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Soft or rigid particles, suspended in a liquid melt, interact with an advancing solidification front in various industrial and natural processes, such as fabrication of particle-reinforced-composites, growth of crystals, cryopreservation, frost heave, and growth of sea ice. The particle dynamics relative to the front determine the microstructure as well as the functional properties of the solidified material. Previous studies have extensively investigated the interaction of foreign objects with a moving solid-liquid interface in pure melts while in most real-life systems, solutes or surface active impurities are almost always present. Here we study experimentally the interaction of spherical oil droplets with a moving planar ice-water interface, while systematically increasing the surfactant concentration in the bulk liquid, using

Foams can resist destabilizaton in ways that appear similar on a macroscopic scale, but the microscopic origins of the stability and the loss thereof can be quite diverse. Here, we compare both the macroscopic drainage and ultimate collapse of aqueous foams stabilized by either a partially hydrolyzed poly(vinyl alcohol) (PVA) or a nonionic low-molecular-weight surfactant (BrijO10) with the dynamics of individual thin films at the microscale. From this comparison, we gain significant insight regarding the effect of both surface stresses and intermolecular forces on macroscopic foam stability. Distinct regimes in the lifetime of the foams were observed. Drainage at early stages is controlled by the different stress-boundary conditions at the surfaces of the bubbles between the polymer and the surfactant. The stress-carrying capacity of PVA-stabilized interfaces is a result of the mutual contribution of Marangoni stresses and surface shear viscosity. In contrast, surface shear inviscidity and much weaker Marangoni stresses were observed for the nonionic surfactant surfaces, resulting in faster drainage times, both at the level of the single film and the macroscopic foam. At longer times, the PVA foams present a regime of homogeneous coalescence where isolated coalescence events are observed. This regime, which is observed only for PVA foams, occurs when the capillary pressure reaches the maximum disjoining pressure. A final regime is then observed for both systems where a fast coalescence front propagates from the top to the bottom of the foams. The critical liquid fractions and capillary pressures at which this regime is obtained are similar for both PVA and BrijO10 foams, which most likely indicates that collapse is related to a universal mechanism that seems unrelated to the stabilizer interfacial dynamics., Langmuir, 38 (35), ISSN:0743-7463, ISSN:1520-5827

Si congeler de la mayonnaise n’est pas recommandé, cela pourrait toutefois nous aider à comprendre la fabrication d’alliages métalliques, la cryopréservation des cellules ou encore la congélation des sols en hiver. Nous nous intéressons ici au cas des gouttes d’huile dans une émulsion, observées par microscopie confocale au cours de la congélation. De nombreux phénomènes physiques (transport, diffusion, solidification, instabilités) prennent place lors de ce processus, offrant aux physicien.ne.s un problème inédit aux multiples ramifications. Ces études pourraient améliorer notre compréhension de plusieurs phénomènes de solidification, naturels comme technologiques.

Complexation of polymers at liquid interfaces is an emerging technique to produce all-liquid printable and self-healing devices and membranes. It is crucial to control the assembly process, but the mechanisms at play remain unclear. Using two different reflectometric methods, we investigate the spontaneous growth of H-bonded PPO-PMAA (polypropylene oxide-polymetacrylic acid) membranes at a flat liquid-liquid interface. We find that the membrane thickness h grows with time t as h similar to t(1/2), which is reminiscent of a diffusion-limited process. However, counterintuitively, we observe that this process is faster as the PPO molar mass increases. We are able to rationalize these results with a model which considers the diffusion of the PPO chains within the growing membrane. The architecture of the latter is described as a gel-like porous network, with a pore size much smaller than the radius of the diffusing PPO chains, thus inducing entropic barriers that hinder the diffusion process. From the comparison between the experimental data and the result of the model, we extract some key piece of information about the microscopic structure of the membrane. This study opens the route toward the rational design of self-assembled membranes and capsules with optimal properties.

Soft or rigid particles, suspended in a liquid melt, interact with an advancing solidification front in various industrial and natural processes, such as fabrication of particle-reinforced-composites, growth of crystals, cryopreservation, frost heave, and growth of sea ice. The particle dynamics relative to the front determine the microstructure as well as the functional properties of the solidified material. The previous studies have extensively investigated the interaction of foreign objects with a moving solid-liquid interface in pure melts while in most real-life systems, solutes or surface active impurities are almost always present. Here we study experimentally the interaction of spherical oil droplets with a moving planar ice-water interface, while systematically increasing the surfactant concentration in the bulk liquid, using \emph{in situ} cryo-confocal microscopy. We demonstrate that a small amount of surfactant in the bulk liquid can instigate long-range droplet repulsion, extending over a length scale of 40 to 100µm, in contrast to the short-range predicted previously (

International audience; The recovery of metals from WEEE, Waste from Electrical and Electronic Equipment, is a major challenge to preserve natural resources. Hydrometallurgy, which consists in leaching metals is a promising method but generates large amounts of polluting effluents. In this study we design aqueous leaching foams, composed of 90% v/v of gas and 10% v/v of HCl solution to oxidize and dissolve copper. We take advantage of the oxidizing power of the dioxygen (O2) present in the air bubbles whose fast transfer through the foams enables an efficient oxidation of copper. We then extend the concept of leaching foams to another gas, ozone, to oxidize silver (Ag). We finally show that using an anionic surfactant to complex cupric ions helps improving the dissolution of the metal. These promising results open new recycling routes for metals contained in WEEE, with a lower environmental footprint.

