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At least 253 records · Page 14

Iridium metallene oxide for acidic oxygen evolution catalysis

Exploring new materials is essential in the field of material science. Especially, searching for optimal materials with utmost atomic utilization, ideal activities and desirable stability for catalytic applications requires smart design of materials’ structures. Herein, we report iridium metallene oxide: 1 T phase-iridium dioxide (IrO 2 ) by a synthetic strategy combining mechanochemistry and thermal treatment in a strong alkaline medium. This material demonstrates high activity for oxygen evolution reaction with a low overpotential of 197 millivolt in acidic electrolyte at 10 milliamperes per geometric square centimeter (mA cm geo –2 ). Together, it achieves high turnover frequencies of 4.2 s UPD –1 (3.0 s BET –1 ) at 1.50 V vs. reversible hydrogen electrode. Furthermore, 1T-IrO 2 also shows little degradation after 126 hours chronopotentiometry measurement under the high current density of 250 mA cm geo –2 in proton exchange membrane device. Theoretical calculations reveal that the active site of Ir in 1T-IrO 2 provides an optimal free energy uphill in *OH formation, leading to the enhanced performance. The discovery of this 1T-metallene oxide material will provide new opportunities for catalysis and other applications.

36 MATERIALS SCIENCE↗

First-principles study of hydrogen- and oxygen-related complexes in ScN

Scandium nitride (ScN) is an attractive material for electronic applications due to its high n-type conductivity. Native defects and unintentional impurities may limit its electron concentration and reduce its mobility; therefore, it is important to control their formation and incorporation. Hydrogen and oxygen are unintentional impurities that are commonly present during growth and processing. They act as shallow donors in ScN and hence may be regarded as harmless or even favorable to achieving n-type conductivity. Here we show, using state-of-the-art first-principles calculations, that these impurities can be detrimental because they readily form complexes with scandium vacancies (V Sc ). Isolated V Sc have relatively high formation energies and thus have low concentrations and little impact on electronic properties. However, complexes between V Sc and either hydrogen or oxygen form more readily than the pristine vacancy and will act as both compensating and scattering centers. Our results point to the importance of controlling the incorporation of hydrogen and oxygen in ScN (and AlScN alloys) to avoid degradation of the electronic properties.

36 MATERIALS SCIENCE↗

Compatibility of LaFe13−x−yMnxSiyH1.6 and Eutectic Liquid GaInSn Alloy

The heat transfer rate of magnetocaloric regenerators is a topic of extensive research and the cyclability of these regenerators is critical to the operation of systems with a high coefficient of performance (e.g., potentially >22, significantly higher than typical vapor compression cooling technologies). To enable a high operating frequency that will result in a high specific cooling power, the heat transfer fluid should have high thermal conductivity and lower specific heat, i.e., higher thermal diffusivity. Eutectic metal alloys possess these qualities, such as gallium–indium–tin (Galinstan), whose thermal diffusivity has been found to be approximately an order of magnitude higher than water. For this study, the effects of eutectic liquid Galinstan exposure on the phase stability of LaFe13−x−yMnxSiyH1.6 magnetocaloric powders in an active magnetic regenerator device were investigated. The powders were characterized before and after exposure to Galinstan using X-ray diffraction, in which the phases were determined using the Rietveld refinement technique and X-ray fluorescence. It was found that after Galinstan exposure, hydrogen containing phases were present in the powder, suggesting that the hydrogen was lost from the magnetocaloric phase. The magnetocaloric phase degradation indicates that the powder was incompatible with the Galinstan metal in an environment with moisture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Active cleaning techniques for removing contamination from optical surfaces in space

Research in developing an active cleaning technique for removing contaminants from optical surfaces in space is reported. In situ contamination/cleaning experiments were conducted on gold and platimum coated mirrors, which were contaminated by exposure to UV radiation in a 1,3, butadiene environment. Argon and oxygen plasma exposure cleaned the mirrors equally well. Silicone cleaning experiments were also conducted. Exposure of the contaminated mirrors to helium, oxygen, and hydrogen plasmas restored the reflectance at the shorter wavelengths and degraded it at the longer wavelengths.

