arXiv subjects

Alessandro Siria

Publications and source records attributed to Alessandro Siria.

At least 19 recordsLinked to original sources

arXiv2024

Evolution of Interfacial Hydration Structure Induced by Ion Condensation and Correlation Effects

Interfacial hydration structures are crucial in wide-ranging applications, including battery, colloid, lubrication etc. Multivalent ions like Mg2+ and La3+ show irreplaceable roles in these applications, which are hypothesized due to their unique interfacial hydration structures. However, this hypothesis lacks experimental supports. Here, using three-dimensional atomic force microscopy (3D-AFM), we provide the first observation for their interfacial hydration structures with molecular resolution. We observed the evolution of layered hydration structures at La(NO3)3 solution-mica interfaces with concentration. As concentration increases from 25 mM to 2 M, the layer number varies from 2 to 1 and back to 2, and the interlayer thickness rises from 0.25 to 0.34 nm, with hydration force increasing from 0.27+-0.07 to 1.04+-0.24 nN. Theory and molecular simulation reveal that multivalence induces concentration-dependent ion condensation and correlation effects, resulting in compositional and structural evolution within interfacial hydration structures. Additional experiments with MgCl2-mica, La(NO3)3-graphite and Al(NO3)3-mica interfaces together with literature comparison confirm the universality of this mechanism for both multivalent and monovalent ions. New factors affecting interfacial hydration structures are revealed, including concentration and solvent dielectric constant. This insight provides guidance for designing interfacial hydration structures to optimize solid-liquid-interphase for battery life extension, modulate colloid stability and develop efficient lubricants.

physics.chem-ph↗

arXiv2024

Liquid-solid friction on crystalline surfaces: a perspective

Liquids flowing against solid surfaces experience friction. While solid friction is familiar to anyone with a sense of touch, liquid friction is much more exotic. At macroscopic scales indeed, the assumption of inifinite friction, i.e. that interfacial liquid molecules stick to solid surfaces, is hard to disprove. Still, it has been known for a few decades that some materials exhibit very strong liquid slippage, leading to a dramatic increase in the permeability of nanoscale tubes to liquid flow. Harnessing liquid friction holds the promise of high-efficiency membrane separation processes, heat recovery systems or blue energy harvesting, making it a highly strategic field for reducing carbon emissions and addressing the climate emergency. In this chapter we review the history of liquid-solid friction measurements, mainly driven by the advent of new techniques and materials. We highlight the most established results and point out some directions that seem to us to be particularly dynamic and promising for the field.

cond-mat.soft↗

arXiv2024

Anomalous friction of supercooled glycerol on mica

The fundamental understanding of friction of liquids on solid surfaces remains one of the key knowledge gaps in the transport of fluids. While the standard perspective emphasizes the role of wettability and commensurability, recent works have unveiled the crucial role of the solid's internal excitations, whether electronic or phononic, on liquid-solid dissipation. In this work, we take advantage of the considerable variation of the molecular timescales of supercooled glycerol under mild change of temperature, in order to explore how friction depends on the liquid's molecular dynamics. Using a dedicated tuning-fork-based AFM to measure the hydrodynamic slippage of glycerol on mica, we report a 2-order of magnitude increase of the slip length with decreasing temperature by only 30°C. However the solid-liquid friction coefficient is found to be a non monotonous function of the fluid molecular relaxation rate, fα, at odd with an expected Arrhenius behavior. In particular, the linear increase of friction with the liquid molecular rate measured at high temperature cannot be accounted for by existing modelling. We show that this unconventional and non-arrhenian friction is consistent with a contribution of the solid's phonons to the liquid-solid friction. This dynamical friction opens new perspectives to control hydrodynamic flows by properly engineering phononic and electronic excitation spectra in channel walls.

cond-mat.soft↗

arXiv2024

Drastic reduction of dynamic liquid-solid friction in supercooled glycerol

This study addresses the influence of internal liquid dynamics on liquid-solid friction. Taking advantage of the wide range of relaxation timescales in supercooled liquids, we use a tuning-fork-based AFM to measure the slippage of supercooled glycerol on mica at 30 kHz. We report a 2-order of magnitude increase of slippage with decreasing temperature by only 30°C. More importantly, as the bulk liquid dynamics are slowed with decreasing temperature, we report a sharp drop of the interfacial friction coefficient in contrast with the usual assumption of thermally activated interfacial dynamics. To rationalize this original behavior, we account for the contribution of solid fluctuations to liquid friction. We show that a minimalistic single phonon-branch model of the mica surface yields semi-quantitative agreement with our measurements. In this picture, the liquid's relaxation rate is the tuning knob between two friction regimes where the wall is seen either as a static corrugated potential or as a thermally fluctuating surface. Remarkably, this study bridges soft and hard condensed matter: hydrodynamic flow controlled by the solid's dynamical modes.

