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Vol 90, No 10 (2017)

Reviews

Thermodynamic Analysis of Alloys in Sodium–Tellurium System in Liquid and Solid States

Morachevskii A.G.

Abstract

The whole set of available data on the thermodynamic properties of liquid alloys and solid phases in the sodium–tellurium system is considered, beginning from the first study in 1970 and till the recent reports in 2015. The application of the sodium–tellurium system in chemical power cells is discussed.

Russian Journal of Applied Chemistry. 2017;90(10):1559-1567
pages 1559-1567 views

Inorganic Synthesis and Industrial Inorganic Chemistry

Formation and Properties of Nickel–Phosphorus–Graphite Composite Coatings in Autocatalytic Deposition

Vinokurov E.G., Abrashov A.A., Nevmyatullina K.A., Vagramyan T.A.

Abstract

It is shown that nickel–phosphorus–graphite composite coatings can be deposited by the autocatalytic deposition method. The optimal concentration of graphite and the duration of ultrasonic treatment of a graphite suspension in solution for deposition of composite coatings based on the nickel–phosphorus alloy were determined. The influence exerted by thermal treatment parameters on the properties of the deposits was examined. The optimal process conditions are suggested.

Russian Journal of Applied Chemistry. 2017;90(10):1568-1571
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Structure and Thermal Stability of Nanostructured Precursor Powders of Copper(I) Sulfide and Selenide

Maskaeva L.N., Markov V.F., Fedorova E.A., Berg I.A., Samigullina R.F., Voronin V.I.

Abstract

The hydrochemical precipitation method at 298 and 333 K with, respectively, thiocarbamide and sodium selenosulfate was used to obtain nanostructured powders of copper sulfide with formula composition Cu2S, which are composed of globules 200–500 nm in diameter, formed by 70–100-nm particles, and copper(I) selenide, composed of crystallites with polyhedral shape, sizes of 80 to 500 nm, and a formula composition Cu1.84Se. An X-ray diffraction analysis revealed the orthorhombic Cu2S structure (space group no. 39-Abm2) with unit cell parameters a = 1.182 nm, b = 2.705 nm, and c = 1.343 nm. Powders of Cu1.84Se copper selenide have a cubic structure (space group Fm3m) with lattice constant a = 0.5693 nm. A thermal analysis demonstrated that the chemically precipitated Cu2S and Cu1.84Se powders have a stable elemental composition up to 200–240°C. An intense oxidation of the samples begins at a temperature exceeding 250°C and is accompanied by a sharp decrease in their content of sulfur (selenium) and by an increase in the content of oxygen.

Russian Journal of Applied Chemistry. 2017;90(10):1572-1578
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Synthesis of Highly Dispersed Zirconium Diboride for Fabrication of Special-Purpose Ceramic

Krutskii Y.L., Maksimovskii E.A., Popov M.V., Netskina O.V., Krutskaya T.M., Cherkasova N.Y., Kvashina T.S., Drobyaz E.A.

Abstract

Reduction of zirconium dioxide with boron carbide and nanofibrous carbon in argon yielded a highly dispersed powder of zirconium diboride. Characteristics of zirconium diboride powders were examined by various analytical methods. The material obtained is represented by a single phase, zirconium diboride. Powder particles are for the most part aggregated. The average size of particles and aggregates is 10.9–12.9 μm with a wide size distribution. The specific surface area of the samples is 1.8–3.6 m2 g–1. The oxidation of zirconium diboride begins at a temperature of 640°C The optimal synthesis parameters were determined: ZrO2: B4C: C molar ratio of 2: 1: 3 (in accordance with stoichiometry), process temperature 1600–1700°C, synthesis duration 20 min.

Russian Journal of Applied Chemistry. 2017;90(10):1579-1585
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Mechanically Stimulated Thermal Synthesis of Lithium Pentaaluminate from Lithium Carbonate and Aluminum Hydroxide

Isupov V.P., Eremina N.V., Borodulina I.A.

