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At least 37 records · Page 2

Structured electrolytes facilitate Grotthuss-type transport for enhanced proton-coupled electron transfer reactions

Concentrated hydrogen-bonded electrolytes (CoHBEs) are structured, electrochemically stable, less-volatile alternatives to aqueous and dilute nonaqueous electrolytes, however, with high viscosities that limit molecular diffusion. This work provides an understanding of the proton conduction mechanism in CoHBEs based on mixtures of acids and azoles and establishes a link between the structurally dictated transport properties and the proton-coupled electron transfer (PCET) reaction rates that can be leveraged for enhancing electrochemical reactions. Diffusion and relaxation NMR studies suggest a breaking of the viscosity–conductivity tradeoff, where at high azole concentrations (>45 mol%), Grotthuss transport is more likely with lowered proton transfer energy barriers between the azole and the acid according to the machine learning (ML) accelerated ab initio path integral MD (AI-PIMD) simulations. Proton conduction pathways are found to be switchable between the hydrogen bonding networks of the acid and the azole, with imidazole chain forming structures better facilitating Grotthuss hopping. Supported by small-angle neutron scattering studies, the chains are found to have six member molecules on average with maximum of 3 to 4 imidazole/imidazoliums at 50 to 60 mol%. Despite their high viscosities, the measured PCET rates for quinones and phenazines measured in the protic CoHBEs present relatively high electron transfer rate constants (k 0 ~ 10 −4 cm/s), validated by rotating disc electrode and scanning electrochemical microscopy measurements. The results demonstrate that strategic tuning of hydrogen-bond donor–acceptor interactions enables the decoupling of proton transport and viscosity, thereby impacting PCET reactions.

electrokinetics↗

Move That Goo!

On May 5, 1961, Alan B. Shepard became the first American in space (K. Mars); since then, NASA has made leaps and bounds in space exploration and continues to develop new technologies. Through their X-Hab program, NASA has teamed up with the National Space Grant Foundation to fund our student-centered project with one main goal: Move That Goo! Liquid amine absorption is a method by which CO2 is removed from an environment and is intended to be the primary method for CO2 removal for NASA’s sustained human presence on extraterrestrial bodies such as the Moon and Mars. Liquid amines can be highly viscous when absorbing CO2, thus the team needed to produce a design that could move a high viscosity fluid while staying under the power requirement of 1 kW and allowing a few square meters in a closed system. Prompted by NASA and with the support of our faculty mentors, we have been tasked with the research, development, production, and testing of a system able to move a high viscosity liquid amine which requires adequate air exposure to absorb carbon dioxide from a habitat atmosphere in low gravity. The system is split into two main groups, fluids, and materials, with two separate teams of students assigned to their half of the design. The fluids team is responsible for everything in the design that directly touches the fluid. The materials team is responsible for the test stand to which the fluids team’s design is attached to as well as additive manufacturing material selection. In the first semester, the team focused on brainstorming ideas, design selection, budget creation, and CAD modeling. Multiple concepts were generated but the team decided on a design to get the high viscosity fluid to move around a rectangular channel using a screw conveyor mechanism. The liquid must be moved by the turning screw from the thermal chamber going around a rectangular trough back to the thermal chamber. The screw and the trough geometry will be important to allow for the high viscosity fluid to flow, utilizing surface tension to maintain contact to the trough as seen in Figure 1 below.

Olivia Angst↗

Isotope effects on the high pressure viscosity of liquid water measured by differential dynamic microscopy

In this paper, differential dynamic microscopy is performed in diamond anvil cells to measure the viscosity of water along the 24 °C isotherm to high-pressure by determination of the tracer diffusion coefficient of monodisperse silica spheres of known diameter and application of the Stokes-Einstein-Sutherland equation. This technique allows liquid samples to be compressed to greater pressure prior to freezing than with other viscometry methods. The highest-pressure measurement was made at 1.67 GPa, considerably deeper into the supercompressed regime than previously reported. The effect of isotopic composition is investigated with samples of normal water, heavy water, and partially deuterated water. When data below 0.25 GPa are excluded a free volume model fits the observed viscosities well yielding a theoretical glass transition density close to that observed in very-high-density amorphous ice. The improved fit above 0.25 GPa coincides with the loss of other anomalous behaviors in liquid water caused by hydrogen bonding and represents a transition to properties closer to those of a simple liquid.

