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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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Energy conversion at liquid/liquid interfaces: artificial photosynthetic systems

This chapter focuses on multielectron reactions in organized assemblies of molecules at the liquid/liquid interface. We describe the thermodynamic and kinetic parameters of such reactions, including the structure of the reaction centers, charge movement along the electron transfer pathways, and the role of electric double layers in artificial photosynthesis. Some examples of artificial photosynthesis at the oil/water interface are considered, including water photooxidation to the molecular oxygen, oxygen photoreduction, photosynthesis of amphiphilic compounds and proton evolution by photochemical processes.

Non-NASA Center↗

Bespoke Liquid/Liquid Interfaces (Final Technical Report)

The goal of DE-SC0001815 was to advance the basic science of liquid:liquid interface formation, to develop a deeper understanding of the mechanisms of phase separation and the essential relationships between solution composition, organization and dynamics that underlie the kinetic regime of solvent extraction. This included learning how interfacial organization and dynamics alters the properties of the primary coordination sphere of ions and the free energy of transport of ions complexes across a phase boundary. We relied primarily upon classical molecular dynamics studies to determine the equilibrium ensembles of these complex systems, but also utilized ab-initio MD and cluster-based density functional theory (DFT) calculations when more detailed investigation of the electronic structure was needed. We continued development of graph-theory based analyses to elucidate hierarchical correlations and expanded into geometric topology methods to quantify the collectively organized structures that can organize at a liquid/liquid interface during solute transport. One of the main conclusions was from the observation of two distinct mechanisms for solute transport - those that derive from amplifications of interfacial heterogeneity and surface roughness, and those wherein surface roughness has been dampened and instead collectively organized macrostructures work to bring solutes into the organic phase. It was our aim to create a concrete chemical model of the underlying driving forces behind interfacial primary and secondary structure formation and to map out the energetic features of solute transport so that tailored liquid/liquid can be developed that have characteristic kinetic features associated with mass transport.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

A nonlinear optical perspective on the chemistry at liquid/liquid interfaces

In this review, we discuss some of the subtle (and not-so-subtle) rules that govern chemistry and transport at liquid/liquid (L/L) interfaces. An overview of the importance of L/L interfaces is provided with context about why these interfaces are so challenging to study. Emphasis is placed on the use of vibrational sum-frequency generation (SFG), a surface-specific spectroscopy, to probe these interfaces at and away from equilibrium. Highlights from our laboratory’s work probing these interfaces in the context of chemical separations and soft-matter electronics are discussed. In conclusion, revealing the rules that govern self-assembly, chemical recognition, and transport at these dynamic, highly heterogeneous interfaces can allow formulation of avenues to control chemical and physical transformations, impacting a range of basic and applied fields.

Doughty, Benjamin L. [Oak Ridge National Laborator↗

Redox chemistry at liquid/liquid interfaces

The interface between two immiscible liquids with immobilized photosynthetic pigments can serve as the simplest model of a biological membrane convenient for the investigation of photoprocesses accompanied by spatial separation of charges. As it follows from thermodynamics, if the resolvation energies of substrates and products are very different, the interface between two immiscible liquids may act as a catalyst. Theoretical aspects of charge transfer reactions at oil/water interfaces are discussed. Conditions under which the free energy of activation of the interfacial reaction of electron transfer decreases are established. The activation energy of electron transfer depends on the charges of the reactants and dielectric permittivity of the non-aqueous phase. This can be useful when choosing a pair of immiscible solvents to decrease the activation energy of the reaction in question or to inhibit an undesired process. Experimental interfacial catalytic systems are discussed. Amphiphilic molecules such as chlorophyll or porphyrins were studied as catalysts of electron transfer reactions at the oil/water interface.

Non-NASA Center↗

Electrical double layers at the oil/water interface

This review presents the historical development and current status of the theory of the electrical double layer at a liquid/liquid interface. It gives rigorous thermodynamic definitions of all basic concepts related to liquid interfaces and to the electrical double layer. The difference between the surface of a solid electrode and the interface of two immiscible electrolyte solutions (ITIES) is analyzed in connection to their electrical properties. The most important classical relationships for the electrical double layer are presented and critically discussed. The generalized adsorption isotherm is derived. After a short review of the classical Gouy-Chapman and Verwey-Niessen models, more recent developments of the double layer theory are presented. These include effects of variable dielectric permittivity, nonlocal electrostatics, hydration forces, the modified Poisson-Boltzmann equation and the ion-dipole plasma. The relative merits of different theories are estimated by comparing them with computer simulation of the ITIES and electrical double layer. Special attention is given to the structure of ITIES and its variation due to adsorption of ions and amphiphilic molecules.

Non-NASA Center↗

Natural nanoparticle complexes at water-water interfaces

Aqueous two-phase systems (ATPSs) with multifunctional attributes have significant promise as biomimetic materials, but current approaches do not harness their full potential. Here, we show that ATPSs can be stabilized to form microcapsules by the interfacial assembly of chitin nanofibers (ChNF) and rod-like cellulose nanocrystals (CNC). The high structural stability of the ChNF/CNC complexes integrates permeability and transport across the membrane at the liquid/liquid interface. Driven by density and osmotic stress gradients, the microcapsules show switchable motility, including cyclic meniscus-climbing and subsurface transport. These observations demonstrate a self-regulating system with potential for cargo transfer, cell biomimicry, as well as ATPSs-based microreactors and microrobots.

