A model for crack formation during active solid pyrolysis of a char-forming solid: crack patterns; surface area generation; volatile mass efflux

A model is developed for the formation and propagation of cracks in a material sample that is heated at its top surface, pyrolyses, and then thermally degrades to form char. In this work the sample is heated uniformly over its entire top surface by a hypothetical flame (a heat source). The pyrolysis mechanism is described by a one-step overall reaction that is dependent nonlinearly on the temperature (Arrhenius form). Stresses develop in response to the thermal degradation of the material by means of a shrinkage strain caused by local mass loss during pyrolysis. When the principal stress exceeds a prescribed threshold value, the material forms a local crack. Cracks are found to generally originate at the surface in response to heating, but occasionally they form in the bulk, away from ever-changing material boundaries. The resulting cracks evolve and form patterns whose characteristics are described. Quantities examined in detail are: the crack spacing in the pyrolysis zone; the crack length evolution; the formation and nature of crack loops which are defined as individual cracks that have joined to form loops that are disconnected from the remaining material; the formation of enhanced pyrolysis area; and the impact of all of the former quantities on mass flux. It is determined that the mass flux from the sample can be greatly enhanced over its nominal (non-cracking) counterpart. The mass efflux profile qualitatively resembles those observed in Cone Calorimeter tests.     

燃料敏感性对内燃机部分预混燃烧(PPC)光谱特性的影响研究

在一台光学发动机上,利用火焰高速成像技术和自发光光谱分析法,研究了燃料敏感性(S)为0和6时对发动机缸内火焰发展和燃烧发光光谱的影响。试验过程中,通过改变喷油时刻(SOI=-25,-15和-5°CA ATDC)使燃烧模式从部分预混燃烧过渡到传统柴油燃烧模式。通过使用正庚烷、异辛烷、乙醇混合燃料来改变燃料敏感性。结果表明,在PPC模式下(-25°CA ATDC),火焰发展过程是从近壁面区域开始着火,而后向燃烧室中心发展,即存在类似火焰传播过程,同时在燃烧室下部未燃区域也形成新的着火自燃点。敏感性对燃烧相位影响较大,对缸内燃烧火焰发展历程影响较小;高敏感性燃料OH和CH带状光谱出现的时刻推迟,表明高敏感性燃料高温反应过程推迟,且光谱强度更低,表明碳烟辐射强度减弱。在PPC到CDC之间的过渡区域(-15°CA ATDC),燃烧火焰发光更亮,燃烧反应速率比-25°CA ATDC时刻的反应速率更快。高、低敏感性燃料对缸压放热率的影响规律与-25°CA ATDC相近,此时的燃烧反应更剧烈,放热率更高,碳烟出现时刻更早。该喷油时刻下的光谱强度高于PPC模式下的光谱强度,说明此时的CO氧化反应与碳烟辐...     

Microgravity droplet combustion: effect of tethering fiber on burning rate and flame structure

Droplets tethering on fibers has become a well established technique for conducting droplet combustion experiments in microgravity conditions. The effects of these supporting fibers are frequently assumed to be negligible and are not considered in the experimental analysis or in numerical simulations. In this work, the effect of supporting fibers on the characteristics of microgravity droplet combustion has been investigated numerically; a priori predictions have then been compared with published experimental data. The simulations were conducted using a transient one-dimensional spherosymmetric droplet combustion model, where the effect of the supporting fiber was implicitly taken into account. The model applied staggered convective flux finite volume method combined with high-order implicit time integration. Thermal radiation was evaluated using a statistical narrow band radiation model. Chemical kinetics and thermophysical properties were represented in rigorous detail. Tether fiber diameter, droplet diameter, ambient pressure and oxygen concentration were varied over a range for n-decane droplets in the simulations. The results of the simulations were compared to previously published experiments conducted in the Japan Microgravity Center (JAMIC) 10 second drop tower and the NASA Glenn Research Center (GRC) 5.2 second drop tower. The model reproduces closely nearly all aspects of tethered n-decane droplet burning phenomena, which included droplet burning history, transient and average burning rate, and flame standoff ratio. The predictions show that the presence of the tethering fiber significantly influences the observed burning rate, standoff ratio, and extinction.     

