基于OH-PLIF的狭长受限空间油气爆炸中间基团浓度分布研究

为了精确测量狭长受限空间油气爆炸过程中的关键自由基团，从而实现对其爆炸流场、火焰传播的精确分析，基于先进的平面激光诱导荧光测量技术（PLIF），设计构建了油气爆炸PLIF测量系统，开展了不同工况下狭长受限空间汽油-空气混合气爆炸实验研究，获得了该爆炸中间基团OH基的浓度分布。实验结果表明，1.1%~2.4%（体积分数）油气浓度之间，OH基浓度先增大后减小；随火焰的传播发展，OH基浓度不断变大，表明爆炸不断强化；爆燃不同时期OH基分布情况不同，表明不同爆燃阶段的燃烧反应区域有较大差异；爆燃前期火焰与壁面之间有“隔离带”，是由未燃气浓度增大导致火焰传播变慢的结果。主要创新点在于通过设计时序控制子系统，解决了非稳态预混燃烧中自由基分布瞬态测量。     

Theoretical kinetic study of the reaction between dimethyl disulfide and OH radicals

The potential energy profile of the reaction between dimethyl disulfide and OH^? radicals is explored by utilizing ab initio and hybrid meta density functional theory methods. Having the energies and structural data of the stationary points, statistical rate theories, such as transition state theory and variable reaction coordinate-transition state theory, are employed to compute the overall rate constants, and discuss the mechanism and product channels. On the basis of the calculations, the overall rate coefficient is predicted to be 2.49?×?10^?10?cm³?molecule^?1?s^?1 at 298?K. It is found that in the most favorable pathway, the reaction proceeds via formation of the relatively unstable intermediate CH₃S^?(OH)SCH₃ decomposing rapidly to yield CH₃S^?+CH₃SOH.     

Real‐time monitoring by proton relaxometry of radical polymerization reactions of acrylamide in aqueous solution

The potential of time‐domain nuclear magnetic resonance (TD‐NMR) for the real‐time monitoring of solution radical polymerizations is demonstrated. A model system composed of a redox‐pair initiator system, acrylamide as monomer and water as solvent was investigated. A second‐generation continuous wave free precession technique was employed to measure the longitudinal relaxation time constant (T₁) of the samples throughout the polymerization reactions. This parameter was shown to be sensitive to the reactant feed free‐radical enhancement of the water molecule relaxation time, making it a good probe to monitor monomer conversion in real time in an automated, non‐destructive fashion. It was found that the T₁ value was better than the transverse relaxation time constant (T₂) for describing the evolution of the polymerization reactions, due to its greater sensitivity to paramagnetic effects. The TD‐NMR signal variation observed was linked to the formation, propagation and termination steps of the radical polymerization kinetics scheme. These first results may contribute to the application of real‐time monitoring of radical polymerization reactions employing low‐cost and robust TD‐NMR spectrometers. © 2018 Society of Chemical Industry     

Combination of nuclear magnetic resonance spectroscopy and nonlinear methods to analyze the copolymerization of phosphonic acid derivatives

We demonstrate in this study that the combination of modern inline monitoring methods [here: inline nuclear magnetic resonance (NMR)] with simulations gains more exact and profound kinetic results than previously used methods like linearization without that combination. The ¹H-NMR spectroscopic data (more than 100 data points) are used to construct the copolymerization diagram. The reactivity ratios are obtained applying the van Herks nonlinear least square method. The examination of the radical copolymerization of 2-hydroxyethyl methacrylate (HEMA) with (2-{[2-(ethoxycarbonyl)prop-2-en-1-yl]oxy}ethyl) phosphonic acid (ECPPA) as important adhesive monomer used in dentistry yields reactivity ratios of r_HEMA = 1.83; r_ECPPA = 0.42. The copolymerization diagram reflects nonideal, non-azeotropic copolymerization. The sequence distribution of the obtained by Monte Carlo simulation indicates the generation of statistical copolymers. As an important finding, it is demonstrated that the repeating units responsible for etching and adhesion are arranged over the whole polymer chain, which is necessary to achieve proper functionality. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 48256.     

