Showing papers on "Surface tension published in 2011"

Comparison between Dicationic and Monocationic Ionic Liquids: Liquid Density, Thermal Properties, Surface Tension, and Shear Viscosity

Abstract: We report the data of liquid density, thermal properties including glass transition temperature, melting point, and decomposition temperature, surface tension, and shear viscosity for imidazolium-based dicationic ionic liquids with the anions of bis(trifluoromethylsulfonyl)amide, bis(pentafluoroethylsulfonyl)amide, tetrafluoroborate, and nitrate. To find the unique and general features of the dicationic ionic liquids, data of their corresponding monocationic ionic liquids are also summarized. The results of the dicationic ionic liquids showed that the density was high; the glass transition temperature and melting point were high, and they were thermally stable. Also the surface tension was large, and the shear viscosity was high in comparison with the reference monocationic ionic liquids. The data of the physical properties including liquid density, surface tension, and shear viscosity of the ionic liquids were also compared with that of alkanediols and alkyl alcohols to find the alkyene-linker and alkyl-...

Deformation of an elastic substrate by a three-phase contact line.

Abstract: Young's classic analysis of the equilibrium of a three-phase contact line ignores the out-of-plane component of the liquid-vapor surface tension. While it is expected that this unresolved force is balanced by the elastic response of the solid, a definitive analysis has remained elusive because of an apparent divergence of stress at the contact line. While a number of theories have been presented to cut off the divergence, none of them have provided reasonable agreement with experimental data. We measure surface and bulk deformation of a thin elastic film near a three-phase contact line using fluorescence confocal microscopy. The out-of-plane deformation is well fit by a linear elastic theory incorporating an out-of-plane restoring force due to the surface tension of the solid substrate. This theory predicts that the deformation profile near the contact line is scale-free and independent of the substrate elastic modulus.

Surfactant Effects on Bubble Motion and Bubbly Flows

Abstract: Small amounts of surfactant can drastically change bubble behavior. For example, a bubble in aqueous surfactant solution rises much slower than one in purified water. This phenomenon is explained by the so-called Marangoni effect caused by a nonuniform concentration distribution of surfactant along the bubble surface. In other words, a tangential shear stress appears on the bubble surface due to the surface tension variation caused by the surface concentration distribution, which results in the reduction of the rising velocity of the bubble. More interestingly, this Marangoni effect influences not only the rising velocity, but also the lateral migration in the presence of mean shear. Furthermore, these phenomena influence the multiscale nature of bubbly flows and cause a drastic change in the bubbly flow structure. In this article, we review the recent studies related to these interesting behaviors of bubbles caused by the surfactant adsorption/desorption on the bubble surface.

Origin of line tension for a Lennard-Jones nanodroplet

Abstract: The existence and origin of line tension has remained controversial in literature To address this issue, we compute the shape of Lennard-Jones nanodrops using molecular dynamics and compare them to density functional theory in the approximation of the sharp kink interface We show that the deviation from Young’s law is very small and would correspond to a typical line tension length scale (defined as line tension divided by surface tension) similar to the molecular size and decreasing with Young’s angle We propose an alternative interpretation based on the geometry of the interface at the molecular scale

Why is surface tension a force parallel to the interface

Abstract: A paperclip can float on water. Drops of mercury do not spread on a surface. These capillary phenomena are macroscopic manifestations of molecular interactions and can be explained in terms of surface tension. We address several conceptual questions that are often encountered when teaching capillarity and provide a perspective that reconciles the macroscopic viewpoints from thermodynamics and fluid mechanics and the microscopic perspective from statistical physics

