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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 199 records · Page 11

The Effect of Slag Heat Treatment on Ingot Quality during Cold Start Electroslag Remelting

Heat treatments of a commercial 40CaF 2 –30CaO–30Al 2 O 3 slag are explored to study their effect on quality of ingots produced using cold start electroslag remelting (ESR). Reducing heat treatment (or roasting) time or temperature for slag degassing can lead to energy savings as well as longer lifetimes for various components. Heat treatments in vacuum with pressure monitoring and air are investigated along with several temperatures, heating rates, and/or holding times. A research scale ESR furnace is used with steel electrodes. Significant differences in ingot quality, such as the occurrence of pores and a rough sidewall near the bottom of the ingot produced using slag heat treated in air at 580 °C, are observed. Further, adjustments in the heat treatment temperature for heat treatment in air eventually lead to an ingot quality comparable to that obtained using slag degassing in a controlled atmosphere at higher temperatures. Using differential thermal analysis, it is found that moisture is primarily removed from the slag at ≈460 °C and 700 °C. A safe slag roasting temperature is concluded to be 750 °C. Improper slag heat treatment leads to hydrogen concentrations from 8 to 15 ppm in about one‐quarter of the ingot volume.

36 MATERIALS SCIENCE↗

Ultrahigh-Temperature Ceramics

Ultrahigh temperature ceramics (UHTCs) are a class of materials that include the diborides of metals such as hafnium and zirconium. The materials are of interest to NASA for their potential utility as sharp leading edges for hypersonic vehicles. Such an application requires that the materials be capable of operating at temperatures, often in excess of 2,000 C. UHTCs are highly refractory and have high thermal conductivity, an advantage for this application. UHTCs are potentially applicable for other high-temperature processing applications, such as crucibles for molten-metal processing and high-temperature electrodes. UHTCs were first studied in the 1960 s by the U.S. Air Force. NASA s Ames Research Center concentrated on developing materials in the HfB2/SiC family for a leading-edge application. The work focused on developing a process to make uniform monolithic (2-phase) materials, and on the testing and design of these materials. Figure 1 shows arc-jet models made from UHTC materials fabricated at Ames. Figure 2 shows a cone being tested in the arc-jet. Other variations of these materials being investigated elsewhere include zirconium based materials and fiber-reinforced composites. Current UHTC work at Ames covers four broad topics: monoliths, coatings, composites, and processing. The goals include improving the fracture toughness, thermal conductivity and oxidation resistance of monolithic UHTCs and developing oxidation-resistant UHTC coatings for thermal-protection-system substrates through novel coating methods. As part of this effort, researchers are exploring compositions and processing changes that have yielded improvements in properties. Computational materials science and nanotechnology are being explored as approaches to reduce materials development time and improve and tailor properties.

Johnson, Sylvia M.↗

Capacitive discharge in flash experiments: A discussion of the charged species

Abstract We report on the discharge of the capacitance formed at the electrodes in flash experiments with yttria stabilized zirconia. The experiments were carried out by disconnecting the current, and, instead, short circuiting the electrodes through a resistor. The time dependent voltage across the resistor was measured; the ratio yielded the discharge current. The current decayed exponentially with time, as expected in an RC circuit, which allowed the measurement of the capacitance. Experiments were carried out in two ways. In one case the specimens were flashed within a glove box filled with Ar (< 1 ppm O 2 ): these yielded electronic conductors. In the other case the specimens were flashed in ambient air: while electronically conducting in‐flash these specimens recover their prior insulating behavior as soon as the current is turned off. The stored charge was two orders of magnitude greater in the Ar experiments. Rather unexpectedly, the sign of the voltage expressed at the electrodes was opposite in experiments carried out in air and in Ar. The capacitance measured in the discharge experiments is attributed to the formation of space charge adjacent to the electrodes. In the case of Ar experiments, the capacitance is very large, approaching 1 F; in this case the space charge is expected to be constituted from ions. In the air experiments the specimen becomes insulating, trapping the electrons as a space charge. Hall effect measurements of the carrier density and X‐ray photoelectron spectroscopy characterization of electronically conducting single crystal specimen of cubic zirconia are reported.

