Showing papers on "Surface tension published in 2012"

Force Field Benchmark of Organic Liquids: Density, Enthalpy of Vaporization, Heat Capacities, Surface Tension, Isothermal Compressibility, Volumetric Expansion Coefficient, and Dielectric Constant

Abstract: The chemical composition of small organic molecules is often very similar to amino acid side chains or the bases in nucleic acids, and hence there is no a priori reason why a molecular mechanics force field could not describe both organic liquids and biomolecules with a single parameter set. Here, we devise a benchmark for force fields in order to test the ability of existing force fields to reproduce some key properties of organic liquids, namely, the density, enthalpy of vaporization, the surface tension, the heat capacity at constant volume and pressure, the isothermal compressibility, the volumetric expansion coefficient, and the static dielectric constant. Well over 1200 experimental measurements were used for comparison to the simulations of 146 organic liquids. Novel polynomial interpolations of the dielectric constant (32 molecules), heat capacity at constant pressure (three molecules), and the isothermal compressibility (53 molecules) as a function of the temperature have been made, based on expe...

Structured surfaces for enhanced pool boiling heat transfer

Abstract: We experimentally investigated surface roughness-augmented wettability on critical heat flux (CHF) during pool boiling with horizontally oriented surfaces. Microstructured surfaces with a wide range of well-defined surface roughness were fabricated, and a maximum CHF of ∼208 W/cm2 was achieved with a surface roughness of ∼6. An analytical force-balance model was extended to explain the CHF enhancement. The excellent agreement found between the model and experimental data supports the idea that roughness-amplified capillary forces are responsible for the CHF enhancement on structured surfaces. The insights gained from this work suggest design guidelines for new surface technologies with high heat removal capability.

Density, viscosity, and surface tension of water+ethanol mixtures from 293 to 323K

Abstract: Density, viscosity, and surface tension of liquids are important physicochemical properties which affect mass and heat transfer in solutions. The density, viscosity, and surface tension of binary mixture of water+ethanol at 293, 298, 303, 308, 313, 318, and 323 K are reported and compared with the available literature data. The findings of these comparisons show how the measured data are reproducible from different laboratories. The molar volume of water+ ethanol mixtures are also calculated using measured density values. The Jouyban-Acree model was used for mathematical correlation of the data. The relative deviation (RD) was used as an error criterion and the RD values for correlation of density, viscosity, surface tension and molar volume data at investigated temperatures are 0.1±0.1%, 10.4±9.5%, 4.2±3.6%, and 0.3±0.3%, respectively. The corresponding RDs for the predicted properties after training using the experimental data at 298 K are 0.2±0.2%, 14.1±15.8%, 5.4±4.6% and 0.4±0.3%, respectively, for density, viscosity, surface tension, and molar volume data. This study shows that the Jouyban-Acree model can correlate/predict physicochemical properties of the mixtures of solvents at different temperatures with acceptable error in calculation.

Surface tension of ionic liquids and ionic liquid solutions

Abstract: Some of the most active scientific research fronts of the past decade are centered on ionic liquids These fluids present characteristic surface behavior and distinctive trends of their surface tension versus temperature One way to explore and understand their unique nature is to study their surface properties This critical review analyses most of the surface tension data reported between 2001 and 2010 (187 references)

Surface tension of Nanofluid-type fuels containing suspended nanomaterials

Abstract: The surface tension of ethanol and n-decane based nanofluid fuels containing suspended aluminum (Al), aluminum oxide (Al2O3), and boron (B) nanoparticles as well as dispersible multi-wall carbon nanotubes (MWCNTs) were measured using the pendant drop method by solving the Young-Laplace equation. The effects of nanoparticle concentration, size and the presence of a dispersing agent (surfactant) on surface tension were determined. The results show that surface tension increases both with particle concentration (above a critical concentration) and particle size for all cases. This is because the Van der Waals force between particles at the liquid/gas interface increases surface free energy and thus increases surface tension. At low particle concentrations, however, addition of particles has little influence on surface tension because of the large distance between particles. An exception is when a surfactant was used or when (MWCNTs) was involved. For such cases, the surface tension decreases compared to the pure base fluid. The hypothesis is the polymer groups attached to (MWCNTs) and the surfactant layer between a particle and the surround fluid increases the electrostatic force between particles and thus reduce surface energy and surface tension.

