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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 1,351 records · Page 75
All sourcesNASA NTRSDOE OSTI
NASA NTRS2017

Kinetics of Moisture Sorption and Reverse Bias Degradation in Chip Tantalum Capacitors

Exposure of chip MnO2 tantalum capacitors to humid environments might result in increased ESR, leakage currents, and first turn-on failures. However, there is a lack of literature data on the effect of moisture on reverse bias behavior of the parts. The presence of moisture can also result in pop-corning when a high water vapor pressure develops when moisture absorbed in pores of tantalum slugs vaporizes instantly during soldering process resulting in damage to capacitors. A study of kinetics of moisture ingress to and release from active elements of capacitors would allow a better understanding of degradation mechanisms and is important for preventing failures. In this work, a technique for investigation of moisture sorption and desorption in solid chip tantalum capacitors that employs tantalum slugs as a humidity sensor have been developed and kinetics of the process analyzed for different types of capacitors at temperatures from room to 125 ºC. A model that relates diffusion characteristics of polymer cases and size of the slugs to characteristic times of moisture sorption has been developed. A strong effect of moisture on long-term degradation of reverse bias currents in MnO2 cathode capacitors has been demonstrated and physical mechanisms discussed.

Teverovsky, Alexander↗
NASA NTRS2017

Kinetics of Moisture Sorption and Reverse Bias Degradation in Chip Tantalum Capacitors

Exposure of chip MnO2 tantalum capacitors to humid environments might result in increased ESR, leakage currents, and first turn-on failures. However, there is a lack of literature data on the effect of moisture on reverse bias behavior of the parts. The presence of moisture can also result in pop-corning when a high water vapor pressure develops when moisture absorbed in pores of tantalum slugs vaporizes instantly during soldering process resulting in damage to capacitors. A study of kinetics of moisture ingress to and release from active elements of capacitors would allow a better understanding of degradation mechanisms and is important for preventing failures. In this work, a technique for investigation of moisture sorption and desorption in solid chip tantalum capacitors that employs tantalum slugs as a humidity sensor have been developed and kinetics of the process analyzed for different types of capacitors at temperatures from room to 125 C. A model that relates diffusion characteristics of polymer cases and size of the slugs to characteristic times of moisture sorption has been developed. A strong effect of moisture on long-term degradation of reverse bias currents in MnO2 cathode capacitors has been demonstrated and physical mechanisms discussed.

Teverovsky, Alexander↗
NASA NTRS2021

Fluid Servicing Road Area SWMUs 037 and 102 Interim Groundwater Monitoring Report Kennedy Space Center, Florida

This Interim Groundwater Monitoring (IGWM) Report presents the findings of the IGWM activities conducted during the 2021 reporting period at the Fluid Servicing Road Area (FSRA) of Kennedy Space Center (KSC), Florida. The IGWM program was implemented at sites where active remediation was not occurring to monitor and track plume footprints and concentrations. FSRA is located east of the Vehicle Assembly Building and includes Components Cleaning Facility (CCF) also known as Solid Waste Management Unit (SWMU) 030; Converter Compressor Building (CCB) also known as SWMU 089; Area South of K7-516 (516S) also known as SWMU 100; Propellants Support Building Area (PSBA) also known as SWMU 102; and Former Drum Storage Area (FDSA) also known as SWMU 037.

Carol Cady↗
DOE OSTI2021

Investigating Effects of Operational Parameters on the Rate of Electrochemical Cleaning of Chromium Deposits on Strontium-Doped Lanthanum Manganite Cathodes in Solid Oxide Fuel Cells

