Studying surfactant mass transport through dynamic interfacial tension measurements: A review of the models, experiments, and the contribution of microfluidics.

Surfactant mass transport towards an interface plays a critical role during formation of emulsions, foams and in industrial processes where two immiscible phases coexist. The understanding of these mechanisms as experimentally observed by dynamic interfacial tension measurements, is crucial. In this review, theoretical models describing both equilibrated systems and surfactant kinetics are covered. Experimental results from the literature are analysed based on the nature of surfactants and the tensiometry methods used. The innovative microfluidic techniques that have become available to study both diffusion and adsorption mechanisms during surfactant mass transport are discussed and compared with classical methods. This review focuses on surfactant transport during formation of droplets or bubbles; stabilisation of dispersed systems is not discussed here.

A Strategy for Power Density Amelioration of Capacitive Reverse Electrodialysis Systems with a Single Membrane.

Blue energy refers to the osmotic energy released while combining solutions of different salinity. Recently, single-membrane-based capacitive reverse electrodialysis cells were developed for blue energy harvesting. The performance of these cells is limited by the low ion-electron flux transfer efficiency of the capacitive electrodes in the current operating regimes. To optimize it, we point out an original boosting strategy of using a secondary voltage source E0 placed in series with the capacitive concentration cell. The net recovered power is defined as the difference between the power dissipated in the load resistor and the power supplied by the secondary voltage. Experimental results indicate a maximum power density of 5.26 W·m-2 (where the salinity difference is 0.17 and 5.13 M), which corresponds to a 59.8% increase compared with its power density of 3.29 W·m-2 without boosting strategy. A good agreement on power density is reached for theoretical simulations and experimental results. Influential factors are systematically studied to further reveal the boosting strategy.

Shear thickening in presence of adhesive contact forces: The singularity of cornstarch.

HYPOTHESIS: A number of dense particle suspensions experience a dramatic increase in viscosity with the shear stress, up to a solid-like response. This shear-thickening process is understood as a transition under flow of the nature of the contacts - from lubricated to frictional - between initially repellent particles. Most systems are now assumed to fit in with this scenario, which is questionable. EXPERIMENT: Using an in-house pressure sensor array, we provide a spatio-temporal map of the normal stresses in the flows of two shear-thickening fluids: a stabilized calcium carbonate suspension, known to fit in with the standard scenario, and a cornstarch suspension, which spectacular thickening behavior remains poorly understood. FINDINGS: We evidence in cornstarch a unique, stable heterogeneous structure, which moves in the velocity direction and does not appear in calcium carbonate. Its nature changes from a stress wave to a rolling solid jammed aggregate at high solid fraction and small gap width. The modeling of these heterogenities points to an adhesive force between cornstarch particles at high stress, also evidenced in microscopic measurements. Cornstarch being also attractive at low stress, it stands out of the classical shear-thickening frame, and might be part of a larger family of adhesive and attractive shear-thickening fluids.

Fluidics for energy harvesting: from nano to milli scales.

A large amount of untapped energy sources surrounds us. In this review, we summarize recent works of water-based energy harvesting systems with operation scales ranging from miniature systems to large scale attempts. We focus particularly on the triboelectric energy, which is produced when a liquid and a solid come into contact, and on the osmotic energy, which is released when salt water and fresh water are mixed. For both techniques we display the state of the art understanding (including electrical charge separation, electro-osmotic currents and induced currents) and the developed devices. A critical discussion of present works confirms the significant progress of these water-based energy harvesting systems in all scales. However, further efforts in efficiency and performance amelioration are expected for these technologies to accelerate the industrialization and commercialization procedure.

Numerical computation of electrical potential on a gas evolving electrode.

Electrochemical systems using a gas evolving electrode, such as metal-air batteries or electrolyzers, are confronted with recurrent problems related to gas production. Indeed, the production of gas at the surface of the electrodes causes a masking of the active surface which induces overvoltages and unstable electrical signals in time. We propose here numerical computations that take into account the spatial heterogeneity of the electrode and allow to account for the size distribution of the produced bubbles. We compare these computations to experiments on a Platinum-Carbon plate cell in the presence or absence of electrolyte flow. They reproduce the observed behavior and allow us to predict the stability of the signals. They are also a guide for the synthesis of efficient electrodes.