Materials Science↗

Indium Tin-Doped Oxide Interactions with Solvent Radiolysis Products

Transparent conductive oxides (TCOs), such as indium tin-doped oxide (ITO), are ubiquitous as components of electronics and are ideal electrode substrates for catalysis, energy transformation reactions, and energy storage applications. Recently, researchers have recognized their effectiveness as electrode materials for manipulating actinide oxidation states in solution. Despite their popularity as electrode materials, prior studies focused extensively on the direct radiolysis of TCO materials in air and rarely examined these effects within a solution, limiting our fundamental understanding of the interactions between solvent radiolysis products and these substrates in high radiation environments. Here, in this study, we characterize the effects of solvent radiolysis products—arising from the gamma irradiation of water, aqueous nitric acid solutions, and n-dodecane—on the composition, surface speciation, and band structure of ITO thin films on a glass substrate as a function of absorbed dose using UV-visible spectroscopy, scanning electron microscopy, photoelectrochemistry, and X-ray photoelectron spectroscopy. Our work demonstrates that mesoporous thin film electrodes of ITO exposed to gamma radiation in each solvent accumulate defects and exhibit solvent and dose dependent changes to their surface and interfacial properties. These electrodes maintain their electrochemical function and improve their photoelectrochemical performance up to at least 100 kGy of accumulated gamma dose, confirming their utility in solvents exposed to ionizing radiation fields.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Hydroxide Exchange Membrane Carbon Capture (HEMCC) Using Nickel Hydroxide Batteries and Flow-through Membranes

Proposed is an electrochemical nickel hydroxide based hydroxide exchange membrane carbon capture (HEMCC) device for Direct Air Capture (DAC) of CO2. DAC has been identified as one of the key net negative carbon technologies to achieve net zero carbon emissions. Net negative carbon technologies are required to offset continued emissions from dilute CO2 sources such as agriculture and construction. The majority of current DAC technologies at scale (>1 KT∙yr-1) are adsorbent based technologies with significant energy cost. The traditional DAC energy cost is primarily driven by the temperature swing required to regenerate the sorbent and has been shown to be 1.8 MWh·ton-1 at the system level. Electrochemical pH swing devices are a growing research area for carbon capture devices with the goal of lowering the energy cost required for DAC. A pH gradient is built by generating OH- at the cathode and consuming OH- at the anode. An acid-base equilibrium with CO2 allows for the capture of CO2 at the cathode and release at the anode. This extends from other electrochemical CO2 capture devices based on pKa shifts of an electrochemically active organic species allowing for the capture and release of CO2. Electrochemical CO2 capture is considered promising based on potentially low energy costs to capture CO2 in comparison with current temperature swing adsorption technologies. This work explores Ni(OH)2 electrodes to produce the pH gradient for CO2 capture and release. At the cathode NiOOH is reduced to Ni(OH)2 while at the anode Ni(OH)2 is oxidized to NiOOH. The symmetrical electrodes allow for a low voltage requirement; the thermodynamic potential difference of standard electrochemical reactions is zero. Most of the voltage observed is to produce the pH gradient with the remainder driving the polarization of the electrodes. There is a resistance component as well, but this is small in comparison due to the low current densities used in the device, nominally 2 mA·cm-1. Two similar devices are presented, a traditional MEA (membrane electrode assembly) and a flow-through MEA. The traditional MEA separates the two Ni(OH)2 electrodes with an 80μm Piperion® membrane. While the flow-through membrane separates the electrodes with a three piece membrane consisting of two 80μm Piperion® membranes with a porous membrane between them. In the traditional MEA system air is passed over the cathode for capture, while the flow-through MEA the air is passed through the porous membrane isolated from the electrodes. The traditional MEA has been used to establish a baseline performance of the device and has been shown to capture CO2 at an energy cost of 1 MWh·ton-1 at the device level. An understanding has been built around the components of that energy cost including the relationship of flux to current density, effect of a regeneration process, transient battery behavior, and gas losses coinciding with changing the polarization of the batteries. The flow-through MEA looks to address of transient battery behavior and gas losses. It allows for denser, higher capacity electrodes, which can lean on traditional Ni-MH battery technology used in alkaline batteries used today. The higher capacities, limit the transient battery effect on flux in the device. Gas losses are addressed by having a continuous inlet air stream to the device and continuous outlet product.

