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Thermocapillary Convection in Bubbles and Drops

When bubbles or drops are present in an immiscible liquid in reduced gravity and the temperature of the liquid is non-uniform, a thermocapillary stress is generated at the interface due to the variation of interfacial tension with temperature. The resulting flow propels the drop freely suspended in the liquid towards warmer regions, so as to minimize the interfacial energy. In this presentation, we will focus on the effect of convective transport of momentum and energy, that are characterized by the Reynolds number and the Marangoni number, respectively. The results of asymptotic analyses for the speed of the drop for low and large values of these parameters will be discussed. These predictions as well as those from numerical simulations will be compared with reduced gravity experimental results obtained from experiments performed aboard the space shuttle.

Balassubramaniam

Surface-Tension Driven Convection

The present experiments are directed to examine surface-tension gradients. The surface-tension induced convection under reduced gravity it's comparison with normal gravity convection with all other identical conditions are studied. The intensities of such flows and their penetration depth below the free surface are also determined. In this way, the dominant role of a free surface in a reduced-gravity environment is indicated. The interface between two fluid phases can influence the motion of fluids when either the interface has finite curvature or when the interfacial tension varies from point to point. In both cases, forces appear in the interfacial region that can affect or generate fluid motions.

Ostrach, S.

Unsteady Thermocapillary Migration of Isolated Drops in Creeping Flow

The problem of an isolated immiscible drop that slowly migrates due to unsteady thermocapillary stresses is considered. All physical properties except for interfacial tension are assumed constant for the two Newtonian fluids. Explicit expressions are found for the migration rate and stream functions in the Laplace domain. The resulting microgravity theory is useful, e.g., in predicting the distance a drop will migrate due to an impulsive interfacial temperature gradient as well as the time required to attain steady flow conditions from an initially resting state.

Dill, Loren H.

Nitrilotriacetamides: Nitric Acid and Water Extraction and Physicochemical Properties

Nitrilotriacetamides are an emerging class of extractants that have been identified as promising candidates for a variety of separation schemes. Systems incorporating these ligands are prone to third-phase formation at high loading, but this can be mitigated by increasing the alkyl chain length or adding a phase modifier (e.g., 1-octanol). In this work, the impacts of these modifications on HNO 3 extraction, H 2 O extraction, and physiochemical properties (interfacial tension, viscosity, and density) are examined. The studies show that ligand alkyl chain length has very little impact on HNO 3 and H 2 O extraction, whereas the addition of 10% octanol significantly increases extraction of both HNO 3 and H 2 O. Viscosity and interfacial ten-sion are impacted by HNO 3 concentration, alkyl chain length, and the presence of phase modifier but remain in a range that should be compatible with commonly used solvent contacting equipment. Additional studies of physiochemical properties at variable ligand concentration suggest that a change in aggregation occurs above approximately 10-50 mM ligand. Thermodynamic modeling of distribution ratios and spectroscopic studies aimed at understanding speciation in the presence of HNO 3 are also reported. Further, these experiments suggest that the first equivalent of extracted HNO 3 interacts with both the central amine and carbonyl groups of the ligand. The spectroscopic changes at higher HNO 3 concentrations are relatively minor, suggesting additional HNO 3 is associated in an outer-sphere manner

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH

Characterizing the pore-scale impacts of enhanced-solubilization solutions on organic-liquid morphology and fluid-fluid interfacial area with microtomography

Synchrotron X-ray microtomography was used to directly quantify the impact of enhanced-solubilization solutions on mobilization of a non-wetting fluid in a natural porous medium. Polyoxyethylene sorbitan monooleate (tween 80), hydroxypropyl-β-cyclodextrin (HPCD), sodium dodecyl sulfate (SDS), and ethanol were used as the solubilization reagents. Tetrachloroethene (PCE) was used as the entrapped organic immiscible liquid. Microtomography images were collected prior to and after successive floods with each reagent solution. The total trapping number was varied by more than three orders of magnitude by changing the velocity and viscosity of the aqueous phase as well as the interfacial tension between fluid phases. The results were compared to those obtained from equivalent experiments conducted with water flooding. Inspection of images indicated that mobilization caused a change in PCE morphology and distribution for all reagents with the exception of HPCD, for which a lower trapping number was determined compared to the other experiments. Mobilization of organic liquid was observed at total trapping numbers that were consistent with prior work. The enhanced-solubilization solutions had minimal impact on the configuration or magnitude of fluid-fluid interfacial area.