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 $$\upmu \mathrm{W}/{\mathrm{cm}}^{2}$$ μ W / cm 2 under a sinusoidal acceleration of 3.9g at 40 Hz. In a variable capacitor configuration, a bias of 0.15 $$\mathrm{V}/\upmu \mathrm{m}$$ V / μ m 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.

Objects, such as droplets, bubbles, or particles, interact with a moving solidification front in several material processing routes. The consequences of this confrontation, varying from instantaneous engulfment to complete rejection of suspended objects, regulates the solidified microstructure and thus, the functional properties of the material. In this study, we utilize in situ cryo-confocal microscopy to investigate the interplay between thermal conductivity mismatch (of the object and the melt) and the role of solute, which both impact the geometry of the ice-water solidification front in different manners. First, we experimentally validate the theoretical predictions of physical models on the distortion of thermal fields in the presence of foreign objects. Subsequently, we report on the dominating effect of solute on the front curvature with the dynamic evolution of premelted films. In the case of cellular front morphology, we depict that particles with a lower thermal conductivity than water induce a distortion of the encircling ice crystals, thereby modifying the final microstructure of the solid. Finally, our results demonstrate that to successfully predict and control the solidification microstructure, in the presence of objects, physical models incorporating both thermal and long-range solute effects are required.

If confocal microscopy is an ubiquitous tool in life science, its applications in chemistry and materials science are still, in comparison, very limited. Of particular interest in these domains is the use of confocal microscopy to investigate temperature-dependent phenomena such as self-assembly, diffusio- or thermophoresis, or crystal growth. Several hurdles must be solved to develop a temperature-controlled stage for laser scanning confocal microscopy, in particular regarding the influence of an elevated temperature gradient close to the microscope objective, which most people try very hard to avoid. Here we report the design of a temperature-controlled stage able to generate stable temperature gradients in both positive and negative temperature range and does not require use of liquid nitrogen. Our setup provides an excellent control of the temperature gradient, which can be coupled with a controlled displacement of the sample, making it useful in particular for a variety of solidification, chemistry, and interfacial problems. We illustrate the benefits of our setup with several case studies of interest in chemistry and materials science: the 3D real-time imaging of ice growth, the segregation of hard particles by growing crystals, the freezing behaviour of single emulsions, the self-shaping of oil droplets upon cooling, and the self-assembly of amphiphile molecules into helical structures. These results show how confocal microscopy coupled with a temperature-controlled stage that provides a controlled temperature gradient is a welcome addition to the toolkit of chemists and materials scientists.

The interaction of objects with a moving solidification front is a common feature of many industrial and natural processes such as metal processing, the growth of single-crystals, the cryopreservation of cells, or the formation of sea ice. Solidification fronts interact with objects with different outcomes, from the total rejection to their complete engulfment. We image the freezing of emulsions in 5D (space, time, and solute concentration) with confocal microscopy. We show the solute induces long-range interactions that determine the solidification microstructure. The local increase of solute concentration enhances premelting, which controls the engulfment of droplets by the front and the evolution of grain boundaries. Freezing emulsions may be a good analogue of many solidification systems where objects interact with a solidification interface., 23 pages, 4 figures, 31 references

Shrinkage of water drops immersed in oil solutions due to spontaneous emulsification in the presence of asphaltene adsorption., Complex molecules from crude oil, such as asphaltenes, can adsorb onto oil/water interfaces. This creates a viscoelastic network that may cause difficulties in oil recovery and oil spills. In addition to stabilization of oil/water emulsions, they may also cause the spontaneous formation of micron-sized droplets. Here, we investigate spontaneous emulsification in the presence of asphaltenes, probing parameters that may affect this phenomenon by observing isolated drops of water immersed in asphaltene/hydrocarbon solutions within a co-flow microfluidic device. The results indicate that the initial internal pressure of the drop strongly influences the rate at which the drop will shrink due to spontaneous emulsification. In addition, the viscoelastic skin formation by the asphaltenes inhibits increases in this pressure that normally accompanies a decrease in drop radius. Understanding this spontaneous emulsification has implications not only for the oil industry, but also to the cosmetics, foods, medical, and pharmaceutical industries.

International audience; In the present work a polymeric transient viscoelastic network is used as a model system to investigate several fundamentals of interfacial viscoelasticity and non-linear behavior, in simple shear, compression and for simple mixed deformations. A supramolecular polymer bilayer, characterized by long but finite relaxation times, is created at the water-air interface using a layer-by-layer assembly method. The possibility of studying the individual layers starting from an unstrained reference state enabled the independent quantification of the equilibrium ther-modynamic properties, and the viscoelastic response of the bilayer could be studied separately for shear and compressional deformations. Time-and frequency-dependent material functions of the layer were determined in simple shear and uniform compression. Moreover, a quasi linear neo-Hookean model for elastic interfaces was adapted to describe step strain experiments on a viscoelastic system by allowing the material properties to be time-dependent. The use of this model made it possible to calculate the response of the system to step deformations. Within the linear response regime, both stress-strain proportionality and the superposition principle were investigated. Furthermore, the onset of non-linear behavior of the extra stresses was characterized in shear and for the first time in pure compression. We conclude by investigating the multilayer system in a rising bubble setup and show that the neo-Hookean model is able to predict the extra and deviatoric surface stresses well, up to moderate deformations.

