Alkali metal emissions in an early-stage pulverized-coal flame: DNS analysis of reacting layers and chemistry tabulation

The intricate coupling between coal pyrolysis, gas phase combustion and the emissions of alkali metal, such as sodium, is studied in the early stage of a temporally evolving three-dimensional planar turbulent jet carrying pulverized-coal particles. Complex chemistry is used to account for both the combustion of volatile hydrocarbons and the sodium containing species. The response of the sodium chemistry is analyzed in the mixture fraction space, along with the topology of the reactions zones. Combustion is found to start preferentially in partially premixed flames, which then evolve toward diffusion-like reactive layers and reach chemical equilibrium. From the direct numerical simulation (DNS) database, the possibility of modeling the dynamics of sodium species using one-dimensional premixed flamelet generated manifolds (FGM) is investigated. A chemical lookup table is constructed for the combustion of the partially premixed volatiles and an additional three-dimensional simulation is performed to compare the tabulated sodium species against their reference counterparts with complex chemistry. Quantitative analysis of the performance of the developed chemistry tabulation confirms the validity of the approach. Perspectives for the modeling of sodium emissions in pulverized-coal furnaces and boilers are finally drawn.     

Optical absorption method for the real-time component analysis of natural gas: Part 1. Analysis of mixtures enriched with ethane and propane

An optical method is developed for the real-time component analysis of natural gas mixtures. The method is based on the measurement of the absorption coefficients of the gas mixture at several wavelengths in the IR spectral range (7–14 μm). The resulting accuracy of the measurements of the methane, ethane, and propane contents in gas mixtures is sufficient for the monitoring of the component composition of natural gas in pipelines.     

无旋性前进重力波传递在均匀流中的Lagrange解析解与试验验证Ⅰ.理论解析解

对于三维空间等深水中,无旋性自由表面周期性规则前进重力波传递在均匀流中的波流场,依质量守恒取一波长的流体质点的运动位移的波长平均高程,所得其标注参数恰为其在原静止水中的位置下,完全以Lagrange方式的参数控制式,解出此波流场至第三阶的全Lagrange形式解且得到检核验证;其中波流交互作用效应存在于Lagrange流速势中,使得波流场中的压力不受均匀流的影响.而Euler形式解所无法描述的流场特性,包括大于前进波周期的流体质点的运动周期,与其受前进波引起的质量传输速度、它们间的关系、及流体质点对其运动周期平均的高程与成因等,都说明是随流体质点所在的高程向下做指数函数样递减;而流体质点的三维空间螺旋曲线式的运动轨迹与烟线,其随均匀流的流向流速而变化的情况,例如其在均匀流于前进波波向有同向的流速分量时,是受流体质点恰在波谷断面处时的流速大小而变的形式,与其在均匀流于前进波波向有反向的流速分量时,则受流体质点恰在波峰断面处时的流速大小而变的形式,有很大不同的倒反形式甚至以封闭曲线形式呈现.最后,说明波流场变成稳定性运动流场时的特性,并证实其在无流时退化成纯前进波的情况.     

Detailed and simplified kinetic models of n-dodecane oxidation: The role of fuel cracking in aliphatic hydrocarbon combustion

A detailed kinetic model is proposed for the combustion of normal alkanes up to n-dodecane above 850 K. The model was validated against experimental data, including fuel pyrolysis in plug flow and jet-stirred reactors, laminar flame speeds, and ignition delay times behind reflected shock waves, with n-dodecane being the emphasis. Analysis of the computational results reveal that for a wide range of combustion conditions, the kinetics of fuel cracking to form smaller molecular fragments is fast and may be decoupled from the oxidation kinetics of the fragments. Subsequently, a simplified model containing a minimal set of 4 species and 20 reaction steps was developed to predict the fuel pyrolysis rate and product distribution. Combined with the base C₁-C₄ model, the simplified model predicts fuel pyrolysis rate and product distribution, laminar flame speeds, and ignition delays as close as the detailed reaction model.     

