Time Scale Of Experiment Research Articles

In Situ Raman Spectroscopy as a Valuable Tool for Monitoring Crystallization Kinetics in Molecular Glasses

The performance of in situ Raman microscopy (IRM) in monitoring the crystallization kinetics of amorphous drugs (griseofulvin and indomethacin) was evaluated using a comparison with the data obtained via differential scanning calorimetry (DSC). IRM was found to accurately and sensitively detect the initial stages of the crystal growth processes, including the rapid glass–crystal surface growth or recrystallization between polymorphic phases, with the reliable localized identification of the particular polymorphs being the main advantage of IRM over DSC. However, from the quantitative point of view, the reproducibility of the IRM measurements was found to be potentially significantly hindered due to inaccurate temperature recording and calibration, variability in the Raman spectra corresponding to the fully amorphous and crystalline phases, and an overly limited number of spectra possible to collect during acceptable experimental timescales because of the applied heating rates. Since theoretical simulations showed that, from the kinetics point of view, the constant density of collected data points per kinetic effect results in the smallest distortions, only the employment of the fast Raman mapping functions could advance the performance of IRM above that of calorimetric measurements.

A hybrid mesoscale-continuum approach to understand and predict melting kinetics of Al powders during laser processing

Abstract Laser interaction with metallic powders during additive manufacturing (AM) leads to fast heating and cooling rates that can affect the quality of the final products due to the formation of defects. One of the first steps towards predicting microstructures generated during AM, therefore, requires an accurate understanding of the laser energy deposition mechanisms that determine the melting kinetics at the level of individual powders. The critical challenge, however, is the availability of computational methods that can model the laser energy absorption, heat transfer, and the related microstructure evolution in individual metal powders at the length and time scales of AM. This manuscript demonstrates the capability of a novel scale-bridging methodology that combines the mesoscale quasi-coarse-grained dynamics (QCGD) simulations with a continuum two-temperature model (TTM) to account for the atomistic mechanisms of laser energy deposition and microstructure evolution and predict the kinetics of melting of individual powders at the experimental time and length scales. The scale-bridging capability of the hybrid QCGD-TTM simulations is demonstrated here by investigating the laser-induced microstructure evolution in aluminum powders with various sizes ranging from 200 nm to 20 µm. The analysis of the evolution of temperature, pressure, phase fraction, and melt fronts suggests the melting mechanism is heterogeneous due to the interaction with a laser, and the melting time is observed to decrease exponentially as the laser intensity increases. The solid-liquid interface velocity can be quantified to identify correlations with interface temperatures, and the predicted values satisfy the theoretically reported limits of crystal stability of metals against homogeneous melting. In addition, the pre-melting is found at the grain boundaries of 20 µm polycrystalline aluminum powder, while a minute contribution to melting is observed. This manuscript demonstrates the capability of the QCGD-TTM method to capture laser-powder interaction and allow the investigation of the kinetics of laser melting.

A foundational framework for the mesoscale modeling of dynamic elastomers and gels

Discrete mesoscale network models, in which explicitly modeled polymer chains are replaced by implicit pairwise potentials, are capable of predicting the macroscale mechanical response of polymeric materials such as elastomers and gels, while offering greater insight into microstructural phenomena than constitutive theory or macroscale experiments alone. However, whether such mesoscale models accurately represent the molecular structures of polymer networks requires investigation during their development, particularly in the case of dynamic polymers that restructure in time. We here introduce and compare the topological and mechanical predictions of an idealized, reduced-order mesoscale approach in which only tethered dynamic bonding sites and crosslinks in a polymer’s backbone are explicitly modeled, to those of molecular theory and a Kremer-Grest, coarse-grained molecular dynamics approach. We find that for short chain networks (∼12 Kuhn lengths per chain segment) at intermediate polymer packing fractions, undergoing relatively slow loading rates (compared to the monomer diffusion rate), the mesoscale approach reasonably reproduces the chain conformations, bond kinetic rates, and ensemble stress responses predicted by molecular theory and the bead–spring model. Further, it does so with a 90% reduction in computational cost. These savings grant the mesoscale model access to larger spatiotemporal domains than conventional molecular dynamics, enabling simulation of large deformations as well as durations approaching experimental timescales (e.g., those utilized in dynamic mechanical analysis). While the model investigated is for monodisperse polymer networks in theta-solvent, without entanglement, charge interactions, long-range dynamic bond interactions, or other confounding physical effects, this work highlights the utility of these models and lays a foundational groundwork for the incorporation of such phenomena moving forward.

