二甲醚/氧气/氩气低压层流预混燃烧研究

利用同步辐射真空紫外单光子电离结合分子束质谱技术,对当量比φ=1.5的低压预混层流二甲醚火焰进行了实验研究。通过测量光电离质谱和光电离效率曲线,探测到了二甲醚/氧气/氩气的燃烧产物和火焰中间物,包括不稳定的分子和自由基。通过测量离子信号的空间分布曲线,计算了二甲醚/氧气/氩气火焰的主要物种C_2H_6O、O_2、Ar、H_2、H_2O、CO和CO_2的摩尔分数曲线,以及主要中间物种如CH_2O、C_2H_2、C_2H_4、CH_3OH、C_2H_2O、C_2H_4O、CH_3、CH_4、HCO、C_3H_3和C_3H_4的摩尔分数曲线,并分析了主要中间物种的产生和消耗过程。     

From inherent correlation to constrained measurement: Model-assisted calibration in MBMS experiments

Synchrotron-based molecular-beam mass spectrometry (MBMS) can provide detailed species-resolved information to help develop, validate and optimize combustion kinetic models. While quantification of stable species can be achieved within 30% uncertainty, the measured mole fractions of reactive intermediates often have large systematic errors, mainly due to the large uncertainties associated with estimated photoionization cross sections. These measurements are therefore less effective in improving the model accuracy, and it remains a challenge to make full use of those data for important reactive intermediates with relatively large uncertainties. In the present work, we propose a model-assisted calibration method to reduce the uncertainty of the measurements for those reactive species in the MBMS experiments. The method takes advantage of the inherent correlation of the systematic uncertainty in the MBMS measurements and uses the accurate model predictions to calibrate the correlated experimental data. By global uncertainty analysis, the kinetic model for the methanol/O₂ flame was analyzed to select the optimal experimental conditions for which the model prediction of the hydroxymethyl radical (CH₂OH) has the smallest uncertainty. Then the correlation factor for the systematic uncertainty is determined by analyzing the new measurement and the model prediction under the designed condition. The correlation factor determined has been successfully used to calibrate the peak mole fraction of the CH₂OH radical in a laminar premixed methanol flame, reported earlier.     

Atomic collision processes relevant for heavy ion beam probes

Atomic collision processes of fast Tl and Cs ions with particles in a high temperature fusion plasma are investigated. At low beam energies (<5 MeV), ion impact collisions and charge exchange processes can be neglected compared to electron ionization processes. At beam energies above 5 MeV and high plasma ion temperatures, collisions with ions start to contribute significantly to signal generation and attenuation. Also, collisions with the neutral background gas in the beamlines can attenuate the ion beam significantly and lower the signal level, if the vacuum pressure is above 10^-4 Torr. For the heavy ion beam probes operating today, only electron impact ionization processes are important and accurate predictions of the secondary signal level and electron density profile measurements are possible because of the good knowledge of electron impact ionization cross sections for Cs ⁺ and Tl⁺ ions     

Examination of a molecular se beam by mass spectrometry with electron ionization

The methodology and results of mass-spectrometric studies of producing positive ions as a result of the dissociative ionization of a molecular selenium beam by electron impact are discussed. The appearance energies of fragment ions were determined from the ionization efficiency curves. The dynamics of production of molecular selenium ions in the temperature range of 420–500 K was also examined. The energy dependences of efficiency of production of singly charged Se _n ⁺ ions for n = 1–4 and the doubly charged selenium ion in the interval from the threshold to 36 eV were studied for the first time. The observed specific features of effective ionization cross sections were analyzed.     

Total, partial, and electron-capture cross sections for ionization of water vapor by 20-150 keV protons

We present experimental results for proton ionization of water molecules based on a novel event by event analysis of the different ions produced (and lost). We are able to obtain mass analyzed product ion signals (e.g., H2O+, OH+, O+, O++, H+) in coincidence with the projectile analyzed after the collision, i.e., either being H+, neutral H after single electron capture during the ionization event, or H- after double electron capture. After proper calibration we are thus able to determine a complete set of cross sections for the ionization of a molecular target by protons including the total and the partial cross sections and in addition also the direct ionization and the electron capture cross sections.     

