Les systèmes fer-oxygène-fluor et fer-soufre-fluor

The action of fluorine and hydrogen fluoride on the oxides and sulfides of iron, as well as that of hydrogen sulfide on iron oxides, has been investigated. In addition, a study has been made of the solid-state reactions between the oxides and fluorides of iron on the one hand and iron fluorides and sulfides on the other. Two oxyfluorides with a rutile- and spinel-type structure have been identified in the iron-oxygen-fluorine system. In contrast, no fluorosulfides have been found. The results have been interpreted on the basis of a comparison between Fe-O, Fe-S and Fe-F bonds.     

Theoretical Study of the AICI Disproportionation Reaction Mechanism on the Al(100) Surface

The surface disproportionation reaction mechanism of aluminum subchloride on the aluminum (100) surfaces has been investigated by the plane-wave density functional theory (DFT).Three kinds of possible reaction mechanism of AlCl disproportionation reaction on the aluminum (100)surfaces have been taken into account. The structures of reactants and products have been optimized, transition states have been confirmed and activation energies have been calculated. The adsorption energy of reactants and desorption energy of products have been determined. All of these have been employed to confirm the reaction mechanism and the rate determining step of AlCl disproportionation reaction on the aluminum (100) surfaces.     

Preparation and characterization of water-in-oil decane/AOT microemulsions containing silver and gold nanoparticles and large amounts of water

Stable microemulsions with water contents as high as 10 vol % have been obtained, including those additionally containing silver and gold nanoparticles. Especial attention has been focused on the influence of water and stabilizer contents on the structure of adsorption layers on nanoparticles. The properties of nanoparticles obtained via the traditional microemulsion synthesis have been compared with the properties of nanoparticles that have preliminarily been concentrated with the help of electrophoresis and dried. The electrophoretic concentration and drying of nanoparticles have been shown to improve the stability of their microemulsions. Microemulsions with the highest content of water have been studied to determine the occurrence of percolation and the influence of nanoparticles on their percolation temperature and electrical conductivity.     

Epoxy oligomer and cyclen polymerization on the air-water interface. Receptor properties of a monolayer

Two-dimensional functional polymer systems have been obtained for the first time based on an epoxy oligomer and 1,4,7,10-tetraazacyclododecane (cyclen). The effect of UV radiation on the efficiency of polymerization in the system has been studied. The morphology of polymer materials formed on the liquid surface as a result of thermo- and UV-induced polymerization has been studied. It has been shown that a polymer Langmuir monolayer based on an epoxy oligomer-cyclen mixture can be used as a sensor for copper ions, and the conditions for the system regeneration have been determined. Changes in the pH of the subphase have been established as causing structural rearrangements in the polymer monolayer, which lead to changes in the optical properties of the latter.     

Theory and mechanism of electron transfer in a condensed medium at high temperatures with allowance for change in vibrational frequencies

An expression for electron transfer rate has been obtained through the solution of a time wave equation by the variational method by defining the wave function as a linear combination of functions corresponding to electron localization on the donor and on the acceptor. A dependence of electron transfer on temperature, on the electronic and vibrational characteristics of the system has been derived. An activation energy temperature-variation effect has been obtained. It has been proved that many-electron transfers are impossible.     

Revert and direct type Liesegang phenomenon of silver iodide

The experimental conditions for Liesegang phenomenon of silver iodide in agar gel columns, and particularly the transition from revert to direct type of periodic precipitations, have been investigated. The theoretically derived Mathur's spacing law, which suits both revert and direct type of Liesegang's rings, has been experimentally verified. An attempt has been made to explain the mechanism of revert and direct type and of the transition of revert to direct type of periodic precipitation on the basis of adsorption on the precipitated silver iodide and of flocculation. The dependence of the transition point on the concentrations of the outer and inner electrolytes has been studied. The time law of Morse and Pierce has been verified. The dependence of the velocity constant ( ) on the concentrations of the outer and inner electrolytes has been studied.     

Copper ferrocyanide — polyurethane foam as a composite ion exchanger for removal of radioactive cesium

A method has been developed for the removal of cesium from the aqueous radioactive waste using a composite ion-exchanger consisting of Copper-Ferrocyanide Powder (CFC) and Polyurethane (PU) Foam. Polyvinyl acetate has been used as a binder in the preparation of CFC-PU foam. The physical properties of CFC such as density, surface area, IR stretching frequency and lattice parameters have been evaluated and also its potassium and copper(II) content have been estimated. Optimization of loading of CFC on PU foam has been studied. The CFC-PU was viewed under microscope to find out the homogeneity of distribution. Exchange capacities of the CFC-PU foam in different media have been determined and column studies have been carried out. Studies have been undertaken on extraction of cesium from CFC foam and also on digestion of spent CFC-PU foam and immobilization of digested solution in cement matrix. The cement matrices have been characterized with respect to density, bio-resistance and leaching resistance.     