Observing the two-dimensional Bose glass in an optical quasicrystal

The presence of disorder substantially influences the behaviour of physical systems. It can give rise to slow or glassy dynamics, or to a complete suppression of transport as in Anderson insulators1, where normally extended wavefunctions such as light fields or electronic Bloch waves become exponentially localized. The combined effect of disorder and interactions is central to the richness of condensed-matter physics2. In bosonic systems, it can also lead to additional quantum states such as the Bose glass3,4—an insulating but compressible state without long-range phase coherence that emerges in disordered bosonic systems and is distinct from the well-known superfluid and Mott insulating ground states of interacting bosons. Here we report the experimental realization of the two-dimensional Bose glass using ultracold atoms in an eight-fold symmetric quasicrystalline optical lattice5. By probing the coherence properties of the system, we observe a Bose-glass-to-superfluid transition and map out the phase diagram in the weakly interacting regime. We furthermore demonstrate that it is not possible to adiabatically traverse the Bose glass on typical experimental timescales by examining the capability to restore coherence and discuss the connection to the expected non-ergodicity of the Bose glass. Our observations are in good agreement with recent quantum Monte Carlo predictions6 and pave the way for experimentally testing the connection between the Bose glass, many-body localization and glassy dynamics more generally7,8.

Structural visualization of inhibitor binding in prolyl oligopeptidase.

The association and dissociation of proteins and ligands are crucial in biophysics for potential drug development [Baron and McCammon, Annu. Rev. Phys. Chem. 64, 151-175 (2013)]. However, identifying and characterizing the reaction pathways for these rare events has been a long-standing challenge. Molecular dynamics (MD) simulations are limited in exploring biophysical processes on experimental timescales, so ligand transport processes through complex transient tunnels formed by proteins during dynamics are often simulated using enhanced sampling MD [Rydzewski and Nowak, Phys. Life Rev. 22-23, 58-74 (2017)]. Erroneously identified ligand binding pathways can affect thermodynamic and kinetic characteristics calculated from MD trajectories. A system that has the potential to be a therapeutic target for neurodegenerative diseases is prolyl oligopeptidase (PREP). This is due to its involvement in promoting protein aggregation and disrupting cellular function through affecting protein-protein interactions (PPI). The recent discovery of a new type of PREP inhibitor that targets PPI raises important questions about the diversity of ligand binding pathways in PREP and their impact on protein dynamics [Pätsi et al., J. Med. Chem. 67, 5421-5436 (2024); Kilpeläinen et al., J. Med. Chem. 66, 7475-7496 (2023); and Walczewska-Szewc et al., Phys. Chem. Chem. Phys. 24, 4366-4373 (2022)]. In this article, using results from enhanced sampling MD, we visually present how the binding process in PREP depends on subtle changes in inhibitors, which could be crucial in treating neurodegenerative disorders.

Understanding the Kinetics of Cation Insertion-Coupled Electron Transfer in Thin Film Electrodes from Cyclic Voltammetry

Cyclic voltammetry is a powerful technique for probing the electrochemical kinetics of energy storage materials. However, interpretation of the cyclic voltammetry kinetics of such materials has been limited by the application of analytical solutions initially developed for ion blocking electrodes, whereby mass transport is limited to semi-infinite diffusion in the electrolyte medium. Here, we utilize established numerical simulation models for finite diffusion coupled with experimental results of a model insertion electrode to demonstrate the relationship between solid-state diffusion and cyclic voltammetry current, peak potential, and capacity. This simulation is publicly available.1 We show that the cyclic voltammetry response of thin film electrode materials undergoing solid-solution ion insertion without significant Ohmic polarization can be explained with finite diffusion. Specifically, we investigate the kinetic behavior of Li+ insertion-coupled electron transfer into thin films of orthorhombic Nb2O5. We observe a general trend in the b-value, a descriptive parameter derived from the relation ip=avb between peak current ip and scan rate v. We find that both in simulation and experiment, we can tune the b-value response between the theoretically limiting values of 0.5 and 1 based on the solid-state diffusion characteristics of the thin film and the experimental timescale. We also show that b-values below 0.5 are possible, and arise due to a combined effect of the potential window of the experiment and confined diffusion. Our findings show the power of a simple 1D finite-diffusion model for predicting the kinetic response of an electrode undergoing ion-coupled electron transfer, and help to inform on how the scan rate selection in voltammetry experiments affects the observed kinetic behavior. https://github.com/mchagnot/Numerical_CV_Sim_1D_Diffusion

Tackling Challenges of Long-Term Electrode Stability in Electrochemical Treatment of 1,4-Dioxane in Groundwater.