Chromium poisoning of the cathode remains a significant obstacle to the stable long-term performance of solid oxide fuel cells. This study reports, a quick, in-situ mitigation method, called electrochemical cleaning. By applying a mild anodic bias, the electrochemical deposition reactions of chromium-containing species are reversed. Chromium vapor species are formed, freeing active electrochemical sites in the air electrode. An LSM/YSZ-based cell was exposed to Cr vapors at 800ºC and then subjected to electrochemical cleaning. Cell performance recovery was evidenced by current-voltage and EIS measurements. Chromium removal was verified using SEM and EDS analyses. The cyclability of the electrochemical cleaning was tested by repeated poisoning and cleaning of another cell. Investigation into the effect of cell operating parameters (current density and cell temperature) on the rate of cleaning is discussed.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2023

Electrocatalytic Oxidative Coupling of Methane on NiFe Exsolved Perovskite Anode: Effect of Water

Oxidative coupling of methane (OCM) can be performed electrocatalytically by utilizing solid oxide cells, which provide a readily controlled oxygen supply through dense electrolytes. La 0.7 Sr 0.2 Ni 0.2 Fe 0.8 O 3 (LSNF) perovskite is an effective anode for OCM. Its surface characteristics and electrocatalytic activity can be improved by reduction and the resultant exsolution of bimetallic NiFe nanoparticles from its bulk. X-ray diffraction (XRD) and environmental transmission electron microscopy proved that the evolution of hetero-phases under reducing environment resulted in bimetallic NiFe nanoparticles being formed on the surface. Further, a 36 % improvement in C 2+ hydrocarbon production rate was achieved due to the reduction of LSNF with the exsolved NiFe nanoparticles. Co-feeding of H 2 O enhanced selective conversion of CH 4 resulting in the production rate of C 2+ hydrocarbons being increased by 56 %. Analysis of impedance spectra and in-situ DRIFTS under a CH 4 +H 2 O atmosphere provided an understanding for the enhancement on the electrocatalytic OCM.

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

A Woven Supramolecular Metal‐Organic Framework Comprising a Ruthenium Bis(terpyridine) Complex and Cucurbit[8]uril: Enhanced Catalytic Activity toward Alcohol Oxidation

Abstract The self‐assembly of a diamondoid woven supramolecular metal–organic framework wSMOF‐1 has been achieved from intertwined [Ru(tpy) 2 ] 2+ (tpy=2,2′,6′,2′′‐terpyridine) complex M1 and cucurbit[8]uril (CB[8]) in water, where the intermolecular dimers formed by the appended aromatic arms of M1 are encapsulated in CB[8]. wSMOF‐1 exhibits ordered pore periodicity in both water and the solid state, as confirmed by a combination of 1 H NMR spectroscopy, UV‐vis absorption, isothermal titration calorimetry, dynamic light scattering, small angle X‐ray scattering and selected area electron diffraction experiments. The woven framework has a pore aperture of 2.1 nm, which allows for the free access of both secondary and primary alcohols and tert ‐butyl hydroperoxide (TBHP). Compared with the control molecule [Ru(tpy) 2 ]Cl 2 , the [Ru(tpy) 2 ] 2+ unit of wSMOF‐1 exhibits a remarkably higher heterogeneous catalysis activity for the oxidation of alcohols by TBHP in n ‐hexane. For the oxidation of 1‐phenylethan‐1‐ol, the yield of acetophenone was increased from 10 % to 95 %.

Zhang, Yun‐Chang↗
DOE OSTI2022

Developing solid-surface plasma facing components for pilot plants and reactors with replenishable wall claddings and continuous surface conditioning. Part A: concepts and questions

