Forms of solid solution ordering upon decreasing temperature

The work reports different forms of solid solution ordering: from the well-known atom redistribution processes over positions and the decomposition of the solid solution to the formation of superstructures, modulated structures, rotation of atomic groups, splitting of sites. For each ordering form as a crystal chemical phenomenon the position of atoms, molecules, and vacancies in the crystal structure of the solid solution is considered and the place of these processes among the main crystal chemical phenomena is determined. The manifestation of order–disorder processes in phase diagrams of systems is also analyzed: from the classical heterogeneous decomposition of solid solutions to the formation of ordered chemical compounds and other phase transitions. The necessity of a thorough study of the atomic-molecular nature of the solid solution ordering by modern X-ray diffraction crystallographic methods and high-resolution electron microscopy is demonstrated. For each ordering form examples are given, the driving force of the process is distinguished, and a brief literature review is presented.     

Short-time isoprene polymerization under the action of a titanium–magnesium catalyst

The short-time polymerization of isoprene under the action of a TiCl₄/MgCl2?i-Bu₃Al heterogeneous catalyst has been investigated. Pulse mixing of the catalyst and monomer in a cylindrical tubular reactor with a certain length followed by ethanol injection has made it possible to carry out polymerization for 0.1?0.7 s. In the first 0.3 s, when there is a considerable rise in the activity of the catalyst, living polymerization of isoprene takes place. In this period, polyisoprene has up to 95% trans-1,4 units. Extending the polymerization time to 0.7 s diminishes the average molar mass of polyisoprene, broadens its molar mass distribution, and decreases the concentration of trans-1,4 units to 83%. The data of this study have been analyzed on the basis of the kinetic continuity of the polymer chain initiation and growth.     

Y-type zeolites for the catalytic oxidative degradation of organic azo dyes in wastewater

Cobalt- and iron-containing catalysts active in the oxidation of organic dyes with hydrogen peroxide have been prepared from granular synthetic NaY and HY zeolites without a binder by ion exchange followed by heat treatment at 350–500°C. It has been demonstrated by X-ray photoelectron spectroscopy that cobalt and iron in these catalysts are in the form of Co²⁺ and Fe³⁺ ions on the support surface. The FeHY and CoNaY catalysts are most effective and stable in the oxidation of the anionic dye carmoisine in weakly acidic and alkaline media.     

Molecular kinetic aspects of vaporization of volatile coordination compounds with organic ligands

We present results of the experimental study and numerical simulation of radiation-convective heat and mass transfer during the sublimation of spherical particles of metal β-diketonates in a high-temperature inert gas flow (argon or helium). The sublimation process is visualized, and experimental data on the temperature variation dynamics and particle size are obtained. It is shown that at stable transfer of the compound from the particle surface the sublimation proceeds with the formation of large pores in its structure. The effect of inert gas properties on the kinetics of the vaporization process of precursor particles with various initial diameters is analyzed in the temperature range from 200 °C to 330 °C. Due to a higher thermal conductivity and heat capacity of helium as compared with argon, the choice of helium as carrier gas causes an increase in the sublimation intensity.     

Effect of Base–Acid Properties of Mixtures of Ethanol with Water on the Enthalpy of Solution of Cyclic Ethers in these Mixtures at <Emphasis Type="Italic">T</Emphasis> = 298.15 K

The enthalpies of solution of the cyclic ethers 1,4-dioxane, 12-crown-4 and 18-crown-6 in mixtures of ethanol and water have been measured within the whole mole fraction range at T = 298.15 K. The enthalpy of solvation has been calculated. In pure ethanol and pure water, the solvation enthalpy of the investigated cyclic ethers depends linearity on the number of –CH₂CH₂– groups in the cyclic ether molecules. Based on the analysis of the preferential solvation model proposed by Waghorne, it can be concluded that the 1,4-dioxane, 15C5 and 18C6 molecules are preferentially solvated by water molecules in the range of low water content in these mixtures. The effect of base–acid properties of ethanol–water mixtures on the enthalpy of solution of cyclic ethers in these mixtures has been analyzed. The enthalpy of solution of cyclic ethers correlates with the acidic properties of ethanol–water mixtures in the range of high and medium water content. The results presented are compared with analogous data obtained for the methanol–water and propan-1-ol–water mixtures.     

Thio acid-mediated conversion of azides to amides – Exploratory studies en route to oroidin alkaloids

The utility of the thio acid-azide coupling reaction to afford amides is explored in imidazole-containing substrates for application in the total synthesis of examples of oroidin alkaloids. Good yields of the expected amides are obtained in both monomeric and dimeric substrates. Bis azides react preferentially at the 2-azido position but hydrosulfenylation and reduction interfere. 2-Thiophenyl and 2-oxo groups were evaluated as 2-amino surrogates, the thioether delivered the expected amide, whereas 2-imidazolone gave a mixture of the expected amide and the hydrosulfenylation product.     

<Emphasis Type="Italic">k</Emphasis>-Sum decomposition of strongly unimodular matrices

Networks are frequently studied algebraically through matrices. In this work, we show that networks may be studied in a more abstract level using results from the theory of matroids by establishing connections to networks by decomposition results of matroids. First, we present the implications of the decomposition of regular matroids to networks and related classes of matrices, and secondly we show that strongly unimodular matrices are closed under k-sums for \(k=1,2\) implying a decomposition into highly connected network-representing blocks, which are also shown to have a special structure.     

Metal Extracts as Precursors for the Production of Metal Powders and Coatings via the Extraction-Pyrolytic Method

The extraction of copper, silver, bismuth, and nickel with carboxylic acids thus providing concentrated metal-containing organic solutions and their crystalline salts has been studied. Micron- and submicron-sized metal powders have been obtained via reduction of these metals carboxylates by heating in benzyl alcohol or ethylene glycol. The synthesis of aspherical silver nanoparticles has been achieved by the reduction of a liquid extract of silver neodecanoate in benzyl alcohol. The possibility of the use of concentrated silver-containing solutions as inks for obtaining of electroconductive images has been demonstrated.     

Cyclic oligoesters as potential materials for polymer nanocomposite production

Publications dedicated to cyclic oligoesters based on cyclic butylene terephthalate were analyzed and summarized. The features of their preparation and structure and their properties were considered with a special focus on advantages and disadvantages of the methods of their preparation: polycondensation at high dilution and depolymerization. The prospects of application of cyclic butylene terephthalate for polymer nanocomposite production were demonstrated. A development strategy for this research area was suggested.

     

Low-Temperature Plasma-Chemical Deposition of Nanocomposite Antifriction Molybdenum Disulfide (Filler)–Silicon Oxide (Matrix) Coatings

It was demonstrated experimentally that the spatial separation of two processes of chemical vapor deposition, one of which provides synthesis of filler (MoS₂) nanoparticles and the other yields the matrix (SiO₂) of the nanocomposite coating, performed ina common reactor, enables an independent control over two process rates and makes it possible to widely vary the composition of the films deposited in this way. The deposition was performed in a double-zone vertical tubular quartz reactor. Molybdenum disulfide particles were produced by pyrolysis of aerosols of ammonium thiomolybdate solutions in dimethylformamide in the upper zone of the reactor, and the plasma-chemical deposition of a nanocomposite coating occurred in the lower zone into which MoS₂ nanoparticles were transported by the gas flow and tetraethoxysilane was delivered. It was shown that the nanocomposite coatings composed of molybdenum disulfide (filler) and silicon oxide (matrix) possess improve the antifriction properties as compared with the matrix (SiO₂ layers), these properties being determined by the relative amounts of MoS₂ nanoparticles in the layer and by their average size.