Electrochemical advanced oxidation is an appealing point-of-use groundwater treatment option for removing pollutants such as 1,4-dioxane, which is difficult to remove by using conventional separation-based techniques. This study addresses a critical challenge in employing electrochemical cells in practical groundwater treatment─electrode stability over long-term operation. This study aims to simulate realistic environmental scenarios by significantly extending the experimental time scale, testing a flow-through cell in addition to a batch reactor, and employing an electrolyte with a conductivity equivalent to that of groundwater. We first constructed a robust titanium suboxide nanotube mesh electrode that is utilized as both anode and cathode. We then implemented a pulsed electrolysis strategy in which reactive oxygen species are generated during the anodic cycle, and the electrode is regenerated during the cathodic cycle. Under optimized conditions, single-pass treatment through the cell (effective area: 2 cm2) achieved a remarkable 65-70% removal efficiency for 1,4-dioxane in the synthetic groundwater for over 100 h continuous operation at a low current density of 5 mA cm-2 and a water flux of 6 L m-2 h-1. The electrochemical cell and pulse treatment scheme developed in this study presents a critical advancement toward practical groundwater treatment technology.

Electroluminescence Rectification and High Harmonic Generation in Molecular Junctions.

The field of molecular electronics has emerged from efforts to understand electron propagation through single molecules and to use them in electronic circuits. Serving as a testbed for advanced theoretical methods, it reveals a significant discrepancy between the operational time scales of experiments (static to GHz frequencies) and theoretical models (femtoseconds). Utilizing a recently developed time-linear nonequilibrium Green function formalism, we model molecular junctions on experimentally accessible time scales. Our study focuses on the quantum pump effect in a benzenedithiol molecule connected to two copper electrodes and coupled with cavity photons. By calculating both electric and photonic current responses to an ac bias voltage, we observe pronounced electroluminescence and high harmonic generation in this setup. The mechanism of the latter effect is more analogous to that from solids than from isolated molecules, with even harmonics being suppressed or enhanced depending on the symmetry of the driving field.

A multiphysics coupling framework for exascale simulation of fracture evolution in subsurface energy applications

Predicting the evolution of fractured media is challenging due to coupled thermal, hydrological, chemical and mechanical processes that occur over a broad range of spatial scales, from the microscopic pore scale to field scale. We present a software framework and scientific workflow that couples the pore scale flow and reactive transport simulator Chombo-Crunch with the field scale geomechanics solver in GEOS to simulate fracture evolution in subsurface fluid-rock systems. This new multiphysics coupling capability comprises several novel features. An HDF5 data schema for coupling fracture positions between the two codes is employed and leverages the coarse resolution of the GEOS mechanics solver which limits the size of data coupled, and is, thus, not taxed by data resulting from the high resolution pore scale Chombo-Crunch solver. The coupling framework requires tracking of both before and after coarse nodal positions in GEOS as well as the resolved embedded boundary in Chombo-Crunch. We accomplished this by developing an approach to geometry generation that tracks the fracture interface between the two different methodologies. The GEOS quadrilateral mesh is converted to triangles which are organized into bins and an accessible tree structure; the nodes are then mapped to the Chombo representation using a continuous signed distance function that determines locations inside, on and outside of the fracture boundary. The GEOS positions are retained in memory on the Chombo-Crunch side of the coupling. The time stepping cadence for coupled multiphysics processes of flow, transport, reactions and mechanics is stable and demonstrates temporal reach to experimental time scales. The approach is validated by demonstration of 9 days of simulated time of a core flood experiment with fracture aperture evolution due to invasion of carbonated brine in wellbore-cement and sandstone. We also demonstrate usage of exascale computing resources by simulating a high resolution version of the validation problem on OLCF Frontier.