Surface Rheology of Saponin Adsorption Layers

Abstract: Extracts of the Quillaja saponaria tree contain natural surfactant molecules called saponins that very efficiently stabilize foams and emulsions. Therefore, such extracts are widely used in several technologies. In addition, saponins have demonstrated nontrivial bioactivity and are currently used as essential ingredients in vaccines, food supplements, and other health products. Previous preliminary studies showed that saponins have some peculiar surface properties, such as a very high surface modulus, that may have an important impact on the mechanisms of foam and emulsion stabilization. Here we present a detailed characterization of the main surface properties of highly purified aqueous extracts of Quillaja saponins. Surface tension isotherms showed that the purified Quillaja saponins behave as nonionic surfactants with a relatively high cmc (0.025 wt %). The saponin adsorption isotherm is described well by the Volmer equation, with an area per molecule of close to 1 nm(2). By comparing this area to the molecular dimensions, we deduce that the hydrophobic triterpenoid rings of the saponin molecules lie parallel to the air-water interface, with the hydrophilic glucoside tails protruding into the aqueous phase. Upon small deformation, the saponin adsorption layers exhibit a very high surface dilatational elasticity (280 ± 30 mN/m), a much lower shear elasticity (26 ± 15 mN/m), and a negligible true dilatational surface viscosity. The measured dilatational elasticity is in very good agreement with the theoretical predictions of the Volmer adsorption model (260 mN/m). The measured characteristic adsorption time of the saponin molecules is 4 to 5 orders of magnitude longer than that predicted theoretically for diffusion-controlled adsorption, which means that the saponin adsorption is barrier-controlled around and above the cmc. The perturbed saponin layers relax toward equilibrium in a complex manner, with several relaxation times, the longest of them being around 3 min. Molecular interpretations of the observed trends are proposed when possible. Surprisingly, in the course of our study we found experimentally that the drop shape analysis method (DSA method) shows a systematically lower surface elasticity, in comparison with the other two methods used: Langmuir trough and capillary pressure tensiometry with spherical drops. The possible reasons for the observed discrepancy are discussed, and the final conclusion is that the DSA method has specific problems and may give incorrect results when applied to study the dynamic properties of systems with high surface elasticity, such as adsorption layers of saponins, lipids, fatty acids, solid particles, and some proteins. The last conclusion is particularly important because the DSA method recently became the preferred method for the characterization of fluid interfaces because of its convenience.

Wetting and spreading of nanofluids on solid surfaces driven by the structural disjoining pressure: statics analysis and experiments.

Abstract: The wetting and spreading of nanofluids composed of liquid suspensions of nanoparticles have significant technological applications. Recent studies have revealed that, compared to the spreading of base liquids without nanoparticles, the spreading of wetting nanofluids on solid surfaces is enhanced by the structural disjoining pressure. Here, we present our experimental observations and the results of the statics analysis based on the augmented Laplace equation (which takes into account the contribution of the structural disjoining pressure) on the effects of the nanoparticle concentration, nanoparticle size, contact angle, and drop size (i.e., the capillary and hydrostatic pressure); we examined the effects on the displacement of the drop-meniscus profile and spontaneous spreading of a nanofluid as a film on a solid surface. Our analyses indicate that a suitable combination of the nanoparticle concentration, nanoparticle size, contact angle, and capillary pressure can result not only in the displacement of the three-phase contact line but also in the spontaneous spreading of the nanofluid as a film on a solid surface. We show here, for the first time, that the complete wetting and spontaneous spreading of the nanofluid as a film driven by the structural disjoining pressure gradient (arising due to the nanoparticle ordering in the confined wedge film) is possible by decreasing the nanoparticle size and the interfacial tension, even at a nonzero equilibrium contact angle. Experiments were conducted on the spreading of a nanofluid composed of 5, 10, 12.5, and 20 vol % silica suspensions of 20 nm (geometric diameter) particles. A drop of canola oil was placed underneath the glass surface surrounded by the nanofluid, and the spreading of the nanofluid was monitored using an advanced optical technique. The effect of an electrolyte, such as sodium chloride, on the nanofluid spreading phenomena was also explored. On the basis of the experimental results, we can conclude that a nanofluid with an effective particle size (including the electrical double layer) of about 40 nm, a low equilibrium contact angle ( 30 vol %) is desirable for the dynamic spreading of a nanofluid system with an interfacial tension of 0.5 mN/m. Our experimental observations also validate the major predications of our theoretical analysis.

Assembled monolayers of hydrophilic particles on water surfaces.

Abstract: A facile and quick approach to prepare self-assembled monolayers of water-dispersible particles on the water surface is presented. Particle suspensions in alcohols were dropped on a water reservoir to form long-range ordered monolayers of various particles, including spherical solid particles, soft hydrogel particles, metal nanoparticles, quantum dots, nanowires, single-wall carbon nanotubes (SWCNTs), nanoplates, and nanosheets. A systematic study was conducted on the variables affecting the monolayer assembly: the solubility parameter of spreading solvents, particle concentration, zeta potential of the particles in the suspension, surface tension of the water phase, hardness of the particles, and addition of a salt in the suspension. This method requires no hydrophobic surface treatment of the particles, which is useful to exploit these monolayer films without changing the native properties of the particles. The study highlights a quick 2D colloidal assembly without cracks in the wafer scale as well as t...

