MOLECULAR DYNAMICS SIMULATION OF ENTROPY AND SURFACE TENSION FOR GRAIN BOUNDARY OF α-Fe

The grain boundary is an interface and the surface tension is one of its important thermodynamic properties. In this paper, the surface tension of the Σ9 grain boundary for α-Fe at various temperatures and pressures is calculated by means of Computer Molecular Dynamics (CMD). The results agree satisfactorily with the experimental data. It. is shown that the contribution of entropy to surface tension of grain boundary can be ignored.

A new method for the determination of surface tension from molecular dynamics simulations applied to liquid droplets

For the determination of surface tension of liquid droplets by molecular dynamics simulations, the most timeconsuming part is the calculation of pressure tensor in the transition layer, which makes it difficult to enhance the precision of the computation. A new method for the calculation of surface tension of liquid droplets to reduce the calculation quantity of pressure tensor in transition layer to the minimum is proposed in this paper. Two thousand particles are taken as example to show how to carry out our scheme.

Molecular dynamics simulation of liquid-vapor surface tension

A molecular dynamics simulation model is established based on the well-known Lennard-Jones 12-6 potential function to determine the surface tension of a Lennard-Jones liquid-vapor interface. The simulation is carried out with argon as the working fluid of a given molecular number at different temperature and different truncated radius. It is found that the surface tension of a Lennard-Jones fluid is likely to be bigger for a bigger truncated radius, and tends to be constant after the truncated radius increased to a certain value. It is also found that the surface tension becomes smaller as the temperature increases.

Size-dependent surface tension of a cylindrical nanobubble in liquid Ar

In view of the continued disputes on the fundamental question of whether the surface tension of a vapour bubble in liquid argon increases, or decreases, or remains unchanged with the increase of curvature radius, a cylindrical vapour bubble of argon is studied by molecular dynamics simulation in this paper instead of spherical vapour bubble so as to reduce the statistical error. So far, the surface tension of the cylindrical vapour bubble has not been studied by molecular dynamics simulation in the literature. Our results show that the surface tension decreases with radius increasing. By fitting the Tolman equation with our data, the Tolman length σ = -0.6225 sigma is given under cut-off radius 2.5σ, where σ = 0.3405 nm is the diameter of an argon atom. The Tolman length of Ar being negative is affirmed and the Tolman length of Ar being approximately zero given in the literature is negated, and it is pointed out that this error is attributed to the application of the inapplicable empirical equation of state and the neglect of the difference between surface tension and an equimolar surface.

Tolman length of simple droplet: Theoretical study and molecular dynamics simulation

In 1949, Tolman found the relation between the surface tension and Tolman length, which determines the dimensional effect of the surface tension. Tolman length is the difference between the equimolar surface and the surface of tension. In recent years, the magnitude, expression, and sign of the Tolman length remain an open question. An incompressible and homogeneous liquid droplet model is proposed and the approximate expression and sign for Tolman length are derived in this paper. We obtain the relation between Tolman length and the radius of the surface of tension(R_(s)) and found that they increase with the Rs decreasing. The Tolman length of plane surface tends to zero. Taking argon for example, molecular dynamics simulation is carried out by using the Lennard–Jones(LJ) potential between atoms at a temperature of 90 K. Five simulated systems are used, with numbers of argon atoms being 10140, 10935, 11760, 13500, and 15360, respectively. By methods of theoretical study and molecular dynamics simulation, we find that the calculated value of Tolman length is more than zero, and it decreases as the size is increased among the whole size range. The value of surface tension increases with the radius of the surface of tension increasing, which is consistent with Tolman’s theory. These conclusions are significant for studying the size dependence of the surface tension.

Droplet Condensation and Transport Properties on Multiple Composite Surface:A Molecular Dynamics Study

To investigate the microscopicmechanism underlying the influence of surface-chemical gradient on heat andmass recovery,a molecular dynamicsmodel including droplet condensation and transport process has been developed to examine heat and mass recovery performance.This work aimed at identify optimal conditions for enhancing heat and mass recovery through the combination of wettability gradient and nanopore transport.For comprehensive analysis,the structure in the simulation was categorized into three distinct groups:a homogeneous structure,a small wettability gradient,and a large wettability gradient.The homogeneous surface demonstrated low efficiency in heat and mass transfer,as evidenced by filmwise condensation.In contrast,the surface with a small wettability gradient experienced a transition from dropwise condensation to filmwise condensation,resulting in a gradual decrease in the efficiency of vapor heat and mass transfer.Only a large wettability gradient could achieve periodic and efficient dropwise condensation heat and mass transfer which was attributed to the rapid droplet coalescence and transport to the nanopore after condensing on the cold surface.

