基于自由体积理论和摩擦理论的流体自扩散系数预测模型

基于自由体积理论和摩擦理论,提出了一个新的用于预测流体自扩散系数的理论模型。基于该理论模型,通过结合文献给出的分子动力学模拟数据,推导出了一个可以用于计算Lennard-Jones流体自扩散系数的半经验方程,与文献给出的分子动力学模拟数据相比,方程的平均相对偏差为3.71%。同时,选取了4种不同分子结构的流体作为计算工质,对其自扩散系数进行了计算,结果显示:与文献给出的实验数据相比,作者提出的方程的平均相对偏差为9.32%。     

缔合型链式硬球自扩散系数方程

将链式硬球模型自扩散系数方程与统计缔合流体理论（SAFT）相结合起来。实际非球状的缔合分子以有缔合点的硬球链来模拟。缔合流体中自扩散系数被认为是由非缔合贡献和氢键缔合贡献两部分组成：链式硬球自扩散系数方程用以计算非缔合流体的自扩散系数，而统计缔合流体理论描述了氢键数与密度和温度的关系，从而得到缔合对自扩散系数的影响，对于水（包括超临界水），醇类和HF等流体在宽广的压力和温度范围内，使用实验数据对本方程进行检验，其自扩散系数的相对平均偏差在7．5％左右。     

氩流体扩散行为的分子动力学模拟研究

采用分子动力学模拟技术(MD),利用L-J势能模型,研究了非受限空间和受限空间中,氩流体的扩散行为。考察了非受限空间中截断半径、粒子数、温度和受限空间中能量系数、狭缝宽度及温度等对氩流体自扩散系数的影响。模拟结果表明,在非受限空间中,氩流体的自扩散系数随温度升高而逐渐增大,其随温度的变化规律符合Arrhenius方程。在受限空间中,随着能量系数的增大和狭缝宽度的减小,氩流体自扩散系数逐渐减小;温度对氩流体自扩散系数的影响规律与非受限空间的类似。在相同温度下,受限空间氩流体的自扩散系数比非受限空间的要低。     

纯CO2体系扩散性质的分子动力学模拟

使用基于COMPASS力场的分子动力学（MD）模拟方法计算了CO2在气相、液相以及超临界区的自扩散系数。计算结果表明温度对扩散系数的影响在密度较低时比较明显,随着密度的升高温度的影响逐渐减弱;密度较高时密度的影响对扩散系数起主导作用。通过研究温度和密度对扩散系数的影响规律,提出了预测CO2自扩散系数的新方程,该方程与模拟值和文献试验值吻合良好。     

软球微扰状态方程的研究

从改进的势能函数出发,由径向分布函数理论和维里方程导出高温下纯流体配位数的计算公式,并与Sandler法结合求得简化的扰动型软球状态方程。用该方程计算的结果与Lennard-Jones模型的计算机模拟PVT数据吻合。     

Monte Carlo法模拟球形-线性Lennard-Jones流体混合物

本文用Monte Carlo方法对球形-线性Lennard-Jones流体混合物进行了计算机模拟。推导出含有该类线性分子的体系能量、压力和化学位的长程校正公式,并用于NPT系综模拟,研究了组成对体系物性的影响,为进一步模拟链状分子及聚合物体系打下基础。     

含临界点的统计缔合流体理论研究(Ⅰ)非极性流体

从适合于临界点的计算出发 ,对统计缔合流体理论方程进行改进 :(1)对链状分子的每个链节考虑其非球形度 ;(2 )提出必须考虑链节成链时对色散作用的影响 .建立了扩展的统计缔合流体理论状态方程 ,对于正构烷烃和异构烷烃的计算表明 ,该方程计算温度范围大 ,从低温区到临界区 ,特别是在临界点附近精度有明显提高 ,临界点的计算值和实验值基本符合 .扩展了理论状态方程的适用性 ,可望用于各种含临界区域流体体系的热力学计算     

基于MPHC活度系数模型关联烃－水体系液－液平衡

基于普遍化范德华配分函数理论，应用由局部组成概念导出的方阱流体配位数模型导出了链状分子混合物的配位数模型，并由此建立了一个新的活度系数模型；将其应用于高度非理想体系汽－液平衡活度系数的关联，结果与Ｗｉｌｓｏｎ方程相当，但方程参数随温度变化较小；其于Ｎｅｗｔｏｎ－Ｒａｐｈｓｏｎ－Ｇａｕｓｓ液－液平衡算法，应用新模型对烃－水体系的液－液平衡进行了关联计算，结果优于ＮＲＴＬ方程     

