Spherical Particles of Zirconia-Titania of Hexagonal Structure from a Neutral Amine Route

Through the sol–gel process, using the so-called neutral amine route, spherical particles of 1:1 zirconia–titania were synthesized from zirconium(IV) and titanium(IV) butoxides as well as 1,12-diaminododecane as precursor species. The obtained product exhibited a hexagonal structure, as determinated by X-ray diffraction data. The obtained material was also characterized by thermogravimetry, differential scanning calorimetry, infrared spectroscopy, scanning electron microscopy, and surface area measurements. Despite the release of template molecules on heating, the spherical morphology was retained up to about 1200°C, at which the disruption of the spheres took place.     

Effects of Adsorbed Polyaniline on Redox Process on MoO3 Surface

The effects exhibited by adsorbed conducting polyaniline on the redox process on a molybdenum oxide surface were studied. Thermogravimetric results indicate a 4% polyaniline deposition. Cyclic voltammograms of the adsorbed polymer on MoO3 show that polyaniline exerts remarkable effects on the molybdenum blue oxidation-reduction process, with oxidation and reduction potentials of 0.33 and 0.18 V, respectively. This effect strongly enhances the electrode response, and can be used as an important tool in qualitative and/or quantitative determinations of molybdenum in solution as well as in any substrate. Copyright 1999 Academic Press.     

The interaction of a gravity current with a circular cylinder mounted above a wall: Effect of the gap size

The flow of a gravity current past a circular cylinder mounted above a bottom wall is studied by means of two-dimensional Navier–Stokes simulations. The investigation focuses on the effects of the gap size on the forces acting on the cylinder. The interaction of the current with the cylinder can be divided into an impact, a transient, and a quasisteady stage. During the impact stage, the gravity current meets the cylinder, and the drag increases towards a maximum, while the lift undergoes a drastic fluctuation which increases noticeably with the gap size. During the quasisteady stage, the flow past the cylinder resembles that observed in constant-density boundary layer flows past cylinders: Karman vortex shedding is observed for sufficiently large gap sizes, while a vorticity cancellation mechanism is responsible for the suppression of vortex shedding at small gap sizes. On the other hand, interesting differences that distinguish the gravity current case from the constant-density case are the presence in the gravity current flow of a component of the mean quasisteady lift due to buoyancy, and another component from the deflection of the wake towards the wall by the constriction of the dense fluid flow downstream of the cylinder, as well as the cancellation of vortex shedding for all gap sizes when the ratio of the channel depth to lock height is decreased from 5 to 1.     

Polarized triplet-minus-singlet absorbance difference spectra measured by absorbance-detected magnetic resonance. An application to photosynthetic reaction centres

A method is presented to measure linear dichroic triplet-minus-singlet absorbance difference spectra using absorbance-detected magnetic resonance of the triplet state in zero magnetic field. Orientational selection is achieved by using a linearly-polarised microwave field. The microwave-induced change in the absorbance of light with the electric vector parallel or perpendicular to the microwave field vector is monitored using a Morvue photoelastic modulator and an analyzing polarizer. The method is applied to reaction centres of the photosynthetic bacterium Rhodopseudomonas viridis.     

The nonlinear evolution of swirling jets

We investigate the mechanisms of vorticity concentration, reorientation and stretching in a swirling jet, whose dynamics is dominated by the competition of a Kelvin-Helmholtz-type vortex sheet instability and a centrifugal Rayleigh instability. To this end, we employ an inviscid Lagrangian vortex filament technique. It is found that the axial jet velocity profile breaks the symmetry of the pure swirling flow. Conversely, the swirl is seen to modify the case dominated by a Kelvin-Helmholtz instability in that it results in the formation of counterrotating vortex rings. A pinch-off mechanism is observed which leads to a dramatic decrease in the local jet diameter. Furthermore, the vortex ring circulation is seen to be time dependent.

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Sommario In questo lavoro si analizza la dinamica della vorticità in un setto rotante in cui siano presenti, ed in competizione reciproca, fenomeni di instabilità di Kelvin-Helmholtz e di Rayleigh. A tale scopo si adotta una metodologia di soluzione non viscosa, Lagrangiana a filamenti vorticosi. Viene mostrato come il profilo di velocità assiale del getto altera la simmetria del moto di pura rotazione. Viceversa, la presenza della rotazione modifica il flusso dominato dall'instabilità di Kelvin-Helmholtz attraverso la formazione di anelli vorticosi controrotanti. L'interazione di questi due campi di velocità porta sia ad una considerevole riduzione del diametro locale del getto, sia ad una variazione temporale della circolazione degli anelli vorticosi.

     

Buoyancy-driven convection around chemical fronts traveling in covered horizontal solution layers

Density differences across an autocatalytic chemical front traveling horizontally in covered thin layers of solution trigger hydrodynamic flows which can alter the concentration profile. We theoretically investigate the spatiotemporal evolution and asymptotic dynamics resulting from such an interplay between isothermal chemical reactions, diffusion, and buoyancy-driven convection. The studied model couples the reaction-diffusion-convection evolution equation for the concentration of an autocatalytic species to the incompressible Stokes equations ruling the evolution of the flow velocity in a two-dimensional geometry. The dimensionless parameter of the problem is a solutal Rayleigh number constructed upon the characteristic reaction-diffusion length scale. We show numerically that the asymptotic dynamics is one steady vortex surrounding, deforming, and accelerating the chemical front. This chemohydrodynamic structure propagating at a constant speed is quite different from the one obtained in the case of a pure hydrodynamic flow resulting from the contact between two solutions of different density or from the pure reaction-diffusion planar traveling front. The dynamics is symmetric with regard to the middle of the layer thickness for positive and negative Rayleigh numbers corresponding to products, respectively, lighter or heavier than the reactants. A parametric study shows that the intensity of the flow, the propagation speed, and the deformation of the front are increasing functions of the Rayleigh number and of the layer thickness. In particular, the asymptotic mixing length and reaction-diffusion-convection speed both scale as square root Ra for Ra>5. The velocity and concentration fields in the asymptotic dynamics are also found to exhibit self-similar properties with Ra. A comparison of the dynamics in the case of a monostable versus bistable kinetics is provided. Good agreement is obtained with experimental data on the speed of iodate-arsenous acid fronts propagating in horizontal capillaries. We furthermore compare the buoyancy-driven dynamics studied here to Marangoni-driven deformation of traveling chemical fronts in solution open to the air in the absence of gravity previously studied in the same geometry [L. Rongy and A. De Wit, J. Chem. Phys. 124, 164705 (2006)].     

