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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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At least 919 records · Page 51
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

A Reductively Stable Electrolyte Realizes Deep Cycling Behavior in Anode‐free Sodium Batteries

For anode‐free sodium batteries to achieve practical consideration, highly reversible chemistries require exceptional ≥99.95% coulombic efficiencies that maintain over prolonged cycling periods. To do so, consumption of this severely limited sodium inventory must be restricted while metal nucleation processes that comprise the in situ formed metal anode are improved. Herein, we describe a fluorine‐free carborane electrolyte that satisfies these criteria by emphasizing reductive stability and weakly coordinating anion behavior as design principles. We find this approach promotes the development of a thin, robust SEI chemistry rich in both organic speciation and boron. The electrolyte described herein exhibits ideal metal nucleation behavior on one‐micron thin carbonaceous current collector surfaces and achieves a metal deposition/stripping efficiency near parity for 400 cycles. This novel anode chemistry is introduced to anode‐free full cell configurations where 87% of the initial discharge capacity is retained after 1000 cycles at 2.0 C. In conclusion, post‐test characterization of deep‐cycled anode‐free cells reveals suppressed capacity fade in these systems is attributed to the chemical stability of the carborane anion.

anode-free↗
DOE OSTI2023

Re-Examination of the N 2 O + O Reaction

The reaction of N 2 O with O is a key step in consumption of nitrous oxide in thermal processes. It has two product channels, NO + NO (R2) and N 2 + O 2 (R3). The rate constant for R2 has been measured both in the forward and the reverse direction at elevated temperature and is well established. However, the rate constant for the N 2 + O 2 channel (R3) has been difficult to quantify and has significant error limits. Here, the direct reaction on the triplet surface has a barrier of around 40 kcal mol –1 , and it is too slow for the N 2 + O 2 channel to have any practical significance. Recently, Pham and Lin (2022) suggested an alternative low activation energy reaction path that involves intersystem crossing and reaction on the singlet surface. In the present work, we re-examined a wide range of experiments relevant for the N 2 O + O reaction through kinetic modeling, paying attention to the impact of artifacts such as impurities and surface reactions. Experimental results from shock tubes and batch reactors on the final NO yield in N 2 O decomposition, covering temperatures of 973–2200 K and pressures of 0.013–11.5 atm, support k 3 ~ 0, consistent with the high activation energy for reaction on the triplet surface and a low probability of ISC.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Atomic-Scale Investigation of Oxidation at the Black Phosphorus Surface

Black phosphorus (BP) exhibits extraordinary electronic properties that are desirable for a wide variety of electronic and optoelectronic applications. However, applications of BP are hindered by its rapid degradation in ambient conditions. Despite significant advances that have been made in understanding the degradation mechanism, no consensus has yet been reached on how BP oxidation occurs at the atomic scale as experimental studies have been mostly restricted to averaged effects of degradation over a micron- to millimeter-sized region. Here, BP oxidation is investigated using scanning tunneling microscopy/spectroscopy (STM/S). Introducing O 2 gas to the BP surface in ultrahigh vacuum at a pressure of 10 –5 mbar for 1 min creates two new types of defects on the surface. We identify these defects as dangling atomic oxygen and phosphorus multivacancies using density functional theory simulations. In addition to the structural changes to the surface, the electronic structure is also drastically altered by the introduction of oxygen. The 300 meV band gap of BP is lifted due to dosing. This change in the electronic structure is reversible through STM tip manipulation. As a result, these are the first experimental results showing the atomic-scale oxidation of BP, an important step toward understanding the degradation process

2D materials↗
NASA NTRS1983

Self-Cleaning Tubular-Membrane Module

Tubular membranes made self-cleaning with aid of flow reversing valve. Sponge balls scrub membrane surfaces as they travel inside membrane tubes. A four-way flow-reversal valve automatically reverses flow in tubes at preset intervals so sponge balls reciprocate along tubes. Baskets at ends of tubes prevent sponges from escaping. Automatic cleaning feature added to existing membrane processing equipment with minimal modifications.