基于MPHC活度系数模型关联烃－水体系液－液平衡

基于普遍化范德华配分函数理论，应用由局部组成概念导出的方阱流体配位数模型导出了链状分子混合物的配位数模型，并由此建立了一个新的活度系数模型；将其应用于高度非理想体系汽－液平衡活度系数的关联，结果与Ｗｉｌｓｏｎ方程相当，但方程参数随温度变化较小；其于Ｎｅｗｔｏｎ－Ｒａｐｈｓｏｎ－Ｇａｕｓｓ液－液平衡算法，应用新模型对烃－水体系的液－液平衡进行了关联计算，结果优于ＮＲＴＬ方程     

微扰理论的应用研究(I)——水-正丁醇二元体系热力学计算

本文对流体分子中的色散能和排斥能采用Lennard-Jones位能函数和Barker-Henderson微扰理论进行计算;偶极定向能采用空间取向平均和微扰理论处理,并用Monte Carlo分子模拟数据进行了验证;还考虑了诱导偶极能.在此基础上,计算了H_2O-nC_4H_9HO二元体系液相组分活度系数,结果满意.     

Estimating the self-diffusion and mutual diffusion coefficients of binary mixtures on the basis of a modified van der Waals model

The previously proposed model is used to determine the values of the self-diffusion coefficient of He, Ne, Ar, Kr, Xe, H₂, D₂, N₂, O2, CO₂, NH₃, and CH₄ in the liquid and dense gaseous states, which were compared with the experimental data obtained at a pressure of ≈200 MPa and a temperature of ≈500 K. The calculations are carried out with the use of the equation of state of these substances in the form of a modified van der Waals model. The self-diffusion model was generalized for the case of mutual diffusion in binary mixtures, which is based on the modified model of the van der Waals state equation for mixtures. The modeled coefficient of mutual diffusion for a great number of binary mixtures of the above-mentioned individual substances is determined, and the results are compared with the known data. Without special calibration for the experiment, the model correctly predicts the relationship of the self-diffusion and mutual diffusion coefficients (with their variation by several orders of magnitude in the case where the density changes from gaseous to liquid) with both pressure and temperature. For most substances considered in the paper, the maximum deviations of calculations from the experiment do not exceed 30–50%.     

On predicting self-diffusion coefficients from viscosity in gases and liquids

The relations between self-diffusion and viscosity for compressed liquids and gases have been reviewed, and a new equation for correlating viscosities over wide ranges of temperature and pressure is proposed. This formula is inspired by the Lennard-Jones Chain model of Yu and Gao for self-diffusion, and represents the viscosities of 15 compounds (1046 data points) with an average absolute deviation of 6.95%. Moreover, as the presented equation and the Yu-Gao model require the same fitting parameters, the ability to calculate self-diffusion coefficients from the viscosity parameter is studied. Some of the classic reviewed relations, such as the Stokes-Einstein formula, are also contrasted with the available experimental data of both transport properties.     

Self- and mutual diffusion coefficient equation for pure fluids, liquid mixtures and polymeric solutions

Transport properties are important information not only for industrial equipment design but also for many research areas. While there is a well-developed theory for gases at low densities, there is no established theory to calculate diffusion coefficients for dense fluids, especially for polymeric solutions. Recently, a database of 96 self-diffusion coefficient data points were obtained from molecular dynamics (MD) simulations for freely jointed Lennard-Jones chains (LJC) with lengths of 2, 4, 8 and 16 at reduced densities ranging from 0.1 to 0.9 and in the reduced temperature interval of 1.5 to 4. These data were used to develop an equation that correlates MD self-diffusion coefficient points with an overall absolute average deviation of 15.3%. The aim of this work is to show that this equation can be used to calculate diffusivities of pure liquids and liquid mixtures, including polymeric solutions. The proposed equation is used for correlating self-diffusion coefficients for 22 pure real substances and then for predicting mutual diffusion coefficients for 12 binary liquid mixtures. The proposed equation is also used to calculate mutual diffusion coefficients for polymeric systems as: polystyrene-toluene at 110 °C, poly(vinyl acetate)-toluene at 35 °C, and poly(vinyl acetate)-chloroform at 35 and 45 °C. Results show that the model developed here seems to be a promising approach for correlating mutual diffusion coefficients not only for small-molecule systems but also for polymer-solvent systems. One advantage of the equation proposed here is that the parameters have physical meaning and most of them can be estimated without any information on binary diffusion data.     

指数-6流体的自扩散系数的分子动力学模拟

Self-diffusion coefficients of exponential-six fluids are studied using equilibrium molecular dynamics simulation technique. Mean-square displacements and velocity autocorrelation functions are used to calculate self-diffusion coefficients through Einstein equation and Green-Kubo formula. It has been found that simulation results are in good agreement with experimental data for liquid argon which is taken as exponential-six fluid. The effects of density, temperature and steepness factor for repulsive part of exponential-six potential on self-diffusion coefficients are also investigated. The simulation results indicate that the self-diffusion coefficient of exponential-six fluid increases as temperature increases and density decreases. In addition, the larger self-diffusion coefficients are obtained as the steepness factor increases at the same temperature and density condition.     

