RESUMEN
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.
RESUMEN
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.
RESUMEN
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.
RESUMEN
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.
Asunto(s)
Colina , Glicol de Etileno , SolventesRESUMEN
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].