Numerical methods for the simulation of a coalescence-driven droplet size distribution

The droplet size distribution in a turbulent flow field is considered and modeled by means of a population balance system. This paper studies different numerical methods for the 4D population balance equation and their impact on an output of interest, the time-space-averaged droplet size distribution at the outlet, which is known from experiments. These methods include different interpolations of the experimental data at the inlet, various discretizations in time and space, and different schemes for computing the coalescence integrals. It will be shown that noticeable changes in the output of interest might occur. In addition, the computational efficiency of the studied methods is discussed.     

Absorption coefficient measurements of particle-laden filters using laser heating: Validation with nigrosin

A laser-heating technique, referred as the laser-driven thermal reactor, was used in conjunction with laser transmissivity measurements to determine the absorption coefficient of particle-laden substrates (e.g., quartz-fiber filters). The novelty of this approach is that it analyzes a wide variety of specific samples (not just filtered samples) and overcomes measurement issues (e.g., absorption enhancement) associated with other filter-based particle absorption techniques. The absorption coefficient was determined for nigrosin-laden, quartz-fiber filters and the effect of the filter on the absorption measurements was estimated when compared to the isolated nigrosin results. The isolated nigrosin absorption coefficient compared favorably with Lorenz–Mie calculations for an idealized polydispersion of spherical particles (based on a measured nigronsin/de-ionized water suspension size distribution) dispersed throughout a volume equivalent to that of the nigrosin-laden filter. To validate the approach, the absorption coefficient of a nigrosin/de-ionized water suspension was in good agreement with results obtained from an ultraviolet/visible spectrometer. In addition, the estimated imaginary part of the refractive index from the Lorenz–Mie calculations compared well with literature values and was used to estimate the absorption coefficient of optically opaque packed nigrosin.     

An algebraic variational multiscale–multigrid method for large-eddy simulation of turbulent variable-density flow at low Mach number

An algebraic variational multiscale–multigrid method is proposed for large-eddy simulation of turbulent variable-density flow at low Mach number. Scale-separating operators generated by level-transfer operators from plain aggregation algebraic multigrid methods enable the application of modeling terms to selected scale groups (here, the smaller of the resolved scales) in a purely algebraic way. Thus, for scale separation, no additional discretization besides the basic one is required, in contrast to earlier approaches based on geometric multigrid methods. The proposed method is thoroughly validated via three numerical test cases of increasing complexity: a Rayleigh–Taylor instability, turbulent channel flow with a heated and a cooled wall, and turbulent flow past a backward-facing step with heating. Results obtained with the algebraic variational multiscale–multigrid method are compared to results obtained with residual-based variational multiscale methods as well as reference results from direct numerical simulation, experiments and LES published elsewhere. Particularly, mean and various second-order velocity and temperature results obtained for turbulent channel flow with a heated and a cooled wall indicate the higher prediction quality achievable when adding a small-scale subgrid-viscosity term within the algebraic multigrid framework instead of residual-based terms accounting for the subgrid-scale part of the non-linear convective term.     

Reactivity of a Cyclopentadienyl Containing Heterobimetallic Alkoxide

The synthesis of the new heteroleptic heterotrimetallic cluster, [(C₅H₅)Sn(μ-OBu^t)₂Ge(OBu^t)Mo(CO)₅] (1) has been achieved by a thermally induced CO substitution of the transition metal derivative, Mo(CO)₆, by the basic germanium atom of the cyclopentadienyl heterobimetallic alkoxide, [(C₅H₅)Sn(μ-OBu^t)₂Ge(OBu^t)]. The microanalysis, molecular weight (monomer in benzene), IR and multinuclear NMR data and X-ray diffraction study is consistent with the formulation of 1. The Sn atom has a trigonal pyramidal coordination environment formed by a aysmmterically π-bonded terminal C₅H₅ ring and two symmetrically bridged tert-butoxy groups. The four-coordinate Ge atom lies at the centre of a distorted tetrahedron and is terminally attached to a tert-butoxy group and a Mo(CO)₅5^? fragment.     