Bioinspired materials↗

Natural and thermocapillary convection in multiple liquid layers

A numerical and experimental investigation is conducted of the fluid dynamics of immiscible liquid layers, as encountered in the liquid encapsulation of electronic melts. Attention is given to the convective flow in multiple liquid layers that are driven by temperature gradients that are either parallel or perpendicular to the liquid/liquid interfaces. The experimental and theoretical results obtained are noted not to be in agreement for differential side-heating of a three-layer system.

Prakash, A.↗

Thermocapillary convection in two immiscible liquid layers with free surface

Thermocapillary convection is studied in two immiscible liquid layers with one free surface, one liquid/liquid interface, and differential heating applied parallel to the interfaces. An analytical solution is introduced for infinite horizontal layers. The defining parameter for the flow pattern is lambda, the ratio of the temperature coefficient of the interfacial tension to that of the surface tension. Four different flow patterns exist under zero gravity conditions. 'Halt' conditions which halt the fluid motion in the lower encapsulated liquid layer have been found. A numerical experiment is carried out to study effects of vertical end walls on the double layer convection in a 2D cavity. The halt condition obtained from the analytical study is found to be valid in the limit of small Reynolds numbers. The flow in the encapsulated liquid layer can be suppressed substantially.

Doi, Takao↗

A Study of Nucleate Boiling with Forced Convection in Microgravity

Boiling is a rather imprecise term applied to the process of evaporation in which the rate of liquid-vapor phase change is large. In seeking to determine the role and significance of body forces on the process, of which buoyancy or gravity is just one agent, it becomes necessary to define the term more precisely. It is generally characterized by the formation and growth of individual vapor bubbles arising from heat transfer to the liquid, either at a solid/liquid or liquid/liquid interface, or volumetrically. The terms 'bubble' boiling and 'nucleate' boiling are frequently used, in recognition of the interactions of surface tension and other forces in producing discrete bubbles at distinctive locations (although not always). Primary considerations are that evaporation can occur only at existing liquid-vapor interfaces, so that attention must be given to the formation of an interface (the nucleation process), and that the latent heat for this evaporation can come only from the superheated liquid, so that attention must also be given to the temperature distributions in the liquid.

Merte, Herman, Jr.↗

Oversaturating Liquid Interfaces with Nanoparticle-Surfactants

Assemblies of nanoparticles at liquid interfaces hold promise as dynamic “active” systems when there are convenient methods to drive the system out of equilibrium via crowding. To this end, we show that oversaturated assemblies of charged nanoparticles can be realized and held in that state with an external electric field. Upon removal of the field, strong interparticle repulsive forces cause a high in-plane electrostatic pressure that is released in an explosive emulsification. We quantify the packing of the assembly as it is driven into the oversaturated state under an applied electric field. Finally, physiochemical conditions substantially affect the intensity of the induced explosive emulsification, underscoring the crucial role of interparticle electrostatic repulsion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamics and Stability of Capillary Surfaces: Liquid Switches at Small Scales

The dynamics and stability of systems of interfaces is central to a range of technologies related to the Human Exploration and Development of Space (HEDS). Our premise is that dramatic shape changes can be manipulated to advantage with minimal input, if the system is near instability. The primary objective is to develop the science base to allow novel approaches to liquid management in low-gravity based on this premise. HEDS requires efficient, reliable and lightweight technologies. Our poster will highlight our progress toward this goal using the capillary switch as an example. A capillary surface is a liquid/liquid or liquid/gas interface whose shape is determined by surface tension. For typical liquids (e.g., water) against gas on earth, capillary surfaces occur on the millimeterscale and smaller where shape deformation due to gravity is unimportant. In low gravity, they can occur on the centimeter scale. Capillary surfaces can be combined to make a switch a system with multiple stable states. A capillary switch can generate motion or effect force. To be practical, the energy barriers of such a switch must be tunable, its switching time (kinetics) short and its triggering mechanism reliable. We illustrate these features with a capillary switch that consists of two droplets, coupled by common pressure. As long as contact lines remained pinned, motions are inviscid, even at sub-millimeter scales, with consequent promise of low-power consumption at the device level. Predictions of theory are compared to experiment on i) a soap-film prototype at centimeter scale and ii) a liquid droplet switch at millimeter-scale.

Steen, Paul H.↗

Low-g simulation testing of propellant systems using neutral buoyancy

A two liquid, neutral buoyancy technique is being used to simulate propellant behavior in a weightless environment. By equalizing the density of two immiscible liquids within a container (propellant tank), the effect of gravity at the liquid interface is balanced. Therefore the surface-tension forces dominate to control the liquid/liquid system configuration in a fashion analogous to a liquid/gas system in a zero gravity environment.

Balzer, D. L.↗