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Results for “liquid-liquid interface”

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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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
DOE OSTI2017

Solvent effects on microstructures and properties of three-dimensional hierarchical TiO{sub 2} microsphere structures synthesized via solvothermal approach

One-step solvothermal method has been proved to be a simple and efficient route to synthesize three-dimensional (3D) hierarchical TiO{sub 2} microsphere structures, but discrepant properties of the solvent media had been claimed as the major factors determining microstructures and properties of the final products. In this study, several typical solvents, including alkane, aromatic hydrocarbons, halohydrocarbon, ketone, organic acid, mono- and dihydric alcohols, were selected to comprehensively investigate the effect of solvents on the morphology, crystal structure, specific surface area, porous property and light harvesting capability of the final products. According to the experimental results, a good interface separating titanium precursor with aqueous phase in the reaction solution, created by non-polar solvents, or polar solvents which are immiscible with titanium precursor, was the decisive factor for the formation of quasi-3D urchin-like TiO{sub 2} microspheres self-assembled from one-dimensional (1D) nanostructures, and concentrated H{sup +} induced by organic acid medium was also helpful. Meanwhile, without the liquid-liquid interface or extremely low solution pH, anatase TiO{sub 2} sphere structures with big specific surface area comprising of nanoparticles or nanosheets would be formed, and performed well in photodegradation of pollutants in water. - Graphical abstract: A good interface separating titanium precursor with aqueous phase is the determining factor to form 3D ordered TiO{sub 2} microspheres self-assembled by 1D nanostructures via solvothermal reaction. Display Omitted - Highlights: • Solvent property is important for the solvothermally synthesized TiO{sub 2} products. • Interface separating titanium precursor with aqueous phase is a determining factor. • Dielectric constant of solvents is also very important. • Low solution pH is helpful for the formation of rod-like building block structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2011

Magnetic nanofilms of nickel prepared at the liquid-liquid interface

Highlights: {yields} Formation of nickel thinfims at the organic-aqueous interface at room temperature. {yields} Thickness of nanofilm is {approx}20 nm. {yields} Ni nanofilms exhibit superparamagnetic behavior. {yields} Thicker Ni films are obtained at a higher temperature (60 {sup o}C). -- Abstract: Thin films of metallic nickel with a thickness of the order of 20 nm have been prepared at the organic-aqueous interface at room temperature by the reaction of nickel cupferronate [Ni(C{sub 6}H{sub 5}N{sub 2}O{sub 2}){sub 2}] in toluene medium and sodium borohydride (NaBH{sub 4}) in aqueous medium. The films were characterized with transmission electron microscopy, scanning electron microscopy and atomic force microscopy. Thicker Ni films could be prepared by carrying out the reaction at the interface at 60 {sup o}C. The Ni nanofilms exhibit superparamagnetic behavior.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Flexible Electronics toward Wearable Sensing

Wearable sensors play a crucial role in realizing personalized medicine, as they can continuously collect data from the human body to capture meaningful health status changes in time for preventive intervention. However, motion artifacts and mechanical mismatches between conventional rigid electronic materials and soft skin often lead to substantial sensor errors during epidermal measurement. Because of its unique properties such as high flexibility and conformability, flexible electronics enables a natural interaction between electronics and the human body. Here, we summarize our recent studies on the design of flexible electronic devices and systems for physical and chemical monitoring. Material innovation, sensor design, device fabrication, system integration, and human studies employed toward continuous and noninvasive wearable sensing are discussed. A flexible electronic device typically contains several key components, including the substrate, the active layer, and the interface layer. The inorganic-nanomaterials-based active layer (prepared by a physical transfer or solution process) is shown to have good physicochemical properties, electron/hole mobility, and mechanical strength. Flexible electronics based on the printed and transferred active materials has shown great promise for physical sensing. For example, integrating a nanowire transistor array for the active matrix and a conductive pressure-sensitive rubber enables tactile pressure mapping; tactile-pressure-sensitive e-skin and organic light-emitting diodes can be integrated for instantaneous pressure visualization. Such printed sensors have been applied as wearable patches to monitor skin temperature, electrocardiograms, and human activities. In addition, liquid metals could serve as an attractive candidate for flexible electronics because of their excellent conductivity, flexibility, and stretchability. Liquid-metal-enabled electronics (based on liquid-liquid heterojunctions and embedded microchannels) have been utilized to monitor a wide range of physiological parameters (e.g., pulse and temperature). Despite the rapid growth in wearable sensing technologies, there is an urgent need for the development of flexible devices that can capture molecular data from the human body to retrieve more insightful health information. We have developed a wearable and flexible sweat-sensing platform toward real-time multiplexed perspiration analysis. An integrated iontophoresis module on a wearable sweat sensor could enable autonomous and programmed sweat extraction. A microfluidics-based sensing system was demonstrated for sweat sampling, sensing, and sweat rate analysis. Roll-to-roll gravure printing allows for mass production of high-performance flexible chemical sensors at low cost. These wearable and flexible sweat sensors have shown great promise in dehydration monitoring, cystic fibrosis diagnosis, drug monitoring, and noninvasive glucose monitoring. Future work in this field should focus on designing robust wearable sensing systems to accurately collect data from the human body and on large-scale human studies to determine how the measured physical and chemical information relates to the individual's specific health conditions. Further research in these directions, along with the large sets of data collected via these wearable and flexible sensing technologies, will have a significant impact on future personalized healthcare.

