On the origin of extremely high strength of ultrafine-grained Al alloys produced by severe plastic deformation

Ultrafine-grained Al alloys produced by high pressure torsion are found to exhibit a very high strength, considerably exceeding the Hall-Petch predictions for the ultrafine grains. The phenomena can be attributed to the unique combination of ultrafine structure and deformation-induced segregations of solute elements along grain boundaries, which may affect the emission and mobility of intragranular dislocations

Relations between the aromaticity and magnetic dipole transitions in the electronic spectra of hetero[8]circulenes

Magnetically induced current densities have been calculated at the second-order MOller-Plesset perturbation theory (MP2) level for seven hetero[8]circulenes and their dicationic and dianionic forms. Calculations of the magnetic dipole transition moments have also been carried out at the algebraic diagrammatic construction (ADC(2)) and the second-order approximate coupled-cluster (CC2) levels. The calculations show that the degree of aromaticity and the size of the magnetic dipole transition moment of the lowest magnetic-dipole allowed excited state are related. We show that neutral hetero[8]circulenes are weakly antiaromatic when the first excited state with a large magnetic dipole transition moment of 10-16 a.u. lies at high energies (approximate to 2.8-3.5 eV). For the dications, this transition often lies at much lower energies. Hetero[8]circulene dications with large magnetic dipole transition moments are strongly antiaromatic. The lowest excited states of the hetero[8]circulene dianions have very small magnetic dipole transition moments implying that they are aromatic.Peer reviewe

Предпосылки применения просвечивающей электронной микроскопии как геохимической методики выявления миграционных минеральных форм над углеводородными залежами

Актуальность исследования обусловлена необходимостью разработки методики нахождения и определения миграционных форм металлических соединений над контурами углеводородных залежей на поверхности Земли, так как существующая в настоящее время информация о возможности переноса металлов с уровня залежи зачастую противоречива, что ставит под сомнение саму возможность геохимических поисков углеводородных залежей на основе информации о содержании металлов в приповерхностных горизонтах. Обсуждаемая методика сбора и анализа позволяет изучать наноразмерные соединения металлов, мигрирующих в составе газового потока до поверхности Земли. Появляется возможность установления происхождения найденного наноразмерного металлического соединения с допустимостью доказать глубинную природу происхождения вещества, найденного на дневной поверхности. Цель работы: обзор и анализ существующих знаний о геохимических методах поисков месторождений нефти и газа; моделирование новой геохимической методики, связанной с исследованием образцов на просвечивающем электронном микроскопе, с возможностью установления частиц в наноразмерном состоянии. Методы исследования: геохимические методы поиска и разведки месторождений нефти и газа, просвечивающая электронная микроскопия. Результаты. Проведен обзор и анализ литературы на тему геохимических методов поисков залежей нефти и газа, проанализированы закономерности особенностей геохимических полей над месторождениями нефти и газа Западно-Сибирской нефтегазоносной провинции. Предложена новая геохимическая методика поисков и разведки, которая способна выявлять минеральные формы нахождения химических элементов в наноразмерном состоянии на просвечивающем электронном микроскопе, в частности находить и идентифицировать миграционные металлические соединения.The relevance of the discussed issue is caused by the necessity to develop the technique for finding and identifying metal compounds migration forms over the boundaries of hydrocarbon deposits on the Earth surface. The existing information on possibility of metal transfer from the level of deposits is often contradictory and it can cast doubt on the possibility of geochemical prospecting of hydrocarbon deposits on the basis of information on metal content in the subsurface horizons. The technique of collection and analysis allows us to study nanoscale metal compounds migrating as a part of gas flow to the Earth surface. It becomes possible to determine the origin of nanoscale metal compounds with the ability to prove the genesis of the deep nature of the substance found on the surface. The main aim of the research is to review and to analyze the existing knowledge on geochemical methods of prospecting for oil and gas; to model a new geochemical method associated with the study of samples on a transmission electron microscope for identifying nanoscale particles. The methods used in the study: geochemistry methods of prospecting and exploration of oil and gas fields, transmission electron microscopy. The results of the research. The authors have reviewed and analyzed the literature on geochemical methods to search for oil and gas deposits and analyzed the patterns of geochemical features and magnetic fields on deposits of the West Siberian oil and gas province. The paper introduces a new prospecting and exploration geochemical and magnetic technique which can help identify nanoscale mineral forms of chemical elements with a transmission electron microscope, in particular find and identify migration metal compounds

