The crystal structure of the inorganic surface films formed on Mg and Li intercalation compounds and the electrode performance

A crystallographic approach was applied to elucidate the influence of the nature of the surface films on the electrochemical behavior of Li and Mg intercalation compounds. This paper presents two examples: (1) protection of graphite electrodes by Li₂CO₃ surface films, and (2) the unique electrochemical behavior of Mg-containing Chevrel phases (MgCP) obtained by different synthetic routes. In the former case, the elucidation of the protection mechanism and the explanation of the high performance of such protected electrodes are based on the analysis of possible Li-ion motion in the carbonate crystal structure. In the latter case, a combination of synthesis, electrochemistry and XRD analysis was used to explain an unusual phenomenon: the difference between the excellent electrochemical behavior of the Chevrel phase (CP) based on Cu-leached Cu₂Mo₆S₈ (CuCP), and the poor electrochemical activity of the high-temperature synthesized MgCP, with the same phase composition. It is shown that this phenomenon is caused by MgO formation on the surface of the latter material. The different surface chemistry of the MgCPs obtained by the two different synthetic routes was substantiated by revealing the correlation between the electrochemical activity and the chemical stability of these materials under ambient atmosphere conditions. Dedicated to Prof. Mikhail A. Vorotyntsev on the occasion of his 60th birthday.     

The Worpitzky identity for the groups of signed and even-signed permutations

Journal of Algebraic Combinatorics - The well-known Worpitzky identity $$\begin{aligned} (x+1)^n = \sum \limits _{k=0}^{n-1} A_{n,k} {{x+n-k} \atopwithdelims (){n}} \end{aligned}$$ provides a...     

Topological ergodic decompositions and applications to products of powers of a minimal transformation

For a minimal distal flow (X, T) and a positive integern, let be the largest distal factor of ordern. The existence of a denseG _δ subset ω ofX is shown, such that forx ∈ ω the orbit closure of (x,x,...,x) ∈ X ⁿ⁺¹ under τ =T ×T ² ... ×T ⁿ⁺¹ is π-saturated. In fact, an analogous statement for a general minimal flow is proved in terms of its PI-tower. On the way we get some topological “ergodic” decomposition theorems.     

Surface layering in ionic liquids: an X-ray reflectivity study

The surface structure and thermodynamics of two ionic liquids, based on the 1-alkyl-3-methylimidazolium cations, were studied by X-ray reflectivity and surface tensiometry. A molecular layer of a density approximately 18% higher than that of the bulk is found to form at the free surface of these liquids. In common with surface layering in liquid metals and surface freezing in melts of organic chain molecules, this effect is induced by the lower dimensionality of the surface. The concentrations of the oppositely charged ions within the surface layer are determined by chemical substitution of the anion. The temperature-dependent surface tension measurements reveal a normal, negative-slope temperature dependence. The different possible molecular arrangements within the enhanced-density surface layer are discussed.     

Miscible blends through hydrogen bonding: effects on polymer properties

Miscible blends through hydrogen bonding have been intensively studied. The effects of a variety of miscible hydrogen bonded polymer blends on properties such as thermal and thermal oxidative stability, moisture sensitivity, modulus and glass transition temperature are discussed. In addition, the preparation of semi-interpenetrating polymer networks (IPNs) and studies of the effect of crosslinking on the miscibility in hydrogen bonded polymer blends are reviewed.     

Synthesis of new cyclic thionosulfites

The reaction of a series of 1,2-diols with S(2)Cl(2), 1,1'-thiobisbenzimidazole (4a), and 1,1'-dithiobisbenzimidazole (4b) provides the corresponding thionosulfites, ROS(S)OR (2), in moderate to good yield.     