Approximate expression of Young's equation and molecular dynamics simulation for its applicability

In 1805, Thomas Young was the first to propose an equation(Young's equation) to predict the value of the equilibrium contact angle of a liquid on a solid. On the basis of our predecessors, we further clarify that the contact angle in Young's equation refers to the super-nano contact angle. Whether the equation is applicable to nanoscale systems remains an open question. Zhu et al. [College Phys. 4 7(1985)] obtained the most simple and convenient approximate formula, known as the Zhu–Qian approximate formula of Young's equation. Here, using molecular dynamics simulation, we test its applicability for nanodrops. Molecular dynamics simulations are performed on argon liquid cylinders placed on a solid surface under a temperature of 90 K, using Lennard–Jones potentials for the interaction between liquid molecules and between a liquid molecule and a solid molecule with the variable coefficient of strength a. Eight values of a between 0.650 and 0.825 are used. By comparison of the super-nano contact angles obtained from molecular dynamics simulation and the Zhu–Qian approximate formula of Young's equation, we find that it is qualitatively applicable for nanoscale systems.

A molecular dynamics study on surface properties of supercooled water

Molecular dynamics simulations were performed to study the surface properties of water in a temperature range from 228 to 293 K by using the extended simple point charge (SPC/E) and four-site TIP4P potentials. The calculated surface tension increases with the decrease of temperature, and moreover the slopes of the surface tension-temperature curves show a weak rise below 273 K, whereas no obvious anomalies appear near 228 K, which accords with the previous experiments. Compared with the measured values, the SPC/E potential shows a good agreement, and the TIP4P potential underestimates the surface tension. The main reason for that may be the reasonable description of the surface structure of supercooled water for the SPC/E. When simulating the orientational distributions of water molecules near the surface, the SPC/E potential produces higher ordering and larger surface potentials than the TIP4P potential.

Using thermodynamic parameters to study self-healing and interface properties of crumb rubber modified asphalt based on molecular dynamics simulation

The thermodynamic property of asphalt binder is changed by the addition of crumb rubber,which in turn influences the self-healing property as well as the cohesion and adhesion within the asphalt-aggregate system.This study investigated the self-healing and interface properties of crumb rubber modified asphalt(CRMA)using thermodynamic parameters based on the molecular simulation approach.The molecular models of CRMA were built with representative structures of the virgin asphalt and the crumb rubber.The aggregate was represented by SiO2 and Al2O3 crystals.The selfhealing capability was evaluated with the thermodynamic parameter wetting time,work of cohesion and diffusivity.The interface properties were evaluated by characterizing the adhesion capability,the debonding potential and the moisture susceptibility of the asphalt-aggregate interface.The self-healing capability of CRMA is found to decrease as the rubber content increases.The asphalt-Al2O3 interface with higher rubber content has stronger adhesion and moisture stability.But the influence of crumb rubber on the interfacial properties of asphalt-SiO2 interface has no statistical significance.Comparing with the interfacial properties of the asphalt-SiO2 interface,the asphalt-Al2O3 interface is found to have a stronger adhesion but a worse moisture susceptibility for its enormous thermodynamic potential for water to displace the asphalt binder.

Molecular dynamics study of the water/n-alkane interface

Molecular dynamics simulations on the interface between liquid water and liquid n-alkane (including octane, nonane, decane, undecane and dodecane) have been performed with the purpose to study the interfacial properties: (Ⅰ) density profile; (Ⅱ) molecular orientation; (Ⅲ) interfacial tension and the temperature effect on the interfacial tension. Simulation results show that at the interface the structures of both water and n-alkane are different from those in the bulk. Water has an orientational preference due to the number of hydrogen bonds per molecule maximized. N-alkane has a more lateral orientation with respect to the interface in order to be in close contact with water. The calculated individual phase bulk density and interfacial tension of water/n-alkane systems are in good agreement with the corresponding experimental ones.

Interactions of ferro-nanoparticles(hematite and magnetite) with reservoir sandstone: implications for surface adsorption and interfacial tension reduction

There are a few studies on the use of ferro-nanofluids for enhanced oil recovery,despite their magnetic properties;hence,it is needed to study the adsorption of iron oxide(Fe2 O3 and Fe3 O4) nanoparticles(NPs) on rock surfaces.This is important as the colloidal transport of NPs through the reservoir is subject to particle adsorption on the rock surface.Molecular dynamics simulation was used to determine the interfacial energy(strength) and adsorption of Fe2 O3 and Fe3 O4 nanofluids infused in reservoir sandstones.Fourier transform infrared spectroscopy and X-ray photon spectroscopy(XPS) were used to monitor interaction of silicate species with Fe2 O3 and Fe3 O4.The spectral changes show the variation of dominating silicate anions in the solution.Also,the XPS peaks for Si,C and Fe at 190,285 and 700 eV,respectively,are less distinct in the spectra of sandstone aged in the Fe3 O4 nanofluid,suggesting the intense adsorption of the Fe3 O4 with the crude oil.The measured IFT for brine/oil,Fe2 O3/oil and Fe3 O4/oil are 40,36.17 and 31 mN/m,respectively.Fe3 O4 infused with reservoir sandstone exhibits a higher silicate sorption capacity than Fe2 O3,due to their larger number of active surface sites and saturation magnetization,which accounts for the effectiveness of Fe3 O4 in reducing IFT.