74 ATOMIC AND MOLECULAR PHYSICS↗

A theoretical/computational framework to measure SiO2 and MgO viscosity at high pressure

The convection of the mantle of Earth and super-Earths is important for many terrestrial phenomena, from plate tectonics to outgassing. Rheological properties, such as viscosity, regulate the transport of thermal energy and mass. However, the viscosity of mantle-relevant materials, such as MgO, at relevant pressures (>120 GPa) are not well constrained. The objective of this work was to develop a computational platform to simulate novel experiments aiming to measure the viscosity of MgO at high pressures. Experiments performed by our collaborators at Johns Hopkins University and Lawrence Livermore National Laboratory use the OMEGA EP laser facility to shock a corrugated MgO interface to 170 GPa, with resulting velocity evolution governed by the viscous Richtmyer-Meshkov instability. We used an in-house hydrocode to simulate this process and thus provide a bound on viscosity by comparing our simulations results to these experiments, as well as to examine the physical processes at play. We simulated the experiments with different values of MgO viscosity (from inviscid to 10,000 Pa∙s) while taking into account the unsteady laser pulse, the material's equation of state, and the rate-dependent constitutive relation for MgO, and the materials' equations of state. Our results suggest that MgO at these conditions has a viscosity within an order of magnitude of 5000 Pa∙s.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Novel Aprotic Heterocyclic Anion-based Ionic Liquids for Carbon Dioxide Capture

Ionic liquids (ILs), or organic salts with melting points at or below room temperature are an incredibly versatile class of materials with many possible applications for NASA’s exploration needs. In particular, appropriately designed ILs can have a high affinity for absorbing carbon dioxide, making them excellent candidates for use as liquid sorbents in cabin air revitalization systems. Unfortunately, many of these ILs have high viscosity, which is only exacerbated by carbon dioxide uptake. High viscosity limits the rate of carbon dioxide uptake. A new class of IL sorbent containing aprotic heterocyclic anions (AHA) has been shown to offer excellent carbon dioxide uptake without a corresponding increase in viscosity. However, there is a paucity of sorption data for these AHA ILs at low partial pressures of carbon dioxide. This paper reports on the characterization of sorption behavior for AHA ILs previously reported in the literature at low concentrations of carbon dioxide and the synthesis and characterization of new, water miscible AHA ILs. Characterization of the new ILs includes measurement of density, viscosity, thermal stability, carbon dioxide capacity, carbon dioxide absorption kinetics, and water-IL vapor liquid equilibrium. Overall, these news ILs are promising alternatives to many of the commonly used IL sorbents.

Eric Townsend Fox↗

Self-lubricated mantle convection: Two-dimensional models

We present results from convection models allowing for self-lubrication of downflows. Models impose a line source of chemically light, low viscosity material at the top of a convecting layer of temperature-dependent viscosity material. Low viscosity surface material serves as an analog to hydrated sediment/crust and the high viscosity upper portion of the convecting layer as an analog to mantle lithosphere. Slow near surface motion in the convecting layer entrains low viscosity material into zones of downflow, which has a lubricating effect. Once entrained lubricant is deeper than the cold high viscosity portion of the convecting layer, rapid upper boundary layer overturn occurs and system properties change (e.g., heat flux doubles). This marks transition to a lubricated state. Before and after transition, transport properties are dominantly determined by, respectively, the viscosity of mantle lithosphere and that of interior mantle. Lubricated and nonlubricated states appear as distinct regions in system output space suggesting that exchange between them is akin to a phase transition. That such exchange depends on a near surface lubricant implies that the geodynamics of planets lacking such lubricants may fundamentally differ from that of planets possessing them.

