On the macroscopic dynamics induced by a model wave-particle collision operator

The macroscopic dynamics of a kinetic equation involving a model wave-particle collision operator of plasma physics is investigated. The Chapman-Enskog asymptotics is first considered in the framework of a hydrodynamic scaling. The obtained macroscopic model still involves a kinetic variable, the particle energy in the rest frame of the fluid, but shares similarities with the compressible Navier-Stokes equation of gas dynamics. Then a diffusive scaling is examined under the hypothesis of small perturbations of a global equilibrium. In this case, the macroscopic model couples the usual incompressible Navier-Stokes with a diffusion equation for the energy distribution function of the particles, constrained by an extended version of the Boussinesq relation. In both cases, the effect of a Lorentz force term is developed, in the perspective of plasma physical modelling. Received June 16, 1997     

Nonlinear Stability of a One-Dimensional Boussinesq Equation

We study nonlinear orbital stability and instability of the set of ground state solitary wave solutions of a one-dimensional Boussinesq equation or one-dimensional Benney–Luke equation. It is shown that a solitary wave (traveling wave with finite energy) may be orbitally stable or unstable depending on the range of the wave's speed of propagation.     

An experimental investigation of the influence of stiffener torsional rigidity on buckling of compression panels

The influence of torsional ridigity of the stiffeners on the buckling of reinforced aluminum-alloy panels has been investigated. Experimental results reveal that stiffener torsional rigidity must be introduced in the analysis of compressed panels, for, if the stiffener has a closed cross section, the stiffener shape may change the buckling mode shape essentially and increase the critical load considerably.José María Mínguez was Postgraduate Student in Engineering, Metallic Structures Group, University of Bath, United Kingdom     

Changes in a coflowing jet structure caused by acoustic forcing

In the present work, the changes in the basic turbulence field of an axisymmetric jet in a coflow when acoustic forcing is applied are investigated. The main objective is to discriminate between changes produced by the acoustic forcing and those produced by the presence of solid particles in a two-phase flow. Power spectra of the axial velocities, u(t), are analyzed to reinforce the idea of the existence of a natural frequency. Time-averaged data are used to characterize the basic flow. This basic flow is compared with the flow altered by the acoustic forcing. By smoothing the phase-averaged rms data (mean statistical curve), the general behavior of the instantaneous fluctuations are unveiled and compared with that of the natural (unforced) jet. In this way, it can be seen that rms values in the forced cases are higher than in the unforced ones, due to the contribution of the external forcing. However, once the coherent structures are extinguished, both forced and unforced jets show a similar trend.     

Confined and Agitated Swirling Flows with Applications in Chemical Engineering

Turbulent, swirling flows are encountered frequently in chemical engineering practice. In this article, experiments and simulations on two classes of swirling flows, viz. agitated flows (stirred tanks), and confined swirling flows are discussed. Results of large-eddy simulations of stirred tank flow are compared with experimental data, mainly phase-resolved LDA data of the flow in the vicinity of the impeller. Next to the average velocity field, also the turbulent kinetic energy, and the anisotropy of the Reynolds stress tensor have been assessed. An important application of confined swirling flow is the cyclone separator (hydrocyclones for the separation of liquids, gas cyclones for gas-solid separation). The flow in a swirl tube geometry exhibiting many of the typical features of swirl flows (e.g. vortex breakdown) is discussed. Furthermore, a large-eddy simulation of the gas flow in a high-efficiency Stairmand cyclone separator is presented. Two examples of process modeling based on flow simulations are briefly treated: orthokinetic agglomeration of crystals in a stirred tank, and particle separation in a cyclone. This revised version was published online in July 2006 with corrections to the Cover Date.     

Observation of Diastereotopic Signals in 15N NMR Spectroscopy

The first example in the literature of a compound showing anisochronous ¹⁵N atoms resulting from diastereotopicity is described. Racemic 1,3‐dimethyl‐2‐phenyloctahydro‐1H‐benzimidazole was prepared and studied by ¹H, ¹³C and ¹⁵N NMR spectroscopy. If convenient conditions were used (monitored by theoretical calculations of ²J_N‐H spin–spin coupling constants), two ¹⁵N NMR signals were observed and corresponded to the diastereotopic atoms. GIAO/density‐functional calculations of chemical shifts were not only in good agreement with the experimental values but also served as prediction tools. This study suggests that ¹⁵N NMR spectroscopy could be used to probe chirality.     

Caterpillar Track Complexes in Template‐Directed Synthesis and Correlated Molecular Motion

Small alterations to the structure of a star‐shaped template totally change its mode of operation. The hexapyridyl template directs the conversion of a porphyrin dimer to the cyclic hexamer, but deleting one pyridine site changes the product to the cyclic decamer, while deleting two binding sites changes the product to the cyclic octamer. This surprising switch in selectivity is explained by the formation of 2:1 caterpillar track complexes, in which two template wheels bind inside the nanoring. Caterpillar track complexes can also be prepared by binding the hexapyridyl template inside the 8‐ and 10‐porphyrin nanorings. NMR exchange spectroscopy (EXSY) experiments show that these complexes exhibit correlated motion, in which the conrotatory rotation of the two template wheels is coupled to rotation of the nanoring track. In the case of the 10‐porphyrin system, the correlated motion can be locked by binding palladium(II) dichloride between the two templates.     

Carboxylic‐Acid‐Passivated Metal Oxide Nanocrystals: Ligand Exchange Characteristics of a New Binding Motif

Ligand exchange is central in the processing of inorganic nanocrystals (NCs) and requires understanding of surface chemistry. Studying sterically stabilized HfO₂ and ZrO₂ NCs using ¹H solution NMR and IR spectroscopy as well as elemental analysis, this paper demonstrates the reversible exchange of initial oleic acid ligands for octylamine and self‐adsorption of oleic acid at NC surfaces. Both processes are incompatible with an X‐type binding motif of carboxylic acids as reported for sulfide and selenide NCs. We argue that this behavior stems from the dissociative adsorption of carboxylic acids at the oxide surface. Both proton and carboxylate moieties must be regarded as X‐type ligands yielding a combined X₂ binding motif that allows for self‐adsorption and exchange for L‐type ligands.     

Textile/Metal–Organic‐Framework Composites as Self‐Detoxifying Filters for Chemical‐Warfare Agents

The current technology of air‐filtration materials for protection against highly toxic chemicals, that is, chemical‐warfare agents, is mainly based on the broad and effective adsorptive properties of hydrophobic activated carbons. However, adsorption does not prevent these materials from behaving as secondary emitters once they are contaminated. Thus, the development of efficient self‐cleaning filters is of high interest. Herein, we report how we can take advantage of the improved phosphotriesterase catalytic activity of lithium alkoxide doped zirconium(IV) metal–organic framework (MOF) materials to develop advanced self‐detoxifying adsorbents of chemical‐warfare agents containing hydrolysable P? F, P? O, and C? Cl bonds. Moreover, we also show that it is possible to integrate these materials onto textiles, thereby combining air‐permeation properties of the textiles with the self‐detoxifying properties of the MOF material.