Decay of inert-gas-discharge plasma in the expansion mode. Part 1: Dynamics of the plasma ionization state,criterion of recombination nonequilibrium,and experimental study of argon plasma decay

The influence of expansion of a pulsed arc plasma on its decay is studied theoretically and experimentally with allowance for deviation from the equilibrium state. The dynamics of the ionization state during the decay of a dense expanding plasma is traced, and a criterion of its recombination nonequilibrium is determined. The results of calculation are compared with experimental data by the example of a pulsed arc in argon.     

A simple model of ultrasound propagation in a cavitating liquid. Part I: Theory, nonlinear attenuation and traveling wave generation

The bubbles involved in sonochemistry and other applications of cavitation oscillate inertially. A correct estimation of the wave attenuation in such bubbly media requires a realistic estimation of the power dissipated by the oscillation of each bubble, by thermal diffusion in the gas and viscous friction in the liquid. Both quantities and calculated numerically for a single inertial bubble driven at 20 kHz, and are found to be several orders of magnitude larger than the linear prediction. Viscous dissipation is found to be the predominant cause of energy loss for bubbles small enough. Then, the classical nonlinear Caflish equations describing the propagation of acoustic waves in a bubbly liquid are recast and simplified conveniently. The main harmonic part of the sound field is found to fulfill a nonlinear Helmholtz equation, where the imaginary part of the squared wave number is directly correlated with the energy lost by a single bubble. For low acoustic driving, linear theory is recovered, but for larger drivings, namely above the Blake threshold, the attenuation coefficient is found to be more than 3 orders of magnitude larger then the linear prediction. A huge attenuation of the wave is thus expected in regions where inertial bubbles are present, which is confirmed by numerical simulations of the nonlinear Helmholtz equation in a 1D standing wave configuration. The expected strong attenuation is not only observed but furthermore, the examination of the phase between the pressure field and its gradient clearly demonstrates that a traveling wave appears in the medium.     

竖直环形通道内液氮流动沸腾的MUSIG模型分析Part 1: 轴向气泡直径和界面面积浓度的预测

近年来群体平衡模型受到了极大的关注。MUSIG模型(多尺寸组模型),为群体平衡模型和双流体模型的结合提供了一个框架。文中介绍了MUSIG模型,并采用MUSIG模型分析了环形通道中的液氮流动沸腾。详细分析了不同壁面热流量、液体入口速度和过冷度时通道内气泡相界面面积、当地气泡直径、空泡系数等参数沿轴向的分布。     

Vibration transmission between coupled plates using finite element methods and statistical energy analysis. Part 2: The effect of window apertures in masonry flanking walls

Part 1 of this paper demonstrated the validity of predictions of vibration transmission across junctions of masonry walls using Finite Element Methods (FEM). Part 2 uses numerical experiments with FEM to calculate the vibration transmission between masonry walls with window apertures at different positions in the flanking wall(s). Results from the numerical experiments are used to assess a simple “rule-of-thumb” estimate for calculating the change in the coupling parameters due to the introduction of an aperture into a flanking wall. Conclusions are drawn concerning use of the “rule-of-thumb” estimate for the coupling loss factor in Statistical Energy Analysis and the vibration reduction index in European standard EN 12354.     

CW-Cavity Ring Down spectroscopy of O3. Part 1: Experiment and analysis of the 6200-6400 cm spectral region

The absorption spectrum of the ¹⁸O₃ isotopologue of ozone has been recorded in the 6200-6400 cm⁻¹ region by high sensitivity CW-Cavity Ring Down Spectroscopy. The spectrum is dominated by the 2ν₁ + 5ν₃ and 2ν₁ + 3ν₂ + 3ν₃ bands at 6270.6 and 6392.2 cm⁻¹, respectively which were treated independently. The rovibrational analysis of the 2ν₁ + 5ν₃ band has evidenced that the (2 0 5) upper state is perturbed by Coriolis resonance interactions with the (0 1 6), (3 0 4) and (3 5 0) states. A total of 659, 89, 131 and 5 transitions were assigned to the 2ν₁ + 5ν₃, ν₂ + 6ν₃, 3ν₁ + 4ν₃ and 3ν₁ + 5ν₂ bands, respectively. In the case of the 2ν₁ + 3ν₂ + 3ν₃ band, 344 transitions were assigned. Some of them were found perturbed by a Coriolis interaction of the (2 3 3) state with the (5 2 0) state.Overall, 681 energy levels were derived from the analysis of the 2ν₁ + 5ν₃ and 2ν₁ + 3ν₂ + 3ν₃ band systems. In both cases, a suitable effective Hamiltonian was elaborated, allowing accounting satisfactorily for the retrieved rovibrational energy levels. In addition, dipole transition moment parameters were determined by a least-squares fit to the measured line intensities. The effective Hamiltonian and transition moment operator parameters were used to generate a list of 1619 transitions given as Supplementary material.     