Lenardic, A.↗

Molecular Modes Elucidate the Nuclear Magnetic Resonance Relaxation of Viscous Fluids

The Bloembergen, Purcell, and Pound (BPP) theory of nuclear magnetic resonance (NMR) relaxation in fluids dating back to 1948 continues to be the linchpin in interpreting NMR relaxation data in applications ranging from characterizing fluids in porous media to medical imaging (MRI). The BPP theory is founded on assuming molecules are hard spheres with 1 H– 1 H dipole pairs reorienting randomly; assumptions that are severe in light of modern understanding of liquids. Nevertheless, it is intriguing to this day that the BPP theory was consistent with the original experimental data for glycerol, a hydrogen-bonding molecular fluid for which the hard-sphere-rigid-dipole assumption is inapplicable. To better understand this incongruity, atomistic molecular simulations are used to compute 1 H NMR T 1 relaxation dispersion (i.e., frequency dependence) in two contrasting cases: glycerol, and a (non hydrogen-bonding) viscosity standard. At high viscosities, simulations predict distinct functional forms of T 1 for glycerol compared to the viscosity standard, in agreement with modern measurements, yet both in contrast to BPP theory. The cause of these departures from BPP theory is elucidated, without assuming any relaxation models and without any free parameters, by decomposing the simulated T 1 response into dynamic molecular modes for both intramolecular and intermolecular interactions. The decomposition into dynamic molecular modes provides an alternative framework to understand the physics of NMR relaxation for viscous fluids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Smyer H-Chondrite Impact-Melt Breccia and Evidence for Sulfur Vaporization

Smyer is an H-chondrite impact-melt breccia containing approx.20 vol% 0.5- to 13-mm-thick silicate-rich melt veins surrounding unmelted subrounded chondritic clasts up to 7 cm in maximum dimension. At the interface between some of the melt veins and chondritic clasts, there are troilite-rich regions consisting of unmelted. crushed 0.2- to 140-micron-size angular silicate grains and chondrule fragments surrounded by troilite and transected by thin troilite veins. Troilite fills every available fracture in the silicates. including some as thin as 0.1 microns. Little metallic Fe-Ni is present in these regions: the FeS/Fe modal ratio ranges from -25: 1 to approx.500: 1, far higher than the eutectic weight ratio of 7.5: 1. The texture of these regions indicates that the sulfide formed from a fluid of very low viscosity. The moderately high viscosity (0.2 poise) and large surface tension of liquid FeS, its inability to wet silicate grain surfaces at low oxygen fugacities. and the supereutectic FeS/Fe ratios in the troilite-rich regions indicate that the fluid was a vapor. It seems likely that during the shock event that melted Smyer, many silicates adjacent to the melt veins were crushed. Upon release of shock pressure. some of the troilite evaporated and dissociated. Molecules of S2 were transported and condensed into fractures and around tiny silicate grains: there, they combined with Fe from small adjacent metallic Fe-Ni grains to form troilite. The Ni content at the edges of some of these metal grains increased significantly; Co from these Ni-rich grains diffused into nearby kamacite. Impact-induced S volatilization may have played a major role in depleting the surface of 433 Eros (and other chondritic asteroids) in S.

Rubin, Alan E.↗

Enhanced X-ray diffraction of in vivo-grown μNS crystals by viscous jets at XFELs

μNS is a 70 kDa major nonstructural protein of avian reoviruses, which cause significant economic losses in the poultry industry. They replicate inside viral factories in host cells, and the μNS protein has been suggested to be the minimal viral factor required for factory formation. Thus, determining the structure of μNS is of great importance for understanding its role in viral infection. In the study presented here, a fragment consisting of residues 448–605 of μNS was expressed as an EGFP fusion protein in Sf9 insect cells. EGFP-μNS (448–605) crystallization in Sf9 cells was monitored and verified by several imaging techniques. Cells infected with the EGFP-μNS (448–605) baculovirus formed rod-shaped microcrystals (5–15 µm in length) which were reconstituted in high-viscosity media (LCP and agarose) and investigated by serial femtosecond X-ray diffraction using viscous jets at an X-ray free-electron laser (XFEL). The crystals diffracted to 4.5 Å resolution. A total of 4227 diffraction snapshots were successfully indexed into a hexagonal lattice with unit-cell parameters a = 109.29, b = 110.29, c = 324.97 Å. The final data set was merged and refined to 7.0 Å resolution. Preliminary electron-density maps were obtained. While more diffraction data are required to solve the structure of μNS (448–605) , the current experimental strategy, which couples high-viscosity crystal delivery at an XFEL with in cellulo crystallization, paves the way towards structure determination of the μNS protein.