Synthesis and microstructure-mechanical property relationships of segmented polyurethanes based on a PCL-PTHF-PCL block copolymer as soft segment

The goal of this work has been the synthesis of novel materials based on a biodegradable polycaprolactone-block-polytetrahydrofurane-block-polycaprolactone diol (PCL-b-PTHF-b-PCL). The segmented thermoplastic polyurethanes (STPU) have been synthesised in bulk without catalyst at different molar ratios and their characterization has been performed by different techniques. The physic-chemical interactions, responsible for the unique polyurethane properties, have been evaluated by total attenuated Fourier transform infrared spectroscopy (ATR-IR) in the amide I region using a Gaussian deconvolution technique and, on the other hand, atomic force microscopy (AFM) has been employed to determine the phase microstructures. The effect of increase the hard segment content (HS) has been discussed from the viewpoint of the miscibility of hard and soft segments, analyzed by differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA). The influence of HS content on the microstructure-mechanical property relationships has also been investigated. Special attention has been focused on the wettability of the samples, measured through water contact angle measurements (WCA), to determine the tendency for biocompatibility of the samples.     

Surface-ionization mass spectrometry of terpene hydrocarbons

The surface ionizations of four terpene hydrocarbons (α-pinene, alloocimene, Δ³-carene, and limonene) on oxidized tungsten wires and ribbons have been investigated. The mass spectra of the ions and the temperature dependences of the currents have been obtained, current densities have been estimated, and monomolecular decompositions of the metastable vibrationally excited ions have been found. The actions on the surface of oxidized tungsten leading to the formation of ionizing particles are considered. The ionizing potentials of the radicals (M - H) obtained on the splitting out of hydrogen atoms from the molecules have been estimated.     

Comparative study of titanium(IV)-based exchangers in aqueous and mixed solvent systems

The antimonate, arsenate, tungstate, molybdate and selenite of titanium have been synthesized. Their composition and chemical and thermal stability have been determined. Effects of pH and temperature on ion-exchange capacity have been studied. Titanium antimonate was found to be the most stable. The utility of these ion-exchangers for analytical separations was examined by determining the distribution coefficients for 26 metal ions in some aqueous, non-aqueous and mixed solvent systems. Quantitative separations of HgCd, PbCu and PbZn have been achieved on titanium tungstate columns, and LaBa mixtures have been separated on a titanium arsenate column.     

Effect of the composition of polyacrylimide-forming copolymers on their processing

Thermomechanical studies of thermosetting copolymers of acrylonitrile with methacrylic acid and acrylamide with acrylic acid that form similar polyacrylimide foam plastics during curing have been performed. The dependence of the glass-transition temperatures of the copolymers on the degrees of intramolecular imidization has been calculated and confirmed experimentally. Procedures to control the curing rate have been proposed. The influence of plasticizing additives on the glass-transition temperatures, imidization, and foaming of foam-forming compositions has been studied. Plasticized powdered foam-forming compositions with delayed imidization have been developed, and temperature conditions for their processing have been determined.     

Diastereoselectivity in the Epoxidation of Substituted Cyclohexenes by Dimethyldioxirane(1)(,)(2)

Three series of compounds based on the cyclohexene framework have been epoxidized by dimethyldioxirane. A pronounced dependence of epoxide diastereoselectivity on substituent has been observed. In addition there is a solvent influence on this stereoselectivity. The results have been explained by invoking steric, H-bonding, and dipole-dipole influences on the epoxide stereochemistry.     

Photosensitivity,substituent and solvent-induced shifts in UV-visible absorption bands of naphthyl-ester liquid crystals: a comparative theoretical approach

The substituent- and solvent-induced shifts in UV-visible absorption bands of naphthyl-ester nematic liquid crystals, viz., 4-octylphenyl-6-octyloxy-2-naphthoate (NAPHE1) and 6-octyloxy-2-naphthylyl-4-octyloxybenzoate (NAPHE2), have been investigated using the DFT, CNDO/S and INDO/S methods. A correlation has been made between molecular charge distribution and phase stability based on Mulliken, Loewdin, AM1, PM3, MNDO, CNDO/S and INDO/S methods. The observed π→π* and n→π* electronic transitions have been reported. The substituent- and solvent-induced shifts in absorption bands, transition energies and energy gaps have been discussed. The photosensitivity of the molecules has been analysed based on these shifts. It has been observed that the substituent has a dominant role on both absorption maxima and energy band gap, whereas the solvent has a dominant role only on absorption maxima, and no effect has been observed on the energy gap. These shifts may provide beneficial consequences in determining the end use of compounds.     