Static wetting on deformable substrates, from liquids to soft solids

Abstract: Young's law fails on soft solid and liquid substrates where there are substantial deformations near the contact line. On liquid substrates, this is captured by Neumann's classic analysis, which provides a geometrical construction for minimising the interfacial free energy. On soft solids, the total free energy includes an additional contribution from elasticity. A linear-elastic model incorporating an out-of-plane restoring force due to solid surface tension was recently shown to accurately predict the equilibrium shape of a thin elastic film due to a large sessile droplet. Here, we extend this model to find substrate deformations due to droplets of arbitrary size. While the macroscopic contact angle matches Young's law for large droplets, it matches Neumann's prediction for small droplets. The cross-over droplet size is roughly given by the ratio of the solid's surface tension and elastic modulus. On thin substrates at this cross-over, the macroscopic contact angle increases, indicating that the substrate is effectively less wetting. For droplets of all sizes, the microscopic behaviour near the contact line follows the Neumann construction giving local force balance.

Three-dimensional lattice Boltzmann model for immiscible two-phase flow simulations.

Abstract: We present an improved three-dimensional 19-velocity lattice Boltzmann model for immisicible binary fluids with variable viscosity and density ratios. This model uses a perturbation step to generate the interfacial tension and a recoloring step to promote phase segregation and maintain surfaces. A generalized perturbation operator is derived using the concept of a continuum surface force together with the constraints of mass and momentum conservation. A theoretical expression for the interfacial tension is determined directly without any additional analysis and assumptions. The recoloring algorithm proposed by Latva-Kokko and Rothman is applied for phase segregation, which minimizes the spurious velocities and removes lattice pinning. This model is first validated against the Laplace law for a stationary bubble. It is found that the interfacial tension is predicted well for density ratios up to 1000. The model is then used to simulate droplet deformation and breakup in simple shear flow. We compute droplet deformation at small capillary numbers in the Stokes regime and find excellent agreement with the theoretical Taylor relation for the segregation parameter β=0.7. In the limit of creeping flow, droplet breakup occurs at a critical capillary number 0.35

Magnetic control over liquid surface properties with responsive surfactants.

Abstract: are well known. Here we report for the first time ionicliquid surfactants that are magneto-responsive, thus offeringthe potential to perturb liquid emulsions simply by theapplication of an external magnetic field. Although ionicliquids(ILs)containingtransitionmetalcomplexeshavebeenknown for some time,

Evaporation of droplets on superhydrophobic surfaces: surface roughness and small droplet size effects.

Abstract: Evaporation of a sessile droplet is a complex, nonequilibrium phenomenon. Although evaporating droplets upon superhydrophobic surfaces have been known to exhibit distinctive evaporation modes such as a constant contact line (CCL), a constant contact angle (CCA), or both, our fundamental understanding of the effects of surface roughness on the wetting transition remains elusive. We show that the onset time for the CCL-CCA transition and the critical base size at the Cassie-Wenzel transition exhibit remarkable dependence on the surface roughness. Through global interfacial energy analysis we reveal that, when the size of the evaporating droplet becomes comparable to the surface roughness, the line tension at the triple line becomes important in the prediction of the critical base size. Last, we show that both the CCL evaporation mode and the Cassie-Wenzel transition can be effectively inhibited by engineering a surface with hierarchical roughness.

Elucidating the mechanism of selective ion adsorption to the liquid water surface

Abstract: Adsorption of aqueous thiocyanate ions from bulk solution to the liquid/vapor interface was measured as a function of temperature by resonant UV second harmonic generation spectroscopy. The resulting adsorption enthalpy and entropy changes of this prototypical chaotrope were both determined to be negative. This surprising result is supported by molecular simulations, which clarify the microscopic origins of observed thermodynamic changes. Calculations reveal energetic influences of adsorbed ions on their surroundings to be remarkably local. Negative adsorption enthalpies thus reflect a simple repartitioning of solvent density among surface, bulk, and coordination regions. A different, and much less spatially local, mechanism underlies the concomitant loss of entropy. Simulations indicate that ions at the interface can significantly bias surface height fluctuations even several molecular diameters away, imposing restrictions consistent with the scale of measured and computed adsorption entropies. Based on these results, we expect an ion’s position in the Hofmeister lyotropic series to be determined by a combination of driving forces associated with the pinning of capillary waves and with a competition between ion hydration energy and the neat liquid’s surface tension.

