Mechanism optimization based on reaction rate rules

Accurate chemistry models form the backbone of detailed computational fluid dynamics (CFD) tools used for simulating complex combustion devices. Combustion chemistry is often very complex and chemical mechanisms generally involve more than one hundred species and one thousand reactions. In the derivation of these large chemical mechanisms, typically a large number of reactions appears, for which rate data are not available from experiment or theory. Rate data for these reactions are then often assigned using so-called reaction classes. This method categorizes all possible fuel-specific reactions as classes of reactions with prescribed rules for the rate constants. This ensures consistency in the chemical mechanism. In rate parameter optimizations found in the published literature, rate constants of single elementary reactions are usually systematically optimized to achieve good agreement between model performance and experimental measurements. However, it is not kinetically reasonable to modify the rate parameters of single reactions, because this will violate consistency of rate parameters of kinetically similar reactions. In this work, the rate rules, that determine the rates for reaction classes are calibrated instead of the rates of single elementary reactions leading to a chemically more consistent model optimization. This is demonstrated by optimizing an n-pentane combustion mechanism. The rate rules are studied with respect to reaction classes, abstracting species, broken C–H bonds, and ring strain energy barriers. Furthermore, the uncertainties of the rate rules and model predictions are minimized and the pressure dependence of reaction classes dominating low temperature oxidation is optimized.     

Mechanochemical preparation of kaempferol intermolecular complexes for enhancing the solubility and bioavailability

Abstract

In this study, complexes of kaempferol (KF) with polysaccharide arabinogalactan (AG) and disodium glycyrrhizinate (Na₂GA) were prepared through mechanochemical technique to improve the solubility and bioavailability of KF. The physicochemical properties and the interactions of KF with AG/Na₂GA were investigated through dissolution, SEM, XRD, and DSC studies. The reduction of particle sizes and destruction of crystal forms revealed the formation of solid dispersion which may have assisted the dissolution of the drug. The accelerated stability study showed higher stability for KF–Na₂GA complex. In vivo pharmacokinetic study was performed to observe the plasma drug concentrations for KF complexes. Mechanochemical complexation of KF with AG/Na₂GA improved the pharmacological activity as evident by the inhibitory potential of the complexes towards carbohydrate metabolic enzymes. In vivo studies were performed in STZ-induced diabetic mice, where the group treated with KF–AG complex showed better liver and kidney function and lower blood glucose levels than pure KF. Therefore, mechanochemical complexes of KF with polysaccharide or glycyrrhizate may serve as a promising formulation for the treatment of diabetes.     

Inverse modelling of an aneurysm’s stiffness using surrogate-based optimization and fluid-structure interaction simulations

Characterization of the mechanical properties of arterial tissues is highly relevant. In this work, we apply an inverse modelling approach to a model accounting for an aneurysm and the distal part of the circulation which can be modified using two independent stiffness parameters. For given values of these parameters, the position of the arterial wall as a function of time is calculated using a forward simulation which takes the fluid-structure interaction (FSI) into account. Using this forward simulation, the correct values of the stiffness parameters are obtained by minimizing a cost function, which is defined as the difference between the forward simulation and a measurement. The minimization is performed by means of surrogate-based optimization using a Kriging model combined with the expected improvement infill criterion. The results show that the stiffness parameters converge to the correct values, both for a zero-dimensional and for a three-dimensional model of the aneurysm.     

Compressive mechanical properties of HTPB propellant at low,intermediate, and high strain rates

Low, intermediate, and high strain rate compression testing (1.7 × 10^?4 to 2500 s^?1) of the hydroxyl‐terminated polybutadiene (HTPB) propellant at room temperature, were performed using a universal testing machine, a hydraulic testing machine, and a split Hopkinson pressure bar (SHPB), respectively. Results show that the stress linearly increases with strain at each condition; the increasing trend of stress at a given strain with the logarithm of strain rate changes from a linear to an exponential form at 1 s^?1. By combining these characteristics, we propose a rate‐dependent constitutive model which is a linearly elastic component as a base model, then multiplied by a rate‐dependent component. Comparison of model with experimental data shows that it can characterize the compressive mechanical properties of HTPB propellant at strain rates from 1.7 × 10^?4 to 2500 s^?1. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43512.     

Non-LTE thermodynamic properties for combustion processes

The nonequilibrium thermodynamic properties of a product-gas derived from fluidized combustion of Pittsburgh seam coal is obtained using a multitemperature statistical thermodynamic computer model. Concentrations of 18 species are determined as a function of translational temperature (500 < T < 2500 K), pressure (0.1, 1.0, and 10 atm), and vibrational-to-translational temperature ratios of 0.5, 1, 2, and 5. The rotational and electronic excitation temperatures are assumed equal to the translational temperature. The partition functions and usual thermodynamic properties are also calculated and a nonequilibrium Mollier diagram is presented. The multitemperature model assumes chemical equilibrium and therefore represents a first step in describing nonequilibrium combustion reactions in a semiclassical manner. The model can be applied to reactions via chemical kinetics and/or an extension to a multichemical nonequilibrium model. The results indicate the relative concentration of species usually considered to be pollutants, under the range of conditions examined.     

Directly operated valve for space cryostats

Space cryostats like that of the Infrared Space Observatory (ISO) need a number of valves for cryogen management at different temperature levels. The ISO cryostat was defined as a hybrid cooling system using liquid hydrogen and superfluid helium during the ISO phase A study. A directly electrically operated bistable latch-valve was developed and prequalification tested for application within the H₂ subsystem and the He ll subsystem of the ISO cryostat. This valve is operable at all temperatures between 1.7 and 300 K and with H₂ and He in all phases (liquid, superfluid, gaseous) occurring within the cryostat. The valve offers very high leak tightness at higher temperatures and sufficient leak-tightness even with He ll. The heat dissipation for actuating the valve at liquid helium temperatures is only 0.03 W s, a value which is, to our knowledge, not reached by any other valve of comparable size and application. The valve operating electrical pulse is shorter than 0.1 s and the valve is held in a closed as well as open position by permanent magnets without using electrical energy.     

Analysis of coal-derived liquid obtained by mild hydrogenation: 2. Neutral oil distilling at 343–464 °C

Coal-derived liquid, from Japanese Taiheiyo coal, obtained under mild hydrogenation was analysed to elucidate the chemical structure of parent coal. The n-hexane soluble neutral part was fractionated into 7 parts by vacuum distillation. The analysis of the lower three fractions has already been reported. The higher boiling three fractions, DS04 (5.1 wt% of neutral oil), DS05 (27.3 wt%) and DS06 (27.7 wt%) were separated by liquid chromatography according to hydrocarbon types and each sub-fraction was analysed by g.c. and g.c.-m.s. Saturates were most abundant and in the distribution of n-alkanes, even carbon number saturates were greater than those of odd carbon. Some sub-fractions contained tricyclic diterpanes, steranes and hopane type triterpanes. Mono-, di- and tri-aromatic diterpanes were also found. Two aromatic ring hydrocarbons with some naphthene rings were the most abundant type.