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At least 19 records

The importance of experimental design on measurement of dynamic interfacial tension and interfacial rheology in diffusion-limited surfactant systems

Pendant bubble and drop devices are invaluable tools in understanding surfactant behavior at fluid–fluid interfaces. The simple instrumentation and analysis are used widely to determine adsorption isotherms, transport parameters, and interfacial rheology. However, much of the analysis performed is developed for planar interfaces. Moreover, the application of a planar analysis to drops and bubbles (curved interfaces) can lead to erroneous and unphysical results. We revisit this analysis for a well-studied surfactant system at air–water interfaces over a wide range of curvatures as applied to both expansion/contraction experiments and interfacial elasticity measurements. The impact of curvature and transport on measured properties is quantified and compared to other scaling relationships in the literature. Our results provide tools to design interfacial experiments for accurate determination of isotherm, transport and elastic properties.

36 MATERIALS SCIENCE↗

Numerical Prediction of Oscillation Behaviors of a Multiphase Core–Shell Droplet During Interfacial Tension Measurement

Interfacial tension between molten high-temperature materials is to be measured using the electrostatic levitation furnace (ELF) and the electromagnetic levitator (ISS-EML) aboard the International Space Station. A levitated compound droplet of a concentric core–shell structure is excited either by an impulsive electromagnetic field or by a superimposed electrostatic field. The oscillation behavior of the compound droplet is analyzed to measure interfacial tension at the interface of the two phases. In support of the space experiments, a computational fluid dynamic model was developed to characterize the oscillation behavior of multiphase core–shell droplet. The developed model predicted the interfacial tension between molten copper-rich and cobalt-rich phases with a difference of 3.3 pct compared to the values reported in literature. The developed model is being utilized to investigate the influence of various test parameters on measured surface tension and also being extended for molten steel–molten slag systems.

36 MATERIALS SCIENCE↗

Interfacial Tension of Polyelectrolyte Complex Coacervate Phases

We consider polyelectrolyte solutions which, under suitable conditions, phase separate into a liquid-like coacervate phase and a coexisting supernatant phase that exhibit an extremely low interfacial tension. Such interfacial tension provides the basis for most coacervate-based applications, but little is known about it, including its dependence on molecular weight, charge density, and salt concentration. By combining a Debye-Huckel treatment for electrostatic interactions with the Cahn-Hilliard theory, we derive explicit expressions for this interfacial tension. In the absence of added salts, we find that the interfacial tension scales as N-3/2(eta/eta(c)-1)(3/2) near the critical point of the demixing transition, and that it scales as eta(1/2) far away from it, where N is the chain length and eta measures the electrostatic interaction strength as a function of temperature, dielectric constant, and charge density of the polyelectrolytes. For the case with added salts, we find that the interfacial tension scales with the salt concentration psi as N-1/4(1-psi/psi(c))(3/2) near the critical salt concentration psi(c). Our predictions are shown to be in quantitative agreement with experiments and provide a means to design new materials based on polyelectrolyte complexation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Local pressure components and interfacial tensions of a liquid film in the vicinity of a solid surface with a nanometer-scale slit pore obtained by the perturbative method

A classical molecular dynamics simulation was conducted for a liquid-solid interfacial system with a nanometer-scale slit pore in order to reveal local thermodynamic states: local pressure components and interfacial tensions of a liquid film in the vicinity of the slit. The simulation also examined the transition mechanism between the two states of the liquid film: (a) liquid film on the slit and (b) liquid film in the slit, based on the local thermodynamic quantities from a molecular point of view. An instantaneous expression of the local pressure components and interfacial tensions, which is based on a volume perturbation, was presented to investigate time-dependent phenomena in molecular dynamics simulations. The interactions between the particles were described by the 12-6 Lennard-Jones potential, and effects of the fluid-solid interaction intensity on the local pressure components and interfacial tensions of the fluid in the vicinity of the slit were examined in detail by the presented perturbative method. The results revealed that the local pressure components tangential to the solid surface in the vicinity of the 1st fluid layer from the solid surface are different in a two dimensional plane, and the difference became pronounced in the vicinity of the corner of the slit, for cases where the fluid-solid interaction intensities are relatively strong. The results for the local interfacial tensions of the fluid inside the slit suggested that the local interfacial tensions in the vicinity of the 2nd and 3rd layers of the solid atoms from the entrance of the slit act as a trigger for the transition between the two states under the influence of a varying fluid-solid interaction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Magnetic Behavior of Ni/NiO Core–Shell Nanoparticles under Electromagnetic Waves for Oil–Water Interfacial Tension Reduction

