The isobutylene-isobutane alkylation process in liquid HF revisited

Details on the mechanism of HF catalyzed isobutylene-isobutane alkylation were investigated. On the basis of available experimental data and high-level quantum chemical calculations, a detailed reaction mechanism is proposed taking into account solvation effects of the medium. On the basis of our computational results, we explain why the density of the liquid media and stirring rates are the most important parameters to achieve maximum yield of alkylate, in agreement with experimental findings. The ab initio Car-Parrinello molecular dynamics calculations show that isobutylene is irreversibly protonated in the liquid HF medium at higher densities, leading to the ion pair formation, which is shown to be a minimum on the potential energy surface after optimization using periodic boundary conditions. The HF medium solvates preferentially the fluoride anion, which is found as solvated [FHF](-) or solvated F(-.)(HF)(3). On the other hand, the tert-butyl cation is weakly solvated, where the closest HF molecules appear at a distance of about 2.9 Angstrom with the fluorine termination of an HF chain.     

Reflection and transmission of waves near the localization threshold

A theory is presented for propagation of waves in bounded media near the mobility edge, based on the self-consistent theory for localization. It predicts a spatially inhomogeneous diffusion constant that leads to scale dependence in enhanced backscattering and transmission.     

两种气液两相流模型的应用和比较

本文应用MUSIG模型[1]和均一直径模型对某溶液堆台架模型堆芯内气液流动传热进行了数值模拟.在MUSIG模型中堆芯内离散相气泡被分为5组不同直径的气泡,用于分析堆芯内气泡的流动变化和大小分布,采用Luo and Svendsen[2]和Prince and Blanch[3]模型描述不同直径气泡组间的破裂和聚合.在均一直径模型中,堆芯内的气体被考虑为同一直径的组分,并且不考虑其破裂与聚合现象.计算得到采用两个模型的模拟结果并且对其进行了对比研究.结果显示应用MUSIG模型的计算结果与台架实验结果吻合更好.     

Six-Fold Degenerate Dark States in a Four-Level Atomic System

With all driving fields on Raman resonance, a tripod-type atomic system quickly evolves into a dark state decoupled from the lossy excited level. The dark state depends strongly on field Rabi frequencies, spontaneous decay rates, and the initial atomic population in a complicated way. Analytical results reveal that it is a sixfold degenerate dark state with its three components superposed both coherently and incoherently due to population redistribution from spontaneous emission.     

Synthesis and solution properties of comblike poly(mono-n-alkyl itaconates). I. Poly(monodecyl itaconate)

The monoester of itaconic acid with n-decyl alcohol was prepared and polymerized. The polymer was fractionated and characterized by viscometry, size-exclusion chromatography (SEC) and light scattering. Some of the common semiempirical relations for flexible and rigid polymers were used in order to obtain the unperturbed dimensions and the conformational parameters. Thermodynamic and dimensional parameters were determined and calculated. The results are compared with those reported previously for similar compounds.     

堆焊熔敷层表面纳米晶层摩擦磨损性能研究

用预压力滚压技术在堆焊修复层表面制备纳米晶层.利用TEM、SEM分析技术研究表面纳米晶层微观结构,利用CETR-3型多功能摩擦磨损试验机考察在干摩擦条件下堆焊层表面纳米晶层的摩擦磨损性能.结果表明堆焊修复层表面经表面纳米化处理后,表面形成厚度约为10μm(晶粒尺寸小于100 nm)的纳米晶层,最表面层平均晶粒尺寸约为10 nm.纳米压痕试验表明纳米晶层的硬度提高,最表面纳米晶层的硬度约为原始堆焊层硬度的3倍.与原始堆焊试样相比,表面纳米化试样的摩擦系数降低了10%,磨损体积降低了25%~30%左右.表面纳米化样品的磨损机制由原始堆焊层的磨粒磨损和黏着磨损转变为磨粒磨损,分析表明晶粒细化导致的高硬度、低塑性是摩擦磨损性能改善和磨损机制改变的主要原因.     

On the existence and stability of periodic orbits in non ideal problems: General results

In this work, motivated by non-ideal mechanical systems, we investigate the following O.D.E. [(x)\dot] = f (x) + eg (x, t) + e²[^(g)] (x, t, e){\dot{x} = f (x) + \varepsilon g (x, t) + \varepsilon^{2}\widehat{g} (x, t, \varepsilon)} , where x ? W ì \mathbbRⁿ{x \in \Omega \subset \mathbb{R}^n} , g,[^(g)]{g,\widehat{g}} are T periodic functions of t and there is a ₀ ∈ Ω such that f ( a ₀) = 0 and f ′( a ₀) is a nilpotent matrix. When n = 3 and f (x) = (0, q (x ₃) , 0) we get results on existence and stability of periodic orbits. We apply these results in a non ideal mechanical system: the Centrifugal Vibrator. We make a stability analysis of this dynamical system and get a characterization of the Sommerfeld Effect as a bifurcation of periodic orbits.     

Comparison of Exact and Perturbative Results for Two Metrics

We compare the exact and perturbative results in two metrics and show that the spurious effects due to the perturbation method do not survive for physically relevant quantities such as the vacuum expectation value of the stress-energy tensor.     

含芴共轭单元的超支化聚合物的合成及表征

以芴和季戊四醇为初始物,分别合成了具有芴共轭单元和季戊四醇多臂结构的两种聚合单体,进一步采用Suzuki反应合成出一种结构新颖的部分共轭结构的超支化聚合物.利用紫外吸收光谱和荧光发射光谱对聚合物予以表征,结果表明,超支化聚合物具有与模型化合物分子相似的发光行为,既可以发出纯正的蓝光,又表现出支化结构对荧光发射的影响.差...     

MICROSTRUCTURE AND FRACTAL FORMATION OF ANNEALED Ge-Au FILM AND Ge-Au/Au BILAYER FILMS

The as-deposited and annealed Ge-Au film and Ge-Au/Au bilayer films have been observed by transmission electron microscopy. The bilayer with a composition of Ge-5at%Au film is amorphous, while the Ge-22at%Au film is polycrystalline. Higher concentration of Au raises the structural heterogeneity and instability. Fractals can be observed in the Ge-5at%Au/Au bilayer samples annealed at 60-100℃. The difference of the fractal patterns generated from Ge-Au/An and a-Ge/Au films call be attributed to the higher heterogeneity and instability in Ge-Au/An bilayers.