Changes in the product composition during the detonation of an unconfined volume of a combustible mixture

For a model problem the solution to which describes the main features of changes in the parameters of the medium in the detonation of an unconfined gas mixture charge of in the air, direct numerical simulation, without of simplifying assumptions on changes in the composition of the mixture, was performed to study changes in the composition of the detonation products, determine the limits of applicability of the chemical equilibrium mixture model, and verify a previously obtained sufficient condition of applicability of the chemical equilibrium mixture model. The results of determining the limits of applicability of the chemical equilibrium mixture model previously obtained using an approximate method were confirmed.     

Determination of the limits of applicability of the chemical equilibrium model to the detonation products of gas mixtures

The applicability of the model of a chemically equilibrium mixture to describing the evolution of the composition of the detonation products during their expansion in three typical problems involving oxygen- and air-based combustible mixtures is examined. For the detonation products of oxygen-based mixtures, the model of a chemical equilibrium mixture provides a good agreement with the kinetic calculations for all practically important initial conditions for these problems. For air-based mixtures, initial conditions at which such an agreement is observed are determined.     

PETN炸药爆轰产物状态方程的理论研究

 采用van der Waals等效单组分流体模型和Ross硬球微扰理论软球修正模型,计算爆轰气相产物的状态方程;用石墨相、金刚石相、类石墨液相和类金刚石液相4种相态描述凝聚成分,由Gibbs自由能最小原理确定不同状态下的凝聚产物相态。对爆轰产物混合系统采用自由能最小原理,通过化学平衡方程组求解炸药爆轰产物系统的平衡组分。使用该理论计算PETN炸药Chapman-Jouguet（CJ）点的爆轰参数,其值与实验值符合得很好;同时计算了以CJ点为起始点的等熵卸载线,并与传统的Jones-Wilkins-Lee（JWL）状态方程的计算结果进行比较,发现计算的γ值是单调递减的,而JWL状态方程计算的γ值却出现了“双峰”现象。分析认为,传统的JWL状态方程给出的“双峰”变化,是由其函数形式自身决定的,并不对应实际物理过程。     

Analysis of the Range of Applicability of Thermodynamic Calculations in the Engineering of Nitride Fuel Elements

The domains of applicability of thermodynamic calculations in the engineering of nitride fuel are analyzed. Characteristic values of the following parameters, which affect directly the concentration equilibration time, are estimated: nuclide production rate; characteristic times to local equilibrium in the considered temperature range; characteristic time needed for a stationary temperature profile to be established; characteristic time needed for a quasi-stationary concentration field to be established on a scale comparable to the size of a fuel pellet. It is demonstrated that equilibrium thermodynamic calculations are suitable for estimating the chemical and phase composition of fuel. However, a two-layer kinetic model should be developed in order to characterize the transport processes in condensed and gaseous phases. The process of diffusive transport needs to be taken into account in order to determine the composition in the hot region at the center of a fuel element.     

An asymptotic expansion of the nonlinear master equation

Recently, a nonlinear master equation has been suggested to account for the effect of diffusion in the fluctuations of nonlinear systems away from equilibrium. An asymptotic expansion of the solutions of this master equation in the inverse of the diffusion constant is presented. The applicability of the method is illustrated with several examples of model chemical reactions.     

Scalar dissipation rates in isothermal and reactive turbulent opposed-jets: 1-D-Raman/Rayleigh experiments supported by LES

Isothermal and reactive turbulent opposed flows are presented, which are appropriate to test the applicability and performance of models for turbulence, mixing, chemical reaction, and turbulence-chemistry interaction. Transient flow and scalar fields are measured using laser Doppler velocimetry and one-dimensionally resolved Raman/Rayleigh spectroscopy. Aside of statistical moments of temperature, mean species, and velocity components, scalar dissipation rate across the mixing and reaction layer is determined on a single-shot base. Using large eddy simulation in connection with a steady flamelet model, it is shown how numerical data can serve to estimate the influence of experimental noise upon a measured quantity, such as scalar dissipation. As a key result, it is shown that an increase in scalar rate of dissipation by chemical reactions is caused by a significant increase in the mixture fraction diffusivity, which outweighs the decrease in mixture fraction gradients. In mixture fraction space, local maxima of scalar dissipation rate are found on the rich side, which cannot be correctly reproduced by the steady flamelet model assuming equal species diffusivity. Furthermore, the impact of experimental noise on conditional probability density functions of scalar dissipation rate is shown (exemplary) to lead to erroneous conclusions from experimental data.     

An efficient approximate method for solving the problem of the establishment of chemical equilibrium in the products of explosion of gas mixtures

A method for calculating the changing composition of the explosion products in the case where the chemical equilibrium is absent but the bimolecular reactions are in quasi-equilibrium is developed. At each time step of numerical integration, the change in the total number of molecules in the system is calculated using a single differential equation written based on the selected kinetic mechanism. Then, the mixture composition is calculated under the assumption that the entropy of the mixture reaches its maximum value at a given internal energy, mass density, and molar mass. It is shown that the proposed method can be used to calculate the characteristics of explosive transformation processes after the induction period.     

