughness of the brush surface. We anticipate that our findings indicate further possibilities in the area of nanoscale motion without external energy supply.

Effect of temperature and surfactants on evaporation and contact line dynamics of sessile drops.

Researches on droplet evaporation has a vast range of applications in different fields. The mechanisms of droplets evaporation have been a topic of investigation for decades. The droplet after spreading on the substrate exhibits constant evaporation rate for a constant base diameter and decreasing contact angle; followed by another evaporation mode with constant contact angle and decreasing base diameter; and finally, evaporation with decreasing of both contact angle and base diameter. In the present study, the evaporation rate and mechanisms influenced by surfactant and temperature effects are analysed. The evaporation was demonstrated to be related to the dynamics of the sessile droplet spreading ability and the depinning event. It remains complex to predict the evaporation of the sessile droplet due to the continuous change in surfactant local concentration. Moreover, the temperature change modifies the surface tension and the induced inner flows. These two questions find answers in the triple line dynamic which controls the evaporation rate. The forces controlling the depinning with surfactant was quantified. A clear constant force was found following depinning. Such dynamic equilibrium demonstrates also the effect of the friction, surface roughness and moreover the limit of surfactant concentration in the triple line direct vicinity. The evaporation rate shows two particularities: one is the classical decrease of the evaporation rate after depinning; the second in case of surfactant, there is an enhancement appearing at later droplet lifetime, which could be a consequence of film evaporation contributing to the evaporation near the triple line. The local evaporation does not change significantly despite the change in the contact angle with respect to surfactant concentration. The substrate temperature enhances evaporation rate. The coupled temperature and surfactant effect show a local evaporation rate decreasing with surfactant concentration increase at ambient temperature (around 20 °C) and enhancement with surfactant concentration at higher temperature.

Hierarchical Self-Assembly of Dipolar ZnO Nanoparticles and Microdroplets.

In this work, we investigated the orientation and the polarization of ZnO nanoparticles, which serve as building blocks of highly monodisperse microspheres, using a droplet microfluidic-assisted synthesis method. We observe, for the first time, a square lattice organization of liquid microdroplets, in a steady state, at the oil/water interface. Such square organization reveals clearly a dipolar organization of ZnO nanoparticles at the surfaces of droplets at the early stage of ZnO nanocrystal aggregation and microsphere formation. We discuss different models of organization of ZnO nanoparticles and show that the well-known tip-streaming effect in droplets in microfluidics explains the reason for the obtained dipolar droplets. The square organization is illustrated and explained.

Heterogeneous nanofluids: natural convection heat transfer enhancement.

Convective heat transfer using different nanofluid types is investigated. The domain is differentially heated and nanofluids are treated as heterogeneous mixtures with weak solutal diffusivity and possible Soret separation. Owing to the pronounced Soret effect of these materials in combination with a considerable solutal expansion, the resulting solutal buoyancy forces could be significant and interact with the initial thermal convection. A modified formulation taking into account the thermal conductivity, viscosity versus nanofluids type and concentration and the spatial heterogeneous concentration induced by the Soret effect is presented. The obtained results, by solving numerically the full governing equations, are found to be in good agreement with the developed solution based on the scale analysis approach. The resulting convective flows are found to be dependent on the local particle concentration φ and the corresponding solutal to thermal buoyancy ratio N. The induced nanofluid heterogeneity showed a significant heat transfer modification. The heat transfer in natural convection increases with nanoparticle concentration but remains less than the enhancement previously underlined in forced convection case.