A convective weakly viscoelastic rotating flow with pressure Neumann condition

The objective of this work is to investigate through the numeric simulation, the effects of the weakly viscoelastic flow within a rotating rectangular duct subject to a buoyancy force due to the heating of one of the walls of the duct. A direct velocity–pressure algorithm in primitive variables with a Neumann condition for the pressure is employed. The spatial discretization is made with finite central differences on a staggered grid. The pressure field is directly updated without any iteration. Numerical simulations were done for several Weissemberg numbers (We) and Grashof numbers (Gr) . The numerical results show that for high Weissemberg numbers (We>7.4 × 10^?5) and for ducts with aspect ratio 2:1 and 8:1, the secondary flow is restabilized with a stretched double vortex configuration. It is also observed that when the Grashof number is increased (Gr>17 × 10^?4) , the buoyancy force neutralizes the effects of the Coriolis force for ducts with aspect ratio 8:1. Copyright © 2008 John Wiley & Sons, Ltd.     

In situ ion beam sputter deposition and X‐ray photoelectron spectroscopy (XPS) of multiple thin layers under computer control for combinatorial materials synthesis

Deposition of ultra‐thin layers under computer control is a frequent requirement in studies of novel sensors, materials screening, heterogeneous catalysis, the probing of band offsets near semiconductor junctions and many other applications. Often large‐area samples are produced by magnetron sputtering from multiple targets or by atomic layer deposition (ALD). Samples can then be transferred to an analytical chamber for checking by X‐ray photoelectron spectroscopy (XPS) or other surface‐sensitive spectroscopies. The ‘wafer‐scale’ nature of these tools is often greater than is required in combinatorial studies, where a few square centimetres or even millimetres of sample is sufficient for each composition to be tested. The large size leads to increased capital cost, problems of registration as samples are transferred between deposition and analysis, and often makes the use of precious metals as sputter targets prohibitively expensive. Instead we have modified a commercial sample block designed to perform angle‐resolved XPS in a commercial XPS instrument. This now allows ion‐beam sputter deposition from up to six different targets under complete computer control. Ion beam deposition is an attractive technology for depositing ultra‐thin layers of great purity under ultra‐high vacuum conditions, but is generally a very expensive technology. Our new sample block allows ion beam sputtering using the ion gun normally used for sputter depth‐profiling of samples, greatly reducing the cost and allowing deposition to be done (and checked by XPS) in situ in a single instrument. Precious metals are deposited cheaply and efficiently by ion‐beam sputtering from thin metal foils. Samples can then be removed, studied and exposed to reactants or surface treatments before being returned to the XPS to examine and quantify the effects. Copyright © 2016 The Authors Surface and Interface Analysis Published by John Wiley & Sons Ltd.     

Composition assessment of ferric oxide by accurate peak fitting of the Fe 2p photoemission spectrum

A quantitative study of the surface composition of ferric oxide employing photoemission spectra is presented. It was possible to accurately reproduce the expected composition (Fe_2.00±0.05O₃) by modeling the background as a combination of Shirley‐type (Shirley–Vegh–Salvi–Castle) and slope backgrounds through the active approach. The line‐shape employed to fit apparent peak asymmetries was the double‐Lorentzian. It was possible to resolve a previously unreported satellite located at ~729 eV. Copyright © 2016 John Wiley & Sons, Ltd.     

Coordination chemistry of 1,3,5-triaza-7-phosphaadamantane (PTA) and derivatives. Part II. The quest for tailored ligands,complexes and related applications

This review paper covers the recent developments (2004–2009) on the tailored synthetic modifications and related coordination chemistry of the water-soluble cage-like aminophosphine ligand 1,3,5-triaza-7-phosphatricyclo-[3.3.1.1]decane (PTA), together with the new applications in the fields of catalysis, material science and medicinal chemistry.     

Characterization of metal glycinate complexes by electrospray Q-TOF-MS/MS and their determination by capillary electrophoresis–ICP-MS: application to premix samples

A method was developed for the determination of metal complexes with glycine (glycinates, [M(Gly)_x(H₂O)_y(SO₄)_z]_n, where M denotes Zn, Cu, Mn and Fe) in premix samples used for the preparation of animal feeds enriched in essential trace elements. The method was based on the extraction of the glycinates with 10 mM ammonium acetate (pH 7.4) followed by their determination using capillary electrophoresis with ICP MS detection. The stability of the glycinates in solution was verified by electrospray TOF-MS. Each supplement was shown to be a mixture of complexes, with polymerization degrees ranging from n = 1 to n = 4 (depending on the metal), that were fully or partially dehydrated. The metal glycine complex moiety was found to be preserved during capillary electrophoresis. The detection limits, calculated as three times the standard deviation of the blank plus the blank, were between 0.05 and 0.2 μg mL⁻¹ (as the metal), and the calibration curves were linear, allowing the analysis of premix samples. Repeatability for glycinate standards was below 12%, and analytical precision was typically within 15%.     