47 OTHER INSTRUMENTATION↗
DOE OSTI2021

Incorporation and Assembly of a Light-Emitting Enzymatic Reaction into Model Protein Condensates

Eukaryotic cells partition enzymes and other cellular components into distinct subcellular compartments to generate specialized biochemical niches. A subclass of these compartments form in the absence of lipid membranes, via liquid-liquid phase separation of proteins to form biomolecular condensates or “membraneless organelles” such as nucleoli, stress granules, and P-bodies. Because of their ability to form compartments from simple starting materials, membraneless organelles are an attractive target for engineering new functionalities in both living cells and protocells. In this work, we demonstrate incorporation of novel enzymatic activity in protein coacervates with a light-generating enzyme, NanoLuc, to produce bioluminescence. Using condensates comprised of the disordered RGG domain of C. elegans LAF-1, we show functionalization of condensates with enzymatic activity in vitro and that localization to protein coacervates enhances the assembly and activity of split enzymes. To build condensates that function as light emitting reactors, we designed a NanoLuc enzyme flanked by RGG domains. Furthermore, the resulting condensates concentrated NanoLuc by 10-fold over bulk solution and display significantly increased net reaction rates. We further show that condensate viscosity impacts light emission due to diffusion-limited behavior. By splitting NanoLuc enzyme into its constituent components, we demonstrate that NanoLuc activity can be reconstituted via co-condensation. Further, we demonstrate control of the spatial localization of enzyme within condensates by targettng NanoLuc to the surface of in vitro condensates. Collectively, this work demonstrates that membraneless organelles can be endowed with localized enzymatic activity, and that this activity can be spatially and temporally controlled via enzyme reconstitution and design of protein surfactants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Kinetics and Mechanism of Ce(IV) Phase Transfer by the Neutral Extractants Tributyl Phosphate and N,N -Di(2-ethylhexyl)isobutyramide

Tributyl phosphate and N,N-di(2-ethylhexyl)isobutyramide (DEHiBA) are uranium-selective extractants that could be used to recover low-enriched uranium from commercial used nuclear fuel. The economic viability of liquid-liquid extraction processes for chemical separations depends on both thermodynamic and kinetic considerations. Here we used microfluidic droplet extraction to measure interfacial phase transfer rate constants for the extraction and stripping of Ce(IV), a non-radioactive actinide surrogate. The Damkohler numbers for each system were calculated and the phase transfer processes were determined to be diffusion-limited under all conditions, contrary to prior studies using constant interface stirred cells and single drop methods. A well-extracted 2:1 DEHiBA/Ce(IV) complex in the organic phase was determined from batch distribution studies, suggesting a different extraction mechanism for Ce(IV) compared with poorly extracted Pu(IV). Finally, phase disengagement rates were found to be rapid in both systems, in agreement with other studies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Learning Coarse-Grained Potentials for Binary Fluids

Even though atomistic and CG models have been used to simulate liquid nanodroplets in vapor, very few rigorous studies of the liquid-liquid interface structure are available, and most of them are limited to planar interfaces. In this work, we evaluate several existing force fields (FF)s, including two atomistic and three CG FFs, with respect to modeling the interface structure and thermodynamic properties of the water-hexane interface. Both atomistic FFs are able to quantitatively reproduce the interfacial tension and the coexisting densities of the experimentally-observed planar interface. We use the atomistic FFs to model water droplets in hexane and use these simulations to test the CG FFs. We found that the tested CG FFs cannot reproduce the interfacial tensions of planar and/or curved interfaces. Finally, we propose a new approach for learning coarse-grained (CG) potentials within the CG SDK (Shinoda-DeVane- Klein) FF framework from atomistic simulation data. We demonstrate that the new potential significantly improves the prediction of both the interfacial tension and structure of water-hexane planar and curved interfaces.