Wetting and Dewetting Transitions on Hierarchical Superhydrophobic Surfaces

Abstract: Many natural superhydrophobic structures have hierarchical two-tier roughness which is empirically known to promote robust superhydrophobicity. We report the wetting and dewetting properties of two-tier roughness as a function of the wettability of the working fluid, where the surface tension of water/ethanol drops is tuned by the mixing ratio, and compare the results to one-tier roughness. When the ethanol concentration of deposited drops is gradually increased on one-tier control samples, the impalement of the microtier-only surface occurs at a lower ethanol concentration compared to the nanotier-only surface. The corresponding two-tier surface exhibits a two-stage wetting transition, first for the impalement of the microscale texture and then for the nanoscale one. The impaled drops are subsequently subjected to vibration-induced dewetting. Drops impaling one-tier surfaces could not be dewetted; neither could drops impaling both tiers of the two-tier roughness. However, on the two-tier surface, drops i...

Imidazolium Ionic Liquid Interfaces with Vapor and Graphite: Interfacial Tension and Capacitance from Coarse-Grained Molecular Simulations

Abstract: A recently developed coarse-grained model (J. Phys. Chem. B, 2010, 114, 12629–12631), previously validated against experimental data for a number of bulk properties, is used in molecular dynamics simulations of two different interfaces involving the ionic liquid [BMI][PF6]. First, simulations of the liquid–vapor interface demonstrate that the model is able to predict the surface tension of the fluid (for which we obtain a value of 39.4 mN·m–1 at 400 K). Second, simulations were performed at constant potential differences applied between two graphite electrodes. From simulations with different applied potentials, the differential capacitances of the positive and negative electrodes can be calculated. It appears that both capacitances (C+ = 3.9 μF·cm–2 for the positive electrode and C– = 4.8 μF·cm–2 for the negative electrode) agree very well with simulations results obtained with an all-atom model. The coarse-grained model also accurately reproduces the two-dimensional structure observed at the graphite–io...

Flow transition within an evaporating binary mixture sessile drop

Abstract: The flow field along the base of an evaporating ethanol-water droplet and its evolution time was measured by particle image velocimetry. Three stages are revealed, a first stage dominated by multiple vortices, a second transition stage characterized by a remarkable spike in outward flow not previously identified, and a third stage dominated by outward flow identical to that found for pure water. Stage I is thought to be driven by surface tension gradients arising from local concentration variation. The spike in outward flow is explained in terms of a transition corresponding to almost total depletion of ethanol. An exponential decay in vorticity during the transition stage is explained in terms of ethanol diffusion from the bulk to the interface. We speculate on the existence of a zero-concentration wave propagating from the apex to the contact line corresponding to the final total depletion of ethanol.

Many-body dissipative particle dynamics simulation of liquid/vapor and liquid/solid interactions.

Abstract: The combination of short-range repulsive and long-range attractive forces in many-body dissipative particle dynamics (MDPD) is examined at a vapor/liquid and liquid/solid interface. Based on the radial distribution of the virial pressure in a drop at equilibrium, a systematic study is carried out to characterize the sensitivity of the surface tension coefficient with respect to the inter-particle interaction parameters. For the first time, the approximately cubic dependence of the surface tension coefficient on the bulk density of the fluid is evidenced. In capillary flow, MDPD solutions are shown to satisfy the condition on the wavelength of an axial disturbance leading to the pinch-off of a cylindrical liquid thread; correctly, no pinch-off occurs below the cutoff wavelength. Moreover, in an example that illustrates the cascade of fluid dynamics behaviors from potential to inertial-viscous to stochastic flow, the dynamics of the jet radius is consistent with the power law predictions of asymptotic analysis. To model interaction with a solid wall, MDPD is augmented by a set of bell-shaped weight functions; hydrophilic and hydrophobic behaviors, including the occurrence of slip in the latter, are reproduced using a modification in the weight function that avoids particle clustering. The dynamics of droplets entering an inverted Y-shaped fracture junction is shown to be correctly captured in simulations parametrized by the Bond number, confirming the flexibility of MDPD in modeling interface-dominated flows.

