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2014 year, number 1

1.
Mechanochemical Approaches to the Development of Materials for Hydrogen Accumulation on the Basis of Metal Hydrides

I. G. KONSTANCHUK1, K. B. GERASIMOV1 and J.-L. BOBET2
1Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences, Ul. Kutateladze 18, Novosibirsk 630128 (Russia)
E-mail: irina@solid.nsc.ru
2Institut de Chimie de la Matiere Condensee de Bordeaux ICMCB-CNRS, Universite Bordeaux 1, 87 Av. Schweitzer, F-33608 Pessac (France)
Keywords: mechanochemical treatment, mechanical alloying, metal hydrides, hydrogen storage
Pages: 1-9

Abstract >>
Various mechanochemical approaches to improving the sorption properties of metal materials accumulating hydrogen are discussed. Some experimental results illustrating the possibilities of each approach are presented. It is established that the sorption characteristics of known metal accumulators of hydrogen can be improved by affecting their structure, morphology and surface properties with the help of the mechanical activation and mechanical alloying with various kinds of additives. The possibility to search for new hydrogen-absorbing materials through the mechanochemical synthesis of metastable composites of components of various natures including thermodynamically immiscible components was demonstrated. These composites may possess a high reactivity with respect to hydrogen and serve as precursors for the synthesis of new phases. The synthesis of intermetallic compounds and hydride phases directly during the mechanochemical treatment also opens opportunities for the preparation of new materials promising for hydrogen storage.



2.
Mechanically Stimulated Low-Temperature Synthesis of Aluminium Nitride

A. S. ABRAAMYAN and G. R. KARAGEDOV
Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences, Ul. Kutateladze 18, Novosibirsk 630128 (Russia)
E-mail: abrrba@mail.ru, garik@solid.nsc.ru
Keywords: aluminium nitride, synthesis, mechanical activation, sintering
Pages: 1115

Abstract >>
Synthesis method is based on grinding coarse aluminium powder in the planetary centrifugal mill in the presence of a surface-active organic substance that promotes a decrease in the size of aluminium particles and covers the resulting products with a film that is impermeable for oxygen. The synthesis is carried out in the flow of high-purity nitrogen. At a temperature of 300400 C, the organic film is evaporated from the precursor particles, aluminium surface, active toward nitriding, shows up, and the reaction takes place at a temperature of about 750 C. The yield of the product is about 100 %, its oxygen content is less than 0.6 mass % (the detection limit for the method used). Because of low temperatures, the resulting powder is weakly agglomerated; particle size varies within the range 350500 nm.



3.
Mechanical Activation of the Mixtures of Kaolinite and Polymer

I. A. VORSINA1, T. F. GRIGORIEVA1, T. A. UDALOVA1, S. V. VOSMERIKOV1, V. A. STRUK2, E. V. OVCHINNIKOV2 and N. Z. LYAKHOV1
1Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences, Ul. Kutateladze 18, Novosibirsk 630128 (Russia)
E-mail: grig@solid.nsk.ru
2Yanka Kupala Grodno State University, Ul. Ozheshko 22, Grodno 230023 (Belarus)
Keywords: mechanical activation, mechanochemical interaction, acidic and basic natural active centres
Pages: 1722

Abstract >>
The products of the joint mechanical activation of kaolinite with polymers (Sevilen, poly-N-vinylpyrrolidone and polyamide PA-6) in a high-energy ball mill were studied by means of IR spectroscopy and X-ray phase analysis. It was established that for definite polymer content of the initial mixture the mechanochemical interaction of kaolinite with polymer occurs, and the chemical bond is formed between them.



