Surface active agents stabilize nanodroplets and enhance haze formation

Although many organic molecules found commonly in the atmosphere are known to be surface-active in aqueous solutions, their effects on the mechanisms underlying haze formation remain unclear. In this paper, based on a simple thermodynamic analysis, we report that the adsorption of amphiphilic organics alone not only lowers the surface tension,but also unexpectedly stabilizes nanodroplets of specific size under water vapor supersaturation. Then we determine how various factors, including relative humidity, water activity effect due to dissolution of inorganic components as well as surface tension effect due to surface adsorption of organic components, cooperatively induce the stability of nanodroplets.The nanodroplet stability behaviors not captured in the current theory would change the formation mechanism of haze droplets, from the hygroscopic growth pathway to a nonclassical two-step nucleation pathway.     

Adsorption and nucleation on smooth surfaces

The nucleation and growth of condensate nuclei on smooth surfaces, e.g., an immiscible liquid or a smooth solid, can occur both by the direct addition of molecules from the vapor and from those adsorbed on the substrate. We show how to generalize nucleation theory to allow for the simultaneous occurrence of both mechanisms. The vapor-condensate-substrate interfacial forces, the contact angle, the critical supersaturation, and the coefficient in the adsorption isotherm are different ways of expressing the affinity between vapor molecules and the substrate surface. The critical supersaturations for nucleation on the surface of an immiscible liquid and nucleation on the surface of a perfectly smooth solid are predicted in terms of these parameters and the relationships among them. For most values of these parameters we find that adsorbed molecules are usually far more important to the nucleation process than those in the vapor phase.     

微液滴在不同能量表面上润湿状态的分子动力学模拟

微小液滴在不同能量表面上的润湿状态对于准确预测非均相核化速率和揭示界面效应影响液滴增长微观机理具有重要意义. 通过分子动力学模拟, 研究了纳米级液滴在不同能量表面上的铺展过程和润湿形态. 结果表明, 固液界面自由能随固液作用强度增加而增加, 并呈现不同液滴铺展速率和润湿特性. 固液作用强度小于1.6的低能表面呈现疏水特征, 继续增强固液作用强度时表面变为亲水, 而固液作用强度大于3.5的高能表面上液体呈完全润湿特征. 受微尺度条件下非连续、非对称作用力影响, 微液滴气液界面存在明显波动, 呈现与宏观液滴不同的界面特征. 统计意义下, 微小液滴在不同能量表面上铺展后仍可以形成特定接触角, 该接触角随固液作用强度增加而线性减小, 模拟结果与经典润湿理论计算获得的结果呈现相似变化趋势. 模拟结果从分子尺度为核化理论中的毛细假设提供了理论支持, 揭示了液滴气液界面和接触角的波动现象, 为核化速率理论预测结果和实验测定结果之间的差异提供了定性解释.     

Predicting initial nucleation events occurred in a metastable nanodroplet during acoustic droplet vaporization

Acoustic droplet vaporization (ADV) capable of converting liquid perfluorocarbon (PFC) micro/nanodroplets into gaseous microbubbles has gained much attention due to its medical potentials. However, its physical mechanisms for nanodroplets have not been well understood due to the disappeared superharmonic focusing effect and the prominent Laplace pressure compared to microdroplets, especially for the initial ADV nucleation occurring in a metastable PFC nanodroplet. The classical nucleation theory (CNT) was modified to describe the ADV nucleation via combining the phase-change thermodynamics of perfluoropentane (PFP) and the Laplace pressure effect on PFP nanodroplets. The thermodynamics was exactly predicted by the Redlich–Kwong equation of state (EoS) rather than the van der Waals EoS, based on which the surface tension of the vapor nucleus as a crucial parameter in the CNT was successfully obtained to modify the CNT. Compared to the CNT, the modified CNT eliminated the intrinsic limitations of the CNT, and it predicted a larger nucleation rate and a lower ADV nucleation threshold, which agree much better with experimental results. Furthermore, it indicated that the nanodroplet properties exert very strong influences on the nucleation threshold instead of the acoustic parameters, providing a potential strategy with an appropriate droplet design to reduce the ADV nucleation threshold. This study may contribute to further understanding the ADV mechanism for PFC nanodroplets and promoting its potential theranostic applications in clinical practice.     