The effects of burner stabilization on Fenimore NO formation in low-pressure, fuel-rich premixed CH4/O2/N2 flames

We investigate the effects of varying the degree of burner stabilization on Fenimore NO formation in fuel-rich low-pressure flat CH₄/O₂/N₂ flames. Towards this end, axial profiles of flame temperature and OH, NO and CH mole fractions are measured using laser-induced fluorescence (LIF). The experiments are performed at equivalence ratios between 1.3 and 1.5. The flame temperature is seen to decrease by 200-300 K, with a concomitant decrease in OH mole fraction, upon reducing the total flow rate from 5 to 3 L/min, thus increasing stabilization. At equivalence ratios between 1.3 and 1.5, this decrease in flow rate lowers the maximum CH mole fraction by a factor of 2, and the NO mole fraction by ∼40% in all flames studied. Integrating the reaction rate for CH + N₂ to estimate Fenimore NO formation, using the rate coefficient in GRI-Mech 3.0, and the measured temperatures and CH profiles show very good agreement with the measured NO mole fraction for ? = 1.3 and 1.4, supporting the current choice for this rate. This agreement also shows that the increase in residence time caused by increased stabilization is an important factor in the ultimate impact of the changes in CH mole fraction on NO formation. The results at ? = 1.5 suggest that substantial quantities of fixed nitrogen species, e.g., HCN, are only slowly oxidized in the post-flame zone under these conditions, leading to a significant discrepancy between the measured NO mole fraction and that obtained by integrating over the CH profile. Detailed calculations using GRI-Mech 3.0 predict the experimental results at ? = 1.3 nearly quantitatively, but show increasing differences with the measurements for both CH and NO profiles with increasing equivalence ratio.     

Formation of positive and negative ions of thymine molecules under the action of slow electrons

The formation of positive and negative molecules of thymine—a base of nucleic acids—under the action of slow electrons is investigated by the method of crossed electron and molecular beams. The method developed makes it possible to measure the molecular beam intensity and determine the energy dependences and absolute values of total cross sections for the formation of positive and negative ions of thymine molecules. It is found that the maximal cross section for the formation of positive ions is reached at an energy of 95 eV and its absolute value is, accordingly, 1.4 × 10^?15 cm². The total cross section for the formation of negative ions is 8.2 × 10^–18 cm² at an energy of 1.1 eV. The mass spectra of thymine molecules are measured and the cross sections of dissociative ionization are determined.     

Measurement of Photoionization Cross Sections of the Excited States of Titanium

实验研究了钛原子在293～321 nm波段的共振增强多光子电离. 采用激光烧蚀和超声射流相结合的实验技术来制备自由原子,由飞行时间质谱仪实现对钛原子光电离产物的检测. 从离子信号强度对和激光强度的依赖关系导出了钛原子价电子激发态的光电离截面. 实验测量的一些激发态光电离截面在0.2～6.0 Mb. 通过对⁴⁶Ti、⁴⁷Ti、⁴⁸Ti的光电离截面测量研究,没有发现明显的同位素依赖性.     

正庚烷燃烧反应中间自由基的光谱测量

采用ICCD瞬态光谱探测系统和化学激波管,在点火温度1 408K,点火压力2.0atm,燃料摩尔分数1.0%,当量比1.0的条件下,拍摄了正庚烷燃烧过程中不同时刻的瞬态发射光谱,光谱曝光时间6μs,拍谱范围200～850nm。确认了在所拍光谱范围内主要是OH,CH和C2自由基的特征辐射光谱,表明小自由基OH,CH和C2是正庚烷燃烧过程中重要的反应中间产物。所拍时间分辨光谱显示,在正庚烷燃烧反应中,OH,CH和C2自由基一出现很快就达到其浓度峰值,但CH和C2自由基随着反应的进行迅速减少至消失,OH自由基持续的时间却长很多。实验结果为了解正庚烷燃烧反应微观过程和验证其燃烧反应机理提供了实验依据。     

Dissociative ionization of the H2O molecule bombarded by swift singly charged and slow highly charged ions

Fragment ion energy spectra of the water molecule have been measured in conventional crossed-beam experiments by the impact of 46 keV/u energy, singly charged ions (SCIs) and 4.3 keV/u energy, highly charged ions (HCIs). Double differential cross sections have been determined and a comparative analysis has been performed. We found that the fragmentation spectra for SCIs and HCIs are very similar, indicating that both collisions lead to the same fragmentation channels. This suggests that the Coulomb explosion of the water molecule is dominantly determined by the charge state of the transient molecular ions, and it is almost independent from the primary ionization mechanism. Differences were observed not only between the SCI and HCI impact-induced fragmentation cross sections, but between those obtained by the 60 keV N⁶⁺ and 70 keV O⁷⁺ projectiles. The differences were attributed to the selectivity of the electron capture process for HCIs. Multiple target ionization cross sections have been deduced from the fragment ion spectra. We found contributions of up to fivefold ionization for SCIs and up to sixfold ionization for HCIs.     