Abstract It is estimated that pilot plants and reactors may experience rates of net erosion and deposition of solid plasma facing component (PFC) material of 10 3 –10 5 kg yr −1 . Even if the net erosion (wear) problem can be solved, the redeposition of so much material has the potential for major interference with operation, including disruptions due to so-called ‘unidentified flying objects (UFOs)’ and unsafe dust levels. The potential implications appear to be no less serious than for plasma contact with the divertor target: a dust explosion or a major UFO-disruption could be as damaging for an actively-cooled deuterium-tritium (DT) tokamak as target failure. It will therefore be necessary to manage material deposits to prevent their fouling operation. This situation appears to require a fundamental paradigm shift with regard to meeting the challenge of taming the plasma–material interface: it appears that any acceptable solid PFC material will in effect be flow-through , like liquid–metal PFCs, although at far lower mass flow rates. Solid PFC material will have to be treated as a consumable , like brake pads in cars. ITER will use high-Z (tungsten) armor on the divertor targets and low-Z (beryllium) on the main walls. The ARIES-AT reactor design calls for a similar arrangement, but with SiC cladding on the main walls. Non-metallic low-Z refractory materials such as ceramics (graphite, SiC, etc) used as in situ replenishable, relatively thin—of order mm—claddings on a substrate which is resistant to neutron damage could provide a potential solution for the main walls, while reducing the risk of degrading the confined plasma. Separately, wall conditioning has proven essential for achieving high performance. For DT devices, however, standard methods appear to be unworkable, but recently powder droppers injecting low-Z material ∼continuously into discharges have been quite effective and may be usable in DT devices as well. The resulting massive generation of low-Z debris, however, has the same potential to seriously disrupt operation as noted above. Powder droppers provide a unique opportunity to carry out controlled studies on the management of low-Z slag in all current tokamaks, independent of whether their protection tiles use low-Z or high-Z material.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2026

Unveiling the High‐Voltage Reactivity and Gas Evolution With Aluminum‐Based Chloride and Oxychloride Catholytes in Solid‐State Sodium Batteries

All-solid-state sodium batteries (ASSBs) employing halide solid electrolytes (SEs) offer a cost-effective and energy-dense alternative to conventional liquid electrolyte systems. However, their high voltage (>4 V vs. Na/Na + ) performance remains limited by interfacial instability between the cathode active material (CAM) and the SE. We present here the electrochemical and interfacial behaviors of crystalline NaAlCl 4 and amorphous sodium–aluminum–oxychloride (NACO) SEs when combined with NaNi 0.5 Mn 0.5 O 2 cathode. While oxygen incorporation in NACO enhances ionic conductivity by nearly three orders of magnitude relative to NaAlCl 4 , it does not improve high-voltage cycling stability. Cells employing NACO exhibit accelerated capacity fade, increased cell impedance growth, and intrinsic oxygen evolution above 4.5 V vs. Na 3 Sn, as revealed by operando electrochemical mass spectrometry. In contrast, the NaAlCl 4 -based cells show no detectable gas release, underscoring their superior high-voltage stability and safety. Time-of-flight secondary-ion mass spectrometry confirms the formation of Al─O and Ni/Mn─Cl species, respectively, in the SE and CAM, indicating redox-driven anion exchange that contributes to kinetic hindrance of high-voltage phase transitions. The findings establish that while oxygen incorporation enhances ionic transport, it can compromise interfacial stability, suggesting pure chloride SEs may offer a more robust and intrinsically safer pathway for developing high-energy ASSBs.

25 ENERGY STORAGE↗
DOE OSTI2023

Verification Testing of OLI Systems Mixed Solvent Electrolyte Model for the Na-K-Mg-Ca-H-Cl-SO 4 -OH-HCO 3 -CO 3 -CO 2 -H 2 ) System to High Ionic Strength at 25°C