Shannon, R. L.↗

Materials considerations

Materials problems are examined that may be encountered within a hydrogen energy system. Emphasis is placed on hydrogen embrittlement, corrosion, oxidation, and erosion. Other factors discussed include: degradation of mechanical properties of structural alloys, system reliability, and maintenance costs.

Gray, H. R.↗

Comparison of reusable insulation systems for cryogenically-tanked earth-based space vehicles

Three reusable insulation systems concepts have been developed for use with cryogenic tanks of earth-based space vehicles. Two concepts utilized double-goldized Kapton (DGK) or double-aluminized Mylar (DAM) multilayer insulation (MLI), while the third utilized a hollow-glass-microsphere, load-bearing insulation (LBI). All three insulation systems have recently undergone experimental testing and evaluation under NASA-sponsored programs. Thermal performance measurements were made under space-hold (vacuum) conditions for insulation warm boundary temperatures of approximately 291 K. The resulting effective thermal conductivity was approximately .00008 W/m-K for the MLI systems (liquid hydrogen test results) and .00054 W/m-K for the LBI system (liquid nitrogen test results corrected to liquid hydrogen temperature). The DGK MLI system experienced a maximum thermal degradation of 38 percent, the DAM MLI system 14 percent, and the LBI system 6.7 percent due to repeated thermal cycling representing typical space flight conditions. Repeated exposure of the DAM MLI system to a high humidity environment for periods as long as 8 weeks provided a maximum degradation of only 24 percent.

Sumner, I. E.↗

Environment assisted degradation mechanisms in aluminum-lithium alloys

Section 1 of this report records the progress achieved on NASA-LaRC Grant NAG-1-745 (Environment Assisted Degradation Mechanisms in Al-Li Alloys), and is based on research conducted during the period April 1 to November 30, 1987. A discussion of work proposed for the project's second year is included. Section 2 provides an overview of the need for research on the mechanisms of environmental-mechanical degradation of advanced aerospace alloys based on aluminum and lithium. This research is to provide NASA with the basis necessary to permit metallurgical optimization of alloy performance and engineering design with respect to damage tolerance, long term durability and reliability. Section 3 reports on damage localization mechanisms in aqueous chloride corrosion fatigue of aluminum-lithium alloys. Section 4 reports on progress made on measurements and mechanisms of localized aqueous corrosion in aluminum-lithium alloys. Section 5 provides a detailed technical proposal for research on environmental degradation of Al-Li alloys, and the effect of hydrogen in this.

Gangloff, Richard P.↗

Influence of Two-Phase Thermocapillary Flow on Liquid Retention in Microscopic Pores

An important feature of screened propellant acquisition devices is the retention capability or maximum maintainable pressure difference across the porous barrier separating the liquid and gas. Previous experiments with liquid hydrogen showed a marked reduction in retention when the tank containing the device was pressurized with hydrogen vapor. These tests, however did not indicate any appreciable degradation in retention with helium pressurization or direct heating through the screen. The objective of this article is to determine if the thermocapillary convection arising from phase change in the microscopic pores of such screens could cause these disparities in performance. A numerical model of flow in a single pore suggests that the thermocapillary-induced gradient in liquid pressure along the surface can strongly affect surface morphology. In an evaporative environment, this gradient exerts a stabilizing influence on surface curvature, and preserves the momentum balance between the liquid and gas. With condensation, it causes a force imbalance and a destabilizing suction in the middle of the pore that reduces retention. Results also indicate that introducing an inert gas, such as helium, suppresses this retention loss mechanism by lowering thermocapillary circulation and its associated interfacial pressure gradient.