59 BASIC BIOLOGICAL SCIENCES↗

Extensional flow of dilute polymer solution

Simultaneous effects of temperature and concentration on tensile viscosity are investigated using a semi-empirical scaling law established to relate the concentration, temperature and deformation rate by a reduced deformation rate variable. Results show the onset of high viscosity occurring in the vicinity of the onset of non-Newtonian viscosity observed in a simple shear flow experiment. High viscosity is also compared with steady and dynamic shear data. Finally, the asymptotic solution of Hassager's kinetic theory of a bead-rod model for macromolecular solutions is compared with the data, indicating that tensile viscosity depends strongly on the molecular weight, the higher the molecular weight, the more sensitive the tensile viscosity in terms of the deformation rate.

Peng, S. T. J.↗

Venus pancake dome formation: Morphologic effects of a cooling-induced variable viscosity during emplacement

The distinctive steep-sided 'pancake' domes discovered in the Magellan images of Venus have morphologies that suggest formation by a single continuous emplacement of a high viscosity magma. A resemblance of the venusian domes to much smaller terrestrial rhyolite and dacite volcanic domes has prompted some authors to suggest that the domes on Venus also have high silica compositions and thus, high viscosities. However, viscosity is a function of crystallinity as well as silica content in a magma, and thus increases as a result of magmatic cooling. To investigate the effect of a cooling-induced viscosity increase on dome morphology, we have modeled the domes as radial viscous gravity currents that cool during emplacement. Various aspects of the investigation are discussed.

Sakimoto, S. E. H.↗

The delineation and interpretation of the earth's gravity field

A series of fluid dynamical experiments in variable viscosity fluid have been made and are in progress to study: (1) the onset of small scale convection relative to lithosphere growth rate; (2) the influence of paired fracture zones in modulating the horizontal scale of small scale convection; (3) the influence of the mantle vertical viscosity structure on determing the mode of small scale convection; and (4) the 3-D and temporal evolution of flows beneath a high viscosity lid. These experiments extend and amplify the present experimental work that has produced small scale convection beneath a downward-moving solidification front. Rapid growth of a high viscosity lid stifles the early onset of convection such that convection only begins once the lithosphere is older than a certain minimum age. The interplay of this convection with both the structure of the lithosphere and mantle provide a fertile field of investigation into the origin of geoid, gravity, and topographic anomalies in the central Pacific. These highly correlated fields of intermediate wavelength (approximately 200 to 2000 km), but not the larger wavelengths. It is the ultimate, dynamic origin of this class of anomalies that is sought in this investigation.

Marsh, Bruce D.↗

Mantle viscosity stratification and flow geometry - Implications for surface motions on earth and Venus

For a fixed heat flow, the surface flow velocity of a convecting layer is not strongly sensitive to the variation of viscosity as a function of depth. Thus, the inferred absence of a low viscosity asthenosphere on Venus can not account for the limited surface motions there. The surface velocity is dependent on the convective geometry. Cartesian geometry convection can produce large surface velocities if the high viscosity surface layer is broken in places by weak zones. On the other hand, a high viscosity surface layer may inhibit the development of large surface velocities in axisymmetric convection.

