arXiv subjects

Jean Comtet

Publications and source records attributed to Jean Comtet.

15 recordsLinked to original sources

arXiv2026

Macromolecular tribology at flowing solid/liquid interfaces

Molecular-scale interactions between solvated macromolecules and solid surfaces govern a large number of processes, from biology to engineering. Yet, despite extensive characterization at the macroscopic level, our molecular understanding of polymer/surface interactions remains limited, particularly under out-of-equilibrium conditions. Here, we combine wide-field single-molecule microscopy with microfluidic transport to directly track the nanoscale dynamics of individual fluorescently tagged macromolecular PEG adsorbates, and investigate their subtle couplings with interfacial hydrodynamic flows. At equilibrium, we evidence marked surface dependence, with macromolecular dynamics switching from heterogeneous non-Brownian diffusion on hydrophilic glass to bidimensional Brownian-like transport in an interfacial physisorbed state on hydrophobic self-assembled monolayers. While for hydrophilic glass, the effect of the flow is restricted to an advective contribution during solvent-mediated flights, we uncover for the hydrophobic surfaces a peculiar regime of mixed macromolecular friction, whereby the adsorbed chain rubs on the solid wall while being continuously dragged by the near-surface hydrodynamic flow through interfacial slippage. Through joint analysis of equilibrium and out-of-equilibrium transport, we finely disentangle these molecular level frictional interactions with both the solid surface and the interfacial liquid. Beyond population-averaged dynamics, we further unveil a broad distribution of friction coefficients associated to individual chains, which we attribute conformational heterogeneities with sluggish reorganization timescale. By enabling direct observations of molecular-scale interfacial dynamics, our approach provides a novel molecular picture of macromolecular friction and adsorbate/surface interactions at flowing solid/liquid interfaces.

cond-mat.soft↗

arXiv2025

Wear in multiple network elastomers arises from the continuous accumulation of molecular damage rather than microcrack growth

Tire wear releases millions of tons of particles annually, bearing immense industrial and environmental impact. However, efforts to mitigate the wear of elastomeric materials remain largely empirical, due to a limited understanding of the underlying damage mechanisms that cause wear. Employing mechanochemical approaches on model multiple network elastomers, we uncover how polymer strand scission events - the elemental damage units in these disordered networks - evolve during frictional wear. Our findings demonstrate that discrete micro-slippage at rough contacting asperities damages the material several micrometers below the surface through stress-activated bond scission events. This steady accumulation of subsurface damage ultimately leads to material erosion through the generation of a degraded viscous layer, painting a new picture of wear as a continuous damage growth process. Our approach further demonstrates an enhanced resilience to wear when tuning material architecture to reduce sensitivity to stress fluctuations, paving the way for knowledge-based strategies to develop more sustainable materials.

cond-mat.soft↗

arXiv2025

Giant mobility of surface-trapped ionic charges following liquid tribocharging

The sliding motion of aqueous droplets on hydrohobic surfaces leads to charge separation at the trailing edge, with implications from triple-line friction to hydrovoltaic energy generation. Charges deposited on the solid surface have been attributed to ions or electrons ripped off from the liquid drop. However, the dynamics and exact physicochemical nature of these surface-trapped charges remains poorly explored. Here, we take advantage of a scanning-based electrostatic mapping technique, to directly quantify the spatiotemporal dynamics of surface deposited charges in the wake of droplets sliding on hydrophobic surfaces. We confirm the ionic nature of these interfacially trapped charges, and evidence that they undergo very fast bidimensional diffusive transport, gliding with low friction at the solid/gas interface. We interpret our observations in the framework of molecular dynamics simulation of hydrated ions adsorbed on solid surfaces, revealing a peculiar transport mechanism limited by purely interfacial friction of the ionic solvation shell with the solid surface. By uncovering the unexpected dynamics of these ionic puddles - a distinct state of interfacial ionic matter - our findings have general implications for molecular-scale ionic transport, electrified matter and wetting dynamics at interfaces.

cond-mat.soft↗

arXiv2022

Liquid-activated quantum emission from pristine hexagonal boron nitride for nanofluidic sensing

Liquids confined down to the atomic scale can show radically new properties. However, only indirect and ensemble measurements operate in such extreme confinement, calling for novel optical approaches enabling direct imaging at the molecular level. Here, we harness fluorescence originating from single-photon emitters at the surface of hexagonal boron nitride (hBN) for molecular imaging and sensing in nanometrically confined liquids. The emission originates from the chemisorption of organic solvent molecules onto native surface defects, revealing single-molecule dynamics at the interface through spatially correlated activation of neighboring defects. Emitter spectra further offer a direct readout of local dielectric properties, unveiling increasing dielectric order under nanometer-scale confinement. Liquid-activated native hBN defects bridge the gap between solid-state nanophotonics and nanofluidics, opening new avenues for nanoscale sensing and optofluidics.

cond-mat.mes-hall↗

arXiv2021

Direct growth of hexagonal boron nitride on photonic chips for high-throughput characterization