Buchen, James↗

Effect of Aluminum Oxide on the Performance of Ionic Liquid-Based Aluminum–Air Battery

The aluminum–air (or oxygen) battery has received intense attention in the past because of its excellent benefits such as low cost and high energy density, but due to the challenging issues such as hydrogen evolution and inactive oxide film formation on the Al surface, it could not be fully applied. In this study, 1-Ethyl 3-Methyl Imidazolium Chloride ([EmIm]Cl) and aluminum chloride (AlCl3) are applied to resolve the aforementioned issues. Ex situ component-level and in situ cell-level open circuit voltage (OCV) tests combined with the physics-based model analyses were conducted to investigate the electrochemical reaction behaviors of the Al–air cell. Especially, the effect of aluminum oxide formation on the anode- and cathode-side reactions were analyzed in detail. The oxide film formed at the Al surface strongly was found to significantly impede the electrochemical reaction at the surface, and the film growth was controlled by decreasing the surface tension by aggressive anions. In the cathode side, the aluminum oxide precipitated in the porous cathode electrode was found to decrease the porous reaction area and block reactant access into the reaction sites. The effects of O2 solubility in the electrolyte, initial porosity and thickness of the porous electrode are compared in detailed, and optimal thickness is suggested.

25 ENERGY STORAGE↗

Molten Salt Electrolytes: Computational Analysis of Transport, Electrochemical Properties and Designing New Mixtures

Electric aircraft propulsion has gained a traction over the last decade due to possible high-energy density electrochemistries with reasonable cycle life and identification of non-flammable chemistries that can guarantee much better safety. Commercial Li-ion batteries cannot reach such high capacities because of weight limitations that arise from the widely used intercalation electrodes. Also, use of organic electrolytes make them highly susceptible to fire on exposure to air and humidity. Currently, use of Lithium metal anode along with conversion electrochemistries such as Li-O2 and Li-S are being pursued to achieve such high energy densities. Safer inorganic solid-state electrolytes, recently discovered Water-in-Salt electrolytes, molten salt electrolytes are some of the alternatives being pursued for a safer/non-flammable battery. Of these safer alternatives, molten-salt electrolytes offer some attractive properties: liquid at operating temperatures resulting in better electrode-wetting, stable interface with Li-metal anodes and good ionic conductivity; their only drawback being high operating temperatures. In this talk, we will discuss some of the computational studies, driven via atomistic simulations, of the properties of molten-salt electrolytes including transport mechanism and interface stability. We will also discuss predicting electrochemical properties of these high-temperature electrolytes. Further, we will discuss a thermodynamic approach to predicting new molten-salt eutectics with lower melting points.

Molten Salt Electrolytes↗

Capturing carbon dioxide from air with charged-sorbents

Emissions reduction and greenhouse gas removal from the atmosphere are both necessary to achieve net-zero emissions and limit climate change. There is thus a need for improved sorbents for the capture of carbon dioxide from the atmosphere, a process known as direct air capture. In particular, low-cost materials that can be regenerated at low temperatures would overcome the limitations of current technologies. In this work, we introduce a new class of designer sorbent materials known as ‘charged-sorbents’. These materials are prepared through a battery-like charging process that accumulates ions in the pores of low-cost activated carbons, with the inserted ions then serving as sites for carbon dioxide adsorption. We use our charging process to accumulate reactive hydroxide ions in the pores of a carbon electrode, and find that the resulting sorbent material can rapidly capture carbon dioxide from ambient air by means of (bi)carbonate formation. Unlike traditional bulk carbonates, charged-sorbent regeneration can be achieved at low temperatures (90–100 °C) and the sorbent’s conductive nature permits direct Joule heating regeneration using renewable electricity. Given their highly tailorable pore environments and low cost, we anticipate that charged-sorbents will find numerous potential applications in chemical separations, catalysis and beyond.