发射光谱法研究甲基环己烷燃烧时激发态自由基时间历程

采用三组单色仪探测系统,测量了甲基环己烷在高温反射激波作用下瞬态燃烧反应过程中三种激发态自由基OH*,CH*和C*₂的特征光辐射,得到了激发态自由基时间历程和光辐射相对强度随温度的变化规律。反射激波温度1 200～1 700 K,激波压力1.5 atm,甲基环己烷摩尔分数0.1%,当量比1.0。在点火燃烧初始阶段三种自由基几乎同时产生,自由基持续时间随着温度的升高而变短。相同温度下CH*和OH*自由基持续时间大于C*₂自由基,在1 400 K以下C*₂自由基发光消失。OH*和CH*自由基发光强度在T<1 400 K时对温度变化不敏感,而在T>1 400 K时CH*自由基峰值随温度快速增长,C*₂和OH*峰值随温度增大比较平缓。将实验结果和化学反应机理模拟结果进行了对比,实验获得的OH*自由基时间历程在低温时和机理预测结果吻合较好,但在高温时有一定差异。CH*自由基时间历程在高温与机理结果吻合较好,在低温时机理预测结果CH*自由基持续时间要长于实验结果。实验测得的结果为含激发态物种化学反应动力学机理的验证和优化提供了依据。     

Electron-impact ionization and dissociative ionization of sulfur in the gas phase

We describe the methods and the results of investigation of the yield of positive ions formed as a result of electron-impact ionization of sulfur. The ionization energy for the basic molecule and the energies corresponding to the emergence of fragment ions are obtained from the ionization efficiency curves. The dynamics of formation of molecular sulfur ions in the temperature range 320–700 K is investigated. The energy dependences of efficiency S _n of the ion formation for n = 1–6 are analyzed, and their appearance energies are determined. The total cross section of sulfur ionization by a monochromatic electron beam is also investigated. Using the linear approximation method, we marked out features on the ionization function curve, which correspond to the ionization and excitation energies for multiply charged ions. The total cross section of the formation of negative sulfur ions is measured in the energy range 0–9 eV.     

Absolute electron scattering cross sections for the CF2 radical

Using a crossed electron-molecular beam experiment, featuring a skimmed nozzle beam with pyrolytic radical production, absolute elastic cross sections for electron scattering from the CF2 molecule have been measured. A new technique for placing measured cross sections on an absolute scale is used for molecular beams produced as skimmed supersonic jets. Absolute differential cross sections for CF2 are reported for incident electron energies of 30-50 eV and over an angular range of 20-135 deg. Integral cross sections are subsequently derived from those data. The present data are compared to new theoretical predictions for the differential and integral scattering cross sections, as calculated with the Schwinger multichannel variational method using the static-exchange and static-exchange plus polarization approximations.     

Interaction of H− ions with foil targets in the charge exchange system of a beam transport channel

The possibility of experimentally modeling the interaction of high energy H⁻ ions with foil targets using beams with more accessible lower energies that have the same dimensionless interaction parameter and similar current characteristics is pointed out. Results are presented from the first stage of a study of the beam-foil stripping of 2 and 7 MeV H⁻ ions. An analysis of the charge composition of the beam after a carbon foil serves as a basis for determining the corresponding cross sections for stripping of the ions and ionization of the product hydrogen atoms. The data from these and other beam-foil experiments are in good agreement with theoretical cross sections on carbon at different energies, as well with calculated values based on the superposition of experimental cross sections for gaseous carbon-containing targets. Zh. Tekh. Fiz. 68, 102–105 (August 1998) Deceased.     

Chemical structure of atmospheric pressure premixed laminar formic acid/hydrogen flames

The work presents an experimental and kinetic modeling study of laminar premixed formic acid [HC(O)OH]/H₂/O₂/Ar flames at different equivalence ratios (φ=0.85, 1.1 and 1.3) stabilized on a flat burner at atmospheric pressure, as well as laminar flame speed of HC(O)OH/O₂/Ar flames (φ=0.5–1.5) at 1 atm. Flame structure as well as laminar flame speed were simulated using three different detailed chemical kinetic mechanisms proposed for formic acid oxidation. The components in the fuel blends show different consumption profiles, namely, hydrogen is consumed slower than formic acid. According to kinetic analysis, the reason of the observed phenomenon is that the studied flames have hydrogen as a fuel but also as an intermediate product formed from HC(O)OH decomposition. Comparison of the measured and simulated flame structure shows that all the mechanisms satisfactorily predict the mole fraction profiles of the reactants, main products, and intermediates. It is noteworthy that the mechanisms proposed by Glarborg et al., Konnov et al. and the updated AramcoMech2.0 adequately predict the spatial variations in the mole fractions of free radicals, such as H, OH O and HO₂. However, some drawbacks of the mechanisms used were identified; in particular, they predict different concentrations of CH₂O. As for laminar flame speed simulations, the Konnov et al. mechanism predicts around two times higher values than in experiment, while the Glarborg et al. and updated AramcoMech2.0 show good agreement with the experimental data.     