4.
Mechanocomposites for the Interacting System WZr

T. F. GRIGORIEVA1, L. N. DYACHKOVA2, S. V. VOSMERIKOV1, I. A. VORSINA1, S. V. TSYBULYA3, T. A. UDALOVA1 and N. Z. LYAKHOV1
1Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences, Ul. Kutateladze 18, Novosibirsk 630128 (Russia)
E-mail: grig@solid.nsc.ru
2Powder Metallurgy Institute, National Academy of Sciences of Belarus, Ul. Platonova 41, Minsk 220005 (Belarus)
3Boreskov Institute of Catalysis, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 5, Novosibirsk 630090 (Russia)
Keywords: tungsten, zirconium, mechanochemical interaction, mechanocomposites, carboxylic acids, poly(N-vinylpyrrolidone)
Pages: 2328

Abstract >>
Mechanocomposites composed of tungsten and zirconiums interacting with the former according to the equilibrium diagram of states were studied. The composition, structure and morphology of the samples obtained at the stages of mechanical activation are considered. The effect of the introduction of organic compounds into W/Zr mechanocomposites is studied.



5.
Interparticle Interactions during Consolidation of Ti3SiC2–Cu Powders Influenced by Preliminary Mechanical Milling

D. V. DUDINA1, V. YU. ULIANITSKY2, I. S. BATRAEV2, M. A. KORCHAGIN1, V. I. MALI2, A. G. ANISIMOV2 and O. I. LOMOVSKY1
1Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences, Ul. Kutateladze 18, Novosibirsk 630128 (Russia)
E-mail: dina1807@gmail.com
2Lavrentyev Institute of Hydrodynamics, Siberian Branch of the Russian Academy of Sciences, Pr. Lavrentyeva 15, Novosibirsk 630090 (Russia)
Pages: 29-36

Abstract >>
Mechanical milling is widely used for the purpose of efficient mixing of the components of particle-reinforced composite materials, which are further obtained in a bulk form by consolidation of the milled powder mixtures. Using the Ti3SiC2–Cu system as an example of a metal matrix composite with a ductile matrix and a reinforcement phase prone to chemical interaction with the matrix at elevated temperatures, we show that the effect of the preliminary mechanical milling of the components is seen not only in the uniformity of distribution of the reinforcing particles in the matrix but also in the consolidation behavior of the powders. The influence of the presence of composite agglomerates in the milled mixture on the processes induced by heating during consolidation is demonstrated by detonation spraying of the mechanically milled and mixed Ti3SiC2Cu powders in comparative experiments and Spark Plasma Sintering of the Ti3SiC2Cu agglomerates of different morphology. Interparticle interactions that are affected by the presence/absence of composite agglomerates and their morphology are the interfacial chemical reactions, the degree of transformation and melting of the copper matrix in the contact regions.



6.
Modified Glauconites of Republic Kazakhstan and Their Sorption Properties

G. S. KUANYSHEVA1, B. D. BALGYSHEVA1, A. B. ASILOV1 and F. KH. URAKAEV2
1Kazakh NationaL University by al-Farabi, Pr. al-Farabi, 71, Almaty 050040 (Kazakhstan)
E-mail: beikut2013@mail.ru
2Institute of Geology and Mineralogy, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Koptyuga 3, Novosibirsk 630090 (Russia)
Keywords: glauconite, glauconite sand, sodium dihydrogen phosphate, mechanical activation, sorbents, fertilizers, microelements
Pages: 3742

Abstract >>
Glauconite and glauconite sand were used as starting materials. To prepare adsorbents on the ground of glauconite, mixtures of glauconite sand and sodium dihydrophosphate NaH2PO4 at various weight ratios (1 : 1, 2 : 1, 3 : 1, 4 : 1) were subjected to the mechanical activation (MA) in a planetary mill. MA products were studied by methods of X-ray phase and thermal analysis. Degrees of sorption for ions of manganese, cuprum, nickel and zinc were determined from appropriate solutions of sulphates within the concentration range of 601000 mg/L.