Gao, Peiyuan↗
DOE OSTI2017

Molecular Dynamics Study of the Bulk and Interface Properties of Frother and Oil with Saltwater and Air

For water treatment purposes, the separation processes involving surfactants and crude oil at seawater-air interfaces are of importance for chemical and energy industries. Little progress has been made in understanding the nanoscale phenomena of surfactants on oily saltwater-air interfaces. This work focuses on using molecular dynamics with a united-atom force field to simulate the interface of linear alkane oil, saltwater, and air with three surfactant frothers: methyl isobutyl carbinol (MIBC), terpineol, and ethyl glycol butyl ether (EGBE). For each frother, although the calculated diffusivities and viscosities are lower than the expected experimental values, our results showed that diffusivity trends between each frother agree with experiments but was not suitable for viscosity. Binary combinations of liquid (frother or saltwater)-air and liquid-liquid interfaces are equilibrated to study the density profiles and interfacial tensions. The calculated surface tensions of the frothers-air interfaces are like that of oil-air, but lower than that of saltwater-air. Only MIBC-air and terpineol-air interfaces agreed with our experimental measurements. For frother-saltwater interfaces, the calculated results showed that terpineol has interfacial tensions higher than those of the MIBC-saltwater. Here, the simulated results indicated that the frother-oil systems underwent mixing such that the density profiles depicted large interfacial thicknesses.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Chemical Potential Driven Reorganization of Anions between Stern and Diffuse Layers at the Air/Water Interface

We report ion adsorption and transfer at charged interfaces play key roles in various industrial and environmental processes. Molecular scale details of ion-ion, ion-water, and ion-surface interactions are still debated. Complex ions, such as SCN - and SeCN - , are particularly interesting due to their unexpected adsorption trends. Here, we combine vibrational sum frequency generation (VSFG) spectroscopy and surface-sensitive synchrotron X-ray studies to provide a detailed description of SeCN - adsorption at a floating charged monolayer. Polarimetry studies show that the average orientation of SeCN - anions with respect to the surface normal decreases from 45° to 22° with the increasing KSeCN concentration. Interfacial SeCN - coverage saturates at very low bulk concentrations, but their orientational organization, distribution between Stern and diffuse layers, and effects on the hydrogen-bonding network of the interfacial water continue to change with increasing bulk KSeCN concentration. These results show that the increasing chemical potential may lead to further reorganization of the adsorbed ions, even though the total interfacial ion population does not change. The reorganization of the interfacial ions and the water may be very important in chemical separations of heavy metals, where metal-anion complexes drive the selective ion transfer at aqueous interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Thiocyanate Ions Form Antiparallel Populations at the Concentrated Electrolyte/Charged Surfactant Interface

Anions play significant roles in the separation of lanthanides and actinides. The molecular-scale details of how these anions behave at aqueous interfaces are not well understood, especially at high ionic strengths. Here, we describe the interfacial structure of thiocyanate anions at a soft charged interface up to 5 M bulk concentration with combined classical and phase-sensitive and molecular dynamics (MD) simulations. At low concentrations thiocyanate ions are mostly oriented with their sulfur end pointing toward the charged surfactants. In this work, the VSFG signal reaches a plateau at around 100 mM bulk concentration, followed by significant changes above 1 M. At high concentrations a new thiocyanate population emerges with their sulfur end pointing toward the bulk liquid. The –CN stretch frequency is different for up and down oriented SCN – ions, indicating different coordination environments. These results provide key molecular-level insights for the interfacial behavior of complex anions in highly concentrated solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Spontaneous and Ion-Specific Formation of Inverted Bilayers at Air/Aqueous Interface

