Frédéric Lantelme

Brownian dynamics: Its application to ionic solutions

The method of molecular dynamics is applied to a solvent‐averaged model of electrolyte solutions, described by a generalized Langevin equation. For Brownian motion without solute–solute interactions, we recover the characteristic features of an infinitely dilute solution. For interacting brownons, the results exhibit a noticeable dependence of the calculated self‐diffusion coefficients on the influence of the Coulomb forces. The model system exhibits ion association when the Coulomb forces are made strong enough.

Application of the molecular dynamics method to a liquid system with long range forces (Molten NaCl)

A significant and characteristic difficulty arising in the use of statistical mechanics to describe the properties of fused salts is due to the extreme range of the electrostatic field; an accurate representation of the Coulomb energy and Coulomb forces may be obtained using Ewalds expansion. Such calculations are tested here on the model case of liquid NaCl at different temperatures. In addition, this method is applied to the description of ionic media by molecular dynamics computations. (A Born-Huggins-Mayer pair potential is used with constants derived from the solid at 298 K.) This treatment introduces cut-off distances and periodic boundary conditions. The influence of these constraints on the conservation of energy and momenta is investigated. Thermodynamic properties of molten NaCl at 1164·5, 1224·5 and 1340·5 K are calculated. The motions of individual ions, anions and cations are described in terms of a velocity self-correlation function and their diffusion coefficients are determined.

Mass effects and transport properties in classical fluids: A molecular dynamics experiment on fused NaCl

The mass dependence of the ionic transport properties has been studied by molecular dynamics calculations on a model of liquid NaCl. It is shown that changes in the mass of one set of constituent particles (cation or anion) have a similar influence on the motion of all particles. Moreover, the change in transport and relaxation coefficients due to isotope substitution in the absence of quantal effects is very small, in contrast with the situation observed in gases and ionic solids. The mean square displacements and the velocity autocorrelation functions are computed in order to evaluate quantitatively the time evolution of the mass effect. An expansion in powers of the mass difference (with respect to a reference system) has been developed to describe the perturbation of the velocity correlation functions.

Chemical and Electrochemical Stability of Copper in Molten KF-2HF

Fluorine is produced from electrolysis of KF/HF mixtures at around 95°C. In the cell configuration, carbon anodes are screwed onto a copper busbar. Much attention has been paid to the stability of copper since the corrosion and re-deposition of this metal on the cathodes is one of the main factors (side reaction) which limit the production yield of fluorine gas, the lifetime of the cells and the development of new electrolyzers. Therefore, in the frame of this study, various experiments were carried out to determine the corrosion rate of copper for a wide range of HF ratio and temperature. A statistics approach of the electrochemical data allowed us to predict the corrosion rate for many the operating conditions. At OCV, copper shows a good corrosion resistance even for high HF ratios. However, under a 6 V anodic polarization, copper corrosion rate raises drastically with an increase of the temperature and / or the HF ratio. Characterization techniques have shown that only a thin copper fluoride layer has been detected on copper at OCV. By contrast, two types of copper fluorides were evidenced at the electrode surface (CuF2 and KCuF3) when a potential was applied to Cu. Under anodic polarization, a thin CuF2 layer is formed at the copper surface whereas KCuF3 is detected at on the electrode surface resulting from the precipitation of Cu2+. For a better interpretation of the results, erosion-corrosion phenomenon issued from the fluorine bubbles impacts and electrolyte movements has been highlighted by weight losses of copper pieces. The breakdown of the passivation layer on copper and the exposition of the surface to the corrosive medium imply a quicker degradation of the metallic pieces.

Pierre Turq, an inspirational scientist in charge and at interfaces

Pierre Turq has made decisive contributions to the theory and to the multiscale simulation of charged systems, such as molten salts, electrolyte solutions and colloidal suspensions, in the bulk, at interfaces and under confinement. His research line focussed on dynamical properties and was characterised by constant efforts to connect his theoretical work to both experiments and practical applications. In this article, his colleagues and former students pay a tribute to his past and current research interests by illustrating some recent developments accomplished in his laboratory.