Abstract

It is shown that the phase composition of lithium aluminates formed when aluminum hydroxide in the form of gibbsite interacts with lithium carbonate in their mixture with Al: Li atomic ratio of 5: 1 depends on the duration of a preliminary mechanical activation of the mixture and on the temperature of the subsequent thermal treatment. A thermal treatment of the starting mixture at temperatures exceeding 800°C yields LiAl5O8 with a substantial admixture of α- and γ-LiAlO2. Raising the duration of the mechanical activation to 5 min and more makes it possible to obtain highly dispersed single-phase LiAl5O8 with a specific surface area larger than 20 m2 g–1

Russian Journal of Applied Chemistry. 2017;90(10):1586-1591
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Control over Rheological Properties of Powdered Formulations Based on Phosphate-Ammonium Salts and Hydrophobized Silicon Oxide

Kondrashova N.B., Val’tsifer I.V., Shamsutdinov A.S., Starostin A.S., Val’tsifer V.A.

Abstract

Surface of silicon oxide (white black BS-120) was hydrophobized with a polymethylhydrosiloxane solution. IR spectroscopy demonstrated that the hydrophobization process involves free silanol groups of the silicon oxide surface. It was found that a stable superhydrophobic state of the surface is observed upon hydrophobization of silicon oxide, with the wetting angle exceeding 150°. Introduction of hydrophobized silicon oxide into a fire-extinguishing powdered formulation based on ammonium phosphates can improve its rheological characteristics. The influence exerted by the fraction composition of dispersed systems based on phosphorus-ammonium salts on their rheological properties was examined.

Russian Journal of Applied Chemistry. 2017;90(10):1592-1597
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Various Technological Processes

Highly Selective Process for Epoxidation of Fatty Acid Methyl Esters with Peroxyacetic Acid

Sapunov V.N., Voronov M.S., Yudaev S.A., Makarov A.A., Kaleeva E.S., Makarova E.M.

Abstract

Specific features of the double-stage process in which unsaturated compounds and, in particular, fatty acid methyl esters of vegetable oils are epoxidated with peroxyacetic acid obtained ex situ in aqueous solutions of acetic acid and hydrogen peroxide under catalysis with Amberlyst 15 Dry ion-exchange resin were examined. It was shown that the independently occurring processes in which the peroxy acid is heterogeneously catalytically formed and epoxy compounds are synthesized can substantially raise the formation selectivity of epoxides with respect to double bonds in fatty acid methyl esters and simplify the simulation of these processes and their technological implementation.

Russian Journal of Applied Chemistry. 2017;90(10):1598-1604
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Hybrid Catalysts Based on Sulfated Zirconium Dioxide and H-beta Zeolite for Alkylation of Isobutane with Isobutylene

Yuferova E.A., Devyatkov S.Y., Fedorov S.P., Semikin K.V., Sladkovskii D.A., Kuzichkin N.V.

Abstract

Physicochemical properties of new hybrid catalysts based on sulfated zirconium oxide supported by zeolite of the Beta structural type were studied. The acid-base characteristics of the catalysts are determined by the amount of the supported component, the maximum concentration of Brønsted acid centers (277 μmol g–1) is reached upon deposition of 1.7 wt % sulfated zirconium oxide. The texture characteristics of the final catalyst are determined by the starting support. Tests of the catalysts in the reaction of isobutane alkylation with isobutylene demonstrated their advantage in selectivity and stability over the classical bulk sulfated zirconium oxide.

Russian Journal of Applied Chemistry. 2017;90(10):1605-1613
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Comparative Study of Titanium-modified HMS Mesoporous Materials via Different Preparing Methods

Li X., Zhang L.

