Open Access Open Access  Restricted Access Access granted  Restricted Access Subscription Access

Vol 89, No 10 (2016)

Reviews

Thermodynamic properties and electrochemical behavior of lithium–germanium alloys

Morachevskii A.G.

Abstract

Published data on the phase diagram of the lithium–germanium system, on the thermodynamic properties of Li–Ge alloys, on their electrochemical behavior in various media, and on prospects for using them in lithium–ion batteries and in other chemical current sources are analyzed.

Russian Journal of Applied Chemistry. 2016;89(10):1561-1572
pages 1561-1572 views

Inorganic Synthesis and Industrial Inorganic Chemistry

Molecular layering of phosphorus oxide structures on the surface of gamma alumina

Malkov A.A., Chernyakova N.V., Zhilyaeva N.A., Malygin A.A.

Abstract

Phosphorus oxide structures were synthesized on the surface of porous gamma alumina, with phosphorus oxychloride and water vapors used as reagents for successive and alternating (up to four times) treatment of a solid-phase matrix by the molecular layering method with in situ monitoring of the process. It was shown that this procedure yields a double-phase system constituted by a core (aluminum oxide) and shell (amorphous phosphorus oxide layer) with a prescribed chemical composition and structure with characteristics dependent on the number of molecular layering cycles. With increasing treatment rate (from 1 to 4) of the solid-phase matrix with halide and water vapors, the concentration of phosphorus in the samples steadily grows. In the process, the specific surface area, pore volume, and pore size in the double-phase system being formed become smaller. The results obtained in the study are of interest for development of catalytic, sorption, and other functional systems of the core–shell type.

Russian Journal of Applied Chemistry. 2016;89(10):1573-1578
pages 1573-1578 views

Study of optical, dimensional, and catalytic properties of nanodispersed CdS–Na2SiO3 powders

Gavrilenko E.A., Biryukov A.A.

Abstract

Composite powders of the CdS–Na2SiO3(SiO2) type were synthesized. It was found that varying the amount of Na2SiO3 introduced in the synthesis stage affects both the texture characteristics of the powders obtained and their optical and photocatalytic properties. All the powders absorb electromagnetic radiation in the visible spectral range (~420–620 nm). It was shown for the example of photodestruction of Nile Blue and Rhodamine C dyes that the powders exhibit good photocatalytic properties under exposure to visible light (λ ≥ 410 nm). One of important advantages of the composites used as photocatalysts is that the transfer of cadmium ions under photoirradiation, characteristic of CdS particles, does not occur.

Russian Journal of Applied Chemistry. 2016;89(10):1579-1587
pages 1579-1587 views

Effect of synthesis parameters on characteristics of expanded graphite

Steksova Y.P., Berdyugina I.S., Shibaev A.A., Ukhina A.V., Maksimovskii E.A., Popov M.V., Bannov A.G.

Abstract

Effect of synthesis parameters on the characteristics of expanded graphite were studied. The starting sample, intercalated graphite, was treated by several methods: thermal shock (400, 1000°C) and programmed heating (400–700°C). The samples were examined by scanning electron microscopy, energy-dispersive spectroscopy, X-ray diffraction analysis, and low-temperature nitrogen adsorption. The programmed-heating method yields better texture characteristics as compared with the thermal shock. The programmed-heating method was used to obtain high-quality expanded graphite with high specific surface area (299 m2 g–1) at a comparatively moderate temperature of 400°C.

Russian Journal of Applied Chemistry. 2016;89(10):1588-1595
pages 1588-1595 views

Effect of aerosol chemical vapor deposition on characteristics of MoS2 particles

Aleksandrov S.E., Filatov K.D., Speshilova A.B., Tyurikov K.S., Andreeva V.D.