Modification of polybenzimidazole: Synthesis and thermal stability of poly(N1-methylbenzimidazole) and poly(N1,N3-dimethylbenzimidazolium) salt

Poly(N₁,N₃-dimethylbenzimidazolium) (PDMBI) salt and poly(N₁-methylbenzimidazole) (PMMBI) were synthesized by methylation of commercial polybenzimidazole [poly-2,2′-(m-phenylene)-5,5′-bibenzimidazole (PBI)]. First, the N-lithium salt of polybenzimidazole was formed by treating polybenzimidazole solution of 1-methyl-2-pyrolidinone (NMP) with lithium hydride at 80°C for 18 h. Ninety percent substitution of PMMBI was obtained by treating the N-lithium salt of PBI with equimolar ratio of iodomethane at room temperature. Upon addition of excess iodomethane to the lithium salt of PBI at 80°C, a polymer was formed that showed 100% substitution on the N₁ nitrogen and about 30% substitution of the methyl group on the N₃ nitrogen in the form of N₁,N₃-dimethylbenzimidazolium iodide salt [PDMBI (30%)]. The content of the benzimidazolium iodide salt was increased to about 90% by dissolving PDMBI (30%) in dimethyl sulfoxide (DMSO) and re-treating with excess iodomethane at 80°C overnight. The modified PBI polymers were characterized by NMR and FTIR. The modified PBI differed in solubility from PBI. PMMBI could be easily dissolved in NMP and PDMBI in DMSO at room temperature. The solution of PDMBI could be mixed with water in all proportions without precipitation. PDMBI could be also dissolved directly in a mixture of DMSO and water (1 : 1). Typical polyelectrolyte behavior of viscosity was found in solution of PDMBI (30%) and PDMBI (90%) when DMSO and a mixture of DMSO and water were used as solvents. A salt effect on viscosity was also found in the mixed solvent solution. Thermogravimetric analysis (TGA) showed that the methyl group on the imidazole ring was unstable above 180°C under nitrogen. When PDMBI was heated under nitrogen, one of the methyl groups was lost with the counterion to result in a neutral PMMBI. © 1993 John Wiley & Sons, Inc.     

Organically modified sols as pseudostationary phases for microchip electrophoresis

We demonstrate that the selectivity of microchip electrophoresis separations is greatly improved by the presence of organically modified silica (Ormosil) sols in the run buffer. A negatively-charged N-(trimethoxysilylpropyl)ethylenediamine triacetic-acid (TETT)-based sol is used for improving the selectivity between nitroaromatic explosives and a methyltrimethoxysilane (MTMOS)-based sol is employed for enhancing the microchip separation of environmental pollutants, aminophenols. These sols are added to the run buffer and act as pseudostationary phases. Their presence in the run buffer changes the apparent mobility of studied solutes, and leads to a higher resolution. The observed mobilities changes reflect the interactions between the Ormosil sols and the solutes. Relevant experimental variables have been characterized and optimized. The diverse chemistry of Ormosil sols should be extremely useful for tailoring the selectivity of a wide range of electrophoresis microchip separations.     

Super- and sub-Poissonian photon statistics for single molecule spectroscopy

We investigate the distribution of the number of photons emitted by a single molecule undergoing a spectral diffusion process and interacting with a continuous wave laser field. The spectral diffusion is modeled based on a stochastic approach, in the spirit of the Anderson-Kubo line shape theory. Using a generating function formalism we solve the generalized optical Bloch equations and obtain an exact analytical formula for the line shape and Mandel's Q parameter. The line shape exhibits well-known behaviors, including motional narrowing when the stochastic modulation is fast and power broadening. The Mandel parameter, describing the line shape fluctuations, exhibits a transition from a quantum sub-Poissonian behavior in the fast modulation limit to a classical super-Poissonian behavior found in the slow modulation limit. Our result is applicable for weak and strong laser fields, namely, for arbitrary Rabi frequency. We show how to choose the Rabi frequency in such a way so that the quantum sub-Poissonian nature of the emission process becomes strongest. A lower bound on Q is found and simple limiting behaviors are investigated. A nontrivial behavior is obtained in the intermediate modulation limit, when the time scales for spectral diffusion and the lifetime of the excited state become similar. A comparison is made between our results and previous ones derived, based on the semiclassical generalized Wiener-Khintchine formula.