7.
Effect of Mechanically Activated Additives on the Thermal Decomposition of Bitumen

S. G. MAMYLOV1, A. I. DONCHUK2, V. G. SURKOV3 and O. I. LOMOVSKY1
1Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences, Ul. Kutateladze 18, Novosibirsk 630128 (Russia)
2SETM Co., Ltd, Ul. Derzhavina, 13, Novosibirsk 630091 (Russia)
3nstitute of Petroleum Chemistry, Siberian Branch of the Russian Academy of Sciences, Pr. Akademicheskiy 4, Tomsk 634021 (Russia)
Keywords: mechanochemical activation of additives, thermolysis of bitumen
Pages: 43-46

Abstract >>
Thermal decomposition of the samples of cold-weather storage bitumen (heating with water vapour) was studied by means of thermogravimetric analysis. Bitumen was treated to remove water according to the regulations and with higher temperature and treatment time than those stated in the regulations. The effect of mechanically activated mineral additive and the additive imitating pyrobitumen on thermolysis was considered. Calculated activation energies of thermal decomposition of bitumen samples are reported.



8.
Investigation of the Reactivity of Mechanically Activated Metal Oxides |in the Radiation-Thermal Synthesis of Ni-Zn Ferrite

M. A. MIKHAILENKO1, U. V. ANCHAROVA1, E. A. SHTARKLEV2, A. YU. VLASOV2, M. V. KOROBEINIKOV2, A. S. KOZLOV3, A. K. PETROV3, B. P. TOLOCHKO1,2 and N. Z. LYAKHOV1
1Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences, Ul. Kutateladze 18, Novosibirsk 630128 (Russia)
E-mail: mikhailenko@solid.nsc.ru
2Budker Institute of Nuclear Physics, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 11, Novosibirsk 630090 (Russia)
3Voevodsky Institute of Chemical Kinetics and Combustion, Siberian Branch of the Russian Academy of Sciences, Ul. Institutskaya 3, Novosibirsk 630090 (Russia)
Keywords: radiation-thermal synthesis, ferrites, mechanocomposite
Pages: 4751

Abstract >>
Radiation-thermal synthesis of ferrite Ni0.75Zn0.25Fe2O4. was investigated. Comparative analysis of the reactivity of mechanically activated mixtures obtained from commercial oxides and from metal nanooxides was carried out. It was shown that the formation of mechanocomposite was necessary for the efficient reaction.



9.
Structure and Electrochemical Properties of LiCo1 – yFey PO4 Solid Solutions High-Voltage Cathode Materials for Lithium-Ion Rechargeable Batteries

O. A. PODGORNOVA and N. V. KOSOVA
Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences, Ul. Kutateladze 18, Novosibirsk 630128 (Russia)
E-mail: kosova@solid.nsc.ru
Keywords: lithium-ion rechargeable cells, cathode materials LiCo1 - yFeyPO4, mechanical activation, crystal structure, cycling
Pages: 5359

Abstract >>
Single-phase superfine LiCo1yFeyPO4 solid solutions were synthesized with the use of a mechanochemically stimulated carbothermal reduction of iron and cobalt oxides throughout the entire range of 0 ≤ y ≤ 1. The mechanical activation was carried out using an AGO-2 planetary mill. According to the scanning electron microscopy, the average primary particle size of the samples synthesized ranges within 200250 nm. According to the XRD phase analysis, all the samples crystallize in the orthorhombic system, with space group Pnma. The volume of the unit cell increases with increasing the content of iron in samples. According to Mssbauer (NGR) spectroscopy, all iron ions are in the oxidation state 2+ in an octahedral environment typical for olivine. Electrochemical properties of Li1 yFeyPO4 were investigated by means of galvanostatic cycling. It has been demonstrated that with the increase of Fe content a marked shift in the potential of the Co2+/Co3+ pair toward lower voltage values occurs, whereas the potential of the Fe2+/Fe3+ pair remains almost unchanged.



