Effect of cerium concentration on corrosion resistance and polymerization of hybrid sol–gel coating on martensitic stainless steel

Stainless steels are increasingly used in the aeronautics field for the manufacture of structural parts. One of them, the X13VD martensitic stainless steel (X12CrNiMoV12-3), known for its good mechanical properties, has a poor corrosion resistance in confined or severe environments. In the past years, Cr(VI) based pre-treatments have been currently used for corrosion protection of different metals, however, they are toxic and due to environmental regulations, they will be definitely banned in a near future. Alternatives to replace Cr(VI) show advantages and drawbacks considering key properties such as: corrosion resistance, adhesion of coatings, fatigue resistance, durability and reliability. However, some of their possible alternatives show high potential. In this paper, a process was developed to improve the corrosion resistance of the martensitic stainless steel. Organic–inorganic hybrid coatings with different cerium concentrations were deposited onto stainless steel by sol–gel process. Corrosion resistance of the coatings was evaluated by electrochemical impedance measurements and it has been proved that cerium concentration of 0.01 M into hybrid coating was an optimal content. Adhesion tests were also carried out by "nanoscratchtest" to characterize the coatings mechanical properties as a function of cerium concentration but results do not clearly show the influence of cerium for the coating adhesion toward the substrate. To try to correlate with the electrochemical properties, liquid 29Si NMR spectroscopy was then performed to investigate hydrolysis and condensation reactions of sol–gel process, and by this method, it was demonstrated that for higher cerium concentration (>0.01 M) there is a modification of the chemical structure of the sol–gel network

A transferable ab-initio based force field for aqueous ions

We present a new polarizable force field for aqueous ions (Li+, Na+, K+, Rb+, Cs+, Mg2+, Ca2+, Sr2+ and Cl-) derived from condensed phase ab-initio calculations. We use Maximally Localized Wannier Functions together with a generalized force and dipole-matching procedure to determine the whole set of parameters. Experimental data is then used only for validation purposes and a good agreement is obtained for structural, dynamic and thermodynamic properties. The same procedure applied to crystalline phases allows to parametrize the interaction between cations and the chloride anion. Finally, we illustrate the good transferability of the force field to other thermodynamic conditions by investigating concentrated solutions.Comment: 31 pages, 8 figure

Effect of thermal treatment on mechanical and tribological properties of hybrid coatings deposited by sol–gel route on stainless steel

This paper deals with the effect of thermal treatment on the mechanical and tribological properties of an organic–inorganic hybrid coating deposited on stainless steel 430. Organic–inorganic coating derived from glycidoxypropyltrimethoxysilane (GPTMS) and aluminum tri-sec-butoxide Al(OsBu)3 were prepared via sol–gel route and deposited by dip-coating process with various thicknesses. A preliminary thermal analysis (DTA, TGA) of xerogel obtained by hydrolysis and condensation reaction of sols, highlighted three characteristic domains of temperature (110–200°C, 250–300°C, 400–500°C). When thermal treatments were applied to the coated stainless steel in these temperature domains, the tribological behavior (wear and friction) underwent strong changes, analyzed from linear ball/plane tribometry. The tribological tests showed a lower friction coefficient and wear after thermal treatment at a temperature in the domain 250–300°C. In order to explain this phenomenon, xerogel structure was studied from XRD and Raman spectroscopy and correlated to the mechanical and adhesive properties and to the tribological behavior

New sol-gel formulations to increase the barrier effect of a protective coating against the corrosion of steels