Interfacial area

Dynamic Nucleation of Supercooled Melts and Measurement of the Surface Tension and Viscosity

We investigate the phenomenon of acoustic pressure-induced nucleation by using a novel approach involving the large amplitude resonant radial oscillations and collapse of a single bubble intentionally injected into a supercooled liquid. Using a combination of previously developed and proven techniques, the bubble is suspended in a fluid host by an ultrasonic field which supplies both the levitation capability as well as the forcing of the radial oscillations. We observe the effects of an increase in pressure (due to bubble collapse) in a region no larger than 100 microns within the supercooled melt to rigorously probe the hypothesis of pressure-induced nucleation of the solid phase. The use of single bubbles operating in narrow temporal and spatial scales will allow the direct and unambiguous correlation between the origin and location of the generation of the disturbance and the location and timing of the nucleation event. In a companion research effort, we are developing novel techniques for the non-contact measurements of the surface tension and viscosity of highly viscous supercooled liquids. Currently used non-invasive methods of surface tension measurement for the case of undercooled liquids generally rely of the quantitative determination of the resonance frequencies of drop shape oscillations, of the dynamics of surface capillary waves, or of the velocity of streaming flows. These methods become quickly ineffective when the liquid viscosity rises to a significant value. An alternate and accurate method which would be applicable to liquids of significant viscosity is therefore needed. We plan to develop such a capability by measuring the equilibrium shape of levitated undercooled melt droplets as they undergo solid-body rotation. The experimental measurement of the characteristic point of transition (bifurcation point) between axisymmetric and two-lobed shapes will be used to calculate the surface tension of the liquid. Such an approach has already been validated through the experimental verification of numerical modeling results. The experimental approach involves levitation, melting, and solidification of undercooled droplets using a hybrid ultrasonic-electrostatic technique in both a gaseous as well as a vacuum environment. A shape relaxation method will be investigated in order to derive a reliable method to measure the viscosity of undercooled melts. The analysis of the monotonic relaxation to equilibrium shape of a drastically deformed and super-critically damped free drop has been used to derive interfacial tension of immiscible liquid combinations where one of the component has high viscosity. A standard approach uses the initial elongation of a droplet through shear flows, but an equivalent method could involve the initial deformation of a drop levitated in a gas by ultrasonic radiation pressure, electric stresses, or even solid body rotation. The dynamic behavior of the free drop relaxing back to equilibrium shape will be modeled, and its characteristic time dependence should provide a quantitative means to evaluate the liquid viscosity.

Trinh, E. H.

Thermal buoyancy and Marangoni convection in a two fluid layered system - A numerical study

Thermal buoyancy and surface tension driven convection is numerically investigated in a system with two, immiscible fluids. The geometry investigated, has an open cavity configuration with the lighter fluid situated on top of the heavier fluid, forming a stable layered system. The upper fluid meniscus and the interface are assumed to be flat and undeformable in the calculations. The governing equations and boundary/interface conditions are solved by a control volume based finite difference scheme for two pairs of immiscible fluids; the water-hexadecane system and a so called generic system. The steady state calculations show, that dramatically different flows are predicted when the interfacial tension effects are included or excluded from the system model. These differences are particularly appreciable in surface tension dominated flows, that are typical of microgravity situations. Complex flow patterns, with induced secondary flows are noticed in both the fluids. In general, the overall system heat transfer is found to increase with increases in the thermal buoyancy and surface tension effects, but the behavior of the system flow and thermal fields is not easy to characterize, when different combinations of these forces are considered.

Ramachandran, N.

Enhanced reactivity at the oil–water interface accelerates the synthesis of zymonic acid in microemulsions

