高焓湍流边界层壁面摩阻产生机制分析

高超飞行器在中低空以极高马赫数飞行时,飞行器表面会遇到湍流与高温非平衡效应耦合作用的新问题.这种高焓湍流边界层壁面摩阻产生机制是新型高超声速飞行器所关注的基础科学问题,厘清此产生机制可以为减阻方法的设计提供指导,具有重要的工程实用价值.本文选取高超声速飞行时楔形体头部斜激波后的高焓流动状态,开展了考虑高温非平衡效应的湍流边界层直接数值模拟研究,并设置同等边界层参数下的低焓完全气体湍流边界层流动作为对比,采用RD (Renard&Deck)分解技术研究了高焓湍流边界层摩阻的主要产生机制,对摩阻产生的主要贡献项积分函数分布进行了详细分析,研究了高温非平衡效应对摩阻产生的影响规律;采用象限分析技术,研究了摩阻分解湍动能生成项的主导流动事件.计算结果表明,高温非平衡效应会使得壁面摩阻脉动条带的流向和展向尺寸均减小.分子黏性耗散项和湍动能生成项是高焓湍流边界层摩阻生成的主要流动过程.分子黏性耗散项主要作用在近壁区,高焓流动的分布与低焓流动存在差异.象限分析表明,上抛和下扫运动是影响摩阻分解中湍动能生成项的主导事件.     

Entropic effect implication for change in polymer coils swelling state in the demixing enthalpy recovery of aqueous poly(vinyl methyl ether) solutions

Time‐dependent demixing enthalpy recovery behavior of aqueous poly(vinyl methyl ether) (PVME) solutions exhibits distinct recovery characteristics in three concentration regions. The absence of recovery behavior below a water concentration of 38.3 wt % indicates that the PVME coil is in a globular state. The typically sigmoidal recovery behavior of demixing enthalpy above 38.3 wt % is ascribed to the reswelling of the collapsed polymer coils induced by the entropic effect. The increase in difference between the upper and lower limits indicates the continued swelling of the PVME coils. Above 65 wt %, a dominant diluting effect can be observed, and a much longer phase separation time is needed to reach the expected lower limit. In contrast, the recovery of demixing enthalpy in a wide range of water concentration (from 38.3 to 90 wt %) exhibits the same feature. The infrared spectroscopy results are in agreement with the above macroscopic differential scanning calorimetry results. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 142–151     

Thermochemistry of Surfactant-Templating of USY Zeolite

With the aim of understanding the thermochemistry of the introduction of mesoporosity in zeolites by using surfactants, high temperature oxide melt solution calorimetry was used to determine the change in the enthalpy of formation of USY zeolite before and after the introduction of mesoporosity. Our results confirm that this process only slightly destabilizes the zeolite by the additional surface area. However, this can be overcome by the stabilizing effect of the interactions between the surfactant and the zeolite framework.     

Fluoroalkyl Radical Generation by Homolytic Bond Dissociation in Pentacarbonylmanganese Derivatives

Thermal decarbonylation of the acyl compounds [Mn(CO)₅(COR_F)] (R_F=CF₃, CHF₂, CH₂CF₃, CF₂CH₃) yielded the corresponding alkyl derivatives [Mn(CO)₅(R_F)], some of which have not been previously reported. The compounds were fully characterized by analytical and spectroscopic methods and by several single-crystal X-ray diffraction studies. The solution-phase IR characterization in the CO stretching region, with the assistance of DFT calculations, has allowed the assignment of several weak bands to vibrations of the [Mn(¹²CO)₄(eq-¹³CO)(R_F)] and [Mn(¹²CO)₄(ax-¹³CO)(R_F)] isotopomers and a ranking of the R_F donor power in the order CF₃<CHF₂<CH₂CF₃≈CF₂CH₃. The homolytic Mn−R_F bond cleavage in [Mn(CO)₅(R_F)] at various temperatures under saturation conditions with trapping of the generated R_F radicals by excess tris(trimethylsilyl)silane yielded activation parameters ΔH^≠ and ΔS^≠ that are believed to represent close estimates of the homolytic bond dissociation thermodynamic parameters. These values are in close agreement with those calculated in a recent DFT study (J. Organomet. Chem. 2018 , 864, 12–18). The ability of these complexes to undergo homolytic Mn−R_F bond cleavage was further demonstrated by the observation that [Mn(CO)₅(CF₃)] (the compound with the strongest Mn−R_F bond) initiated the radical polymerization of vinylidene fluoride (CH₂=CF₂) to produce poly(vinylidene fluoride) in good yields by either thermal (100 °C) or photochemical (UV or visible light) activation.     

