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At least 613 records · Page 34

A guide to transient absorption spectroscopy for porous crystalline materials in photocatalysis

Transient absorption spectroscopy has become an increasingly accessible method for probing the fundamental mechanisms of photocatalytic reaction and has provided important mechanistic insights across a wide range of systems. However, recent studies on metal-organic framework and covalent-organic framework based photocatalysts employ transient absorption primarily as a supplementary characterization technique rather than as a tool for gaining mechanistic insight. This perspective identifies recurring limitations in current practices and outlines strategies for more deliberate application of transient absorption spectroscopy in photocatalysis. By emphasizing clarity in data presentation and interpretation, we aim to elevate transient absorption spectroscopy from a routine characterization tool to a powerful approach for elucidating mechanistic photophysics of framework materials that govern their photocatalytic performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Characterization of Arsenic and Selenium in Coal Fly Ash to Improve Evaluations for Disposal and Reuse Potential (Final Technical Report)

Coal fly ash is a high volume waste material that is discarded in landfills and surface water impoundments across the U.S. and is also widely recycled for a variety of applications. The leaching of potential of contaminants of concern, such as arsenic (As) and selenium (Se), is often the driver of risk assessments for coal ash disposal and reuse. The extent of leachable As and Se depends on several factors related to environmental conditions and fly ash characteristics. Previous studies employed various methods to delineate the concentration, chemical form, and distribution of As and Se in fly ash materials. However, few studies have attempted to directly correlate these properties to mobilization parameters relevant to disposal and reuse. Instead, the coal residuals industries often rely upon standardized leaching protocols that can be laborious or involve hazardous chemicals. The goals of the project were to: 1) Develop and evaluate a characterization protocol that can be used to screen fly ash samples for leachability of As and Se; 2) Characterize As, Se, and associated constituents of fly ash particles at multiple length scales (nanometer to micrometer) to determine if elemental associations differ as a function of the resolution of characterization; and 3) Establish a predictive model for the chemical composition of coal ash produced annually at major U.S. coal fired power facilities on 50-year national coal supply records. For the first objective, we performed leaching experiments with 52 fly ash samples collected from 15 different U.S. power plants and representing coal feedstocks from the three major domestic coal regions. For this work, we assessed the mobilization potential of As and Se in fly ash based on standardized leaching protocols and performed multivariate and lasso regression analyses to explore correlations of leachable As and Se contents with characteristics such as major element contents, loss on ignition (LOI) and pH. The results of regression models indicated that major elements (Fe, Ca, Al) for a wide range of fly ashes can serve as predictor variables for the leaching potential of As, but not for Se. LOI and pH were not important predictive variables in the models. Both regression approaches resulted in relatively strong fits for leachable As (correlation coefficient R 2 = 0.78 for both models) compared to models for leachable Se (R 2 = 0.49). Overall, these results suggest that correlation models combined with on-site elemental analysis with portable analyzers may enable a screening method for leachable As in coal ash. For the second objective, we utilized nanoscale 2-D imaging (30-50 nm spot size) with the Hard X-ray Nanoprobe (HXN) in combination with microprobe X-ray capabilities (~5 µm resolution) to determine As and Se elemental associations in fly ash particles. Speciation of As and Se was also measured at the nano- to microscale with X-ray absorption spectroscopy. The enhanced resolution of HXN showed As and Se that were diffusely located around or comingled with Ca- and Fe-rich particles. The results also showed nanoparticles of Se attached to the surface of fly ash grains. Overall, a comparison of As and Se species across scales highlights the heterogeneity and complexity of chemical associations for these trace elements of concern in coal fly ash. For the final objective, we developed a predictive model for major element composition of coal ash in reserve at disposal sites of major U.S. coal fired power plants. This model was constructed from coal purchase records of 705 power stations from 1973-2022 and was trained on coal ash composition data showing that coal ash elemental composition is strongly associated with the source of feedstock coal. The model showed regional shifts in the major element contents of ash produced by power plants in the last 50 years, particularly for calcium and iron (expressed as %CaO and %Fe 2 O 3 ), as coal-fired power stations changed their source of coal over this time frame. Our approach enables an estimation of coal ash chemical composition that is stored in waste impoundments at individual power stations. Such information can help delineate the regional market potential for material applications that would utilize coal ash harvested from disposal sites across the U.S.