Abstract

Influence exerted by the main technological parameters in the process in which nano- and microparticles of molybdenum disulfide are formed by the aerosol chemical vapor deposition method from a gas phase containing aerosol particles of (NH4)2MoS4‒C3H7NO solutions on the dimension characteristics, structure, and composition of the products being formed was studied. It was shown that the shape, size, and structure of the particles being formed are determined by the processes occurring in the first, streamwise, reactor zone. The temperature of this zone is the most important technological parameter. The concentration of ammonium thiomolybdate in solution makes it possible to gradually vary the size of disulfide particles in a wide range (from tens of nanometers to micrometers). In the conditions under study, the technological conditions have no effect on the chemical composition of the products being synthesized, which is always described by the formula MoS2. The results obtained can be used in development of industrial apparatus and technology for synthesis of molybdenum disulfide nano- and microparticles to be used as the antifriction component of lubricating materials.

Russian Journal of Applied Chemistry. 2016;89(10):1596-1600
pages 1596-1600 views

Thermochemical synthesis of luminescent materials in the Y2O3–ZnO system doped with Eu3+ ions

Davydova O.V., Drobyshevskaya N.E., Poddenezhnyi E.N., Boiko A.A., Zdravkov A.V., Khimich N.N.

Abstract

Powders were synthesized in the yttrium oxide + zinc oxide system doped with europium oxide by the method of redox combustion of a mixture of yttrium, zinc, and europium nitrates in the presence of saccharose (fuel). The structure and the physicochemical and luminescent properties of the particles being formed and of a ceramic on their basis were examined.

Russian Journal of Applied Chemistry. 2016;89(10):1601-1606
pages 1601-1606 views

Applied Electrochemistry and Metal Corrosion Protection

Synthesis and electrochemical performance of the Li-rich cathode material Li1.17Ni0.12Co0.13Mn0.58O2 for lithium-ion batteries

Popovich A.A., Maximov M.Y., Silin A.O., Novikov P.A., Koshtyal Y.M., Rumyantsev A.M.

Abstract

Lithium-riched cathode material for lithium-ion batteries, Li1.17Ni0.12Co0.13Mn0.58O2, was synthesized via crystallization from a solution of metal acetates, followed by a thermal treatment of the material obtained as a powder. The phase, elemental, and granulometric compositions of the material were examined, as well as the morphology of the powder particles obtained. The discharge capacity of the material in relation to the charging voltage was found from the results of electrochemical tests, and endurance tests were performed. The discharge capacity upon 85 charge/discharge cycles at voltages in the range 2.8–4.8 and a current of 0.1C was about 180 mA h g–1.

Russian Journal of Applied Chemistry. 2016;89(10):1607-1611
pages 1607-1611 views

Indirect electrochemical oxidation of aniline in acid electrolyte with active oxygen species

Kornienko G.V., Kenova T.A., Kornienko V.L., Maksimov N.G., Balhareva M.Y.

Abstract

Kinetics and selectivity of the aniline oxidation on a boron-doped diamond electrode and lead dioxide anode (Pb/PbO2) in an acid electrolyte were studied under various generation conditions of active oxygen species. The resulting kinetic dependences can be described by a pseudo-first-order equation. The apparent rate constants of the process were determined for two electrolysis modes: direct anodic oxidation and oxidation with addition of hydrogen peroxide. UV spectroscopy was used to determine that the aniline destruction process occurs via formation of a number of intermediate products (benzoquinone, carboxylic acids). It was shown that the aniline destruction process can occur with a rather high efficiency (~80–90%) on the electrode types under study.

Russian Journal of Applied Chemistry. 2016;89(10):1612-1618
pages 1612-1618 views

Catalysis

Choice of a catalyst and technological scheme for synthesis of solketal

Dmitriev G.S., Terekhov A.V., Zanaveskin L.N., Khadzhiev S.N., Zanaveskin K.L., Maksimov A.L.

Abstract

Results are presented obtained in tests of various homogeneous and heterogeneous catalysts in a synthesis of solketal (2,2-dimethyl-4-hydroxymethyl-1,3-dioxolane). It is shown that, all other conditions being the same, the highest catalytic activity is observed for sulfuric acid and beta zeolite. Data are presented on how the equilibrium constant of the reaction of glycerol ketalization depends on temperature. A technological scheme of the process for synthesis of solketal is suggested and its description is presented.

