CH4/空气简化动力学机理数值验证

选择绕圆柱预混燃烧算例，验证CH₄/空气三种简化动力学机理（16s41r、15s19r和53s325r）.考虑均匀来流，忽略湍流和湍流与燃烧相互作用以及燃料扩散效应，假设层流有限反应速率，采用保自由流5阶WENO格式求解多组分Euler方程组，得到CH₄/空气预混燃烧流场温度等值线、沿驻点线压力和温度及其CH₄、CO和CO₂质量百分数分布.结果表明：三种简化动力学机理给出的流场均出现弓形激波和火焰面，弓形激波和火焰驻点距离及其形状、诱导区宽度和简化动力学机理相关.当圆柱直径增大，弓形激波和火焰向圆柱上游移动，对应的驻点距离均增大，诱导区宽度变短，点火延时变小，但火焰和弓形激波位置次序未变化.53s325r模型要比16s41r模型和15s19r模型精度要高，点火延时覆盖的压力和温度范围也较宽，所有简化机理均未完全反应，在较大圆柱直径下游达到化学平衡.     

Reinvestigation of the ν2 + 2ν3 subband in the overtone icosad of 12CH4 using cavity ring-down (CRD) spectroscopy of a supersonic jet expansion

We report a detailed reinvestigation of the ν₂?+?2ν₃ combination band of methane ¹²CH₄ centred at (7510.3378?±?0.003)?cm^?1 ((225.154263?±?0.0001)?THz) within the icosad of the overtone absorption. A new experimental setup is described, allowing us to carry out cw-laser cavity ring-down spectroscopy (cw-CRDS) at instrumental resolution in the MHz range in seeded supersonic jet expansions down to rotational temperature of 7?K compared to previous cw-CRDS measurements in our group achieving about 50?K in expansions of neat CH₄. We provide a careful re-analysis on the basis of our new experimental results for the Q and R branch transitions including data obtained between about 7 and 300?K under various conditions. We resolve previously observed discrepancies of assignments and are able to present a definitive assignment for lines involving angular momentum quantum numbers up to J?=?4. The analysis of relative intensities in spectra taken at rotational and effective translational temperatures between about 50?K and less than 10?K indicate conservation of nuclear spin symmetry upon supersonic jet expansion, in agreement with previous results using other techniques and covering other spectral ranges.     

Nonlinear interaction mechanisms of disturbances in supersonic flat-plate boundary layers

Due to the complexity of compressible flows, nonlinear hydrodynamic stability theories in supersonic boundary layers are not sufficient. In order to reveal the nonlinear interaction mechanisms of the rapidly amplified 3-D disturbances in supersonic boundary layers at high Mach numbers, the nonlinear evolutions of different disturbances in flat-plate boundary layers at Mach number 4.5, 6 and 8 are analyzed by numerical simulations. It can be concluded that the 3-D disturbances are amplified rapidly when the amplitude of the 2-D disturbance reaches a certain level. The most rapidly amplified 3-D disturbances are Klebanoff type (K-type) disturbances which have the same frequency as the 2-D disturbance. Among these K-type 3-D disturbances, the disturbances located at the junction of upper branch and lower branch of the neutral curve are amplified higher. Through analyzing the relationship between the amplification rate and the spanwise wavenumber of the 3-D disturbances at different evolution stages, the mechanism of the spanwise wavenumber selectivity of K-type 3-D disturbances in the presence of a finite amplitude 2-D disturbance is explained.     

Conformation‐Specific Circular Dichroism Spectroscopy of Cold,Isolated Chiral Molecules

The CD spectroscopy of a chiral compound in solution yields an average CD value derived from all of the conformations of a chiral molecule. By contrast, CD spectroscopy of cold chiral molecules in the gas phase distinguishes specific conformers of a chiral molecule, but the weak CD effect has limited the practical application of this technique. Reported herein is the first resonant two‐photon ionization CD spectra of ephedrines in a supersonic jet using circularly polarized laser pulses, which were generated by synchronizing the oscillation of the photoelastic modulator with the laser firing. The spectra exhibited well‐resolved CD bands which were specific for the conformations and vibrational modes of each enantiomer. The CD signs and magnitudes of the jet‐cooled chiral molecules were very sensitive to their conformations and thus offered crucial information for determining the three‐dimensional structures of chiral species, as conducted in combination with quantum chemical calculations.     

GC–MS with photoionization of cold molecules in supersonic molecular beams—Approaching the softest ionization method

A new type of photoionization ion source was developed for the ionization of cold molecules in supersonic molecular beams (named Cold PI). The system was based on a GC–MS with supersonic molecular beams and its fly‐through EI of cold molecules ion source (Cold EI) plus quadrupole mass analyzer. A continuously operated deuterium VUV photoionization lamp was added and placed above and between the supersonic nozzle and skimmer whereas the Cold EI ion source served only as a portion of the ion transfer ion optics. The supersonic nozzle and skimmer were voltage biased and the VUV light crossed the supersonic expansion about 10 mm from the nozzle. We obtained over three orders of magnitude enhancement in the relative abundance of the molecular ion of squalane in Cold PI versus in photoionization of this compound as a thermal compound. Accordingly, we also proved that standard photoionization is not as soft ionization method as previously perceived for large compounds. We found that Cold PI is as soft as and possibly softer than field ionization; thus, it could be the softest known ionization method. The ionization yield was about 200–300 times weaker than with Cold EI yet our limit of detection was about 200 femtogram in SIM mode for cholesterol and pyrene which is reasonable. Practically, all hydrocarbons gave only molecular ions with rather uniform response whereas alcohols gave some molecular ions plus major fragment ions particularly with a loss of water (similarly to field ionization). We tested Cold PI in the GC–MS analysis of diesel fuels and analyzed the time averaged data for group type information. We also found that we can analyze the diesel fuels by fast under 20‐s flow injection analysis in which the generated averaged mass spectrum of molecular ions only could serve for the characterization of fuels.     