HL-2M 装置电子回旋共振加热及电流驱动系统设计与研制进展

根据 HL-2M 装置物理实验加热的需求,完成了总功率为 8MW 的电子回旋共振加热及电流驱动 (ECRH/ECCD)系统设计,开展了波源、传输及天线等关键部件研制。8MW ECRH/ECCD 系统,由 8 套 105GHz/  1MW/3s 波源系统、8 条内径为 63.5mm 的真空传输线及三套极向实时可控的发射天线构成。目前,已完成 ECRH/ECCD 系统关键部件研制及其相关的桌面与高功率性能测试。测试结果表明,微波源回旋管输出微波功率 达到1MW/3s,在真空度为 10^‒2Pa 的过模波纹圆波导传输线中能低耗稳定传输,发射天线极向全量程角度转动响 应时间在 50ms 以内。      

Gravity currents propagating over periodic arrays of blunt obstacles: Effect of the obstacle size

Gravity currents are considered that propagate over a series of identical ribs with square cross sections. Both large-eddy simulations and a shallow-water approach are applied to assess the influence of rib height and Reynolds number. The simulations elucidate the physical mechanisms governing the time-dependent evolution of the drag force, which are dominated by the formation of a recirculation region immediately downstream of each rib, in conjunction with a supercritical, jet-like flow region above and behind the rib, and an upstream propagating hydraulic jump that forms as a result of the interaction between the gravity current and the neighboring rib immediately downstream. The corresponding shallow-water analysis yields fair agreement, indicating that simplified models can provide useful information for the present class of flows.     

C-H-pi interactions in 1-n-butyl-3-methylimidazolium tetraphenylborate molten salt: solid and solution structures

The crystal structure of 1-n-butyl-3-methylimidazolium tetraphenylborate molten salt (1) shows C-H-pi interactions between the hydrogens of the imidazolium cation and the phenyl rings of the tetraphenylborate anion. The imidazolium ring is surrounded by three tetraphenylborate anions that are connected with the same cation by C-H-pi (phenyl rings) interactions. The nearest inter-ion interaction is found between the N-CH-N proton of the cation and the B-phenyl centroid (2.349 A) with a nearly T-shaped geometry. The inter-ionic solution structure of 1 has been investigated by the detection of inter-ionic contacts in 1H NOESY NMR spectra between the protons of the cation and the anion. The 1H-NMR spectra of molten salt 1 is almost independent of its concentration in [D6]DMSO solution, the imidazolium proton chemical shifts are in the expected region and there are no observable NOE effects between the protons of the cation with those of the anion, indicating that 1 behaves in [D6]DMSO as a solvent-separated ion pair. In CDCl3 the 1H-NMR spectra of 1 are concentration dependent and all the imidazolium protons are shielded as compared with those observed in [D6]DMSO. Moreover, the 1H NOESY NMR spectra show all the peaks affected by the interaction between the protons of the imidazolium cation and those of the anion, indicating that in CDCl3 1 possesses a contact ion pair structure. The NCHN proton of the cation exhibits the greatest shielding (up to -4.5 ppm). an indication of the existence of C-H-pi interactions, even in solution. The calculated distance of this proton to the phenyl centroid is 2.3 A for a C-H -pi angle of 180 degrees. The apparent volumes for the cation and anion, calculated from the measured 13C-NMR relaxation times, increase from 38 and 140 A3 in [D6]DMSO to 360 and 600 A3 in CDCl3, respectively; this indicates the formation of floating aggregates of the type (1)(n) in CDCl3 via weak hydrogen bonds, with increasing concentration.     

Effects of Adsorbed Polyaniline on Redox Processes on As(2)O(3) Surfaces

Polyaniline deposited on As(2)O(3) surface resulted in a new material, which was characterized by infrared spectoscopy, thermogravimetry, differential scanning calorimetry, scanning electron microscopy, X-ray diffraction, and cyclic voltammetry. The mass percentage of polymer deposited on oxide surface is approximately 13%. The scanning electron microscopy images as well as the X-ray diffraction patterns provided conclusive evidence that the oxide surface is coated by the polymer. The cyclic voltammograms of the polyaniline adsorbed on As(2)O(3) surface showed that the adsorbate exerts remarkable effects on redox processes on this oxide. The pure oxide exhibited two oxidation/reduction peaks at 0.25/-0.06 and 0.47/-0.25 V attributed tentatively to the processes As(2)O(3)(s)+6H(+)+6e(-)=2As(s)+3H(2)O and As(s)+3H(+)+3e(-)=AsH(3)(g), respectively. The polyaniline-coated sample exhibited a better-defined voltammogram in which the first oxidation peak of the oxide had its intensity increased about four times. Copyright 2000 Academic Press.