Molecular dynamics computations of brine-CO2 interfacial tensions and brine-CO2-quartz contact angles and their effects on structural and residual trapping mechanisms in carbon geo-sequestration

Abstract: In the context of carbon geo-sequestration projects, brine–CO 2 interfacial tension γ and brine–CO 2 –rock surface water contact angles θ directly impact structural and residual trapping capacities. While γ is fairly well understood there is still large uncertainty associated with θ . We present here an investigation of γ and θ using a molecular approach based on molecular dynamics computer simulations. We consider a system consisting of CO 2 /water/NaCl and an α -quartz surface, covering a brine salinity range between 0 and 4 molal. The simulation models accurately reproduce the dependence of γ on pressure below the CO 2 saturation pressure at 300 K, and over predict γ by ∼20% at higher pressures. In addition, in agreement with experimental observations, the simulations predict that γ increases slightly with temperature or salinity. We also demonstrate that for non-hydroxylated quartz surfaces, θ strongly increases with pressure at subcritical and supercritical conditions. An increase in temperature significantly reduces the contact angle, especially at low-intermediate pressures (1–10 MPa), this effect is mitigated at higher pressures, 20 MPa. We also found that θ only weakly depends on salinity for the systems investigated in this work.

Highly Concentrated Aqueous Suspensions of Graphene through Ultrasonic Exfoliation with Continuous Surfactant Addition

Abstract: Highly concentrated suspensions of graphene stabilized with surfactant were prepared using ultrasonic exfoliation. Concentrations of up to 1.5% w/w (15 mg/mL) were achieved through the continuous addition of the surfactant during the exfoliation process. Previous methods typically add the surfactant only once, prior to the commencement of sonication. The vast increase in the available solid–liquid interfacial area through delamination results in the rapid depletion of the surfactant from solution through adsorption. This leads to a change in the liquid–vapor surface tension outside of the optimum range for the efficient production of graphene sheets. By continuously replacing the surfactant to lower the surface tension during sonication and the production of the graphene surface area, the concentration of particles was significantly increased. Cationic, anionic, and nonionic surfactants were studied and all showed significant increases in the concentration of graphene produced using this continuous additi...

Effect of oxidation on the mechanical properties of liquid gallium and eutectic gallium-indium

Abstract: Liquid metals exhibit remarkable mechanical properties, in particular large surface tension and low viscosity. However, these properties are greatly affected by oxidation when exposed to air. We measure the viscosity, surface tension, and contact angle of gallium and a eutectic gallium-indium alloy while controlling such oxidation by surrounding the metals with an acid bath of variable concentration. Rheometry measurements reveal a yield stress directly attributable to an oxide skin that obscures the intrinsic behavior of the liquid metals. We demonstrate how the intrinsic viscosity can be obtained with precision through a scaling technique that collapses low- and high-Reynolds number data. Measuring surface tension with a pendant drop method, we show that the oxide skin generates a surface stress that mimics surface tension and develop a simple model to relate this to the yield stress obtained from rheometry. We find that yield stress, surface tension, and contact angle all transition from solid-like to ...

Effect of oxidation on the Mechanical Properties of Liquid Gallium and Eutectic Gallium-Indium

Abstract: Liquid metals exhibit remarkable mechanical properties, in particular large surface tension and low viscosity. However, these properties are greatly affected by oxidation when exposed to air. We measure the viscosity, surface tension, and contact angle of gallium (Ga) and a eutectic gallium-indium alloy (eGaIn) while controlling such oxidation by surrounding the metal with an acid bath of variable concentration. Rheometry measurements reveal a yield stress directly attributable to an oxide skin that obscures the intrinsic behavior of the liquid metals. We demonstrate how the intrinsic viscosity can be obtained with precision through a scaling technique that collapses low- and high-Reynolds number data. Measuring surface tension with a pendant drop method, we show that the oxide skin generates a surface stress that mimics surface tension and develop a simple model to relate this to the yield stress obtained from rheometry. We find that yield stress, surface tension, and contact angle all transition from solid-like to liquid behavior at the same critical acid concentration, thereby quantitatively confirming that the wettability of these liquid metals is due to the oxide skin.

Breakup of Liquid Filaments

Abstract: Whether a thin filament of liquid separates into two or more droplets or eventually condenses lengthwise to form a single larger drop depends on the liquid's density, viscosity, and surface tension and on the initial dimensions of the filament. Surface tension drives two competing processes, pinching-off and shortening, and the relative time scales of these, controlled by the balance between capillary and viscous forces, determine the final outcome. Here we provide experimental evidence for the conditions under which a liquid filament will break up into drops, in terms of a wide range of two dimensionless quantities: the aspect ratio of the filament and the Ohnesorge number. Filaments which do not break up into multiple droplets demand a high liquid viscosity or a small aspect ratio.