Hydrophobically modified polymers are good candidates for the stabilization of liquid interfaces thanks to the high anchoring energy of the hydrophobic parts. In this article we probe the interfacial anchoring of a series of home-made hydrophobically modified polymers with controlled degree of grafting by studying their behavior upon large area dilations and compressions. By comparing the measured interfacial tension to the one that we expect in the case of a constant number of adsorbed monomers, we are able to deduce whether desorption or adsorption occurs during area variations. We find that the polymer chains with the longest hydrophobic grafts desorb at larger compressions compared to the polymers with the shortest grafts, because of their larger desorption energy. Furthermore, for a given graft length, we observe more desorption for polymers with the highest grafting densities. We attribute this counter intuitive result to the fact that at high grafting densities, the length of the polymer loops is shorter, and hence the elastic penalty upon compression is larger for these layers, leading to a faster desorption. Comparing the elastic penalty to thermal energy, kBT, enables deducing a critical grafting density above which desorption of grafts is expected upon compression, which is consistent with our experimental results. In the case of large area dilations, the experiments reveal that the number of adsorbed anchors remains constant in the case of chains with a low grafting density while chains with the highest degree of grafting seem to show some degree of adsorption during the dilatation. Therefore, in these highly grafted chains there may be unadsorbed grafts remaining in the vicinity of the interface, which may adsorb quickly at the interface upon dilatation.

International audience; Encapsulation of chemicals using polymer membranes enables to control their transport and delivery for applications such as agrochemistry or detergency. To rationalize the design of polymer capsules, it is necessary to understand how the membranes' mechanical properties control the transport and release of the cargo. In this article, we use microfluidics to produce model polymer capsules and study in situ their behavior in controlled elongational flows. Our model capsules are obtained by assembling polymer mono and hydrogen-bonded bilayers at the surface of an oil droplet in water. We also use microfluidics to probe in situ the mechanical properties of the membranes in a controlled elongational flow generated by introducing the capsules through a constriction and then in a larger chamber. The deformation and relaxation of the capsules depend on their composition and especially on the molecular interactions between the polymer chains that form the membranes and the anchoring energy of the first layer. We develop a model and perform numerical simulations to extract the main interfacial properties of the capsules from the measurement of their deformations in the microchannels.

International audience; Molecular interactions in thin liquid films, such as the disjoining pressure, are involved in interfacial phenomena such as emulsion and foam stabilization. In this article we show that through light stimulation we can control remotely the disjoining pressure in a thin liquid film stabilized by a photosurfactant. We stabilize a horizontal thin liquid film using a cationic photosurfactant, AzoTAB, bearing an azobenzene moiety on the hydrophobic tail which can switch from a trans to a cis conformation upon light stimulation. As the film is illuminated at specific wavelengths the AzoTAB molecules switch continuously their conformation and consequently their interface affinity. The main consequence of stimulating the film with light is increasing the ratio of cis in the film. This provokes a desorption flux, and an increase in the concentration of free surfactants, as the CMC of the cis isomer is higher than that of the trans isomer. Therefore the electrostatic repulsion between the surfactant layers that stabilize the film decreases, inducing an instability in the film thickness. For films with a thickness between 20 nm and 60 nm, we observe the formation of spherical caps up to 100 μm wide, whose shape is controlled by the competition between surface tension and disjoining pressure. The motion of these caps in the film is restrained by the surface viscosity of the surfactant layers. In addition, for thicknesses below 40 nm and depending on light intensity, we can observe flat stratified islands up to 100 μm wide, with thickness steps corresponding to the size of a surfactant micelle. We suggest that this second instability is due to the oscillation of the disjoining pressure isotherm under light.

International audience; The biorefinery of microalgae necessitates innovative choices of soft and energy-efficient processes to guarantee the integrity of fragile molecules and develop eco-friendly production. A wet processing of biomass is proposed, which avoids expensive drying steps. It includes harvesting, cell disruption, and fractionation of the target compounds. Membrane filtration is a promising clean fractionation step. In this paper, the recovery of lipids from starving Parachlorella kessleri aqueous extracts by cross-flow filtration was studied. A model solution was formulated to test four membranes of different materials (PVDF, PES, PAN) and cut-offs (200 kDa - 1.5 µm). The hydrophilic PAN 500kDa membrane presented the best performance (flux stability, permeate flux, lipid retention, and cleanability) and was therfore selected for filtrating real aqueous extracts. Similar permeation fluxes were obtained with model and real products: 34 -41Lh-1m-2 respectively. The coalescence of lipid droplets was observed with model solutions but not with real products, less concentrated. The lipids from the real products were wholly retained by the PAN membrane, whereas some of the polysaccharides and proteins were able to permeate. An optimization of the coupling between culture, cell disruption, clarification, and filtration would allow a good concentration and purification of the lipids from microalgae.