Sarbolouki, M. N.↗
NASA NTRS1983

Small Gas Turbine Combustor Primary Zone Study

A development process is described which consists of design, fabrication, and preliminary test evaluations of three approaches to internal aerodynamic primary zone flow patterns: (1) conventional double vortex swirl stabilization; (2) reverse flow swirl stabilization; and (3) large single vortex flow system. Each concept incorporates special design features aimed at extending the performance capability of the small engine combustor. Since inherent geometry of these combustors result in small combustion zone height and high surface area to volume ratio, design features focus on internal aerodynamics, fuel placement, and advanced cooling. The combustors are evaluated on a full scale annular combustor rig. A correlation of the primary zone performance with the overall performance is accomplished using three intrusion type gas sampling probes located at the exit of the primary zone section. Empirical and numerical methods are used for designing and predicting the performance of the three combustor concepts and their subsequent modifications. The calibration of analytical procedures with actual test results permits an updating of the analytical design techniques applicable to small reverse flow annular combustors.

Sullivan, R. E.↗
NASA NTRS1982

The dynamics of the Venus ionosphere. II - The effects of the time scale of the solar wind dynamic pressure variations

The effects on the upper dayside Venus ionosphere of a slow increase in solar wind dynamic pressure are simulated numerically with a one-dimensional (spherically symmetric) Lagrangian hydrodynamical code. The simulation is started with an extended ionosphere in pressure equilibrium with the solar wind at the ionopause. The pressure at the ionopause is gradually increased to five times the initial pressure with rise times of 5, 15, and 30 min. It is found that, for rise times greater than about 10 min, the compression of the ionopause is nearly adiabatic, with the ionopause moving downward at velocities of approximately 1-2 km/sec until it reaches a maximally compressed state, at which time the motion reverses. For short rise times the compression produces a shock wave similar to that occurring in the case of a sudden increase in pressure. The global implications of these processes are discussed within the context of Pioneer Venus observations and future theoretical work on this problem is outlined.

Stein, R. F.↗
NASA NTRS1988

The keyhole region in VPPA welds

The morphology and properties of the Variable Polarity Plasma Arc (VPPA) weld composite zone are intimately related to the physical processes associated with the keyhole. The effects of microsegregation and transient weld stress on macrosegregation in the weld tool are examined. In addition the electrical character of straight and reverse polarity portions of the arc cycle were characterized. The results of the former study indicate that alloy 2219 is weldable because large liquid volumes are available during latter stages of weld solidification. Strains in the pool region, acting in conjunction with weld microsegregation can produce macrosegregation great enough to produce radiographic contrast effects in welds. Mechanisms of surface copper enrichment were identified. The latter study has demonstrated that increased heat is delivered to workpieces if the reverse polarity proportion of the weld cycle is increased. Current in the straight polarity portion of the welding cycle increased as the reverse cycle proportion increased. Voltage during reverse polarity segments is large.

Walsh, Daniel W.↗
NASA NTRS2003

Reversing Flows and Heat Spike: Caused by Solar g-Modes?

The Quasi Biennial Oscillation in the Earth s upper atmosphere has an analog deep inside the Sun. As on Earth, the flow is east or west, it is at low latitude, and it reverses direction in a roughly periodic manner. The period in the solar case is 1.3 years. It was detected using solar oscillations similar to the way earthquakes are used to study the Earth's interior. But its cause was not known. We showed that global oscillations (g-modes) can supply enough angular momentum to drive zonal flows with the observed reversal period. This required a calculation of wave dissipation rates inside each flow and in the turbulent layer that separates any two flows of opposite sign. Heat that this process leaves behind causes a thermal spike inside the Sun at the same depth. This may explain an anomaly in observed sound speed that has had no sure explanation.