Chemical reactions in microscale compartments, such as aerosols and emulsions, can exhibit significantly faster reaction rates relative to macroscale containers. This enhancement in chemistry is often due to the elevated importance of surfaces as reaction vessels are reduced to picoliter volumes. While most studies have focused on the air-water interface of droplets, there are comparably fewer studies of reactions in micron-scale aqueous solutions encapsulated by oil. Here we investigate the condensation reaction of pyruvic acid (PA) to form zymonic acid (ZA) and water. Using microfluidics and optical trapping, chemical kinetics are measured in monodisperse micron-sized emulsion droplets in situ via Raman spectroscopy. Relative to a macroscopic bulk solution, which exhibits little to no reaction over many days, we find efficient production of ZA over the same time period. A kinetic model is developed to elucidate the role of the interface in accelerating the microdroplet reaction kinetics. After quantifying the surface partitioning of PA from interfacial tension measurements, the rate coefficient for the condensation reaction at the oil-water interface is determined to be 1.8 × 10-2 M-1 s-1. This rate coefficient is estimated to be 105 larger than the reaction rate in bulk aqueous solutions. Compared to previous studies of accelerated ZA formation at the air-water interface on nanodroplets, we find that the reaction at the oil-water interface is 20 times more efficient. Despite this difference, the overall ZA formation rate in emulsions is significantly slower than in the same-sized aerosols, which arises from the weaker partitioning of PA to the oil-aqueous relative to air-water interface. These results highlight the interplay between interfacial partitioning and reactivity in accelerating chemistry in microcompartments and provides new insights into how interfacial composition influences condensation reactions.

Wallace, Brandon J

Stabilization of Miscible Aqueous Phases via Diffusion‐Controlled Multifunctional Nanoparticle‐Ligand Complexation

Liquid‐in‐liquid structuring by harnessing miscible aqueous domains can be achieved by inducing thermodynamically defined phase separation using aqueous solutions of incompatible solutes, where immiscibility is dictated by the concentrations of the solutes. For instance, in aqueous two‐phase systems (ATPSs), the interfacial tension between the two different aqueous solutions is so small that it stabilizes the phase‐separated domains, but not their shape, thus falling short of designing tunable, robust structures. Here, we introduce a diffusion‐controlled strategy that enables liquid‐in‐liquid compartmentalization absent a thermodynamically defined interface or bulk liquid‐liquid phase separation using a barrier formed in situ at the initial contact boundary of an aqueous dispersion of multifunctional nanoparticles and a solution of multifunctional ligands in pure water or a water/alcohol mixture. The nanoparticles and ligands are entropically driven to disperse uniformly but interact at the initial contact boundary more rapidly than bulk mixing, forming a layer that establishes a barrier akin to a semi‐permeable membrane and allows the formation of tubular compartments. A wealth of opportunities is enabled by the proposed technique, where examples in separations, soft electronic devices, and ultralight porous electromagnetic shielding materials are shown.

cryogels

Shape‐Evolving Structured Liquids

Migration, division, and reconfiguration - functions essential to living systems - are driven by active processes. Developing synthetic mimics is an outstanding challenge. Lipid bilayers that bound natural systems are locally deformed by active species, e.g., microtubules, but the resulting non-equilibrium shapes relax when active species motion ceases, and the shape changes lack immediate control. A fully synthetic system is described, driven by active particles encapsulated by a reconfigurable nanoparticle-surfactant membrane that undergoes shape fluctuations reminiscent of living cells. These shape changes are preserved after particle activity stops. Surfactant concentration tunes the interfacial tension over three orders of magnitude, making on-demand shape evolution possible. Directional migration, division, and reconfiguration across multiple scales are possible, leading to a new class of biomimetic, reconfigurable, and responsive materials, paving the way for autonomous synthetic machines.

Kim, Paul Y

Adsorption of Mixed Micelles of Polysorbate 80 and Oleic Acid to the Air–Water Interface

The solubilization of long chain amphiphiles with limited solubility into mixed micelles composed of highly soluble surfactants plays a crucial role in modulating the stability and functionality of formulations in pharmaceutical and food systems. Subsequently, the mixed micelles adsorb from solution to the air−water surface, defining the transport mechanism of the insoluble amphiphiles to the interface. We use X-ray reflectivity to measure the composition and provide insight into the structure of these mixed monolayers, and, alongside interfacial tension measurements, we provide an understanding of how the bulk composition determines the surface composition and the dynamics of tension reduction. We use a model system consisting of an insoluble fatty acid, oleic acid (OA), and a soluble micelle-forming surfactant, polysorbate 80 (PS80). PS80 forms spherical micelles, and, above the critical micelle concentration (cmc), OA is readily solubilized inside the micelles. We show that the adsorption of PS80/OA mixed micelles to the air−water interface rapidly reduces the tension and lowers the equilibrium tension in proportion to the OA concentration. X-ray reflectivity data, fit using Parratt-slab models, quantitively demonstrates that the monolayers become enriched with OA, and we show how the OA intercalates into the PS80 monolayers.