Ab Initio Study of Phosphorescence of Hetero[8]circulenes

Peer reviewe

First-principles method for calculating the rate constants of internal-conversion and intersystem-crossing transitions

A method for calculating the rate constants for internal-conversion (k(IC)) and intersystem-crossing (k(ISC)) processes within the adiabatic and Franck-Condon (FC) approximations is proposed. The applicability of the method is demonstrated by calculation of k(IC) and k(ISC) for a set of organic and organometallic compounds with experimentally known spectroscopic properties. The studied molecules were pyrromethene-567 dye, psoralene, hetero[8]circulenes, free-base porphyrin, naphthalene, and larger polyacenes. We also studied fac-Alq(3) and fac-Ir(ppy)(3), which are important molecules in organic light emitting diodes (OLEDs). The excitation energies were calculated at the multi-configuration quasi-degenerate second-order perturbation theory (XMC-QDPT2) level, which is found to yield excitation energies in good agreement with experimental data. Spin-orbit coupling matrix elements, non-adiabatic coupling matrix elements, Huang-Rhys factors, and vibrational energies were calculated at the time-dependent density functional theory (TDDFT) and complete active space self-consistent field (CASSCF) levels. The computed fluorescence quantum yields for the pyrromethene-567 dye, psoralene, hetero[8]circulenes, fac-Alq(3) and fac-Ir(ppy)(3) agree well with experimental data, whereas for the free-base porphyrin, naphthalene, and the polyacenes, the obtained quantum yields significantly differ from the experimental values, because the FC and adiabatic approximations are not accurate for these molecules.Peer reviewe

Fast electrochemical doping due to front instability in organic semiconductors

The electrochemical doping transformation in organic semiconductor devices is studied in application to light-emitting cells. It is shown that the device performance can be significantly improved by utilizing new fundamental properties of the doping process. We obtain an instability, which distorts the doping fronts and increases the doping rate considerably. We explain the physical mechanism of the instability, develop theory, provide experimental evidence, and perform numerical simulations. We further show how improved device design can amplify the instability thus leading to a much faster doping process and device kinetics.Comment: 4 pages, 4 figure

Effect of surface friction on ultrafast flame acceleration in obstructed cylindrical pipes

The Bychkov model of ultrafast flame acceleration in obstructed tubes [Valiev et al., “Flame Acceleration in Channels with Obstacles in the Deflagration-to-Detonation Transition,” Combust. Flame 157, 1012 (2010)] employed a number of simplifying assumptions, including those of free-slip and adiabatic surfaces of the obstacles and of the tube wall. In the present work, the influence of free-slip/non-slip surface conditions on the flame dynamics in a cylindrical tube of radius R, involving an array of parallel, tightly-spaced obstacles of size αR, is scrutinized by means of the computational simulations of the axisymmetric fully-compressible gasdynamics and combustion equations with an Arrhenius chemical kinetics. Specifically, non-slip and free-slip surfaces are compared for the blockage ratio, α, and the spacing between the obstacles, ΔZ, in the ranges 1/3 ≤ α ≤ 2/3 and 0.25 ≤ ΔZ/R ≤ 2.0, respectively. For these parameters, an impact of surface friction on flame acceleration is shown to be minor, only 1∼4%, slightly facilitating acceleration in a tube with ΔZ/R = 0.5 and moderating acceleration in the case of ΔZ/R = 0.25. Given the fact that the physical boundary conditions are non-slip as far as the continuum assumption is valid, the present work thereby justifies the Bychkov model, employing the free-slip conditions, and makes its wider applicable to the practical reality. While this result can be anticipated and explained by a fact that flame propagation is mainly driven by its spreading in the unobstructed portion of an obstructed tube (i.e. far from the tube wall), the situation is, however, qualitatively different from that in the unobstructed tubes, where surface friction modifies the flame dynamics conceptually