Vapour-to-Liquid Nucleation in Associating Lennard-Jones Fluids with Multiple Association Sites

The excess Helmholtz free energy functional for associating Lennard-Jones （L J） fluid is formulated in terms of a weighted density approximation for short-ranged interactions and a Weeks-Chandler-Andersen approximation for long-range attraction. Within the framework of density functional theory, phase equilibria, vapour-liquid surface tension and vapour-liquid nucleation properties including the density profile, work of formation, excess number of particles and critical supersaturation are investigated for associating LJ fluids with different numbers of association sites （M =1,2, 3, 4） per particle. The influences of association energy and association sites on phase equilibria, surface tension and vapour-liquid nucleation properties are discussed.     

Density functional theory of vapor to liquid heterogeneous nucleation: Lennard–Jones fluid on solid substrate

Density functional theory has been applied to investigate the vapor to liquid heterogeneous nucleation on a flat solid surface, by invoking a model free energy density functional along with an exponential density model. The effects of supersaturation of the vapor and the strength of the solid-fluid interaction on the nucleation barrier have been investigated for Lennard–Jones fluid with 12–6 fluid–fluid and 9–3 solid–fluid interaction model. The spinodal decomposition of vapor has been observed at higher supersaturation or at higher strength of the solid–fluid interaction. The shape, density profile and the free energy of formation of droplets of any arbitrary size have been obtained in this work.     

A molecular dynamics study of effective parameters on nano-droplet surface tension

The main purpose of this paper is to numerically study the effect of droplet radius, temperature, and surface wettability on droplet surface tension. Moreover, the validity of Young-Laplace equation (Y-L) for nano-droplet is examined. Simulations of droplet surrounded by its vapor and droplet on solid surface are carried out and the results are compared to each other in order to comprehend the role of surface wettability on droplet surface tension. The pair potential for the liquid-liquid and liquid-solid interaction is considered using Lennard-Jones model. Different numbers of atoms and surface wettabilities are employed to generate droplet of different radiuses. In addition, contact angle of droplet on solid surface is computed. Pressure tensor and density profile is locally calculated. Furthermore, liquid pressure is evaluated far from the interface using the virial theorem and gas pressure is obtained using an equation of state. In order to calculate the surface tension, two different approaches are employed; Young-Laplace equation and direct molecular dynamics (MD) simulation. The surface tension increases with increase in droplet radius and it is seen that the surface wettability does not directly influence the surface tension.     

Heterogeneous nucleation and depletion effect in nanowire growth

Recent experiments by Ross and co-workers proved the possibility of a mononuclear regime with heterogeneous nucleation as well as jerky growth in the vapor–liquid–solid (VLS) process for silicon nanowires. In this work, a theoretical model is presented which incorporates the effects of (i) a mononuclear regime with layer by layer growth, (i) heterogeneous nucleation of each new layer at the edge of a Au–Si droplet, (iii) drop of supersaturation after each successful nucleation and respective fast layer growth, (iv) time-dependent nucleation barrier during each new waiting period and (v) correlation between subsequent waiting periods (non-Markovian sequence of waiting periods).     

A kinetic model for droplet growth in the transition regime

A variant of the moment expansion method, used in an earlier paper to describe the flow of a gas toward an absorbing sphere, is applied to a more realistic model of a droplet condensing from a supersaturated vapor. In the simplest version a spherical droplet absorbs all incoming vapor molecules, but spontaneously emits molecules with a Maxwellian distribution at the droplet temperature and with the corresponding saturated vapor density. From a solution of the stationary linearized Boltzmann equation with these boundary conditions we obtain expressions for the heat and mass currents toward the sphere as a function of the supersaturation and the temperature difference between the droplet and the vapor at infinity. For small droplet radii the known free flow limit is obtained in a natural way. From the calculated expressions for the heat and mass current we derive evolution equations for the radius and temperature of the droplet. The temperature evolves more rapidly and can thus be eliminated adiabatically; the resulting growth curve for the radius shows a sharp transition from a kinetically controlled regime for small radii to a regime dominated by heat conduction for large radii. The effect of incomplete absorption at the surface is also studied. The actual calculations are carried out for Maxwell molecules, with parameters corresponding to argon at 0.65T _c and 100% supersaturation.     