Schmidt, George R.↗

Nonlinear model predictive control for mode‐switching operation of reversible solid oxide cell systems

Abstract Solid oxide cells (SOCs) are a promising dual‐mode technology for the production of hydrogen through high‐temperature water electrolysis, and the generation of power through a fuel cell reaction that consumes hydrogen. Switching between these two modes as the price of electricity fluctuates requires reversible SOC operation and accurate tracking of hydrogen and power production set points. Moreover, a well‐functioning control system is important to avoid cell degradation during mode‐switching operation. In this article, we apply nonlinear model predictive control (NMPC) to an SOC module and supporting equipment and compare NMPC performance to classical proportional‐integral (PI) control strategies, while switching between the modes of hydrogen and power production. While both control methods provide similar performance across various metrics during mode switching, NMPC demonstrates a significant advantage in reducing cell thermal gradients and curvatures (mixed spatial‐temporal partial derivatives), thereby helping to mitigate long‐term degradation.

08 HYDROGEN↗

Red-Ox Robust SOFC Stacks for Affordable, Reliable Distributed Generation Power Systems

While SOFC systems are expected to operate reliably and with limited degradation in steady state or transient performance, SOFC stacks may ultimately fail due to the loss of structural integrity of one or several of the cells as a result of the weakening of the materials and interfaces due to physico-chemical changes that occur during continuous operation as a result of plastic and creep deformations, modification of the temperature profile, and/or degradation of the electrochemical performance of the cells. Degradation mechanisms originating from the cell components include coarsening of the microstructure over time; decomposition of materials; chemical reaction of electrode materials with electrolyte at the interface; delamination from each other; and for the anode, coking and sulfur poisoning. Of all the reliability issues that may occur for SOFCs, the main limitation for Ni-based cermet anodes (e.g., NiO-YSZ) is the poor stability during reduction-oxidation (red-ox) cycling. This project was aimed at the development of ceramic anode SOFCs based on SFCM (SrFe0.2Co0.4Mo0.4O3), which is a conductive perovskite that is red-ox stable. Additionally, the project involved the development of a red-ox robust stack. Scale up of SFCM-based cells to a large format (10 cm by 10 cm) cell size was achieved as well as a maximum power density of 0.9 W/cm 2 at 600 °C (>0.6 W/cm 2 at 0.6 V). Up to a 10-cell stack was successfully assembled and demonstrated, and cells showed similar performance in reformed, pipeline natural gas as in hydrogen. Finally, a 3-cell stack was red-ox cycled without degradation for 40 cycles at ~600 °C.

03 NATURAL GAS↗

A Nanoscale Ternary Amide‐rGO Composite with Boosted Kinetics for Reversible H 2 Storage

Abstract Metal amides are attractive candidates for hydrogen storage due to their high volumetric and gravimetric hydrogen densities. However, the sluggish kinetics and competing side reactions during hydrogen uptake and release limit their practical use. Here, a novel nanoconfined Li 2 Mg(NH) 2 @reduced graphene oxide (rGO) composite is presented, which is fabricated using a melt‐infiltration method with a minimum weight penalty of only 2 wt.%. The presence of rGO ensures close contact between the active phases, effectively preventing aggregation during cycling process. As a result, the reversible capacity of Li 2 Mg(NH) 2 @rGO reaches 4.42 wt.%, with no capacity degradation observed after multiple cycling. Theoretical calculations show that rGO catalyzes the hydrogen bond cleavage at the Mg‐amide/Li hydride interface, leading to local dehydrogenation hotspots and significantly improves kinetics of dehydrogenation compared to the bulk counterpart. This study provides a promising strategy for designing metal imide‐based composites to overcome the kinetic limitations and improve their reversible hydrogen storage performance.

