Analytical pyrolysis with in situ thermally assisted derivatisation, Py(HMDS)-GC/MS, for the chemical characterization of archaeological birch bark tar

An analytical method based on pyrolysis in the presence of hexamethyldisilazane followed by gas chromatographic/mass spectrometric analysis, Py(HMDS)-GC/MS, was used for the first time to study birch bark tar, an adhesive that has been used since the Palaeolithic period. Py(HMDS)-GC/MS enabled us to obtain information simultaneously both on polymerised and solvent soluble fractions of birch bark tar. A very particular chromatographic pattern was obtained, which was mainly characterised by the presence of homologous series of linear saturated and unsaturated monocaboxylic fatty acids, and homologous series of straight-chain alkenes and alkanes. The pattern can be linked to suberin and suberan, which are known to be present in birch barks. In addition, lupane-type triterpenoids were also revealed. Py(HMDS)-GC/MS was initially applied to a reference material, and was then used to study the archaeological adhesives from a wooden spindle recovered in a Gallo-Roman burial (3rd century AD) and from the golden sheath of a Thracian dagger (8th-7th centuries BC) recovered in Belogradets (Bulgaria).     

ps-LIF measurements of minor species concentration in a counterflow diffusion flame interacting with a vortex

Interactions of vortices and flame fronts may be considered as the basic structural elements of turbulent combustion. Additionally, they play an important role in flame instabilities as well as extinction and ignition processes. An ideal geometry to study these interactions is the counterflow diffusion burner with an additional actuator-driven nozzle for the generation of a vortex ring. This burner has already been well-characterized by other methods including CARS, LDA and PLIF. We present first quantitative measurements of minor species concentration in this flame using a short-pulse laser and time- and spatially resolved fluorescence detection with a streak camera. Quench-free OH concentrations are obtained by analysis of the time-resolved profiles. The high power density of the laser pulses allowed linewise detection of hydrogen using a three-photon excitation scheme. Simultaneously, shape and position of the vortex was monitored using two-dimensional detection of flame emissions. Spatially resolved concentration profiles of H and OH are presented for different interaction heights and times in the vortex. For steady flames, comparisons with model calculations are shown. Received: 19 July 2000 / Revised version: 13 December 2000 / Published online: 21 February 2001     

Vinyl polymerization of norbornene catalyzed by 2‐Py‐amidine Ni(II) complex/methylaluminoxane systems

Two 2‐Py‐amidine ligands (2‐Py―NH―C(Ph)═N―Ar, Ar = 2,6‐Me₂C₆H₃ and 2,6‐ⁱPr₂C₆H₃) and the corresponding Ni(II) complexes ( 1 and 2 ) were synthesized and characterized using elemental analysis and FT‐IR, UV–visible, ¹H NMR and ¹³C NMR spectroscopies. X‐ray crystal structures indicate that the chelate ring conformation of the less bulky complex 1 is relatively planar compared with that of the bulky complex 2 . Paramagnetic ¹H NMR and ¹³C NMR studies show that, in solution, the time‐average structures of complexes 1 and 2 have mirror symmetry. Both complexes 1 and 2 were used as catalyst precursors for norbornene polymerization with methylaluminoxane as a co‐catalyst. The effects of Al/Ni ratio, temperature and structure of precursors on the catalytic performance were investigated. Copyright © 2014 John Wiley & Sons, Ltd.     

Solubility of Propene in Water and in a Mineral Medium for the Cultivation of a XanthobacterStrain

Solubility measurements of propene in water at atmospheric pressure and at thirteen temperatures in the range 293.15–323.15 K were carried out with a precision of 0.3%, using an apparatus based on the saturation method. The mole fractions, at a gas partial pressure of 101.325 kPa, were fitted to a Clarke–Glew–Weiss equation, which was used to calculate the standard molar Gibbs energy, enthalpy, and entropy changes for the process of transferring the propene molecules from the gaseous to the water phase. Solubility measurements of propene in the growth medium ofXanthobacter Py2 at 298.15, 303.15, and 308.15 K were also carried out at atmospheric pressure. These experimental data, expressed in Ostwald coefficients at the total pressure of 101.325 kPa, were about 2% lower than their water counterparts.     

Spatially resolved absolute concentration and fluorescence-lifetime determination of H2CO in atmospheric-pressure CH4/air flames

Using laser-induced fluorescence (LIF), spatially resolved concentration profiles of formaldehyde (H₂CO) were obtained in the preheating zone of atmospheric-pressure premixed CH₄/air flames stabilized on the central slot of a multiple-slot burner similar in construction to domestic boilers. The isolated pQ₁(6) rotational line (339.23 nm) in the 2¹ ₀4¹ ₀ vibronic combination transition in the ?¹A₂- ¹A₁ electronic band system around 339 nm was excited in the linear LIF intensity regime. For a quantification of quenching effects on the measured LIF signal intensities, relative fluorescence quantum yields were determined from direct fluorescence lifetime as a function of height above the slot exit. Absolute H₂CO number densities in the flames were evaluated from a calibration of measured LIF signal intensities versus those obtained in a low-pressure sample with a known H₂CO vapor pressure. Peak concentrations in the slightly lean and rich flames reached (994±298) and (174±52) ppm, respectively. Received: 25 September 2000 / Published online: 30 November 2000     

Compressible Rayleigh-Taylor Instability with Preheat in Inertial Confinement Fusion

The compressible Rayleigh-Taylor instability of accelerated ablation front is analysed in consideration of the preheat effects, and the corresponding eigen-problem is solved numerically using the fourth-order accurate two- point compact difference scheme. Both the growth rate and perturbation profiles are obtained, and the obtained growth rate is close to the results of direct numerical simulation. Our results show that the growth rate is more reduced and the cutoff wave length becomes longer as preheat increases.     

Effect of scalar nonlinearity on zonal flow generation by Rossby waves

Effects of scalar nonlinearity on the generation of zonal flow by Rossby waves in shallow rotating fluid are considered. Zonal flows are generated via the action of Reynolds stress due to vector nonlinearity together with the effects of scalar nonlinearity. It is shown that the scalar nonlinearity reduces the amplitude threshold of the zonal flow instability. In addition, it increases the range of wave vectors of unstable modes subjected to the instability. The growth rate of the instability as a function of the spectrum of primary waves is calculated. The spectrum is assumed to be arbitrary with emphasizing the case of two monochromatic waves.