Films were deposited onto AISI 430 stainless steel substrates by dip-coating technique. The aim is to reach the AISI 304L stainless steel anti-corrosion properties by a coated AISI 430 stainless steel system. Sol formulation is done from the starting precursors tetraethylorthosilicate (TEOS) and 3(trimethoxysilyl) propyl methacrylate (MAP). After the hydrolysis of these precursors, sol-gel reactions occur before the addition (or not) of a controlled quantity of cerium nitrate. The addition of the PEG (polyethylene glycol), used as plasticizer has been studied in this paper and both physical and chemical properties of the synthesized hybrid films were studied by varying PEG ratios. Based on SEM observations and mass gain measurements, the thickness of the films has been adjustable. Another parameter plays a key role: the drying step of the whole system. It has been investigated and optimized in this paper to lead to coatings with a high barrier effect. The efficiency of the anti-corrosion protection of hybrid-coated stainless steel was investigated by potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS) after immersion of the material in a 3.5% NaCl solution. Double-layered systems were successfully developed and a good compromise between PEG content and drying conditions has been found. Potentiodynamic polarization curves showed that the hybrid coating prepared using a TEOS/MAP/PEG yielded the best anti-corrosion performances. It acts as an efficient barrier similar to AISI 304 stainless steel used as reference, increasing the total impedance and significantly reducing the current densities

Diffusion coefficient and shear viscosity of rigid water models

We report the diffusion coefficient and viscosity of popular rigid water models: Two non polarizable ones (SPC/E with 3 sites, and TIP4P/2005 with 4 sites) and a polarizable one (Dang-Chang, 4 sites). We exploit the dependence of the diffusion coefficient on the system size [Yeh and Hummer, J. Phys. Chem. B 108, 15873 (2004)] to obtain the size-independent value. This also provides an estimate of the viscosity of all water models, which we compare to the Green-Kubo result. In all cases, a good agreement is found. The TIP4P/2005 model is in better agreement with the experimental data for both diffusion and viscosity. The SPC/E and Dang-Chang water overestimate the diffusion coefficient and underestimate the viscosity.Comment: 10 pages, 2 figures. To be published in J. Phys.: Condens. Matte

Dynamics in Clays - Combining Neutron Scattering and Microscopic Simulation

International audienceMobility of ions and water in clays is at the heart of their remarkable properties of water retention and ion-exchange. It has been addressed here using two microscopic techniques: neutron scattering and molecular dynamics simulations. Neutron scattering gives access exclusively to water dynamics in clays, due to the exceptional sensitivity of neutrons to H atoms. The data interpretation can be challenging, especially for natural clays such as montmorillonite, with inhomogeneous swelling characteristics. A great improvement is achieved with the use of synthetic materials, as demonstrated here on the case of synthetic (fluoro)hectorite. The standard analytical models for long-range diffusive motion, isotropic translation and its derivative, powder averaged two dimensional translation, have been used to interpret the neutron scattering data. They both agree on the order of magnitude for the diffusion coefficient of water in monohydrated and bihydrated clays, 10−10 m2s−1 and 10−9 m2s−1 respectively. While the two-dimensional nature of water diffusion in clays is seen clearly from molecular dynamics simulations, its signature in neutron scattering data is obscured by the powder-averaging of the signal. A novel method, based on a multi-resolution analysis of scattering functions from powder samples, allows never-the-less a clear determination of the dimensionality of water motion in the system. Extracting information on local water motion is difficult on the basis of neutron scattering data only. Various models for localised motion, rotation on a sphere or jump diffusion, have been proposed and used to interpret the observed neutron data, however their applicability is questionable in light of information from molecular dynamics simulations. Aside from aiding the interpretation of neutron scattering data, MD simulations are most valuable in providing information on the behaviour of ions in clays. MD estimates the interlayer ion coefficients as of the some order of magnitude as water, even if the details of ionic motion are strikingly different between the two ions considered here, Na+ and Cs+. Further, MD has also allowed to address the topic of ion exchange between clay interlayers and bulk aqueous solution. The microscopic picture of water and ion motion in clays, emerging from neutron scattering and MD simulations, should be treated as a building block of the overall modelling of macroscopic transport in clays, the ultimate property of interest for many clay applications

Carbon Dioxide in Montmorillonite Clay Hydrates: Thermodynamics, Structure, and Transport from Molecular Simulation

