Mathematical Modeling of Aluminum Diboride Combustion in an Air Flow

A mathematical model and the results of calculating the ignition and combustion of energetic condensed systems based on mono- and polydispersed aluminum diboride particles in air flows in constant-cross-section channels are reported. The kinetic characteristics of the transformations that separate aluminum diboride particles formed by gasification of energetic condensed systems undergo in a high-temperature oxidizing medium were determined using the dependences of the ignition induction period and combustion time on the air temperature and diameter and initial temperature of the particles. These dependences, in turn, were calculated using the model of parallel chemical reactions. The range of combustion conditions corresponding to the initial air temperatures from 300 to 2000 K and Mach numbers in the channel from 0.1 to 1.5 was considered. The influence of the aluminum diboride particle size and of the rate and initial temperature of the air flow on the combustion efficiency was demonstrated. The relationships between the combustion completeness factor of aluminum diboride particles at various initial parameters of the air flow and gasification products of energetic condensed systems at various fuel mixture equivalence ratios, corresponding to the diffusion and kinetic combustion, were determined. The conditions of the transition between the diffusion and kinetic control modes were found.

     

Combustion of aluminum particles in a high-temperature furnace under various O2/CO2/H2O atmospheres

The study focusing on the combustion of flowing aluminum particles and the properties of condensed phase products has important guiding significance for the practical application of aluminum-based propellants. Based upon an in-house built dynamic combustion experimental system, the dynamic combustion process of aluminum particles and the properties of condensed phase products under different atmospheres were studied in detail. The microstructure, size distribution and active aluminum content of samples were analyzed by field emission scanning electron microscopy, laser particle analyzer and inductively coupled plasma atomic emission spectroscopy. By monitoring the temperature distribution at different points in the furnace, the heat release of the samples at different positions is approximated, and the combustion efficiency is calculated. In the atmosphere containing CO₂, the maximum combustion efficiency can reach the value of 94.41%, followed by that in H₂O atmosphere, which had the value of 81.19%. Finally, under the N₂ containing atmosphere, the combustion is the weakest, and has the value of only 53.91%, confirming that the combustion followed the following descending order: CO₂?>?H₂O?>?N₂. The condensed phase products were mainly composed of agglomerates formed by the aggregation of particles and alumina smoke. It is well known that the reaction of the sample in the furnace not only follows the melt-dispersion mechanism, but also the diffusion mechanism. The high-speed camera captured four typical combustion forms of aluminum particles during flow, which are stable combustion, release of alumina smoke, crushing and extinction. The average burning time of four stages were studied. The two reaction mechanisms occurring under the same reaction conditions are determined by the nature of aluminum particles themselves.

     

甲基肼/四氧化二氮反应化学动力学模型构建及分析

甲基肼(MMH)和四氧化二氮(NTO)是常用的液体火箭发动机推进剂,但目前对其反应机理的研究还十分有限.本文首先构建了一个包含23种组分和20个基元反应的MMH/NTO反应动力学模型;对MMH/NTO自燃着火过程进行的验证计算表明,该机理能够合理地描述MMH/NTO的自燃温升过程,准确预测反应物系统的着火延迟时间及平衡温度,并能合理地反映MMH/NTO反应物系统着火延迟时间对反应初始压力以及氧燃比的依赖关系;通过灵敏度分析方法指出了影响MMH/NTO着火过程的关键反应.模拟分析了在不同压力和氧燃比条件下MMH/NTO系统的自燃温升过程,结果表明,随着压力的升高,系统着火延迟时间变短,平衡温度升高;在一定范围内增大氧燃比,着火延迟时间变长,平衡温度先升高后减小.     

城市生活垃圾的燃烧特性

选取城市生活垃圾中的九种典型级分进行热重特性试验，根据热失重曲线得出反应动力力学参数及反应速率控制方程，提出燃烧指数表征垃圾的燃烧特性。研究结果表明，垃圾中不同的组分的燃烧特性判别很大，不同的垃圾控制燃烧反应的过程是不同的，废塑料，废纸和废棉布类符合两段燃烧模型，且低温段的动力学参数Ｅ和Ａ远大于高温段，其余六处组分可用一段模型来描述，计算得出的失重关系式能较好地反映垃圾燃烧的失重过程，挥 分高的垃     

Analysis on First-stage Ignition of n-Heptane at Low Temperatures with a Lumped Skeletal Mechanism