cond-mat.soft↗

arXiv2023

Disentangling $1/f$ noise from confined ion dynamics

Ion transport through biological and solid-state nanochannels is known to be a highly noisy process. The power spectrum of current fluctuations is empirically known to scale like the inverse of frequency, following the long-standing yet poorly understood Hooge's law. Here, we report measurements of current fluctuations across nanometer-scale two-dimensional channels with different surface properties. The structure of fluctuations is found to depend on channel's material. While in pristine channels current fluctuations scale like $1/f^{1+a}$ with $a = 0 - 0.5$, the noise power spectrum of activated graphite channels displays different regimes depending on frequency. Based on these observations, we develop a theoretical formalism directly linking ion dynamics and current fluctuations. We predict that the noise power spectrum take the form $1/f \times S_\text{channel}(f)$, where $1/f$ fluctuations emerge in fluidic reservoirs on both sides of the channel and $S_\text{channel}$ describes fluctuations inside it. Deviations to Hooge's law thus allow direct access to the ion transport dynamics of the channel -- explaining the entire phenomenology observed in experiments on 2D nanochannels. Our results demonstrate how current fluctuations can be used to characterize nanoscale ion dynamics.

cond-mat.soft↗

arXiv2023

Strong electronic winds blowing under liquid flows on carbon surfaces

The interface between a liquid and a solid is the location of plethora of intrincate mechanisms at the nanoscale, at the root of their specific emerging properties in natural processes or technological applications. However, while the structural properties and chemistry of interfaces have been intensively explored, the effect of the solid-state electronic transport at the fluid interface has been broadly overlooked up to now. It has been reported that water flowing against carbon-based nanomaterials, such as carbon nanotubes or graphene sheets, does induce electronic currents, but the mechanism at stake remains controversial. Here, we unveil the molecular mechanisms underlying the hydro-electronic couplings by investigating the electronic conversion under flow at the nanoscale. We use a tuning fork-Atomic Force Microscope (AFM) to deposit and displace a micrometric droplet of both ionic and non-ionic liquids on a multilayer graphene sample, while recording the electrical current across the carbon flake. We report measurements of an oscillation-induced current which is several orders of magnitude larger than previously reported for water on carbon , and further boosted by the presence of surface wrinkles on the carbon layer. Our results point to a peculiar momentum transfer mechanism between fluid molecules and charge carriers in the carbon walls mediated by phonon excitations in the solid. Our findings pave the way for active control of fluid transfer at the nanoscale by harnessing the complex interplay between collective excitations in the solid and the molecules in the fluid.

cond-mat.mes-hall↗

arXiv2021

Amplitude Nanofriction Spectroscopy

Atomic scale friction, an indispensable element of nanotechnology, requires a direct access to, under actual growing shear stress, its successive live phases: from static pinning, to depinning and transient evolution, eventually ushering in steady state kinetic friction. Standard tip-based atomic force microscopy generally addresses the steady state, but the prior intermediate steps are much less explored. Here we present an experimental and simulation approach, where an oscillatory shear force of increasing amplitude leads to a one-shot investigation of all these successive aspects. Demonstration with controlled gold nanocontacts sliding on graphite uncovers phenomena that bridge the gap between initial depinning and large speed sliding, of potential relevance for atomic scale time and magnitude dependent rheology.

cond-mat.mtrl-sci↗

arXiv2021

Nanotribology of ionic liquids: transition to yielding response in nanometric confinement with metallic surfaces

