Characterisation of Ba2In2 − x Sn x O5 + x/2 oxide ion conductors

The Ba₂In_2 − x Sn _x O_5 + x/2 solid solution was confirmed up to x = 1 by solid-state reaction. X-ray diffraction at room and at elevated temperatures, Raman scattering and impedance spectroscopy were used to characterise the samples. The structure refinement of the composition x = 0.1 from neutron diffraction data reveals that tin is preferentially located in the tetrahedral layers of the brownmillerite. Paper presented at the 11th EuroConference on the Science and Technology of Ionics, Batz-sur-Mer, Sept. 9–15, 2007     

Cycles in dense digraphs

Let G be a digraph (without parallel edges) such that every directed cycle has length at least four; let β(G) denote the size of the smallest subset X ? E(G) such that G?X has no directed cycles, and let γ(G) be the number of unordered pairs {u, v} of vertices such that u, v are nonadjacent in G. It is easy to see that if γ(G) = 0 then β(G) = 0; what can we say about β(G) if γ(G) is bounded?

We prove that in general β(G) ≤ γ(G). We conjecture that in fact β(G) ≤ ½γ(G) (this would be best possible if true), and prove this conjecture in two special cases:

• when V(G) is the union of two cliques
• when the vertices of G can be arranged in a circle such that if distinct u, v, w are in clockwise order and uw is a (directed) edge, then so are both uv, vw.

     

Electron super-rich radicals in the gas phase. A neutralization-reionization mass spectrometric and ab initio/RRKM study of diaminohydroxymethyl and triaminomethyl radicals

Diaminohydroxymethyl (1) and triaminomethyl (2) radicals were generated by femtosecond collisional electron transfer to their corresponding cations (1+ and 2+, respectively) and characterized by neutralization-reionization mass spectrometry and ab initio/RRKM calculations at correlated levels of theory up to CCSD(T)/aug-cc-pVTZ. Ion 1+ was generated by gas-phase protonation of urea which was predicted to occur preferentially at the carbonyl oxygen with the 298 K proton affinity that was calculated as PA = 875 kJ mol-1. Upon formation, radical 1 gains vibrational excitation through Franck-Condon effects and rapidly dissociates by loss of a hydrogen atom, so that no survivor ions are observed after reionization. Two conformers of 1, syn-1 and anti-1, were found computationally as local energy minima that interconverted rapidly by inversion at one of the amine groups with a <7 kJ mol-1 barrier. The lowest energy dissociation of radical 1 was loss of the hydroxyl hydrogen atom from anti-1 with ETS = 65 kJ mol-1. The other dissociation pathways of 1 were a hydroxyl hydrogen migration to an amine group followed by dissociation to H2N-C=O* and NH3. Ion 2+ was generated by protonation of gas-phase guanidine with a PA = 985 kJ mol-1. Electron transfer to 2+ was accompanied by large Franck-Condon effects that caused complete dissociation of radical 2 by loss of an H atom on the experimental time scale of 4 mus. Radicals 1 and 2 were calculated to have extremely low ionization energies, 4.75 and 4.29 eV, respectively, which belong to the lowest among organic molecules and bracket the ionization energy of atomic potassium (4.34 eV). The stabilities of amino group containing methyl radicals, *CH2NH2, *CH(NH2)2, and 2, were calculated from isodesmic hydrogen atom exchange with methane. The pi-donating NH2 groups were found to increase the stability of the substituted methyl radicals, but the stabilities did not correlate with the radical ionization energies.     

Uniqueness of highly representative surface embeddings

Let Σ be a (connected) surface of “complexity” κ; that is, Σ may be obtained from a sphere by adding either ½κ handles or κ crosscaps. Let ρ ≥ 0 be an integer, and let Γ be a “ρ-representative drawing” in Σ; that is, a drawing of a graph in Σ so that every simple closed curve in Σ that meets the drawing in < ρ points bounds a disc in Σ. Now let Γ′ be another drawing, in another surface Σ′ of complexity κ′, so that Γ and Γ′ are isomorphic as abstract graphs. We prove that. (i) If ρ ≥ 100 log κ/ log log κ (or ρ ≥ 100 if κ ≤ 2) then κ′ ≥ κ, and if κ′ = κ and Γ is simple and 3-connected there is a homeomorphism from Σ to Σ′ taking Γ to Γ′, and. (ii) if Γ is simple and 3-connected and Γ′ is 3-representative, and ρ ≥ min (320, 5 log κ), then either there is a homeomorphism from Σ to Σ′ taking Γ to Γ′, or κ′ ≥ κ + 10^-4 ρ². © 1996 John Wiley & Sons, Inc.     

Effective Rheology of Two-Phase Flow in Three-Dimensional Porous Media: Experiment and Simulation

We present an experimental and numerical study of immiscible two-phase flow of Newtonian fluids in three-dimensional (3D) porous media to find the relationship between the volumetric flow rate (Q) and the total pressure difference (\(\Delta P\)) in the steady state. We show that in the regime where capillary forces compete with the viscous forces, the distribution of capillary barriers at the interfaces effectively creates a yield threshold (\(P_t\)), making the fluids reminiscent of a Bingham viscoplastic fluid in the porous medium. In this regime, Q depends quadratically on an excess pressure drop (\(\Delta P-P_t\)). While increasing the flow rate, there is a transition, beyond which the overall flow is Newtonian and the relationship is linear. In our experiments, we build a model porous medium using a column of glass beads transporting two fluids, deionized water and air. For the numerical study, reconstructed 3D pore networks from real core samples are considered and the transport of wetting and non-wetting fluids through the network is modeled by tracking the fluid interfaces with time. We find agreement between our numerical and experimental results. Our results match with the mean-field results reported earlier.     

Audio and sound archives as a resource for voice science: A preliminary review

Archives of voice recordings could provide a source of information for voice scientists and clinicians interested in voice analysis and in cultural and historical changes of vocal styles and qualities. Large collections of sound recordings exist that could be used as databases for such inquiries, although no comprehensive list of such collections currently exists. A preliminary survey of major collections is presented. Voice scientists and voice archivists have many common areas of interest in the recording, reproduction, copying, and analysis of sound. The Recording and Research Center, as part of its ongoing research in establishment of standards for voice analysis, has begun an archive of laboratory recordings. A protocol for recording trained, normal, abnormal, and neurologically impaired voices is in development. This survey of sound archives will continue as well.     

Traces and determinants of linear operators

A general theory of tracestr _D A and determinantsdet _D (I+A) in normed algebrasD of operators acting in Banach spacesB is proposed. In this approach trace and determinant are defined as continuous extensions of the corresponding functionals from finite dimensional operators. We characterize the algebras for which such extensions exist and describe sets of possible values of traces and determinants for the same operator in different algebras. In spite of the fact that the extended traces and determinants may differ in different algebrasD, operatorI+A (withA D) is invertible inB if and only ifdet _D (I+A) does not vanish. Cramer's rule and formulas for the resolvent are obtained and they are expressed in different algebras by the same formulas viadet _D (I+A) andtr _D (A). A large set of examples and illustrations are also presented.     

Formation constants at high ionic strength-II. The ionic strength correction of formation constants using a simplified pitzer equation

A simplified approach to the correction of equilibrium constants from one ionic strength and/or medium to another is developed. A computer program capable of performing these calculations is presented together with results of its application to the NH (3)H (+), CH (3)COO (-)H (+), CH (3)CH (2)COO (-)H (+), - OOCCH (2)COO (-)H (+) and HOOCCH (2)COO (-)H (+) systems.