Two-stage ignition exists in the low-temperature combustion process of n-heptane and the first-stage ignition also shows a negative temperature coefficient(NTC) phenomenon. To study key reactions and understand chemical principles affecting the first-stage ignition of n-heptane, a lumped skeletal mechanism with 62 species is obtained based on the detailed NUIGMech1.0 mechanism using the directed relation graph method assisted by sensitivity analysis and isomer lumping. The lumped mechanism shows good performance on ignition delay time under wide conditions. The study revealed that the temperature after the first-stage ignition is higher and a larger amount of fuel is consumed at lower initial temperatures. The temperature at the first-stage ignition is relatively insensitive to the initial temperature. Further sensitivity analysis and reaction path analysis carried out based on the lumped mechanism show that the decomposition of RO₂ to produce alkene and HO₂is the most important reaction to inhibit the first-stage ignitions. The chain branching explosion closely related to the first-stage ignition will be terminated when the rate constant for the RO₂ decomposition is larger than that of the isomerization of RO₂ to produce QOOH. The NTC behavior as well as other characteristics of the first-stage ignition can be rationalized from the competition between these two reactions.     

Single-stage conversion of associated petroleum gas and natural gas to syngas in combustion and auto-ignition processes

Single-stage conversion of alkane mixtures simulating associated petroleum gas (APG) to syngas is studied in a static installation and in a flow reactor based on the rocket combustion chamber. Yields of the desired reaction products close to their thermodynamically equilibrium values are obtained. A range of experimental parameters, in which ignition delays of APG-oxygen mixtures exhibit negative or zero temperature coefficients, is determined for the first time. Such a behavior of ignition delays is proved to be a fundamental property of fuel-rich APG mixtures. The range of abnormal temperature dependence of ignition delays is shown to be extended as the initial pressure rises, which makes it possible to significantly increase the reaction rate by increasing the initial working pressure.     

Formation of calcium in the products of iron oxide–aluminum thermite combustion in air

The composition of condensed products resulting from the combustion of thermite mixtures (Al + Fe₂O₃) in air is studied by precise methods. It is shown that during combustion, calcium is formed and stabilized in amounts of maximal 0.55 wt %, while is missing from reactants of 99.7 wt % purity. To explain this, it is hypothesized that a low-energy nuclear reaction takes place alongside the reactions of aluminum oxidation and nitridation, resulting in the formation of calcium (Kervran–Bolotov reaction).     

反应NH~4ClO~4+Mg+K~2Cr~2O~7的非线性化学动力学2: 固相 振荡燃烧的化学模 型

建立了NH~4ClO~4+Mg+K~2Cr~2O~7固相振荡燃烧体系的非吸热三变量立方自催化化学模型,应用非线性数学分析方法,研究了固相振荡燃烧的非线性化学动力学机理,并对此进行了数值模拟,结果反映了这一振荡燃烧体系所具有的非线性化学动力学特性。     

Thermal analysis studies on combustion characteristics of seaweed

Combustion experiments of three typical seaweeds (Gracilaria cacalia, Enteromorpha clathrata and Laminaria japonica) have been studied using a DTA-60H Thermal Analyzer and the combustion processes and characteristics are studied. Thermogravimetric experiments are carried out on the samples with 0.18 mm particle size at the heating rate of 20°C min⁻¹. The results indicate that the ignition mode of seaweed is homogeneous and the combustion process is composed of dehydration, the pyrolysis and combustion of volatile, transition stage, the combustion of char as well as the reaction at high temperature. And the combustion characteristic parameters are obtained such as ignition temperature, maximum rate of combustion, burnout temperature etc. The combustion models of these seaweeds are also analyzed. The combustion characteristics and model differences between the seaweed and woody biomass are caused by the differences of volatile components. The combustibility indexes of seaweeds calculated are better than that of woody biomass, and the index of Gracilaria cacalia is the best. At last, activation energies are determined using Arrhenius model that is solved by binary linear regression method.     

Tailoring (n,m) structure of single-walled carbon nanotubes by modifying reaction conditions and the nature of the support of CoMo catalysts

The (n,m) population distribution of single-walled carbon nanotubes obtained on supported CoMo catalysts has been determined by photoluminescence and optical absorption. It has been found that the (n,m) distribution can be controlled by varying the gaseous feed composition, the reaction temperature, and the type of catalyst support used. When using CO as a feed over CoMo/SiO2 catalysts, increasing the synthesis temperature results in an increase in nanotube diameter, without a change in the chiral angle. By contrast, by changing the support from SiO2 to MgO, nanotubes with similar diameter but different chiral angles are obtained. Finally, keeping the same reaction conditions but varying the composition of the gaseous feed results in different (n,m) distribution. The clearly different distributions obtained when varying catalysts support and/or reaction conditions demonstrate that the (n,m) distribution is a result of differences in the growth kinetics, which in turn depends on the nanotube cap-metal cluster interaction.     