纳米材料中的界面现象

在课程教学中融入科学前沿实例不仅可以阐明所学基本原理的实际意义,还可以为基本原理的灵活应用提供范例,启发学生独立思考能力。界面化学是物理化学课程中的重要学习内容,但由于在常规尺度的多相体系中界面现象并不显著,学生对该部分知识常有忽视。近年来纳米材料已成为国内外研究的热点。纳米材料由于其高界面分子比例而表现出更为显著的界面现象。将界面化学的基本原理应用于纳米材料的研究中,已取得了一系列令人瞩目的成果。本文首先对附加压力、接触角等相关界面现象的基本原理进行梳理,然后分别介绍根据这些基本原理所发展出的分子马达、光控微流控器件、液体门控技术以及超疏水表面四项科技突破。

基于Cr-O-C钝化层改变多晶Cu表面能和表层位错的脱模力与脱模精度

Cr-O-C钝化层可以提高精密电铸脱模精度,但Cr-O-C钝化层对基底表面的钝化规律和对表层的影响尚未清楚。利用分子动力学方法,在多晶Cu表面沉积离散的Cr、O和C原子,获得不同比例和数量的Cr-O-C钝化层。计算结果表明,不同比例的Cr、O和C原子均可以大幅降低多晶Cu的表面能;随着原子数量的增加,多晶Cu的表面能呈下降趋势;Cr-O-C钝化层增加了多晶Cu表层的位错密度;新增加的位错以Shockley位错为主;在一定沉积原子数量内,位错密度有极值。在多晶Cu表面电沉积不同密度的Cr、O和C原子,通过接触角测试验证了Cr-O-C钝化层降低多晶Cu表面能的结论。电沉积脱模强度和脱模表面粗糙度结果显示,随着沉积原子数的增加,脱模强度和脱模表面粗糙度均降低。研究结果可为利用离散Cr-O-C界面辅助精密电铸脱模提供一种解释。

琥珀酸衍生物类非离子型表面活性剂的合成及性能评价

利用N-十二烷基琥珀酸酐、L-亮氨酸和聚醚醇为原料合成了两种非离子型表面活性剂,并通过核磁共振氢谱验证了分子结构;通过表面张力仪分别测试了两种非离子型表面活性剂在不同浓度下的表面张力,并根据γ-lgc曲线确定了临界胶束浓度;通过析水率研究了表面活性剂的乳化性能;使用分子动力学模拟技术,研究了表面活性剂在油水界面处的聚集形态以及与油和水之间的作用。结果表明,与表面活性剂1相比,表面活性剂2含更多的非离子亲水组分,因此降低表面张力效果更好;表面活性剂1及表面活性剂2的临界表面张力(γ_(CMC))分别为25.54、24.46 mN/m;在低浓度下,两种非离子型表面活性剂均具有较高的析水率,乳化效果不佳,但在高浓度下乳化效果较好,采用两种非离子型表面活性剂制备的乳液均具有一定的稳定性;表面活性剂分子的静电势分布影响了其亲水和亲油的性质。

基于分子动力学方法的致密砂岩储层CO_(2)驱油研究进展

随着致密砂岩储层CO_(2)-EOR项目的不断增加,亟需对CO_(2)与致密砂岩储层流体在孔隙介质中的相互作用机理进行研究,但室内实验难以观察到CO_(2)与流体在孔隙通道中的动态过程,而分子动力学模拟则可以弥补传统实验和数值方法的不足。为此,围绕该方法在CO_(2)-EOR研究中的2大重点——界面行为与受限空间运移行为,对包括萃取、溶胀、降黏、降低界面张力、最小混相压力、润湿性等6个方面界面行为的相关研究成果进行了系统梳理,结合前人对CO_(2)与致密砂岩储层流体在受限空间中运移行为的研究成果,提出了分子动力学在致密砂岩储层CO_(2)-EOR研究中的关键科学问题。研究结果表明:①分子动力学能够很好地将CO_(2)萃取原油中—轻烃组分的过程进行可视化,建议根据原油实际组分构成分析CO_(2)的萃取能力,从而弄清CO_(2)萃取原油中各组分的优先顺序及效率;②有关CO_(2)分子对原油溶胀降黏作用的研究,大多数成果中的原油组分体系较为单一,建议根据实际储层的原油组分,系统探讨高温高压条件下CO_(2)的溶胀降黏作用;③对于CO_(2)与油水两相之间界面张力的研究更多是在体相中进行展开,而在纳米受限空间界面行为的研究还有待完善;④有关地层水在孔隙壁面的润湿性研究,对不同因素之间的协同效应影响润湿性的机理尚不明确。结论认为,随着量子力学研究的不断深入以及计算性能的日益强大,该方法可以在更大尺度上进行复杂体系的计算,以其为基础的油藏、页岩油气藏CO_(2)-EOR机理等研究将会取得较大的突破。