Russian Journal of Applied Chemistry. 2016;89(10):1619-1624
pages 1619-1624 views

Granulated rhodium catalysts of sodium borohydride hydrolysis for generators of high-purity hydrogen

Simagina V.I., Netskina O.V., Komova O.V.

Abstract

Sodium borohydride hydrolysis in a flow reactor with turbulent mixing of reactants in a catalytic bed by the evolving hydrogen bubbles was studied. The stability of catalytic systems decreases in the order 1% Rh/Sibunit > 1% Rh/TiO2 > 1% Rh/γ-Al2O3. The decrease in the hydrogen generation rate is caused by the formation of a metaborate film on the catalyst surface, by the loss of the active component, and by disintegration of support granules and their removal with the flow of the spent liquid. High granule strength and macroporous structure of 1% Rh/Sibunit ensure stable generation of hydrogen.

Russian Journal of Applied Chemistry. 2016;89(10):1625-1631
pages 1625-1631 views

Sorption and Ion Exchange Processes

Sorption of iodine-containing vapor onto chitosan

Belyakova O.A., Shipovskaya A.B.

Abstract

The kinetics of sorption of vapor over aqueous and aqueous-alcoholic solutions of potassium iodide and potassium iodine–iodide and over crystalline iodine onto chitosan powder or film was studied. The vapor diffusion coefficients in the initial and final sorption steps were calculated from the data obtained. For all the chitosan–sorbate vapor systems studied, the mass transfer relationships are not described by Fick’s law and are characterized by anomalous sorption kinetics. The properties of chitosan powder after the uptake of the sorbate vapor were evaluated by electronic and IR spectroscopy, X-ray diffraction, and differential thermal and thermal gravimetric analysis. Sorption of iodine-containing vapor onto the polymer is accompanied by complexation of the components. The iodine–chitosan complexes are stable in storage and resistant to heat treatment. The results obtained served as a basis for developing a procedure for preparing kinetically and thermally stable powdered iodinated chitosan derivatives.

Russian Journal of Applied Chemistry. 2016;89(10):1632-1641
pages 1632-1641 views

Influence of pH on distribution coefficients of lithium and impurity elements in sorption

Volkova T.S., Rudskikh V.V., Dzhevello K.A.

Abstract

The possibility of purifying lithium-containing solutions to remove chemical impurities by sorption in the batch mode was examined. Sulfonic (KU 2-8, Purolite C100, Resinex KW-8), carboxylic (SG-1, Purolite C104FL, Resinex KW-H), and phosphoric acid (Purolite S957) cation-exchange resins were used as sorbents. The distribution coefficients of lithium and impurity elements (sodium, potassium, magnesium, calcium, iron) at different pH values were determined experimentally. The lithium/impurity separation factors were calculated.

Russian Journal of Applied Chemistry. 2016;89(10):1642-1646
pages 1642-1646 views

Macromolecular Compounds and Polymeric Materials

Highly heat-resistant poly(о-hydroxy amide) binders of polyfunctional composites for microelectronics

Lebedeva G.K., Bazhenova A.S., Rudaya L.I., Gofman I.V., Marfichev A.Y., Bol’shakov M.N., Sokolova I.M., Chigirev D.S., Ramsh S.M., Shamanin V.V.

Abstract

A series of structurally similar poly(o-hydroxy amides), homo- and copolymers with different bridging fragments in the amine component, were synthesized. The heat resistance and electrophysical parameters of powdered polymer samples, of micrometer-thick films formed on substrates from reaction solutions of these polymers, and of films of photosensitive formulations based on them, containing photosensitive diazonaphthalenone component, were studied. Introduction of hexafluoropropane fragment into the macromolecule enhances the heat resistance of the polymer (powders and films) and decreases the dielectric permittivity of the films, compared to the reference poly(o-hydroxy amide) derived from 3,3'-dihydroxy-4,4'-diaminodiphenylmethane. The tetramethylsiloxane fragment considerably decreases the heat resistance of polymer powders and films, but improves the dielectric parameters of the coatings. Introduction of the diphenyl oxide fragment into poly(o-hydroxy amide) complicated the formation of high-resolution microrelief in films of the photosensitive formulation owing to a sharp decrease in the solubility of the films in alkaline solutions. Suitable electrophysical parameters and thermal characteristics of the polymers obtained, their capability for film formation, compatibility with photosensitive components, and possibility of the formation of high-resolution positive microrelief upon exposure allow these polymers to be recommended as promising polymeric binders for highly heat-resistant organic dielectrics and protective coatings for microelectronics.