54 ENVIRONMENTAL SCIENCES↗

Progress and Prospects of Inorganic Solid-State Electrolyte-Based All-Solid-State Pouch Cells

Here, all-solid-state batteries have piqued global research interest because of their unprecedented safety and high energy density. Significant advances have been made in achieving high room-temperature ionic conductivity and good air stability of solid-state electrolytes (SSEs), mitigating the challenges at the electrode–electrolyte interface, and developing feasible manufacturing processes. Along with the advances in fundamental study, all-solid-state pouch cells using inorganic SSEs have been widely demonstrated, revealing their immense potential for industrialization. This review provides an overview of inorganic all-solid-state pouch cells, focusing on ultrathin SSE membranes, sheet-type thick solid-state electrodes, and bipolar stacking. Moreover, several critical parameters directly influencing the energy density of all-solid-state Li-ion and lithium–sulfur pouch cells are outlined. Finally, perspectives on all-solid-state pouch cells are provided and specific metrics to meet certain energy density targets are specified. This review looks to facilitate the development of inorganic all-solid-state pouch cells with high energy density and excellent safety.

25 ENERGY STORAGE↗

Underwater plasma breakdown characteristics with respect to highly pressurized drilling applications

Deep earth drilling is a key technique to extract oil, gas, and geothermal heat from the earth. Many complex energy focusing methods have been explored as an alternative approach to reach these resources but most of them require high energy. However, by utilizing short time span liquid plasma discharges, energy focusing can be achieved within traditional drilling systems. These discharges induce a rapid expansion process and a resulting shockwave. It is believed that this focused energy will lower the required cutting force to progress through the rock. Lowering the required cutting force will allow for lower drill bit wear, quicker rate of penetration, and an overall cost savings of the project. Plasma breakdown characteristics at drilling relevant pressures, ranging from 1 to 350 atm, were studied. A resistance–capacitance circuit with an air gapped spark switch was utilized to generate pulsed plasma between the pressurized electrodes. It was found that the required breakdown voltage increases as the pressure increases. It was also found that a plasma channel formation and an associated breakdown may or may not occur between the electrodes at different pressures due to variation in required breakdown voltages. Breakdown time-lag in the dielectric medium (tap water, 780 μS cm –1 ) increased as the pressure was increased, which indicated a higher voltage drop at higher pressures (>100 atm). The plasma generated cavitation bubble with an associated shockwave occurred as pressures were increased. However, the bubble radius and the bubble duration decreased as the pressure was increased. The plasma generated shockwave speeds fall within the expected speed of sound in water. Lastly, preliminary rock cracking tests were performed on granite at high pressures (340 and 272 atm) and it was found that plasma is able to create cracks in the rock.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Carbon dioxide concentrator

Passed exhaled air through electrochemical cell containing alkali metal carbonate aqueous solution, and utilizes platinized electrodes causing reaction of oxygen at cathode with water in electrolyte, producing hydroxyl ions which react with carbon dioxide to form carbonate ions.

Williams, C. F.↗

Evaluation of CBS 600 carburized steel as a gear material

Gear endurance tests were conducted with one lot of consumable-electrode vacuum-melted (CVM) AISI 9310 gears and one lot of air-melt CBS 600 gears. The gears were 8 pitch with a pitch diameter of 8.89 centimeters (3.5 in.). Bench-type rolling-element fatigue tests were also conducted with one lot of CVM AISI 9310, three lots of CVM CBS 600, and one of air-melt CBS 600 material. The rolling-element bars were 0.952 centimeter (0.375 in.) in diameter. The CBS 600 material exhibited pitting fatigue lives in both rolling-element specimens and gears at least equivalent to that of CVM AISI 9310. Tooth fracture failure occurred with the CBS 600 gears after overrunning a fatigue spall, but it did not occur with the CVM AISI 9310 gears. Tooth fracture in the CBS 600 was attributed to excessive carbon content in the case, excessive case depth, and a higher than normal core hardness.