The morphology of aerosol particles consisting of hydrophobic and hydrophilic phases: hydrocarbons, alcohols and fatty acids as the hydrophobic component

Abstract: The morphology of bi-phase aerosol particles containing phase separated hydrophobic and hydrophilic components is considered, comparing simulations based on surface and interfacial tensions with measurements made by aerosol optical tweezers. The competition between the liquid phases adopting core–shell and partially engulfed configurations is considered for a range of organic compounds including saturated and unsaturated hydrocarbons, aromatics, alcohols, ketones, carboxylic acids, esters and amines. When the solubility of the organic component and the salting-out of the organic component to the surface by the presence of concentrated inorganic solutes in the aqueous phase are considered, it is concluded that the adoption of a partially engulfed structure predominates, with the organic component forming a surface lens. The aqueous surface can be assumed to be stabilised by a surface enriched in the organic component. The existence of acid–base equilibria can lead to the dissociation of organic surfactants and to significant lowering of the surface tension of the aqueous phase, further supporting the predominance of partially engulfed structures. Trends in morphology from experimental measurements and simulations are compared for mixed phased droplets in which the organic component is decane, 1-octanol or oleic acid with varying relative humidity. The consequences of partially engulfed structures for aerosol properties are considered.

Aggregation behavior of amino acid ionic liquid surfactants in aqueous media.

Abstract: Self-aggregation of amino acid ionic liquid surfactants (AAILSs) in aqueous solution has been investigated through surface tension, conductivity, steady-state fluorescence, dynamic light scattering (DLS), and transmission electron microscopy (TEM). The critical aggregation concentration (cac) of AAILSs obtained from different techniques showed fairly good agreement. Surface tension measurements have been used to derive surface adsorption properties such as adsorption efficiency (pC20), effectiveness of surface tension reduction (Πcac), and minimum surface area per molecule (Amin) at the air–water interface. Temperature-dependent conductivity measurements have been used to obtain the degree of counterion binding (β), and the thermodynamic parameters such as standard free energy (ΔGagg0), enthalpy (ΔHagg0), and entropy (ΔSagg0) of aggregation. The aggregation number (Nagg) for various AAILSs has been derived by using the fluorescence quenching technique. Size of the aggregates has been obtained from DLS and...

Amphiphilic Silica Nanoparticles at the Decane−Water Interface: Insights from Atomistic Simulations

Abstract: The properties of 3 nm-diameter silica nanoparticles with different surface chemistry were systematically investigated at the decane−water interface using molecular dynamics simulations. Our results show that the decane−water interfacial tension is not much influenced by the presence of the nanoparticles. The three-phase contact angle increases with nanoparticle surface hydrophobicity. Contact angles observed for the nanoparticles at 300 and at 350 K differ very little. The contact angle of the nanoparticle with randomly dispersed hydrophobic groups is smaller than that observed in Janus nanoparticles of equal overall surface chemistry composition. The energy necessary to desorb Janus nanoparticles from the interface is usually higher than that required to desorb the corresponding homogeneous nanoparticles. Desorption from the interface into the aqueous phase is preferred over that into the organic phase for all except one of the nanoparticles considered. Structural and dynamic properties including nanopa...

Dielectric decrement as a source of ion-specific effects

Abstract: Many theoretical studies were devoted in the past to ion-specific effects trying to interpret a large body of experimental evidence, such as surface tension at air/water interfaces and force measurements between charged objects. Although several mechanisms were suggested to explain the results, such as dispersion forces and specific surface-ion interactions, we would like to suggest another source of ion-specificity originating from the local variations of the dielectric constant due to the presence of ions in the solution. We present a mean-field model to account for the heterogeneity of the dielectric constant caused by the ions. In particular, for ions that decrease the dielectric constant we find a depletion of ions from the vicinity of charged surfaces. For a two-plate system, the same effect leads to an increase of the pressure in between two surfaces. Our results suggest that the effect of ions on the local dielectric constant should be taken into account when interpreting experiments that address ion-specific effects.