The increasing demand for oil and gas has led to a hope of developing more efficient recovery methods. It is well known that nanoparticles adsorbed at the oil–water interface, but there is no consensus that has been reached on whether magnetic nanoparticles under electromagnetic waves affect the interfacial tension. In this paper, nickel/nickel oxide nanoparticles have been synthesized using sol–gel auto combustion method. The product was characterized using x-ray diffraction, Raman spectroscopy, field emission scanning electron microscopy, Fourier transforms infrared spectroscopy and vibrating sample magnetometer. The results show the Ni/NiO phases and the ferromagnetic nature of the sample. The Ni/NiO nanofluids were prepared to investigate the effect on oil–water interfacial tension in enhanced oil recovery under electromagnetic waves using an inverted pendant drop method. The results show a significant decrease in interfacial tension under electromagnetic waves of frequency 2.2 kHz at low wt.% of Ni/NiO and at room temperature. The decrease in the interfacial tension has been observed by increasing the temperature to 90 °C using temperature controller. The decrease in the interfacial tension could be due to the interaction of oscillating B-field of waves and magnetic domains of adsorbing nanoparticles at the oil–water interface which disturbed the oil–water interface.

36 MATERIALS SCIENCE↗

The ensemble switch method for computing interfacial tensions

We present a systematic thermodynamic integration approach to compute interfacial tensions for solid-liquid interfaces, which is based on the ensemble switch method. Applying Monte Carlo simulations and finite-size scaling techniques, we obtain results for hard spheres, which are in agreement with previous computations. The case of solid-liquid interfaces in a variant of the effective Asakura-Oosawa model and of liquid-vapor interfaces in the Lennard-Jones model are discussed as well. We demonstrate that a thorough finite-size analysis of the simulation data is required to obtain precise results for the interfacial tension.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Local pressure components and interfacial tension at a liquid-solid interface obtained by the perturbative method in the Lennard-Jones system

A classical molecular dynamics simulation was conducted for a system composed of fluid molecules between two planar solid surfaces, and whose interactions are described by the 12-6 Lennard-Jones form. This paper presents a general description of the pressure components and interfacial tension at a fluid-solid interface obtained by the perturbative method on the basis of statistical thermodynamics, proposes a method to consider the pressure components tangential to an interface which are affected by interactions with solid atoms, and applies this method to the calculation system. The description of the perturbative method is extended to subsystems, and the local pressure components and interfacial tension at a liquid-solid interface are obtained and examined in one- and two-dimensions. The results are compared with those obtained by two alternative methods: (a) an evaluation of the intermolecular force acting on a plane, and (b) the conventional method based on the virial expression. The accuracy of the numerical results is examined through the comparison of the results obtained by each method. The calculated local pressure components and interfacial tension of the fluid at a liquid-solid interface agreed well with the results of the two alternative methods at each local position in one dimension. In two dimensions, the results showed a characteristic profile of the tangential pressure component which depended on the direction tangential to the liquid-solid interface, which agreed with that obtained by the evaluation of the intermolecular force acting on a plane in the present study. Such good agreement suggests that the perturbative method on the basis of statistical thermodynamics used in this study is valid to obtain the local pressure components and interfacial tension at a liquid-solid interface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Liquid metal actuation by electrical control of interfacial tension

By combining metallic electrical conductivity with low viscosity, liquid metals and liquid metal alloys offer new and exciting opportunities to serve as reconfigurable components of electronic, microfluidic, and electromagnetic devices. Here, we review the physics and applications of techniques that utilize voltage to manipulate the interfacial tension of liquid metals; such techniques include electrocapillarity, continuous electrowetting, electrowetting-on-dielectric, and electrochemistry. These techniques lower the interfacial tension between liquid metals and a surrounding electrolyte by driving charged species (or in the case of electrochemistry, chemical species) to the interface. The techniques are useful for manipulating and actuating liquid metals at sub-mm length scales where interfacial forces dominate. We focus on metals and alloys that are liquid near or below room temperature (mercury, gallium, and gallium-based alloys). The review includes discussion of mercury—despite its toxicity—because it has been utilized in numerous applications and it offers a way of introducing several phenomena without the complications associated with the oxide layer that forms on gallium and its alloys. The review focuses on the advantages, applications, opportunities, challenges, and limitations of utilizing voltage to control interfacial tension as a method to manipulate liquid metals.

