Self-diffusion coefficient measurements at high temperature by PFG NMR

We have developed a new experimental setup for the measurement of self-diffusion coefficients at high temperature (up to 1500 K) in corrosive liquids. It is based on pulsed field gradient NMR using a 10 mm liquid probe with two channels F-H/X modified and coupled with laser heating. The values obtained thanks to this setup are in good agreement with the available data obtained using the reference method, i.e., the capillary method. We present here results on ¹⁹F, ⁷Li, ²³Na, ²⁷Al in molten fluorides. In alkali fluoride mixtures, the self-diffusion coefficients depend weakly on the composition (nature and concentration of the different alkali) but mainly on temperature. In cryolite (Na₃AlF₆), the diffusion evidences AlF_x^3 ? x species.     

Asymptotic Analysis of Shell-like Inclusions with High Rigidity

We study the problem of an elastic shell-like inclusion with high rigidity in a three-dimensional domain by means of the asymptotic expansion method. The analysis is carried out in a general framework of curvilinear coordinates. After defining a small real adimensional parameter ε, we characterize the limit problems when the rigidity of the inclusion has order of magnitude \frac1e\frac{1}{\varepsilon } and \frac1e³\frac{1}{\varepsilon^{3}} with respect to the rigidities of the surrounding bodies. Moreover, we prove the strong convergence of the solution of the initial three-dimensional problem towards the solution of the simplified limit problem.     

Self-assembly, foaming, and emulsifying properties of sodium alkyl carboxylate/guanidine hydrochloride aqueous mixtures

Unsaturated fatty acids may be extracted from various agricultural resources and are widely used as soaps in the industry. However, there also exist a large variety of saturated and hydroxy fatty acids in nature, but their metal salts crystallize at room temperature in water, hampering their use in biological and chemical studies or for industrial applications. Addition of guanidine hydrochloride (GuHCl) to sodium salt of myristic acid has been shown to prevent its crystallization in water, forming stable flat bilayers at room temperature. Herein, we extend this finding to two other saturated fatty acids (palmitic and stearic acids) and two hydroxyl fatty acids (juniperic and 12 hydroxy stearic acids) and study more deeply (by using small angle neutron scattering) the supramolecular assemblies formed in both saturated and hydroxyl fatty acid systems. In addition, we take the advantage that crystallization no longer occurs at room temperature in the presence of GuHCl to study the foaming and emulsifying properties of those fatty acid dispersions. Briefly, our results show that all fatty acids, even juniperic acid, which is a bola lipid, are arranged in a bilayer structure that may be interdigitated. Depending on the nature of the fatty acid, the systems exhibit good foamability and foam stability (except for juniperic acid), and emulsion stability was good. Those findings should be of interest for using saturated long chain (and hydroxyl) fatty acids as surfactants for detergency or even materials chemistry.     

On the choice and influence of the number of boosting steps for high-dimensional linear Cox-models

In biomedical research, boosting-based regression approaches have gained much attention in the last decade. Their intrinsic variable selection procedure and ability to shrink the estimates of the regression coefficients toward 0 make these techniques appropriate to fit prediction models in the case of high-dimensional data, e.g. gene expressions. Their prediction performance, however, highly depends on specific tuning parameters, in particular on the number of boosting iterations to perform. This crucial parameter is usually selected via cross-validation. The cross-validation procedure may highly depend on a completely random component, namely the considered fold partition. We empirically study how much this randomness affects the results of the boosting techniques, in terms of selected predictors and prediction ability of the related models. We use four publicly available data sets related to four different diseases. In these studies, the goal is to predict survival end-points when a large number of continuous candidate predictors are available. We focus on two well known boosting approaches implemented in the R-packages CoxBoost and mboost, assuming the validity of the proportional hazards assumption and the linearity of the effects of the predictors. We show that the variability in selected predictors and prediction ability of the model is reduced by averaging over several repetitions of cross-validation in the selection of the tuning parameters.     

Sintering kinetics and oxide ion conduction in Sr-doped apatite-type lanthanum silicates,La9Sr1Si6O26.5

These last past years, a major interest has been devoted to decrease the working temperature of solid oxide fuel cells (SOFCs) down to about 700 °C.Apatite materials (La_10 ? xSr_xSi₆O_27?x/2) are attractive candidates for solid electrolytes, with a high ionic conductivity at these intermediate temperatures. An apatite powder (x = 1) with a 0.75 µm mean particle size, produced by solid state reaction, was tape cast to obtain green sheets with a thickness of about 260 µm.On one hand, the densification mechanism of the apatite ceramic during the intermediate solid state sintering has been approached. It appeared from the kinetical tests performed under isothermal conditions between 1250 and 1550 °C, that densification could be controlled by the diffusion at grain boundaries of the rare-earth element, La, with an activation energy of 470 kJ/mol.On the other hand, conductivity measurements were performed on apatite samples sintered at 1400 and 1500 °C. The ionic conductivity was mainly sensitive to the presence of secondary phases at 1400 °C. The ionic conductivity of the apatite sintered at 1500 °C (mean grain size = 3.9 µm) is equal to 1.2 × 10^? 2 S/cm at 700 °C.     

Transport of long neutral polymers in the semidilute regime through a protein nanopore

We investigate the entrance of single poly(ethylene glycol) chains into an α-hemolysin channel. We detect the frequency and duration of the current blockades induced by large neutral polymers, where chain radius is larger than pore diameter. In the semidilute regime, these chains pass only if the monomer concentration is larger than a well-defined threshold. Experiments are performed in a very large domain of concentration and molecular mass, up to 35% and 200 kDa, respectively, which was previously unexplored. The variation of the dwell time as a function of molecular mass shows that the chains are extracted from the semidilute solution in contact with the pore by a reptation mechanism.     

Distances in evidence theory: Comprehensive survey and generalizations

The purpose of the present work is to survey the dissimilarity measures defined so far in the mathematical framework of evidence theory, and to propose a classification of these measures based on their formal properties. This research is motivated by the fact that while dissimilarity measures have been widely studied and surveyed in the fields of probability theory and fuzzy set theory, no comprehensive survey is yet available for evidence theory. The main results presented herein include a synthesis of the properties of the measures defined so far in the scientific literature; the generalizations proposed naturally lead to additions to the body of the previously known measures, leading to the definition of numerous new measures. Building on this analysis, we have highlighted the fact that Dempster’s conflict cannot be considered as a genuine dissimilarity measure between two belief functions and have proposed an alternative based on a cosine function. Other original results include the justification of the use of two-dimensional indexes as (cosine; distance) couples and a general formulation for this class of new indexes. We base our exposition on a geometrical interpretation of evidence theory and show that most of the dissimilarity measures so far published are based on inner products, in some cases degenerated. Experimental results based on Monte Carlo simulations illustrate interesting relationships between existing measures.     

Smart Foams: Switching Reversibly between Ultrastable and Unstable Foams

Smart foams: Ultrastable foams with an optimal foamability are obtained using hydroxy fatty acids tubes. The stabilization results from the adsorption of monomers at the air-water interface and from the presence of tubes in the plateau borders. Upon heating, tubes transform to micelles, leading to foam destabilization and thus to the first foams to exhibit temperature-tuneable stability.