This technical report summarizes model verification results and summary statistics for 41 evaporite mineral solubility cases evaluated by Savannah River National Laboratory using OLI Systems’ aqueous electrolyte thermodynamic modeling software. The 41 verification cases containing a total of 60 solubility curves comprise mineral solubility data from low to high ionic strength at 25°C for the eight-component system Na-K-Mg-Ca-H-Cl-SO 4 -OH-HCO 3 -CO 3 -CO 2 -H 2 O as reported by Harvie et al. (1984). Thermodynamic calculations were executed using OLI Systems’ Stream Analyzer computation module within the OLI Studio software platform (Ver. 11.0, Rev. 11.0.1.9). The Mixed Solvent Electrolyte (MSE) thermodynamic framework was chosen for this investigation because of its superiority in modeling high ionic-strength inorganic salt solutions and actinide redox chemistry and solubility, both of which are relevant to the geological repository conditions at the Waste Isolation Pilot Plant in Carlsbad, New Mexico. Mineral solubility data in various inorganic salt solutions were digitized and extracted from figures generated by Harvie et al. (1984). For each of the 60 solubility curves, a case-specific chemistry model and input file were generated in OLI Studio using OLI Stream Analyzer and the MSE (H 3 O + ion) public databank provided by OLI Systems. Model simulation results were exported to Microsoft Excel to calculate summary statistics and to generate graphs comparing the OLI model predictions to the solubility data. Summary statistics include residuals (model – data) and concordance (accuracy × precision, where precision is indicated by the Pearson correlation coefficient and accuracy accounts for bias and scale differential). Private databanks were not developed, and activity coefficient model regressions were not performed to improve OLI model fits to the data. Of the 41 model verification plots, 83% have a mean of the percent residuals less than or equal to 25%. Similarly, 75% display a concordance greater than or equal to 0.75. Only seven of the 41 verification plots fail to show good agreement between the model and data. Of these seven, three are relevant to the WIPP repository because they involve the Mg-OH-Cl-SO 4 -CO 3 aqueous system. The remaining four address salt solubilities at the pH extremes (strong acid and strong base). It should be noted that in two of the three Mg-OH-Cl-SO 4 -CO 3 system cases, the regressed Harvie et al. (1984) solubility curve also deviated from the data. Lack of agreement between the OLI model-predicted solubility curves and the data is attributable to one or more of the following: specific solid species are not included in the OLI MSE databank; there is significant variation among the different solubility datasets chosen by Harvie et al. (1984); the OLI MSE model’s thermodynamic parameters were determined using different solubility datasets; and the activity coefficient parameters for certain relevant ion-ion and ion-molecule pairs have not been optimized via data regression. Two recommendations for future work are to (1) evaluate solubility data for the Mg-OH-Cl-SO 4 -CO 3 system at high ionic strength and, if necessary, develop a private OLI MSE database that includes missing species and, where necessary, regressed standard state properties and interaction parameters; (2) perform similar verification testing of the OLI model for actinide solubility data.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

Volumetric Additive Manufacturing of Dormant Catalytic Chemistries to Generate Silicone Micro‐ and Millifluidic Devices and Instant Molds

Tomographic volumetric additive manufacturing (T‐VAM) rapidly prints solid objects within minutes, accessing photochemistries that are traditionally challenging for layer‐based additive manufacturing methods. This includes high‐viscosity materials, air‐free chemistries, and solid‐state systems. Catalytic chemistries are appealing as a pathway to engineering advanced materials, including tough thermosets, silicone elastomers, and complex block copolymers. However, photoactivated dormant catalytic chemistries, where the catalyst irreversibly activates upon exposure to light, are incompatible with typical tomographic VAM approaches. To address this limitation, a zero‐dose optimization strategy is devised to preserve dormant catalysts in desired regions by keeping them unexposed to light. VAM printed micro‐ and millifluidic devices and instant molds are successfully produced within minutes in silicones polymerized using photoactivated dormant platinum photohydrosilylation catalysts. The printed channels are programmed to be 500 and 2500 µm for the micro‐ and millifluidic devices, and print fidelity is assessed by X‐ray computed tomography. This work demonstrates the potential of zero‐dose optimization to expand the range of chemistries accessible for VAM, enabling the rapid fabrication of complex devices.