乙烯分子在狭缝炭孔内的毛细相变和自扩散

The grand canonical Monte Carlo (GCMC), the canonical Monte Carlo by using equal probability perturbation, and the molecular dynamics (MD) methods were used to study the capillary phase-transition (capillary condensation and evaporation) and self-diffusion for a simple Lennard-Jones model of ethylene confined in slit carbon pores of 2.109 nm at temperatures between 141.26 K and 201.80 K. The critical point of capillary phase-transition was extrapolated by the critical power law and the law of rectilinear diameter from the capillary phase-transition data in the near critical region. The effects of temperature and fluid density on the parallel self-diffusion coefficients of ethylene molecules confined in the slit carbon pores were examined. The results showed that the parallel selfdiffusion coefficients in the capillary phase transition area strongly depended on the fluids local densities in the slit carbon pores.     

The effect of liquid viscosity on sheared granular flows

This work investigates the effect of transport properties in sheared granular flows with adding different silicone oils. We performed a series of experiments in a shear cell device using 2-mm soda lime beads as the granular materials by adding little amount of different silicone oils. The viscosity of silicone oils added was changed in different tests. By particle tracking method, the velocities, the velocity fluctuations and the self-diffusion coefficients were measured and analyzed. It was found that for the granular system with adding the more viscous silicone oil, the system became less active due to the greater shear force and cohesive force, which resulted in the decrease of velocity fluctuations and diffusions. Three bi-directional stress gages were installed to the upper wall to measure the normal and shear stresses of the granular materials along the upper wall. Thus, the effective viscosities of the wet granular material systems could be evaluated. The dimensionless normal and shear stresses, and the effective viscosity in the wet sheared granular flow were found to decrease with the increase of the viscosity of the added silicone oil. The influence of the viscosity of added fluid on these transport properties of wet granular systems will be discussed.     

用径向分布函数及Lennard-Jones位能模型计算真实流体的PVT性质

用顺序解析平衡法,结合Ｌｅｎｎａｒｄ－Ｊｏｎｅｓ（Ｌ－Ｊ）位能函数模型计算径向分布函数,然后直接代入统计热力学所给出的理论状态方程预测真实流体的ＰＶＴ性质。Ｌ－Ｊ位能模型参数由临界温度Ｔｃ和临界压力Ｐ确定。结果表明该方法能成功地预测非极性和弱极性纯流体的ＰＶＴ性质。当分子尺寸小于正己烷时,除临界温度附近之外,预测的饱和液体体积的平均相对误差一般小于５％,对于分子尺寸更大的流体,可应用象Ｋｉｈａｒａ模型这样的三参数位能模型来提高预测精度。     

Effects of uniaxial tensile strain on the release of small molecules from silicone rubber

Silicone rubber materials may be subject to mechanical strains which can affect the transport properties of small molecules loaded in the materials such as plasticizers and active molecules, hence deteriorating their intended mechanical properties or affecting their performance as carriers of active molecules. Therefore, it is important to understand the effects of mechanical strains on transport of small molecules in the silicone rubber matrix. In this work, silicone rubber sheets loaded with 2 wt% triacetin were stretched and held at four different lengths up to 125% engineering strain. The mass transfer coefficients and diffusion coefficients of triacetin in the strained silicone rubber were determined by monitoring the release of triacetin using headspace gas chromatography–mass spectrometry. It was found that there was no significant change of diffusion coefficient as the applied strain increased, which might result from two microstructure changes that had conflicting effects on diffusion: chain orientation and free volume deformation.     

Prediction of the self-diffusion coefficients in aqueous KCl solution using molecular dynamics: A comparative study of two force fields

Molecular dynamic simulation was used to calculate the self-diffusion coefficients of ions in aqueous KCl solution. The simulations were performed for enough time (12 ns) in the form of all-atom to determine the accurate values of the self-diffusion coefficients. The values of the self-diffusion coefficients were calculated by Einstein equation. Two different force fields of Dang and Deublein were employed in the simulations, and we found that at low ion concentration (equal or less than 3mol/(kg of H₂O)), the Dang force field is more accurate for prediction of the selfdiffusion coefficient of K⁺ ions and Deublein force field is more accurate for Cl^? ions. An Arrhenius type equation was used to model the temperature dependence of the self-diffusion coefficients and the diffusion activation energies at different ion concentrations were reported.