Abstract

The current work is focused on the testing of titanium modified hexagonal mesoporous silica (HMS) for catalysts in epoxidation of cyclohexene. Two samples were prepared via the chemical liquid deposition (CLD) and the chemical vapor deposition (CVD), namely Ti/HMS-L and Ti/HMS-V, respectively. HMS and Ti/HMS were characterized by XRD, N2-adsorption, ICP-AES, UV-Vis. The samples were also evaluated by the epoxidation of cyclohexene with cumene hydroperoxide (CHP) as oxidant. It is revealed that Ti/HMS samples possess typical hexagonal mesoporous structure in which most of titanium species exist in the form of framework tetracoordinated state. Meanwhile, Ti/HMS-V is more seriously affected than Ti/HMS-L since the former was prepared at higher temperature. Ti/HMS-V gives more excellent catalytic performance than Ti/HMS-L, which is likely because the former has more isolated and framework titanium species. Either Ti/HMS-V or Ti/HMS-L can be used only 1 time in epoxidation experiment.

Russian Journal of Applied Chemistry. 2017;90(10):1614-1619
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DFT Study of Cyanide Oxidation on Ge-Doped Carbon Nanotubes

Najafi M.

Abstract

In recent years, the discovery of efficient catalyst with low price to cyanide (CN) oxidation in normal temperature is a major concern in the industry. In present study, in first step the carbon nanotubes (CNTss) were doped with Ge and the surface of Ge-doped CNTss via O2 molecule were activated. In second step the CN oxidation on activated Ge-CNTss surface via Langmuir–Hinshelwood (LH) and Eley–Rideal (ER) mechanisms was investigated. Results show that O2 activated Ge-CNTs surface can oxidize the CN molecule via Ge-CNTs–O–O* + CN → Ge-CNTs–O–O*–CN → Ge-CNTs–O* + OCN and Ge-CNTs–O* + CN → Ge-CNTs + OCN reactions. Results show that CN oxidation on activated Ge-CNTs surface via the LH mechanism has lower energy barrier than ER mechanism. Finally, calculated parameters reveal that activated Ge-CNTss is acceptable catalyst with low price and high performance for CN oxidation in normal temperature.

Russian Journal of Applied Chemistry. 2017;90(10):1620-1626
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Comparative Study of the Support Role on the Activity of Copper Species for Nitric Oxide Reduction

Panahi P.N., Delahay G.

Abstract

In this work three different supports (γ-Al2O3, ZSM-5, and SAPO-34) of varying degree of acid sites and textural properties were used to evaluate the influence of support specifics in the Cu/supported nanocatalysts on NO conversion. The nanocatalysts were prepared by homogeneous deposition precipitation (HDP) method and characterized by N2 pore size distribution, TEM, H2-TPR for investigation the reducibility of the copper species and acidity measurement by NH3 adsorption. The Cu/ZSM-5 and Cu/SAPO-34 catalysts were more active for NO conversion than Cu/γ-Al2O3 catalyst. The characterization and conversion differences in the copper supported on different types of support indicated that these differences arise from the differences in surface area, pore size distribution, and acidity of the supports. The higher SCR-DeNO activity of Cu/ZSM-5 and Cu/SAPO-34 nano-catalysts can be explained by higher surface area and acidity of ZSM-5 and SAPO-34 supports. These catalysts also have larger amount of reducible Cu species compared to Cu/γ-Al2O3 which correlates with the structure of the support used. Considering these findings, the NO conversion ability of Cu/supported catalysts has been correlated with support structure and acidity.

Russian Journal of Applied Chemistry. 2017;90(10):1627-1633
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Preparation and Properties of Thermoplastic Expandable Microspheres with P(AN-MMA) Shell

Gao Y., Zhang N., Zhu L., Hou Z.

Abstract

Thermoplastic expandable microspheres (TEMs) having a core/shell structure were prepared via suspension polymerization with acrylonitrile (AN) and methyl methacrylate (MMA) as monomers and i-butane as blowing agent. The relationship between monomer compositions and expansion properties of the TEMs was explored. When the weight ratio of AN and MMA is 1: 1, suspension polymerization could yield TEMs having good expansion properties and heat stability at 120–130°C. The maximum expansion volume is 22.5 times of the original volume. The temperatures at the maximum expansion volume (Tm.e.), at the onsets of expansion (To.e.) and the onset of shrinkage (To.s.) are 80, 120–130, and 145°C, respectively. The micromorphologies were observed by polarizing optical microscope (POM), the results show that the TEMs have a core/shell structure. The blowing agent content in TEMs is–20 wt %, which was determined by thermogravimetric analysis (TGA). Dynamic light-scattering (DLS) measurements show that the TEMs have an average particle size of–20 μm and a wide particle size distribution. The presence of low-molecular alcohol in water phase could help to reduce the particle size distribution.