Additive Manufacturing↗
DOE OSTI2026

Entropy-defect synergy for dual luminescence mechanism in spinel: Time-resolved anti-counterfeiting and fingerprint visualization

Multimodal luminescent materials, while promising for anti-counterfeiting, often lack dynamic time-dependent responses and controllable spatial distribution, limiting their encryption capabilities in the spatiotemporal dimension. Here, this work presents a coordinated control strategy based on entropy and defect engineering, and uses a backpropagation (BP) neural network for material screening to successfully prepare spinel Mg 0.8 (Fe 0.04 Co 0.04 Ni 0.04 Cu 0.04 Zn 0.04 )Cr 2 O 4 (MgA 5 CO) phosphors with time-dependent dynamic luminescence behavior. This phosphor simultaneously activated the d-d transition luminescence (∼618 nm) derived from Co 2+ /Cr 3+ and the defect luminescence (∼398 nm) related to zinc vacancies (V Zn ) in a single-phase solid solution. The phosphor exhibits a time-dependent color evolution from pink to purple under fixed-wavelength excitation, due to the different excited-state dynamics and decay lifetimes associated with the d-d transition and defect luminescence. Structural characterization and spectral analysis confirmed the existence of V Zn and its significant role in defect luminescence process. The fluorescent and dynamic luminescent properties of entropy-based spinel oxide enable its use in advanced anti-counterfeiting applications like fingerprint recognition and color-changing dedicated anti-counterfeiting mark, showing promise in high-end and time-dynamic anti-counterfeiting fields. This research not only developed a new type of fluorescent dynamic anti-counterfeiting material, but also provided a new idea for constructing advanced optical functional materials with multiple luminescence mechanisms.

Defect project↗
DOE OSTI2021

Long-life LiNi 0.5 Mn 1.5 O 4 /graphite lithium-ion cells with an artificial graphite-electrolyte interface

The high operating voltage of a spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) cathode leads to electrolyte decomposition and accelerated deterioration of the electrode/electrolyte interface in lithium-ion cells. Aggressive side reactions prevent long-term cycling and hinder its practical application. Advanced characterization shows that the high-voltage operation makes the graphite anode react with the electrolyte, particularly with the lithium salt in the electrolyte, resulting in massive active lithium inventory loss and capacity fade. The side reactions at the graphite are identified as the main culprit for the LNMO/graphite full cell decay. Here, we demonstrate that an artificial solid-electrolyte interface layer consisting of an ultra-thin Al 2 O 3 film, generated via atomic layer deposition (ALD) at the graphite surface, can successfully isolate the graphite from the electrolyte and inhibit the undesired reactions. Consequently, the capacity and cycling stability of the LNMO/graphite cell are drastically improved. After 300 cycles, the capacity retention of LNMO/graphite cell increases from 57.7% to 98.6% with the ALD-coated graphite. Furthermore, our findings provide valuable insights into the LNMO/graphite cell degradation and suggest a simple and robust, yet highly effective, approach for the practical viability of high-voltage lithium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Bridging the gap between simulated and experimental ionic conductivities in lithium superionic conductors

Lithium superionic conductors (LSCs) are of major importance as solid electrolytes for next-generation all-solid-state lithium-ion batteries. While ab initio molecular dynamics have been extensively applied to study these materials, there are often large discrepancies between predicted and experimentally measured ionic conductivities and activation energies due to the high temperatures and short time scales of such simulations. Here, we present a strategy to bridge this gap using moment tensor potentials (MTPs). We show that MTPs trained on energies and forces computed using the van der Waals optB88 functional yield much more accurate lattice parameters, which in turn leads to accurate prediction of ionic conductivities and activation energies for the Li 0·33 La 0·56 TiO 3 , Li 3 YCl 6 and Li 7 P 3 S 11 LSCs. NPT MD simulations using the optB88 MTPs also reveal that all three LSCs undergo a transition between two quasi-linear Arrhenius regimes at relatively low temperatures. This transition can be traced to an increase in the number and diversity of diffusion pathways, in some cases with a change in the dimensionality of diffusion. Furthermore, this work presents not only an approach to develop high accuracy MTPs, but also outlines the diffusion characteristics for LSCs which is otherwise inaccessible through ab initio computation.