Developing better separation technologies for rare earth metals, an important aspect of a sustainable materials economy, is challenging due to their chemical similarities. Identifying molecular scale interactions that amplify the subtle differences between the rare earths can be useful in developing new separation technologies. Here, we describe ion-dependent monolayer to inverted bilayer transformation of extractant molecules at the air/aqueous interface. The inverted bilayers form with Lu 3+ ions but not with Nd 3+ . By introducing Lu 3+ ions to preformed monolayers, we extract kinetic parameters corresponding to the monolayer to inverted bilayer conversion. Further, temperature-dependent studies show Arrhenius behavior with an energy barrier of 40 kcal/mol. The kinetics of monolayer to inverted bilayer conversion is also affected by the character of the background anion, although anions are expected to be repelled from the interface. Our results show the outsized importance of ion-specific effects on interfacial structure and kinetics, pointing to their role in chemical separation methods.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Isotropic-to-Nematic Transition in Salt-Free Polyelectrolyte Coacervates from Coarse-Grained Simulations

Recent interest in complex coacervation between oppositely charged polyelectrolytes (PEs) has been fueled by its relevance to biology in the context of membraneless organelle formation within living cells. For PEs with limited flexibility (such as double-stranded DNA), theoretical treatments and recent experiments have reported the emergence of liquid crystalline order (LCO) within the resulting coacervate phases. In this work, we study the underlying physics of this phenomenon using coarse-grained molecular dynamics simulations of symmetric semiflexible-semiflexible and asymmetric semiflexible-flexible coacervates. By comparing coacervates with the corresponding semidilute solutions of neutral polymers, we demonstrate that the presence of Coulomb interactions in coacervates facilitates orientational ordering, in agreement with theoretical predictions. Quantitative comparisons between our simulations and theory indicate that, for asymmetric nematic coacervates, the strong orientational ordering of stiff polyanions induces a weak ordering of the flexible polycations-an effect that was not anticipated by available theoretical studies. Simulations reveal that, for nematic coacervates, the preferred orientation of the PE chains at the liquid-liquid coacervate-supernatant interface is parallel, and the alignment of semiflexible PEs is homogeneous. The results presented here provide new molecular-level insights into the intracoacervate LCO and will help motivate further experimental and theoretical activities in this area.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Reconfigurable Liquids Stabilized by DNA Surfactants

Polyelectrolyte microcapsules can be produced either by the layer-by-layer assembly technique or the formation of polyelectrolyte complexes at the liquid-liquid interface. In this work, we describe the design and construction of DNA microcapsules using the cooperative assembly of DNA and amine-functionalized polyhedral oligomeric silsesquioxane (POSS-NH 2 ) at the oil-water interface. "Janus-like" DNA surfactants (DNASs) assemble in situ at the interface, forming an elastic film. By controlling the jamming and unjamming behavior of DNASs, the interfacial assemblies can assume three different physical states: solid-like, elastomer-like, and liquid-like, similar to that seen with thermoplastics upon heating, that change from a glassy to a rubbery state, and then to a viscous liquid. By the interfacial jamming of DNASs, the liquid structures can be locked-in and reconfigured, showing promising potentials for drug delivery, biphasic reactors, and programmable liquid constructs.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Origins of Clustering of Metalate–Extractant Complexes in Liquid–Liquid Extraction

Effective and energy-efficient separation of precious and rare metals is very important for a variety of advanced technologies. Liquid-liquid extraction (LLE) is a relatively less energy intensive separation technique, widely used in separation of lanthanides, actinides, and platinum group metals (PGMs). In LLE, the distribution of an ion between an aqueous phase and an organic phase is determined by enthalpic (coordination interactions) and entropic (fluid reorganization) contributions. The molecular scale details of these contributions are not well understood. Preferential extraction of an ion from the aqueous phase is usually correlated with the resulting fluid organization in the organic phase, as the longer-range organization increases with metal loading. However, it is difficult to determine the extent to which organic phase fluid organization causes, or is caused by, metal loading. In this study, we demonstrate that two systems with the same metal loading may impart very different organic phase organizations and investigate the underlying molecular scale mechanism. Small-angle X-ray scattering shows that the structure of a quaternary ammonium extractant solution in toluene is affected differently by the extraction of two metalates (octahedral PtCl 6 2- and square-planar PtCl 6 2- ), although both are completely transferred into the organic phase. The aggregates formed by the metalate-extractant complexes (approximated as reverse micelles) exhibit a more long-range order (clustering) with PtCl 6 2- compared to that with PtCl 6 2- . Vibrational sum frequency generation spectroscopy and complementary atomistic molecular dynamics simulations on model Langmuir monolayers indicate that the two metalates affect the interfacial hydration structures differently. Furthermore, the interfacial hydration is correlated with water extraction into the organic phase. Overall, these results support a strong relationship between the organic phase organizational structure and the different local hydration present within the aggregates of metalate-extractant complexes, which is independent of metalate concentration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Interfacial Assembly and Jamming of Soft Nanoparticle Surfactants into Colloidosomes and Structured Liquids