Analysis of impurities in pharmaceuticals by LC‐MS with cold electron ionization

Pharmaceuticals require careful and precise determination of their impurities that might harm the user upon consumption. Although today, the most common technique for impurities identification is liquid chromatography‐mass spectrometry (LC‐MS/MS), it has several downsides due to the nature of the ionization method. Also, the analyses in many cases are targeted thus despite being present, some of the compounds will not be revealed. In this paper, we propose and show a new method for untargeted analysis and identification of impurities in active pharmaceutical ingredients (APIs). The instrument used for these analyses is a novel electron ionization (EI) LC‐MS with supersonic molecular beams (SMB). The EI‐LC‐MS‐SMB was implemented for analyses of several drug samples spiked with an impurity. The instrument provides EI mass spectra with enhanced molecular ions, named Cold EI, which increases the identification probabilities when the compound is identified with the aid of an EI library like National Institute of Standards and Technology (NIST). We analyzed ibuprofen and its impurities, and both the API and the expected impurity were identified with names and structures by the NIST library. Moreover, other unexpected impurities were found and identified proving the ability of the EI‐LC‐MS‐SMB system for truly untargeted analysis. The results show a broad dynamic range of four orders of magnitude at the same run with a signal‐to‐noise ratio of over 10 000 for the API and almost uniform response.     

Simulation on the Effect of Brownian Motion on Nanoparticle Trajectories in a Pulsed Microplasma Cluster Source

We describe a simulation of the nanoparticle trajectories in a pulsed cluster beam source. Clusters, formed by condensation of atomic vapor in a helium bath, and considered here as rigid spheres having a diameter of 1.5nm, were tracked during their travel inside the source cavity, an aerodynamic lens, and a cylindrical nozzle. Steady state supersonic laminar flow of helium is considered in an axi-symmetric geometry aiming to simulate, within some limitations, the conditions under which cluster formation takes place in a pulsed microplasma cluster source. In spite of the unsteady nature of the pulsed source, the time scale characterizing particle motion in the flow field is significantly smaller than the characteristic time constant for the evolution of gas pressure in the source. For this reason, a steady simulation can shed some light on the understanding of processes governing nanoparticle motion in a pulsed vaporization source. The extent to which the Brownian diffusion can affect the particle extraction from the source is investigated. Simulations have shown that the Brownian motion perturbs the clusters from the trajectories dictated by the carrier gas and increases the rate of cluster deposition on the source internal walls. However, it does not hinder the aerodynamic focalization produced by the lens even in nano-size cluster regime. This result is qualitatively confirmed by experiment.     

对可压缩流体若干问题的讨论

根据气体幼力学中一维定常等熵等流的基本方程组,得出的一维定常等熵管流的速度变化与管截面变化关系式,定性一讨论了一维定常等熵管流的截面变化对气流速度的影响。     

Effect of the stagnation temperature on supersonic flow parameters: Application for air in nozzles

When the stagnation temperature of a perfect gas increases, the specific heats and their ratio do not remain constant any more and start to vary with this temperature. The gas remains perfect and its state equation always remains valid, except it will be called a calorically imperfect gas. The aim of this research is to develop the relations of the necessary thermodynamics and geometrical ratios and to study the supersonic flow at high temperature (lower than the threshold of dissociation). The results are found by the resolution of nonlinear algebraic equations and integration of complex analytical functions where the exact calculation is impossible. The dichotomy method is used to solve the nonlinear equation, and the Simpson algorithm is used for the numerical integration of the found integrals. A condensation of the nodes is used, since the functions to be integrated have a high gradient at the extremity of the interval of integration. A comparison is made with a calorifcally perfect gas to determine the error of this. An application is made for air in a supersonic nozzle. The text was submitted by the authors in English.     

超声速燃烧火焰稳定凹腔质量交换特性的数值研究

对超声速冷流条件下用于超燃冲压发动机的凹腔火焰稳定器的质量交换特性进行研 究. 采用混合RANS/LES方法对非定常流场进行数值模拟，考虑了凹腔的长深比和后缘角度两 个关键参数. 计算得到了凹腔剪切层拟序结构的演化过程. 对凹腔压力振荡历程进行幅频分 析，所得到的频率和理论分析结果及一些计算结果十分吻合. 结果表明，凹腔的长深比和后 缘倾角对凹腔质量交换过程都有较大的影响. 凹腔驻留时间随着长深比的增加而增加. 随着 后缘倾角减小，长深比较小的凹腔的驻留时间增加，长深比较大的凹腔则完全相反. 该计算 结果为凹腔设计提供了新认识.