We present electrostrictive materials with excellent properties for vibrational energy harvesting applications. The developed materials consist of a porous carbon black composite, which is processed using water-in-oil emulsions. In combination with an insulating layer, the investigated structures exhibit a high effective relative dielectric permittivity (up to 182 at 100 Hz) with very low effective conductivity (down to 2.53 10−8 S m−1). They can generate electrical energy in response to mechanical vibrations with a power density of 0.38 W m−3 under an applied bias electric field of 32 V. They display figures or merit for energy harvesting applications well above reference polymer materials in the field, including fluorinated co- and ter-polymers synthetized by heavy chemical processes. The production process of the present materials is based on non hazardous and low-cost chemicals. The soft dielectric materials are highly flexible (Young's modulus of ~1 MPa) making them also suited for highly sensitive capacitive sensors.

International audience; Samples of nitrogen-starved Parachlorella kessleri containing intact cells (IC), cells ground by bead milling (BM), and cells subjected to high-pressure cell disruption (HPD), together with their supernatants after centrifugation, were compared for granulometry and lipid profiles. The effects of disruption on the lipid profile and organisation were evaluated. The quantity of lipids available for extraction increased with disruption, and up to 81% could be recovered in supernatants after centrifugation, but a marked reorganization occurred. The proportion of amphiphilic free fatty acids and lysophosphatidylcholine increased during disruption due to their release or owing to lipid degradation by enzymes or physical conditions. This effect was more marked in HPD than in BM. Lipids contained in the aqueous phase, after disruption and centrifugation, were enriched in unsaturated fatty acids, BM leading to larger droplets than HPD. The larger liquid lipid droplet would be easier to recover in the following downstream processing. Key words Microalgae, bead milling, high-pressure cell disruption, lipids Highlights Disruption increases the quantity of extractable lipids. A large proportion of lipids is recovered in supernatants. Bead milling yields larger droplets, easier to recover.

Using surface-tension measurements, we study the brush-limited adsorption dynamics of a range of amphiphilic polymers, PAAH-[Formula: see text]-[Formula: see text] composed of a poly(acrylic acid) backbone, PAAH, grafted with a fraction [Formula: see text] of alkyl moieties, containing either n = 8 or n = 12 carbon atoms, at pH conditions where the PAAH backbone is not charged. At short times, the surface tension decreases more sharply as the degree of grafting increases, while, at long times, the adsorption dynamics becomes logarithmic in time and is slower as the degree of grafting increases. This logarithmic behavior at long times indicates the building of a free-energy barrier which grows over time. To account for the observed surface tension evolution with the degree of grafting we propose a scenario, where the free-energy barrier results from both the deformation of the incoming polymer coils and the deformation of the adsorbed brush. Our model involves only two fitting parameters, the monomer size and the area needed for one molecule during adsorption and is in agreement with the experimental data. We obtain a reasonable value for the monomer size and find an area per adsorbed polymer chain of the order of 1 nm2, showing that the polymer chains are strongly stretched as they adsorb.

International audience; We report on experiments that consist of deforming a collection of monodisperse droplets produced by a microfluidic chip through a flow-focusing device. We show that a proper numerical modeling of the flow is necessary to access the stress applied by the latter on the droplet along its trajectory through the chip. This crucial step enables the full integration of the differential equation governing the dynamical deformation, and consequently the robust measurement of the interfacial tension by fitting the experiments with the calculated deformation. Our study thus demonstrates the feasibility of quantitative in situ rheology in microfluidic flows involving, e.g., droplets, capsules, or cells.

Drying of particle suspensions is an ubiquitous phenomenon with many natural and practical applications. In particular, in unidirectional drying, the evaporation of the solvent induces flows which accumulate particles at the liquid/air interface. The progressive build-up of a dense region of particles can be used, in particular, in the processing of advanced materials and architectures while the development of heterogeneities and defects in such systems is critical to their function. A lot of attention has thus been paid to correlate the flow and particles dynamics to the ordering of particles. However, dynamic observation at the particle scale and its correlation with local particle ordering are still missing. Here we show by measuring the particle velocities with high frame rate laser scanning confocal microscopy that the ordering of weakly Brownian particles during directional drying in a Hele-Shaw cell opened on one side depends on the particle velocity. Under the ambient and experimental conditions presented in the following, the particle velocities accumulate in two branches. A higher degree of ordering is found for the branch of faster particle velocity which we explain by an increase in the pressure drop which drags the particles into a denser packing as the flow velocity increases. This counter-intuitive behaviour is the opposite to what is found with Brownian particles, which can reorganize by Brownian motion into denser packing during drying, as long as the flow velocity is not too high. These results show that different kinetic conditions can be used to obtain dense, defect-free regions of particles after drying. In particular, it suggests that rapid, directional drying could be used to control the crystallinity of particle deposits., 10 pages, 12 figures

International audience; Using an emulsion road and optimizing the dispersion process, we prepare polymer carbone nanotubes (CNT) and polymer reduced graphene oxide (rGO) composites. The introduction of conductive nanoparticles into polymer matrices modifies the electronic properties of the material. We show that these materials exhibit giant electrostriction coefficients in the intermediate filler concentration (below 1 wt %). This makes them very promising for applications such as capacitive sensors and actuators. In addition, the values of the piezoresistivity measured in the high filler concentration situation are at least an order of magnitude greater than the one reported in the literature. This opens the way to use these materials for stress or strain sensor applications considering their giant responses to mechanical deformations.