Mayr, Hans G.↗
NASA NTRS2010

Suppressing Loss of Ions in an Atomic Clock

An improvement has been made in the design of a compact, highly stable mercury- ion clock to suppress a loss of ions as they are transferred between the quadrupole and higher multipole ion traps. Such clocks are being developed for use aboard spacecraft for navigation and planetary radio science. The modification is also applicable to ion clocks operating on Earth: indeed, the success of the modification has been demonstrated in construction and operation of a terrestrial breadboard prototype of the compact, highly stable mercury-ion clock. Selected aspects of the breadboard prototype at different stages of development were described in previous NASA Tech Briefs articles. The following background information is reviewed from previous articles: In this clock as in some prior ion clocks, mercury ions are shuttled between two ion traps, one a 16- pole linear radio-frequency trap, while the other is a quadrupole radio-frequency trap. In the quadrupole trap, ions are tightly confined and optical state selection from a 202Hg lamp is carried out. In the 16-pole trap, the ions are more loosely confined and atomic transitions are interrogated by use of a microwave beam at approximately 40.507 GHz. The trapping of ions effectively eliminates the frequency pulling that would otherwise be caused by collisions between clock atoms and the wall of a gas cell. The shuttling of the ions between the two traps enables separation of the state-selection process from the clock microwave-resonance process, so that each of these processes can be optimized independently of the other. This is similar to the operation of an atomic beam clock, except that with ions the beam can be halted and reversed as ions are shuttled back and forth between the two traps. When the two traps are driven at the same radio frequency, the strength of confinement can be reduced near the junction between the two traps, depending upon the relative phase of the RF voltage used to operate each of the two traps, and can cause loss of ions during each transit between the traps and thereby cause loss of the 40.507-GHz ion-clock resonance signal. The essence of the modification is to drive the two traps at different frequencies typically between 1.5 and 2 MHz for the quadrupole trap and a frequency a few hundred kHz higher for the 16- pole trap. A frequency difference of a few hundred kHz ensures that the ion motion caused by the trapping electric fields is small relative to the diameter of the traps. Unlike in the case in which both traps are driven at the same frequency, the trapping electric fields near the junction are not zero at all times; instead, the regions of low electric field near the junction open and close at the difference frequency. An additional benefit of making the 16-pole trap operate at higher frequency is that the strength or depth of the multipole trap can be increased independent of the quadrupole ion trap.

Prestage, John↗
DOE OSTI2024

Thermal Activation of Zirconium(IV) Acetylacetonate Catalysts to Enhance Polyurethane Synthesis and Reprocessing

Carbamate formation and exchange catalysts enable efficient polyurethane (PU) manufacturing, as well as emerging recycling and reprocessing methods for PU thermosets. Zirconium β-diketonate complexes, such as Zr acetylacetonate [Zr(acac) 4 ], are effective alternatives to toxic organotin catalysts that have been used for PU reprocessing. Here, we report that Zr(acac) 4 undergoes a thermally activated process in the PU network during reprocessing that transforms it into a more active carbamate exchange catalyst. This process is associated with the irreversible loss of acetylacetonate ligands and is not observed for the more sterically hindered Zr 2,2,6,6-tetramethyl-3,5-heptanedione [Zr(tmhd) 4 ] complex. Crossover experiments between PU thermoplastics indicated enhanced carbamate exchange after the thermal activation of Zr(acac) 4 in the presence of one of the PUs, whereas a sample of Zr(acac) 4 activated in the absence of the PU had no catalytic activity. Thermal gravimetric analysis suggested that this process is associated with the loss of one protonated acac ligand. Stress relaxation analysis of PU thermosets indicated a distinct change in the characteristic relaxation time associated with the thermal activation of Zr(acac) 4 at temperatures above 140 °C; no such change was observed for samples reprocessed using Zr(tmhd) 4 . Density functional theory and molecular experiments suggest that irreversible ligand exchange of acac with alkoxide or carbamate reduces the activation energy for urethane formation and reversion. Furthermore, the Zr(acac) 4 catalyst activated in the presence of a PU’s polyol precursor provided more porous and less dense PU foams compared to those made using the unactivated Zr(acac) 4 catalyst. Furthermore, these findings are important for developing improved PU synthesis and recycling processes. Thermally activating a catalyst during reprocessing may provide more nuanced control of the in-use and reprocessing characteristics of PU thermosets.

Alcohols↗
DOE OSTI2024

Ketjenblack-Supported and Unsupported ZrO 2 –ZrN Nanoparticle Systems for Enabling Efficient Electrochemical Nitrogen Reduction to Ammonia

Artificial N 2 fixation via the electrocatalytic nitrogen (N 2 ) reduction reaction (NRR) has been recently promoted as a rational route toward reducing energy consumption and CO 2 emission as compared with the traditional Haber–Bosch process. Nevertheless, optimizing NRR relies on developing highly efficient electrocatalysts. Herein, we report on the reliable and reproducible synthesis of two promising electrocatalysts in either the presence or absence of Ketjenblack (KB), namely, ZrO 2 –ZrN@KB and ZrO 2 –ZrN systems, synthesized through the nitriding of Zr. Both materials had never previously been considered for NRR, to the best of our knowledge. Nevertheless, both of these electrocatalysts incorporated a combination of tetragonal ZrO 2 , ZrON, and cubic ZrN and showed excellent activity and durability toward NH 3 formation. Moreover, the maximum NH3 production rate of 84.1 μg h –1 mg –1 at -0.7 V vs a reversible hydrogen electrode (RHE) was achieved with the ZrO 2 –ZrN electrocatalyst with an impressive Faradaic efficiency of 21.2% at -0.6 V vs RHE, indicating a high selectivity associated with the NRR. Additionally, the catalysts demonstrated excellent stability during the electrolysis process and recycling tests. Here we postulate that the combination of exposed active sites of ZrN and ZrO 2 likely contributes to the enhanced NRR performance attributed to ZrO 2 –ZrN.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1954