Control of Ostwald Ripening by Using Surfactants with High Surface Modulus

Abstract: We describe results from systematic measurements of the rate of bubble Ostwald ripening in foams with air volume fraction of 90%. Several surfactant systems, with high and low surface modulus, were used to clarify the effect of the surfactant adsorption layer on the gas permeability across the foam films. In one series of experiments, glycerol was added to the foaming solutions to clarify how changes in the composition of the aqueous phase affect the rate of bubble coarsening. The experimental results are interpreted by a new theoretical model, which allowed us to determine the overall gas permeability of the foam films in the systems studied, and to decompose the film permeability into contributions coming from the surfactant adsorption layers and from the aqueous core of the films. For verification of the theoretical model, the gas permeability determined from the experiments with bulk foams are compared with values, determined in an independent set of measurements with the diminishing bubble method (single bubble attached at large air-water interface) and reasonably good agreement between the results obtained by the two methods is found. The analysis of the experimental data showed that the rate of bubble Ostwald ripening in the studied foams depends on (1) type of used surfactant-surfactants with high surface modulus lead to much slower rate of Ostwald ripening, which is explained by the reduced gas permeability of the adsorption layers in these systems; (2) presence of glycerol which reduces the gas solubility and diffusivity in the aqueous core of the foam film (without affecting the permeability of the adsorption layers), thus also leading to slower Ostwald ripening. Direct measurements showed that the foam films in the studied systems had very similar thicknesses, thus ruling out the possible explanation that the observed differences in the Ostwald ripening are due to different film thicknesses. Experiments with the Langmuir trough were used to demonstrate that the possible differences in the surface tensions of the shrinking and expanding bubbles in a given foam are too small to strongly affect the rate of Ostwald ripening in the specific systems studied here, despite the fact that some of the surfactant solutions have rather high surface modulus. The main reason for the latter observation is that the rate of surface deformation of the coarsening bubbles is extremely low, on the order of 10(-4) s(-1), so that the relaxation of the surface tension (though also slow for the high surface modulus systems) is still able to reduce the surface tension variations down to several mN/m. Thus, we conclude that the main reason for the reduced rate of bubble Ostwald ripening in the systems with high surface modulus is the low solubility and diffusivity of the gas molecules in the respective condensed adsorption layers (which have solid rather than fluid molecular packing).

Micelle formation by N-alkyl-N-methylpyrrolidinium bromide in aqueous solution

Abstract: The micellization of the ionic liquid N-alkyl-N-methylpyrrolidinium bromide (CnMPB, n = 12, 14 and 16) in aqueous solutions was investigated by surface tension measurements, electrical conductivity and static luminescence quenching. The effectiveness of the surface tension reduction (Πcmc), maximum surface excess concentration (Γmax) and the minimum area (Amin) occupied per surfactant molecule at the air/water interface can be obtained from the surface tension measurements at 25 °C. The critical micelle concentration (cmc) at different temperatures and a series of thermodynamic parameters (ΔG0m, ΔH0m and ΔS0m) of micellization were evaluated from electrical conductivity measurements in the temperature range of 25–45 °C. The thermodynamic parameters show that the micelle formation is entropy-driven at low temperature and enthalpy-driven at high temperature. Furthermore, the micelle aggregation number (Nagg) of CnMPB was calculated according to the Turro-Yekta method through static luminescence quenching and found that Nagg (49, 55, and 59) increased with the hydrophobic chain length of CnMPB.

External‐Energy‐Independent Polymer Capsule Motors and Their Cooperative Behaviors

Abstract: The design and development of mobile nano-, micro-, and millimeter-scale autonomous systems have been perused over several decades. Here, we introduce a millimeter-sized polymer capsule motor with specific features and functionalities. It runs without any external energy sources or the consumption of external fuels such as H(2)O(2) or glucose. The occurrence of motion is due to the asymmetric release of organic solvent from the capsule and the asymmetric change in the surface tension of the surrounding liquid. The capsule moves from a place of lower surface tension to a place of higher surface tension (Marangoni effect) in an attempt by the system to attain the desirable lowest-free-energy state. The operation of the motor is versatile in terms of the environment, as it moves on a wide variety of liquid/air interfaces, including water, sea water, organic solvent/water mixtures, and acids. A high-motion velocity was observed, with a travelling distance of over 20 meters. The manipulation of its motion was achieved upon functionalization with nickel powder and application of an external magnetic field. Long-range interaction behaviors and surface-cleaning effects due to the chemotaxis effect were also demonstrated when the capsule was functionalized with sodium dodecyl sulfate (SDS). We believe that a plethora of applications can be envisioned with this motor, such as cargo delivery, manipulation of matter, sensing and detection, biorecognition, and environmental remediation.