Russian Journal of Applied Chemistry. 2017;90(10):1634-1639
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Microstructural Study of Nylon-6/Gelatin Composite Nanofibers

Koosha K., Habibi S., Talebian A.

Abstract

Electrospinning is a simple and effective technology for fabricating nanofibers and polymer blending provides strength and minimal defects of electrospun ones. Therefore, in the present study, fabrication, and characterization of nylon-6/gelatin electrospun nanofibers using low-toxic solvents was investigated as means to improve the morphological deficiencies of gelatin nanofibers and facilitate its electrospinnability. The morphology of electrospun nylon-6/gelatin nanofibers were characterized using scanning electron microscope (SEM). SEM results showed that electrospun blend nanofibers had smooth surface with average diameter of from 40 to 100 nm; while, the miscibility of the blend and thermal behavior of nanofibers were determined using Fourier transform-infrared spectroscopy (FTIR) and differential scanning calorimeter (DSC). Water contact-angle measurement (WCA) was employed to investigating the wettability of nanofibers.

Russian Journal of Applied Chemistry. 2017;90(10):1640-1647
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Kinetic and Thermodynamic Specific Features of Hydrogenation of Hexene-1, Heptene-1, and Cyclohexene on Catalyst Containing Copper Nanoparticles

Shafigulin R.V., Filimonov N.S., Filippova E.O., Shmelev A.A., Bulanova A.V.

Abstract

Kinetics of hydrogenation of hexene-1, heptene-1, and cyclohexene on copper nanoparticles was studied. To examine the thermodynamic specific features, the entropy of formation of an activated complex, rate constants, and conversion were calculated. A conclusion that the key role is played by the entropy factor in the formation of the activated complex is made on the basis of the data obtained. The similarity between the mechanisms by which activated complexes are formed in the hydrogenation of hexene-1, heptene-1, and cyclohexene and in that of hexyne-1, hexadiene-1,5, and benzene with the use of nickel nanoparticles was confirmed. The results obtained enable a conclusion about the high catalytic activity of copper nanoparticles in reactions of hydrogenation of unsaturated hydrocarbons in the temperature range 140–200°C at a pressure of 2 atm.

Russian Journal of Applied Chemistry. 2017;90(10):1648-1654
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Liquid-Phase Hydrogenation of Aromatic Mononitro Compounds on Supported Porous Catalysts at Partial Hydrogen Pressures Lower than 0.1 MPa

Dorokhov V.F., Kuznetsov M.V., Barelko V.V.

Abstract

The influence of the hydrogen partial pressure varied in the interval (4.3–100) × 103 Pa on the kinetics of liquid-phase catalytic hydrogenation of aromatic mononitro compounds in the presence of platinum and iridium supported on activated carbon in various percent ratios (Pt/C-2.5% and Ir/C-5%) was studied for 3,4-dichloronitrobenzene as example. A decrease in the hydrogen partial pressure leads to a significant decrease in the rate of the nitro compound consumption and in the yield of the intermediate arylhydroxylamine. A kinetic mechanism of hydrogenation of the nitro compound, satisfactorily describing the experimental data, was suggested.

Russian Journal of Applied Chemistry. 2017;90(10):1655-1665
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Solid-State Hydrogen-Generating Composites Based on Sodium Borohydride: Effect of the Heat Treatment of Boron–Cobalt Catalysts on the Hydrogen Generation Rate

Netskina O.V., Komova O.V., Prosvirin I.P., Pochtar’ A.A., Ozerova A.M., Simagina V.I.

Abstract

Calcined boron–cobalt catalysts prepared by reduction of cobalt chloride in an aqueous sodium borohydride solution can be successfully used as components of pelletized solid-state hydrogen-generating composites based on sodium borohydride. Morphological changes and phase and chemical transformations occurring in the catalysts with an increase in the calcination temperature were studied. The catalyst performance in hydrolysis of sodium borohydride was determined. The hydrogen generation rate depends on the specific surface area of the calcined sample.