Room Temperature Ionic Liquids (RTILs) are molten salts which exhibit uniques physical and chemical properties, commonly harnessed for lubrication and energy applications. The pure ionic nature of RTIL leads to strong electrostatic interactions among the liquid, furthermore exalted in the presence of interfaces and confinement. In this work, we use a tuning-fork based dynamic Surface Force Tribometer (TF-SFT), which allows probing both the rheological and the tribological properties of RTILs films confined between a millimetric sphere and a surface, over a wide range of confinements. When the RTIL is confined between metallic surfaces, we evidence an abrupt change of its rheological properties below a threshold confinement. This is reminiscent of a recently reported confinement induced capillary freezing, here observed with a wide contact area. In parallel, we probe the tribological response of the film under imposed nanometric shear deformation and unveil a yielding behaviour of the interfacial solid phase below this threshold confinement. This is characterized by a transition from an elastic to a plastic regime, exhibiting striking similarities with the response of glassy materials. This transition to yielding of the RTIL in metallic confinement leads overall to a reduction in friction and offers a self-healing protection of the surfaces avoiding direct contact, with obvious applications in tribology.

cond-mat.soft↗

arXiv2021

Atomic rheology of gold nanojunctions

Despite extensive investigations of dissipation and deformation processes in micro- and nano- sized metallic samples, the mechanisms at play during deformation of systems with ultimate, molecular size remain elusive. While metallic nanojunctions, obtained by stretching metallic wires down to the atomic level are a system of choice to explore atomic scale contacts, it has not been possible up to now to extract the full equilibrium and out of equilibrium rheological flow properties of matter at such scales. Here, by using a quartz-tuning fork based Atomic Force Microscope (TF-AFM), we combine electrical and rheological measurement on angström-size gold junctions to study the non linear rheology of this model atomic system. By submitting the junction to increasing sub-nanometric deformations we uncover a transition from a purely elastic regime to a plastic, and eventually to a viscous-like fluidized regime, akin to the rheology of soft yielding materials, though orders of magnitude difference in length scale. The fluidized state furthermore highlights capillary attraction, as expected for liquid capillary bridges. This shear fluidization cannot be captured by classical models of friction between atomic planes, pointing to unexpected dissipative behavior of defect-free metallic junctions at the ultimate scales. Atomic rheology is therefore a powerful tool to probe the structural reorganization of atomic contacts.

cond-mat.mes-hall↗

arXiv2020

Mechanically activated ionic transport across single-digit carbon nanotubes

Fluid and ionic transport at nanoscale recently highlighted a wealth of exotic behaviours. However, the artificial nanofluidic devices are still far from the advanced functionalities existing in biological systems, such as electrically and mechanically activated transport. Here we focus on the ionic transport through 2 nm-radius individual multiwalled carbon nanotubes (CNT), under the combination of mechanical and electrical forcings. Our findings evidence mechanically activated ionic transport under the form of an ionic conductance which depends quadratically on the applied pressure. Our theoretical study relates this behaviour with the complex interplay between electrical and mechanical drivings, and shows that the superlubricity of CNT is a prerequisite to attain mechanically activated transport. The pressure sensitivity shares similarities with the response of biological mechanosensitive ion channels observed here for the first time in an artificial system. This paves the way to build new active nanofluidic functionalities inspired by the complex biological machinery.

cond-mat.mes-hall↗

arXiv2020

Beyond the Tradeoff: Dynamic Selectivity in Ionic Transport and Current Selectivity

Traditionally, ion-selectivity in nanopores and nanoporous membranes is understood to be a consequence of Debye overlap, in which the Debye screening length is comparable to the nanopore radius somewhere along the length of the nanopore(s). This criterion sets a significant limitation on the size of ion-selective nanopores, as the Debye length is on the order of 1 - 10 nm for typical ionic concentrations. However, the analytical results we present here demonstrate that surface conductance generates a dynamical selectivity in ion transport, and this selectivity is controlled by so-called Dukhin, rather than Debye, overlap. The Dukhin length, defined as the ratio of surface to bulk conductance, reaches values of hundreds of nanometers for typical surface charge densities and ionic concentrations, suggesting the possibility of designing large-nanopore (10 - 100 nm), high-conductance membranes exhibiting significant ion-selectivity. Such membranes would have potentially dramatic implications for the efficiency of osmotic energy conversion and separation techniques. Furthermore, we demonstrate that this mechanism of dynamic selectivity leads ultimately to the rectification of ionic current, rationalizing previous studies showing that Debye overlap is not a necessary condition for the occurrence of rectifying behavior in nanopores.