Critical phenomena in the cellular mode of filtration combustion in the presence of heat loss

Critical conditions for combustion failure due to heat loss to the environment are examined. The process of filtration combustion is considered under conditions where a cellular structure of the front is realized, because the planar combustion front loses its stability and splits into separate cells of exothermic chemical conversion, which propagate in self-sustained mode. The size and structure of the cells of chemical interaction depend nonlinearly on the governing parameters, including the rate of heat loss to the environment. Within the framework of a mathematical model of filtration combustion, the steady-state dynamics of the combustion process and the structure of the cell of exothermic chemical reaction of a powder mixture with a gaseous reagent with the formation of solid products are simulated. The specifics of the evolution of the cell before combustion failure as a function of the heat loss rate are studied.     

固体炸药爆轰的一种考虑热学非平衡的反应流动模型

基于固体炸药爆轰过程中化学反应混合区内的固相反应物与气相生成物处于力学平衡状态及热学非平衡状态的事实,提出一种考虑热学非平衡效应的反应流动模型来描述固体炸药的爆轰流动现象.该爆轰流动模型的主要特点是,在反应混合物Euler方程和固相反应物质量守恒方程的基础上,通过附加一套关于固相反应物的组分物理量的流动控制方程来表达固相反应物与气相生成物之间的热学非平衡效应.根据反应混合区内固相反应物与气相生成物这两种化学组分保持各自内能守恒的混合规则,并借助它们具有压力相等的性质以及满足体积分数总和为1的条件,推导获得的附加方程有：固相反应物的内能演化方程、体积分数演化方程及反应混合物的压力演化方程.这样,建立的爆轰模型包括：反应混合物的质量守恒方程、动量守恒方程、总能量守恒方程、压力演化方程,以及固相反应物的质量守恒方程、内能演化方程、体积分数演化方程.对所获得的爆轰模型方程组采用一个时空二阶精度的有限体积法进行数值求解,典型爆轰问题算例结果表明本文提出的固体炸药爆轰模型是合理的.     

The polarization of chemical reactions

Microwaves have been widely used in organic chemical syntheses, but the mechanism is still unclear. The aim of this paper is to study the polarization of polar molecule reactions in the liquid phase. A novel model is proposed to describe the polarization of chemical reactions. In this model, the polarization is expressed by the summation of the orientational polarization of the liquid mixture and the polarization increment due to the chemical process. On the basis of the assumption of local equilibrium, the chemical process is divided into a series of equilibrium systems. We derive the general expression for the polarization increment according to the mass balance equations. By considering a simple chemical process, we give a specific expression for the polarization. Copyright © 2015 John Wiley & Sons, Ltd.     

Experimental study of incomplete oxidation of methane in a ring channel

Chemical transformations at incomplete methane oxidation in the air medium were studied experimentally at reaction activation on the wall of an annular microchannel. Methane was oxidized incompletely on a rhodium catalyst deposited on an inner wall of the channel. Concentrations of the products of chemical transformations were measured in the outlet gas mixture for different reactor temperatures and stay times. We have determined the range of channel wall temperatures and stay times of the mixture corresponding to an increase in the portion of hydrogen and carbon dioxide indicating transition from predominant methane combustion to cascade chemical reactions with activation of steam and carbon dioxide methane conversions. It is shown that the kinetic model of chemical transformations of methane in the air medium depends significantly on the temperature of channel walls and stay time of the mixture. The effect of outer diffusion deceleration on the rate of chemical transformations at incomplete methane oxidation under the strained conditions is determined. The work was financially supported by the Russian Foundation for Basic Research (Grant No. 05-08-65526).     

A mixing controlled direct chemistry (MCDC) model for diesel engine combustion modelling using large eddy simulation

A mixing controlled direct chemistry (MCDC) combustion model with sub-grid scale (SGS) mixing effects and chemical kinetics has been evaluated for Large Eddy Simulation (LES) of diesel engine combustion. The mixing effect is modelled by a mixing timescale based on mixture fraction variance and sub-grid scalar dissipation rate. The SGS scalar dissipation rate is modelled using a similarity term and a scaling factor from the analysis of Direct Numerical Simulation (DNS) data. The chemical reaction progress is estimated from a kinetic timescale based on local internal energy change rate and equilibrium state internal energy. An optical research engine operating at conventional operating conditions and Low Temperature Combustion (LTC) conditions was used for evaluation of the combustion model. From the simulation results, the effect of SGS scalar mixing is evaluated at different stages of combustion. In the context of LES, the new approach provides improved engine modelling results compared to the Direct Chemistry Solver (DCS) combustion model.     

