Evaluation of toluene LIF thermometry detection strategies applied in an internal combustion engine

In the context of toluene laser-induced fluorescence (LIF) thermometry, the two common LIF detection strategies, namely one-color and two-color detection, have been simultaneously applied to compare each strategy’s ability to accurately resolve thermal gradients during an engine cycle within an optically accessible internal combustion (IC) engine. Temperature images are obtained from high-speed toluene LIF measurements and are combined with high-speed particle image velocimetry. The combination with flow data and Mie scattering images facilitates the interpretation of differences between the toluene LIF detection strategies. Two-color temperature images are limited in their ability to detect thermal gradients near the end of compression due to larger precision uncertainties. Local regions of cold gases in the two-color images are better identified with the guidance of the one-color images when homogeneous toluene mixtures preside. During expansion, large differences exist between one- and two-color temperature images and likely caused by local mixture fraction heterogeneities that bias the one-color detection strategy. Toluene condensation occurs during the expansion and exhaust stroke and causes local mixture fraction heterogeneities in the combustion chamber. Liquid toluene is in contact with solid surfaces and crevices of the combustion chamber and can evaporate during compression or expansion causing both local temperature and mixture stratification. This work demonstrates the advantage of high-speed imaging and use of multiple image diagnostics to reveal the development of natural temperature and mixture stratification in a motored IC engine. This work also suggests that natural temperature stratification typically regarded from gas-wall heat transfer may also be caused by liquid droplet evaporation on solid surfaces. Such phenomenon, however, is expected to be pertinent for all modern-day engine operating systems.     

Sterisch gehinderte Stickstoffbasen zur selektiven Extraktion von Silber

Zusammenfassung Lösungen von sterisch gehinderten Pyridinbasen wie 4-Octadecylthio-2,6-dimethylpyridin (= Lut-S-18 = III) und anderen sterisch gehinderten aliphatischen (und cycloaliphatischen) Stickstoffbasen in Heptanon-3 werden für die radiochemisch verfolgte Extraktion von Silber(I)-Ionen aus wäßriger Lösung eingesetzt. In Gegenwart von 0,5 M NaNO₃ extrahiert die Pyridinbase Lut-S-18 im pH-Bereich 5–10 bis zu 88% des Silbers in einem einzelnen Extraktionsschritt. Das Extraktionsmittel Lut-S-18 ist selektiv für Silber in dem Sinne, daß unter den genannten Bedingungen die Aquokationen Co²⁺, Ni²⁺, Cu²⁺ und Zn²⁺ nur in sehr geringem Ausmaß extrahiert werden. Die Rückextraktion des Silbers aus der organischen Phase kann leicht mit verdünnter Ammoniak-Lösung durchgeführt werden. Die Amine 3-Amino-2,4-dimethylpentan und 2,2,6,6-Tetramethylpiperidin sind auch gute Extraktionsmittel für Silber, aber sie wirken weniger selektiv.

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Sterically hindered nitrogen bases for the selective extraction of silver

Summary Heptanone-3 solutions of sterically hindered pyridine bases such as 4-octadecylthio-2,6-dimethylpyridine (= Lut-S-18=III) and of other sterically hindered aliphatic (and cycloaliphatic) nitrogen bases are used for the radiochemically monitored extraction of silver(I) ions from aqueous solution. In the presence of 0.5 M NaNO₃ the pyridine base Lut-S-18 extracts up to 88% of the silver in a single extraction step in the pH range 5–10. The extraction agent Lut-S-18 is selective for silver in the sense that under the conditions described the aquo cations Co²⁺, Ni²⁺, Cu²⁺, and Zn²⁺ are extracted to a very minor extent only. Back extraction of the silver from the organic phase is easily achieved with dilute ammonia solution. The amines 3-amino-2, 4-dimethylpentane and 2,2,6,6-tetramethylpiperidine are also good extraction agents for silver, but they are less selective.