Russian Journal of Applied Chemistry. 2016;89(10):1647-1654
pages 1647-1654 views

Properties of modified polymers based on syndiotactic 1,2-polybutadiene

Glazyrin A.B., Abdullin M.I.

Abstract

The influence of the chemical modification on the properties of syndiotactic 1,2-polybutadiene derivatives that contain various functional groups in macromolecules and show promise for practical use was studied. The dependence of the glass transition point and the fluidity and rheological properties of modified polydiene melts on the nature of the functional group in the macrochain and on the degree of the polymer functionalization was revealed. The possibility of directional synthesis of modified polymer products with the required operation characteristics on the basis of syndiotactic 1,2-polybutadiene was demonstrated.

Russian Journal of Applied Chemistry. 2016;89(10):1655-1661
pages 1655-1661 views

Effect of mechanical treatment on the aggregative stability of latex and on consumption of coagulants in rubber recovery

Verezhnikov V.N., Nikulin S.S., Zorina A.V., Ermolaeva A.K., Kretinina N.I.

Abstract

The effect that mechanical treatment of SKS-30 ARK latex by mixing in a gap between coaxial cylinders exerts on the latex resistance to an electrolyte and on the polymer yield in coagulation with two types of coagulants, sodium chloride and N,N-dimethylaminopropyl carboxy betaines derived from vegetable oil fatty acids, was studied. Such treatment decreases the rapid coagulation threshold and increases the coagulum yield. The effect is caused by partial breakdown of hydrate shells of particles as a result of mechanical action in a shear stress field.

Russian Journal of Applied Chemistry. 2016;89(10):1662-1666
pages 1662-1666 views

Influence of conditions for preparing butyl acrylate–vinyl butyl ether copolymers using the compensation procedure on their molecular-mass parameters and thickening power in dioctyl sebacate

Semenycheva L.L., Valetova N.B., Moikin A.A., Pegeev N.L., Matkivskaya Y.O., Kurskii Y.A.

Abstract

New butyl acrylate–vinyl n-butyl ether copolymers were synthesized using initiating systems trialkylborane–oxygen, trialkylborane–di-tert-butylperoxytriphenylantimony, and azobis(isobutyronitrile) with compensation dosing of the active monomer. The kind of the initiator does not influence the composition and structure of the copolymers, according to the data of IR and 13С NMR spectroscopy, but influences their molecular-mass parameters, according to the data of gel permeation chromatography. The new copolymers dissolved in dioctyl sebacate (synthetic base of lubricating oils) well compete with related imported thickening additives in the thickening effect at temperatures from–40 to 100°С and in the resistance to mechanical degradation. Simple ways to control in the synthesis step the thickening effect of the polymers are suggested.

Russian Journal of Applied Chemistry. 2016;89(10):1667-1672
pages 1667-1672 views

Various Technological Processes

Synthesis and characterization of chitosan–poly(acrylamide–co-acrylic acid) magnetic nanocomposite hydrogels for use in catalysis

Abou El Fadl F.I.

Abstract

A novel hydrogel based on chitosan–poly(acrylamide-co-acrylic acid) (CAA) with different formulations were synthesized by the effect of gamma radiation. The magnetic CAA hydrogels were also synthesized and characterized by using different techniques, e.g., TEM and XRD. The prepared hydrogels and magnetic hydrogel nanocomposite were utilized for in situ cobalt nanoparticle preparation and employed as a reaction media in catalytic reduction of 2-nitrophenol (2-NP), to 2-aminophenol (2-AP). The experimental parameters that affect the reduction rates such as temperature and amount of catalyst were also, investigated.