Heat transfer, diffusion, and evaporation

Although it has long been known that the differential equations of the heat-transfer and diffusion processes are identical, application to technical problems has only recently been made. In 1916 it was shown that the speed of oxidation of the carbon in iron ore depends upon the speed with which the oxygen of the combustion air diffuses through the core of gas surrounding the carbon surface. The identity previously referred to was then used to calculate the amount of oxygen diffusing to the carbon surface on the basis of the heat transfer between the gas stream and the carbon surface. Then in 1921, H. Thoma reversed that procedure; he used diffusion experiments to determine heat-transfer coefficients. Recently Lohrisch has extended this work by experiment. A technically very important application of the identity of heat transfer and diffusion is that of the cooling tower, since in this case both processes occur simultaneously.

GASES - DIFFUSION↗
DOE OSTI2024

A multiscale model to understand the interface chemistry, contacts, and dynamics during lithium stripping

A reversible Li-metal electrode, paired with a solid electrolyte, is critical for attaining higher energy density and safer batteries beyond the current lithium-ion cells. A stable stripping process may be even harder to attain as the stripping process will remove Li-atoms from the surface, and naturally reduce surface contact area, if not self-corrected by other mechanisms, such as diffusion and plastic deformation under an applied external stack pressure. Here, we capture these mechanisms occurring at multiple length- and time- scales, i.e., interface interactions, vacancy hopping, and plastic deformation, by integrating density functional theory (DFT) simulations, kinetic Monte Carlo (KMC), and continuum finite element method (FEM). By assuming the self-affine nature of multiscale contacts, we predict the steady-state contact area as a function of stripping current density, interface wettability, and stack pressure. We further estimate the exponential increase of overpotential due to contact area loss to maintain the same stripping current density. We demonstrate that a lithiophilic interface requires less stack pressure to reach the same steady-state contact area fraction than a lithiophobic interface. A “tolerable steady-state” contact area loss for maintaining stable stripping is estimated at 20 %, corresponding to a 10 % increase in overpotential. To constrain contact loss within the tolerance, the required stack pressure is 0.1, 0.5, and 2 times the yield strength of lithium metal for three distinct interfaces, lithiophilic Li/lithium oxide(Li2O), Li/lithium lanthanum zirconium oxide(LLZO), and lithiophoblic Li/lithium fluoride(LiF), respectively. The modeling results agree with experiments on the impact of the stack pressure quantitatively, while the discrepancy in stripping rate sensitivity is attributed to the simplifying interface interaction in our simulations. Overall, this multiscale simulation framework demonstrates the importance of electrochemical-mechanical coupling in understanding the dynamics of the Li/SE interface during stripping.

Feng, Min↗
DOE OSTI2020

Understanding Charge Storage in Hydrated Layered Solids MOPO 4 (M = V, Nb) with Tunable Interlayer Chemistry

Hydrated layered solids are interesting charge storage hosts with potentially high electrochemical activity and interlayer tunability. Although it is often possible to tune their interlayer distance by a pillaring strategy, the poor electrochemical stability of such artificial structures remains a major issue in device operation. Here we investigate the charge storage properties of MOPO 4 (M = V, Nb) hydrates with a nanosheet morphology to understand the influence of the interlayer environment on cycling stability, as well as ion selectivity. While in hydrated VOPO 4 interlayer H 2 O molecules act as compressible springs to enable fast Li-/Na-ion transport kinetics and reasonable structural reversibility, NbOPO 4 layers with bridging PO 4 groups serving as permanent linkers exhibit highly stable cyclability for Li-ions, owing to a zero-volume-change ion transport process. However, the latter suffers from a much larger migration energy barrier for Na-ions. Lastly, our findings not only highlight a structurally intriguing material system, but also provide insights into reviving materials with an originally unstable interlayer chemical environment, and shed light on the design principles for creating electrochemically stable charge storage hosts.

