Neodymium and gadolinium extraction from molten fluorides by reduction on a reactive electrode

This work describes the electrochemical extraction on a reactive cathode (Cu, Ni) of two lanthanides Ln (Ln = Nd and Gd) from molten LiF-CaF2 medium at 840 and 920°C for Nd and 940°C for Gd. Extraction runs have been performed and the operating conditions (cathodic material and temperature) optimised. The titration of the Nd and Gd concentrations in the melt during extraction used square wave voltammetry. At the end of each run, the residual Ln content was checked by ICP-AES; the extraction efficiencies of the two lanthanides were found to be more than 99.8% on both reactive substrates

Electrodeposition of alloys or compounds in molten salts and applications

This article deals with the different modes of preparation of alloys or intermetallic compounds using the electrodeposition in molten salts, more particularly molten alkali fluorides. The interest in this process is to obtain new materials for high technology, particularly the compounds of reactive components such as actinides, rare earth and refractory metals. Two ways of preparation are considered: (i) electrocoating of the more reactive metal on a cathode made of the noble one and reaction between the two metals in contact, and (ii) electrocoating on an inert cathode of the intermetallic compound by coreduction of the ions of each elements. The kinetic is controlled by the reaction at the electrolyte interface. A wide bibliographic survey on the preparation of various compounds (intermetallic compounds, borides, carbides…) is given and a special attention is paid to the own experience of the authors in the preparation of these compounds and interpretation of their results

Cyclic Voltammetric Experiment - Simulation. Comparisons of the Complex Mechanism Associated with Electrochemical Reduction of Zr4+ in LiCl-KCl Eutectic Molten Salt

Nuclear energy increasingly represents an important option for generating largely clean CO2-free electricity and zirconium is a fission product that is expected to be present in irradiated fuels. The present investigation addresses the electrochemical reduction of Zr4+ to Zro in LiCl - KCl eutectic molten salt in the temperature range 425–550◦C using cyclic voltammetry (CV), square-wave voltammetry (SWV) and bulk electrolysis. Simulations of the CV data indicate that the initial reduction proceeds through surface confined steps: Zr4+* + 2e− ↔Zr2+* and Zr2+* + 2e− ↔Zr* processes (* adsorbed species) followed by a peak-shaped complex diffusion controlled step that consists of a combination of closely spaced processes associated with the reactions Zr4+ + 4e− →Zr and Zr4+ + 3e− →Zr+*. Zr+*, probably in the form of ZrCl* is then further reduced to Zro* at even more negative potentials. The simulations provide the first quantitative analysis of the thermodynamics and kinetics of the Zr4+ reduction in the LiCl-KCl eutectic

A multimaterial based on metallic copper and spinel oxide made by powder bed laser fusion: A new nanostructured material for inert anode dedicated to aluminum electrolysis

Coherent 3D parts of cermets, made of spinel ferrite and metallic copper, are prepared in a nitrogen atmosphere by powder bed additive manufacturing of a mixture of oxide and metallic powders. The cermets obtained are constituted by the association of blocks of about 500 μm, which create between them, a relatively large porosity (# 35%). Each block is subdivided into intimately nested zones that are either predominantly metallic or predominantly oxide type. In the metal parts, a dispersion of oxide crystals is observed, whose size varies from ten nanometers to a few micrometers. A similar distribution of metal particles in the oxide zones is also demonstrated. The chemical compositions of metallic and oxide phases are slightly different from those in the initial powders. Due to the high energy density of the laser, the melting temperature of the metal and oxides could be reached and therefore this could explain the chemical composition variations in the phases and the shape of oxide and metallic nanometric grains. The process used can therefore be described as powder bed fusion. These nanostructured cermets have been used as "inert" anodes for the electrolysis of aluminum in molten cryolite. Although penalized by a high porosity, 5 mm in diameter anodes allowed to carry out an electrolysis for 4 h. Since Spark Plasma Sintering can greatly reduce their porosity, while retaining their specific microstructure, the implementation of additive manufacturing for producing "inert" anodes is therefore of real interest

Turbulent Combustion of Polydisperse Evaporating Sprays with Droplet Crossing: Eulerian Modeling and Validation in the Infinite Knudsen Limit

The accurate simulation of the dynamics of polydisperse evaporating sprays in unsteady gaseous flows with large-scale vortical structures is both a crucial issue for industrial applications and a challenge for modeling and scientific computing. The difficulties encountered by the usual Lagrangian approaches make the use of Eulerian models attractive, aiming at a lower cost and an easier coupling with the carrier gaseous phase. Among these models, the multi-fluid model allows for a detailed description of the polydispersity and size-velocity correlations for droplets of various sizes. The purpose of the present study is twofold. First, we extend the multi-fluid model in order to cope with crossing droplet trajectories by using the quadrature method of moments in velocity phase space conditioned by size. We identify the numerical difficulties and provide dedicated numerical schemes in order to preserve the velocity moment space. Second, we conduct a comparison study and demonstrate the capability of such an approach to capture the dynamics of an evaporating polydisperse spray in a 2-D free jet configuration. We evaluate the accuracy and computational cost of Eulerian models and related discretization schemes vs. Lagrangian solvers and show that, even for finite Stokes number, the standard Eulerian multi-fluid model can be accurate at reasonable cost