A synthesis approach for reproducing the response of aircraft panels to a turbulent boundary layer excitation

Random wall-pressure fluctuations due to the turbulent boundary layer (TBL) are a feature of the air flow over an aircraft fuselage under cruise conditions, creating undesirable effects such as cabin noise annoyance. In order to test potential solutions to reduce the TBL-induced noise, a cost-efficient alternative to in-flight or wind-tunnel measurements involves the laboratory simulation of the response of aircraft sidewalls to high-speed subsonic TBL excitation. Previously published work has shown that TBL simulation using a near-field array of loudspeakers is only feasible in the low frequency range due to the rapid decay of the spanwise correlation length with frequency. This paper demonstrates through theoretical criteria how the wavenumber filtering capabilities of the radiating panel reduces the number of sources required, thus dramatically enlarging the frequency range over which the response of the TBL-excited panel is accurately reproduced. Experimental synthesis of the panel response to high-speed TBL excitation is found to be feasible over the hydrodynamic coincidence frequency range using a reduced set of near-field loudspeakers driven by optimal signals. Effective methodologies are proposed for an accurate reproduction of the TBL-induced sound power radiated by the panel into a free-field and when coupled to a cavity.     

M?ssbauer analysis of high-energy mechanical-milled sand fraction of a magnetic soil developing on basalt

A sample of the coarse sand fraction from the soil material of the A-horizon (0?C0.2 m from the soil surface) of a dusky red magnetic Oxisol was submitted to high-energy mechanical milling for different times. This assay aimed mainly at (a) monitoring the individualization of strongly aggregated mineral particles, and (b) measuring the effect of the milling pressure on the mineralogy changes of the material. These data are also intended to experimentally subside any physical model describing the mechanical behavior of the superficial soil layer that is subjected to intensive machine management, in agriculture fields. Powder X-ray data reveal that some mineralogical phases, notably gibbsite, disappear soon after the first few hours milling. The 298 K-transmission Mössbauer spectrum for the non-milled sand sample shows a qualitatively typical pattern for the sand fraction of basalt derived soils, with magnetically ordered sextets, assignable mainly to hematite and maghemite, and an intense central (super)paramagnetic Fe^3?+? doublet. For the milled samples, spectra revealed progressive spectral reduction of the magnetic hyperfine structure, with concomitant increase of relative subspectral areas due to (super)paramagnetic phases, as the milling time increased. This result is consistent with the reduction of measured saturation magnetization, from 4.96(8) J T^???1 kg^???1, for the non-milled sample, to 3.26(7) J T^???1 kg^???1, for the sample milled for 8 hours.     

Cadmium determination in biological samples by direct solid sampling flame atomic absorption spectrometry

A direct solid sampling flame atomic absorption spectrometric procedure for trace determination of cadmium in biological samples has been developed. Test samples (0.05–2.00 mg) were ground and weighed into small polyethylene vials, which were connected to the device for solid sample introduction into a conventional air/acetylene flame. Test samples were carried as a dry aerosol to a quartz cell, placed between the burner and the optical path, which had a perpendicular entrance and a slit in the upper part. The atomic vapor generated in the flame produced a transient signal that was totally integrated within 1 s. The effect of operating conditions and the extent of grinding on the analytical signal were evaluated. Background signals were always low and a characteristic mass of 0.29 ng Cd was obtained. Calibration was performed using different masses of solid certified reference materials. Results obtained for certified and in-house reference materials were typically within the 95% confidence interval of the certified and/or reference value, and the precision, expressed as relative standard deviation, was between 3.8 and 6.7%. The proposed system is simple and it might be adapted to conventional atomic absorption spectrometers allowing the determination of Cd in more than 80 test samples per hour, excluding weighing.     

Quantitative determination of trace concentration of organics in water by solvent extraction and fused silica capillary gas chromatography: aliphatic and polynuclear hydrocarbons

Solvent extraction procedures with six different solvents on aqueous model systems of aliphatic (C12-C22) and polynuclear aromatic hydrocarbons (PAHs: Naphthalene, acenaphtene, fluorene, phenanthrene, anthracene, fluoranthene and pyrene) were studied for the analysis in the trace concentration range (20-50 ng ml-1) by fused silica capillary gas chromatography. Recovery efficiencies, reproducibilities and detection limits for each analyte and procedure are reported. The effect of the PAHs on the extracting rate of the aliphatic hydrocarbons at the trace concentration range is discussed.