Fabrication and evaluation of single- and dual-channel (Pi-design) microchip electrophoresis with electrochemical detection

A new dual-channel microchip capillary electrophoresis (MCE) has been developed on glass substrates for the first time with electrochemical detection. Dual-channel (called Pi-design) as well as single-channel microchips have been fabricated on soda-lime glass using photolithography, wet etching and thermal bonding. Moreover, a laser writing system has been applied for the fabrication of photomasks with the different microchip designs (single- and dual-channel configurations). The microfabricated channels have been characterized by optical, confocal and scanning electron microscopy. The resulting single- and dual-channel microchips have been evaluated using an end-channel amperometric detector based on one (single-channel) or two (dual-channel) 100-mum gold wires aligned at the outlet of the separation channel. Parameters affecting the separation of several phenolic compounds (dopamine, p-aminophenol and hydroquinone) have been studied in the glass microchips. Thus, the influence of separation voltage, detection potential and background electrolyte has been examined in the single-channel microchip. Different total length microchannel has been compared. Furthermore, the possibility of carrying out two simultaneous measurements has been demonstrated in the new dual-channel microchip electrophoresis. The injection format has been checked and resulted to be critical, in such a way that a special and new form is employed for obtaining simultaneous signals at both channels. Analytical characteristics, such as sensitivity and reproducibility have been evaluated and resulted very adequate.     

Synthesis of nanocrystalline BiSbO<Subscript>4</Subscript>

Reaction of hydrochloric acid solutions of bismuth and antimony with ammonia has been studied and effect of coprecipitation conditions of resultant hydroxides on their reactivity has been determined. Annealing conditions for coprecipitation products have been optimized. Effect of surfactants of different nature and concentration on the phase composition, size, and shape of resulting particles have been examined. Nanocrystalline samples of BiSbO₄ have been synthesized.     

Sorption of Copper(II) Ions with Nanosized Magnesium Phosphate

A new approach to the preparation of a nanosized sorbent based on magnesium phosphate has been developed. The patterns of copper(II) ions sorption with nanosized magnesium phosphate from aqueous solutions have been investigated. The sorption parameters have been determined, and the kinetics and mechanism of the processes have been elucidated. The high sorption ability of the nanoscale sorbent has been shown in comparison with existing sorbents based on magnesium phosphate.     

Functionalization of an amorphous ethylene-propylene copolymer by free radical initiated grafting of unsaturated molecules

Functionalization of an amorphous ethylene-propylene copolymer, EPM, has been performed by means of homogeneous grafting reactions of unsaturated molecules such as dibutylmaleate, diethylfumarate, itaconic anhydride, and maleic anhydride, initiated by free radicals. Dicumylperoxide and dibenzoylperoxide have been used as a free radical source and their efficiency has been compared. A different reactivity of the unsaturated molecules has been evidenced. The influence of the nature of the solvent on the functionalization degree has been investigated, revealing a noticeable effect of the solvent either on the amounts of grafted molecules or on the secondary reactions which lead to partial degradation of the functionalized EPM chains.     

Regimes of water droplet evaporation on copper substrates

Distilled water droplet evaporation has been studied on copper substrate surfaces with different degrees of roughness. Data on variations in the contact diameter have been employed to distinguish between the regimes of distilled water droplet spreading over the copper surfaces that proceed after the viscous regime. For each isolated regime, the duration has been determined as a fraction of the total evaporation time and the main physical processes have been described. Variations in contact angles have been analyzed as depending on copper surface temperature. It has been established that, as the substrate temperature is elevated, wetting becomes better, while the adhesion work remains almost unchanged, thereby indicating the absence of chemical and structural transformations at the liquid–substrate interface.     

Determination of the sorption characteristics of glauconite during extraction of a pharmaceutical from an aqueous medium

A technique for preparing enriched glauconite on the basis of a natural mineral from the Beloozyorskoe field of Saratov oblast has been developed. The results of a study of the chemical composition, surface structure, and certain physicochemical properties of the samples of the sorbent are presented. The sorption of ambroxol hydrochloride ions from aqueous solutions has been studied using natural and enriched glauconite. The sorption isotherms, are approximated by the Langmuir equation, have been obtained, and the values of the maximum sorptive capacities have been calculated. Based on the obtained data, conclusions have been drawn on using the studied natural mineral sorbents to extract the above-mentioned substance from aqueous solutions.