Large Eddy Simulations of a piloted lean premix jet flame using finite-rate chemistry

A Large Eddy Simulation (LES) model capable of accurately representing finite-rate chemistry effects in turbulent premixed combustion is presented. The LES computations use finite-rate chemistry and implicit LES combustion modelling to simulate an experimentally well-documented lean-premixed jet flame stabilized by a stoichiometric pilot. The validity of the implicit LES assumption is discussed and criteria are expressed in terms of subgrid scale Damköhler and Karlovitz numbers. Simulation results are compared to experimental data for velocity, temperature and species mass fractions of CH₄, CO and OH. The simulation results highlight the validity and capability of the present approach for the flame and in general the combustion regime examined. A sensitivity analysis to the choice of the finite-rate chemistry mechanism is reported, this analysis indicates that the one and two-step global reaction mechanisms evaluated fail to capture the reaction layer with sufficient accuracy, while a 20-species skeletal mechanism reproduces the experimental observations accurately including the key finite-rate chemistry indicators CO and OH. The LES results are shown to be grid insensitive and that the grid resolution within the bounds examined is far less important compared to the sensitivity of the finite-rate chemistry representation. The results are analyzed in terms of the flame dynamics and it is shown that intense small scale mixing (high Karlovitz number) between the pilot and the jet is an important mechanism for the stabilization of the flame.     

Numerical study of the effect of turbulence on rate of reactions in the MILD combustion regime

In this paper, the importance of fluctuations in flow field parameters is studied under MILD combustion conditions. In this way, a turbulent non-premixed CH₄+H₂ jet flame issuing into a hot and deficient co-flow air is modeled using the RANS Axisymmetric equations. The modeling is carried out using the EDC model to describe the turbulence-chemistry interaction. The DRM-22 reduced mechanism and the GRI2.11 full mechanism are used to represent the chemical reactions of H₂/methane jet flame. Results illustrate that although the fluctuations in temperature field are small and the reaction zone volume are large in the MILD regime, the fluctuations in temperature and species concentrations are still effective on the flow field. Also, inappropriate dealing with the turbulence effect on chemistry leads to errors in prediction of temperature up to 15% in the present flame. By decreasing of O₂ concentration of hot co-flow air, the effect of fluctuations in flow field parameters on flame characteristics are still significant and its effect on species reaction rates does not decrease. On the other hand, although decreasing of jet inlet Reynolds number at constant inlet turbulence intensity addresses to smaller fluctuations in flow filed, it does not lead to lower the effect of turbulence on species distribution and temperature field under MILD combustion conditions.     

Kinetic parameters,collision rates,energy exchanges and transport coefficients of non-thermal electrons in premixed flames at sub-breakdown electric field strengths

The effects of an electric field on the collision rates, energy exchanges and transport properties of electrons in premixed flames are investigated via solutions to the Boltzmann kinetic equation. The case of high electric field strength, which results in high-energy, non-thermal electrons, is analysed in detail at sub-breakdown conditions. The rates of inelastic collisions and the energy exchange between electrons and neutrals in the reaction zone of the flame are characterised quantitatively. The analysis includes attachment, ionisation, impact dissociation, and vibrational and electronic excitation processes. Our results suggest that Townsend breakdown occurs for E/N = 140 Td. Vibrational excitation is the dominant process up to breakdown, despite important rates of electronic excitation of CO, CO₂ and N₂ as well as impact dissociation of O₂ being apparent from 50 Td onwards. Ohmic heating in the reaction zone is found to be negligible (less than 2% of peak heat release rate) up to breakdown field strengths for realistic electron densities equal to 10¹⁰ cm^?3. The observed trends are largely independent of equivalence ratio. In the non-thermal regime, electron transport coefficients are insensitive to mixture composition and approximately constant across the flame, but are highly dependent on the electric field strength. In the thermal limit, kinetic parameters and transport coefficients vary substantially across the flame due to the spatially inhomogeneous concentration of water vapour. A practical approach for identifying the plasma regime (thermal versus non-thermal) in studies of electric field effects on flames is proposed.     