反应NH~4ClO~4+Mg+K~2Cr~2O~7的非线性化学动力学1: 固相振 荡燃烧的实验现 象

在外界环境条件恒定的情况下,反应体系NH~4ClO~4+Mg+K~2Cr~2O~7的燃烧过程是不均匀的,燃烧和光强呈周期性的强弱变化,给出了典型的化学振荡现象。本文介绍了NH~4ClO~4+Mg+K~2Cr~2O~7体系的固相振荡燃烧配方,对新配方进行了实验,研究了这个体系的固相振荡燃烧现象的非线性特性,分析了固相化学振荡的非线性化学反应动力学机理。     

Features of the temperature dependence for the rates of gas-phase reactions of combustion

The specific character of the dependence for the rate of most gas-phase reactions of combustion on temperature and reagent concentrations is found to be determined by the ratio of the rates of the multiplication and death of active intermediate particles. It is shown that the stepwise acceleration of the process and the transition to the combustion mode upon raising the initial temperature by 1–2 K and crossing over a critical value is due to a change in the character of the rate’s temperature dependence as a result of the sign changing from negative to positive to reflect the difference between the rates of chain branching and termination. It is concluded that this difference’s change in sign upon varying the content of reagents imposes limits on concentration.     

氢气对正丁烷/空气混合物催化着火的热作用和化学作用

通过对正丁烷/氢气/空气混合物在Pt 催化表面的详细反应机理分析, 研究了氢气添加对正丁烷/空气混合物催化着火过程的影响. 研究发现, 在正丁烷/空气混合中添加氢气有助于正丁烷在更低的温度下实现催化着火, 而且不同的氢气添加量对混合物的着火温度和着火过程呈现不同的影响: 当氢气添加量较小时, 氢气的作用主要呈现为热影响; 而当氢气添加量较大时, 氢气的作用主要呈现为化学影响. 这些结果与实验结果是一致的. 本文进一步确定了发挥不同作用的氢气添加量的范围, 并分别对热作用和化学作用情况下的着火启动反应进行了动力学分析.     

Molecular dynamics study of the response of nanostructured Al/Ni clad particles system under thermal loading

Molecular dynamics simulations are used to study the exothermic alloying reactions by imposing a thermal loading on a local area of nanostructured Al/Ni clad particles. The combustion parameters, such as particles size, density, and ignition temperature, are characterized. Reducing the size of Al/Ni clad particles makes the propagation velocity of reaction front increase but lowers both the adiabatic combustion temperature and pressure of the system. However, increasing either mass density or ignition temperature makes the propagation velocity of reaction front increase and raises the adiabatic temperature and pressure as well. We estimate the propagation velocity of the chemical reaction front to range from 35.70 to 44.06 m/s.     

Self-propagating high-temperature synthesis in the solid-phase triphenylphosphine-chloramine system

The macrokinetics and products of self-propagating high-temperture synthesis (SHS) in the solid-phase triphenylphosphine—chloramine system were studied by TGA-DTA, XRD, and³¹P NMR techniques. The temperature of SHS ignition (59°C), the velocity of reaction waves (1.6–5.0 mm s⁻¹), and the maximum temperature (155–239°C) in the SHS wave were measured. The chemical composition of the product obtained was established: phosphine oxide, triphenyl-N-(phenylsulfoyl)-phosphinimine, benzenesulfonamide, NaCl, and water. The scheme of chemical reactions occurring during SHS was proposed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 301–305, February, 1999.     

正十二烷高温机理简化及验证

由于详细化学反应机理在模拟燃烧室燃烧时,计算量极大,很难被广泛运用。为了满足工程设计要求,采用替代燃料的简化机理进行计算不失为一种行之有效的方法。本文基于误差传播的直接关系图法和敏感性分析法对正十二烷180组分1962步高温机理(温度大于1100 K)进行简化,获得40组分234步化学反应机理。在温度为1100–1650 K,压力为0.1–4 MPa条件下,采用简化机理及详细机理对不同当量比、压力下着火延迟时间进行模拟,模拟结果与实验数据吻合得较好。通过对不同压力及温度下火焰传播速度进行模拟,验证了简化机理能够正确地反映正十二烷的燃烧特性。利用C_(12)H_(26)/OH/H_2O/CO_2等重要组分随时间变化的数据,验证了简化机理能够准确描述燃烧过程反应物消耗、基团变化、生成物产生的过程,并表明该机理具有较高的模拟精度。利用该简化机理对本生灯进行数值分析,结果表明该机理能够准确地反映火焰区温度和组分浓度的变化。紧凑的正十二烷高温简化机理不仅能够正确体现其物理化学特性,而且能够用于三维数值模拟,具有较高的工程运用价值和应用前景。     