The mechanism of a splash on a dry solid surface

Abstract: From rain storms to ink jet printing, it is ubiquitous that a high-speed liquid droplet creates a splash when it impacts on a dry solid surface. Yet, the fluid mechanical mechanism causing this splash is unknown. About fifty years ago it was discovered that corona splashes are preceded by the ejection of a thin fluid sheet very near the vicinity of the contact point. Here we present a first-principles description of the mechanism for sheet formation, the initial stages of which occur before the droplet physically contacts the surface. We predict precisely when sheet formation occurs on a smooth surface as a function of experimental parameters, along with conditions on the roughness and other parameters for the validity of the predictions. The process of sheet formation provides a semi-quantitative framework for studying the subsequent events and the influence of liquid viscosity, gas pressure and surface roughness. The conclusions derived from this framework are in quantitative agreement with previous measurements of the splash threshold as a function of impact parameters (the size and velocity of the droplet) and in qualitative agreement with the dependence on physical properties (liquid viscosity, surface tension, ambient gas pressure, etc.) Our analysis predicts an as yet unobserved series of events within micrometres of the impact point and microseconds of the splash.

Contact angles on a soft solid: from Young's law to Neumann's law

Abstract: The contact angle that a liquid drop makes on a soft substrate does not obey the classical Young’s relation, since the solid is deformed elastically by the action of the capillary forces. The finite elasticity of the solid also renders the contact angles differently from those predicted by Neumann’s law, which applies when the drop is floating on another liquid. Here, we derive an elastocapillary model for contact angles on a soft solid by coupling a mean-field model for the molecular interactions to elasticity. We demonstrate that the limit of a vanishing elastic modulus yields Neumann’s law or a variation thereof, depending on the force transmission in the solid surface layer. The change in contact angle from the rigid limit to the soft limit appears when the length scale defined by the ratio of surface tension to elastic modulus γ/E reaches the range of molecular interactio

Nanoparticle effects on the water-oil interfacial tension

Abstract: Although it is well known that solid particles adsorb at interfaces, no consensus has been reached on whether the adsorbed nanoparticles affect interfacial tension. In this work the Wilhelmy plate method is implemented in mesoscale dissipative particle dynamics simulations to study the influence of nanoparticles on the water-oil interfacial tension. The results are compared with predictions that neglect nanoparticle-nanoparticle interactions at the interface. We find that the two estimates can differ significantly. In the regime where nanoparticle-nanoparticle repulsion is large, the Wilhelmy plate method suggests interfacial tension reduction, which appears to be a strong function of nanoparticle surface coverage. Some experimental data from the literature, in apparent disagreement, are reinterpreted based on this insight.

Evaluating the behavior of electrolytic gas bubbles and their effect on the cell voltage in alkaline water electrolysis

Abstract: The behavior of electrolytic gas bubbles and their effect on the cell voltage in water electrolysis were studied theoretically and experimentally. A fundamental force analysis was employed to predict the critical diameter for the departure of the electrolytic gas bubbles. Good agreement between the predictions and observations was obtained. It was found that increasing the electrode potential strengthened the force due to the interfacial tension and increased the critical diameter, while increasing the electrolyte concentration led to a reduction. This was explained by the changes in both the contact angle and surface tension. Many more fine gas bubbles were observed at high current density, which was explained by that the enhanced natural convection forced bubbles to depart prematurely. The cell voltage was only slightly reduced by the electrolyte circulation, which reduced the critical diameter for bubble departure. This confirmed that the layer of fine bubbles represented a significant energy barrier, ...

Surface tension and aggregation properties of novel cationic gemini surfactants with diethylammonium headgroups and a diamido spacer.

Abstract: A series of novel cationic gemini surfactants with diethylammonium headgroups and a diamido spacer were synthesized, and their surface and bulk properties were investigated by surface tension, electrical conductivity, fluorescence, viscosity, dynamic light scattering (DLS), and transmission electron microscopy (TEM) measurements. An interesting phenomenon, that is, the obvious decline in surface tension upon increasing concentration above the critical micelle concentration (cmc), was found in these gemini surfactant solutions, and two explanations were proposed. This surface tension behavior could be explained by the rapid increase in the counterion activity in the bulk phase or the continued filling of the interface with increasing surfactant concentration above the cmc. More interestingly, not only vesicles but also the surfactant-concentration-induced vesicle to larger aggregate (spongelike aggregate) transition and the salt-induced vesicle and spongelike aggregate to micelle transition were found in t...

