Finite-size effects in dissipative particle dynamics simulations

We have performed dissipative particle dynamics (DPD) simulations to evaluate the effect that finite size of transversal area has on stress anisotropy and interfacial tension. The simulations were carried out in one phase and two phases in parallelepiped cells. In one-phase simulations there is no finite-size effect on stress anisotropy when the simulation is performed using repulsive forces. However, an oscillatory function of stress anisotropy is found for attractive-repulsive interactions. In the case of liquid-liquid interfaces with repulsive interaction between molecules, there is only a small effect of surface area on interfacial tension when the simulations are performed using the Monte Carlo method at constant temperature and normal pressure. An important but artificial finite-size effect of interfacial area on surface tension is found in simulations in the canonical ensemble. Reliable results of interfacial tension from DPD simulations can be obtained using small systems, less than 2000 particles, when they interact exclusively with repulsive forces.     

Dissipative particle dynamics simulations of polymersomes

A DPD model of PEO-based block copolymer vesicles in water is developed by introducing a new density based coarse graining and by using experimental data for interfacial tension. Simulated as a membrane patch, the DPD model is in excellent agreement with experimental data for both the area expansion modulus and the scaling of hydrophobic core thickness with molecular weight. Rupture simulations of polymer vesicles, or "polymersomes", are presented to illustrate the system sizes feasible with DPD. The results should provide guidance for theoretical derivations of scaling laws and also illustrate how spherical polymer vesicles might be studied in simulation.     

The array and interfacial activity of sodium dodecyl benzene sulfonate and sodium oleate at the oil/water interface

There is a close correlation between the interfacial activity and the adsorption of the surfactant at the interface, but the detailed molecular standard information was scarce. The interfacial activity of two traditional anionic surfactants sodium dodecyl benzene sulfonate (SDBS) and sodium oleate (OAS) were studied by experimental and computer simulation methods. With the spinning drop method and the suspension drop method, the interfacial tension of oil/aqueous surfactant systems was measured, and the influence of surfactant concentration and salinity on the interfacial tension was investigated. The dissipative particle dynamics (DPD) method was used to simulate the adsorption of SDBS and OAS at the oil/water interface. It was shown that it is beneficial to decrease interfacial tension if the hydrophobic chains of the surfactant and the oil have similar structure. The accession of inorganic salts causes surfactant molecules to form more compact and ordered arrangements and helps to decrease the interfacial tension. There is an osculation relation between interfacial density and interfacial activity. The interfacial density calculated by molecular simulation is an effective parameter to exhibit the interfacial activity.     

MesoDyn Simulation Study on Phase Diagram of Aerosol OT/isooctane/water System

There is a growing interest in the study of surfactant self-assemble in oil/water/surfactant system because of their applications not only in traditional colloid chemistry but in analytical, synthetic, and medicinal chemistry as well1,2. In these systems, one of the most commonly studied surfactants which can form reverse micelles is sodium bis(2-ethylhexyl) sulfosuccinate, i.e. Aerosol OT (AOT)3. The properties of the AOT reverse micelles have been discussed by some experimental methods4…     

生物表面活性剂鼠李糖脂及其复配体系界面行为和性质的介观模拟

采用介观模拟耗散颗粒动力学（DPD）方法研究不同结构的鼠李糖脂在油/水界面行为差异和结构对活性的影响,并探讨了其与不同类型表面活性剂如十二烷基硫酸钠（SDS）、十二烷基苯磺酸钠（SDBS）、脂肪醇聚氧乙烯醚（AEO3）复配时体系的界面性质,给出不同结构的鼠李糖脂的行为特点及与常用合成表面活性剂在油/水界面的相互作用规律...     

用耗散粒子动力学方法研究高分子链取向对形变液滴回缩法测定界面张力值的影响

在利用形变液滴回缩法(DDRM)测量了分子共混体系界面张力的过程中, 要求椭球液滴内高分子链应力松弛速度远快于椭球的回缩速度. 我们建立高分子链取向模型, 用耗散粒子动力学研究高分子链的取向及应力松弛对界面张力测量值的影响. 结果表明, 当高分子链沿着流场方向取向时, 应力是否完全松弛对界面张力测量值的影响较大, 当高分子链取向方向垂直于流场方向时, 应力是否松弛对测量值影响较小.     