Russian Journal of Applied Chemistry. 2017;90(10):1666-1673
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Applied Electrochemistry and Metal Corrosion Protection

Preparation of a Film Electrolyte Based on Calcium Zirconate on a Porous Electrode by a Chemical Liquid-Phase Method

Khaliullina A.S., Dunyushkina L.A.

Abstract

A modification of a solution method for preparing solid oxide electrolyte films was developed. It is based on using a suspension consisting of a solution of inorganic salts and of a nanodispersed precursor powder prepared from the same solution. As demonstrated by the example of calcium zirconate, this procedure allows the number of applications of the liquid-phase precursor, required to obtain a dense electrolyte film on a porous support, to be considerably decreased relative to the procedure using a salt solution. The influence of the concentration of the precursor powder in the suspension on the microstructure of CaZr0.9Y0.1O3–δ films was analyzed.

Russian Journal of Applied Chemistry. 2017;90(10):1674-1679
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Preparation of Conducting Composite Materials Based on Polymer Nanofibers and Polypyrrole

Matrenichev V.V., Shishov M.A., Popryadukhin P.V., Sapurina I.Y., Ivan’kova E.M., Dobrovol’skaya I.P., Yudin V.E.

Abstract

Conducting materials based on polypyrrole-modified nanofibers of polylactides of different molecular masses and copolymers of ε-caprolactam (–NH–(CH2)5–CO–) and hexamethylenediamine adipate (–H(CH2)6NHCO(CH2)4CO–) were prepared. As shown by scanning electron microscopy, oxidative polymerization of pyrrole on the polymer nanofiber matrix depends on the nanofib er hydrophilicity. The heterophase synthesis of polypyrrole on the surface of hydrophilic nanofibers of the aliphatic copolyamide allowed uniform coating of the material surface with polypyrrole nanoparticles. The surface resistivity of the composite material was about 0.4 kΩ sq–1.

Russian Journal of Applied Chemistry. 2017;90(10):1680-1685
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Effect of the Copper Oxide Sintering Additive on the Electrical and Electrochemical Properties of Anode Materials Based on Sr2Fe1.5Mo0.5O6–δ

Osinkin D.A., Lobachevskaya N.I., Bogdanovich N.M.

Abstract

The effect of introducing 1–3 wt % copper oxide sintering additive on the electrical and electrochemical characteristics of promising anode materials for solid oxide fuel cells based on Sr2Fe1.5Mo0.5O6–δ was studied. The total conductivity increases with increasing amount of copper oxide. The maximum conductivity in humid hydrogen at 800°C, 45 S cm–1, was reached on introducing 3 wt % CuO. The sintering additive enhances the electrochemical activity of Sr2Fe1.5Mo0.5O6–δ and Sr2Fe1.5Mo0.5O6–δCe0.8Sm0.2O1.9 anodes. A decrease in the sintering temperature of the anodes containing CuO with the electrolyte based on lanthanum gallate directly correlates with the electrochemical activity of the anodes. The minimum value of the polarization resistivity, 0.15 Ω cm2 at 800°С in a humid hydrogen atmosphere, was obtained for the composite anode with 3 wt % CuO sintered at a temperature of 1050°С.

Russian Journal of Applied Chemistry. 2017;90(10):1686-1692
pages 1686-1692 views

Specific Technological Processes

Synthesis of Modified Pectin and Its Flocculating Properties

Proskurina V.E., Shabrova E.S., Rakhmatullina A.P., Galyametdinov Y.G.

Abstract

Modified polysaccharide was synthesized by the reaction of amylopectin with a cationic monomer, (1,2-epoxyprop-3-yl)triethylammonium chloride, in alkaline solution in the presence of Fenton’s reagent. The influence of the concentrations of amylopectin, gelatin, their polymer-inorganic hybrids, and modified pectin on their flocculating properties in free (unrestricted) sedimentation of ocher suspension as a model disperse system was studied. Amylopectin exerts a stabilizing effect, whereas the modified pectin and polymer-inorganic hybrid exert a flocculating effect. The influence of the mode of introducing polymer additives on the flocculating effect and aggregation of ocher particles was analyzed.