Solvents govern rheology and jamming of polymeric bead suspensions.

Despite their apparent simplicity, suspensions of hard spheres in a Newtonian fluid show complex non-Newtonian behaviors and remain poorly understood. Recent works have pointed out the crucial role of interparticle contact forces in these behaviors. Here, we show that the same (polystyrene) particles, when immersed in different Newtonian solvents, show different behaviors at both the microscopic and macroscopic scales. Thanks to interparticle force measurements in each solvent together with rheological measurements, we show how the fine details of the pairwise particle interactions impact the macroscopic behavior. The rheological properties (shear thinning, shear thickening, jamming solid fraction value) of the suspensions, made up of same particles, are shown to depend on the nature of the solvent. Here, we highlight several mechanisms at the particle scale: the swelling of polymeric particles in an organic solvent, the role of colloidal repulsive forces and inertia for particles in a water solution, and the variation of the friction coefficient as a function of the load for particles immersed in silicone oils. Our study provides new quantitative data to test micromechanical models and simulations. It questions the interpretation of previous experimental works. Finally, it shows the need to systematically characterize the interparticle normal and tangential forces when studying a given suspension of hard spheres in a Newtonian fluid.

Can unmixed complex forming polymer surfactant formulations be injected into oil reservoirs or aquifers without clogging them?

In the context of enhanced oil recovery or soil remediation, we study the role of interactions between polymers and surfactants on the injectivity of formulations containing mixtures of polymers and surfactants. We show that contrary to the first intuition, the formation of aggregates in polymers surfactants formulations is not necessarily a hindrance to the injection of these formulations into pores. It is important above all to compare the size of aggregates according to the applied shear rate and the pore size to find the formulations that may induce clogging. We highlight a new positive and unexpected phenomenon. The small aggregates that do not lead to clogging ensure the transport of the surfactant vesicles in the porous medium and limit the adsorption of the latter.

Aging of cornstarch particles suspended in aqueous solvents at room temperature.

Starch suspensions are often used as model systems to demonstrate extreme shear-thickening effects. We study the aging of cornstarch particles in aqueous suspensions at room temperature by granulometry and rheological measurements. When starch is diluted in glycerol, no long-term changes are observed. The situation differs when water is used as solvent. For volume fractions up to 20 vol %, when the cornstarch suspensions in water are stored under continual agitation, we observe an increase in viscosity. When the cornstarch suspension is aged under quiescent conditions, no evolution of the particle size is observed. In the concentrated situation, the rheological properties vary independent of the storage condition. We show that the increase in viscosity is related to air trapped in the pore space and to the swelling of the granules and leakage of the amylopectin component of the starch into the surrounding water. The relative importance of the two processes depends upon the particle concentration and upon the energy brought to the system.

Highly conductive colloidal carbon based suspension for flow-assisted electrochemical systems.

Carbon suspension electrodes are promising for flow-assisted electrochemical energy storage systems. They serve as flowable electrodes in electrolyte solutions of flow batteries, or flow capacitors. They can also be used for other applications such as capacitive deionization of water. However, developments of such suspensions remain challenging. The suspensions should combine low viscosity and high electronic conductivity for optimized performances. In this work, we report a flowable aqueous carbon dispersion which exhibits a viscosity of only 2 Pa.s at a shear rate of 5 s-1 for a concentration of particles of 7 wt%. This suspension displays an electronic conductivity of 65 mS/cm, nearly two orders of magnitude greater than previously investigated related materials. The investigated suspensions are stabilized by sodium alginate and arabic gum in the presence of ammonium sulfate. Their use in flowable systems for the storage and discharge of electrical charges is demonstrated.

Effect of electrolyte flow on a gas evolution electrode.

In this study, the effect of flow of the electrolyte on an electrolysis cell and a zinc cell is investigated. The gain of energy brought by the flow is discussed and compared to the viscous losses in the cells. We point out that the balance between the gained electrical power and the viscous loss power is positive only if the hydrodynamic resistance of the circuit is correctly designed and further comment on the economical viability of the whole process. A model of the studied phenomena is proposed in the last section. This analytical model captures the dynamics of the process, gives the optimal flowing conditions and the limits of the energetical rentability of the process. This study shows that the use of flowing electrolyte in zinc-air batteries can be energetically profitable with the appropriate flowing conditions.