Adapting optical microscopy methods for nanoscale characterization of defects in two-dimensional (2D) materials is a vital step for photonic on-chip devices. To increase the analysis throughput, waveguide-based on-chip imaging platforms have been recently developed. Their inherent disadvantage, however, is the necessity to transfer the 2D material from the growth substrate to the imaging chip which introduces contamination, potentially altering the characterization results. Here we present a unique approach to circumvent these shortfalls by directly growing a widely-used 2D material (hexagonal boron nitride, hBN) on silicon nitride chips, and optically characterizing the defects in the intact as-grown material. We compare the direct growth approach to the standard wet transfer method, and confirm the clear advantages of the direct growth. While demonstrated with hBN in the current work, the method is easily extendable to other 2D materials.

physics.optics↗

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 angstr\"om-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↗

arXiv2021

Anomalous interfacial dynamics of single proton charges in binary aqueous solutions

Understanding the dynamics of charge exchange between a solid surface and a liquid is fundamental to various situations, ranging from nanofiltration to catalysis and electrochemistry. Charge transfer is ultimately determined by physicochemical processes (surface group dissociation, ion adsorption, etc...) occurring in the few layers of molecules at the interface between the solid and the liquid. Unfortunately, these processes remain largely uncharted due to the experimental challenges in probing interfacial charge dynamics with sufficiently high spatial and temporal resolution. Here, we resolve at the single-charge scale, the dynamics of proton charges at the interface between an hBN crystal and binary mixtures of water and organic amphiphilic solvents (e.g. alcohol), evidencing a dramatic influence of solvation on interfacial dynamics. Our observations rely on the application of spectral Single Molecule Localization Microscopy (sSMLM) to two types of optically active defects at the hBN surface, which act as intrinsic optical markers for both surface protonation and interaction with apolar alkyl groups of the organic solvent. We use sSMLM to reveal interfacial proton charge transport as a succession of jumps between the titratable surface defects, mediated by the transport of the solvated proton charge along the solid/liquid interface. By changing the relative concentration of water in binary mixtures, we evidence a non-trivial effect on interfacial proton charge dynamics, leading at intermediate water concentration to an increased affinity of the proton charge to the solid surface, accompanied by an increased surface diffusivity. These measurements confirm the strong role of solvation on interfacial proton charge transport and establish the potential of single-molecule localization techniques to probe a wide range of dynamic processes at solid/liquid interfaces.

cond-mat.soft↗

arXiv2020

Super-resolved optical mapping of reactive sulfur-vacancy in 2D transition metal dichalcogenides

Transition metal dichalcogenides (TMDs) represent an entire new class of semiconducting 2D materials with exciting properties. Defects in 2D TMDs can crucially affect their physical and chemical properties. However, characterization of the presence and spatial distribution of defects is limited either in throughput or in resolution. Here, we demonstrate large area mapping of reactive sulfur-deficient defects in 2D-TMDs coupling single-molecule localization microscopy with fluorescence labeling using thiol chemistry. Our method, reminiscent of PAINT strategies, relies on the specific binding by reversible physisorption of fluorescent probes to sulfur-vacancies via a thiol group and their intermittent emission to apply localization of the labeled defects with a precision down to 15 nm. Tuning the distance between the fluorophore and the docking thiol site allows us to control F\"oster Resonance Energy Transfer (FRET) process and reveal large structural defects such as grain boundaries and line defects, due to the local irregular lattice structure. Our methodology provides a simple and fast alternative for large-scale mapping of non-radiative defects in 2D materials and paves the way for in-situ and spatially resolved monitoring of the interaction between chemical agent and the defects in 2D materials that has general implications for defect engineering in aqueous condition.

physics.app-ph↗

arXiv2020

Quantifying and mapping covalent bond scission during elastomer fracture

Many new soft but tough rubbery materials have been recently discovered and new applications such as flexible prosthetics, stretchable electrodes or soft robotics continuously emerge. Yet, a credible multi-scale quantitative picture of damage and fracture of these materials has still not emerged, due to our fundamental inability to disentangle the irreversible scission of chemical bonds along the fracture path from dissipation by internal molecular friction. Here, by coupling new fluorogenic mechanochemistry with quantitative confocal microscopy mapping, we uncover how many and where covalent bonds are broken as an elastomer fractures. Our measurements reveal that bond scission near the crack plane can be delocalized over up to hundreds of micrometers and increase by a factor of 100 depending on temperature and stretch rate, pointing to an intricated coupling between strain rate dependent viscous dissipation and strain dependent irreversible network scission. These findings paint an entirely novel picture of fracture in soft materials, where energy dissipated by covalent bond scission accounts for a much larger fraction of the total fracture energy than previously believed. Our results pioneer the sensitive, quantitative and spatially-resolved detection of bond scission to assess material damage in a variety of soft materials and their applications.

cond-mat.soft↗

arXiv2019

Direct observation of water mediated single proton transport between hBN surface defects