Russian Journal of Applied Chemistry. 2017;90(10):1693-1699
pages 1693-1699 views

Aerogels Based on Calcium Alginate and Silicon Dioxide and Modified with Carbon Nanotubes for Selective Sorption of Argon from a Mixture with Oxygen

Ivanova E.N., Burmistrova N.N., Alekhina M.B., Tsygankov P.Y., Ivanov S.I.

Abstract

Two kinds of aerogels, those based on silicon dioxide and on calcium aginate, modified with multiwalled carbon nanotubes, were synthesized by the sol–gel method. The aerogels were tested as adsorbents for separating the argon–oxygen gas mixture. The adsorbent based on calcium alginate with 30 wt % content of multiwalled carbon nanotubes exhibits increased selectivity to argon in its adsorption from a mixture with oxygen.

Russian Journal of Applied Chemistry. 2017;90(10):1700-1705
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Possible Ways to Prevent Ash Slagging in Peat Gasification in the Filtration Combustion Mode

Tsvetkov M.V., Zyukin I.V., Freiman V.M., Salganskaya M.V., Tsvetkova Y.Y.

Abstract

Ways to decrease slagging of the solid residue from peat combustion in the filtration combustion mode were studied. Addition of silicon oxide to the fuel considerably reduces the ash slagging. The melting points of the ash residues from fuels of different compositions were determined.

Russian Journal of Applied Chemistry. 2017;90(10):1706-1711
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Macromolecular Compounds and Polymeric Materials

Photocatalytic Activity of Titanium Dioxide Nanoparticles Immobilized in the Polymer Network of Polyacrylamide Hydrogel

Mansurov R.R., Safronov A.P., Lakiza N.V., Beketov I.V.

Abstract

Composite hydrogels based on polyacrylamide immobilized nanoparticles of commercial (P25 brand) titanium dioxide and of titanium dioxide nanoparticles prepared by electric explosion of a wire were synthesized. The enthalpy of interaction at the polyacrylamide/TiO2 interface was determined by microcalorimetry using the thermochemical cycle method. Interaction of polyacrylamide polymer chains with the surface of TiO2 nanoparticles is energetically unfavorable. The absence of interactions between the hydrogel polymer network and surface of TiO2 nanoparticles favors manifestation of the UV-induced photocatalytic activity of TiO2 nanoparticles immobilized in the hydrogel. Immobilization in the polyacrylamide hydrogel matrix decreases the photocatalytic activity of P25 brand TiO2 nanoparticles, but does not affect the photocatalytic activity of titanium dioxide nanoparticles prepared by the electric explosion method. The photocatalytic activity of TiO2 nanoparticles immobilized in the bulk of polyacrylamide hydrogel evaluated by the decomposition of Methyl Orange dye is controlled by the diffusion rate of the dye molecules into the bulk of the hydrogel and depends also on the aggregation of TiO2 nanoparticles in the hydrogel matrix.

Russian Journal of Applied Chemistry. 2017;90(10):1712-1721
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Specific Features of Radical Formation in the Trialkylborane–Oxygen System and the Gluing Mechanism of Acrylate Composites

Dodonov V.A., Starostina T.I.

Abstract

Fundamental study of how radicals are generated, with involvement of trialkylboranes combined with oxygen and organoelement peroxides, was carried out. It was shown that the complex process of gluing of polymeric materials with low-energy surface predominantly occurs under the action of trialkylborane unblocked from the amine complex and oxygen dissolved in the gluing formulation and also under the action of growth radicals produced in the trialkylborane–peroxide–acrylate system in the closed-system mode at room temperature. The curing process of the gluing formulation occurs in the course of time both in the bulk and on the substrate surface.

Russian Journal of Applied Chemistry. 2017;90(10):1722-1726
pages 1722-1726 views