Townsend, D. P.↗

Half-cell electrode assessments of a crossover-tolerant direct methanol fuel cell with a platinum group metal-free cathode

In this work, a platinum group metal- free (PGM-free) Fe-N-C oxygen reduction reaction (ORR) catalyst derived from metal organic framework precursors (Fe-MOF) is evaluated at the cathode side of a direct methanol fuel cell (DMFC). A wide range of methanol concentrations were used, and the performance of the DMFC using air was evaluated and compared to a commercial Pt/C cathode. We conducted our tests with a custom, integrated H 2 reference electrode that separately provided the anode and cathode overpotentials. This allowed us to perform a Tafel analysis on both electrodes and understand the dominant polarizations involved at the PGM-free cathode and the PtRu/C anode. Overall, we achieved a high cell performance using a Fe-N-C based catalyst under liquid methanol and air operation with a peak power density of 111 mW/cm 2 , where the cathode presented a markedly larger contribution to the voltage loss versus the anode. Additionally, we used nanoscale X-ray computed tomography (nano-CT) to image the Fe-N-C cathode and investigate the ionomer and pore size distributions allowing us to identify areas of improvement for catalyst layer fabrication.

30 DIRECT ENERGY CONVERSION↗

Super NiCd Open-Circuit Storage and Low Earth Orbit (LEO) Life Test Evaluation

This presentation discusses Air Force tests performed on super NiCd cells to measure their performance under conditions simulating Low Earth Orbit (LEO) conditions. Super NiCd cells offer potential advantages over existing NiCd cell designs including advanced cell design with improved separator material and electrode making processes, but handling and storage requires active charging. These tests conclude that the super NiCd cells support generic Air Force qualifications for conventional LEO missions (up to five years duration) and that handling and storage may not actually require active charging as previously assumed. Topics covered include: Test Plan, Initial Characterization Tests, Open-Circuit Storage Tests, and post storage capacities.

Baer, Jean Marie↗

Protonated phosphonic acid electrodes for high power heavy-duty vehicle fuel cells

We report that state-of-the-art automotive fuel cells that operate at about 80 °C require large radiators and air intakes to avoid overheating. High-temperature fuel cells that operate above 100 °C under anhydrous conditions provide an ideal solution for heat rejection in heavy-duty vehicle applications. Here we report protonated phosphonic acid electrodes that remarkably improve the performance of high-temperature polymer electrolyte membrane fuel cells. The protonated phosphonic acids comprise tetrafluorostyrene-phosphonic acid and perfluorosulfonic acid polymers, where a perfluorosulfonic acid proton is transferred to the phosphonic acid to enhance the anhydrous proton conduction of fuel cell electrodes. By using this material in fuel cell electrodes, we obtained a fuel cell exhibiting a rated power density of 780 mW cm -2 at 160 °C, with minimal degradation during 2,500 h of operation and 700 thermal cycles from 40 to 160 °C under load.