Aqueous proton transport at interfaces is ubiquitous and crucial for a number of fields, ranging from cellular transport and signaling, to catalysis and membrane science. However, due to their light mass, small size and high chemical reactivity, uncovering single proton surface transport at room temperature and in aqueous environment has so far remained out-of-reach of conventional atomic-scale surface science techniques, such as STM. Here, we use single-molecule localization microscopy techniques to resolve optically the transport of individual excess protons at the interface of hexagonal boron nitride crystals and aqueous solutions at room temperature. Our label-free approach relies on the successive protonation and activation of optically active defects at the surface of the crystal allowing us to resolve interfacial proton transport at the single molecule scale with nanometric resolution and over micrometer range. Proton trajectories are revealed as a succession of jumps between proton-binding defects, mediated by interfacial water. We demonstrate unexpected interfacial proton mobility under illumination, limited by proton desorption from individual defects. The proposed mechanism is supported by ab initio molecular dynamics simulations of defected and pristine hBN/water interface. Our observations provide direct experimental evidence at the single molecule scale that interfacial water provides a preferential pathway for lateral proton transport. Our findings have fundamental and general implications for water-mediated molecular charge transport at interfaces.

cond-mat.mes-hall↗

arXiv2019

Wide-field spectral super-resolution mapping of optically active defects in hBN

Point defects can have significant impacts on the mechanical, electronic and optical properties of materials. The development of robust, multidimensional, high-throughput and large-scale characterization techniques of defects is thus crucial, from the establishment of integrated nanophotonic technologies to material growth optimization. Here, we demonstrate the potential of wide-field spectral single-molecule localization microscopy (spectral SMLM) for the determination of ensemble spectral properties, as well as characterization of spatial, spectral and temporal dynamics of single defects in CVD-grown and irradiated exfoliated hexagonal boron-nitride (hBN) materials. We characterize the heterogeneous spectral response of our samples, and identify at least two types of defects in CVD-grown materials, while irradiated exfoliated flakes show predominantly only one type of defect. We analyze the blinking kinetics and spectral emission for each type of defects, and discuss their implications with respect to the observed spectral heterogeneity of our samples. Our study shows the potential of wide-field spectral SMLM techniques in material science and paves the way towards quantitative multidimensional mapping of defect properties.

physics.optics↗

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

Passive phloem loading and long-distance transport in a synthetic tree-on-a-chip

Vascular plants rely on differences of osmotic pressure to export sugars from regions of synthesis (mature leaves) to sugar sinks (roots, fruits). In this process, known as Münch pressure flow, the loading of sugars from photosynthetic cells to the export conduit (the phloem) is crucial, as it sets the pressure head necessary to power long-distance transport. Whereas most herbaceous plants use active mechanisms to increase phloem concentration above that of the photosynthetic cells, in most tree species, for which transport distances are largest, loading seems to occur via passive symplastic diffusion from the mesophyll to the phloem. Here, we use a synthetic microfluidic model of a passive loader to explore the nonlinear dynamics that arise during export and determine the ability of passive loading to drive long-distance transport. We first demonstrate that in our device, phloem concentration is set by the balance between the resistances to diffusive loading from the source and convective export through the phloem. Convection-limited export corresponds to classical models of Münch transport, where phloem concentration is close to that of the source; in contrast, diffusion-limited export leads to small phloem concentrations and weak scaling of flow rates with the hydraulic resistance. We then show that the effective regime of convection-limited export is predominant in plants with large transport resistances and low xylem pressures. Moreover, hydrostatic pressures developed in our synthetic passive loader can reach botanically relevant values as high as 10 bars. We conclude that passive loading is sufficient to drive long-distance transport in large plants, and that trees are well suited to take full advantage of passive phloem loading strategies.

physics.bio-ph↗

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↗

arXiv2016

Phloem loading through plasmodesmata: a biophysical analysis

In many species, sucrose en route out of the leaf migrates from photosynthetically active mesophyll cells into the phloem down its concentration gradient via plasmodesmata, i.e., symplastically. In some of these plants the process is entirely passive, but in others phloem sucrose is actively converted into larger sugars, raffinose and stachyose, and segregated (trapped), thus raising total phloem sugar concentration to a level higher than in the mesophyll. Questions remain regarding the mechanisms and selective advantages conferred by both of these symplastic loading processes. Here we present an integrated model - including local and global transport and the kinetics of oligomerization - for passive and active symplastic loading. We also propose a physical model of transport through the plasmodesmata. With these models, we predict that: 1) relative to passive loading, oligomerization of sucrose in the phloem, even in the absence of segregation, lowers the sugar content in the leaf required to achieve a given export rate and accelerates export for a given concentration of sucrose in the mesophyll; and 2) segregation of oligomers and the inverted gradient of total sugar content can be achieved for physiologically reasonable parameter values, but even higher export rates can be accessed in scenarios in which polymers are allowed to diffuse back into the mesophyll. We discuss these predictions in relation to further studies aimed at the clarification of loading mechanisms, fitness of active and passive symplastic loading, and potential targets for engineering improved rates of export.

physics.bio-ph↗