The interfacial tension concept,as revealed by fluctuations

A simple, didactic model that could have conclusively interpreted the complexity of specific salt (Hofmeister-) effects on protein solubility and function, using a single physical quantity as a central parameter, has long been missing. Via surveying a row of recent papers we show in this review that a phenomenological formalism based on the salt-induced change of protein–water interfacial tension (∆γ) is able to account for a wide range of Hofmeister effects, including also such “exceptions”, where inverse or “V-shaped” Hofmeister series occurs. A close relationship between protein–water interfacial tension and conformational fluctuations is pinpointed on theoretical grounds, then it is shown how one can use a complex experimental arsenal to demonstrate conformational fluctuations on two prototypical proteins, the membrane protein bacteriorhodopsin and the cytoplasmic protein myoglobin. Finally, via the results of recent and new molecular dynamics simulations on a model peptide, the tryptophan-cage miniprotein, independent evidences are given in favor of the interfacial tension concept, at the same time demonstrating the predictive power of the theory. It is shown that salt-induced fluctuation changes of surface-exposed amino acid groups can be used as a sensitive measure for mapping the local features of Hofmeister effects on protein conformations. General implications of the interfacial tension concept are also discussed.     

Molecular behavior and synergistic effects between sodium dodecylbenzene sulfonate and Triton X-100 at oil/water interface

Significant synergistic effects between sodium dodecylbenzene sulfonate (SDBS) and nonionic nonylphenol polyethylene oxyether, Triton X-100 (TX-100), at the oil/water interface have been investigated by experimental methods and computer simulation. The influences of surfactant concentration, salinity, and the ratio of the two surfactants on the interfacial tension were investigated by conventional interfacial tension methods. A dissipative particle dynamics (DPD) method was used to simulate the adsorption properties of SDBS and TX-100 at the oil/water interface. The experiment and simulation results indicate that ultralow (lower than 10(-3) mN m(-1)) interfacial tension can be obtained at high salinity and very low surfactant concentration. Different distributions of surfactants in the interface and the bulk solution corresponding to the change of salinity have been demonstrated by simulation. Also by computer simulation, we have observed that either SDBS or TX-100 is not distributed uniformly over the interface. Rather, the interfacial layer contains large cavities between SDBS clusters filled with TX-100 clusters. This inhomogeneous distribution helps to enhancing our understanding of the synergistic interaction of the different surfactants. The simulation conclusions are consistent with the experimental results.     

烷基苯磺酸盐在油水界面行为的介观模拟

采用耗散颗粒动力学(DPD)方法在介观层次上模拟了表面活性剂烷基苯磺酸盐在油/水界面的排布行为, 考察了分子结构、浓度、盐度、油相等因素对表面活性剂界面密度和界面效率的影响, 并探讨了利用表面活性剂复配协同效应提高界面活性的理论机制. 分子模拟给出的分子水平的微观信息为强化采油技术中配方筛选和表面活性剂的有效应用提供指导.     

Interfacial tension and wetting in colloid-polymer mixtures

We calculate the interfacial tension and the wetting behavior in phase separated colloid-polymer mixtures both for ideal and excluded volume interacting polymers. Within the recently developed extension of the free volume theory to include polymer interactions the interfacial tension of the free interface is calculated by adding a van der Waals squared gradient term. The wetting behavior at a hard wall is calculated following a Cahn-Fisher-Nakanishi approach taking the one- and two-body colloid-wall interactions into account. Comparing results for interacting polymers with those for ideal polymers we find that for interacting polymers the interfacial tension does not increase as steeply as a function of the gas-liquid colloid density difference. Furthermore, the wetting transition shifts to higher polymer concentrations, even to above the triple line. The predictions for both the interfacial tension and the wetting are compared to recent experiments.     

Temperature and molecular weight dependence of interfacial tension between immiscible polymer pairs by the square gradient theory combined with the Flory–Orwoll–Vrij equation-of-state theory

Interfacial tension between immiscible polymer pairs was predicted by using a square gradient theory in conjunction with the Flory–Orwoll–Vrij equation-of-state expression for the free energy of mixing. The contact interaction parameter was determined by fitting the equation-of-state theory to experimental cloud points taken from the literature, and the square gradient coefficient was estimated from the relation derived from a scattering function. The modified square gradient theory could successfully predict both the magnitude and temperature dependence of interfacial tension between polystyrene and poly(methyl methacrylate), although no adjustable parameters were used in calculating interfacial tension. The molecular weight dependence of interfacial tension was also successfully predicted. The contribution of free volume on interfacial tension is analyzed for two systems: polystyrene/poly(methyl methacrylate) and polystyrene/poly(dimethyl siloxane) blends. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36: 2683–2689, 1998     