Modeling and analysis of passive worm propagation in the P2P file-sharing network

A number of worms, named P2P (peer-to-peer) passive worms, have recently surfaced, which propagate in P2P file-sharing networks and have posed heavy threats to these networks. In contrast to the majority of Internet worms, it is by exploiting users’ legitimate activities instead of vulnerabilities of networks in which P2P passive worms propagate. This feature evidently slows down their propagation, which results in them not attracting an adequate amount of attention in literature. Meanwhile, this feature visibly increases the difficulty of detecting them, which makes it very possible for them to become epidemic. In this paper, we propose an analytical model for P2P passive worm propagation by adopting epidemiological approaches so as to identify their behaviors and predict the tendency of their propagation accurately. Compared with a few existing models, dynamic characteristics of P2P networks are taken into account. Based on this proposed model, the sufficient condition for the global stability of the worm free equilibrium is derived by applying epidemiological theories. Large scale simulation experiments have validated both the proposed model and the condition.     

Aqueous One-pot Synthesis of Glycopolymers by Glycosidase-catalyzed Glycomonomer Synthesis Using 4,6-Dimetoxy Triazinyl Glycoside Followed by Radical Polymerization

Glycopolymers have attracted increased attention as functional polymeric materials, and simple methods for synthesizing glycopolymers remain needed. This paper reports the aqueous one-pot and chemoenzymatic synthesis of four types of glycopolymers via two reactions: the β-galactosidase-catalyzed glycomonomer synthesis using 4,6-dimetoxy triazinyl β-D-galactopyranoside and hydroxy group-containing (meth)acrylamide and (meth)acrylate derivatives as the activated glycosyl donor substrate and as the glycomonomer precursors, respectively, followed by radical copolymerization of the resulting glycomonomer and excess glycomonomer precursor without isolating the glycomonomers. The resulting glycopolymers bearing galactose moieties exhibited specific and strong interactions with the lectin peanut agglutinin as glycoclusters.     

TC4合金表面Cu/石墨复合镀层的摩擦磨损行为

采用无氰电镀工艺在TC4合金表面制备了Cu/石墨复合镀层，研究了镀层的组织结构和摩擦磨损行为。结果表明，采用无氰电镀方法能够在TC4合金表面制备出组织致密且与基体结合紧密的Cu/石墨复合镀层，但增加镀层中石墨的含量会降低镀层与基体合金的结合强度，并导致硬度小幅下降。摩擦磨损实验结果表明，Cu/石墨复合镀层具有优良的摩擦磨损防护性能，归因于石墨有效降低了镀层的摩擦系数和磨损率；对镀层磨损形貌、磨损产物和摩擦系数的综合分析结果表明，纯铜镀层的摩擦磨损机制主要为犁削磨损、黏着磨损和剥层磨损，Cu/石墨复合镀层的磨损机制为轻微的削层磨损和疲劳磨损。     

含煤盆地深层“超饱和”煤层气形成条件

中国深层煤层气资源丰富，但总体勘探和认识程度较低，尚未形成较为系统的深层煤层气地质理论。通过解剖分析准噶尔盆地白家海凸起和鄂尔多斯盆地临兴区块深层"超饱和"煤层气井的试气/生产动态，估算原地游离气的含气量，分析了深层"超饱和"煤层气的形成条件。研究表明：①深层"超饱和"煤层气储层中除吸附气外，还含有原地游离气，用常规试气方法可直接获得气流，煤层气的产出不明显依赖于排水降压；②埋藏超过一定深度，在煤阶和温度的综合作用下，煤的吸附能力将随埋深的继续增加而降低，煤层中吸附气的饱和度有增加的趋势，在达到吸附饱和后，出现原地游离气并形成"超饱和"煤层气，盆地深层具有"超饱和"煤层气形成的优势条件；③由于地温梯度和压力梯度的不同，不同盆地"超饱和"煤层气出现的临界深度不同，异常高压和异常高热流可以降低深层"超饱和"煤层气形成的临界深度；④深层"超饱和"煤层气开发具有大大缩短见气时间、充分利用地层能量和累积产水量低等优势，有望成为未来煤层气勘探开发的一个重要领域。     

A Distribution‐freeCUSUMChart for Monitoring Variability of AutocorrelatedProcesses

We present a distribution‐free tabular cumulative sum chart for monitoring the variability of an autocorrelated process. A quantity known as the asymptotic variance parameter is employed as a measure of the variability, and a distribution‐free tabular cumulative sum chart is applied to variance estimates calculated from batches of nonoverlapping samples. The proposed chart is applicable to a stationary process with a general marginal distribution and a general autocorrelation structure. It also determines control limits analytically without trial‐and‐error simulations. The performance of the proposed chart is tested on stationary processes with both normal and nonnormal marginals with various autocorrelation structures. Copyright © 2014 John Wiley & Sons, Ltd.