Integration of a soft dielectric composite into a cantilever beam for mechanical energy harvesting, comparison between capacitive and triboelectric transducers.

Flexible dielectrics that harvest mechanical energy via electrostatic effects are excellent candidates as power sources for wearable electronics or autonomous sensors. The integration of a soft dielectric composite (polydimethylsiloxane PDMS-carbon black CB) into two mechanical energy harvesters is here presented. Both are based on a similar cantilever beam but work on different harvesting principles: variable capacitor and triboelectricity. We show that without an external bias the triboelectric beam harvests a net density power of 0.3 [Formula: see text] under a sinusoidal acceleration of 3.9g at 40 Hz. In a variable capacitor configuration, a bias of 0.15 [Formula: see text] is required to get the same energy harvesting performance under the same working conditions. As variable capacitors' harvesting performance are quadratically dependent on the applied bias, increasing the bias allows the system to harvest energy much more efficiently than the triboelectric one. The present results make CB/PDMS composites promising for autonomous portable multifunctional systems and intelligent sensors.

Density waves in shear-thickening suspensions.

Shear thickening corresponds to an increase of the viscosity as a function of the shear rate. It is observed in many concentrated suspensions in nature and industry: water or oil saturated sediments, crystal-bearing magma, fresh concrete, silica suspensions, and cornstarch mixtures. Here, we reveal how shear-thickening suspensions flow, shedding light onto as yet non-understood complex dynamics reported in the literature. When shear thickening is important, we show the existence of density fluctuations that appear as periodic waves moving in the direction of flow and breaking azimuthal symmetry. They come with strong normal stress fluctuations of the same periodicity. The flow includes small areas of normal stresses of the order of tens of kilopascals and areas of normal stresses of the order of hundreds of pascals. These stress inhomogeneities could play an important role in the damage caused by thickening fluids in the industry.

Emulsion Destabilization by Squeeze Flow.

There is a large debate on the destabilization mechanism of emulsions. We present a simple technique using mechanical compression to destabilize oil-in-water emulsions. Upon compression of the emulsion, the continuous aqueous phase is squeezed out, while the dispersed oil phase progressively deforms from circular to honeycomb-like shapes. The films that separate the oil droplets are observed to thin and break at a critical oil/water ratio, leading to coalescence events. Electrostatic interactions and local droplet rearrangements do not determine film rupture. Instead, the destabilization occurs like an avalanche propagating through the system, starting at areas where the film thickness is smallest.

Impact of the Wetting Length on Flexible Blade Spreading.

We study the spreading of a Newtonian fluid by a deformable blade, a common industrial problem, characteristic of elastohydrodynamic situations. Here, we consider the case of a finite reservoir of liquid, emptying as the liquid is spread. We evidence the role of a central variable: the wetting length l_{w}, which sets a boundary between the wet and dry parts of the blade. We show that the deposited film thickness e depends quadratically with l_{w}. We study this problem experimentally and numerically by integration of the elastohydrodynamic equations, and finally propose a scaling law model to explain how l_{w} influences the spreading dynamics.

Stress Field inside the Bath Determines Dip Coating with Yield-Stress Fluids in Cylindrical Geometry.

We study experimentally and theoretically the thickness of the coating obtained by pulling out a rod from a reservoir of yield-stress fluid. Opposite to Newtonian fluids, the coating thickness for a fluid of large enough yield stress is determined solely by the flow inside the reservoir and not by the flow inside the meniscus. The stress field inside the reservoir determines the thickness of the coating layer. The thickness is observed to increase nonlinearly with the sizes of the rod and of the reservoir. We develop a theoretical framework that describes this behavior and allows us to precisely predict the coating thickness.

Chasing Aqueous Biphasic Systems from Simple Salts by Exploring the LiTFSI/LiCl/H2O Phase Diagram.