高碳烃宽温度范围燃烧机理构建及动力学模拟

发动机中燃料点火特性以及燃烧能量的释放对于发动机设计具有非常重要的作用,为了提高燃料的燃烧效率以及减少燃料在燃烧过程中污染物的排放,基于反应动力学机理对燃料燃烧过程的模拟就显得十分必要。因此需要更加深入的认识碳氢燃料的燃烧机理,探索其在燃烧过程中十分复杂的化学反应网络。为了发展能够适用于实际燃料多工况条件(宽温度范围、宽压力范围和不同当量比)燃烧的燃烧机理,基于碳氢燃料机理自动生成程序ReaxGen构建了正癸烷燃烧详细机理(包含1499个物种,5713步反应)和正十一烷燃烧详细机理(包含1843个物种,6993步反应)。详细机理主要由小分子核心机理和高碳烃类(C5以上)机理两部分组成。为了验证机理的合理性与可靠性,本文对于高碳烃燃烧新机理在点火延时时间以及物种浓度曲线进行了动力学分析,并与实验数据及国内外同类机理进行了对比,结果表明本文提出的正癸烷和正十一烷燃烧新机理在比较宽泛的温度、压力和当量比条件下都具有较高的模拟精度,为发展精确航空煤油燃烧模型提供了基础数据。同时考虑到详细机理的复杂性以及机理分析的计算量大和时耗长,本文基于误差传播的直接关系图形(Directed Relation Graph with Error Propagation,DRGEP)方法简化得到的包含709组分2793反应的正癸烷和包含820组分3115反应的正十一烷简化机理,使用DRGEP方法时所采用的数据点选自压力范围从1.0×10~5 Pa到1.0×10~6Pa,当量比范围从0.5到2.0,初始温度范围从600到1400时恒压点火的模拟结果在点火延迟时间附近区域的抽样,同时在正癸烷机理简化中选取正癸烷、O_2和N_2作为初始预选组分,正十一烷的机理简化中主要选取正十一烷、O_2和N_2作为初始预选组分,得到的简化机理在比较宽泛的条件下的预测结果与详细机理吻合很好。最后结合敏感度分析方法分析了正癸烷和正十一烷的点火延迟敏感性,考察了机理中影响点火的关键反应。结果表明:这些机理能够合理描述正癸烷和正十一烷的自点火特性,在工程计算流体力学仿真设计中有很好的应用前景。     

The non-Markovian quantum master equation in the collective-mode representation: application to barrier crossing in the intermediate friction regime

The calculation of chemical reaction rates in the condensed phase is a central preoccupation of theoretical chemistry. At low temperatures, quantum-mechanical effects can be significant and even dominant; yet quantum calculations of rate constants are extremely challenging, requiring theories and methods capable of describing quantum evolution in the presence of dissipation. In this paper we present a new approach based on the use of a non-Markovian quantum master equation (NM-QME). As opposed to other approximate quantum methods, the quantum dynamics of the system coordinate is treated exactly; hence there is no loss of accuracy at low temperatures. However, because of the perturbative nature of the NM-QME it breaks down for dimensionless frictions larger than about 0.1. We show that by augmenting the system coordinate with a collective mode of the bath, the regime of validity of the non-Markovian master equation can be extended significantly, up to dimensionless frictions of 0.5 over the entire temperature range. In the energy representation, the scaling goes as the number of levels in the relevant energy range to the third power. This scaling is not prohibitive even for chemical systems with many levels; hence we believe that the current method will find a useful place alongside the existing techniques for calculating quantum condensed-phase rate constants.     

Microwave-assisted architectural control fabrication of 3D CdS structures

A facile microwave-assisted solvothermal method was developed for the controlled synthesis of novel 3D CdS structures. Dendrite-, star-, popcorn- and hollow sphere-like CdS structures could be obtained by changing the reaction conditions including the reaction temperature and the amounts of reagents and solvents. The products were examined by using X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy, Raman and photoluminescence spectroscopy. Results revealed that the final structures were related to the solvent properties such as surface tension and viscosity. The degree of supersaturation is also responsible for the morphology variation and it can be adjusted by the reaction temperature. The CdS products with different morphologies exhibited interesting shape-dependent optical properties and photocatalytic activities.     

增压O_2/CO_2气氛下煤燃烧特性实验研究

增压O2/CO2燃烧是一种可高效分离回收CO2的新兴燃烧技术,其燃烧机理与常压空气、常压O2/CO2燃烧存在较大差异。在加压热重分析仪上研究了增压条件下总压、氧浓度、气氛及粒径等反应参数对美国烟煤和淮北无烟煤燃烧特性的影响,确定了煤的着火温度,并对其进行燃烧动力学分析。结果表明,增压O2/CO2气氛下,随着压力或氧浓度的增加,DTG曲线向低温区移动,煤样整体燃烧速率加快。压力提升、氧浓度增加及煤粉细化均可改善O2/CO2气氛下煤样的着火特性。常压O2/CO2气氛下煤粉燃烧基本属于一级反应;增压O2/CO2气氛下,低温区属于0.5级反应,而高温区属于1.5级反应。