Near-threshold electron-impact ionization of calcium atoms

The electron-impact ionization of calcium atoms is studied in the near-threshold energy range (from 6.11 to 16 eV). Experiments were performed by the method of intersecting electron and atomic beams with the recording of formed positive calcium ions. The electron beam (ΔE _1/2 = 0.15 eV) was formed using a hypocycloidal electron monochromator. An analysis of the specific features of ionization cross sections revealed a contribution from the excitation and decay of low-lying autoionization atomic states, which converge to the excitation thresholds of the 3d, 4p, and 5s ionic levels, and resonances (long-lived states of negative ions). The specific features of cross sections are identified using the experimental and theoretical data on photoionization (photoabsorption).     

正癸烷燃烧反应中OH,CH和C2自由基的瞬态发射光谱

采用ICCD瞬态光谱测量系统和加热激波管,在点火压力2.0atm,点火温度1 100～1 600K,当量比1.0,燃料摩尔分数1.0%条件下,实时测得了正癸烷/氧气/氩气燃烧过程的瞬态发射光谱,光谱范围200～850nm。结果显示燃烧过程中主要发射光谱带归属于小分子中间产物OH,CH和C2自由基,光谱强度的变化反映了燃烧过程中三种自由基浓度的变化历程;正癸烷燃烧过程中光谱强度峰值之比大于同为链烷烃的正庚烷相应OH/CH峰强度之比,揭示出两种链烃燃烧反应机理有较大差异。实验还获得了正癸烷燃烧过程中能显示谱带转动结构的CH和C2高分辨特征发射光谱。实验结果对了解正癸烷燃烧性质和验证正癸烷燃烧反应机理很有意义。     

Angular and energy distribution of electrons produced by 200–500 keV protons in gases

The cross beam method was used to measure double differential ionization cross sections for electron production by 200–500 keV protons incident on a molecular beam. The ejected secondary electrons were detected by an electron multiplier and an electrostatic 90 °-spectrometer which was movable in the scattering chamber from 18 °–155 ° with respect to the incident proton direction. After the elimination of disturbing electric and magnetic fields, electrons were measured at energies down to 1 eV. The absorption of the very slow electrons along their path through the spectrometer could be minimized by using a relatively low gas pressure in the scattering chamber of a few 10^?5 Torr. The efficiency of the electron detector was determined with an electron source whose emission rate per solid angle was known. Absolute cross sections and their angular dependence were obtained by measuring the slow electrons—ejected with a relatively high rate—without the molecular beam; these data being used to normalize the electron spectra acquired with the molecular beam. Ionization cross sections with 300 keV protons incident on helium are discussed and except for the very slow electrons, a good agreement is found with results of Ruddet al.     

电子与多电荷离子的碰撞电离(英文)

主要揭示了不同电离机制对高电荷态离子单电离和多重电离的贡献 ,包括直接电离 (一步过程 )、激发 自电离 (两步过程 )以及内壳Auger过程 ,研究了高电荷态镨离子的电子碰撞电离. Electron-impact ionization of ions is one of the most fundamental processes in every kind of plasma. Especially in high-temperature plasmas-whether in laboratory (nuclear fusion) or in astrophysics (atmosphere of stars)-atoms become ionized into multiply-charged ions by electron impact. The main purpose of our investigations is to unravel the contributions from different ionization mechanisms-like direct ionization (one-step process), excitation-autoionization (two-step process) and...     

含温有界原子模型下电子与离子碰撞激发和电离截面的理论研究

采用扭曲波玻恩交换近似方法，在自由原子模型下计算了电子与离子碰撞激发、电离截面，计算值与实验一致；在含温有界平均原子模型下，系统研究了不同温度、密度等离子体中离子的电子碰撞直接电离截面，发现由于温度、密度效应导致离子的能级漂移，引起等离子体中离子的碰撞电离截面比自由原子情形发生较大变化. 关键词： 平均原子模型 扭曲波波恩交换近似 电离截面