Milling of Organic Solids in a Jet Mill. Part 1: Determination of the Selection Function and Related Mechanical Material Properties

The particle size distribution of pharmaceutically active materials and other fine chemicals determines the performance of the final product to a large extent. Often milling of these particles is necessary. It is not possible to determine the milling conditions solely on the basis of the particle size distribution of the starting material, because the (mechanical) properties of the material also determine the desired milling conditions. It is often not possible to optimize milling conditions experimentally because the amount of material available is frequently highly limited. A theoretical approach towards predicting the best milling conditions is needed. The purpose of this study was to develop a method to predict the desired milling conditions given a specific (organic) solid material. The selection function and the breakage distribution function are usually the starting points in modeling the milling process. The selection function is the parameter that includes the material and mill properties. Dimensional analysis made it possible to correlate the selection function with material properties. A set of theories available in the literature enable prediction of the material properties. For different compounds (lactose, paracetamol, a steroidal compound, and two heterocyclic compounds) the selection functions were calculated. The calculations predict differences: lactose reduces slowly in size, while one of the heterocyclic compounds shows the most intense fracture.     

The mechanism of heat transfer in nanofluids: state of the art (<Emphasis Type="Italic">review</Emphasis>). Part 1. Synthesis and properties of nanofluids

Here is the review of experimental and theoretical results on the mechanism of heat transfer in nanofluids. A wide scope of problems related to the technology of nanofluid production, experimental equipment, and features of measurement methods is considered. Experimental data on heat conductivity of nanofluids with different concentrations, sizes, and material of nanoparticles are presented. Results on forced and free convection in laminar, and turbulent flows are analyzed. The available models of physical mechanisms of heat transfer intensification and suppression in nanofluids are presented. There are significant divergences in data of different researchers; possible reasons for this divergence are analyzed.     

竖直环形通道内液氮流动沸腾的MUSIG模型分析第二部分: 径向气泡直径和界面面积浓度的预测

由于考虑了气泡的破裂和聚合,同两流体模型相比,MUSIG模型(多尺寸组模型)能更准确地描述流场内气泡直径。采用MUSIG模型详细分析了不同壁面热流量,液体入口速度,过冷度以及不同管道高度时通道内气泡相界面面积、当地气泡直径、空泡系数等参数沿径向的分布。分析结果表明,MUSIG模型可用来预测泡弹状流型转变区的流动参数,也即该模型拓展了两流体模型的使用范围。     

Kinetics of Formation and Evolution of Phase Structure in Multipolymer: 1. The Application of Semilogarithmic Plot Method to Early Stage of Phase Dispersion

Kinetics of phase dispersion of binary blends of polypropylene and poly(cis-butadiene) rubber during the processing in a batch mixer was investigated by a back small-angle laser scattering (BSALS) online system. It was found experimentally that the scattering intensity I(q, t) followed an exponential growth with time during the early dispersion stage from 1 s to 65 s, while at t > 65 s, the slope levels off with time. A theory in which two critical parameters, W(q) and D_d, were calculated was proposed to describe the early stage of phase dispersion; the former parameter is defined as the rate of decreasing dispersed phase dimension, and the latter, evaluated from the slope of W(q) versus q² plot, is the dispersion coefficient. W(q) remains constant with the increment of dispersed phase. W(q) has a self-similarity with q for different compositions. The slope β, defined as the dispersion acceleration evaluated by linear fit in the nonscaling interval, was determined to explain the similar evolution mechanisms for the different velocity distributions of W(q). The dispersion coefficient D_d increases with the increment of the dispersed phase, and does not vary with shear rates.     