Russian Journal of Applied Chemistry. 2016;89(10):1673-1680
pages 1673-1680 views

Preparation and properties of hyperbranched polymer containing functionalized Nano-SiO2 for low-moderate permeability reservoirs

Lai N., Wu T., Ye Z., Zhou N., Xu Q., Zeng F.

Abstract

A novel water-soluble hyperbranched polymer (AA/AM/SMNS) consisting of functionalized Nano-SiO2 as the core was synthesized by free-radical polymerization for low-moderate permeability reservoirs. The AA/AM/SMNS was carefully characterized by spectroscopic and electronic technologies. It was found that the microscopic structures of AA/AM/SMNS was denser and more regular in comparison to the linear polymer HPAM. The hydrodynamic radius of AA/AM/SMNS was 197 nm, less than the HPAM radius of 244 nm with similar molecular weight, so that the AA/AM/SMNS had a good matching relationship with pore throat in midpermeability reservoirs (100–500 mD). Besides, the introduction of Nano-SiO2 endowed the AA/AM/SMNS remarkable thermal stability, shear resistance and viscoelasticity. Based on core flooding experiments, the AA/AM/SMNS could build high resistance factor and residual resistance factor in the corresponding porous medium. Furthermore, the sheared AA/AM/SMNS solution of 1500 mg L–1 performed excellent oil recovery of 15.47% in the 300 mD porous medium, which suggested the hyperbranched polymer based on modified Nano-SiO2 have a valuable prospect for enhancing oil recovery in low-moderate permeability reservoirs.

Russian Journal of Applied Chemistry. 2016;89(10):1681-1693
pages 1681-1693 views

Synthesis and performance evaluation of a water-soluble copolymer as high-performance fluid loss additive for water-based drilling fluid at high temperature

Xiping M., Zhongxiang Z., Daiyong H., Wei S.

Abstract

Drilling fluids are widely used in the drilling of deep wells to clean and transport the rock cuttings, maintain the sidewall of oil well, lubricate and cool the drilling bit, and control the formation pressures. The present work aims at improving the high-temperature resistance of water-based drilling fluid by using the newly synthesized fluid loss additive named PAASD. This copolymer was obtained through the solution polymerization of four kinds of monomers. The synthesis conditions with the optimal API filtration were studied by single synthetic experiment, and the chemical structure of final product was confirmed by FTIR spectroscopy. The target product was carried out with thermal stability analysis, rheological property, filtrate property, temperature resistant capacity, salt tolerance capacity, micro-crosslink structure property, particle size distribution and the compatibility performance experiment. The results showed that PAASD was an efficient fluid loss additive, and the API filtration of fresh water drilling fluid containing 2% PAASD was only 5.2 mL, it was 10.6 mL after aging at the condition of 200°C and 16 h. Besides, PAASD has a good thermal stability, salt tolerance, and it could improve the rheological property of drilling fluid system obviously. Therefore, it could be used as fluid loss additive of water-based drilling fluid in salty and high-temperature environment.

Russian Journal of Applied Chemistry. 2016;89(10):1694-1705
pages 1694-1705 views

Preparation of thiolation poly(aryl ether ketone) nanofiber mat and its adsorption of Hg2+ ions

Feng L., Li F., Zhang Z., Yan L.

Abstract

Thioacetylation poly(aryl ether ketone) (AcSPEK-C) as the precursor of thoilation poly(aryl ether ketone) (SHPEK-C) was synthesized via chloromethylation and thioacetylation of a phenolphthalein poly(aryl ether ketone) (PEK-C) successively. Then AcSPEK-C nanofiber mat was prepared by electrospinning technique, after the deacetylation and the acidification reaction, the SHPEK-C nanofiber mat with the average diameter of 570 nm (SEM test) was successfully obtained ultimately. DSC test showed that SHPEK-C had a single glass transition temperature (Tg =300°C). Adsorption isotherms and adsorption kinetics of the static adsorption process were used to examine the fundamental adsorption properties of Hg2+ ions. The results showed that the maximum adsorption capacity was 3.75 mmol Hg g−1. In addition, the SHPEK-C superfine fibrous membrane also showed high recyclable removal efficiency through the adsorption/desorption experiments.

