Effect of Surface Chemistry on the Electrical Double Layer in a Long-Chain Ionic Liquid.

Room temperature ionic liquids (ILs) can create a strong accumulation of charges at solid interfaces by forming a very thin and dense electrical double layer (EDL). The structure of this EDL has important consequences in numerous applications involving ILs, for example, in supercapacitors, sensors, and lubricants, by impacting the interfacial capacitance, the charge carrier density of semiconductors, as well as the frictional properties of the interfaces. We have studied the interfacial structure of a long chain imidazolium-based IL (1-octyl-3-methylimidazolium dicyanamide) on several substrates: mica, silica, silicon, and molybdenum disulfide (MoS2), using atomic force microscopy (AFM) experiments and molecular dynamics (MD) simulations. We have observed 3 types of interfacial structures for the same IL, depending on the chemistry of the substrate and the water content, showing that the EDL structure is not an intrinsic property of the IL. We evidenced that at a low water content, neutral and apolar (thus hydrophobic) substrates promote a thin layer structure, where the ions are oriented parallel to the substrate and cations and anions are mixed in each layer. In contrast, a strongly charged (thus hydrophilic) substrate yields an extended structuration into several bilayers, while a heterogeneous layering with loose bilayer regions was observed on an intermediate polar and weakly charged substrate and on an apolar one at a high bulk water content. In the latter case, water contamination favors the formation of bilayer patches by promoting the segregation of the long chain IL into polar and apolar domains.

Apparent Non-Newtonian Behavior of Ionic Liquids.

A significant viscosity variation with the shear rate has been observed for several ionic liquids in rheometry experiments above a critical shear rate. Depending on the liquid and the rheological conditions, both viscosity increase and decrease have been reported. So far, these variations have been interpreted as a signature of a non-Newtonian behavior. However, the measured critical shear rates are orders of magnitude below the ones predicted by numerical simulations. In this work, we perform new rheometry experiments with both ionic liquids and Newtonian liquids to elucidate this discrepancy. For these two types of liquids, both a viscosity decrease and increase have been measured depending on the geometry of the rheometer and the zero-shear viscosity of the liquid. We interpret the viscosity decrease as resulting from viscous heating, since the viscosity of the investigated liquids is also highly temperature-dependent, and the viscosity increase as resulting from the development of instabilities at high shear rates.

Capillary force on a tilted cylinder: Atomic Force Microscope (AFM) measurements.

HYPOTHESIS: The capillary force in situations where the liquid meniscus is asymmetric, such as the one around a tilted object, has been hitherto barely investigated even though these situations are very common in practice. In particular, the capillary force exerted on a tilted object may depend on the dipping angle i. EXPERIMENTS: We investigate experimentally the capillary force that applies on a tilted cylinder as a function of its dipping angle i, using a home-built tilting Atomic Force Microscope (AFM) with custom made probes. A micrometric-size rod is glued at the end of an AFM cantilever of known stiffness, whose deflection is measured when the cylindrical probe is dipped in and retracted from reference liquids. FINDINGS: We show that a torque correction is necessary to understand the measured deflection. We give the explicit expression of this correction as a function of the probes' geometrical parameters, so that its magnitude can be readily evaluated. The results are compatible with a vertical capillary force varying as 1/cosi, in agreement with a recent theoretical prediction. Finally, we discuss the accuracy of the method for measuring the surface tension times the cosine of the contact angle of the liquid on the probe.

Functionalized AFM probes for force spectroscopy: eigenmode shapes and stiffness calibration through thermal noise measurements.

The functionalization of an atomic force microscope (AFM) cantilever with a colloidal bead is a widely used technique when the geometry between the probe and the sample must be controlled, particularly in force spectroscopy. But some questions remain: how does a bead glued at the end of a cantilever influence its mechanical response? And more importantly for quantitative measurements, can we still determine the stiffness of the AFM probe with traditional techniques?In this paper, the influence of the colloidal mass loading on the eigenmode shape and resonant frequency is investigated by measuring the thermal noise on rectangular AFM microcantilevers with and without beads attached at their extremities. The experiments are performed with a home-made ultra-sensitive AFM, based on differential interferometry. The focused beam from the interferometer probes the cantilever at different positions and the spatial shapes of the modes are determined up to the fifth resonance, without external excitation. The results clearly demonstrate that the first eigenmode is almost unchanged by mass loading. However the oscillation behavior of higher resonances presents a marked difference: with a particle glued at its extremity, the nodes of the modes are displaced towards the free end of the cantilever. These results are compared to an analytical model taking into account the mass and inertial moment of the load in an Euler-Bernoulli framework, where the normalization of the eigenmodes is explicitly worked out in order to allow a quantitative prediction of the thermal noise amplitude of each mode. A good agreement between the experimental results and the analytical model is demonstrated, allowing a clean calibration of the probe stiffness.

Why can artificial membranes be fabricated so rapidly in microfluidics?

Droplet interface bilayers are a convenient tool to produce and explore lipid membrane properties. We discuss why their formation time in microfluidics can be three to six orders of magnitude faster compared to conventional bulk settings.

Hydrodynamic interaction between a spherical particle and an elastic surface: a gentle probe for soft thin Films.

We study the hydrodynamic interaction between a sphere and an elastic surface at a nanoscale with a dynamic surface force apparatus. We show that the interplay between viscous forces and elastic deformations leads to very rich scaling properties of the force response, providing a unique signature of the surface elastic behavior. These properties are illustrated on three different examples: a thick elastomer, a thin elastomer film, and a layer of micrometric bubbles. We show that this fluid probing allows one to measure the Young's modulus of surfaces and soft thin layers at distance, without any direct solid-solid contact.

Nanohydrodynamics: the intrinsic flow boundary condition on smooth surfaces.

A dynamic surface force apparatus is used to determine the intrinsic flow boundary condition of two simple liquids, water and dodecane, on various smooth surfaces. We demonstrate the impact of experimental errors and data analysis on the accuracy of slip length determination. In all systems investigated, the dissipation is described by a well-defined boundary condition accounting for a whole range of separation, film thickness, and shear rate. A no-slip boundary condition is found in all wetting situations. On strongly hydrophobic surfaces, water undergoes finite slippage that increases with hydrophobicity. We also compare the relative influence of hydrophobicity and liquid viscosity on boundary flow by using water-glycerol mixtures with similar wetting properties.

High friction on a bubble mattress.

Reducing the friction of liquid flows on solid surfaces has become an important issue with the development of microfluidics systems, and more generally for the manipulation of fluids at small scales. To achieve high slippage of liquids at walls, the use of gas as a lubricant--such as microbubbles trapped in superhydrophobic surfaces--has been suggested. The effect of microbubbles on the effective boundary condition has been investigated in a number of theoretical studies, which basically show that on flat composite interfaces the magnitude of the slippage is proportional to the periodicity of the gaseous patterns. Recent experiments aiming to probe the effective boundary condition on superhydrophobic surfaces with trapped bubbles have indeed shown high slippage in agreement with these theoretical predictions. Here, we report nanorheology measurements of the boundary flow on a surface with calibrated microbubbles. We show that gas trapped at a solid surface can also act as an anti-lubricant and promote high friction. The liquid-gas menisci have a dramatic influence on the boundary condition, and can turn it from slippery to sticky. It is therefore essential to integrate the control of menisci in fluidic microsystems designed to reduce wall friction.