Experimental, analytical, and numerical quantification of the Marangoni effect in static refractory finger test

This study investigated the local corrosion of alumina and magnesia refractory in CaO–Al2O3–SiO2–MgO slag due to the Marangoni effect, which is a key factor for localized wear in different industrial processes, using experimental, analytical, and numerical approaches. The objective is to explore the Marangoni effect using computational fluid dynamics simulation aiming to provide insights into the dominant slag flow patterns influencing refractory corrosion and to determine whether the observed corrosion groove can be attributed solely to the Marangoni effect. Static finger tests were conducted at temperatures of 1500 and 1550 °C employing a continuous wear testing device. A two-dimensional axisymmetrical section model of the test assembly was created, incorporating concentration-dependent surface tension gradients and surface tension forces to replicate the Marangoni flow. As the surface-tension simulation required time steps in the order of 10−5 s, modeling up to the experimental time scale cannot be realized. Consequently, the simulation outcomes were extrapolated to anticipate the groove radii of the experimental corrosion steps. Corrosion rates were derived from measurements and analytical methodologies. Established analytical equations for corrosion under surface-tension-flows were adapted to enhance the accuracy of corrosion rate estimation. However, the analytical considerations yielded poor estimates. Meanwhile, the employed simulation model successfully generated plausible predictions of the Marangoni flow. Drawing from the extrapolated simulation outcomes, the projected groove radii exhibited a close correspondence to the measured values, demonstrating a relative error of approximately 3 %, 11 %, and 15 % for the magnesia system at 1500 °C and alumina systems at 1500 and 1550 °C, respectively. Taking into account the uncertainties inherent in the methodological approach, the disparities in the alumina values suggest the involvement of mechanisms beyond the Marangoni effect in the localized wear. Consequently, this study effectively clarifies the impact of the Marangoni effect on the local wear of the examined material systems.

Spreading of a viscoelastic drop on a solid substrate

We study the spreading of Newtonian viscous (aqueous glycerin solution) and viscoelastic (aqueous polymer solution) drops on solid substrates with different wettabilities. For drops of the same zero-shear viscosity, we find in the early stages of spreading that viscoelastic drops (i) spread faster and (ii) their contact radius shows a different power law vs time than Newtonian drops. We argue that the effect of viscoelasticity is only observable for experimental time scales of the order of or larger than the internal relaxation time of the viscoelastic polymer solution. We attribute this behaviour to the shear thinning of the viscoelastic polymer solution. When approaching the contact line, the shear rate increases and the steady-state viscosity of the viscoelastic drop is lower than that of the Newtonian drop. We support our experimental findings with a simple (first-order) perturbation model that qualitatively agrees with our findings.

Importance of grain boundary processes for plasticity in the quartz-dominated crust: Implications for flow laws

When H2O is present along grain boundaries, the deformation processes responsible for plasticity in silicate mineral aggregates can deviate from what may be conventionally expected. Although a necessary component of understanding crustal deformation processes, there is no theoretical framework that incorporates grain boundary processes into polycrystalline quartz rheology. To address this issue, we carried out high-pressure and high-temperature deformation experiments on fine-grained quartz aggregates. Our study illustrates that grain boundary migration (GBM) through dissolution-precipitation (in the presence of an aqueous fluid) and grain boundary sliding (GBS) may act as accommodation mechanisms to prevent hardening from dislocation glide. GBM and GBS can relax incompatibilities resulting from an inadequate number of independent slip systems, plastic anisotropy between neighbouring grains, and non-planar grain boundaries together with grain boundary junctions. As demonstrated earlier in the literature, GBM may act as a recrystallization mechanism counteracting hardening, but also is a potential mechanism that allow H2O to enter in the quartz crystal (hydrolization) at the experimental time-scale. The above serial processes occur over a range of more than two orders of magnitude in grain size (∼3 to 200 μm) and explain a grain-size-insensitive stress exponent (n = 2) and low activation energy (Q = 110 kJ/mol). In the absence of a switch to grain size sensitive deformation mechanisms induced by grain size reduction, our results imply that only a modest weakening (∼5 times the strength of the protolith) is needed (or possible) to localize shear zones in the Earth's crust.

Protein Effects on the Excitation Energies and Exciton Dynamics of the CP24 Antenna Complex.

In this study, the site energy fluctuations, energy transfer dynamics, and some spectroscopic properties of the minor light-harvesting complex CP24 in a membrane environment were determined. For this purpose, a 3 μs-long classical molecular dynamics simulation was performed for the CP24 complex. Furthermore, using the density functional tight binding/molecular mechanics molecular dynamics (DFTB/MM MD) approach, we performed excited state calculations for the chlorophyll a and chlorophyll b molecules in the complex starting from five different positions of the MD trajectory. During the extended simulations, we observed variations in the site energies of the different sets as a result of the fluctuating protein environment. In particular, a water coordination to Chl-b 608 occurred only after about 1 μs in the simulations, demonstrating dynamic changes in the environment of this pigment. From the classical and the DFTB/MM MD simulations, spectral densities and the (time-dependent) Hamiltonian of the complex were determined. Based on these results, three independent strongly coupled chlorophyll clusters were revealed within the complex. In addition, absorption and fluorescence spectra were determined together with the exciton relaxation dynamics, which reasonably well agrees with experimental time scales.