International audienceWe report a Monte Carlo and molecular dynamics simulations study of carbon dioxide in hydrated sodium montmorillonite, including thermodynamical, structural, and dynamical properties. In order to simulate the behavior of a clay caprock in contact with a CO2 reservoir, we consider clays in equilibrium with H2O−CO2 mixtures under conditions close to relevant ones for geological storage, namely a temperature T = 348 K, and pressures P = 25 and 125 bar, and under which two bulk phases coexist: H2O-rich liquid on the one hand and CO2-rich gas (P = 25 bar) or supercritical fluid (P = 125 bar) on the other hand. We first use grand canonical MC simulations to determine the number of stable states in clay, their composition, and the corresponding equilibrium interlayer distances. The vertical, horizontal, and radial distribution functions of the confined mixture, subsequently obtained using molecular dynamics, reveal some structural feature induced by the presence of CO2. Finally, the simulations indicate that carbon dioxide considerably influences the diffusion of mobile species in clays. We discuss these results by comparing them with those obtained for the bulk mixtures, as well as for Na-montmorillonite in equilibrium with a pure water reservoir water at the same temperature and pressure

Numerical study of density functional theory with mean spherical approximation for ionic condensation in highly charged confined electrolytes

We investigate numerically a Density Functional Theory (DFT) for strongly confined ionic solutions in the Canonical Ensemble by comparing predictions of ionic concentration profiles and pressure for the double-layer configuration to those obtained with Monte Carlo (MC) simulations and the simpler Poisson--Boltzmann (PB) approach. The DFT consists of a bulk (ion-ion) and an ion-solid part. The bulk part includes nonideal terms accounting for long-range electrostatic and short-range steric correlations between ions and is evaluated with the Mean Spherical Approximation and the Local Density Approximation. The ion-solid part treats the ion-solid interactions at the mean-field level through the solution of a Poisson problem. The main findings are that ionic concentration profiles are generally better described by PB than by DFT, although DFT captures the non-monotone co-ion profile missed by PB. Instead, DFT yields more accurate pressure predictions than PB, showing in particular that nonideal effects are important to describe highly confined ionic solutions. Finally, we present a numerical methodology capable of handling nonconvex minimization problems so as to explore DFT predictions when the reduced temperature falls below the critical temperature

Effect of cerium on structure modifications of a hybrid sol–gel coating, its mechanical properties and anti-corrosion behavior

An organic–inorganic hybrid coating was developed to improve the corrosion resistance of the aluminum alloy AA 2024-T3. Organic and inorganic coatings derived from glycidoxypropyltrimethoxysilane (GPTMS) and aluminum tri-sec-butoxide Al(OsBu)3, with different cerium contents, were deposited onto aluminum by dip-coating process. Corrosion resistance and mechanical properties were investigated by electrochemical impedance measurements and nano-indentation respectively. An optimal cerium concentration of 0.01 M was evidenced. To correlate and explain the hybrid coating performances in relation to the cerium content, NMR experiments were performed. It has been shown that when the cerium concentration in the hybrid is higher than 0.01 M there are important modifications in the hybrid structure that account for the mechanical properties and anti-corrosion behavior of the sol–gel coating

Lithium conducting solid electrolyte Li1.3Al0.3Ti1.7(PO4)3 obtained via solution chemistry

NaSICON-type lithium conductor Li1.3Al0.3Ti1.7(PO4)3 (LATP) is synthesized with controlled grain size and composition using solution chemistry. After thermal treatment at 850 C, sub-micronic crystallized powders with high purity are obtained. They are converted into ceramic through Spark Plasma Sintering at 850–1000 C. By varying the processing parameters, pellet with conductivities up to 1.6 * 10−4 S/cm with density of 97% of the theoretical density have been obtained. XRD, FEG-SEM, ac-impedance and Vickers indentation were used to characterize the products. The influence of sintering parameters on pellet composition, microstructure and conductivity is discussed in addition to the analysis of the mechanical behavior of the grains interfaces