Liquid mixture excess properties by the hard sphere model

The excess properties of mixing were calculated for seven systems Ar-CH₄; Ar-N₂; Ar-O₂; Ar-CO; CO-CH₄; O₂-N₂; N₂-CO, using the Caranhan and Starling equation of state of rigid spheres and the Longuet-Higgins and Widom model. Two sets of calculations were done one using the experimentalG ^E to calculateS ^E ,H ^E andV ^E , and the other making use of Miller’s cross parameter values. The calculated values are compared with those of Snider and Herrington and Miller’s values and also with the experimental values. The agreement was found to be good.     

Optical shuttering action in nematic phase of SMHBLC: observation of a ribbon-like texture

In this study, complexes belonging to supramolecular hydrogen-bonded liquid crystal homologous series are synthesized and characterized. Hydrogen bond is formed between p-n-alkyloxy benzoic acids (nBAO, where n?=?5–11) and chlorobenzoic acid (ClBAO), respectively. The isolated homologues are characterized by various techniques such as polarizing optical microscopic (POM) studies, differential scanning calorimetry (DSC), and Fourier transform–infrared spectroscopy. Based on the POM and DSC studies, the phase diagram has been constructed and discussed. A new smectic ordering, labeled as smectic R, has been characterized, which exhibits a ribbon-like texture. This phase is observed in the complexes pertaining to the higher homologous series. Tilt angle in this phase has been experimentally deduced and the results are fitted to the power law which concurs with the mean-field theory predicted value. Optical shuttering action in the homologue has been detected in the nematic phase and the results are also discussed.     

黏弹性流体充模过程中凝固现象的数值模拟

建立了黏弹性流体在充模过程中带有相变的气一液两相模型,该模型分别由气、液两相的质量守恒方程、动量守恒方程、能量守恒方程描述,并通过引入Heaviside函数将气一液两相的方程组统一为一个方程组;建立了一个对型腔内熔体和气体都适用的修正的焓方法来描述充模过程中的相变,采用基于同位网格的有限体积方法对模型进行求解,水平集方法捕捉充模过程中的界面演化,模拟出了黏弹性流体在充模过程中的凝固现象,得出了充模过程中型腔内的温度、压力、第一法向应力差等随时间的变化;并讨论了型腔壁面温度、熔体温度、注射速度对充模过程中凝固现象的影响,研究结果表明:型腔壁面温度越高,凝固层越薄;熔体温度越高,凝固层越薄;注射速度越高,凝固层越薄,故提高型腔壁面温度、熔体温度、注射速度可以减少或消除型腔壁面附近的凝固层。     

氯化镉与对甲基苯胺配位反应的热化学研究

用新型的具有恒定温度环境的反应热量计,以一定比例的 HCl（3.0 mol·L-1）与无水乙醇的混合溶液作为量热溶剂,分别测定了反应物[CdCl2·5/2H2O,p-tol]和产物[Cd（p-tol）2Cl,H2O]的溶解焓,设计了一个新的热化学循环,得到了氯化镉与对甲基苯胺配位反应的反应焓△rHm=-7.598kJ·mol1-,并计算出了配合物Cd（p-tol）2Cl2的标准生成焓.推荐其值为:△rHm=（p-tol）2Cl2,s]=-490.773kJ·mol-1     

Combined study of thermochemical properties of nitroform and its salts

A combined method for determination of the standard enthalpies of formation of nitroform and its salts was proposed. The enthalpies of dissolution of nitroform and its ammonium, hydrazinium, guanidinium, and potassium salts in water were measured. The enthalpy of combustion of hydrazinium salt of nitroform was determined by a combustion calorimetry, and its standard enthalpy of formation was calculated. The enthalpy of formation of trinitromethyl anion in indefinitely diluted aqueous solution −24.94±0.79 kJ mol⁻¹, was calculated on the basic of the data obtained for enthalpies of formation and dissolution of ammonium and hydrazinium salts of nitroform. Standard enthalpies of formation of nitroform and its salts were calculated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2451–2454, December, 1998.     

Thermochemical Investigations of Calcium Carbonate Phase Transitions I. Thermal activated vaterite—calcite transition

The vaterite—calcite transition above 630 K has been studied by isothermal and non-isothermal differential scanning calorimetry. Vaterite samples prepared under different conditions were investigated. The transition temperature is strongly dependent on the sample preparation. The observed transition enthalpy H_tr is nearly equal for different samples and experimental conditions. From 28 measurements a value of H_tr–(3.12±0.11) kJ mol^–1 was obtained. The activation energy for the polymorphic transition was calculated from the Arrhenius plot and by use of isoconversional methods, as a function of the degree of conversion. The influence of the kinetic model distortion and experimental uncertainties on the obtained data was discussed. The actual value of the activation energy was assessed at E_a=(250±10) kJ mol^–1 for nearly all examined samples. Functions, corresponded to the model mechanism of nuclei formation and growth, provide the unambiguous consideration of the transition kinetic for the investigated vaterite samples. Differences in the dynamic behaviour of several samples at the transition are established.This revised version was published online in November 2005 with corrections to the Cover Date.