Structure of nonpolarizable water/nitrobenzene interface: potential distribution, ion adsorption, and interfacial tension

Adsorption of hydrophobic and hydrophilic ions at the nonpolarizable interface between two immiscible electrolyte solutions was investigated. The results were analyzed in three different models: (i) Gouy-Chapman model, (ii) ions as hard spheres, and (iii) ion pair formation at the interface. In the Gouy-Chapman model, an analytical expression for the interfacial tension was obtained. It predicts that interfacial tension should be proportional to the square root of the electrolyte concentration, which does not agree with experimental data. Modeling ions as hard spheres only slightly improves the agreement. The third model of interfacial ion pairing as the main origin of adsorption was analyzed using the amphiphilic isotherm (Markin-Volkov isotherm). A good agreement between ion-pairing theory and experimental values was achieved. The MV isotherm takes into account the limited number of adsorption sites, final size of molecules, complex formation at the interface, and interaction between adsorbed particles. The analysis revealed repulsion between adsorbed tetraalkylammonium ions at the nitrobenzene/water interface and demonstrated linear dependence between adsorption site area and the size of a molecule.     

Ions at the water-oil interface: interfacial tension of electrolyte solutions

A theory, based on a modified Poisson-Boltzmann equation, is presented that allows us to calculate the excess interfacial tension of an electrolyte-oil interface accurately. The chaotropic (structure-breaking) ions are found to adsorb to the water-oil interface as the result of large polarizability, weak hydration, and hydrophobic and dispersion interactions. However, kosmotropic (structure-making) anions as well as potassium and sodium ions are found to be repelled from the interface. The adsorption of I(-) and ClO(4)(-) is found to be so strong as to lower the interfacial tension of the water-oil interface, in agreement with the experimental data. The agreement between the calculated interfacial tensions and the available experimental data is very good. The theory is used to predict the interfacial tensions of six other potassium salts, for which no experimental data is available at the moment.     

氢氧化钙粉末界面张力的测定

以Washburn方程为理论依据,采用毛细管上升法,设计了简易实验装置,测定了氢氧化钙粉末在水、二甲基亚砜和甘油中的润湿接触角.在此实验结果基础上,利用Y-G-G-F-V方程建立了计算固相表面张力和液-固界面张力的表达式,并分别计算出氢氧化钙粉末的表面张力、氢氧化钙与水、二甲基亚砜和甘油的液-固界面张力,为固体粉末的表...     

Mixed emulsifying agents

Summary One per cent of aluminium hydroxide and bentonite was taken in suspension and their interfacial tension was determined with kerosene oil as dispersed phase byCenco-Du Noüy Interfacial Tensiometer No. 70545 after necessary calibrations and applying the correction factorF (9). Natural colloids (gum acacia, gelatin) and soaps were added into these suspensions in various concentrations and interfacial tension was determined. It was found that the addition of natural colloids, decreases the interfacial tension and the emulsions are finer and more stable. With the increasing quantities of these natural colloids to the suspensions, a further reduction in the interfacial tension is noticed, thereby such a corresponding emulsion formed has a higher interfacial area and stability factor. Similarly copper arsenate, lead arsenate, calcium arsenate and aluminium arsenate were taken and interfacial tension was measured with the addition of various quantities of natural colloids. The results arrived at, further show the lowering of interfacial tension with the conformity of finer emulsions having higher stability factors. Bordeaux mixtures, Burgundy mixtures, and copper phosphate were also taken and similar results were arrived at as shown in table 2 and 3. The above facts reveal a relationship between sedimentation and interfacial tension; low interfacial tension to low sedimentation values represent greater wettabilities of the solids on the addition of colloidal solutions. In this way was tested quantitatively the theory that the stability of an emulsion depends on relative interfacial tension and, as an approximate correlary, on the dispersibilities or wettabilities of the emulsifier in the two phases because whatever different causes may be operative in the stabilization of different emulsions, the one fundamental underlying principle applicable to all cases is the wetting of solid agent by the two liquids. With 3 tables     

Triton X-100/甲苯/水三元体系界面张力的耗散颗粒动力学模拟

采用耗散颗粒动力学方法在介观层次上模拟了非离子表面活性剂Triton X-100 在油/水界面上的分布行为, 并把用于油/水二元体系界面张力的计算方法拓展到含表面活性剂的三元体系. 利用该方法可以得到与实验数值吻合的界面张力数据. 另外, 模拟结果直观展示了表面活性剂界面张力与界面密度的关系, 为表面活性剂复配增效理论提供了依据. 该模拟方法给出的微观信息可以为驱油体系配方筛选和表面活性剂有效应用提供指导.     

