Hydrogen Bond Donors Dictate the Frictional Response in Deep Eutectic Solvents.

Deep eutectic solvents (DESs) show promise as boundary lubricants between sliding surfaces, taking advantage of their physical stability, chemical stability, and tunability. Here, we study friction forces across nanofilms of two archetypal DES mixtures: choline chloride + ethylene glycol and choline chloride + glycerol. Using a surface force balance, we control the film thickness (to subnanometer precision) and determine the friction force simultaneously. Measurements are made at different mole fractions of the choline chloride salt and the molecular solvent, allowing us to determine the role of each species in the observed behavior. We find that the nature of the molecular solvent is dominant in determining the lubrication behavior, while the fraction of ChCl is relatively less important. By analyzing the steps in friction and the gradient of friction with load as the layers squeeze away from between the surfaces, we learn various mechanistic aspects of lubrication across the DES nanofilms of relevance to design and optimization of these promising fluids.

The surface force balance: direct measurement of interactions in fluids and soft matter.

Over the last half-century, direct measurements of surface forces have been instrumental in the exploration of a multitude of phenomena in liquid, soft, and biological matter. Measurements of van der Waals interactions, electrostatic interactions, hydrophobic interactions, structural forces, depletion forces, and many other effects have checked and challenged theoretical predictions and motivated new models and understanding. The gold-standard instrument for these measurements is thesurface force balance(SFB), orsurface forces apparatus, where interferometry is used to detect the interaction force and distance between two atomically smooth planes, with 0.1 nm resolution, over separations from about 1 µm down to contact. The measured interaction forcevs.distance gives access to the free energy of interaction across the fluid film; a fundamental quantity whose general form and subtle features reveal the underlying molecular and surface interactions and their variation. Motivated by new challenges in emerging fields of research, such as energy storage, biomaterials, non-equilibrium and driven systems, innovations to the apparatus are now clearing the way for new discoveries. It is now possible to measure interaction forces (and free energies) with control of electric field, surface potential, surface chemistry; to measure time-dependent effects; and to determine structurein situ. Here, we provide an overview the operating principles and capabilities of the SFB with particular focus on the recent developments and future possibilities of this remarkable technique.

Correction: The eutectic point in choline chloride and ethylene glycol mixtures.

Correction for 'The eutectic point in choline chloride and ethylene glycol mixtures' by Hannah J. Hayler et al., Chem. Commun., 2022, 58, 12728-12731, https://doi.org/10.1039/D2CC04008E.

Structure and anomalous underscreening in ethylammonium nitrate solutions confined between two mica surfaces.

The observation of long-range interactions across ionic liquids and highly concentrated electrolytes, extending far beyond the Debye-Hückel prediction and beyond the range predicted in liquid state theory, has been called 'anomalous underscreening'. A number of theoretical and experimental works have explored this phenomenon over recent years, although its origin is not yet fully understood. Most of the experimental studies of anomalous underscreening until now involved aprotic ionic liquids, and so it is of interest to explore interactions in protic ionic liquids where the distribution of charge in the fluid is different in nature. Here we present direct measurements of the interaction force as a function of separation distance, measured using a surface force balance, across solutions of a protic ionic liquid ethylammonium nitrate (EAN) and its mixtures with water over a range of volume fractions from 10 vol% to 100 vol% EAN. The results reveal intricate details about near-surface ordering and dynamics at the EAN-mica interface as well as anomalous underscreening consistent with that observed in the past with aprotic ionic liquids.

Zwitterions fine-tune interactions in electrolyte solutions.

Cellular organisms regulate electrolyte composition in the cytosol to optimize intracellular molecular interactions at the same time as balancing external osmotic pressure. While osmotic pressure can be tuned using multiple ionic, zwitterionic, and nonionic solutes, interactions between proteins and other macromolecules are sensitive to the precise composition of the medium. Nonetheless, the roles of individual ions and nonionic solutes in mediating cellular interactions remain relatively unexplored, and standard buffer solutions used in laboratory studies often contain only a few simple salts. Here, we report on model experiments investigating the combined effect of ionic and zwitterionic solutes on interaction forces across electrolytes, revealing a clear role for zwitterions in modifying interactions compared to simple salt solutions. First, we find that zwitterions act to disrupt water layering at interfaces, leading to smoothed interaction potentials. Second, we find that zwitterions strengthen electrostatic repulsions by enhancing effective surface charge. Third, zwitterions enhance the effective dielectric permittivity of the solution, and this "dielectricizer" effect extends the range of electrostatic repulsions compared to solutions without zwitterion present. The latter two effects are likely important in stabilizing proteins and other macromolecules when external osmotic and mechanical pressure are very high and simple ionic solutes alone would lead to collapse.

The eutectic point in choline chloride and ethylene glycol mixtures.

The choline chloride (ChCl) and ethylene glycol (EG) mixture has become established as a paradigmatic deep eutectic solvent (DES). Here, we present measurements of the phase behaviour of this mixture over a wide composition range, and provide an extended phase diagram. The eutectic point was found to lie at -28 ± 1 °C and 0.01 < xChCl < 0.02, sharply contrasting with the previously expected eutectic composition. Our observations confirm that the eutectic temperature is not 'deep' compared to the ideal solution theory prediction. We also observe a cold-crystallisation at T = -65 °C which may have been formerly misinterpreted as the eutectic point.

