Solutocapillary transport of oxygen bubbles in a diffusion-bubbling membrane core.

Bubbles are extensively explored as gas and energy carriers. However, despite notable progress, the bubble transport mechanisms are still poorly understood. At the present time there is not sufficient understanding of whether the body or surface forces play a major role in bubble transport in liquid interfacial systems. This understanding is important to be able to drive oxygen bubble transport. Here, we show the crucial role of solutocapillary forces in oxygen bubble transport in the core of a diffusion-bubbling membrane with a high density of solid/liquid and gas/liquid interfaces that operates under the oxygen chemical potential gradient. In order to describe the transport of oxygen bubbles in the membrane core, we developed a mathematical model. Both the velocity of bubbles and oxygen flux through this membrane predicted by this model agree with experiments. An in-depth understanding of the bubble transport mechanism presented in this study could eventually lead the way to more efficient bubble membrane gas separation, bubble energy generation, and bubble-assisted therapy in the future.

Investigation of the Information Possibilities of the Parameters of Vibroacoustic Signals Accompanying the Processing of Materials by Concentrated Energy Flows.

Creating systems for monitoring technology processes based on concentrated energy flows is an urgent and challenging task for automated production. Similar processes accompany such processing technologies: intensive thermal energy transfer to the substance, heating, development of the melting and evaporation or sublimation, ionization, and expansion of the released substance. It is accompanied by structural and phase rearrangements, local changes in volumes, chemical reactions that cause perturbations of the elastic medium, and the propagation of longitudinal and transverse waves in a wide frequency range. Vibrational energy propagates through the machine's elastic system, making it possible to register vibrations on surfaces remotely. Vibration parameters can be used in monitoring systems to prevent negative phenomena during processing and to be a tool for understanding the processes' kinetics. In some cases, it is the only source of information about the progress in the processing zone.

Oxygen-Selective Diffusion-Bubbling Membranes with Core-Shell Structure: Bubble Dynamics and Unsteady Effects.

Oxygen is the second-largest-volume industrial gas that is mainly produced using cryogenic air separation. However, the state-of-the-art cryogenic technology thermodynamic efficiency has approached a theoretical limit as near as is practicable. Therefore, there is stimulus to develop an alternative technology for efficient oxygen separation from air. Mixed ionic electronic-conducting (MIEC) ceramic membrane-based oxygen separation technology could become this alternative, but commercialization aspects, including cost, have revealed inadequacies in ceramic membrane materials. Currently, diffusion-bubbling molten oxide membrane-based oxygen separation technology is being developed. It is a potentially disruptive technology that would propose an improvement in oxygen purity and a reduction in capital costs. Bubbles play an important role in ensuring the oxygen mass transfer in diffusion-bubbling membranes. However, there is not sufficient understanding of the bubble dynamics. This understanding is important to be able to control transport properties of these membranes and assess their potential for technological application. The aim of this feature article is to highlight the progress made in developing this understanding and specify the directions for future research.

Bubble nucleation in core-shell structured molten oxide-based membranes with combined diffusion-bubbling oxygen mass transfer: experiment and theory.

Oxygen-selective membranes are likely to play a leading part in the future separation processes relevant to energy engineering. A newly developed molten copper and vanadium oxide-based diffusion-bubbling membrane with core-shell structure and fast combined oxygen mass transfer is a promising candidate for efficient oxygen separation. In this work, the oxygen bubble nucleation and transport properties of the diffusion-bubbling membrane were experimentally and theoretically studied. Bubble size distribution and cumulative oxygen flux have been plotted as functions of oxygen partial pressure. The relationship between the bubble density, oxygen partial pressure, and oxygen permeation flux was established. The oxygen flux and bubble density vary in the ranges of 3.2 × 10-8-1.4 × 10-7 mol cm-2 s-1 and 1.3 × 1013-5.8 × 1013 m-3 at ΔPO2 = 0.1-0.75 atm, respectively. The mechanisms of homogeneous, heterogeneous, pseudo-classical and non-classical nucleation are reviewed within the framework of the Cahn-Hilliard model. It is shown that the homogeneous nucleation mechanism is most likely in the membrane core. The estimated values of the interfacial tension, energy barrier, and rate nucleation are 0.02 J m-2, 5 kT, and 4 × 1029 m-3 s-1, respectively.

Relativistic environmental effects in (29)Si NMR chemical shifts of halosilanes: light nucleus, heavy environment.