Natural J coupling (NJC) analysis of the electron lone pair effect on NMR couplings: 2. The anomeric effects on 1 J (C,H) couplings and its dependence on solvent

The electronic origin of the influence of the anomeric effect (negative hyperconjugative interaction, NHI) on the Fermi contact (FC) term of ¹ J(C, H) couplings has been studied from a theoretical point of view at the DFT-B3LYP level. The HN=CH₂, molecule was chosen as the primary model compound, in which both FC ¹ J(C, H) couplings were decomposed into bond contributions with the natural J coupling dissection approach (NJC). Differences between the ¹ J (C, H)^FC couplings for C——H bonds in synperiplanar and antiperiplanar orientations with respect to the nitrogen non-bonding electron pair closely follow the experimental trend. They are made up chiefly of three NJC contributions: ‘bond’, ‘direct lone pair’ and the ‘carbon-core orbitals’. The NHI influence on these terms was studied by applying the natural bond orbital (NBO) deletion procedure to the charge transfer interaction into the antiperiplanar (C——H) antibond (n(N)→(C——H)?) prior to the NJC dissection calculation. The dielectric solvation effect on both the total FC terms and the respective NJC contributions was estimated by carrying out the calculations using the polarization continuum model. Inhibition of the anomeric effect is evident when the solvent polarity is increased. NHI saturates rapidly with increasing solvent dielectric. Specific solute-solvent interaction effects on ¹ J(C, H) couplings were estimated by evaluating molecular complex models of the form CH₂=HN…S (S = H₂O and DMSO).     

The growth of the passive film on iron in 0.05 M NaOH studied in situ by Raman micro‐spectroscopy and electrochemical polarisation. Part I: near‐resonance enhancement of the Raman spectra of iron oxide and oxyhydroxide compounds

Raman spectroscopy, in principle, is an excellent technique for the study of molecular species developed on metal surfaces during electrochemical investigations. However, the use of the more common laser wavelengths such as the 514.5‐nm line results in spectra of less than optimal intensity, particularly for iron oxide compounds. In the present work, near‐resonance enhancement of the Raman spectra was investigated for the iron oxide and iron oxyhydroxide compounds previously reported to be present in the passive film on iron, using a tuneable dye laser producing excitation wavelengths between 560 and 637 nm. These compounds were hematite (α‐Fe₂O₃), maghemite (γ‐Fe₂O₃), magnetite (Fe₃O₄), goethite (α‐FeOOH), akaganeite (β‐FeOOH), lepidocrocite (γ‐FeOOH) and feroxyhyte (δ‐FeOOH). Optimum enhancement, when compared to that with the 514.5‐nm line, was obtained for all the iron oxide and oxyhydroxide standard samples in the low wavenumber region (<1000 cm⁻¹) using an excitation wavelength of 636.4 nm. Particularly significant enhancement was obtained for lepidocrocite, hematite and goethite. Copyright © 2010 John Wiley & Sons, Ltd.     

The role of F A1:Ag+ defects in laser light generation and coadsorption of CO and halogen atoms at the KCl and KBr surface sites. First principles calculations

F _A1:Ag⁺ color center at the low coordination (100) and (110) surface sites of KCl and KBr thin films play an important role in providing tunable laser oscillation and adsorbatesubstrate interactions. Double-well potentials at this site are investigated using ab initio molecular electronic structure calculations. The calculated Stokes shifted (optical transition bands), opticaloptical conversion efficiencies, the probability of orientational destruction, exciton (energy) transfer and Glasner-Tompkins empirical rule suggest that laser light generation is sensitive to (i) the lattice anion, (ii) the coordination number of surface ions, and (iii) the choice of the basis set centered on the anion vacancy. The adsorbate-substrate interactions were found to be dependent on the electronegativity of the adatom and on the lattice anion. Optimised geometries and the coadsorption of CO and (F, Cl, Br, I) on KCl and KBr (100) crystals are presented. Calculated chemisorption energies for CO on the (halogen atom/defect free sites of KCl and KBr (100) crystals) showed that the coadsorption of halogen atom tends to block other adsorbate-substrate interactions at the nearest neighbour sites. Thus if halogen atom coverage increases, the CO prefers to be adsorbed on the K⁺ site of the KCl and KBr (100) surfaces and on KBr relative to KCl.