Dynamic simulation of the hydrodynamic interaction among immersed particles in Stokes flow

A numerical method for the dynamic simulation of the hydrodynamic interaction among particles in Stokes flow is developed. The method couples the quasi-static Stokes equations for the fluid with the equilibrium equations for the particles. The boundary element method is used to represent the velocity at a general field point in terms of surface velocities and stresses. However, neither the stresses nor the velocities are assumed to be known on the surface of the particles. Kinematic equations relating the linear and angular velocities at the centroids of the particles to the surface velocities are combined with the discretized boundary element equations and the equilibrium equations to generate a system of linear equations. The associated coefficient matrix is correspondent to the grand resistance matrix which relates the velocities of the particles to a given geometry.     

Three-stage auto-ignition of n-heptane and methyl-cyclohexane mixtures at lean conditions in a flat piston rapid compression machine

One approach to enhancing the thermal efficiency of combustion systems is to burn fuels at ultra-lean conditions (equivalence ratio below 0.5). It has been recently reported that the auto-ignition of some hydrocarbon fuels, under specific temperature, pressure, and mixture conditions, releases heat in three distinctive stages. The three auto-ignition stages can be divided as a first low-temperature auto-ignition stage with conventional low temperature, and a high-temperature stage separated into two sub-stages. This study presents ignition delay time measurements of n-heptane and methyl-cyclohexane (MCH) mixtures in a flat piston rapid compression machine (RCM) under ultra-lean conditions. It provides experimental evidence of three-stage auto-ignition. This phenomenon of delayed high-temperature heat release is seldom reported in the literature and this is the first time to be reported for these types of fuels. The experiments cover two binary n-heptane/MCH mixtures of 15/85 and 70/30 by volume, pressures of 11 bar and 16 bar, temperature range of 700 to 900 K, and equivalence ratio of 0.4. The RCM optical access was utilized for high-speed chemiluminescence imaging. Detailed chemical kinetic simulations in a homogenous batch reactor with variable volume were conducted to further interrogate the three-stage auto-ignition phenomenon. Chemiluminescence shows that three-stage auto-ignition occurs in the adiabatically compressed end-gas, which indicates that this phenomenon is chemically-driven and is not induced by a thermal stratification in the RCM experiments. The model predicts the features of three-stage auto-ignition, which were experimentally observed at temperatures approximately below 750 K. As expected, significant discrepancies are observed in the ignition delays of experiment and simulation in the negative temperature coefficient (NTC) region. The simulation of the n-heptane/MCH 70/30 mixture shows better agreement with experiments in the Positive Temperature Coefficient (PTC) region compared to the 15/85 mixture.     

Lumineszenzdatierung als Schlüssel zur Vergangenheit

In this article, we describe the basic principles of luminescence dating, for which knowledge and methods of solid state physics and radiochemistry play a major role. The type of dated event – the last heating or daylight exposure – opens up a broad spectrum of applications of this method for periods ranging from 10² up to several 10⁵ years. Through the cooperation of dating specialists with geoscientists and archaeologists, luminescence dating is nowadays an essential tool for addressing problems in Earth‐science and human history.     

ChemInform Abstract: Investigation of Praseodymium Fluorides: A Combined Matrix‐Isolation and Quantum‐Chemical Study.

Reaction products of laser‐ablated praseodymium atoms with fluorine in excess neon, argon, krypton, or neat fluorine at 4—10 K are investigated by IR spectroscopy and quantum chemical DFT and coupled‐cluster calculations.     

Selective area laser deposition of FCC beta silicon carbide

Silicon Carbide (SiC) has been deposited onto an alumina substrate by the thermal decomposition of the gaseous precursor tetramethylsilane (TMS). A 500 W ytterbium fibre laser was used to heat the surface of an alumina substrate locally, resulting in deposition of SiC at the sample surface. The SiC deposit was analysed using energy dispersive X‐ray spectroscopy and X‐ray diffraction (XRD). The deposit was confirmed to be silicon carbide and found to be face centre cubic (FCC) crystal structure. Raman spectroscopy was used to measure the stoichiometry of the deposit which initially was found to be carbon rich. Further analysis by Raman spectroscopy suggests the deposit may be more stoichiometric following a two hour thermal treatment of the sample at 600 degrees celcius in an atmosphere of air.     

Imines in the Titanium Coordination Sphere – Transformation of Imidoyl Chlorides to Nitrilium Ions

In the reaction of TiCl₄ in benzene as solvent with the imidoyl chloride p‐Tolyl(Cl)C=NPh ( 1 ) the abstraction of the chloride substituent is observed, leading to the nitrilium salt [p‐Tolyl–C≡N–Ph]⁺[Ti₂Cl₉]^– ( 2 ) in quantitative yield. The highly electrophilic salt 2 is characterized by IR‐ and NMR spectroscopy. The observed band for the C≡N stretching mode of 2 clearly indicates the formation of a nitrilium ion. Especially a characteristic line broadening of the ¹³C{¹H}‐NMR signals related to carbon atoms next to the nitrogen is observed. By ¹⁵N,¹H‐HMBC NMR experiments it is shown that the nitrogen signal of 2 is significantly shifted to high‐field in relation to nitriles and imines. The molecular structure of 2 was confirmed by single‐crystal X‐ray diffraction. The C≡N bond length and the linearity of the C–C≡N–C unit in 2 confirm the triple bond character of this bond.     

Activation of Molecular Hydrogen by Bis(η5,η1‐pentafulvene)‐titanium Complexes – Efficient Formation of Titanium(III)hydrides

The synthesis and crystal structures of two dinuclear titanocene hydride complexes are reported. Both complexes, namely bis(η⁵‐(di‐para‐tolylmethyl)cyclopentadienyl)titanium hydride dimer, [(η⁵‐C₂₀H₁₉)₂Ti(μ‐H)]₂ ( 2a ), and bis(η⁵‐2‐adamantylcyclopentadienyl)‐titanium hydride dimer, [(η⁵‐C₁₅H₁₉)₂Ti(μ‐H)]₂ ( 2b ), are formed via activation of molecular hydrogen by the corresponding bis(η⁵,η¹‐pentafulvene)titanium complexes 1a and 1b at ambient temperatures and pressures in high yields. The hydride complexes 2a and 2b exhibit planar [Ti₂H₂] cores and, as a result of the heterolytic cleavage of molecular hydrogen, substituted Cp Ligands were formed during the reaction.     

Factors determining the chemoselectivity of phosphorus-modified palladium catalysts in the hydrogenation of chloronitrobenzenes

The precursor nature effect on the state of the Pd–P surface layer in palladium catalysts and on their properties in the liquid-phase hydrogenation of chloronitrobenzenes under mild conditions has been investigated. A general feature of the Pd–P-containing nanoparticles obtained from different precursors and white phosphorus at P/Pd = 0.3 (PdCl₂ precursor) and 0.7 (Pd(acac)₂ precursor) is that their surface contains palladium in phosphide form (BE(Pd3d _5/2) = 336.2 eV and BE(Р2р) = 128.9 eV) and Pd(0) clusters (BE(Pd3d_5/2) = 335.7 eV). Factors having an effect on the chemoselectivity of the palladium catalysts in chloronitrobenzenes hydrogenation are considered, including the formation of small palladium clusters responsible for hydrogenation under mild conditions.