Structural pathways for ultrafast melting of optically excited thin polycrystalline Palladium films

Due to its extremely short timescale, the non-equilibrium melting of metals is exceptionally difficult to probe experimentally. The knowledge of melting mechanisms is thus based mainly on the results of theoretical predictions. This work reports on the investigation of ultrafast melting of thin polycrystalline Pd films studied by optical laser pump – X-ray free-electron laser probe experiments and molecular-dynamics simulations. By acquiring X-ray diffraction snapshots with sub-picosecond resolution, we capture the sample's atomic structure during its transition from the crystalline to the liquid state. Bridging the timescales of experiments and simulations allows us to formulate a realistic microscopic picture of the crystal-liquid transition. According to the experimental data, the melting process gradually accelerates with the increasing density of deposited energy. The molecular dynamics simulations reveal that the transition mechanism progressively varies from heterogeneous, initiated inside the material at structurally disordered grain boundaries, to homogenous, proceeding catastrophically in the crystal volume on a picosecond timescale comparable to that of electron-phonon coupling. We demonstrate that the existing models of strongly non-equilibrium melting, developed for systems with relatively weak electron-phonon coupling, remain valid even for ultrafast heating rates achieved in femtosecond laser-excited Pd. Furthermore, we highlight the role of pre-existing and transiently generated crystal defects in the transition to the liquid state.

Numerical investigation of drop–film interactions with a thixotropic liquid

We investigate numerically the influence of thixotropic effects on the impact of a drop onto a thin film, a fundamental process in many technical systems. Direct numerical simulations are performed with a Volume-of-Fluid (VOF) method based multiphase flow solver whose capabilities are expanded in order to enable simulations of a thixotropic liquid. The thixotropic behavior is modeled by a rate kinetic equation for the structural integrity of the assumed microstructure of the liquid. The corresponding structural parameter is described by an additional VOF-variable. After a validation of the implementations, we vary systematically the two parameters of the thixotropic model for a selected impact scenario in order to identify thixotropic effects during the impact and on the overall impact morphology. The two parameters are the mutation number Mu=texp/tθ as the ratio of the experimental time scale to the time scale of the structural rebuilding and the parameter β, which describes the effectivity of the shear-induced structural disintegration. The parameter study leads to a regime map with three different regimes. For Mu>10, the liquid behaves purely shear-thinning. High shear rates during the early stages of the impact lead to a low apparent viscosity at the crown base and to an enhanced crown growth. For Mu<0.1, the liquid behaves irreversible thixotropic or rheodestructing, respectively. Structural rebuilding is negligible and every deformation leads to a further disintegration of the microstructure. In this regime, a thin region of disintegrated microstructure develops within the liquid, spanning from the location of high shear stresses at the bottom into the crown rim. In between these two regimes, purely thixotropic effects become significant. A complex microstructure develops during the impact, in which features of both regimes occur combined, leading to a pronounced viscosity gradient along the crown wall. A comparison of the resulting maximum crown heights reveals that various combinations of Mu and β values can lead to the same maximum crown height whereas the crown shapes prior to this point in time can be very different.

Impact of supercritical carbon dioxide on the frictional strength of and the transport through thin cracks in shale

Understanding the mechanical and transport behavior of thin (i.e. small aperture) cracks slipping under supercritical carbon dioxide (sc-CO2) conditions is essential to evaluate the integrity of sealing formations with buoyant sc-CO2 below and the success of waterless fracturing. The two major items of interest in this work are frictional strength and permeability change of the crack. We used a triaxial cell that permits in situ visualization to conduct and monitor slippage along the faces of narrow cracks subjected to triaxial stresses. Such cracks are analogs to small geological faults. We tested carbonate-rich, 1-inch diameter Wolfcamp shale samples that are saw cut 30° to vertical to create a thin crack. Friction coefficients ranged from about 0.6 to 0.8 consistent with expectations for brittle rocks. The sc-CO2 generally did not alter friction coefficient over the time scale of experiments. From a transport perspective, saturating cracks with sc-CO2 substantially decreased permeability of the crack by 26%–52%, while slip resulted in a variety of permeability responses. Overall, the combined impact of sc-CO2 saturation and slip reduced fault permeability for all tests. Our observations support the notion that the sealing capacity of some caprocks improves when saturated with sc-CO2 and that some slip of small fractures is not necessarily detrimental to caprock integrity.

