Physicochemical investigation into the specific features of the phase transformations in electrodeposited nanocrystalline oxotungstate films

The structure of oxotungstate films (as-deposited and subjected to heat treatment at temperatures of up to 600°C) prepared through electrodeposition on platinum and gold polycrystalline substrates is investigated using different physicochemical methods. It is shown that the oxotungstate films consist of X-ray amorphous hydrated mixtures of isopoly compounds, predominantly in the form of paratungstates with [H₂W₁₂O₄₂]¹⁰⁻ anions. The structural transformation with an increase in the temperature in air is accompanied by the loss of water, the transformation of paratungstate anions into more oxidized forms, their destruction, and the crystallization of nonstoichiometric hydroxylated oxide phases.

     

Study of the Process of Reversible Insertion of Lithium into Nanostructured Materials Based on Germanium

Russian Journal of Electrochemistry - Nanostructured germanium samples prepared by electrochemical deposition from aqueous solution of 0.05 М germanium oxide onto titanium substrate are...     

The influence of compression conditions on the peculiarities of self-propagating exothermal reaction in Al–Ni powder reactive materials

The paper deals with the effect of the compression conditions on the propagation front velocity of exothermal reaction and the specific heat release in Al–Ni powder reactive materials with mean particle sizes of 70–110 nm. It was shown that the velocity increases from 2.7 to 8 cm s^?1 and comes to saturation with the lowering of the porosity (η) from 0.91 to 0.34, while the dependence of the specific heat release has its maximum for η?=?0.5. The results of the X-ray diffraction analysis obtained in situ during the sample heating suggest that the sequence of phase transformations in the system does not depend on the porosity. In all cases, first in the temperature range of ~?500–540 °C the NiAl compound is formed. With the further heating up to ~?640 °C, the Ni₃Al, Ni₂Al₃ and NiAl₃ compounds are additionally formed. The calculation of kinetic parameters was performed using the obtained curves of the differential scanning calorimetry: activation energy, pre-exponential factor and reaction model. The comparison of the calculated results and the scanning electron microscopy data has shown that such behavior of the Al–Ni system with the porosity lowering occurs due to the growth of the transformation degree and is associated with the presence in the final powder mixture of mutually non-contacting Al and Ni agglomerates with the dimensions of over 10 μm.     

Petrov modules and zeros of Abelian integrals

We prove that the Petrov module _f associated to an arbitrary semiweighted homogeneous polynomial f? C[x,y] is free and finitely generated. We compute its generators and use this to obtain a lower bound for the maximal number of zeros of complete Abelian integrals.     

Influence of structural defects on the electrocatalytic activity of platinum

Structural defects play major role in catalysis and electrocatalysis. Nanocrystalline (or nanostructured) materials composed of nanometer-sized crystallites joined via grain boundaries have been recognized for their specific structure and properties, differentiating them from single crystals, coarsely grained materials or nanometer-sized supported single-grained particles (Gleiter, Nanostruct Mater 1:1–19, 1992). In this paper, we use Pt electrodes, prepared by electrodeposition on glassy carbon and gold supports, as model nanocrystalline materials to explore the influence of grain boundaries and other structural defects on electrocatalysis of CO and methanol oxidation. We build on the recently established correlations between the nanostructure (lattice parameter, grain size, and microstrains) of electrodeposited Pt and the deposition potential (Plyasova et al., Electrochim. Acta 51:4447–4488, 2006) and use the latter to obtain materials with variable density of grain boundary regions. The activity of electrodeposited Pt in the oxidation of methanol and adsorbed CO exceeds greatly that for Pt(111), polycrystalline Pt, or single-grained Pt particles. It is proposed that active sites in nanostructured Pt are located at the emergence of grain boundaries at the surface. For methanol electrooxidation, the electrodes with optimal nanostructure exhibit relatively high rates of the “direct” oxidation pathway and of the oxidation of strongly adsorbed poisoning intermediate (CO_ads), but not-too-high methanol dehydrogenation rate constant. These electrodes exhibit an initial current increase during potentiostatic methanol oxidation explained by the CO_ads oxidation rate constant exceeding the methanol decomposition rate constant.

Reaction of substituted chalcones with methyl 1-bromocycloalkanecarboxylates and zinc

Methyl 1-bromocyclopentane-and 1-bromocyclobutanecarboxylates react with zinc and substituted chalcones to form spiro-3,4-dihydropyran-2-one derivatives: 8, 10-diaryl-7-oxaspiro[4.5]dec-8-en-6-ones and 7,9-diaryl-6-oxaspiro[3.5]non-7-en-5-ones, respectively.     

Controlled spin pattern formation in multistable cavity–polariton systems

Theoretical studies are performed of planar cavity–polariton systems under resonant optical excitation. We show that if the cavity is spatially anisotropic, the polariton spin is highly sensitive to the pump polarization direction, which can be used to modulate the circular polarization of the output light. In particular, when the right- and left-circular components of the incident wave have equal intensities and mutually opposite angular momenta, the pump has strictly linear yet angle-dependent polarization and as such brings about a periodic angular variation of the polariton spin. Free motion of polaritons is the other factor determining the shape of the cavity-field distribution. Such externally driven and highly tunable spin patterns represent a counterpart of spin shaping in nonresonantly excited Bose–Einstein condensates of cavity polaritons.     

Direct numerical simulation of the turbulent flows of power-law fluids in a circular pipe

Fully developed turbulent pipe flows of power-law fluids are studied by means of direct numerical simulation. Two series of calculations at generalised Reynolds numbers of approximately 10000 and 20000 were carried out. Five different power law indexes n from 0.4 to 1 were considered. The distributions of components of Reynolds stress tensor, averaged viscosity, viscosity fluctuations, and measures of turbulent anisotropy are presented. The friction coefficient predicted by the simulations is in a good agreement with the correlation obtained from experiment. Flows of power-law fluids exhibit stronger anisotropy of the Reynolds stress tensor compared with the flow of Newtonian fluid. The turbulence anisotropy becomes more significant with the decreasing flow index n. An increase in apparent viscosity away from the wall leads to the damping of the wall-normal velocity pulsations. The suppression of the turbulent energy redistribution between the Reynolds stress tensor components observed in the simulations leads to a strong domination of the axial velocity pulsations. The damping of wall-normal velocity pulsations leads to a reduction of the fluctuating transport of momentum from the core toward the wall, which explains the effect of drag reduction.     

Experimental study of the formation of high-resistivity zones at the gel/buffer interface in CE

A novel, nondamaging method for experimental characterization of the formation and propagation of high-resistivity zones in CE, based on the measurement of time-dependent Joule heating on the outer capillary surface is proposed. The method detects propagation of resistive regions in capillaries in real time and allows the estimation of their velocity and resistance. The presented experimental data are in agreement with the results of the computer simulation as well as with previous data on the subject. The proposed method is useful for the development of new polymers as well as for the refinement and optimization of new CE protocols.     

Novel planar chiral phosphite: Preparation and use in the synthesis of Pd(II) complexes and in Pd-catalyzed allylic alkylation

The planar chiral diaryl phosphorimidite ligand containing additional C-stereocenters and neutral and cationic palladium(II) chelates with this ligand, cis-[Pd(η²-P,N)Cl₂] and [Pd(Allyl)(η²-P,N)]BF₄, were synthesized for the first time. The possibility of using these compounds in asymmetric allylic alkylation of 1,3-diphenylallyl acetate with dimethyl malonate in an optical yield of up to 73% was demonstrated.