An experimental and kinetic modeling study of a premixed nitromethane flame at low pressure

A premixed nitromethane/oxygen/argon flame at low pressure (4.67 kPa) has been investigated using tunable vacuum ultraviolet (VUV) photoionization and molecular-beam mass spectrometry. About 30 flame species including hydrocarbons, oxygenated and nitrogenous intermediates have been identified by measurements of photoionization efficiency spectra. Mole fraction profiles of the flame species have been determined by scanning burner position at some selected photon energies. The results indicate that N₂ and NO are the major nitrogenous products in the nitromethane flame. Compared with previous studies on nitromethane combustion, a number of unreported intermediates, including C₃H₄, C₄H₆, C₄H₈, C₂H₂O, C₂H₄O, CH₃CN, H₂CNHO, C₃H₃N and C₃H₇N, are observed in this work. Based on our experimental results and previous modeling studies, a detailed oxidation mechanism including 69 species and 314 reactions has been developed to simulate the flame structure. Despite some small discrepancies, the predictions by the modeling study are in reasonable agreement with the experimental results.     

利用迈克耳孙干涉仪重建蜡烛火焰温度场

利用教学实验中的迈克耳孙干涉仪,进行蜡烛火焰温度场的测量.对干涉条纹进行了处理和细化,并分别用阿贝尔变换法和环带法对蜡烛火焰的温度场进行了计算,得到蜡烛火焰横截面上温度场的定量结果.     

Phase transition in CeSe, EuSe and LaSe under high pressure

The high pressure phase transition and elastic behavior of rare earth monoselenides (CeSe, EuSe and LaSe) which crystallize in a NaCl-structure have been investigated using the three body interaction potential (TBIP) approach. These interactions arise due to the electronshell deformation of the overlapping ions in crystals. The TBP model consists of a long range Coulomb, three body interactions and the short range overlap repulsive forces operative up to the second neighboring ions. The authors of this paper estimated the values of the phase transition pressure and the associated volume collapse to be closer than other calculations. Thus, the TBIP approach also promises to predict the phase transition pressure and pressure variations of elastic constants of lanthanide compounds.      

Direct evaluation of the subgrid scale scalar flux in turbulent premixed flames with conditioned dual-plane stereo PIV

With the dual-plane stereo PIV technique the instantaneous three-dimensional resolved rate-of-strain tensor is directly measured in turbulent premixed flames. Simultaneously, also the instantaneous subgrid scale (SGS) scalar flux is measured with fine resolution, where for the latter term the conditioned particle image velocimetry (CPIV) technique is applied. The subgrid resolution reaches 118 μm, allowing a 9 × 9 resolution of a subgrid filter with width Δ = 1 mm. This combined measurement approach allows the a-priori comparison of models for the SGS scalar flux term with direct measurements which is important for large eddy simulation methods in turbulent premixed flames. Two different flame conditions of a premixed V-shaped turbulent flame are investigated where the turbulence intensity is varied by a factor of nearly three. The instantaneous radial and axial SGS fluxes are compared with the following three models: gradient model with Smagorinsky approach for the turbulent viscosity, Clark model, and extended gradient model with an anisotropy term. None of these models shows a good correlation with the directly measured flux. The anisotropy term alone (being nearly similar to the Clark model) shows, however, a right trend behaviour. An analysis of the data indicates a significant dependency of the experimentally determined SGS flux on the Favre averaged reaction progress (spatially averaged over the SGS area). A relatively simple closure for the SGS flux, which describes the dilatation due to the gasdynamic expansion, and which is a function proportional to , shows a rather good correlation with direct measurement for some of the components. A successful SGS scalar flux model for premixed turbulent flames most likely needs to include at least two different effects.     

Development of rotational CARS for combustion diagnostics using a polarization approach

Rotational Coherent anti-Stokes Raman spectroscopy (CARS) has the last decades been developed into a useful tool for thermometry and concentration measurements in combustion. In this paper, we present a novel polarization approach of the technique, which will enhance its potential and widen the range of conditions at which it can be utilized. The theory of the polarization approach is described in detail. It is shown that by specific arrangement of the polarizations of the laser beams, total suppression of the non-resonant background signal can be obtained, and thus by probing only the resonant CARS signal the diagnostic utility of the technique increases. The main benefit of the approach is in situations where the non-resonant background signal is relatively high in comparison with the resonant signal. The high potential of polarization rotational CARS for thermometry is demonstrated in some illustrative examples, for example, nitrogen thermometry on the fuel side of diffusion flames, and carbon monoxide thermometry in the product gas of ethylene/oxygen/argon-flames.     