Non-contacting laser-based acousto-seismics at the laboratory scale: towards near-real-time monitoring of granular analogue models

SUMMARY In this work we present a novel, experimentally efficient set-up for performing non-contacting laser vibrometry on geologic materials and their analogues. We show it is possible to acoustically monitor a granular material experiment in real time compared to the typical timescale of analogue modelling experiments. We acquire non-contacting waveform data with consistently high signal-to-noise ratio. Compared to previously used standard contacting transducers, the novel joint use of sources and receivers that are both laser-based resulted in measured signals with improved waveforms and temporal bandwidths. These data acquisition improvements, in our case where surface waves are prominent in the data, enable enhanced multichannel surface wave processing, for example, in terms of reliable dispersion curve estimates. We find, given the high waveform fidelity of our acquisition system, that the observed surface waves are highly sensitive to relatively small changes in the medium’s elastic properties, making them a demonstrably reliable to monitor any processes that affect elasticity in these models in near real time. As a demonstration, we continuously monitor a scaled analogue model containing granular glass beads. By continuously monitoring—that is, performing repeatable active-source acousto-seismic surveys at short time-lapse intervals—over a period of 10 hr, we find that an increase of relative humidity of 10 per cent can lead to as much as a factor of two increase in surface wave group velocities. Finally, we discuss future applications of the developed method by considering surface wave inversion for fault and stress monitoring during the deformation of a model.

Comparison of reduced model predictions for divertor detachment onset and reattachment timescales in ASDEX Upgrade and JET experiments

Building on prior analysis of ASDEX Upgrade (AUG) experiments (Henderson et al 2023 Nucl. Fusion 63 086024), this study compares simple analytical formula predictions for divertor detachment onset and reattachment timescales in JET experiments. Detachment onset primarily scales with divertor neutral pressure, impurity concentration, power directed to the targets, machine size, and integral perpendicular power decay length. JET experiments, focusing on seeding mixtures of Ne and Ar, align with the detachment onset predictions. Radiation efficiencies among the impurities show good agreement with the model predictions, contrasting with AUG observations which suggested higher efficiency for Ar and lower efficiency for Ne. The time taken to re-ionise the neutral volume in front of the outer target in fully detached divertor conditions was measured following both abrupt increases in injected neutral beam power and, separately, cutting of the impurity gas flow. Re-ionisation of the neutrals occurs within approximately 1 s on JET, which aligns with the simple model prediction derived from AUG data. While the AUG results are not new, their comparison with the JET results enhances understanding, reinforcing confidence in using simple models to predict future reactor scenarios.

Year-long optical time scale with sub-nanosecond capabilities

An atomic time scale is a method for marking events and the passage of time by using atomic frequency standards. Thanks to the superior performance of atomic clocks based on optical transitions, time scales generated with optical clocks have the potential to be more accurate and stable than those based on microwave clocks. In this work, we demonstrate an experimental optical time scale based on the INRiM Yb optical lattice clock and a hydrogen maser as a flywheel oscillator, showing sub-nanosecond accuracy over months-long periods and nanosecond accuracy over a 1-year period. The obtained results show that optical time scales have competitive performances even when the optical clock has a limited and non-uniformly distributed up-time. Consequently, we are working to include the Yb clock within the ensemble of clocks routinely used for the generation of the Italian time scale. Furthermore, these results represent a crucial step towards the future redefinition of the second of the International System of Units based on an optical transition.

A diffusion model for liquid metal dealloying. Application to NiCu precursors dealloyed in liquid Ag

Liquid metal dealloying is a promising technique to elaborate porous metallic materials with potential applications for catalysis and energy storage. It consists in the selective dissolution of an element out of a precursor alloy by immersing it in a liquid bath. To model this process, we introduce a one-dimensional diffusion model that relies on the thermodynamic properties of the ternary system, and on a maximum velocity criterion of the reaction front. The model is compared to experimental measurements conducted on NiCu samples dealloyed in liquid Ag. Regarding the kinetics, the model enables to reach experimental time-scales, replicate experimental trends, and reveal the influence of the ligament structure on the dealloying rate. Also, by assuming thermodynamic equilibria between solid and liquid phases in the dealloyed region, the microstructure gradient obtained numerically is in satisfactory agreement with experimental measurements. These numerical results are obtained without adjustable parameters, which opens the possibility to predict dealloyed microstructures as function of the process parameters (precursor and bath composition, dealloying time and temperature, etc.).