Quasi-steady stages in the process of premixed flame acceleration in narrow channels

The present paper addresses the phenomenon of spontaneous acceleration of a pre-mixed flame front propagating in micro-channels, with subsequent deflagration-to-detonation transition. It has recently been shown experimentally [M. Wu, M. Burke, S. Son, and R. Yetter, Proc. Combust. Inst. 31, 2429 (2007)], computationally [D. Valiev, V. Bychkov, V. Akkerman, and L.-E. Eriksson, Phys. Rev. E 80, 036317 (2009)], and analytically [V. Bychkov, V. Akkerman, D. Valiev, and C. K. Law, Phys. Rev. E 81, 026309 (2010)] that the flame acceleration undergoes different stages, from an initial exponential regime to quasi-steady fast deflagration with saturated velocity. The present work focuses on the final saturation stages in the process of flame acceleration, when the flame propagates with supersonic velocity with respect to the channel walls. It is shown that an intermediate stage may occur during acceleration with quasi-steady velocity, noticeably below the Chapman-Jouguet deflagration speed. The intermediate stage is followed by additional flame acceleration and subsequent saturation to the Chapman-Jouguet deflagration regime. We elucidate the intermediate stage by the joint effect of gas pre-compression ahead of the flame front and the hydraulic resistance. The additional acceleration is related to viscous heating at the channel walls, being of key importance at the final stages. The possibility of explosion triggering is also demonstrated

Single-layer polymeric tetraoxa[8]circulene modified by s-block metals : toward stable spin qubits and novel superconductors

Tunable electronic properties of low-dimensional materials have been the object of extensive research, as such properties are highly desirable in order to provide flexibility in the design and optimization of functional devices. In this study, we account for the fact that such properties can be tuned by embedding diverse metal atoms and theoretically study a series of new organometallic porous sheets based on two-dimensional tetraoxa[8]circulene (TOC) polymers doped with alkali or alkaline-earth metals. The results reveal that the metal-decorated sheets change their electronic structure from semiconducting to metallic behaviour due to n-doping. Complete active space self-consistent field (CASSCF) calculations reveal a unique open-shell singlet ground state in the TOC-Ca complex, which is formed by two closed-shell species. Moreover, Ca becomes a doublet state, which is promising for magnetic quantum bit applications due to the long spin coherence time. Ca-doped TOC also demonstrates a high density of states in the vicinity of the Fermi level and induced superconductivity. Using the ab initio Eliashberg formalism, we find that the TOC-Ca polymers are phonon-mediated superconductors with a critical temperature T-C = 14.5 K, which is within the range of typical carbon based superconducting materials. Therefore, combining the proved superconductivity and the long spin lifetime in doublet Ca, such materials could be an ideal platform for the realization of quantum bits.Peer reviewe

Decomposition process in a FeAuPd alloy nanostructured by severe plastic deformation

The decomposition process mechanisms have been investigated in a Fe50Au25Pd25 (at.%) alloy processed by severe plastic deformation. Phases were characterized by X-ray diffraction and microstructures were observed using transmission electron microscopy. In the coarse grain alloy homogenized and aged at $450 ^{circ}\mathrm{C}$, the bcc \alpha-Fe and fcc AuPd phases nucleate in the fcc supersaturated solid solution and grow by a discontinuous precipitation process resulting in a typical lamellar structure. The grain size of the homogenized FeAuPd alloy was reduced in a range of 50 to 100nm by high pressure torsion. Aging at $450 ^{circ}\mathrm{C}$ this nanostructure leads to the decomposition of the solid solution into an equi-axed microstructure. The grain growth is very limited during aging and the grain size remains under 100nm. The combination of two phases with different crystallographic structures (bcc \alpha-Fe and fcc AuPd) and of the nanoscaled grain size gives rise to a significant hardening of the allo