A study of the characteristics of the combustion of a Ti +0.5C granular mixture in an inert gas flow

The characteristics of the combustion of a Ti +0.5C granular mixture in a quartz tube under conditions of blowing with argon are studied. The gas flow (cocurrent filtration) is provided by a fixed pressure drop (<1 atm) across the feedstock bed. The dynamics of gas evolution during the combustion the Ti + 0.5C granular mixture, both in the presence and absence of blowing is investigated. The blowing is demonstrated to influence the chemical and phase composition of the condensed synthesis products. It is shown that blowing the Ti + 0.5C granular mixture with a cocurrent argon flow of increases the burning rate.     

爆轰产物物态方程及CHBr3相变的理论研究

 由吉布斯自由能最小计算处于化学平衡状态的气体和固体混合系统的平衡组分。以BKW和VLW作为爆轰产物的物态方程对几种炸药爆轰参数作了预言，计算结果与实验值吻合得非常好。另外，还对CHBr₃的冲击压缩分解作了化学平衡计算，给出了冲击压缩曲线，对文献[6]中提出的CHBr₃在55~60 GPa存在相变的看法提出了质疑。     

火星进入热环境预测的热力学模型数值分析

采用数值模拟目的 研究不同热力学模型中火星飞行器表面的热环境.研究发现,驻点区域流动近似为热力学平衡,随着飞行高度增加,流动逐渐偏向热力学非平衡.当壁面为非催化壁时,不同热力学模型所得热流基本一致,当壁面为完全催化壁时,热力学非平衡模型所得热流更高,这种差异由化学反应特征温度差异引起,并随着流动的热力学非平衡特性增加而增加.     

热解碳化学气相沉积中的多重定态和非平衡相变的研究

讨论在热解碳化学气相沉积过程中出现的多重定态和非平衡相变这一典型的非平衡物理现象的机理和发展趋势.通过理论分析和实验结果的分析发现热解碳化学气相沉积的化学反应是一个典型的非平衡化学反应,其中在沉积过程中出现的生成碳黑的过程是一个典型的非平衡相变.在这一非平衡化学反应中,自由基的反应模型符合Schlogl模型.在这一非平衡化学反应中,有线性区和非线性区,线性区的产物是热解碳,而非线性区是碳黑.在线性区,反应速率方程是唯一的、线性的,而在非线性区,反应速率方程是多重的、非线性的. 关键词： 非平衡化学反应 非平衡相变 化学气相沉积 Schlogl模型 热解碳     

Effect of viscosity on stability and accuracy of the two-component lattice Boltzmann method with a multiple-relaxation-time collision operator investigated by the acoustic attenuation model

A two-component lattice Boltzmann method (LBM) with a multiple-relaxation-time (MRT) collision operator is presented to improve the numerical stability of the single relaxation time (SRT) model. The macroscopic and the momentum conservation equations can be retrieved through the Chapman—Enskog (C-E) expansion analysis. The equilibrium moment with the diffusion term is calculated, a diffusion phenomenon is simulated by utilizing the developed model, and the numerical stability is verified. Furthermore, the binary mixture channel model is designed to simulate the sound attenuation phenomenon, and the obtained simulation results are found to be consistent with the analytical solutions. The sound attenuation model is used to study the numerical stability and calculation accuracy of the LBM model. The simulation results show the stability and accuracy of the MRT model and the SRT model under different viscosity conditions. Finally, we study the influence of the error between the macroscopic equation of the MRT model and the standard incompressible Navier—Stokes equation on the calculation accuracy of the model to demonstrate the general applicability of the conclusions drawn by the sound attenuation model in the present study.     

混合物冲击压缩后平衡态的研究

 将混合物组元颗粒在三维网格内按组元比例随机分布,采用热动力学有限元数值方法,对其冲击压缩过程进行数值模拟。研究了混合物在冲击压缩下趋于热动力平衡过程、热平衡特征时间、压力平衡特征时间和平衡后的热力学状态,得出热平衡特征时间与颗粒度的平方近似成正比,而力平衡特征时间与颗粒度近似成正比。数值模拟了多种合金的冲击压缩特性,其结果与混合物物态方程的体积相加模型、一次冲击绝热线的叠加原理和实验等不同方法获得的结果作了比较,除冲击温度外,各方法得到的结果一致;体积相加模型和叠加原理不能给出合理的混合物冲击温度,但数值模拟能给出合理的混合物冲击温度。     

Numerical Method and Composition at and out of Chemical Equilibrium in a Multitemperature Plasma. Application to a Pure Nitrogen Plasma

The disequilibrium between the temperatures (excitation, rotation, vibration, translation) in plasmas lead us to specific chemical potentials. Then, they are used to develop a mass action law in a multitemperature plasma. This mass action law enables us to determine the composition of a pure nitrogen mixture out of thermal equilibrium. The composition evolution versus time is determined from a kinetic method modified to take into account different temperature hypotheses. The composition and different thermodynamic properties of a pure nitrogen mixture are given at the chemical equilibrium, then versus time for various temperature hypotheses and thermal disequilibriums.