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

Mapping Composition Evolution through Synthesis, Purification, and Depolymerization of Random Heteropolymers

Random heteropolymers (RHPs) consisting of three or more comonomers have been routinely used to synthesize functional materials. While increasing the monomer variety diversifies the side-chain chemistry, this substantially expands the sequence space and leads to ensemble-level sequence heterogeneity. Most studies have relied on monomer composition and simulated sequences to design RHPs, but the questions remain unanswered regarding heterogeneities within each RHP ensemble and how closely these simulated sequences reflect the experimental outcomes. Here, we quantitatively mapped out the evolution of monomer compositions in four-monomer-based RHPs throughout a design-synthesis-purification-depolymerization process. By adopting a Jaacks method, we first determined 12 reactivity ratios directly from quaternary methacrylate RAFT copolymerization experiments to account for the influences of competitive monomer addition and the reversible activation/deactivation equilibria. The reliability of in silico analysis was affirmed by a quantitative agreement (<4% difference) between the simulated RHP compositions and the experimental results. Furthermore, we mapped out the conformation distribution within each ensemble in different solvents as a function of monomer chemistry, composition, and segmental characteristics via high-throughput computation based on self-consistent field theory (SCFT). These comprehensive studies confirmed monomer composition as a viable design parameter to engineer RHP-based functional materials as long as the reactivity ratios are accurately determined and the livingness of RHP synthesis is ensured.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2003

Magnetic Control of Solutal Buoyancy Driven Convection

Volumetric forces resulting from local density variations and gravitational acceleration cause buoyancy induced convective motion in melts and solutions. Solutal buoyancy is a result of concentration differences in an otherwise isothermal fluid. If the fluid also exhibits variations in magnetic susceptibility with concentration then convection control by external magnetic fields can be hypothesized. Magnetic control of thermal buoyancy induced convection in ferrofluids (dispersions of ferromagnetic particles in a carrier fluid) and paramagnetic fluids have been demonstrated. Here we show the nature of magnetic control of solutal buoyancy driven convection of a paramagnetic fluid, an aqueous solution of Manganese Chloride hydrate. We predict the critical magnetic field required for balancing gravitational solutal buoyancy driven convection and validate it through a simple experiment. We demonstrate that gravity driven flow can be completely reversed by a magnetic field but the exact cancellation of the flow is not possible. This is because the phenomenon is unstable. The technique can be applied to crystal growth processes in order to reduce convection and to heat exchanger devices for enhancing convection. The method can also be applied to impose a desired g-level in reduced gravity applications.

Ramachandran, N.↗
NASA NTRS2018

Reversed Tantalum Capacitor Problem: A Failure to Fail, a Case Study

Reverse Ta capacitors are not expected to last for any length of time much less the over 74000 hours that they have been flying on Express (i.e. ExPRESS (Expedite the Processing of Experiments to the Space Station) Logistics Carrier (ELC) on the International Space Station. The report looks at the effects of moisture and temperature have on the capacitors. The removal of moisture has a far greater role in the survival of the capacitors than one would expect. Over 10000 hours of testing will be reviewed.

Shue, Jack↗
NASA NTRS2019

Boundary Condition Controls on the High-Sand-Flux Regions of Mars

Wind has been an enduring geologic agent throughout the history of Mars, but it is often unclear where and why sediment is mobile in the current epoch. We investigated whether eolian bed-form (dune and ripple) transport rates are depressed or enhanced in some areas by local or regional boundary conditions (e.g., topography, sand supply/availability). Bedform heights, migration rates, and sand fluxes all span two to three orders of magnitude across Mars, but we found that areas with the highest sand fluxes are concentrated in three regions: Syrtis Major, Hellespontus Montes, and the north polar erg. All regions are located near prominent transition zones of topography (e.g., basins, polar caps) and thermophysical properties (e.g., albedo variations); these are not known to be critical terrestrial boundary conditions. The two regions adjacent to major impact basins (Hellas and Isidis Planitia) showed radially outward upslope winds driving sand movement, although seasonally reversing wind regimes were also observed. The northern polar dunes yielded the highest known fluxes on the planet, driven by summer katabatic winds modulated by the seasonal CO2 cap retreat—processes not known to affect terrestrial dunes. In contrast, southern dune fields (<45°S) were less mobile, likely as a result of seasonal frost and ground ice suppressing sand availability. Results suggest that, unlike on Earth, large-scale topographic and thermophysical variabilities play a leading role in driving sand fluxes on Mars.

Matthew Chojnacki↗