08 HYDROGEN↗

A study of hydrogen environment effects on microstructure property behavior of NASA-23 alloy and related alloy systems

This work is part of the overall advanced main combustion chamber (AMCC) casting characterization program of the Materials and Processes Laboratory of the Marshall Space Flight Center. The influence of hydrogen on the tensile properties and ductility behavior of NASA-23 alloy were analyzed. NASA-23 and other referenced alloys in cast and hipped conditions were solution treated and aged under selected conditions and characterized using optical metallography, scanning electron microscopy, and electron microprobe analysis techniques. The yield strength of NASA-23 is not affected much by hydrogen under tensile tests carried at 5000 psig conditions; however, the ultimate strength and ductility properties are degraded. This implies that the physical mechanisms operating would be related to the plastic deformation process. The fracture surfaces characteristics of NASA-23 specimens tensile tested in hydrogen, helium, and air were also analyzed. These revealed surface cracks around specimen periphery with the fracture surface showing a combination of intergranular and transgranular modes of fracture. It is seen that the specimens charged in hydrogen seem to favor a more brittle fracture mode in comparison to air and helium charged specimens. The AMCC casting characterization program is to be analyzed for their hydrogen behavior. As a result of this program, the basic microstructural factors and fracture characteristics in some cases were analyzed.

Diwan, Ravinder M.↗

Formula for the Removal and Remediation of Polychlorinated Biphenyls in Painted Structures

An activated metal treatment system (AMTS) removes and destroys polychlorinated biphenyls (PCBs) found in painted structures or within the binding or caulking material on structures. It may be applied using a "paint-on and wipe-off" process that leaves the structure PCB-free and virtually unaltered in physical form. AMTS is used in conjunction with a solvent solution capable of donating hydrogen atoms. AMTS as a treatment technology has two functions: first, to extract PCBs from the material, and second, to degrade the extracted PCBs. The process for removing PCBs from structures is accomplished as an independent step to the degradation process. The goal is to extract the PCBs out of the paint, without destroying the paint, and to partition the PCBs into an environmentally friendly solvent. The research to date indicates this can be accomplished within the first 24 hours of AMTS contact with the paint. PCBs are extremely hydrophobic and prefer to be in the AMTS over the hardened paint or binder material. The solvent selected must be used to open, but not to destroy, the paint s polymeric lattice structure, allowing pathways for PCB movement out of the paint and into the solvent. A number of solvent systems were tested and are available for use within the AMTS. The second process of the AMTS is the degradation or dehalogenation of the PCBs. The solvent selection for this process is limited to solvents that are capable of donating a hydrogen atom to the PCB structure. Additional AMTS formulation properties that must be addressed for each site-specific application include viscosity and stability. The AMTS must be thick enough to remain where it is applied. Several thickening agents have been tested. Adding a stabilizing agent ensures that the AMTS will not evaporate and leave unprotected, activated metal exposed. During AMTS formulation testing, a number of reagents were evaluated to ensure the rate of dehalogenation was not inhibited by its addition to the system.

Quinn, Jacqueline↗

Control of hydrogen concentrations by microbial sulfate reduction in two contrasting anoxic coastal sediments

