The ortho-to-para conversion in solid hydrogen,catalyzed by hydrogen atoms

The combined techniques of ESR and NMR were used to investigate the process of ortho-para conversion in solid molecular hydrogen, containing small amounts ( 500 ppm) of hydrogen atoms as impurity. Although the impurity atoms catalyze the effective conversion of the neighboring ortho-H₂, the total catalyzed conversion rate at temperatures from 2.2 K to 4.4 K is much less than expected from the rate of the H atoms recombination. A possible explanation is given in terms of the diffusion of H atoms, which is confined to some defects in the crystal.     

Stereoisomers composition of 4-[(1′-methylpropyl)-oxycarbonyl]-2-oxetanone and related compounds,as precursors of fuctional polyesters,determined by chiral gas chromatography

Summary The configurational analysis of racemic and optically active stereoisomers of 4-[(1-methylpropyl)oxycarbonyl]-2-oxetanone has been carried out by using chiral gas chromatography. This technique has been successful in the stereoisomers composition determination of these -substituted -lactones prepared by two different routes and used as monomers in the preparation of malic acid stereocopolymers. Result are in good agreement with those obtained from high resolution ¹H NMR, in the presence of an Europium salt, as chiral shift reagent. This method has been extended to 3-methyl-4-[(1,2,2-trimethyl propyl)oxycarbonyl]-2-oxetanone. The exact knowledge of precursors configurational structure is very important in regard to the obtention of the corresponding polystereoisomers with a strictly controlled enantiomeric or diastereoisomeric composition and consequently with predictable properties.     

Electrochemical and thermodynamic properties of ytterbium trichloride in molten caesium chloride

This work presents the electrochemical study of YbCl₃ in molten CsCl in the temperature range 973-1073 K. Transient electrochemical techniques have been used in order to investigate the reduction mechanism, transport parameters and thermodynamics properties of the reaction YbCl₂+1/2Cl₂=YbCl₃. The results obtained show that the reduction reaction is reversible being controlled by the rate of the mass transfer. The diffusion coefficient of [YbCl₆]^3- complex ions was determined. The apparent standard electrode potential of the soluble-soluble redox system Yb³⁺/Yb²⁺ was obtained by cyclic voltammetry.     

Multi-objective design optimization of a new space radiator

In this work different multi-objective techniques are used to the conceptual design of a new kind of space radiator. Called VESPAR (Variable Emittance Space Radiator), the radiator has an effective variable emittance which makes it able to reduce or avoid the demand for heater power to warm up equipment during cold case operations in orbit. The multi-objective approach was aimed on obtaining a radiator that minimize its mass while at the same time minimize the need for heater power during cold case. Four multi-objective algorithms were used: Elitist Non-dominated Sorting Genetic Algorithm (NSGA-II), Multi-Objective Genetic Algorithm (MOGA), Multi-Objective Simulating Annealing (MOSA) and Multi-Objective Generalized Extremal Optimization (M-GEO). The first three algorithms were used under the modeFrontier^® optimization software package, while M-GEO is a recently proposed multi-objective implementation of the Generalized Extremal Optimization (GEO) algorithm. The Pareto frontier showing the trade-off solutions between radiator mass and heater power consumption is obtained by the four algorithms and the results compared. An assessment of the performance of M-GEO on this problem, compared to the other well-known multi-objective algorithms is also made.     

Retardation of the merocyanine-spiropyran conversion in macromolecules

Summary The flash photolysis of photochromic poly(spiropyranmethacrylate) in solutions was studied. The rates of the thermal decoloration reaction in the polymer solutions are lower than in solutions of the monomer, that was attributed to the steric hindrance of the reaction in macromolecules.     

Kinetic modeling of the laser-induced breakdown spectroscopy plume from metallic lead

We report initial results of a study aimed toward developing a computational fluid dynamics (CFD) model to simulate the laser-induced breakdown spectroscopy (LIBS) plume for the purpose of understanding the physical and chemical factors that control the LIBS signature. The kinetic model developed for modeling studies of the LIBS plume from metallic lead includes a set of air reactions and ion chemistry as well as the oxidization, excitation, and ionization of lead atoms. At total of 38 chemical species and 220 reactions are included in the model. Experimental measurements of the spatial and temporal dependence of a number of lead emission lines have been made of the LIBS plume from metallic lead. The mechanism of generation of excited Pb states in the LIBS plume is analyzed through kinetic modeling and sensitivity analysis. Initial CFD model results for the LIBS plume are presented.     

Thermally Sprayed Coatings as Interlayers for DLC-Based Thin Films

This article examines the usefulness of a thick thermally sprayed interlayer (plasma-sprayed Ni-50%Cr, plasma-sprayed Al₂O₃-13%TiO₂, or high-velocity oxygen-fuel-sprayed WC-17%Co) for enhancing the wear resistance and the corrosion protectiveness of a diamond-like carbon (DLC)-based thin film deposited onto a carbon steel substrate. Scratch tests indicate that the Al₂O₃-13%TiO₂ and WC-17%Co interlayers definitely increase the critical spallation load of the thin film, but the Al₂O₃-13%TiO₂ interlayer itself undergoes brittle fracture under high-contact loads. Accordingly, during ball-on-disk tests at room temperature, no cracking and spallation occur in the DLC-based film deposited onto the WC-17%Co interlayer, whereas the one onto the Al₂O₃-13%TiO₂ interlayer is rapidly removed because the interlayer itself is fractured. At 300 °C, by contrast, the DLC-based film on the Al₂O₃-13%TiO₂ interlayer offers the best tribological performance, possibly thanks to the increased toughness of the ceramic interlayer at this temperature. Electrochemical polarization tests indicate that the thin film/WC-Co systems possess the lowest corrosion current density.     

Welfare and competition effects of electricity interconnection between Ireland and Great Britain

This study analyzes the effects of additional interconnection on welfare and competition in the Irish electricity market. I simulate the wholesale electricity markets of the island of Ireland and Great Britain for 2005. I find that in order for the two markets to be integrated in 2005, additional interconnection would have to be large. The amount of interconnection decreases for high costs of carbon, since this causes the markets to become more similar. This suggests that in the absence of strategic behavior of firms, most of the gains from trade derive not from differences in size between countries, but from technology differences and are strongly influenced by fuel and carbon costs. Social welfare increases with interconnection, although at a decreasing rate. As the amount of interconnection increases, there are also positive effects on competition in Ireland, the less competitive of the two markets. Finally, it is unlikely that private investors will pay for the optimal amount of interconnection since their returns are significantly smaller than the total social benefit of interconnection.