Electrotunable friction with ionic liquid lubricants.

Room-temperature ionic liquids and their mixtures with organic solvents as lubricants open a route to control lubricity at the nanoscale via electrical polarization of the sliding surfaces. Electronanotribology is an emerging field that has a potential to realize in situ control of friction-that is, turning the friction on and off on demand. However, fulfilling its promise needs more research. Here we provide an overview of this emerging research area, from its birth to the current state, reviewing the main achievements in non-equilibrium molecular dynamics simulations and experiments using atomic force microscopes and surface force apparatus. We also present a discussion of the challenges that need to be solved for future applications of electrotunable friction.

Surface Reconstruction of Fluoropolymers in Liquid Media.

Surface reconstruction is the rearrangement of atoms or molecules at an interface in response to a stimulus, driven by lowering the overall free energy of the system. Perfluoroalkyl acrylate polymers with short side chains undergo reconstruction at room temperature when exposed to water. Here, we use contact angle aging to examine the liquid- and temperature- dependency of surface reconstruction of plasma polymerized perfluoroalkyl acrylates. We use a first order kinetic model to examine the dynamics of reconstructive processes. Our results show that, above the bulk melting point of the polymers, the contact angles of both polar and nonpolar (hydrocarbon) liquids show a time dependency well fit by the model. We conclude that surface reconstruction can be driven by the preferential segregation of hydrocarbon and fluorocarbon moieties as well as by polar interactions. This has implications in terms of using fluorocarbons to design oleophobic surfaces (and vice versa) and in terms of designing fluorocarbon and/or hydrocarbon surfaces with switchable wettability.

Controlling adhesion using AC electric fields across fluid films.

We demonstrate reversible and switchable actuation using AC electric fields to bring two surfaces separated by a thin film of ionic fluid in and out of adhesive contact. Using a surface force balance we apply electric fields normal to a crossed-cylinder contact and measure directly the adhesive force and surface separation with sub-molecular resolution. Taking advantage of the oscillatory structural force acting between the surfaces across the fluid, which we show to be unaffected by the AC field, we pick between the distinct (quantized) adhesive states through precise tuning of the field. This proof-of-concept indicates exquisite control of surface interactions using an external field.

Surface Forces and Structure in a Water-in-Salt Electrolyte.

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.

Nanolubrication in deep eutectic solvents.

We report surface force balance measurements of the normal surface force and friction between two mica surfaces separated by a nanofilm of the deep eutectic solvent ethaline. Ethaline, a 1 : 2 mixture of choline chloride and ethylene glycol, was studied under dry conditions, under ambient conditions and with added water, revealing surface structural layers and quantised frictional response highly sensitive to water content, including regions of super-lubric behaviour under dry conditions and with added water. We also report exceptionally long-ranged electrostatic repulsion far in excess of that predicted by Debye-Hückel theory for a system with such high electrolyte content, consistent with previously reported observations of "underscreening" in ionic liquid and concentrated aqueous electrolyte systems [Smith et al., J. Phys. Chem. Lett., 2016, 7(12), 2157].

A polymer coating which is sticky yet repulsive to water and slippery yet attractive for oils.

A one-step process has been developed to produce a polymer coating which is hydrophobic and oleophilic, but which oil slides off and water adheres to at all tilt angles - including when vertically inclined or inverted. The polymer is transparent, and the plasma coating process is independent of substrate composition and geometry.

A new methodology for a detailed investigation of quantized friction in ionic liquids.

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.

Solidification and superlubricity with molecular alkane films.

Hydrocarbon films confined between smooth mica surfaces have long provided an experimental playground for model studies of structure and dynamics of confined liquids. However, fundamental questions regarding the phase behavior and shear properties in this simple system remain unsolved. With ultrasensitive resolution in film thickness and shear stress, and control over the crystallographic alignment of the confining surfaces, we here investigate the shear forces transmitted across nanoscale films of dodecane down to a single molecular layer. We resolve the conditions under which liquid-solid phase transitions occur and explain friction coefficients spanning several orders of magnitude. We find that commensurate surface alignment and presence of water at the interfaces each lead to moderate or high friction, whereas friction coefficients down to [Formula: see text] are observed for a single molecular layer of dodecane trapped between crystallographically misaligned dry surfaces. This ultralow friction is attributed to sliding at the incommensurate interface between one of the mica surfaces and the laterally ordered solid molecular film, reconciling previous interpretations.

Interfacial Structure and Boundary Lubrication of a Dicationic Ionic Liquid.

We report measurements of the normal surface forces and friction forces between two mica surfaces separated by a nanofilm of dicationic ionic liquid using a Surface Force Balance. The dicationic ionic liquid 1,10-bis(3-methylimidazolium)decane di[bis(trifluoromethylsulfonyl)imide] forms a layered structure in nanoconfinement, revealed by oscillatory structural forces. Friction measurements performed at different film thicknesses display quantized friction, i.e., discontinuities in friction as layers are squeezed out and friction coefficients dependent on the number of liquid layers confined between the surfaces. The details of the friction traces indicate a liquidlike film, and, surprisingly, decreasing friction with increasing water content; we discuss possible mechanisms underlying these observations. This latter trait may be helpful in applications where ionic liquid lubricants cannot be insulated against humid environments.