The influence of aliovalent impurities on the oxidation kinetics of nickel at high temperatures

The influence of chromium and sodium on the nickel oxidation kinetics has been studied as a function of temperature (1373-1673 K) and oxygen activity (10−10⁵ Pa O₂), using microthermogravimetric techniques. It has been shown that the oxidation of Ni-Cr and Ni-Na alloys, like that of pure nickel, follows strictly the parabolic rate law being thus diffusion controlled. In agreement with the defect model of Ni_1−yO, it has been found that the oxidation rate of the Ni-Cr alloy is higher than that of pure nickel, the reaction rate is pressure independent and the activation energy of this process is lower. This implies that the concentration of double ionized cation vacancies in a Ni_1−yO-Cr₂O₃ solid solution is fixed on a constant level by trivalent chromium ions, substitutionally incorporated into the cation sublattice of this oxide. In the case of the Ni-Na alloy, on the other hand, the oxidation rate is lower than that of pure nickel, the activation energy is higher and the oxidation rate increases more rapidly with oxygen pressure. These results can again be explained in terms of the doping effect, by assuming that univalent sodium ions dissolve substitutionally in the cation sublattice of nickel oxide.     

The CH3D absorption spectrum in the 1.58 μm transparency window of methane: Empirical line lists at 81 K and 294 K and temperature dependence

In spite of its low isotopic abundance in methane (about 5×10⁻⁴), CH₃D contributes greatly to the very weak absorption in the 1.58 μm methane transparency window. This methane window deserves to be characterized in details because it is important for planetary applications in particular for Titan and the giant planets. In this work, we recorded the CH₃D spectrum by high sensitivity differential absorption spectroscopy (α_min≈5×10⁻⁸ cm⁻¹) both at room temperature and at 81 K. A list of more than 9000 lines was constructed from the 81 K spectrum for the 6099–6530 cm⁻¹ region. In order to get the temperature dependence of the line intensities, the low energy values have to be determined. The rovibrational assignments available in the literature provide low energy values for about 380 strong transitions of the region. This is insufficient to characterize the temperature dependence of the CH₃D absorption between 6200 and 6400 cm⁻¹. In this interval, a list of 5500 lines was constructed from the room temperature spectrum. The empirical energy values of the transitions were derived from the ratio of the intensities at 81 K and 294 K. The exact and empirical lower state energies included in the final line lists provided as Supplementary Material, allow for accounting for the temperature dependence of the CH₃D spectrum in the entire 6099–6530 cm⁻¹ region.Our measurements have been compared to the spectroscopic parameters and assignments available in the literature in particular those adopted in the HITRAN database. Improvements and corrections are proposed for the wavenumber calibration and for some lower state energies.     

Novel superconducting phases in copper oxides and iron-oxypnictides: NMR studies

We reexamine the novel phase diagrams of antiferromagnetism (AFM) and high-T_c superconductivity (HTSC) for a disorder-free CuO₂ plane based on an evaluation of local hole density (p) by site-selective Cu-NMR studies on multilayered copper oxides. Multilayered systems provide us with the opportunity to research the characteristics of the disorder-free CuO₂ plane. The site-selective NMR is the best and the only tool used to extract layer-dependent characteristics. Consequently, we have concluded that the uniform mixing of AFM and SC is a general property inherent to a single CuO₂ plane in an underdoped regime of HTSC. The T=0 phase diagram of AFM constructed here is in quantitative agreement with the theories in a strong correlation regime which is unchanged even with mobile holes. This Mott physics plays a vital role for mediating the Cooper pairs to make T_c of HTSC very high. By contrast, we address from extensive NMR studies on electron-doped iron-oxypnictides La1111 compounds that the increase in T_c is not due to the development of AFM spin fluctuations, but because the structural parameters, such as the bond angle α of the FeAs₄ tetrahedron and the a-axis length, approach each optimum value. Based on these results, we propose that a stronger correlation in HTSC than in FeAs-based superconductors may make T_c higher significantly.     

Solution-combusting preparation of mono-dispersed Mn3O4 nanoparticles for electrochemical applications

Manganese oxide (Mn₃O₄) nanoparticles with average diameter of 15 nm were prepared using alcohol solution of manganese chloride as starting material via a facile solution-combusting method. The flame core zone was chosen to prepare mono-dispersed and high crystalline products, which were employed to modify glassy carbon electrode and detect dopamine via cyclic voltammetry. The results exhibited excellent electrochemical sensitivity. A linear relationship between the concentration of dopamine and its oxidation peak current was obtained by differential pulse voltammetry, which will find wide application in the biological detection.     