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Herrn Prof. Dr. K. H. Lieser zum 65. Geburtstag gewidmet

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Die Autoren danken der Deutschen Forschungsgemeinschaft und dem Verband der Chemischen Industrie e.V. für Unterstützung sowie der Firma E. Merck, Darmstadt, für Zusammenarbeit. Die Durchführung der radiochemischen Messungen wurde durch das Entgegenkommen der Arbeitsgruppe von Herrn Prof. Dr. K. H. Lieser wesentlich erleichtert. Einige der aliphatischen Stickstoffbasen wurden freundlicherweise von der Fa. Hüls zur Verfügung gestellt.     

A kinetic study of the air oxidation of pyrogallol and purpurogallin

Pyrogallol (1,2.3-benzentriol, 1 ) reacts with dioxygen in weakly alkaline solutions to form purpurogallin (2,3,4,6-tetrahydroxy-5H-benzocycloheptene-5-one, 2 ) which then reacts to form purpurogalloquinone ( 3 ) which then decays to a product absorbing at 440 nm. The formation of 3 requires 1.5 mol O₂ per mol 1 , and 1.0 mol per mol 2 . No O₂ is consumed during the decay of 3 , and this reaction, being insensitive to O₂ concentrations and the presence of both superoxide dismutase (SOD) and catalase, does not appear to be an oxidation. The first-order rate of decay of 3 decreases with increasing pH. 1 and 3 react at pH 9.0 with a second-order rate constant of ca. 100 M^?1 s^?1. SOD inhibits the oxidation of 1 and 2 . Slight and variable apparent inhibition of the oxidation of 2 and 3 by SOD may be due to trace impurities in 2 , but not contamination by 1 . The peak concentration of 3 is attained more rapidly during the oxidation of 1 than during the oxidation of 2 . A kinetic scheme based on parallel oxidation of 1 by dioxygen and superoxide, and it which the semiquinone of 1 oxidizes 2 , is partially successful in simulating the observed kinetic behavior.     

Atom transfer radical polymerization of methyl methacrylate using copper-based homogeneous and heterogeneous catalysts

This study aimed at polymerization of methyl methacrylate with novel catalysts in the atom transfer radical polymerization (ATRP) condition at 90 °C. This was accomplished using CuBr/N-(2-aminoethyl)-3-aminopropyltrimethoxysilane (CuBr–AEAPTMS) as a homogeneous catalyst and one time with CuBr@AEAPTMS/SBA-15 as a heterogeneous catalyst. Catalysts were characterized using TGA, FT-IR, and UV–Vis spectroscopy. The structural analysis of the polymer was carried out by ¹³C NMR spectroscopy and GPC. Three characteristic parts of polymer produced by ATRP method including the initiator, monomer units, and end group was shown in ¹³C NMR spectra. In addition, the presence of C–Br unit showed that the polymerization process is alive. The ¹H NMR analysis was used for kinetic investigation of methyl methacrylate polymerization with homogeneous and heterogeneous catalysts that showed high monomer conversion (98 and 90% after 35 min, respectively) and good control of molecular weight with a dispersity (Р= 1.5–1.7). In addition, the plot of ln ([monomer]₀/[monomer] _t ) versus time gave linear relationships indicating a constant concentration of the propagating species throughout the polymerization. Finally, the results of the polymerization using heterogeneous catalyst compared with homogeneous catalyst revealed that it was according to ATRP method.     

Microwave-assisted synthesis of novel 2,3-dihydro-4-pyridinones

Novel 2,3-dihydro-4-pyridinones were synthesized via the reaction of curcumin and primary amines or amine acetates under microwave irradiation. Montmorillonite K-10 was used as a catalyst. Reaction times did not exceed 120 s. The structures of the compounds were established by elemental analysis and from their mass, 1H- and 13C-NMR spectra.     