In this article we examine the foamability and foam stability of a series of PEI/silica gel suspensions with varying particle concentrations in the presence of a neutral surfactant, C 12 E 23 . These suspensions, which were recently developed for 3D printing applications, exhibit a finite yield stress whose value can be tuned by varying the particle concentration and the pH. Our study aims at evaluating whether this system is suitable to produce stable foams that could be further be used as precursors for the 3D printing of porous materials and to evaluate the relation between the yield stress and the foam stability against drainage and ripening. At pH7 where all the suspensions are in the fluid state, the maximum air fraction reaches 80% however the foams are very unstable to drainage. At pH 10.5, the suspensions are in the gel state due to Van der Waals driven aggregation of the particles. In the gel state, the obtained maximum air fraction decreases with the suspension concentration, from ϕ air = 80% for the 12.8 wt% suspension to ϕ air = 65% for the 15.5 wt% suspension. The most concentrated suspension, i.e 19.7 wt% could not be foamed. At pH 10.5, the yield stress of the 12.8 wt% suspension is 10 Pa, which enables to overcome the buoyancy acting on the particles and therefore arrest drainage. However the yield stress is too low to overcome the Laplace pressure in the bubbles, therefore Ostwald ripening is observed. The 15.5 wt% suspension exhibits a yield stress of 200 Pa, which is high enough to arrest drainage. Ostwald ripening occurs at early times and is arrested when the bubble radius reaches 400 μm as the yield stress equals the Laplace pressure. The results obtained in this study show that there is an optimal silica concentration which combines good foamability and large stability to drainage and Ostwald ripening. These materials are promising for the development of 3D printable foams even though the size of the bubbles will limit the spatial resolution of the printing to a few millimeters.

Highly monodisperse poly(N-isopropylacrylamide), PNiPAM, microgels were prepared by the conventional radical polymerization of NiPAM in the presence of dimethylamino ethyl methacrylate (DMAEMA) monomers at various concentrations. The effect of DMAEMA on the polymerization of PNiPAM microgels was examined at constant initiator (V50) and cross-linker (MBA) concentrations. The presence of DMAEMA in the synthesis batch allows for the preparation of PNiPAM microgels with controlled size and a narrow size distribution. The oil(dodecane)/water interfacial properties of the model PNiPAM microgels were then investigated. The pendant drop technique was used to measure the interfacial tensions as a function of temperature. Over the whole range of temperature (20-45 degrees C), the interfacial tension remains low (on the order of 17 mN/m) and goes through a minimum (12 mN/m) at a temperature of about 34 degrees C, which well matches the volume phase transition temperature (VPTT) of PNiPAM microgels. Below the VPTT, the decrease in the interfacial tension with temperature is likely to be due to the adsorption of dense layers because of the decrease of the excluded volume interactions. Above the VPTT, we suggest that the increase in the interfacial tension with temperature comes from the adsorption of loosely packed PNiPAM microgels. We also studied the effect of temperature on the stability of emulsions. Dodecane in water emulsions, which form at ambient temperature, are destabilized as the temperature exceeds the VPTT. In light of the interfacial tension results, we suggest that emulsion destabilization arises from the adsorption of aggregates above the VPTT and not from an important desorption of microgels. Aggregate adsorption would bring a sufficiently high number of dodecane molecules into contact with water to induce coalescence without changing the interfacial tension very much.

We found that the drying process of the droplet of water-poly(N,N-dimethylacrylamide) (PDMA) solution on a glass substrate shows a somewhat unusual behavior. In this system, the contact line starts to recede at an early stage of drying, and as it recedes, it leaves a macroscopic polymer film behind. The resulting film has a volcano-like profile, but the peak is not located at the edge of the film but in the middle of the film. We studied the drying process changing the polymer concentration and the wetting property of the substrate. We found that the onset of the contact-line recession depends upon the initial contact angle greatly, while the receding contact angle does not depend upon the initial contact angle. We conjecture that this phenomenon is caused by the Marangoni force, which acts to bring the surface of the solution inward because of the negative dependence of the surface tension on the polymer concentration.

In this paper, we report on the competition between evaporation and hydrodynamics for advancing drops of polymer solutions. We thus study advancing drops which are allowed to evaporate. Drying drives the accumulation of polymer at the contact line, whereas the advancing motion tends to homogenize the drop. At high velocity, we experimentally verify classical hydrodynamics predictions. At intermediate velocities, drying dominates and the contact line becomes more viscous than the bulk droplet. In the limiting case of very low velocities, the contact line can be partially pinned on the substrate because of the formation of a glassy defect at the contact line.

