RESUMEN
Water-in-salt electrolytes are a fascinating new class of highly concentrated aqueous solutions with wide electrochemical stability windows that make them viable as aqueous battery electrolytes. However, the high ion concentration of water-in-salt electrolytes means that these systems are poorly understood when compared to more dilute electrolyte solutions. Here, we present direct surface force measurements across thin films of a water-in-salt electrolyte at several concentrations. We find that the electrolyte adopts a layered structure at charged interfaces composed of a nanostructure of a hydrated cation and nonaqueous anion-rich domains. These observations will aid in the interpretation of capacitance and double-layer behavior of water-in-salt electrolytes with consequences for their use in energy storage devices.
RESUMEN
When confined at the nanoscale between smooth surfaces, an ionic liquid forms a structured film responding to shear in a quantized way, i.e., with a friction coefficient indexed by the number of layers in the gap. So far, only a few experiments have been performed to study this phenomenon, because of the delicate nature of the measurements. We propose a new methodology to measure friction with a surface force balance, based on the simultaneous application of normal and lateral motions to the surfaces, allowing for a more precise, comprehensive and rapid determination of the friction response. We report on proof-of-concept experiments with an ionic liquid confined between mica surfaces in dry or wet conditions, showing the phenomenon of quantized friction with an unprecedented resolution. First, we show that the variation of the kinetic friction force with the applied load for a given layer is not linear, but can be quantitatively described by two additive contributions that are respectively proportional to the load and to the contact area. Then, we find that humidity improves the resistance of the layers to be squeezed-out and extends the range of loads in which the liquid behaves as a superlubricant, interpreted by an enhanced dissolution of the potassium ions on the mica leading to a larger surface charge. There, we note a liquid-like friction behavior, and observe in certain conditions a clear variation of the kinetic friction force over two decades of shearing velocities, that does not obey a simple Arrhenius dynamics.
RESUMEN
Buckminsterfullerenes (C60) are near-spherical molecules, which freely rotate at room temperature in the solid state and when dissolved in solution. An intriguing question arises as to whether C60 molecules can act as "molecular ball bearings," that is, preventing direct contact between two solid surfaces while simultaneously dissipating shear stress through fast rotation. To explore this, we performed measurements of friction across a solution of C60 in the boundary lubrication regime. High-resolution shear and normal force measurements between mica sheets separated by C60 solution were made using a surface force balance to provide single-asperity contact and sub-nanometer resolution in film thickness. We find that, even at a small volume fraction, C60 forms a solidlike amorphous boundary film sustaining a high normal load, suggesting that this system undergoes a glass transition under confinement. The C60 film gives rise to a low friction coefficient up to moderate applied loads, and we discuss the possible relevance of the ball-bearing effect at the molecular scale.
RESUMEN
Small-scale heterogeneities have long been understood to give rise to contact angle hysteresis. More recently, the question of how they influence contact line dynamics has generated interest. Models that express the hysteresis or dynamics in terms of defect properties exist but have yet to be conclusively tested by experiment. Here we produce heterogeneous surfaces and thoroughly characterize individual defects. Precise dynamical measurements allow us to conclude that there is no evidence of a thermally activated dynamics due to their presence, but that the hysteresis scales with their concentration and the square of their height, as predicted by some simple models.
RESUMEN
At the nanometer scale, the motion of a contact line separating a dry from a wet region is limited by the presence of surface heterogeneities that pin it. Here we revisit the seminal model proposed by Joanny and de Gennes to include the influence of thermal noise and viscosity using a Langevin model with two degrees of freedom: the average position of the contact line and its distortion. We identify the conditions under which the dynamics in a velocity-driven experiment can in fact be described by a constant forcing at small scale. We then relate the asymptotic properties of the relation between force and contact line velocity to the properties of the defects. In particular, we show that Kramers' approximation misses the strong asymmetry between advancing and receding directions. Finally, we show how to use the model to fit experimental data and extract the salient features of the surface energy landscape.
RESUMEN
How a liquid drop sits or moves depends on the physical and mechanical properties of the underlying substrate. This can be seen in the hysteresis of the contact angle made by a drop on a solid, which is known to originate from surface heterogeneities, and in the slowing of droplet motion on deformable solids. Here, we show how a moving contact line can be used to characterize a molecularly thin polymer layer on a solid. We find that the hysteresis depends on the polymerization index and can be optimized to be vanishingly small (<0.07°). The mechanical properties are quantitatively deduced from the microscopic contact angle, which is proportional to the speed of the contact line and the Rouse relaxation time divided by the layer thickness, in agreement with theory. Our work opens the prospect of measuring the properties of functionalized interfaces in microfluidic and biomedical applications that are otherwise inaccessible.
RESUMEN
The contact angle of a liquid drop moving on a real solid surface depends on the speed and direction of motion of the three-phase contact line. Many experiments have demonstrated that pinning on surface defects, thermal activation and viscous dissipation impact contact line dynamics, but so far, efforts have failed to disentangle the role of each of these dissipation channels. Here, we propose a unifying multiscale approach that provides a single quantitative framework. We use this approach to successfully account for the dynamics measured in a classic dip-coating experiment performed over an unprecedentedly wide range of velocity. We show that the full contact line dynamics up to the liquid film entrainment threshold can be parametrized by the size, amplitude and density of nanometer-scale defects. This leads us to reinterpret the contact angle hysteresis as a dynamical crossover rather than a depinning transition.