25 ENERGY STORAGE↗
DOE OSTI2021

Line tension induced character angle dependence of dislocation mobility in FCC alloys

Here, we explore the character angle dependence of dislocation-solute interactions in a face-centered cubic random Fe0.70Ni0.11Cr0.19 alloy through molecular dynamics (MD) simulations of dislocation mobility. Using the MD mobility data, we determine the phonon and thermally activated solute drag parameters which govern mobility for each dislocation character angle. The resulting parameter set indicates that, surprisingly, the solute energy barrier does not depend on character angle. Instead, only the zero-temperature flow stress—which is dictated by the activation area for thermal activation—is dependent on character angle. By analyzing the line roughness from MD simulations and the geometry of a bowing dislocation line undergoing thermal activation, we conclude that the character angle dependence of the activation area in this alloy is governed by the dislocation line tension, rather than the dislocation-solute interaction itself. Our findings motivate further investigation into the line geometry of dislocations in solid solutions.

36 MATERIALS SCIENCE↗
DOE OSTI2024

In Situ Monitoring the Nucleation and Growth of Nanoscale CaCO 3 at the Oil–Water Interface

Interfaces can actively control the nucleation kinetics, orientations, and polymorphs of calcium carbonate (CaCO 3 ). Prior studies have revealed that CaCO 3 formation can be affected by the interplay between chemical functional moieties on solid–liquid or air–liquid interfaces as well as CaCO 3 ’s precursors and facets. Yet little is known about the roles of a liquid–liquid interface, specifically an oil–liquid interface, in directing CaCO 3 mineralization which are common in natural and engineered systems. Here, in this study, by using in situ X-ray scattering techniques to locate a meniscus formed between water and a representative oil, isooctane, we successfully monitored CaCO 3 formation at the pliable isooctane–water interface and systematically investigated the pivotal roles of the interface in the formation of CaCO 3 (i.e., particle size, its spatial distribution with respect to the interface, and its mineral phase). Different from bulk solution, ∼5 nm CaCO 3 nanoparticles form at the isooctane–water interface. They stably exist for a long time (36 h), which can result from interface-stabilized dehydrated prenucleation clusters of CaCO 3 . There is a clear tendency for enhanced amounts and faster crystallization of CaCO 3 at locations closer to isooctane, which is attributed to a higher pH and an easier dehydration environment created by the interface and oil. Our study provides insights into CaCO 3 nucleation at an oil–water interface, which can deepen our understanding of pliable interfaces interacting with CaCO 3 and benefit mineral scaling control during energy-related subsurface operation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Improving Carbonate-Promoted C–H Carboxylation Using Mesoporous Carbon Supports

C–H carboxylation is an attractive way to utilize CO 2 for chemical production provided that it does not consume resource-intensive reagents. Alkali carbonates dispersed into the pores of mesoporous supports display strongly basic reactivity under CO 2 , allowing them to be used as base promoters for C–H carboxylation of (hetero)arenes in the absence of other reagents or catalysts. Mesoporous oxides are convenient support materials, but only a relatively small fraction of the dispersed carbonate (ca. 10-20%) is converted to carboxylate products when metal oxide supports are used. Here we compare mesoporous oxide and carbon supports and investigate the dependence of carbonate reactivity on pore structure. We show that using mesoporous carbons supports can increase the carbonate conversion by 2–4x when compared to oxide supports. This improved carbonate reactivity is maintained across a variety of mesoporous carbons with different pore structures (ordered vs. disordered) and pore diameters, indicating that the dispersed carbonate is intrinsically more reactive on the surface of a carbon material compared to an oxide surface. Reaction of the carboxylate products with dimethyl carbonate yields isolable methyl esters as the final product and regenerates the dispersed carbonate. We show that mesoporous carbon supports are robust to at least 5 cycles of successive C–H carboxylation and methylation with dimethyl carbonate. Furthermore, understanding how the support structure affects dispersed carbonate reactivity is valuable for advancing C–H carboxylation toward practical application and utilizing these materials in other CO 2 transformations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