International audience; We investigate the drainage dynamics of thin liquid foam films containing PNiPAM microgel suspensions with two cross-linking densities (1.5 and 5 mol% BIS) and at two microgel concentrations (0.1 and 1% wt). For this purpose, we use a thin-film pressure balance apparatus that can apply a controlled and sudden hydrostatic pressure on a film, and record the subsequent film thinning as a function of time. Once the film thickness has reached a stationary value, we test the adhesion between the interfaces of the film by reducing the pressure and measuring the angle between the film and the meniscus. This angle increases on reduction of pressure for adhesive films, which resists the separation of their interfaces. Non-adhesive films separate easily, and the meniscus angle stays constant. At a low microgel concentration, the more densely cross-linked microgels (5 mol% BIS) tend to drain into more adhesive films than the more loosely cross-linked particles (1.5 mol% BIS). The adhesion results from particles that bridge the two air–water interfaces of the film and are shared between them. In these cases, the film, which is initially stabilized by a bilayer of microgel particles, rearrange to a state where the microgels bridge the interfaces. These results are discussed and compared with previous studies at a low concentration of microgels, which have shown that emulsions stabilized with densely cross-linked microgels are more adhesive and less resistant to mechanical stresses than those obtained with lower cross-linking densities. In addition, micron-scale depleted zones with no microgels are observed in the films stabilized with the 5 mol% BIS particles, which eventually lead to the rupture of the films. At 1% wt, the films drain slowly, are not adhesive and have the thickness of a bilayer of microgel; while at 0.1% wt, the films have the thickness of a monolayer of microgel, are adhesive and show bridging. From the thin liquid foam film thicknesses we extract a rough estimation of the radii of adsorbed particles in the thick films before applying the pressure. Our results are consistent with particles being adsorbed in a spread conformation for the 0.1% wt sample and in a compressed conformation for the 1% wt sample. In line with previous studies on emulsions, we conclude that a larger surface coverage may reduce rearrangements, thus preventing bridging.

In the first part, we provide the background describing the adsorption dynamics in surfactant solutions, including the cases of kinetically and diffusion controlled dynamics. The second part deals with the dynamics of polymer molecules at interfaces. We provide a review of the mechanisms involved in the adsorption dynamics of polymer molecules at liquid interfaces. We show that there are energy barriers, of steric or electrostatic nature which tend to slow down the adsorption of polymer molecules in comparaison to surfactant systems. We also review results concerning the surface shear and compression properties of adsorbed and spread polymer monolayers at liquid interfaces. In particular, we describe existing models describing the mushroom to brush transition, which occurs in polymer layers as the surface concentration increases. At last, we review recent experimental results concerning the diffusion of polymer molecules at interfaces.

International audience; We probe the drainage and imbibition dynamics of foams in which the continuous aqueous phase is a transient gel-like network. To produce these foams, we provide a new method – a PVA (polyvinyl alcohol) solution is first foamed and then a cross-linker, Borax, is added, which binds reversibly to the PVA chains. The resulting foams are ultra-stable-over a month. We find that the typical time for gravitational drainage of the continuous phase can be slowed down from hours to several weeks by tuning the Borax concentration. We show that the Borax concentration controls both the bulk viscosity of the continuous phase and the surface viscosity of the air–water interfaces. From these results we suggest that the PVA molecules adsorbed at the bubble interfaces are highly cross-linked by the Borax molecules. We find that the capillary rise of a dyed liquid into these foams is orders of magnitude faster than the drainage flow, meaning that these foams can quickly absorb liquids. These results show that these foams could be used to clean or decontaminate surfaces covered with liquid wastes. Indeed we show that the PVA–Borax foam can easily be spread on a surface, absorb a liquid without destabilizing and be dried afterward to recover the waste.

We investigate the shear surface rheology of a thermosensitive polymer, PNIPAM (poly(N-isopropylacrylamide)), adsorbed at the air−water interface using an interfacial stress rheometer. This polymer is characterized by a lower critical solution temperature, LCST, of 32 °C; i.e., PNIPAM chains undergo a coil to globule transition as the temperature is increased above the LCST. We measure a spectacular increase in the surface shear elasticity and viscosity of PNIPAM layers as a function of the temperature around the LCST due to an increase in the amount of adsorbed species as the solvent quality decreases for PNIPAM chains. Moreover, the layers undergo a transition from a Newtonian liquidlike state to an elastic state due to an increase in intermolecular entanglements. We also show that the heating protocols have a strong influence on the rheological properties of the layers. In particular, we show that when the solutions are continuously heated from ambient temperature to well above the LCST, PNIPAM chains ...

Using the oscillating drop method as well as the interfacial stress rheometer (ISR), we measure the surface dilational and shear properties of adsorbed layers of oppositely charged polymer−surfactant complexes at the air−water interface. These data are compared to foam volume data measured for the corresponding solutions. We show that the shear surface moduli G‘ and G‘ ‘ exhibit a maximum at a molar ratio of polymer monomers and surfactant in solution equal to 1. This maximum is strongly correlated to surface ellipticity measurements that indicate a strong adsorption of polymer−surfactant complexes at the air−water interface. These hydrophobic interfacial complexes generate a viscoelastic layer due to the polymer chain entanglements and hydrophobic interactions between bound surfactant. The viscous behavior of the surface layers is further characterized via creep, frequency sweep measurements, and surface aging experiments. Over a 10 h period we find that G‘ and G‘ ‘ increase logarithmically with time, re...

The adsorption and complexation of polystyrene sulfonate (a highly charged anionic polyelectrolyte) and dodecyltrimethylammonium bromide (a cationic surfactant) at the air-water interface can lead to interfacial gels that strongly influence foam-film drainage and stability. The formation and characteristics of these gels have been studied by combining surface tension, ellipsometry, and foam-film drainage experiments. Simultaneously, the solution electromotive force is measured and used to track the polymer-surfactant interactions in the bulk solution. We find that surface gelation occurs above the critical aggregation concentration in solution but before bulk precipitation of the polymer-surfactant complexes. Furthermore, we reveal that strong readsorption of polymer-surfactant complexes occurs during the resolubilization of the precipitated complexes at high surfactant concentrations (i.e., >>critical micelle concentration). Seemingly overlooked in the past, this readsorption significantly influences the surface rheological properties and foam-film drainage of these systems.