Simultaneous application of the gradient theory and Monte Carlo molecular simulation for the investigation of methane/water interfacial properties.

Abstract: This work is dedicated to the simultaneous application of the gradient theory of fluid interfaces and Monte Carlo molecular simulations for the description of the interfacial behavior of the methane/water mixture. Macroscopic (interfacial tension, adsorption) and microscopic (density profiles, interfacial thickness) properties are investigated. The gradient theory is coupled in this work with the SAFT-VR Mie equation of state. The results obtained are compared with Monte Carlo simulations, where the fluid interface is explicitly considered in biphasic simulation boxes at both constant pressure and volume (NPT and NVT ensembles), using reliable united atom molecular models. On one hand, both methods provide very good estimations of the interfacial tension of this mixture over a broad range of thermodynamic conditions. On the other hand, microscopic properties computed with both gradient theory and MC simulations are in very good agreement with each other, which confirms the consistency of both approaches. Interfacial tension minima at high pressure and prewetting transitions in the vicinity of saturation conditions are also investigated.

Dynamics of wet particles in rotating drums: Effect of liquid surface tension

Abstract: A numerical model based on the discrete element method was developed to simulate the wet particle flow in a rotating drum. The model explicitly considered the capillary force between particles and liquid distribution within the packed bed. Physical experiments under similar conditions were carried out to validate the model, showing that the simulation and experiment results were quite comparable in terms of the flow patterns, maximum flow repose angle, and the frequency of avalanching. Flow properties in two different states were investigated with the focus on the effect of liquid surface tension. In the quasistatic state with the drum rotating at very low speeds, discrete avalanches were observed after the flow reached the maximum repose angle. However, flow properties had changed well before avalanches occurred. The microscopic analysis indicated that the strength caused by the capillary force reached a minimal when avalanches started. The maximum repose angle increased with increasing capillary force a...

Use of Artificial Neural Network-Group Contribution Method to Determine Surface Tension of Pure Compounds

Abstract: This work aims at applying an artificial neural network-group contribution method to represent/predict the surface tension of pure chemical compounds at different temperatures and atmospheric pressure. To propose a comprehensive, reliable, and predictive tool, about 4700 data belonging to experimental surface tension values of 752 chemical compounds at different temperatures and atmospheric pressure have been studied. The investigated compounds belong to 78 chemical families containing 151 functional groups (group contributions), which include organic and inorganic liquids. Using this dedicated strategy, we obtain satisfactory results quantified by the following statistical parameters: absolute average deviations of the represented/predicted properties from existing experimental values, 1.7 %, and squared correlation coefficient, 0.997.

Investigation of interfacial and structural properties of CTAB at the oil/water interface using dissipative particle dynamics simulations

Abstract: We have used dissipative particle dynamics (DPD) to simulate the system of cetyltrimethylammonium bromide (CTAB) monolayer at the oil/water interface. The interfacial properties (interfacial density, interfacial thickness, and interfacial tension), structural properties (area compressibility modulus, end to end distance, and order parameter), and their dependence on the oil/water ratio and the surfactant concentration were investigated. Three different microstructures, spherical oil in water (o/w), interfacial phase, and water in oil (w/o), can be clearly observed with the oil/water ratio increasing. Both the snapshots and the density profiles of the simulation show that a well defined interface exists between the oil and water phases. The interface thickens with CTAB concentration and oil/water ratio. The area compressibility modulus decreases with an increase in the oil/water ratio. The CTAB molecules are more highly packed at the interface and more upright with both concentration and oil/water ratio. The root mean square end-to-end distance and order parameter have a very weak dependence on the oil/water ratio. But both of them show an increase with CTAB concentration, indicating that the surfactant molecules at the interface become more stretched and more ordered at high concentration. As CTAB concentration increases further, the order parameter decreases instead because the bending of the interface. At the same time, it is shown that CTAB has a high interfacial efficiency at the oil/water interface.