Aqueous biphasic systems (ABSs), in which two aqueous phases with different compositions coexist as separate liquids, were first reported more than a century ago with polymer solutions. Recent observations of ABS forming from concentrated mixtures of inorganic salts and ionic liquids raise the fundamental question of how "different" the components of such mixtures should be for a liquid-liquid phase separation to occur. Here we show that even two monovalent salts sharing a common cation (lithium) but with different anions, namely, LiCl and lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), may result in the formation of ABSs over a wide range of compositions at room temperature. Using a combination of experimental techniques and molecular simulations, we analyze the coexistence diagram and the mechanism driving the phase separation, arising from the different anion sizes. The understanding and control of ABS may provide new avenues for aqueous-based battery systems.

A new way to measure viscosity in droplet-based microfluidics for high throughput analysis.

In this work, we propose a new way to measure the viscosity of samples in a microfluidic device. By analysing the shape of droplets after an expansion, we can measure the viscosity of the phase inside the droplet knowing the surface tension between the two liquids, the flow rate, the geometry of the channel and the viscosity of the continuous phase. This work paves the way for future high throughput studies in the framework of digital microfluidics.

Shear Rheology Control of Wrinkles and Patterns in Graphene Oxide Films.

Drying graphene oxide (GO) films are subject to extensive wrinkling, which largely affects their final properties. Wrinkles were shown to be suitable in biotechnological applications; however, they negatively affect the electronic properties of the films. Here, we report on wrinkle tuning and patterning of GO films under stress-controlled conditions during drying. GO flakes assemble at an air-solvent interface; the assembly forms a skin at the surface and may bend due to volume shrinkage while drying. We applied a modification of evaporative lithography to spatially define the evaporative stress field. Wrinkle alignment is achieved over cm2 areas. The wavelength (i.e., wrinkle spacing) is controlled in the µm range by the film thickness and GO concentration. Furthermore, we propose the use of nanoparticles to control capillary forces to suppress wrinkling. An example of a controlled pattern is given to elucidate the potential of the technique. The results are discussed in terms of classical elasticity theory. Wrinkling is the result of bending of the wet solid skin layer assembled on a highly elastic GO dispersion. Wavelength selection is the result of energy minimization between the bending of the skin and the elastic deformation of the GO supporting dispersion. The results strongly suggest the possibility to tune wrinkles and patterns by simple physicochemical routes.

Giant Electrostriction of Soft Nanocomposites Based on Liquid Crystalline Graphene.

High electromechanical coupling is critical to perform effective conversion between mechanical and electrical energy for various applications of electrostrictive polymers. Herein, a giant electrostriction effect is reported in liquid crystalline graphene-doped dielectric elastomers. The materials are formulated by a phase-transfer method which allows the solubilization of graphenic monolayers in nonpolar solvents. Dielectric spectroscopy is combined with tensile test devices to measure the true electrostriction coefficients with differentiating the Maxwell stress effect. Because of their liquid crystal structure, the resultant composites show an ultralarge electrostriction coefficient (∼10-14 m2/V2 at 0.1 Hz) coupled with good reproducibility during cycles at high deformation rates. This work offers a promising pathway to design high-performance electrostrictive polymer composites as well as to provide insights into mechanisms of true electrostriction in electrically heterogeneous systems. The use of obtained materials as a supersensitive capacitive sensor is demonstrated.

Shear thinning in non-Brownian suspensions.

We study the flow of suspensions of non-Brownian particles dispersed into a Newtonian solvent. Combining capillary rheometry and conventional rheometry, we evidence a succession of two shear thinning regimes separated by a shear thickening one. Through X-ray radiography measurements, we show that during each of those regimes, the flow remains homogeneous and does not involve particle migration. Using a quartz-tuning fork based atomic force microscope, we measure the repulsive force profile and the microscopic friction coefficient µ between two particles immersed into the solvent, as a function of normal load. Coupling measurements from those three techniques, we propose that (1) the first shear-thinning regime at low shear rates occurs for a lubricated rheology and can be interpreted as a decrease of the effective volume fraction under increasing particle pressures, due to short-ranged repulsive forces and (2) the second shear thinning regime after the shear-thickening transition occurs for a frictional rheology and can be interpreted as stemming from a decrease of the microscopic friction coefficient at large normal load.