cond-mat.soft↗

arXiv2020

Ionic Coulomb blockade as a fractional Wien effect

Recent advances in nanofluidics have allowed exploration of ion transport down to molecular scale confinement, yet artificial porins are still far from reaching the advanced functionalities of biological ion machinery. Achieving single ion transport that is tuneable by an external gate -- the ionic analogue of electronic Coulomb blockade (CB) -- would open new avenues in this quest. However, an understanding of ionic CB beyond the electronic analogy is still lacking. Here we show that the many-body dynamics of ions in a charged nanochannel result in a quantised and strongly nonlinear ionic transport, in full agreement with molecular simulations. We find that ionic CB occurs when, upon sufficient confinement, oppositely charged ions form 'Bjerrum pairs', and the conduction proceeds through a mechanism reminiscent of Onsager's Wien effect. Our findings open the way to novel nanofluidic functionalities, such as an ionic-CB-based ion pump inspired by its electronic counterpart.

cond-mat.soft↗

arXiv2020

Dramatic pressure-sensitive ion conduction in conical nanopores

Ion transporters in Nature exhibit a wealth of complex transport properties such as voltage gating, activation, and mechanosensitive behavior. When combined, such processes result in advanced ionic machines achieving active ion transport, high selectivity, or signal processing. On the artificial side, there has been much recent progress in the design and study of transport in ionic channels, but mimicking the advanced functionalities of ion transporters remains as yet out of reach. A prerequisite is the development of ionic responses sensitive to external stimuli. In the present work, we report a counterintuitive and highly nonlinear coupling between electric and pressure-driven transport in a conical nanopore, manifesting as a strong pressure-dependence of the ion conductance. This result is at odds with standard linear response theory and is akin to a mechanical transistor functionality. We fully rationalize this behavior on the basis of the coupled electrohydrodynamics in the conical pore by extending the Poisson-Nernst-Planck-Stokes framework. The model is shown to capture the subtle mechanical balance occurring within an extended spatially charged zone in the nanopore. The pronounced sensitivity to mechanical forcing offers leads in tuning ion transport by mechanical stimuli. The results presented here provide a promising avenue for the design of tailored membrane functionalities.

cond-mat.soft↗

arXiv2019

Molecular streaming and its voltage control in ångström scale channels

The field of nanofluidics has shown considerable progress over the past decade thanks to key instrumental advances, leading to the discovery of a number of exotic transport phenomena for fluids and ions under extreme confinement. Recently, van der Waals assembly of 2D materials allowed fabrication of artificial channels with angström-scale precision. This ultimate confinement to the true molecular scale revealed unforeseen behaviour for both mass and ionic transport. In this work, we explore pressure-driven streaming in such molecular-size slits and report a new electro-hydrodynamic effect under coupled pressure and electric force. It takes the form of a transistor-like response of the pressure induced ionic streaming: an applied bias of a fraction of a volt results in an enhancement of the streaming mobility by up to 20 times. The gating effect is observed with both graphite and boron nitride channels but exhibits marked material-dependent features. Our observations are rationalized by a theoretical framework for the flow dynamics, including the frictional interaction of water, ions and the confining surfaces as a key ingredient. The material dependence of the voltage modulation can be traced back to a contrasting molecular friction on graphene and boron nitride. The highly nonlinear transport under molecular-scale confinement offers new routes to actively control molecular and ion transport and design elementary building blocks for artificial ionic machinery, such as ion pumps. Furthermore, it provides a versatile platform to explore electro-mechanical couplings potentially at play in recently discovered mechanosensitive ionic channels.

cond-mat.soft↗

arXiv2019

MicroMegascope based dynamic Surface Force Apparatus

Surface Force Apparatus (SFA) allows to accurately resolve the interfacial properties of fluids confined between extended surfaces. The accuracy of the SFA makes it an ubiquitous tool for the nanoscale mechanical characterization of soft matter systems. The SFA traditionally measures force-distance profiles through interferometry with subnanometric distance precision. However, these techniques often require a dedicated and technically demanding experimental setup, and there remains a need for versatile and simple force-distance measurement tools. Here we present a MicroMegascope based dynamic Surface Force Apparatus capable of accurate measurement of the dynamic force profile of a liquid confined between a millimetric sphere and a planar substrate. Normal and shear mechanical impedance is measured within the classical Frequency Modulation framework. We measure rheological and frictional properties from micrometric to molecular confinement. We also highlight the resolution of small interfacial features such as ionic liquid layering. This apparatus shows promise as a versatile force-distance measurement device for exotic surfaces or extreme environments.