International audience; We probe the mechanical shear and compression properties of hydrogen-bonded polymer multilayers directly assembled at the oil-water interface using interfacial rheology techniques. We show that the polymer multilayers behave mechanically like a transient network, with elastic moduli that can be varied over 2 orders of magnitude by controlling the type and strength of physical interactions involved in the multilayers, which are controlled by the pH and the hydrophobicity of the polymer. Indeed, the interplay of hydrogen and hydrophobic interactions enables one to obtain a tighter and stronger network at the interface. Moreover, we show how a simple LBL process applied directly on emulsion droplets leads to encapsulation of a model oil, dodecane, as well as perfume molecules.

International audience; We review some results from the literature describing the structure and dynamics of polymer molecules adsorbed at liquid interfaces as well as their behavior in foams. The first part describes theoretical and experimental results concerning the structure and dynamics of model polymer systems, i.e. homopolymers and copolymers. In the second part, we review experimental results concerning mixtures of polymers and surfactants that are widely used to stabilize foams. In such mixtures, the surfactants and the polymer molecules form complexes in the bulk solution and at liquid interfaces which help stabilizing the foams. We review the physicochemical parameters that influence the adsorption dynamics and the viscoelastic properties of the interfaces as well as the foam properties of such mixtures. (C) 2014 Academie des sciences. Published by Elsevier Masson SAS. All rights reserved.

International audience; We investigate the stabilization of air-water interfaces by mixtures of negatively charged latex particles (sulfate polystyrene) and cationic surfactants (alkyl trimethylammonium bromides). First we report results concerning the binding of surfactant molecules to the latex particles. As the surfactant concentration increases, the charge of the particles reverses, from negative to positive, because C(n)TAB first binds electrostatically to the latex particles and then through hydrophobic interaction with the monolayer already adsorbed on the particles as well as directly with the hydrophobic surface of the latex. Over a large range of surfactant concentrations around the charge inversion, a strong flocculation is observed and 100 mu m large aggregates form in the suspension. Unlike previous studies published on mixtures of inorganic particles with oppositely charged surfactants, we show that we can vary the sign of the zeta potential of the particles without changing the contact angle of the particles over a large range of surfactant concentrations. Indeed, the latex particles that we study are more hydrophobic than inorganic particles, hence adding moderate concentrations of the surfactant results in a weak variation of the contact angle while the charge of the particles can be reversed. This enables decoupling of the effect of zeta potential and contact angle on the interfacial properties of the mixtures. Our study shows that the contact angle and the charge of the particles are not sufficient parameters to control the foam properties, and the key-parameters are the flocculation state and the shear energy applied to produce the foam. Indeed, flocculated samples, whatever the sign of the zeta potential, enable production of a stable armour at the interface. The large aggregates do not adsorb spontaneously at the interface because of their large size, however when a large shear energy is used to produce the foam very stable foam is obtained, where particles are trapped at interfaces. We suggest that the large aggregates may be broken during shear and may reform at the interface to form a solid armour. A simple calculation taking into account the adsorption dynamics of the aggregates as a function of their size is consistent with this hypothesis.

The use of Interdigitated Array (IDA) Microelectrodes for detection of low levels of biogenic amines has been demonstrated in stationary solutions and flow systems [M. Morita, et al., Electrochemica Acta 42 (20--21) (1997) 3177--3183]. This technique is highly sensitive. We have evaluated this technology as applied to High Pressure Liquid Chromatography with Electrochemical Detection (HPLC-EC) for analysis of microdialysate and tissue samples. With this new technology we demonstrated a x 10 fold increase in sensitivity in comparison to our existing technology. We are now able to detect dopamine at a level of 53 x 10(-18) moles on column and serotonin at 26 x 10(-18) moles on column. This technology now permits analysis of biogenic amines in samples from brain areas not previously amenable to this type of experiment.

International audience; We report the behavior of thermosensitive soft microgel particles adsorbed at the air-water interface. We study the effect of temperature on the adsorption, interfacial diffusion, and surface rheology of pure N-isopropylacrylamide (NiPAM) microgel particles at the air-water interface. We find that the surface tensions of the solutions are the same as those of polyNiPAM solution; hence, their adsorption properties are dominated by the surface activity of the NiPAM repeat units of the particles. Particle-tracking experiments show that the particles adsorb irreversibly at the interface and form stable clusters at very low concentrations, e.g., 5.10(-3) wt%. We suggest that attractions between dangling arms or capillary interaction may be responsible for the formation of these clusters. For concentrations above 10(-2) wt%, the interface is filled with particles, and their Brownian diffusivity is arrested. The compression elastic moduli-measured using the pendant drop method-are one or two orders of magnitude below those obtained for hard particles and NiPAM chains, and their value is probably dominated by the intrinsic compressibility of the particles. The thin liquid films made from microgels exhibit a symmetric drainage, consistent with a high surface viscosity, but their lifetime is surprisingly short, illustrating the fragility of the films. We observed the formation of a monolayer of microgels bridging the two interfaces of the film outside the dimple. This zone grows and thins over time to a point where the microgels are highly compressed and stretched, resulting in the rupture of the film