On intrinsic oscillation in radiation-affected diffusion flames

A linear stability analysis is conducted to study the onset of near-limit flame oscillation with radiative heat loss in 1-D chambered planar flames using multi-scale activation-energy asymptotics. The oscillatory instability near the radiation-induced extinction limit at large Damköhler numbers is identified, in additional to the one near the kinetic limit at small Damköhler numbers. It is shown that radiative loss assumes a similar role as varying the thermal diffusivity of the reactants. Thus, flame oscillation near the radiative limit is still thermal-diffusive in nature although it may develop under unity Lewis numbers. The unstable range of Damköhler numbers near the radiative limit shows quite similar parametric dependence on the Lewis numbers of reactants, Le_F and Le_O, the stoichiometry, ?, and the radiative loss as that near the kinetic limit. They both increase monotonically with Le_O and ? and increase then decrease with Le_F. Increasing radiative loss extends the parameter range under which flame oscillations may develop. However, they show different dependence on the temperature difference between the supplying reactants. Unless radiative loss approaches its maximum value the system can sustain, flame oscillation near the radiative limit is only possible within a limited range of ΔT, whereas it is promoted monotonically with decreasing ΔT near the kinetic limit. Furthermore, while radiative loss shows small effect on the nondimensional oscillation frequency, the dimensional frequency of flame oscillations near the radiative limit can be substantially smaller than that near the kinetic limit.     

High-pressure laminar flame speeds and kinetic modeling of carbon monoxide/hydrogen combustion

Laminar flame speeds were accurately measured for CO/H₂/air and CO/H₂/O₂/helium mixtures at different equivalence ratios and mixing ratios by the constant-pressure spherical flame technique for pressures up to 40 atmospheres. A kinetic mechanism based on recently published reaction rate constants is presented to model these measured laminar flame speeds as well as a limited set of other experimental data. The reaction rate constant of CO + HO₂ → CO₂ + OH was determined to be k = 1.15 × 10⁵T^2.278 exp(−17.55 kcal/RT) cm³ mol⁻¹ s⁻¹ at 300-2500 K by ab initio calculations. The kinetic model accurately predicts our measured flame speeds and the non-premixed counterflow ignition temperatures determined in our previous study, as well as homogeneous system data from literature, such as concentration profiles from flow reactor and ignition delay time from shock tube experiments.     

Measurement and modeling of the sooting propensity of binary fuel mixtures

The sooting behaviour of binary fuel mixtures was evaluated both experimentally and through computer simulations. The soot volume fraction in laminar diffusion flames of mixtures of ethylene/propane, methane/ethylene, methane/propane, methane/ethane, methane/butane, ethane/propane and ethane/ethylene fuels was measured using 2-dimensional line of sight attenuation. A synergistic effect was observed for the ethylene/propane, methane/ethylene, methane/ethane and ethane/ethylene mixtures. The synergistic effect translated into a higher soot concentration for a mixture fraction than could be yielded by the added contribution of both pure fuels. Such an effect was not observed for the methane/propane, methane/butane and ethane/propane mixtures. Through experiments in which the flame temperature was kept constant, it was determined that the synergistic effect in the methane/ethylene mixture is very temperature dependent whereas, that in the ethylene/propane mixture is not. This phenomenon was further studied through the modeling of the ethylene/propane mixture. Numerical simulations were carried out using two different soot models. The simulations confirmed the presence of a synergistic effect. It was found that the effect could be directly correlated to a synergistic effect in the concentration of n-C₄H₅ and n-C₄H₃, which could be traced back to an interaction between ethylene and methyl radical species. These results yield further insight into the pathways to soot formation and highlight the importance of further analyzing binary fuel mixtures as a means of understanding soot formation in practical devices using industrial fuels.     

Many body effects in the electronic and optical properties of the (1 1 1) surface of diamond

The (1 1 1) face is the cleavage surface of diamond. Understanding its properties is very important for the growing technological interest on the chemistry of diamond surfaces. Within DFT the most stable reconstruction is the Pandey chain model, the atoms on the chain being neither buckled nor dimerised. However this geometry gives rise to a semi metallic band structure in contrast with experimental findings that show the presence of a gap ranging from 0.5 to 2 eV. Here we show that the same equilibrium geometry and thus the same metallic band structure is found relaxing the surface using screened exchange (sX) or Hartree-Fock (HF) functionals. We will discuss in detail how breaking the equivalence of the atoms on the chain affects the band structure and we will show that a buckling would yield a semiconducting surface, but is energetically unfavorable. A semiconducting character can be restored, within the equilibrium geometry, if quasiparticle corrections are carefully included within an iterative GW scheme. The result of the theoretical reflectance anisotropy spectra (RAS) at a DFT-RPA level are also presented and discussed. As expected, a strong anisotropy signal is found at low energies due to transitions between surface states inside the fundamental gap.     

旋转液体中固体颗粒运动的进一步讨论

通过分析旋转液体中的压强分布,说明了浸在液体中的固体颗粒向轴心运动的原因,以及该规律的实际应用.