Kiefer, Walter S.↗

Ultra-Low Viscosity and High Magnetic Susceptibility Magnetic Ionic Liquids Featuring Functionalized Diglycolic Acid Ester Rare-Earth and Transition Metal Chelates

Magnetic ionic liquids (MILs) comprise a subcategory of ionic liquids (ILs) and contain a paramagnetic metal center allowing them to be readily manipulated by an external magnetic field. While MILs are popularly employed as solvents in catalysis, separations, and organic synthesis, most low viscosity combinations possess a hydrophilic character that limits their use in aqueous matrices. To date, no study has reported the synthesis and characterization of hydrophobic MILs with viscosities similar to those of hydrophilic MILs and organic solvents while simultaneously exhibiting enhanced magnetic and thermal properties. In this study, diglycolic acid esters are employed as ligands to chelate with paramagnetic metals to produce cations that are paired with metal chelates composed of hexafluoroacetylacetonate ligands to form MILs incorporating multiple metal centers in the cation and anion. Viscosity values below 31.6 cP were obtained for these solvents, the lowest ever reported for hydrophobic MILs. Solubilities in nonpolar solvents such as benzene were observed to be as high as 50% (w/v) MIL-to-solvent ratio while being insoluble in water at concentrations as low as 0.01% (w/v). Effective paramagnetic moment values for these solvents ranged from 5.33 to 15.56 Bohr magnetons (μB), with mixed metal MILs containing multiple lanthanides in the anion generally offering higher magnetic susceptibilities. MILs composed of ligands containing octyl substituents were found to possess thermal stabilities up to 190 °C. The synthetic strategies explored in this study exploit the highly tunable nature of the employed cation and anion pairs to design versatile ultra-low viscosity magnetoactive solvents that possess tremendous potential and applicability in liquid–liquid separation systems, catalysis, and microfluidics where the mechanical movement of the solvent can be easily facilitated using electromagnets.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

First Ever Field Pilot on Alaska's North Slope to Validate the Use of Polymer Floods for Heavy Oil EOR a.k.a Alaska North Slope Field Laboratory (ANSFL)

Alaska’s high viscosity oil resources that range between 20–30+ billion barrels represent about a third of known North Slope original oil in place (OOIP). These resources are primarily concentrated in the Schrader Bluff formation (also called West Sak on the Western North Slope) and Ugnu reservoirs and are categorized as “viscous oils” and “heavy oils” owing to their in-situ viscosities between 5–10,000 cP and up to a million+ cP respectively. The viscous oil deposits are relatively deeper (2,000 – 5,000 ft), whereas the heavy oils are somewhat shallower (2,000 – 4,000 ft). The typically shallow depths and the proximity to the continuous permafrost results in relatively lower formation temperatures and pressures, and consequently higher viscosities. The vertical depth vs. viscosity delineated in Paskvan et al. (2016) differentiates the viscous and heavy oils. As depicted in Paskvan et al. (2016), currently the main focus (referred to as “developing”) is on the viscous oils in the Schrader Bluff formation in the Milne Point Unit (MPU). Notwithstanding this Alaska North Slope (ANS) specific categorization, we use the industry adopted, all-inclusive term “heavy oil” for all high viscosity oils. Resource characterization and additional details can be found in topical publications of Paskvan et al. (2016) and Targac et al. (2005). Despite the vast resource base, the development pace, vis-à-vis the production of heavy oils has been very slow and limited due to multiple factors such as cost, logistics, challenging arctic environment, poor waterflood sweep efficiency due to mobility contrasts, and significantly high minimum miscibility pressures (MMP). Most importantly, typical or standard thermal methods that are commonplace elsewhere (Canada, California) are inapplicable due to the continuous permafrost. As a consequence, cumulative production of heavy and viscous oils is a little over 1% of OOIP slope wide and currently, there is hardly any production from Ugnu. However, on a broader level, these unfavorable factors are outweighed by the fact that (1) these resources, within the established infrastructure, are too large to ignore because of their strategic importance to the Nation and the State of Alaska and (2) Prudhoe Bay type diluent crude oil is still available for heavy oil transport through the Trans Alaska Pipeline System (TAPS). Similarly, from a reservoir standpoint, the following factors also are important offsets: (1) favorable rock characteristics of Schrader Bluff; (2) the promise demonstrated by the initial scoping studies (Seright 2010, 2011) suggesting significant increase of heavy oil recovery using polymer flooding; (3) successful field implementation in Canada, China and elsewhere in the world, and (4) availability of the existing pairs of horizontal injector-producer in Schrader Bluff The foregoing was recognized as the best readily available opportunity for significant investment by the US Department of Energy and the field operator Hilcorp Alaska LLC to conduct the first ever field scale experiment to test the polymer flooding technology to unlock the vast heavy oil resources on ANS. With this primary goal in mind, the research team embarked on a ~4.5 years long project that focused on the field polymer pilot complemented by supporting laboratory and simulation studies. As documented in this final report, over the course of the project, many lessons have been learned and valuable field and supporting laboratory data has been collected, which also is complemented by numerical reservoir simulations. We have been able to establish the injectivity of polymer solution, evidence of significant reduction in the water cut of previously waterflooded pattern, effective propagation of a hydrolyzed polyacrylamide (HPAM), benefits of low salinity water, provide practical guidance on handling of produced fluids containing breakthrough polymer, fit-for-purpose forecast-worthy history matched simulation model, polymer EOR benefit of 700-1000 bopd over waterflood, and most importantly a low polymer utilization factor of ~1.7 lb/stb. In summary this project is deemed as a scientific, technical and economic success, having met all objectives, fulfilled deliverables and within budget, providing impetus to apply polymer EOR throughout the Milne Point Field paving the way for even heavier viscosity oils in the Ugnu area, eventually extending the economic life of TAPS.