Nanoparticle surfactant (NPS) offers a powerful strategy to generate all-liquid constructs that integrate the inherent properties of the NPs into 3D architectures. In this report using the co-assembly of fluorescent polymeric nanoparticles and amine-functionalized polyhedral oligomeric silsesquioxane, the assembly and jamming behavior of a new type of NPS at the oil-water interface is uncovered. Unlike "solid" inorganic nanoparticles, "soft" polymeric nanoparticles can reorganize when jammed, leading to a relaxation and deformation of the interfacial assemblies, for example, the 3D printed sugar-coated haw stick-like liquid tubules. With NPS serving as emulsifiers, stable Pickering emulsions are prepared that can be converted into robust colloidosomes with pH responsiveness, showing numerous potential applications for encapsulation and controlled release.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Dendrite-Free Potassium–Oxygen Battery Based on a Liquid Alloy Anode

The safety issue caused by the dendrite growth is not only a key research problem in lithium-ion batteries but also a critical concern in alkali metal (i.e., Li, Na, and K) oxygen batteries where a solid metal is usually used as the anode. Herein, we demonstrate the first dendrite-free K-O-2 battery at ambient temperature based on a liquid Na K alloy anode. The unique liquid liquid connection between the liquid alloy and the electrolyte in our alloy anode-based battery provides a homogeneous and robust anode electrolyte interface. Meanwhile, we manage to show that the Na K alloy is only compatible in K-O-2 batteries but not in Na-O-2 batteries, which is mainly attributed to the stronger reducibility of potassium and relatively more favorable thermodynamic formation of KO, over NaO2 during the discharge process. It is observed that our K-O-2 battery based on a liquid alloy anode shows a long cycle life (over 620 h) and a low discharge charge overpotential (about 0.05 V at initial cycles). Moreover, the mechanism investigation into the K-O-2 cell degradation shows that the 02 crossover effect and the ether electrolyte instability are the critical problems for K-O-2 batteries. In a word, this study provides a new route to solve the problems caused by the dendrite growth in alkali metal oxygen batteries.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Small- and Wide-Angle X-ray Scattering Studies of Liquid–Liquid Phase Separation in Silicate Melts

Incongruent liquid-liquid phase separation is a common phenomenon in molten oxides, but there are few structural studies due to the high temperatures involved ca. >1600oC. In this work, we present a high-energy x-ray combined small/wide angle scattering (SAXS/WAXS) method that can directly probe non-equilibrium phase diagrams. The Porod exponent in the SAXS signal is extracted, which measures the roughness of the interface formed between different phases. Problematic volatilization of silica in Al 2 O 3 -, CaO-, and MgO-bearing silica-rich liquids were minimized using levitation, laser heating and rapid time-resolved measurements (lasting tens of seconds), to probe the kinetics of the phase separation process. The WAXS measurement simultaneously probes the local atomic structure of the liquid state and shows that the primary structural changes are associated with the SiO 2 network. Cation coordination numbers extracted from pair distribution functions support the model that the origin of phase separation in binary silicate systems is due to Coulombic repulsions between poorly screened cations. For CaO-SiO 2 , the liquid-liquid phase separation is found to correlate with a pause in the temperature dependent atomic disorder associated with SiO4 tetrahedra.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Sculpting Liquids with Two-Dimensional Materials: The Assembly of Ti 3 C 2 T x MXene Sheets at Liquid–Liquid Interfaces

The self-assembly of nanoscale materials at the liquid-liquid interface allows for fabrication of three-dimensionally structured liquids with nearly arbitrary geometries and tailored electronic, optical, and magnetic properties. Two-dimensional (2D) materials are highly anisotropic, with thicknesses on the order of a nanometer and lateral dimensions upward of hundreds of nanometers to micrometers. Controlling the assembly of these materials has direct implications for their properties and performance. We here describe the interfacial assembly and jamming of Ti 3 C 2 T x MXene nanosheets at the oil-water interface. Planar, as well as complex, programmed three-dimensional all-liquid objects are realized. Finally, our approach presents potential for the creation of all-liquid 3D-printed devices for possible applications in all-liquid electrochemical and energy storage devices and electrically active, all-liquid fluidics that exploits the versatile structure, functionality, and reconfigurability of liquids.

2D materials↗