Investigation of vapour--liquid nucleation properties for spherical and chain-like fluids by density functional theory

The excess Helmholtz free energy functional for nonpolar chain-like molecules is formulated in terms of a weighted density approximation （WDA） for short-range interactions and a Weaks Chandler Andersen （WCA） approximation and a Barker Henderson （BH） theory for long-range attraction. Within the framework of density functional theory （DFT）, vapour liquid interracial properties including density profile and surface tension, and vapour-liquid nucleation properties including density profile, work of formation and number of particles are investigated for spherical and chain- like molecules. The obtained vapour liquid surface tension and the number of particles in critical nucleus for Lennard- Jones （L J） fluids are consistent with the simulation results. The influences of supersaturation, temperature and chain length on vapour liquid nucleation properties are discussed.[第一段]     

基于范德瓦尔斯表面张力模式液滴撞击疏水壁面过程的研究

液滴撞击疏水壁面过程的研究在介观流体力学和微流体作用材料科学的研究中具有重要的理论意义和工程价值. 论文在SPH方法中引入范德瓦尔斯状态方程处理液滴表面张力, 考虑流体粒子之间远程吸引, 近程排斥的内部作用力, 提出了流体粒子与疏水壁面粒子间势能函数与表面张力相结合的作用模式. 通过模拟真空条件下两个静止的等体积液滴相互融合的过程, 验证了计算模式在模拟液滴的表面张力中的有效性. 采用该模式模拟的液滴撞击疏水壁面过程, 不仅能够有效地模拟液滴撞击壁面后的变形过程, 而且清晰地模拟出液滴的回弹、腾空以及二次撞壁现象的完整过程. 模拟结果与液滴撞击疏水壁面的实验结果以及VOF模拟结果符合较好, 表明本文所提出的表面张力和疏水壁面作用力处理模式对模拟液滴撞壁过程具有实际应用价值.     

低压蒸汽滴状冷凝表面温度分布实验研究

本文利用自组装技术制备了铜基十八烷基硫醇疏水表面(SAM),通过红外热像仪分析了低压条件下液滴表面和换热表面的温度分布以及液滴脱落引起的温度分布演变。实验结果表明:低压蒸汽冷凝条件下,冷凝表面局部温度分布不均匀;单个液滴表面温度呈中心高边缘低的凸型分布;随着液滴半径的增加,液滴表面温度升高;相同操作压力下,随着过冷度的增加,液滴表面温度降低。在液滴脱落过程中,液滴表面温度逐渐升高,同时裸露出的换热表面局部过冷度增大,局部表面温度呈现出中心低周围高的凹型温度分布,随之恢复到液滴脱落前的温度。随着蒸汽压力降低,冷凝临界过冷度增加,导致裸露表面上具有更低温度的中心区域核化点密度高,最终加剧了整个换热表面液滴尺寸分布的非均匀程度。     

纳米结构超疏水表面冷凝现象的三维格子玻尔兹曼方法模拟

采用三维多相流格子玻尔兹曼方法 (lattice Boltzmann method, LBM),对纳米结构超疏水表面液滴的冷凝行为进行模拟研究.通过Laplace定律和光滑表面的本征接触角理论对三维LBM模型进行定量验证.模拟分析了超疏水表面纳米阵列的几何尺寸和润湿性的局部不均匀性对冷凝液滴形核位置和最终润湿状态的影响规律.结果表明,较高的纳米阵列使液滴在纳米结构间隙的上部侧面和底部优先形核长大,通过采用上下不均匀的间隙可避免液滴在底部形核长大,而在上部侧面形核的冷凝液滴在生长过程中向上运动,其润湿状态由Wenzel态转变为Cassie态;较低的纳米阵列使液滴在纳米结构底部优先形核长大,液滴的最终润湿状态为Wenzel态;润湿性不均匀的纳米结构表面使液滴在阵列顶端亲水位置处优先形核长大,成为Cassie态.冷凝液滴在不同几何尺寸的纳米结构表面上的最终润湿状态的模拟结果与文献报道的实验结果符合良好.通过模拟还发现,冷凝液滴在生长过程中的运动行为与液滴统计平均作用力的变化有关.本文的LBM模拟再现了三维空间中液滴的形核、长大和润湿状态转变等物理现象.     

Simulation of the operation of a laminar-flow diffusion chamber to study homogeneous nucleation: Part II

A new mathematical model of the operation of a laminar-flow diffusion chamber is studied numerically. The domains of applicability of the standard mathematical model, which have been qualitatively estimated earlier, are confirmed. The nature of the carrier gas is found to substantially influence the volume of the nucleation zone in the chamber. In particular, the nucleation zone volume in the case of argon as a carrier gas is one order of magnitude larger than that in the case of helium, all other things being equal. Analysis of Vohra and Heist’s experiments using the new mathematical model shows that nonlinear interaction between growing droplets is of key importance at a relatively high vapor supersaturation. The role of a locally nonuniform supersaturation field arising near droplets in the nucleation zone is estimated.     