25 ENERGY STORAGE↗

Efficient Ionization Investigation for Flow Control and Energy Extraction

Nonequilibrium ionization of air by nonthermal means is explored for hypersonic vehicle applications. The method selected for evaluation generates a weakly ionized plasma using pulsed nanosecond, high-voltage discharges sustained by a lower dc voltage. These discharges promise to provide a means of energizing and sustaining electrons in the air while maintaining a nearly constant ion/neutral molecule temperature. This paper explores the use of short approx.5 nsec, high-voltage approx.12 to 22 kV, repetitive (40 to 100 kHz) discharges in generating a weakly ionized gas sustained by a 1 kV dc voltage in dry air at pressures from 10 to 80 torr. Demonstrated lifetimes of the sustainer discharge current approx.10 to 25 msec are over three orders of magnitude longer than the 5 nsec pulse that generates the electrons. This life is adequate for many high speed flows, enabling the possibility of exploiting weakly ionized plasma phenomena in flow-fields such as those in hypersonic inlets, combustors, and nozzles. Results to date are obtained in a volume of plasma between electrodes in a bell jar. The buildup and decay of the visible emission from the pulser excited air is photographed on an ICCD camera with nanosecond resolution and the time constants for visible emission decay are observed to be between 10 to 15 nsec decreasing as pressure increases. The application of the sustainer voltage does not change the visible emission decay time constant. Energy consumption as indicated by power output from the power supplies is 194 to 669 W depending on pulse repetition rate.

Schneider, Steven J.↗

Multidimensional modeling of non-equilibrium plasma generated by a radio-frequency corona discharge

Low-temperature plasma (LTP) ignition concepts rely on the production of radical and charged species to speed up the onset of combustion in spark-ignition engines. These features are responsible for the superior performance of LTP igniters under extremely dilute combustion operation that is not achievable by conventional spark igniters. Additionally, LTP discharges extend the lifetime of the igniters, due to the avoidance of spark processes. For these reasons, the engine research community and the automotive industry have shown growing interest in this technology in the recent years. As of today, computational fluid-dynamics (CFD) codes typically used by the multi-dimensional engine modeling community do not have reliable models to describe LTP ignition processes. One key missing piece of information is the physical and chemical properties of the plasma and their effect on combustion ignition. Most non-equilibrium plasma simulations reported in literature are based on simplified, canonical geometries, with simple discharge excitation schemes. Here we conduct multi-dimensional modeling of the non-equilibrium plasma generated by an application-relevant radio-frequency (RF) corona discharge in air. Three test cases are simulated, characterized by different environmental pressure levels and peak electrode voltage values at room temperature. Streamer penetration, electron number density, atomic oxygen production, and bulk gas temperature distribution in the first 10 sinusoidal pulses are presented and discussed. This model can be used as a key tool for an in-depth understanding of RF-corona discharge for automotive applications and provides the basis for future implementations of dedicated LTP ignition models in CFD codes.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Roll-to-Roll Advanced Materials Manufacturing DOE Laboratory Collaboration - Early Stage R&D: Phase 2 and FY21 (Final Report)

R2R processing is used to manufacture a wide range of products for various applications which span many industrial business sectors. The overall R2R methodology has been in use for decades and this continuous technique traditionally involves deposition of material(s) onto substrates or membranes that are on moving webs, carriers or other continuous belt-fed or conveyor-based processes that enable successive steps to build a final product. Established methods that typify R2R processing include tape casting, silk-screen printing, reel-to-reel vacuum deposition/coating, and R2R lithography. Products supported by R2R manufacturing include micro-electronics, electro-chromic window films, PVs, fuel cells for energy conversion, battery electrodes and electrolytes for energy storage, and barrier and membrane materials for decarbonization and air and water filtration. Due to innovation in materials and process equipment, high-quality yet very low-cost multilayer technologies have the potential to be manufactured on a very cost-competitive basis. To move energy-related products from high-cost niche applications to the commercial sector, the means must be available to enable manufacture of these products in a cost-competitive manner. Fortunately, products such as fuel cells, thin- and mid-film PVs, batteries, electrochromic and piezoelectric films, water separation membranes, and other energy saving technologies readily lend themselves to manufacture using R2R approaches. However, more early-stage research is needed to solve the challenge of linking the materials (particles, polymers, solvents, additives) used in ink and slurry formulations and the coating and heated drying processes to the ultimate performance of the final R2R product, especially for a process that uses multiple layers of deposition to achieve the end product.

36 MATERIALS SCIENCE↗