02 PETROLEUM↗

The Spreading of Variable-Viscosity Axisymmetric Radial Gravity Currents: Applications to the Emplacement of Venusian 'Pancake' Domes

The Magellan images of Venus have revealed a number of intriguing volcanic features, including the steep-sided or 'pancake' domes. These volcanic domes or flows have morphologies that suggest formation by a single continuous emplacement of lava with a higher viscosity than that of the surrounding basaltic plains. Numerous investigators have suggested that such high viscosity is due to high silica content, leading to the conclusion that the domes are evidence of evolved magmatic products on Venus. However, viscosity depends on crystallinity as well as on silica content: high viscosity could therefore also be due to a cooler (and therefore higher crystal content) lava. Models of dome emplacement which include both cooling and composition factors are thus necessary in order to determine the ranges of crystallinity and silica content which might lead to the observed gross dome morphologies. Accordingly, in this study domes are modelled as radial viscous gravity currents with an assumed cooling-induced viscosity increase to include both effects. Analytical and numerical results indicate that pancake dome formation is feasible with compositions ranging from basaltic to rhyolitic. Therefore, observations of gross dome morphology alone are insufficient for determining composition and the domes do not necessarily represent strong evidence for evolved magmatism on Venus.

Sakimoto, S. E. H.↗

Oil-Free Rotor Support Technologies for an Optimized Helicopter Propulsion System

An optimized rotorcraft propulsion system incorporating a foil air bearing supported Oil-Free engine coupled to a high power density gearbox using high viscosity gear oil is explored. Foil air bearings have adequate load capacity and temperature capability for the highspeed gas generator shaft of a rotorcraft engine. Managing the axial loads of the power turbine shaft (low speed spool) will likely require thrust load support from the gearbox through a suitable coupling or other design. Employing specially formulated, high viscosity gear oil for the transmission can yield significant improvements (approx. 2X) in allowable gear loading. Though a completely new propulsion system design is needed to implement such a system, improved performance is possible.

DellaCorte, Christopher↗

Radar scattering properties of steep-sided domes on Venus

More than 100 quasi-circular steep-sided volcanic domes, with diameters ranging from 6 to 60 km, have been observed on the surface of Venus by the Magellan radar mapper. Assuming that they have the shape of a solidified high-viscosity Newtonian fluid, their radar scattering properties can be studied in detail from Magellan images, since a typical radar swath resolves each dome into several tens of thousands of measurements of radar cross section at incidence angles varying fom 15 deg to 55 deg. Through examination of 20 domes in detail, it appears that many of those situated on lava plains scatter radar in a manner that is indistinguishable from that of the surrounding material, suggesting that either (1) they were formed of a relatively high-density high-viscosity material, e.g., andesite, rather than a lower-density one, e.g., rhyolite or dacite; or (2) that their surfaces share a common origin with those of their surroundings, e.g., through in situ weathering or aeolian deposition.

Ford, Peter G.↗