Kinetics of oxygen exchange in strontium titanate

The kinetics of oxygen exchange are of primary importance for the application of titanates as fast resistive oxygen sensors. The sensor’s conductivity is correlated with the oxygen partial pressure pO₂ of the surrounding atmosphere: Due to oxygen surface transfer and subsequent diffusion of oxygen vacancies V _O ^·· , a pO₂ change gives rise to a conductivity change of the sample. While bulk diffusion usually occurs very fast, the surface transfer reaction becomes the rate determining step for thin samples and for low temperatures. We have shown that in the case of acceptor doped SrTiO₃ the kinetics of the surface transfer reaction can be strongly influenced through stoichiometric changes brought about by thin coatings of alkaline earth metal oxides (e.g. SrO). In contrast to the commonly used jump method (conductivity response to a sudden pO₂ change in the time domain), a model is presented which is based on the frequency-domain analysis of amplitude and phase shift of the response signal obtained from a pO₂ modulation in a fast kinetic measurement set-up. This method allows not only for measuring response times in the sub-millisecond range but also for distinguishing between behaviour either controlled by volume diffusion or by surface transfer reaction. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15 – 21, 2002.     

On the Second Law of Thermodynamics and the Piston Problem

The piston problem is investigated in the case where the length of the cylinder is infinite (on both sides) and the ratio m/M is a very small parameter, where m is the mass of one particle of the gaz and M is the mass of the piston. Introducing initial conditions such that the stochastic motion of the piston remains in the average at the origin (no drift), it is shown that the time evolution of the fluids, analytically derived from Liouville equation in a previous work, agrees with the Second Law of thermodynamics. We thus have a non equilibrium microscopical model whose evolution can be explicitly shown to obey the two laws of thermodynamics.     

Une axiomatisation de la substitution

We investigate the notion of substitution in an abstract way, without defining it explicitly. We single out the essential features of the operation of performing a substitution in order to define a concept of substitutive structure, called logos. We then prove a completeness theorem making precise and justifying the intuition that formulas true for the usual substitution can be proved from the logos axioms only. To cite this article: M. Crabbé, C. R. Acad. Sci. Paris, Ser. I 338 (2004).     

Mathematical and numerical analysis of a simplified time-dependent viscoelastic flow

A time-dependent model corresponding to an Oldroyd-B viscoelastic fluid is considered, the convective terms being disregarded. Global existence in time is proved in Banach spaces provided the data are small enough, using the implicit function theorem and a maximum regularity property for a three fields Stokes problem. A finite element discretization in space is then proposed. Existence of the numerical solution is proved for small data, so as a priori error estimates, using again an implicit function theorem. Supported by the Swiss National Science Foundation. Fellowship PBEL2–114311.     

An alternative approach for non-linear optimal control problems based on the method of moments

We propose an alternative method for computing effectively the solution of non-linear, fixed-terminal-time, optimal control problems when they are given in Lagrange, Bolza or Mayer forms. This method works well when the nonlinearities in the control variable can be expressed as polynomials. The essential of this proposal is the transformation of a non-linear, non-convex optimal control problem into an equivalent optimal control problem with linear and convex structure. The method is based on global optimization of polynomials by the method of moments. With this method we can determine either the existence or lacking of minimizers. In addition, we can calculate generalized solutions when the original problem lacks of minimizers. We also present the numerical schemes to solve several examples arising in science and technology.     

Anodic stripping coulometry with collection for absolute trace analysis of lead, using flow-through electrochemical cells with porous working electrodes

Summary Flow-through electrochemical cells with porous working electrodes made of crushed reticulated vitreous carbon and plated with mercury were used for absolute analysis of trace amounts of lead by anodic stripping coulometry with collection (ASCWC) in a flow system. The role of mercury coating, flow rate and pH were investigated. The coulombic content of the collection peak corresponded to the theoretical values calculated by Faraday's law in a concentration range from about 10^–9 to 10^–6 mol/l. The relative error and the relative standard deviation was +0.15% and 0.8%, respectively for 2×10^–6 mol/l analyte concentration. The absolute detection limit (3 s) was 0.1 ng of Pb, the linear response range 7×10⁴. One leave from: Department of Analytical Chemistry, Slovak Technical University, CS-812 37 Bratislava, Czechoslovakia     

Left, right, and inner socles of associative systems

We investigate the basic properties of the different socles that can be considered in not necessarily semiprime associative systems. Among other things, we show that the socle defined as the sum of minimal (or minimal and trivial) inner ideals is always an ideal. When trivial inner ideals are included, this inner socle contains the socles defined in terms of minimal left or right ideals. This revised version was published online in June 2006 with corrections to the Cover Date.     

Interpretation of the polyelectrolyte and antipolyelectrolyte effects of poly(N‐vinylimidazole‐co‐sodium styrenesulfonate) hydrogels

Hydrogels of N‐vinylimidazole (VI) and sodium styrenesulfonate (SSS) were synthesized in aqueous solution by radical crosslinking copolymerization with N,N′‐methylene‐bis(acrylamide) as crosslinker. Swelling in several saline solutions was measured for hydrogel samples synthesized with different comonomer concentrations (C_T = 10, 25, or 40%) and with SSS mole fractions covering a broad range (f_SSS = 0–0.7), while the crosslinker ratio was 2 wt % in all cases. The degree of swelling in aqueous solution with a specific ionic strength (μ), plotted versus the SSS composition of the feed, shows a minimum for any set of samples synthesized with a fixed C_T. The dependence of swelling on μ shows both polyelectrolyte (f_SSS beyond the minimum) and antipolyelectrolyte behaviors (in the low f_SSS limit). It was found that the nonGaussian factor of the crosslinking density and the polymer‐solvent interaction parameter increase with f_SSS for any C_T. Moreover, in the low f_SSS limit, the osmotic swelling pressure is governed not only by the ionic contribution, but also by the polymer‐solvent mixing and, the concentration of mobile counterions inside the gel is not proportional to the net fixed charge but to the addition of cationic and anionic side groups, what discards the formation of ionic pairs. The antipolyelectrolyte effect is interpreted as due to the increasing protonation of VI as μ goes up. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 1683–1693, 2007