Introduction Molecular hydrogen is produced by the fermentation of organic matter and consumed by organisms including hydrogenotrophic methanogens and sulfate reducers in anoxic marine sediment. The thermodynamic feasibility of these metabolisms depends strongly on organic matter reactivity and hydrogen concentrations; low organic matter reactivity and high hydrogen concentrations can inhibit fermentation so when organic matter is poor, fermenters might form syntrophies with methanogens and/or sulfate reducers who alleviate thermodynamic stress by keeping hydrogen concentrations low and tightly controlled. However, it is unclear how these metabolisms effect porewater hydrogen concentrations in natural marine sediments of different organic matter reactivities. Methods We measured aqueous concentrations of hydrogen, sulfate, methane, dissolved inorganic carbon, and sulfide with high-depth-resolution and 16S rRNA gene assays in sediment cores with low carbon reactivity in White Oak River (WOR) estuary, North Carolina, and those with high carbon reactivity in Cape Lookout Bight (CLB), North Carolina. We calculated the Gibbs energies of sulfate reduction and hydrogenotrophic methanogenesis. Results Hydrogen concentrations were significantly higher in the sulfate reduction zone at CLB than WOR (mean: 0.716 vs. 0.437 nM H 2 ) with highly contrasting hydrogen profiles. At WOR, hydrogen was extremely low and invariant (range: 0.41–0.52 nM H 2 ) in the upper 15 cm. Deeper than 15 cm, hydrogen became more variable (range: 0.312–2.56 nM H 2 ) and increased until methane production began at ~30 cm. At CLB, hydrogen was highly variable in the upper 15 cm (range: 0.08–2.18 nM H 2 ). Ratios of inorganic carbon production to sulfate consumption show AOM drives sulfate reduction in WOR while degradation of organics drive sulfate reduction in CLB. Discussion We conclude more reactive organic matter increases hydrogen concentrations and their variability in anoxic marine sediments. In our AOM-dominated site, WOR, sulfate reducers have tight control on hydrogen via consortia with fermenters which leads to the lower observed variance due to interspecies hydrogen transfer. After sulfate depletion, hydrogen accumulates and becomes variable, supporting methanogenesis. This suggests that CLB’s more reactive organic matter allows fermentation to occur without tight metabolic coupling of fermenters to sulfate reducers, resulting in high and variable porewater hydrogen concentrations that prevent AOM from occurring through reverse hydrogenotrophic methanogenesis.

Microbiology↗

Hydrogen Peroxide-Water-Ethanol-Monopropellant Blend for CubeSat Propulsion

Monopropellant propulsion that provides high performance and low hazards compared to state-of-art hydrazine are being investigated under NASA, DOD and commercially sponsored green propellant research and development programs. This NASAeffort looks at phosphate stabilized 50% hydrogen peroxide/water –ethanol blends to evaluate their stability and combustion behavior in submillimeter diameter microtube combustion apparatus for cubesat propulsion applications. Exploratory 7-day stabilitytests find no pressure rise in a sealed test tube environment at room temperature indicating at least short term stability of the mixture. Temperature rise during combustion testing in resistively heated nickel microtube apparatus shows that micro-combustion is achieved in the tube. Propellant density is approximately 1.2 g/cm3compared to 1.0 g/cm3for hydrazine. Theoretical specific impulse of the stoichiometric blend is 219 s at a chamber pressure of 20 psia and an area ratio of 30:1. Density-specific impulseof this blendis263 swhile hydrazine is only about 215-220 sin small reaction control system thrusters. This provides about 20-22% more density-specific impulse for the cubesat compared to hydrazine. The theoreticalcombustion temperature is2168°F, whichis thermally compatible with stainless steel materials of constructionand the nickel catalystused in the tests. Combustion test results are given for stoichiometric, as well as fuel-leanand fuel-richpropellant formulations. Thesetests focus on thermally and catalytically supported combustionin the microtube, whichrequires a microtube preheat temperature of about 900°F and sufficient residence time to achieve combustion that is stable and anchored in the tubewithout blowing through the tube unreacted. Thrust class is expected to be in the 10 mN range based on flow rate and estimated specific impulse.Power requirements are generally below 25 Wto heat the tube. Steady state combustion testing is typically conducted for 3 minutes and shows littledegradation of the hardware over multiple test cyclesindicating thatthere is little catalyst degradation over time and littlecatalyst deactivation due tothe phosphate stabilizer inthe hydrogen peroxide.

Monopropellant↗

Water Vapor Resistant SiC/SiC Composite for Hydrogen-Based Turbines (Final Scientific Technical Report)