Viscoelasticity and metastability limit in supercooled liquids

A supercooled liquid is said to have a kinetic spinodal if a temperature Tsp exists below which the liquid relaxation time exceeds the crystal nucleation time. We revisit classical nucleation theory taking into account the viscoelastic response of the liquid to the formation of crystal nuclei and find that the kinetic spinodal is strongly influenced by elastic effects. We introduce a dimensionless parameter lambda, which is essentially the ratio between the infinite frequency shear modulus and the enthalpy of fusion of the crystal. In systems where lambda is larger than a critical value lambda(c) the metastability limit is totally suppressed, independently of the surface tension. On the other hand, if lambda相似文献   

Instabilities in droplets spreading on gels

We report a novel surface-tension driven instability observed for droplets spreading on a compliant substrate. When a droplet is released on the surface of an agar gel, it forms arms or cracks when the ratio of surface-tension gradient to gel strength is sufficiently large. We explore a range of gel strengths and droplet surface tensions and find that the onset of the instability and the number of arms depend on the ratio of surface tension to gel strength. However, the arm length grows with an apparently universal law L proportional t(3/4).     

The theory of droplet diffusiophoresis for concentrated solutions

The theoretical diffusiophoresis velocity is obtained for a droplet of a concentrated solution suspended in a binary gaseous mixture. The droplet is characterized by a high thermal conductivity. The droplet radius is assumed to be much greater than the mean free path for gaseous-mixture molecules. One of the gaseous-mixture molecular components is the vapor of the droplet solvent. According to the formula obtained in this study, the droplet is driven toward lower concentration of the volatile gaseous-mixture component by diffusive slip and in the opposite direction by phase transition. An increase in the relative mass concentration of the volatile solvent in the droplet enhances effects associated with the dependence of surface tension on the volatile-component concentration and the reactive transport due to the surface nonuniformity of phase transition. As the relative mass concentration of the volatile solvent in the droplet approaches unity, the effect of diffusive slip tends to vanish.     

Breakdown of classical nucleation theory near isostructural phase transitions

We report simulations of crystal nucleation in binary mixtures of hard spherical colloids with a size ratio of 1:10. The stable crystal phase of this system can be either dense or expanded. We find that, in the vicinity of the solid-solid critical point where the crystallites are highly compressible, small crystal nuclei are less dense than large nuclei. This phenomenon cannot be accounted for by either classical nucleation theory or by the Gibbsian droplet model. We argue that the observed behavior is due to the surface stress of the crystal nuclei. The observed effect highlights a general deficiency of the most frequently used thermodynamic theories for crystal nucleation. Surface stress should lead to an experimentally observable expansion of crystal nuclei of colloids with short-ranged attraction and of globular proteins.     

Theory of the nucleation of protein macromolecular ions

Protein molecules are amphoteric and exist in aqueous solution as macromolecular ions that carry a charge which depends upon temperature and pH. Despite the repulsive Coulomb forces acting between them, protein macromolecular ions can form crystals in pH buffered solutions of strong electrolytes. It is proposed that the first step in the mechanism of crystallization is the formation of crystal nuclei made from partially discharged macromolecular ions that have exchanged H⁺ with the buffer. We suggest that the strength of the bare Coulomb repulsive force is weakened by the Debye-Hückel plasma screening provided by the inert electrolyte. This screening causes the rate of nucleus formation to increase with increasing ionic strength. Extending classic nucleation theory to account for these various charge effects, the results are applied to the case of lysozyme and a calculation is made of the dependence of the steady state nucleation rate upon temperature, pH, ionic strength, and protein supersaturation. It is found that the nucleation rate increases with increasing temperature and increasing ionic strength. Under condition of fixed temperature, supersaturation, and inionic strength, the nucleation rate has local maxima at low pH, where individual lysozyme macro ions are highly charged, and at pH ? 11, where they have zero average net charge. At both pH values, the nucleus that determines the rate has minimum size. In contrast to standard nucleation theory, which ignores charge, it is found that the size of the nucleus that controls the rate is different from the size of the nucleus that has the lowest concentration. All other conditions being the same, it is predicted that lysozyme crystals should nucleate most rapidly near pH = 2 and near pH = 11.