Transient interfacial tension and dilatational rheology of diffuse polymer-polymer interfaces

We demonstrate the influence of molecular weight and molecular weight asymmetry across an interface on the transient behavior of the interfacial tension. The interfacial tension was measured as a function of time for a range of polymer combinations with a broad range of interfacial properties using a pendant/sessile drop apparatus. The results show that neglecting mutual solubility, assumed to be a reasonable approximation in many cases, very often does not sustain. Instead, a diffuse interface layer develops in time with a corresponding transient interfacial tension. Depending on the specific combination of polymers, the transient interfacial tension is found to increase or decrease with time. The results are interpreted in terms of a recently proposed model [Shi et al., Macromolecules 37, 1591 (2004)], giving relative characteristic diffusion time scales in terms of molecular weight, molecular weight distribution, and viscosities. However, the time scales obtained from this theoretical approach do not give a conclusive trend. Using oscillatory dilatational interfacial experiments the viscoelastic behavior of these diffusive interfaces is demonstrated. The time evolution of the interfacial tension and the dilatational elasticity show the same trend as predicted by the theory of diffuse interfaces, supporting the idea that the polymer combinations under consideration indeed form diffuse interfaces. The dilatational elasticity and the dilatational viscosity show a frequency dependency that is described qualitatively by a simple Fickian diffusion model and quantitatively by a Maxwell model. The characteristic diffusion times provided by the latter show that the systems with thick interfaces (tens of microseconds and more) can be considered as slower diffusive systems compared to the systems with thinner interfaces (a few micrometers in thickness and less) can be considered as fast diffusive systems.     

PE/PEO/PE-PEO 对称三元共混体系相行为的耗散粒子动力学模拟研究

建立了对应实验体系聚乙烯/聚氧化乙烯/聚乙烯-聚氧化乙烯嵌段共聚物(PE/PEO/PE-PEO)的对称三元共混模型,并采用耗散粒子动力学(DPD)模拟方法对其相行为进行了理论研究.研究结果表明,随着均聚物体积分数的增加,体系的平衡相态发生由层状相(LAM)到双连续微乳液(BME)再到相分离(PS)的转变,相态演化规律和...     

The effects of Lowe-Andersen temperature controlling method on the polymer properties in mesoscopic simulations

Lowe-Andersen (LA) temperature controlling method [C. P. Lowe, Europhys. Lett. 47, 145 (1999)] is applied in a series of mesoscopic polymer simulations to test its validity and efficiency. The method is an alternative for dissipative particle dynamics simulation (DPD) technique which is also Galilean invariant. It shows excellent temperature control and gives correct radial distribution function as that from DPD simulation. The efficiency of LA method is compared with other typical DPD integration schemes and is proved to be moderately efficient. Moreover, we apply this approach to diblock copolymer microphase separation simulations. With LA method, we are able to reproduce all the results from the conventional DPD simulations. The calculated structure factors of the microphases are consistent with the experiments. We also study the microphase evolution dynamics with increasing chiN and find that the bath collision frequency Gamma does not affect the order of appearing phases. Although the thermostat does not affect the surface tension, the order-disorder transition (ODT) is somewhat sensitive to the values of Gamma, i.e., the ODT is nonmonotonic with increasing Gamma. The dynamic scaling law is also tested, showing that the relation obeys the Rouse theory with various Gamma.     

Investigation of excess adsorption, solvation force, and plate-fluid interfacial tension for Lennard-Jones fluid confined in slit pores

The excess Helmholtz free energy functional is formulated in terms of a modified fundamental measure theory [Y. X. Yu and J. Z. Wu, J. Chem. Phys. 117, 10156 (2002)] for a short ranged repulsion and a first-order mean-spherical approximation theory [Y. P. Tang, J. Chem. Phys. 118, 4140 (2003)] for a long ranged attraction. Within the framework of the density functional theory, the density profile, excess adsorption, solvation force, and plate-fluid interfacial tension of a Lennard-Jones fluid confined in slit pores are predicted, and the results agree well with the simulation data. The phase equilibria inside the slit pores are determined according to the requirement that temperature, chemical potential, and grand potential in coexistence phases should be equal, and the plate-fluid interfacial tensions at equilibrium states are predicted consequently.