36 MATERIALS SCIENCE↗

Roles of Interfacial Tension in Regulating Internal Organization of Low Bandgap Polymer Bulk Heterojunction Solar Cells by Polymer Additives

The role of a tertiary polymer-based additive is investigated in increasing the efficiency of inverted low bandgap polymer:fullerene bulk heterojunction (BHJ) solar cells. Charge separation in polymer BHJ solar cells relies on the phase separation between electron accepting fullerene derivatives and photoactive polymers. Proper distribution of individual phases of suitable crystallinities within the active layer is a key factor for efficient charge transport/extraction and high photovoltaic performance. Here in this paper, it is demonstrated that the minor addition of a tertiary amorphous polymer, polystyrene (PS), with optimized molecular weights can increase the overall photovoltaic efficiency of poly[N-9-heptadecanyl-2,7-carbazole-alt-5,5-(4,7-di-2-thienyl-2,1,3-benzothiadiazole)]:phenyl-C 61 butyric acid methyl ester (PCDTBT:PCBM) inverted BHJ solar cells, through the interfacial-tension-driven increase in crystallinities of photoactive phases and redistribution of PCBM molecules away from the top hole-collecting anode interface. Complementary studies correlating polymer interfacial tension, blend internal structure, charge transport, and photovoltaic characteristics show that tertiary, high molecular-weight polymers can serve as effective additives for improving the performance of low bandgap polymer solar cells.

25 ENERGY STORAGE↗

Changes in Interfacial Tension with Time in Two-Liquid-Phase Systems

Interfacial tension (IFT) is a thermodynamic property of the interface between two immiscible fluids. This property has been identified as an important factor in an advanced solvent extraction system because it correlates with settling time and miscibility. The IFT in a variety of two phase systems has been partially characterized by Los Alamos National Laboratory (LANL) scientists. Information about the change in IFT is gathered in this study to more fully characterize these two-phase systems. Metal loaded aqueous solutions are of particular interest, as they simulate a solvent extraction system. Based in part on this body of research, LANL scientists will select the appropriate organic solvent and aqueous pH to develop an advanced solvent extraction system which will remove heavy metals from acidic solutions. Previous studies show that the factor which has the greatest effect on discrete IFT measurements is the ratio of aqueous density to organic density1. It is expected that this density ratio will play an important role in time-dependent IFT measurements as well. The two phases will be brought into equilibrium before beginning the tests, so it is also expected that IFT will not drastically change over a two hour time period.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pseudoplasticity and Dynamic Interfacial Tension Relaxation Effects on Nucleate Pool Boiling in Aqueous Polymeric Liquids

Nucleate pool boiling heat transfer and its ebullient dynamics in polymeric solutions at atmospheric pressure saturated conditions are experimentally investigated. Three grades of hydroxyethyl cellulose (HEC) are used, which have intrinsic viscosity in the range 5.29 ≤ [ η ] ≤ 10.31 [dl/g]. Their aqueous solutions in different concentrations, with zero-shear viscosity in the range 0.0021 ≤ η 0 ≤ 0.0118 [N∙s/m 2 ], exhibit shear-thinning rheology in varying degrees, as well as gas–liquid interfacial tension relaxation and wetting. Boiling heat transfer in solutions with constant molar concentrations of each additive, which are greater than their respective critical polymer concentration C * , is seen to have anomalous characteristics. There is degradation in the heat transfer at low heat fluxes, relative to that in the solvent, where the postnucleation bubble dynamics in the partial boiling regime is dominated by viscous resistance of the polymeric solutions. At higher heat fluxes, however, there is enhancement of boiling heat transfer due to a complex interplay of pseudoplasticity and dynamic surface tension effects. The higher frequency vapor bubbling train with high interfacial shear rates in this fully developed boiling regime tends to be influenced by increasing shear-thinning and time-dependent differential interfacial tension relaxation at the dynamic gas–liquid interfaces.

Engineering↗

Mathematical model for self-propelled droplets driven by interfacial tension

We propose a model for the spontaneous motion of a droplet induced by inhomogeneity in interfacial tension. The model is derived from a variation of the Lagrangian of the system and we use a time-discretized Morse flow scheme to perform its numerical simulations. Our model can naturally simulate the dynamics of a single droplet, as well as that of multiple droplets, where the volume of each droplet is conserved. We reproduced the ballistic motion and fission of a droplet, and the collision of two droplets was also examined numerically.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Impact of Pressure-Dependent Interfacial Tension and Contact Angle on Capillary Heterogeneity Trapping of CO2 in Storage Aquifers