Electrochemical oxidation of binary copper-nickel alloys in cryolite melts

Anodic oxidation of copper, nickel and two copper-nickel alloys was studied in cryolite melts at 1000°C. In an oxide-free melt, anodic dissolution of each material was observed, and the dissolution potential increases with the content of copper. SEM characterization of a Cu55-Ni45 alloy showed that nickel is selectively dissolved according to a de-alloying process. In an alumina-containing melt, a partial passivation occurs at the copper-containing electrodes, at potentials below the oxygen evolution potential. A passive film forms on the copper electrode, while on the nickel electrode no dense oxide layer develops. Copper-nickel alloys were found to form a mixed oxide layer. At higher potentials, the formation of oxygen bubbles on the electrodes results in a degradation of the passive films and a strong corrosion

Weak and strong fillability of higher dimensional contact manifolds

For contact manifolds in dimension three, the notions of weak and strong symplectic fillability and tightness are all known to be inequivalent. We extend these facts to higher dimensions: in particular, we define a natural generalization of weak fillings and prove that it is indeed weaker (at least in dimension five),while also being obstructed by all known manifestations of "overtwistedness". We also find the first examples of contact manifolds in all dimensions that are not symplectically fillable but also cannot be called overtwisted in any reasonable sense. These depend on a higher-dimensional analogue of Giroux torsion, which we define via the existence in all dimensions of exact symplectic manifolds with disconnected contact boundary.Comment: 68 pages, 5 figures. v2: Some attributions clarified, and other minor edits. v3: exposition improved using referee's comments. Published by Invent. Mat

The Need to Develop Standard Measures of Patient Adherence for Big Data: Viewpoint

Despite half a century of dedicated studies, medication adherence remains far from perfect, with many patients not taking their medications as prescribed. The magnitude of this problem is rising, jeopardizing the effectiveness of evidence-based therapies. An important reason for this is the unprecedented demographic change at the beginning of the 21st century. Aging leads to multimorbidity and complex therapeutic regimens that create a fertile ground for nonadherence. As this scenario is a global problem, it needs a worldwide answer. Could this answer be provided, given the new opportunities created by the digitization of health care? Daily, health-related information is being collected in electronic health records, pharmacy dispensing databases, health insurance systems, and national health system records. These big data repositories offer a unique chance to study adherence both retrospectively and prospectively at the population level, as well as its related factors. In order to make full use of this opportunity, there is a need to develop standardized measures of adherence, which can be applied globally to big data and will inform scientific research, clinical practice, and public health. These standardized measures may also enable a better understanding of the relationship between adherence and clinical outcomes, and allow for fair benchmarking of the effectiveness and cost-effectiveness of adherence-targeting interventions. Unfortunately, despite this obvious need, such standards are still lacking. Therefore, the aim of this paper is to call for a consensus on global standards for measuring adherence with big data. More specifically, sound standards of formatting and analyzing big data are needed in order to assess, uniformly present, and compare patterns of medication adherence across studies. Wide use of these standards may improve adherence and make health care systems more effective and sustainable

Deposition of tin oxide, iridium and iridium oxide films by metal-organic chemical vapor deposition for electrochemical wastewater treatment

In this research, the specific electrodes were prepared by metal-organic chemical vapor deposition (MOCVD) in a hot-wall CVD reactor with the presence of O2 under reduced pressure. The Ir protective layer was deposited by using (Methylcyclopentadienyl) (1,5-cyclooctadiene) iridium (I), (MeCp)Ir(COD), as precursor. Tetraethyltin (TET) was used as precursor for the deposition of SnO2 active layer. The optimum condition for Ir film deposition was at 300 °C, 125 of O2/(MeCp)Ir(COD) molar ratio and 12 Torr of total pressure. While that of SnO2 active layer was at 380 °C, 1200 of O2/TET molar ratio and 15 Torr of total pressure. The prepared SnO2/Ir/Ti electrodes were tested for anodic oxidation of organic pollutant in a simple three-electrode electrochemical reactor using oxalic acid as model solution. The electrochemical experiments indicate that more than 80% of organic pollutant was removed after 2.1 Ah/L of charge has been applied. The kinetic investigation gives a two-step process for organic pollutant degradation, the kinetic was zero-order and first-order with respect to TOC of model solution for high and low TOC concentrations, respectively