Effects of combined dimension reduction and tabulation on the simulations of a turbulent premixed flame using a large-eddy simulation/probability density function method

A turbulent lean-premixed propane–air flame stabilised by a triangular cylinder as a flame-holder is simulated to assess the accuracy and computational efficiency of combined dimension reduction and tabulation of chemistry. The computational condition matches the Volvo rig experiments. For the reactive simulation, the Lagrangian Large-Eddy Simulation/Probability Density Function (LES/PDF) formulation is used. A novel two-way coupling approach between LES and PDF is applied to obtain resolved density to reduce its statistical fluctuations. Composition mixing is evaluated by the modified Interaction-by-Exchange with the Mean (IEM) model. A baseline case uses In Situ Adaptive Tabulation (ISAT) to calculate chemical reactions efficiently. Its results demonstrate good agreement with the experimental measurements in turbulence statistics, temperature, and minor species mass fractions. For dimension reduction, 11 and 16 represented species are chosen and a variant of Rate Controlled Constrained Equilibrium (RCCE) is applied in conjunction with ISAT to each case. All the quantities in the comparison are indistinguishable from the baseline results using ISAT only. The combined use of RCCE/ISAT reduces the computational time for chemical reaction by more than 50%. However, for the current turbulent premixed flame, chemical reaction takes only a minor portion of the overall computational cost, in contrast to non-premixed flame simulations using LES/PDF, presumably due to the restricted manifold of purely premixed flame in the composition space. Instead, composition mixing is the major contributor to cost reduction since the mean-drift term, which is computationally expensive, is computed for the reduced representation. Overall, a reduction of more than 15% in the computational cost is obtained.     

La1．6（MoO4）3∶Eu3＋0．4纳米晶合成及发光特性

采用燃烧法合成了La1．6（MoO4）3∶Eu3＋0．4纳米晶末,研究了其声子-掺杂-晶格相互作用和发光性质。 X射线粉末衍射（XRD）分析表明,在500～900℃退火后,La1．6（MoO4）3∶Eu3＋0．4样品为单一晶相。对样品进行了光致发光（PL）测量,激发Mo6＋-O2－电荷迁移带,观察到Eu3＋的系列发光,表明Mo6＋-O2－带和Eu3＋间存在能量传递,中心波长分别在λ1＝469 nm和λ2＝426 nm处的两个one-phonon边带,相应的声子能量分别为767和1202 cm－1,分别对应于Mo O和Mo—O—Mo伸缩振动。同时,计算了两个局域模电子-声子耦合强度的黄昆因子分别为S1＝0.055和S2＝0.037,为揭示其三价离子高传导特性及其负热膨胀物理特性提供了实验基础。     

On-line Sulfur Isotope Analysis of Organic Material by Direct Combustion: Preliminary Results and Potential Applications

Abstract

Sulfur isotopes have received little attention in ecology studies because plant and animal materials typically have low sulfur concentrations (< 1 wt.%) necessitating labor-intensive chemical extraction prior to analysis. To address the potential of direct combustion of organic material in an elemental analyzer coupled with a mass spectrometer, we compared results obtained by direct combustion to results obtained by sulfur extraction with Eschka's mixture. Direct combustion of peat and animal tissue gave reproducibility of better than 0.5‰ and on average, values are 0.8‰ higher than values obtained by Eschka extraction. Successful direct combustion of organic material appears to be a function of sample matrix and sulfur concentration. Initial results indicate that direct combustion provides fast, reliable results with minimal preparation. Pilot studies underway include defining bear diets and examining fluctuations between freshwater and brackish water in coastal environments.