Summary Carbon dioxide (CO2) capillary trapping increases the total amount of CO2 that can be effectively immobilized in storage aquifers. This trapping, manifesting itself as accumulated CO2 columns at a continuum scale, is because of capillary threshold effects that occur below low-permeability barriers. Considering that capillary pressure is dictated by heterogeneous pore throat size, the trapped CO2 column height and associated CO2 saturation will vary spatially within a storage aquifer. This variation will be influenced by two pressure-dependent interfacial parameters—CO2/brine interfacial tension (IFT) and CO2/brine/rock contact angle. Our objective is to understand how the pressure dependence of these two parameters affects the heterogeneity of capillary trapped CO2 at a continuum scale. Our conceptual model is a 1D two-zone system with the upper zone being a flow barrier (low permeability) and the lower zone being a flow path (high permeability). The inputs to this model include microfacies-dependent capillary pressure vs. saturation curves and permeability values. The input capillary pressure curves were collected in the literature that represents carbonate microfacies (e.g., dolograinstone) in a prevalent formation in the Permian Basin. We then used the Leverett j-function to scale the capillary pressure curve for the two zones that are assigned with the same or different microfacies. During scaling, we considered the influence of pressure on both the IFT and contact angle of CO2/brine/dolomite systems. We varied the zone permeability contrast ratio from 2 to 50. We then assumed capillary gravity equilibriums and calculated the CO2 saturation buildup corresponding to various trapped CO2 column heights. The CO2 saturation buildup is defined as the CO2 saturation in the lower layer minus that in the upper one. We found that the saturation buildup can be doubled when varying pressure in a storage aquifer, after considering pressure-dependent IFT and contact angles. Thus, assuming these two parameters to be constant across such aquifers would cause large errors in the quantification of capillary trapping of CO2. The whole study demonstrates the importance of considering pressure-dependent interfacial properties in predicting the vertical distribution of capillary trapped CO2. It has important implications in developing a better understanding of leakage risks and consequent storage safety.

Engineering↗

Dynamic stability of a crude oil/brine interface: Effect of anion type

The chemical composition of the aqueous phase plays an essential role in water-based enhanced-oil recovery processes. The aqueous phase ionic profile affects the snap-off response of a crude oil-brine system by linking it to the brine-crude oil interfacial rheology. In this work, we focus on the effect of the anion on the snap-off response. To this end, a sample of crude oil from the Minnelusa Sandstone formation in Wyoming was selected, and several aqueous solutions were prepared with salts containing sodium cation and different anions (chlorides, sulfates, and phosphates) at two ionic strength values, 0.6 M and 6 mM, as cases of high- and low-salinity water. Interfacial tension, interfacial viscoelasticity and interface stability were analyzed as functions of aging time using pendant drop, dilatational rheology, and liquid bridge techniques, respectively. Here the results show that solutions with higher ionic strength led to the formation of more rigid interfaces, i.e. higher elastic modulus, and faster formation kinetics. In the low-salinity regime, solutions with polyvalent anions produce more viscoelastic interfaces at faster rates than solutions with monovalent anions. Finally, an excellent correlation (R 2 greater than 0.97) between the relative stability of the interfacial film, predicted in liquid bridge tests, and the ratio of interfacial tension and interfacial elastic modulus was found.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Directing the adsorption and assembly of laponite nano-discs at oil–water interfaces

Achieving tunable controls on the adsorption and self-assembly of nanoscale building blocks at immiscible fluid interfaces is essential for synthesizing advanced materials, stabilizing emulsions, and the sustainable storage and recovery of fluids. Although extensive efforts have been directed toward resolving the assembly of spherical nanoparticles at water–hydrocarbon interfaces, 2D nanoparticles have received far less attention. In this study, we developed novel controls to direct the adsorption and assembly of 2D laponite nano-discs (diameter = ∼30 nm and thickness = ∼1 nm) at water–heptane interfaces using traces of sodium dodecyl sulfate (SDS) surfactant, demonstrated by advanced in situ small-angle X-ray scattering, atomic force microscopy, spinning drop tensiometer measurements and molecular dynamics simulations. The results show that SDS surfactant displaces the adsorbed laponite nano-discs from the interface toward the aqueous phase. The extent of this displacement increases with SDS concentration such that high SDS concentrations convert laponite-rich interfaces to SDS-rich interfaces free of laponite nano-discs. This transformation is associated with significant alterations in the rheological and nanomechanical properties of the host interface. In this context, reduction in interfacial tension and interfacial stiffness and an increase in the interfacial deformation is observed on increasing the SDS concentration from 0 to 0.1 wt%. The displacement of laponite nano-discs from the interface is driven by strong electrostatic interactions between the hydrophilic SDS group and interfacial water molecules. These studies unlock new insights into the adsorption and assembly of 2D nanoscale particles at water–hydrocarbons interfaces that are relevant for various applications related to energy and environmental science and engineering.

interfacial tension↗