A perspective on the interfacial properties of nanoscopic liquid drops

Abstract: The structural and interfacial properties of nanoscopic liquid drops are assessed by means of mechanical, thermodynamical, and statistical mechanical approaches that are discussed in detail, including original developments at both the macroscopic level and the microscopic level of density functional theory (DFT). With a novel analysis we show that a purely macroscopic (static) mechanical treatment can lead to a qualitatively reasonable description of the surface tension and the Tolman length of a liquid drop; the latter parameter, which characterizes the curvature dependence of the tension, is found to be negative and has a magnitude of about a half of the molecular dimension. A mechanical slant cannot, however, be considered satisfactory for small finite-size systems where fluctuation effects are significant. From the opposite perspective, a curvature expansion of the macroscopic thermodynamic properties (density and chemical potential) is then used to demonstrate that a purely thermodynamic approach of this type cannot in itself correctly account for the curvature correction of the surface tension of liquid drops. We emphasize that any approach, e.g., classical nucleation theory, which is based on a purely macroscopic viewpoint, does not lead to a reliable representation when the radius of the drop becomes microscopic. The description of the enhanced inhomogeneity exhibited by small drops (particularly in the dense interior) necessitates a treatment at the molecular level to account for finite-size and surface effects correctly. The so-called mechanical route, which corresponds to a molecular-level extension of the macroscopic theory of elasticity and is particularly popular in molecular dynamics simulation, also appears to be unreliable due to the inherent ambiguity in the definition of the microscopic pressure tensor, an observation which has been known for decades but is frequently ignored. The union of the theory of capillarity (developed in the nineteenth century by Gibbs and then promoted by Tolman) with a microscopic DFT treatment allows for a direct and unambiguous description of the interfacial properties of drops of arbitrary size; DFT provides all of the bulk and surface characteristics of the system that are required to uniquely define its thermodynamic properties. In this vein, we propose a non-local mean-field DFT for Lennard-Jones (LJ) fluids to examine drops of varying size. A comparison of the predictions of our DFT with recent simulation data based on a second-order fluctuation analysis (Sampayo et al 2010 J. Chem. Phys. 132 141101) reveals the consistency of the two treatments. This observation highlights the significance of fluctuation effects in small drops, which give rise to additional entropic (thermal non-mechanical) contributions, in contrast to what one observes in the case of planar interfaces which are governed by the laws of mechanical equilibrium. A small negative Tolman length (which is found to be about a tenth of the molecular diameter) and a non-monotonic behaviour of the surface tension with the drop radius are predicted for the LJ fluid. Finally, the limits of the validity of the Tolman approach, the effect of the range of the intermolecular potential, and the behaviour of bubbles are briefly discussed.

Concentration Dependence of the Interfacial Tension for Aqueous Two-Phase Polymer Solutions of Dextran and Polyethylene Glycol

Abstract: We studied the interfacial tension between coexisting phases of aqueous solutions of dextran and polyethylene glycol. First, we characterized the phase diagram of the system and located the binodal. Second, the tie lines between the coexisting phases were determined using a method that only requires measuring the density of the coexisting phases. The interfacial tension was then measured by a spinning drop tensiometer over a broad range of polymer concentrations close to and above the critical point. In this range, the interfacial tension increases by 4 orders of magnitude with increasing polymer concentration. The scaling exponents of the interfacial tension, the correlation length, and order parameters were evaluated and showed a crossover behavior depending on the distance to the critical concentration. The scaling exponent of the interfacial tension attains the value 1.50 ± 0.01 further away from the critical point, in good agreement with mean field theory, but the increased value 1.67 ± 0.10 closer to this point, which disagrees with the Ising value 1.26. We discuss possible reasons for this discrepancy. The composition and density differences between the two coexisting phases, which may be taken as two possible order parameters, showed the expected crossover from mean field behavior to Ising model behavior as the critical point is approached. The crossover behavior of aqueous two-phase polymer solutions with increasing concentration is similar to that of polymer solutions undergoing phase separation induced by lowering the temperature.