New material innovations are needed for the extreme environments of next generation, hydrogen-fueled turbine engines. Ceramic matrix composites (CMCs) offer high-temperature capability but are susceptible to degradation in high-temperature water vapor. Pratt & Whitney’s (P&W) baseline silicon carbide (SiC)/SiC CMC was initially applied to design a component in a hydrogen-fueled engine, verifying the existence of a design space and extracting boundary conditions to inform testing parameters. Several material innovations, including two fibers, interface coatings (IFC), and self-healing matrices (SHM), were investigated to improve high-temperature performance in water vapor. A boron-doped pyrocarbon (B-PyC) IFC and a SHM matrix with layers of zirconium nitride (ZrN) or zirconium diboride (ZrB 2 ) were developed to fabricate minicomposites with either standard Hi-Nicalon™ Type S (HNS) fibers or new Tyranno® SA4 fibers (SA4). The B-PyC IFC is functional but lacks in providing improved durability. A matrix consisting of thick layers of SiC and thin layers of ZrB 2 shows promise as a SHM that can effectively seal matrix cracks in this extreme environment. Minicomposites with HNS fibers generally outperform those with SA4 fibers.

08 HYDROGEN↗

Development of a Contingency Gas Analyzer for the Orion Crew Exploration Vehicle

NASA's experience with electrochemical sensors in a hand-held toxic gas monitor serves as a basis for the development of a fixed on-board instrument, the Contingency Gas Analyzer (CGA), for monitoring selected toxic combustion products as well as oxygen and carbon dioxide on the Orion Crew Exploration Vehicle (CEV). Oxygen and carbon dioxide are major components of the cabin environment and accurate measurement of these compounds is critical to maintaining a safe working environment for the crew. Fire or thermal degradation events may produce harmful levels of toxic products, including carbon monoxide (CO), hydrogen cyanide (HCN), and hydrogen chloride (HCl) in the environment. These three components, besides being toxic in their own right, can serve as surrogates for a panoply of hazardous combustion products. On orbit monitoring of these surrogates provides for crew health and safety by indicating the presence of toxic combustion products in the environment before, during and after combustion or thermal degradation events. Issues identified in previous NASA experiences mandate hardening the instrument and components to endure the mechanical and operational stresses of the CEV environment while maintaining high analytical fidelity. Specific functional challenges involve protecting the sensors from various anticipated events- such as rapid pressure changes, low cabin pressures, and extreme vibration/shock exposures- and extending the sensor lifetime and calibration periods far beyond the current state of the art to avoid the need for on-orbit calibration. This paper focuses on lessons learned from the earlier NASA hardware, current testing results, and engineering solutions to the identified problems. Of particular focus will be the means for protecting the sensors, addressing well known cross-sensitivity issues and the efficacy of a novel self monitoring mechanism for extending sensor calibration periods.

Niu, Bill↗

Maximizing long-term biohydrogen production with Clostridium thermocellum for high solids conversion of lignocellulosic biomass

Biological hydrogen production from lignocellulosic biomass sustainably couples organic waste reduction with renewable energy generation. Efficient conversion is challenged by the structural complexity of lignocellulose and resulting recalcitrance to enzymatic degradation. Clostridium thermocellum natively breaks down biomass with highly effective hemi-/cellulases systems (i.e., cellulosomes) and generates hydrogen in anaerobic cultivation, creating a compelling platform for lignocellulosic biohydrogen production. Achieving commercially viable production rates requires balancing high biomass loading and throughput against uniform mixing conditions required for enzyme dispersion, pH and temperature control, and efficient hydrogen and metabolite removal in continuous operation. To address these barriers to process intensification, we implemented novel reactor and process designs for high-solids lignocellulosic biomass fermentations using the C. thermocellum KJC19-9 strain, genetically engineered for co-utilization of cellulose and hemicellulose sugars (i.e., xylose). Via computational fluid dynamics (CFD) modeling and experimental validation, we achieved a >50% improvement in biohydrogen production with an improved anchor-type impeller morphology, coupled to a threefold reduction in agitation rate. To further reduce rheological constraints and accumulation of toxic metabolites, we then transitioned the process to sequencing fed-batch operation. The resulting process generated 24.87 L H 2 L −1 from 160 g L −1 of deacetylated and mechanically refined (DMR)-pretreated corn stover biomass over 16 days while solubilizing >95% of influent cellulose and hemicellulose, setting a new performance benchmark for continuous production of biohydrogen from lignocellulose.

08 HYDROGEN↗