Diffusion-controlled Adsorption Kinetics of Surfactant at Air/Solution Interface

For the diffusion-controlled adsorption, the expression of dynamic surface adsorption P（t） was ob- tained by solving the diffusion equation. Two cases, i.e. the short and long time limits, were mainly discussed in this paper. From the measured dynamic surface tension of aqueous surfactant sodium dodecyl sulfate （SDS） solutions at 25 ℃, the adsorption kinetics of SDS at air/solution interface was studied. It was proved that for both of the short and long time limits, the adsorption process of SDS was controlled by diffusion.

分子模拟技术融入物理化学实验教学设计

随着计算机技术的迅猛发展,分子模拟技术已经成为物理化学实验教学中的一种重要现代化教学手段。以Irving-Kirkwood方法求解两相界面张力为例,将分子模拟技术引入物理化学实验教学设计中。首先,介绍界面张力的基本概念,并引入分子模拟求解界面张力的基本原理。其次,由学生自行设计两相分子模型并编写分子模拟代码。最后,通过实验仿真求解介质/液体和介质/晶体两个界面张力,并理解界面张力与限域晶体的熔点变化规律之间的联系。通过理论联系实践的培养方式,加深学生对基础理论知识的理解,提高学生的学习兴趣,进而塑造良好的科学文化素养。

走进奇妙的分子聚集态世界——渗透扩散及表面张力的魅力

化学世界丰富多彩。认识多姿、多彩的材料形成过程,揭示产物生成的奥秘,通过对宏观化学现象的观察,推测产物生长的微观过程,增强学生对化学的学习兴趣,是化学实验教学的主要目的之一。本实验以“界面反应”为切入点,以多彩多姿分子聚集体为目标产物,通过自主设计的反应器,以多孔陶瓷砂芯为隔离层,利用渗透和扩散效应、表面张力及界面反应机理,在砂芯表面可控形成白色、蓝色、绿色、粉色等多彩中空纤维状及珊瑚礁状等多姿的分子聚集体。本科普实验方法安全、新颖、简单,现象明显,具有很高的观赏性,旨在达到在探索微观世界形成过程中发现化学无穷魅力,认识“美丽化学”“奇妙化学”的真实内涵,激发学生对化学学科学习热情之目的。

动态表面张力的测定及应用研究综述

表面张力是表征溶液性质的重要物理参数,添加不同类型的表面活性剂,降低表面张力的状态也会不同,其中,动态表面张力的测定能表征表面活性剂分子在溶液内部及表面的运动特性,通过测定动态表面张力,既能表征溶液表面张力降低速率的快慢,也能体现表面活性剂分子在气-液两相吸附的差异。介绍动态表面张力的常用测定方法,归纳各种测定方法的适用范围,综述国内外动态表面张力测定在各领域的应用研究成果及价值。

丁二酸-水纳米气溶胶液滴表面张力的分子动力学研究

表面张力在纳米气溶胶颗粒的吸湿生长研究中具有重要意义,然而现有实验方法不能对其准确测量.本文基于分子动力学方法模拟了丁二酸气溶胶颗粒吸湿生长形成稳定液滴的动力学过程,在此基础上,建立模型计算了液滴的表面张力,进而探究了温度、粒径和丁二酸浓度对纳米液滴表面张力的影响机制.结果表明,随着温度从260 K升高到320 K,液滴内分子间作用力的减弱导致了液滴表面张力的减小,且表面张力的减小程度随丁二酸浓度的增大而增大,究其主要原因在于液滴中丁二酸分子的径向分布随温度和丁二酸浓度变化的差异;随着粒径的增大,液滴表面张力先增大后趋于定值,且粒径对表面张力的显著影响区间随着丁二酸浓度的增大而缩短;研究还发现,丁二酸分子的表面活性导致液滴表面张力随着丁二酸浓度的增大而减小,且减小趋势符合对数函数形式,尤其是在粒径小于6.12 nm时,同时,基于Szyszkowski公式对液滴的表面张力进行了拟合.本文研究成果能为气溶胶颗粒的吸湿生长和相关动力学过程预测理论及模型的改进提供参数依据.