36 MATERIALS SCIENCE

Toward Lithium Recovery Using Modular (and Membraneless) Phase Separation and Extraction (MPSE) Technology with Ionic Liquid (IL) Solvents: Effect of Coatings

In this work, a single-channel slope-plate Modular and Membrane-less Phase Separation and Extraction (MPSE) device was fabricated using 3D printing. The slope-plate was designed with an insertable glass slide to enable surface modification with coatings. Self-assembled monolayers (SAMs) and perfluoropolyether (Zdol) coatings were applied to tailor surface wettability and enhance phase separation. Using a model biphasic system of water and hexadecane, both coatings significantly improved the separation efficiency compared to the uncoated device by promoting selective wetting. Building on these results, lithium extraction from a simulated saline solution was investigated using 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf₂]) as the ionic liquid (IL) extractant. The IL effectively extracted Li⁺ from the aqueous phase in bulk extraction, demonstrating its potential for lithium recovery. However, the low interfacial tension between the IL and aqueous phases posed challenges for phase separation. The application of SAM and Zdol coatings effectively mitigated this issue. Overall, integrating tailored surface chemistry with the slope-plate MPSE design shows great promise as an efficient and scalable platform for studying liquid–liquid separation and optimizing ionic liquid–based extraction processes for lithium recovery from saline sources.

3D printing

Engineered Water for Improved Oil Recovery from Fractured Reservoirs (Final Scientific/Technical Report)

The goal of this proposal is to field test the novel technology of engineered water (modifying ionic composition and/or adding surfactants or nanoparticles) injection to improve oil recovery from the carbonate matrix in fractured reservoirs. Carbonate reservoirs tend to be oil-wet/mixed-wet due to positively charged carbonate mineral surfaces and negatively charged acidic/asphaltic components in the oil. Many carbonate reservoirs are also highly fractured. Water injection does not work efficiently in fractured oil-wet reservoirs because water does not imbibe into the matrix. The water composition can be engineered with ionic modification, surfactants and nanoparticles which can change the wettability of carbonate rocks towards more water-wet conditions which can imbibe water into the matrix and push the oil into the fractures. The engineered water can also lower interfacial tension and minimize capillary forces so that gravity can push the oil up and out of the matrix. Wettability alteration also increases water relative permeability which can also improve oil recovery in non-fractured carbonate reservoirs. This technology, if successful, can be a game changer for West Texas carbonates.

02 PETROLEUM

A permeable rotating-wheel solvent extractor

Column-type device reported employs circular permeable structures of wire mesh screen for extracting solvents from systems with low density differences and low interfacial tensions. Rotating screen wheels of structure fasten to shaft; stationary screen structures are supported by circular bands connected by radial metal arms.

Kahn, D. R.

Convection phenomena at reduced gravity of importance for materials processing

The basic aspects of convection processes are delineated. It is shown that even in weak gravitational fields buoyancy can induce fluid motions. Furthermore, at reduced gravity other nongravity forces such as surface or interfacial tensions, g-jitter, therma-volume expansions, density differences due to phase changes, and magnetic and electric fields can induce fluid motions. The various types of flow possible with these various driving forces are described and criteria for determining the extent and nature of the resulting flows and heat transfer are presented. The various physical mechanisms that can occur separately and in combination are indicated and the present state of knowledge of each of the phenomena is outlined.

Ostrach, S.

Convection phenomena of importance for materials processing in space

The basic aspects of convection processes are delineated. It is shown that even in weak gravitational fields buoyancy can induce fluid motion. Furthermore, at reduced gravity, other nongravity forces such as surface or interfacial tensions, g jitter, thermal volume expansions, density differences due to phase changes, and magnetic and electric fields can induce fluid motions. The types of flows possible with these various driving forces are described, and criteria for determining the extent and nature of the resulting flows and heat transfer are presented. The different physical mechanisms that can occur separately and in combination are indicated, and the present state of knowledge of each of the phenomena is outlined. Specific research problems are described for many of the types of convection that are necessary to obtain greater understanding of their implications for space processing.

Ostrach, S.

Optical modulators based on electrocapillarity

Electrically addressable variable-power optical elements of small (less than 1-mm) dimensions that can be used as optical modulators are described, and experimental results are presented. The devices use the curved interface between two immiscible liquids as an optical element. The electrocapillarity effect is used to change the interfacial tension and hence the curvature and power of the interface. Both the transmission and reflection systems are described.

Lea, M. C.