Russian Journal of Applied Chemistry. 2016;89(10):1706-1712
pages 1706-1712 views

The effect of various compatibilizers on thermal, mechanical, and morphological properties of polystyrene/polypropylene blends

Latreche L., Haddaoui N., Cagiao M.E.

Abstract

The effects of various compatibilizers on thermal, mechanical and morphological properties of 50/50 polypropylene/polystyrene blends were investigated. Various compatibilizers, polystyrene-(ethylene/butylenes/ styrene) (SEBS), ethylene vinyl acetate (EVA), polystyrene-butylene rubber (SBR) and blend of compatibilizers SEBS/PP-g-MAH, EVA/PP-g-MAH, and SBR/PP-g-MAH were used. Differential scanning calorimetry, thermogravimetric analysis, wide-angle X-ray scattering, scanning electron microscopy, microhardness, and Izod impact strength were adopted. It was found that the influence of various compatibilizers was appeared on all the properties studied. The properties of the blends compatibilized with SEBS, EVA, and SBR are very distinct from those of blends compatibilized with blend of compatibilizers. Results show that compatibilized blends with the blend of compatibilizers EVA/PP-g-MAH, SBR/PP-g-MAH, and SEBS/PP-g-MAH or SBR were relatively more stable than the uncompatibilized blend and blend compatibilized with SEBS or EVA. The compatibilizer does not only reduce the interfacial tension or increase the phase interfacial adhesion between the immiscible polymers, but greatly affects the degree of crystallinity of blends.

Russian Journal of Applied Chemistry. 2016;89(10):1713-1721
pages 1713-1721 views

Effect of silylation temperature on the physicochemical properties and catalytic performance of Ti-containing hexagonal mesoporous silica

Li X.

Abstract

Ti-HMS (hexagonal mesoporous silica, HMS) was vapor silylated at 150–450°C. The samples were characterized by Si29 CP/MAS NMR, FTIR, TG, XRD, and N2-adsorption, respectively, as well as evaluated by the continuous epoxidation of propylene with cumene hydroperoxide (CHP) as oxidant. There showed only a peak at 14 ppm assigned to (CH3)3Si*OSi(OSi)3 species in NMR spectra when silylated at low temperatures. The samples at higher temperatures (>250°C) gave an additional peak at 20 ppm, which was assigned to novel titanium species of (CH3)3Si*OTi(OSi)3. The intensity of peaks relevant to trimethyl groups increased with the silylation temperature at 150–350°C and decreased at 350–450°C due to decomposing of organic groups. The intensity reached the highest point at 350°C. The catalytic results showed that the propylene oxide yield also changed as the same trend and reached the longest life of 100% PO yield at 350°C silylation. In conclusion, 350°C is an optimal silylation temperature.

Russian Journal of Applied Chemistry. 2016;89(10):1722-1727
pages 1722-1727 views

Brief Communications

Procedure for lepidolite concentrate processing

Onalbaeva Z.S., Samoilov V.I., Kulenova N.A., Zhakupova G.B., Adylkanova M.A., Kokaeva G.A., Abdulina S.A.

Abstract

Lithium recovery from lepidolite was studied experimentally, and a sulfuric acid procedure for lithium recovery was suggested. It ensures the maximal degree of lithium recovery from this mineral at minimal power consumption. The suggested procedure creates prerequisites for large-scale involvement of lepidolite into lithium metallurgy, taking into account large amount of developed lepidolite deposits and steadily growing demand for lithium products.

Russian Journal of Applied Chemistry. 2016;89(10):1728-1730
pages 1728-1730 views

Erratum

Erratum to: “Activated carbons of varied nature in recovery of gold”

Kishibayev K.K., Tokpayev R.R., Atchabarova A.A., Efremov S.A., Voropaeva N.L., Fernández-Sanjurjo M.J., Nechipurenko S.V., Nauryzbayev M.K., Tassibekov K.S., Karpachev V.V.
Russian Journal of Applied Chemistry. 2016;89(10):1731-1731
pages 1731-1731 views