Vertical Electronic Spectra of the Isovalent Molecules H2CNH,H2SiNH,H2CPH and H2SiPH on the Basis of MRD-CI Calculations

Abstract

Large-scale multi-reference single and double-excitation configuration interaction (MRD-CI) calculations are employed for the study of the isovalent compounds H₂CNH, HLSiNH, hLCPH and H₂SiPH in their ground state equilibrium geometry. The dipole moments and charge distributions are given. The vertical excitation energies to the intravalence states ^3,1 (n, π*) and ^3,1(π,π*) and to the first members of the Rydberg series originating from n and - MO's respectively are predicted; the first two ionization potentials and the Rydberg term values are also calculated. In H₂CNH, mixing of Rydberg and valence-shell states with CN stretching is analyzed. The trends in relative stability of electronic and ionized states can be directly related to increased orbital stability of n relative to π as soon as a first-row constituent is replaced by a second-row atom. The calculations explain the diffuse character of the uv spectrum of imines; they treat the molecules H₂SiNH and H₂SiPH for the first time and present a large number of data for all four molecules which can serve as a basis for future experimental investigations on these and related compounds.     

Detection and identification of the designer benzodiazepine flubromazepam and preliminary data on its metabolism and pharmacokinetics

The appearance of pyrazolam in Internet shops selling ‘research chemicals’ in 2012 marked the beginning of designer benzodiazepines being sold as recreational drugs or ‘self medication’. With recent changes in national narcotics laws in many countries, where two uncontrolled benzodiazepines (phenazepam and etizolam), which were marketed by pharmaceutical companies in some countries, were scheduled, clandestine laboratories seem to turn to poorly characterized research drug candidates as legal substitutes. Following the appearance of pyrazolam, it comes with no surprise that recently, flubromazepam (7‐bromo‐5‐(2‐fluorophenyl)‐1,3‐dihydro‐2H‐1,4‐benzodiazepin‐2‐one), a second designer benzodiazepine, was offered on the market. In this article, this new compound was characterized using nuclear magnetic resonance, gas chromatography‐mass spectrometry (GC–MS), liquid chromatography–mass spectrometry (LC–MS/MS) and liquid chromatography quadrupole time‐of‐flight MS (LC–Q–ToF–MS). Additionally, a study was carried out, in which one of the authors consumed 4 mg of flubromazepam to gain preliminary data on the pharmacokinetic properties and the metabolism of this compound. For this purpose, serum as well as urine samples were collected for up to 31 days post‐ingestion and analyzed applying LC–MS/MS and LC–Q‐ToF‐MS techniques. On the basis of this study, flubromazepam appears to have an extremely long elimination half‐life of more than 100 h. One monohydroxylated compound and the debrominated compound could be identified as the predominant metabolites, the first allowing a detection of a consumption for up to 28 days post‐ingestion when analyzing urine samples in our case. Additionally, various immunochemical assays were evaluated, showing that the cross‐reactivity of the used assay seems not to be sufficient for safe detection of the applied dose in urine samples, bearing the risk that it could be misused in drug‐withdrawal settings or in other circumstances requiring regular drug testing. Furthermore, it may be used in drug‐facilitated crimes without being detected. Copyright © 2013 John Wiley & Sons, Ltd.     

Electrical conductivity of poly(vinylidene fluoride)/polyaniline blends under oscillatory and steady shear conditions

Blends of poly(vinylidene fluoride) (PVDF) and polyaniline (PAni) were prepared through melt blending in a batch mixer. The morphology, rheological behavior and electrical conductivity were investigated through transmission electron microscopy (TEM) and combined electro-rheological measurements. Through TEM analysis, it was possible to observe that all blends showed typical phase separation with the presence of conductive polymer aggregates. Deformations imposed during a strain sweep caused, not only disturbance of the linear viscoelastic behavior, but also changes in electrical conductivity. The oscillatory shear altered the morphology, breaking the PAni domains into smaller ones. This effect increases the distance between them and, consequently, resulted in a decrease of the electrical conductivity. The measurements under quiescent conditions and steady shear proved that the disturbance in morphology for PVDF/PAni system is non-recoverable. Through combined electrical and rheological measurements, it was possible to achieve good correlation between the electrical and flow behavior of PVDF/PAni blends.