physics.ins-det↗

arXiv2018

MicroMegascope

Atomic Force Microscopy (AFM) allows to reconstruct the topography of surface with a resolution in the nanometer range. The exceptional resolution attainable with the AFM makes this instrument a key tool in nanoscience and technology. The core of the set-up relies on the detection of the mechanical properties of a micro-oscillator when approached to a sample to image. Despite the fact that AFM is nowadays a very common instrument for research and development applications, thanks to the exceptional performances and the relative simplicity to use it, the fabrication of the micrometric scale mechanical oscillator is still a very complicated and expensive task requiring a dedicated platform. Being able to perform atomic force microscopy with a macroscopic oscillator would make the instrument more versatile and accessible for an even larger spectrum of applications and audiences. We present for the first time atomic force imaging with a centimetric oscillator. We show how it is possible to perform topographical images with nanometric resolution with a grams tuning fork. The images presented here are obtained with an aluminum tuning fork of centimeter size as sensor on which an accelerometer is glued on one prong to measure the oscillation of the resonator. In addition to the stunning sensitivity, by imaging both in air and in liquid, we show the high versatility of such oscillator. The set up proposed here can be extended to numerous experiments where the probe needs to be heavy and/or very complex as well as the environment.

physics.ins-det↗

arXiv2017

Atomic Force Nanoscope

Atomic Force Microscopy (AFM) allows to probe matter at atomic scale by measuring the perturbation of a nanomechanical oscillator induced by near-field interaction forces. The quest to improve sensitivity and resolution of AFM has forced the introduction of a new class of resonators with dimensions well below the micrometer scale. In this context, nanotube resonators are the ultimate mechanical oscillators because of their one dimensional nature, small mass and almost perfect crystallinity, coupled to the possibility of functionalisation, these properties make them the perfect candidates as ultra sensitive, on-demand force sensors. However their tiny dimensions make the measurement of the mechanical properties a very challenging task in particular when working in cavity free geometry at ambient temperature. By using a highly focused electron beam, we show that the mechanical response of nanotubes can be quantitatively measured while approaching to a surface sample. By coupling electron beam detection of individual nanotubes with a custom AFM we can image the surface topography of a sample by measuring in real time the mechanical properties of the nanoresonators. The combination of very small size and mass together with the high resolution of the electron beam detection method offers unprecedented opportunities for the development of a new class of Atomic Force Nanoscope (AFN).

cond-mat.mes-hall↗

arXiv2016

Nanoscale capillary freezing of ionic liquids confined between metallic interfaces and the role of electronic screening

Room temperature Ionic liquids (RTIL) received considerable attention as a new class of materials with fundamental importance for energy storage \cite{Armand2009, Uesugi2013} and active lubrication \cite{Palacio2010, Dold2015, Smith2013a}. Their unique properties result from the competition of strong electrostatic interactions with properly designed molecular structure to avoid crystalization at room temperature. They are however unsual liquids, which challenge fundamentally the classical frameworks of electrolytes. In particular their behavior at electrified interfaces remains elusive with very rich and exotic responses relevant to their electrochemical activity \cite{Kornyshev2014,Merlet2012,Perkin2013,Atkin2009,Rotenberg2015,Endres2012,Bovio2009a,Bovio2009,Yokota2010}. In this work, we use quartz tuning fork based AFM nanorheological measurements to explore the properties of RTIL in nanometric confinement. We unveil a dramatic change of the RTIL towards a solid-like phase below a threshold thickness, pointing to a capillary freezing in confinement. This threshold thickness is found to be intimately related to the metallic nature of the confining materials, with more metallic surfaces facilitating capillary freezing. This behavior is interpreted theoretically in terms of the shift of the freezing transition, taking into account the influence of the electronic screening on RTIL wetting of the confining surfaces, as described by the simple Thomas-Fermi approach. Our findings provides fresh views on the properties of confined RTIL with important implications for their statics and dynamics inside nanoporous metallic structures. This also suggests applications to tune nanoscale lubrication with the phase-changing RTIL, by varying the nature as well as the patterning of the subtrate, and the application of active polarisation.

cond-mat.mtrl-sci↗