Relativistic calculations of (29)Si NMR shielding constants (chemical shifts) in the series of halosilanes SiX(n)H(4-n) (X = F, Cl, Br and I) are performed within a full four-component relativistic Dirac's scheme using relativistic Dyall's basis sets. Three different theoretical levels are tested in the computation of (29)Si NMR chemical shifts in comparison with experiment: namely, four-component relativistic GIAO-DFT, four-component relativistic GIAO-RPA, and a hybrid scheme of a nonrelativistic GIAO-MP2 with taking into account relativistic corrections using the four-component relativistic GIAO-RPA. The DFT results give larger relativistic effects as compared to the RPA data which might be rationalized in terms of the manifestation of correlation effects taken into account at the DFT level and not accounted for at the uncorrelated RPA level. Taking into account solvent effects slightly improves agreement with experiment, however, being not a matter of principle. Generally, relativistic pure nonempirical wave function methods perform much better as compared to relativistic DFT methods when benchmarked to experiment.

Towards the versatile DFT and MP2 computational schemes for 31P NMR chemical shifts taking into account relativistic corrections.

The main factors affecting the accuracy and computational cost of the calculation of (31)P NMR chemical shifts in the representative series of organophosphorous compounds are examined at the density functional theory (DFT) and second-order Møller-Plesset perturbation theory (MP2) levels. At the DFT level, the best functionals for the calculation of (31)P NMR chemical shifts are those of Keal and Tozer, KT2 and KT3. Both at the DFT and MP2 levels, the most reliable basis sets are those of Jensen, pcS-2 or larger, and those of Pople, 6-311G(d,p) or larger. The reliable basis sets of Dunning's family are those of at least penta-zeta quality that precludes their practical consideration. An encouraging finding is that basically, the locally dense basis set approach resulting in a dramatic decrease in computational cost is justified in the calculation of (31)P NMR chemical shifts within the 1-2-ppm error. Relativistic corrections to (31)P NMR absolute shielding constants are of major importance reaching about 20-30 ppm (ca 7%) improving (not worsening!) the agreement of calculation with experiment. Further better agreement with the experiment by 1-2 ppm can be obtained by taking into account solvent effects within the integral equation formalism polarizable continuum model solvation scheme. We recommend the GIAO-DFT-KT2/pcS-3//pcS-2 scheme with relativistic corrections and solvent effects taken into account as the most versatile computational scheme for the calculation of (31)P NMR chemical shifts characterized by a mean absolute error of ca 9 ppm in the range of 550 ppm.

Elemental and Thermochemical Analyses of Materials after Electrical Discharge Machining in Water: Focus on Ni and Zn.

The mechanism of the material destruction under discharge pulses and material removal mechanism based on the thermochemical nature of the electrical erosion during electrical discharge machining of conductive materials were researched. The experiments were conducted for two structural materials used in the aerospace industry, namely austenite anticorrosion X10CrNiTi18-10 (12kH18N10T) steel and 2024 (D16) duralumin, machined by a brass tool of 0.25 mm in diameter in a deionized water medium. The optimized wire electrical discharge machining factors, measured discharge gaps (recommended offset is 170-175 µm and 195-199 µm, respectively), X-ray photoelectron spectroscopy for both types of materials are reported. Elemental analysis showed the presence of metallic Zn, CuO, iron oxides, chromium oxides, and 58.07% carbides (precipitation and normal atmospheric contamination) for steel and the presence of metallic Zn, CuO, ZnO, aluminum oxide, and 40.37% carbides (contamination) for duralumin. For the first time, calculating the thermochemistry parameters for reactions of Zn(OH)2, ZnO, and NiO formation was produced. The ability of Ni of chrome-nickel steel to interact with Zn of brass electrode was thermochemically proved. The standard enthalpy of the Ni5Zn21 intermetallic compound formation (erosion dust) ΔH0298 is -225.96 kJ/mol; the entropy of the crystalline phase Scint is 424.64 J/(mol·K).

Trivinylphosphine and trivinylphosphine chalcogenides: stereochemical trends of ³¹P-¹H spin-spin coupling constants.

A combined theoretical and experimental study of the stereochemical behavior of (31)P-(1)H spin-spin coupling constants has been performed in the series of trivinylphosphine and related trivinylphosphine oxide, sulfide and selenide. Theoretical energy-based conformational analysis of the title compounds performed at the MP2/6-311G** level reveals that each of the four compounds of this series exists in the equilibrium mixture of five true-minimum conformers, namely s-cis-s-cis-s-cis, s-cis-s-cis-gauche, syn-s-cis-gauche-gauche, anti-s-cis-gauche-gauche and gauche-gauche-gauche, which were taken into account in the conformational averaging of (31)P-(1)H spin-spin couplings calculated at the second-order polarization propagator approach/aug-cc-pVTZ-J level of theory. All (31)P-(1)H spin-spin coupling constants involving phosphorus and either of the vinyl protons are found to demonstrate a marked stereochemical dependences with respect to the geometry of the coupling pathway and internal rotation of the vinyl group around the P-C bond which is of major importance in the stereochemical studies of the unsaturated phosphines and phosphine chalcogenides.