10.
Na2FePO4F as a Novel Cathode Material for Sodium and Lithium Accumulators

V. R. PODUGOLNIKOV1,2 and N. V. KOSOVA1
1Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences, Ul. Kutateladze 18, Novosibirsk 630128 (Russia)
E-mail: kosova@solid.nsc.ru
2Novosibirsk State University, Ul. Pirogova 2, Novosibirsk 630090 (Russia)
Keywords: Na2FePO4F, mechanochemical synthesis, crystal structure, chemical and electrochemical exchange of Na for Li
Pages: 6167

Abstract >>
A solid-phase waste-free and energy-saving synthesis with the use of mechanical activation of single-phase cathode material Na2FePO4F (sp. gr. Pbcn) for sodium and lithium accumulator has been implemented. It has been demonstrated that the product is formed already at the stage of mechanical activation (MA) and is crystallized in the course of subsequent annealing up to 600 , whereas heating up to 700 results in decomposing the product formed to give Na3PO4, Fe3O4, Na0.11FeF3 and Na3Fe2(PO4)3. Electrochemical properties of Na2FePO4F have been studied in a cell with a lithium anode and lithium electrolyte. According to results of the studies the specific capacity of Na2FePO4F surface-modified with carbon is equal to 115 mA ⋅ h/g at a rate of cycling amounting to C/10. It has been found that the process of chemical and electrochemical replacing Li by Na in the structure of Na2FePO4F is completed by the formation of a compound with the composition NaLiFePO4F (sp. gr. Pbcn).



11.
Investigation of the Effect of Mixture Composition and Humidity on the Specific Surface Area and Phase Composition of Lithium γ-Monoaluminate Formed during the Mechanochemical Synthesis from Lithium Carbonate and Aluminium Hydroxide

YA. E. TATARINOVA1,2 and V. P. ISUPOV2
1Novosibirsk State University, Ul. Pirogova 2, Novosibirsk 630090 (Russia)
2Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences, Ul. Kutateladze 18, Novosibirsk 630128 (Russia)
E-mail: isupov@solid.nsc.ru
Keywords: mechanical activation, aluminium hydroxide, lithium carbonate, lithium γ–monoaluminate
Pages: 6973

Abstract >>
Lithium γmonoaluminate was obtained as a result of mechanochemical activation of the mixture of lithium carbonate and aluminium hydroxide in AGO-2 planetary activator, followed by the thermal treatment. The effect of mixture composition and humidity on the phase composition and specific surface of lithium γmonoaluminate was studied. It was shown that in the variation of the composition and humidity of the mixture the specific surface area of the final product decreases significantly (from 13 to 0.2 m2/g).



12.
Anomalous Effect of Graphite on the Degree of Wear of Copper Milling Bodies of the Mechanochemical Reactor

F. KH. URAKAEV, YU. M. BORZDOV, E. I. PETRUSHIN, V. S. SHEVCHENKO and N. P. POKHILENKO
Sobolev Institute of Geology and Mineralogy, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Koptyuga 3, Novosibirsk 630090 (Russia)
E-mail: urakaev@igm.nsc.ru
Keywords: diamond, mechanical activation, mechanochemical reactors, milling bodies, abrasive reaction wear, effect of graphite
Pages: 7579

Abstract >>
The anomalous effect of graphite on the degree of wear of copper milling bodies was studied quantitatively. It was shown that mechanical activation of the system diamondgraphitesilicon with copper milling bodies led to the formation of copper-containing semi-products and stable coatings on the surface of milling bodies.



