Operando Isotopic Exchange in Solid Oxide Fuel Cells: Oxygen-Transport Dependency on Applied Potential

The oxygen isotopic exchange technique is a powerful tool to investigate the oxygen transport kinetics in an oxide solid. In a solid oxide fuel cell, isotopic surface exchange and diffusion coefficients are classically determined by using the Isotopic Exchange Depth Profiling method followed by ex situ SIMS characterizations. Despite its relevance, the utilization of in situ or operando techniques to measure the isotopic exchange under an electrical bias remains marginal. We developed here a set-up which enables operando monitoring of oxygen exchange in SOFC type cells under polarization. The system has been used for studying the oxygen mobility dependency upon polarization on a symmetrical Pt/YSZ/Pt cell (YSZ: yttria-stabilized zirconia). Homomolecular and heterolytic exchange reactions were undertaken to investigate the oxygen activation step and discriminate the limiting step among the sequence of elementary steps which constitute the oxygen transport process in the SOFC system. Oxygen ions incorporation into the dense ionic conductor was identified to be the rate determining step, and its first order rate constant dependency on applied potential was established.     

Partial control of delay-coordinate maps

Nonlinear Dynamics - Delay-coordinate maps have been widely used recently to study nonlinear dynamical systems, where there is only access to the time series of one of their variables. Here, we...     

Thermodynamical consistency of the dual-phase-lag heat conduction equation

Dual-phase-lag equation for heat conduction is analyzed from the point of view of non-equilibrium thermodynamics. Its first-order Taylor series expansion is consistent with the second law as long as the two relaxation times are not negative.     

A door to model reduction in high-dimensional parameter space

Model reduction techniques such as Proper Generalized Decomposition (PGD) are decision-making tools that are about to revolutionize many domains. Unfortunately, their computation is still problematic for problems involving many parameters, for which one has to face the “curse of dimensionality”. An answer to this challenge is given in solid mechanics by the so-called “parameter-multiscale PGD”, which is based on Saint-Venant's principle. In this article, a model problem composed of up to a thousand parameters is presented, showing that the method is able to overcome the “curse of dimensionality”.     

Separation and kinetic analysis of the thermo-oxidative reactions of polyacrylonitrile upon heat treatment

A polyacrylonitrile (PAN) homopolymer and a copolymer with methyl acrylate were analyzed by differential scanning calorimetry (DSC) in order to establish a method for the kinetic analysis of the stabilization reaction steps during heat treatment. The application of a program rarely used for the study of the chemical transformation of PAN and its copolymers resulted in five separate steps, which can be assigned with large probability to various cyclization and oxidation reactions. A more exact identification of the reactions needs further measurements and considerations. Overlapping peaks appearing in the DSC traces were deconvoluted and then quantitatively analyzed to obtain kinetic parameters. The kinetics of the processes were described by the Kissinger model. The model could be fitted well to four of the five processes that may indicate that these belong to individual reactions of the first order. The parameters obtained agree well with the few values of similar investigations published in the literature up to now. The results have large practical relevance, since the kinetic parameters obtained can be used in the preparation of intermediates and for the optimization of the stabilization process.     

Evidence for shape deformations of fragments in deep inelastic collisions

The number and energy spectra of neutrons evaporated by the heavy and light fragments in deep inelastic collisions have been obtained for the system 240 MeV⁴⁰Ar +¹⁹⁷Au. They indicate that at the scission point the deformation energy is a large part of the total excitation energy espe cially for the light fragment. In the last two years, neutron emission has been studied in deep inelastic reactions^1?6. All the results are similar: the incident energy which is lost during the process is transformed into excitation energy of the final fragments and is shared between the two products proportionnally to their masses. This means that the nuclear temperature was uniform in the composite system. The excitation energy equilibration time is really very short since equilibration is achieved after reaction times as small as 10^?22 s^2,6. Moreover, no preequilibrium emission (direct neutrons-) has been observed.     

Critical behaviour of the linear birefringence in 3d-Heisenberg antiferromagnets : RbMnF3, KNiF3 and KCoF3

The linear birefringence of stress induced single antiferromagnetic T-domains of RbMnF₃, KNiF₃ and KCoF₃ has been measured in the vicinity of T_N. We deduce the critical behaviour in such 3d-Heisenberg systems, showing a symmetry breaking at the transition involving a unique wave vector of the order parameter in the Brillouin zone. The critical exponent $\text{β}$ of the linear birefringence has been found to be larger than 2β, in agreement with the theoretical predictions of G. Gehring.