Conformational analysis and stereochemical dependences of (31)P-(1)H spin-spin coupling constants of bis(2-phenethyl)vinylphosphine and related phosphine chalcogenides.

Theoretical energy-based conformational analysis of bis(2-phenethyl)vinylphosphine and related phosphine oxide, sulfide and selenide synthesized from available secondary phosphine chalcogenides and vinyl sulfoxides is performed at the MP2/6-311G** level to study stereochemical behavior of their (31)P-(1)H spin-spin coupling constants measured experimentally and calculated at different levels of theory. All four title compounds are shown to exist in the equilibrium mixture of two conformers: major planar s-cis and minor orthogonal ones, while (31)P-(1) H spin-spin coupling constants under study are found to demonstrate marked stereochemical dependences with respect to the geometry of the coupling pathways, and to the internal rotation of the vinyl group around the P(X)-C bonds (X = LP, O, S and Se), opening a new guide in the conformational studies of unsaturated phosphines and phosphine chalcogenides.

Extreme and Topological Dissipative Solitons with Structured Matter and Structured Light.

Structuring of matter with nanoobjects allows one to generate soliton-like light bundles with extreme characteristics-temporal duration and spatial dimensions. On the other hand, structuring of light gives the possibility to form light bundles with complicated internal structure; their topology could be used for information coding similar to that in self-replicating RNA molecules carrying genetic code. Here we review the both variants of structuring. In the first variant, we consider a linear molecular chain and organic film interacting resonantly with laser radiation. Demonstrated are optical bistability, switching waves, and dissipative solitons, whose sizes for molecular J-aggregates can reach the nanometer range. We also discuss some theoretical approaches to take into account multi-particle interaction and correlations between molecules. In the second variant, light structuring in large-size laser medium with saturable amplification and absorption is achieved by preparation of the initial field distribution with a number of closed and unclosed vortex lines where the field vanishes. Various types of topological solitons, parameter domains of their stability, and transformation of the solitons with slow variation of the scheme parameters are presented.

An Oxygen-Permeable Bilayer MIEC-Redox Membrane Concept.

Mixed ionic-electronic conducting (MIEC) membranes attract the attention because of their high potential for oxygen separation and energy conversion applications. The different fabrication methods of asymmetric membranes consisting of a thin MIEC layer on porous support were developed. The basically dense but not completely hermetic thin layers were achieved. To overcome this problem, we suggest a new concept of bilayer MIEC-Redox membrane. This solid/liquid composite membrane consists of a gastight MIEC thin external layer and a thick internal layer in which the redox reactions and oxygen bubbling occur. Here, we report the transport properties of a copper oxide-based MIEC-Redox membrane.

Novel Molten Oxide Membrane for Ultrahigh Purity Oxygen Separation from Air.

We present a novel solid/liquid Co3O4-36 wt % Bi2O3 composite that can be used as molten oxide membrane, MOM ( Belousov, V. V. Electrical and Mass Transport Processes in Molten Oxide Membranes. Ionics 22 , 2016 , 451 - 469 ), for ultrahigh purity oxygen separation from air. This membrane material consists of Co3O4 solid grains and intergranular liquid channels (mainly molten Bi2O3). The solid grains conduct electrons, and the intergranular liquid channels predominantly conduct oxygen ions. The liquid channels also provide the membrane material gas tightness and ductility. This last property allows us to deal successfully with the problem of thermal incompatibility. Oxygen and nitrogen permeation fluxes, oxygen ion transport number, and conductivity of the composite were measured by the gas flow, volumetric measurements of the faradaic efficiency, and four-probe dc techniques, accordingly. The membrane material showed the highest oxygen selectivity jO2/jN2 > 10(5) and sufficient oxygen permeability 2.5 × 10(-8) mol cm(-1) s(-1) at 850 °C. In the range of membrane thicknesses 1.5-3.3 mm, the oxygen permeation rate was controlled by chemical diffusion. The ease of the MOM fabrication, combined with superior oxygen selectivity and competitive oxygen permeability, shows the promise of the membrane material for ultrahigh purity oxygen separation from air.

Curvilinear motion of multivortex laser-soliton complexes with strong and weak coupling.

We reveal the existence of stable dissipative soliton complexes with curvilinear motion of their center of mass. This type of motion results from the field distribution asymmetry and is well pronounced for asymmetric complexes of laser solitons with strong coupling. We present results of numerical simulations of such complexes in a model of wide-aperture lasers or laser amplifiers with saturable gain and absorption. The complex consists of a pair of strongly coupled vortex solitons weakly coupled with a number of other vortex solitons. Similar complexes are expected to exist in different spatially distributed nonlinear dissipative systems, including schemes with discrete dissipative solitons.