Neutron reflectivity measurements at the oil/water interface for the study of stimuli-responsive emulsions⋆.

Stable stimuli-responsive emulsions between oil and water are formed with an amphiphilic block copolymer bearing polystyrene (PS) and poly(dimethylaminoethyl methacrylate) (PDMAEMA) moieties. Different kinds of emulsions like direct, multiple or inverse ones are reproducibly formed as a function of chemical parameters such as p H and salt concentration. To test the correlation between the different nature of the emulsion and the conformation of the polymer chain at the interface, neutron reflectometry at the oil/water interface was carried out. An original sample cell was built and the procedure to get reliable results with it on the FIGARO reflectometer at the Institut Laue-Langevin is described. Results show that for direct emulsions, the copolymer is much more extended on the water side than on the oil side. In the case where multiple emulsions are stabilized, the conformation is strongly modified and is compatible with a more equilibrated extension of the chain on both sides. The inverse case shows that the extension in oil is stronger than in water. These results are discussed in term of polymer brushes (charged or neutral) extension with respect to salt addition and hydrophobic interactions.

Behaviour of hybrid inside/out Janus nanotubes at an oil/water interface. A route to self-assembled nanofluidics?

Imogolites are natural aluminosilicate nanotubes that have a diameter of a few nanometers and can be several microns long. These nanotubes have different chemical groups on their internal (Si-OH) and external (Al-OH-Al) surfaces, that can be easily functionalised independently on both surfaces. Here we show that taking advantage of the particular shape and chemistry of imogolite, it is possible to prepare inside/out Janus nanotubes. Two kinds of symmetric Janus nanotubes are prepared: one with an external hydrophilic surface and an internal hydrophobic cavity (imo-CH3) and one with an external hydrophobic surface and a hydrophilic internal cavity (OPA-imo). The behaviour of such inside/out Janus nanotubes at oil/water interfaces is studied. The OPA-imo adsorbs strongly at the oil/water interface and is very efficient in stabilising water-in-oil emulsions through an arrested coalescence mechanism. Imo-CH3 also adsorbs at the oil/water interface. It stabilises oil-in-water emulsions by inducing slow oil-triggered modifications of the viscosity of the continuous phase. The possible transport of small molecules inside the imo-CH3 nanotubes is evidenced, opening up routes towards self-assembled nanofluidics.

Nonlocal effects in sand flows on an inclined plane.

The flow of sand on a rough inclined plane is investigated experimentally. We directly show that a jammed layer of grains spontaneously forms below the avalanche. Its properties and its relation with the rheology of the flowing layer of grains are presented and discussed. In a second part, we study the dynamics of erosion and deposition solitary waves in the domain where they are transversally stable. We characterize their shapes and velocity profiles. We relate their translational velocity to the stopping height and to the mass trapped in the avalanche. Finally, we use the velocity profile to get insight into the rheology very close to the jamming limit.

Correction: Breaking of the Bancroft rule for multiple emulsions stabilized by a single stimulable polymer.

Correction for 'Breaking of the Bancroft rule for multiple emulsions stabilized by a single stimulable polymer' by L. Besnard et al., Soft Matter, 2014, 10, 7073-7087.

Breaking of the Bancroft rule for multiple emulsions stabilized by a single stimulable polymer.

We investigated emulsions of water and toluene stabilized by (co)polymers consisting of styrene (S) and 2-(dimethylamino)ethyl methacrylate (DMAEMA) monomer units with different compositions and structures such as a PDMAEMA homopolymer, a P(S-co-DMAEMA) random copolymer and various PS-b-PDMAEMA and PS-b-(S-co-DMAEMA) block copolymers. The model system is used to study the fundamental conditions under which the different kinds of polymer-stabilized emulsions (direct oil in water, inverse water in oil and multiple emulsions) are stabilized or destabilized by pH change (at constant temperature). Polymer properties like chain conformation at the toluene-water interface as probed by SANS and neutron reflectivity at the liquid-liquid interface, the oil-water partitioning of the polymer chains (Bancroft's rule of thumb) as determined by UV spectroscopy and interfacial tensions measured by the rising and spinning drop techniques are determined. Overall, results evidence that the curvature sign, as defined by positive and negative values as the chain segments occupy preferentially the water and toluene sides of the interface respectively, reliably predicts the emulsion kind. In contrast, the Bancroft rule failed at foreseeing the emulsion type. In the region of near zero curvature the crossover from direct to inverse emulsions occurs through the formation of either unstable coexisting direct and inverse emulsions (i) or multiple emulsions (ii). The high compact adsorption of the chains at the interface as shown by low interfacial tension values does not allow to discriminate between both cases. However, the toluene-water partitioning of the polymeric emulsifier is still a key factor driving the formation of (i) or (ii) emulsions. Interestingly, the stabilization of the multiple emulsions can be tuned to a large extent as the toluene-water polymer partitioning can be adjusted using quite a large number of physico-chemical parameters linked to polymer architecture like diblock length ratio or polymer total molar mass, for example. Moreover, we show that monitoring the oil-water partitioning aspect of the emulsion system can also be used to lower the interfacial tension at low pH to values slightly higher than 0.01 mN m(-1), irrespective of the curvature sign.

Acoustic gaps in a chain of magnetic spheres.

Acoustic gaps are normally observed in granular inhomogeneous structures made of composite materials. The modulation of the elastic properties in such media creates the coherent effects of scattering and interference that ultimately lead to frequency intervals where sound propagation is forbidden. Contrastingly, we report here an experimental observation of acoustic gaps in homogeneous media; specifically, in granular chains. The beads used in our study are magnetic. Therefore, instead of modulating the elastic properties of the chain, we modulate the magnetization (i.e., the contact forces). We also observe that the propagation speed of acoustic signals through the magnetic chains used in this study is at odds with the speed predicted by Hertz's law.

Electrowetting --a versatile tool for controlling microdrop generation.

Integrating insulator-covered electrodes into a microfluidic flow focusing device (FFD) we demonstrate enhanced flexibility and control of the flow of two non-miscible liquids based on electrowetting (EW). In the parameters space, determined by liquid inlet pressures, we identify a specific region where drops can only be generated and addressed via EW. In this regime we show that the size distribution and the frequency of drop generation can be controlled by the applied voltage and the width of voltage pulses. Moreover it turns out that with EW the drop size and the frequency can be tuned independently. Finally we show that the same drop generation phenomena can also be observed in the presence of surfactants.