Spectrophotometric determination of copper(II) in pharmaceutical,biological and water samples by 4-(2′-benzothiazolylazo)-salicylic acid

A highly sensitive method is proposed to determine copper(II) ions by forming a stable complex through their interaction with 4-(2′-benzothiazolylazo)-salicylic acid (BTAS) at room temperature and pH of about 5.0. The complex gave a maximum absorption at λ = 485 nm with a molar absorptivity coefficient of 2.35·10⁴ l/(mol·cm). The linear range for the copper determination is 0.63–5.04 mg/l. The method can be applied to determine copper ions in different biological specimens like some drugs and water samples.     

Search for sub-eV mass solar axions by the CERN Axion Solar Telescope with 3He buffer gas

The CERN Axion Solar Telescope (CAST) has extended its search for solar axions by using (3)He as a buffer gas. At T=1.8 K this allows for larger pressure settings and hence sensitivity to higher axion masses than our previous measurements with (4)He. With about 1 h of data taking at each of 252 different pressure settings we have scanned the axion mass range 0.39 eV?m(a)?0.64 eV. From the absence of excess x rays when the magnet was pointing to the Sun we set a typical upper limit on the axion-photon coupling of g(aγ)?2.3×10(-10) GeV(-1) at 95% C.L., the exact value depending on the pressure setting. Kim-Shifman-Vainshtein-Zakharov axions are excluded at the upper end of our mass range, the first time ever for any solar axion search. In the future we will extend our search to m(a)?1.15 eV, comfortably overlapping with cosmological hot dark matter bounds.     

Extinction coefficient imaging of turbid media using dual structured laser illumination planar imaging

We demonstrate a technique, named dual structured laser illumination planar imaging (SLIPI), capable of acquiring depth-resolved images of the extinction coefficient. This is achieved by first suppressing the multiply scattered light intensity and then measuring the intensity reduction caused by signal attenuation between two laser sheets separated by Δz mm. Unlike other methods also able to measure this quantity, the presented approach is based solely on side-scattering detection. The main advantages of dual SLIPI is that it accounts for multiple scattering, provides two-dimensional information, and can be applied on inhomogeneous media.     

Obtaining certificates for complete synchronisation of coupled oscillators

In this paper, we provide a novel reformulation of sufficient conditions that guarantee global complete synchronisation of coupled identical oscillators to make them computationally implementable. To this end, we use semidefinite programming techniques. For the first time, we can efficiently search for and obtain certificates for synchronisability and, additionally, also optimise associated cost functions. In this paper, a Lyapunov-like function (certificate) is used to certify that all trajectories of a networked system consisting of coupled dynamical systems will eventually converge towards a common one, which implies synchronisation. Moreover, we establish new conditions for complete synchronisation, which are based on the so called Bendixson’s Criterion for higher dimensional systems. This leads to major improvements on the lower bound of the coupling constant that guarantees global complete synchronisation. Importantly, the certificates are obtained by analysing the connection network and the model representing an individual system only. In order to illustrate the strength of our method we apply it to a system of coupled identical Lorenz oscillators and to coupled van der Pol oscillators.     

Fabrication, characterization, and measurement of viscosity of α-Fe2O3-glycerol nanofluids

Magnetic nanofluids, ferrofluids, are a special category of smart nanomaterials, consisting of stable dispersion of magnetic nanoparticles in different fluids. In this study, magnetic nanoparticles of hematite, α-Fe₂O₃, were prepared by solvothermal method using Fe(NO₃)₃ as a starting material. The nanoparticles were characterized by X-ray diffraction (XRD) and transmission electronic microscope (TEM).To the best of our knowledge, this is the first research on the rheological properties of nanofluids of α-Fe₂O₃ nanoparticles and glycerol. The experimental results showed that the viscosity of α-Fe₂O₃-glycerol nanofluids increases with increasing the particle volume fraction and decreases with increasing temperature. Our results clearly showed that the α-Fe₂O₃-glycerol nanofluids are non-Newtonian shear-thinning and their shear viscosity depends strongly on temperature. The experimental data were compared with some theoretical models. The measured values of the effective viscosity of nanofluids are underestimated by the theoretical models.