Densification mechanism of polyacrylonitrile-based carbon fiber during heat treatment

Polyacrylonitrile (PAN)-based carbon fibers were heat treated at various temperatures for varying durations to simulate the graphitization process in the manufacture of C/C composites. Densification of the resulting fibers was confirmed by density measurement. The composition and structure of the fibers were investigated by means of elemental analysis, X-ray diffraction and Raman spectroscopy. For specified isothermal heat treatment time, the structural parameters depended strongly on heat treatment temperature. The nitrogen content decreased with increased heat treatment temperature and extended time at constant temperature. Nitrogen loss was complete at temperatures above 1900 °C. The graphite crystallite size increased rapidly with increasing heat treatment temperature, and slowly with extended isothermal heat treatment time. At 2100 °C a more ordered graphitic structure appeared. Denitrogenation induced “puffing”, which made the fibers expand. Decrease in density in the heat treatment temperature range 1500-1900 °C originated from the abrupt evolution of nitrogen, and above 1900 °C the graphitization transition induced steadily increasing density. Densification of the carbon fibers was determined both by the rate of denitrogenation and the rearrangement of carbon atoms.     

Dirichlet norms,capacities and generalized isoperimetric inequalities for Markov operators

We define the notion of p-capacity for a reversible Markov operator on a general measure space and prove that uniform estimates for the ratio of capacity and measure are equivalent to certain imbedding theorems for the Orlicz and Dirichlet norms. As a corollary we get results on connections between embedding theorems and isoperimetric properties for general Markov operators and, particularly, a generalization of the Kesten theorem on the spectral radius of random walks on amenable groups for the case of arbitrary graphs with non-finitely supported transition probabilities.     

On Gauss's proof of Seeber's Theorem

Summary Gauss proved Seeber's Theorem, that the determinant of a reduced positive definite ternary quadratic form is at least half the product of its diagonal coefficients, by means of two determinantal identities whose origin has remained unclear. We examine Gauss's method from a general standpoint, as a method whereby, in certain circumstances, a polynomial in several variables may be shown to be non-negative on a convex polytope by representing it as a positive multilinear combination of the linear forms which determine the polytope. We show that Gauss's identities may be obtained in this manner and that the two identities can in fact be replaced by a simpler single identity which also gives Oppenheim's precise minimum for the determinant.     

Harmonic maps with fixed singular sets

Suppose Ω is a smooth domain in R^m,N is a compact smooth Riemannian manifold, andZ is a fixed compact subset of Ω having finite (m − 3)-dimensional Minkowski content (e.g.,Z ism − 3 rectifiable). We consider various spaces of harmonic mapsu: Ω →N that have a singular setZ and controlled behavior nearZ. We study the structure of such spacesH and questions of existence, uniqueness, stability, and minimality under perturbation. In caseZ = 0,H is a Banach manifold locally diffeomorphic to a submanifold of the product of the boundary data space with a finite-dimensional space of Jacobi fields with controlled singular behavior. In this smooth case, the projection ofu εH tou |ϖΩ is Fredholm of index 0. R. H.’s research partially supported by the National Science Foundation.     

Convergence to equilibrium of critical branching particle systems and superprocesses,and related nonlinear partial differential equations

We consider a class of multitype particle systems in ^d undergoing spatial diffusion and critical stable multitype branching, and their limits known as critical stable multitype Dawson-Watanabe processes, or superprocesses. We show that for large classes of initial states, the particle process and the superprocess converge in distribution towards known equilibrium states as time tends to infinity. As an application we obtain the asymptotic behavior of a system of nonlinear partial differential equations whose solution is related to the distribution of both the particle process and the superprocess.Research partially supported by CONACyT (Mexico), CNRS (France) and BMfWuF (Austria).     

Inégalités de Gagliardo-Nirenberg pour les semi-groupes d'opérateurs et applications

One shows the equivalence between an abstract form of a Gagliardo-Nirenberg inequality and an estimate of the decay of the L ¹–L norm of a semigroup of operators. This equivalence, contrary to the one with the classical Sobolev inequalities, allows the treatment of situations where the decay is exponential. Related results and applications are given.

Cet article a pu être terminé pendant un séjour de l'auteur à l'université d'Edimbourg.