Papers by Author: Olivier Politano

Abstract: Sulfidation of undoped and aluminum doped zinc oxide materials has been performed by TGA under a H₂S atmosphere in order to evaluate the impact of the doping element on sulfidation reaction kinetics and mechanism. The presence of aluminum seems to slow-down the reaction kinetics. This phenomenon might be explained by a modification of the solid state diffusion processes involved in ZnO sulfidation reaction and the related ZnS outward growth, assuming the presence of aluminum atoms inside ZnO and ZnS phases. In order to determine solid state diffusion mechanisms controlling the reaction kinetics, molecular dynamics simulations were performed using a Coulomb-Buckingham potential. Firstly, the diffusion of the different elements (Zn, O, S) was simulated for both the oxide and sulfide phases considering a vacancy mechanism. Secondly, simulations of the oxide phase doped by a trivalent cation were also performed. The results obtained in this preliminary work are presented and compared to the literature.

Abstract: The interaction of water molecules on a nickel surface was studied using ReaxFF (reactive force field) molecular dynamics. This approach was originally developed by van Duin et al. to study the hydrocarbon chemistry and the catalytic properties of organic compounds. To our knowledge, this method has not been used to study the corrosion processes of nickel exposed to water, which is what we set out to achieve in the present investigation. To do so, calculations were first performed using ReaxFF in order to reproduce certain well-known properties of pure nickel and nickel-water systems. This allowed us to study the adsorption of a single water molecule interacting with an optimized nickel surface. We also investigated the interaction of 405 molecules of water (ρ=0.99 g.cm^-3) on the (100), (110) and (111) surfaces of a single crystal of nickel at 300 K. The results show that a water bilayer is adsorbed on nickel surfaces: the first water layer is directly bonded to the surface, whereas the molecules in the first and second layers are held together by hydrogen bonds.

Abstract: A molecular dynamics study of a layered Ni-Al-Ni system is developed using an embedded atom method potential. The specific geometry is designed to model a Ni-Al nanometric metallic multilayer. The system is initially thermalized at the fixed temperature of 600 K. We first observe the interdiffusion of Ni and Al at the interfaces, which is followed by the spontaneous phase formation of B2-NiAl in the Al layer. The solid-state reaction is associated with a rapid system's heating which further enhances the diffusion processes. NiAl phase is organized in small regions separated by grain boundaries. This study confirms the hypothesis of a layer-by-layer development of the new phase. For longer times, the temperature is notably higher (> 1000 K) and the system may partly lose some its B2-NiAl microstructure in favor of the formation of Ni₃Al in L12 configuration. This work shows the spontaneous development of a real exothermic solid-state reaction in metallic nanosystems mostly constituted by interfaces.

Abstract: We investigated the oxidation of nanocrystalline aluminum surfaces by using variable charge molecular dynamics at 600 K under three oxygen pressures: 1, 10 and 20 atm. The interaction potential was described by the electrostatic plus (Es+) model that allows dynamical charge transfer among atoms. We mainly focused on the effect of the oxygen pressure on the oxidation kinetic, the chemical composition and the microstructure of the oxide films formed. The results show that oxidation kinetics as well as chemical composition and microstructure depend on the applied oxygen pressure. The oxide film thickness tends to a limiting value equal to ~3 nm. Finally, we obtained a partially crystalline oxide films for all oxygen pressures and we observed that the degree of crystallinity increases with time.

Abstract: The intrinsic diffusion coefficients in diffusion aluminide coatings based on Fe-30Cr were determined at 1000oC. The diffusion fluxes were given by the Nernst Planck formulae and the Darken method for multicomponent systems was applied. This paper summarizes some numerical results to determine the composition dependent diffusivities in Fe-Cr-Al systems. The method presented in this study to obtain average intrinsic diffusion coefficients is as an alternative to the Dayananda method. Our method based on empirical parameters allowed us to predict the concentration profile during the interdiffusion process.

Abstract: Variable charge molecular dynamic simulations have been performed to study the diffusion mechanisms of oxygen atoms (O) in nickel (Ni) in the temperature range 950-1600 K and the very first steps of oxidation of monocrystalline nickel surfaces at 300 K and 950 K. The oxygen diffusivity can be well described by an Arrhenius law over the temperature range considered. The oxygen diffusion coefficient has been analysed and values of Ea = 1.99 eV for the activation energy and D0 = 39 cm2.s-1 for the pre-exponential factor were obtained. The first steps growth of the oxide layer show that after the dissociative chemisorption of the oxygen molecules on nickel surface, the oxidation leads to an island growth mode as observed experimentally.

Abstract: This paper presents a numerical method to determine the composition dependent diffusivities and to predict the concentration profile during the interdiffusion process. The intrinsic diffusion coefficients in diffusion aluminide coatings (Fe-Al) were determined at 1000oC. The obtained diffusion coefficient for iron in Fe3Al or FeAl is in the range 10-10 to 10-9 cm2.s-1. The aluminum diffusion coefficient varies from 10-11 to 10-7 cm2.s-1 in the same phases.The present approach also permits to model the reactive diffusion in the Fe-Al systems.

Abstract: In this paper we give a brief presentation of the approaches we have recently developed on the oxidation of metals. Firstly, we present an analytical model based on non-equilibrium thermodynamics to describe the reaction kinetics present during the oxidation of a metal. Secondly, we present the molecular dynamics results obtained with a code specially tailored to study the oxidation and growth of an oxide film of aluminium. Our simulations present an excellent agreement with experimental results.