International audience; We study the influence of UV light on the drainage flows of foams and thin-liquid films stabilized by photoswitchable azobenzene surfactants, whose shape and hydrophobicity can be modified using UV illumination. This model system, the dynamics of which was well characterized in a previous study, enables us to trigger a controlled variation of the surface excess and surface tension. In both geometries we observe light-induced flows which are able to suppress the drainage flow induced by gravity. However, we show that the physical origin of the flows is different in both geometries. At the scale of a few films in the so-called 'two-bubble' experiment the comparisons of the physical length scales, i.e. the radius of the meniscus and the film thickness, to the chemical "reservoir length" (Γ/c) show that the flux of the surfactant at the interface in the presence of UV light is different in the films and in the meniscus, inducing a Marangoni flow from the meniscus to the film, which is stronger than gravity and capillary suction. The velocity of this flow can be tuned by the light intensity and the surfactant concentration. In the real foams, however, we show that the above mechanism is not relevant because the radii of curvature of the Plateau borders are orders of magnitude lower than in the two-bubble experiment, thus the capillary suction prevents such transfer between the films and the Plateau borders. Instead, the decrease of the drainage velocity is shown to be due to a gradient of the surface tension in the illuminated zone hence to a local variation of the capillary pressure. This study underlines the importance of characterizing the radius of the Plateau borders for the understanding of foams, as this key parameter sets the order of magnitude of capillary pressure, film thickness and amount of available surfactant. We also show that this photosurfactant is a new toolbox for the understanding of foam stability.

International audience; We report evidence for photocontrolled stability and breakage of aqueous foams made from solutions of a cationic azobenzene-containing surfactant over a wide range of concentrations. Exposure to UV or visible lights results in shape and polarity switches in the surfactant molecule, which in turn affects several properties including critical micelle concentration, equilibrium surface tension, and the air water interfacial composition (cis isomers are displaced by trans ones). We demonstrate that the trans isomer stabilizes foams, whereas the cis isomer forms unstable foams, a property that does not correlate with effects of light on surface tension, nor with total surfactant concentration. Achieving in situ breakage of foam is accordingly ascribed to the remote control of the dynamics of adsorption/desorption of the surfactant, accompanied by gradients of concentrations out of equilibrium. Photomodulation of adsorption kinetics and/or diffusion dynamics on interfaces is reached here by a noninvasive clean trigger, bringing a new tool for the study of foams

In this article, we study the drying kinetics of a sessile droplet containing latex particles. We find that a depletion film is left at the edge of the drops, whose width is controlled by two geometric parameters, the contact angle and the diameter of the particles. We show that this effect can be used to sort colloidal mixtures because nanometric colloids always segregate at the edge of the drop, whereas micrometric colloids are blocked further away from the edge. We also provide a simple method to measure the velocity of a micrometric latex as it flows toward the contact line. We find that the particles strongly accelerate at the end of the drying process. Using Deegan's prediction for the rate of evaporation in the vicinity of the contact line, we quantitatively explain this phenomenon by the fact that the contact angle vanishes at the end of the drying process, therefore inducing a strong increase in the flux of water and particles close to the edge. The decrease in the contact angle also controls the width of the ringlike deposit.

The wettability of coatings is very sensitive to the amount of solvent they may contain. When a droplet of volatile solvent, such as water, is deposited on a substrate, its vapor may quickly condensate just ahead of the contact line. We give an estimation of the extent of solvent uptake by a coating of variable thickness e , in front of an advancing contact line of given velocity U . Depending on the values of e and U , we observe three regimes: at low velocity and for a thin coating, the coating adsorbs a fraction of solvent that can quickly equilibrate across its entire thickness, so that it mainly appears solvophilic, while this is not the case for a thick coating. For high velocities, regardless the coating thickness, the coating ahead of the contact line does not have enough time to adsorb a significant amount of solvent, so that it mainly appears solvophobic. All these phenomena appear to be controlled by a molecular cut-off length.

We present experimental results concerning the advancing motion of drops of polymer solutions in the presence of controlled evaporation. We find that at high advancing velocities the classical Cox-Voinov law is verified, i.e. the advancing contact angle varies linearly with the capillary number. Below a critical velocity the contact angle increases as the advancing velocity is reduced. These results can be explained by taking into account the divergence of the rate of evaporation close to the contact line leading to an accumulation of polymer close to the edge of the drop. The induced local increase of the viscosity explains the increase of the contact angle. We show that the accumulation of polymer over a few nanometers is sufficient to slow down the contact line.

Thermal motion gives rise to fluctuations in free surfaces; measurement of the thermally excited waves on such surfaces provides information on the mechanical properties of the medium. We have developed an optical tool to probe the thermally excited waves on free surfaces: surface fluctuation specular reflection (SFSR) spectroscopy. It consists in measuring the fluctuations in the position of a laser beam that is specularly reflected onto the free surface of a medium. The position of the reflected beam is sensitive to the roughness of the probed surface; the thermal waves are detected by subtracting the light intensities collected on the two quadrants of a photodiode, on which the beam is centered. We show how the measured signal is related to the medium properties. We also present measurements performed on Newtonian liquids as well as on a viscoelastic solid; we show that in all cases, there is a very good agreement between experimental and computed spectra. SFSR thus applies to a broad range of materials. It moreover offers a very good temporal resolution and should provide a useful tool for dynamical measurements on complex fluids.