13.
Volcanogenic Nanosized Carbon Aerosol in the Stratosphere

V. V. ZUEV, N. E. ZUEVA, P. K. KUTSENOGIY and E. S. SAVELYEVA
Institute of Monitoring of Climatic and Ecological Systems, Siberian Branch of the Russian Academy of Sciences, Pr. Akademicheskiy 10/3, Tomsk 634055 (Russia)
E-mail: vvzuev@imces.ru
Keywords: volcanic eruption, eruptive column, stratosphere, temperature, solar radiation, ozone depression, sulphuric acid aerosol, carbon particles
Pages: 8186

Abstract >>
The temperature anomalies and long-term depressions of ozone in the stratosphere observed after large-scale volcanic eruptions are poorly explained from the point of view of modern ideas about composition of the stratospheric aerosol of the volcanogenic nature. However, such post-volcanic phenomena could occur in case when the aerosol comp its surface. The basic opportunity of forming nanosized carbon aerosol (less than 0.1 μm in size) in the stratosphere in case of powerful Plinian type volcanic eruptions is shown in the paper. Estimates of the amount and lifetime of these particles allow explaining long-term temperature anomalies and the ozone depression in the stratosphere after volcanogenic perturbations.



14.
Influence of High Molecular Mass Components of Oil on the Soil and Production Process of Potato Plants

L. A. IGNATIEV
Institute of Soil Science and Agricultural Chemistry, Siberian Branch of the Russian Academy of Sciences, Pr. Akademika Lavrentyeva 8/2, Novosibirsk (Russia)
E-mail: arsey@issa.nsc.ru
Keywords: high molecular mass oil components, disposal methods, toxicity, plant production process, agrochemical properties of soil, translocation effect
Pages: 8791

Abstract >>
An effect of various concentrations of high molecular mass components of oil as wastes of petroleum production on the soil state and plant production processes was studied. From the standpoint of toxicity, its permissible concentrations values thereof for the normal vital function of plants were determined. A positive effect of oil on some agrochemical soil properties has been revealed, which opens up prospects for developing a biological method of utilization of oil wastes disposal.



15.
Effect of Sodium Sulphide Concentration on the Adsorption Kinetics and Photocatalytic Oxidation on Zinc Oxide

E. I. KAPINUS, S. V. KAMYSHAN and E. V. MANUYLOV
Institute for Sorption and Problems of Endoecology, National Academy of Sciences of Ukraine, Ul. Generala Naumova 13, Kyiv 03164 (Ukraine)
E-mail: eugenekapinus@yahoo.com
Keywords: sodium sulphide, zinc oxide, adsorption kinetics, photocatalytic oxidation kinetics
Pages: 9398

Abstract >>
Adsorption and photocatalytic oxidation kinetics for sulphide ions on zinc oxide in aqueous solutions has been studied. It has been found that the rate constants of sodium sulphide adsorption and photocatalytic oxidation on zinc oxide decrease with increasing the substrate concentration, which indicates an auto-inhibition of these processes due to blocking the surface of zinc oxide by sodium sulphide.



16.
Dynamics of Thermal Decomposition of Black Coal from the Tavantolgoy Deposit in Mongolia

N. I. KOPYLOV1, YU. D. KAMINSKY1, ZH. DUGARZHAV2 and B. AVID2
1Institute of Solid State Chemistry and Mechanochemistry, Siberian Branch of the Russian Academy of Sciences, Ul. Kutateladze 18, Novosibirsk 630128 (Russia)
E-mail: kolyubov@narod.ru
2Institute of Chemistry and Chemical Technology, Mongolian Academy of Sciences, Ul. Mira, 4, Ulaanbaatar 210351 (Mongolia)
E-mail: dugar21mn@yahoo.com
Keywords: Tavantolgoy deposit, black coal, thermolysis, gas components, low-melting, volatile fractions, baking, porosity, briquetting
Pages: 99104

Abstract >>
Integrated investigation of the thermolysis of black coal from the Tavantolgoy deposit (Mongolia) was carried out. It was discovered that coal decomposes during thermolysis within temperature range 300500 with the evolution of gas, low-melting and low-boiling phases, intensively increases in volume and gets agglomerated. As a result, rather strong porous cake is formed. Its volume is 1.52 times larger than the volume of the initial sample. It was shown that coal from the Tavantolgoy deposit (without any binding additives) can be used for briquetting.