01 COAL, LIGNITE, AND PEAT↗

Fabrication of High Temperature Cermet Materials for Nuclear Thermal Propulsion

Processing techniques are being developed to fabricate refractory metal and ceramic cermet materials for Nuclear Thermal Propulsion (NTP). Significant advances have been made in the area of high-temperature cermet fuel processing since RoverNERVA. Cermet materials offer several advantages such as retention of fission products and fuels, thermal shock resistance, hydrogen compatibility, high conductivity, and high strength. Recent NASA h d e d research has demonstrated the net shape fabrication of W-Re-HfC and other refractory metal and ceramic components that are similar to UN/W-Re cermet fuels. This effort is focused on basic research and characterization to identify the most promising compositions and processing techniques. A particular emphasis is being placed on low cost processes to fabricate near net shape parts of practical size. Several processing methods including Vacuum Plasma Spray (VPS) and conventional PM processes are being evaluated to fabricate material property samples and components. Surrogate W-Re/ZrN cermet fuel materials are being used to develop processing techniques for both coated and uncoated ceramic particles. After process optimization, depleted uranium-based cermets will be fabricated and tested to evaluate mechanical, thermal, and hot H2 erosion properties. This paper provides details on the current results of the project.

Hickman, Robert↗

Multiplexed Holographic Data Storage in Bacteriorhodopsin

Biochrome photosensitive films in particular Bacteriorhodopsin exhibit features which make these materials an attractive recording medium for optical data storage and processing. Bacteriorhodopsin films find numerous applications in a wide range of optical data processing applications; however the short-term memory characteristics of BR limits their applications for holographic data storage. The life-time of the BR can be extended using cryogenic temperatures [1], although this method makes the system overly complicated and unstable. Longer life-times can be provided in one modification of BR - the "blue" membrane BR [2], however currently available films are characterized by both low diffraction efficiency and difficulties in providing photoreversible recording. In addition, as a dynamic recording material, the BR requires different wavelengths for recording and reconstructing of optical data in order to prevent the information erasure during its readout. This fact also put constraints on a BR-based Optical Memory, due to information loss in holographic memory systems employing the two-lambda technique for reading-writing thick multiplexed holograms.

Mehrl, David J.↗

Electron beam analysis of particulate cometary material

Electron microscopy will be useful for characterization of inorganic dust grains in returned comet nucleus samples. The choice of instrument(s) will depend primarily on the nature of the samples, but ultimately a variety of electron-beam methods could be employed. Scanning and analytical (transmission) electron microscopy are the logical choise for morphological, mineralogical, and bulk chemical analyses of dust grains removed from ices. It may also be possible to examine unmelted ice/dust mixtures using an environmental scanning electron microscope equipped with a cryo-transfer unit and a cold stage. Electron microscopic observations of comet nuclei might include: (1) porosities of dust grains; (2) morphologies and microstructures of individual mineral grains; (3) relative abundances of olivine, pyroxene, and glass; and (4) the presence of phases that might have resulted from aqueous alteration (layer silicates, carbonates, sulfates).

Bradley, John↗

Combining Fractional Calorimetry with Statistical Methods to Characterize Thermal Runaway

Fractional thermal runaway calorimetry (FTRC) techniques were introduced to examine thermal runaway (TR) behavior of lithium-ion (Li-ion) cells. Specifically, FTRC considers the total energy released vs. the fraction of the total energy that is released through the cell casing vs. through the ejecta material. This device has been expanded to universally support FTRC testing of additional cell types including 21700-format, D-Cell format, and large prismatic format Li-ion cells. The TR behavior as influenced by cell format, manufacturer, chemistry, capacity, and in situ safety features are described in this presentation.

Walker, William↗

Application of an alkylammonium method for characterization of phyllosilicates in CI chondrites

Many meteorites and interplanetary dust particles (IDP's) with primitive compositions contain significant amounts of phyllosilicates, which are generally interpreted as evidence of protoplanetary aqueous alteration at an early period in the solar system. These meteorites are chondrites of the carbonaceous and ordinary varieties. Characterization of phyllosilicates in these materials is important because of the important physico-chemical information they hold, e.g., from well characterized phyllosilicates, thermodynamic stability relations and hence the conditions of formation of phyllosilicates in the parent body of the meteorite can be predicted. Although we are at a rudimentary level of understanding of the minerals resulting from the aqueous alteration in the early solar nebula, we know that the most common phyllosilicates present in chondritic extraterrestrial materials are serpentines, smectites, chlorites, and micas. The characterization of fine grained minerals in meteorites and IDP's rely heavily on electron beam instruments, especially transmission electron microscopy (TEM). Typically, phyllosilicates are identified by a combination of high resolution imaging of basal spacings, electron diffraction analysis, and chemical analysis. Smectites can be difficult to differentiate from micas because the smectites loose their interlayer water and the interlayers collapse to the same basal spacing as mica in the high vacuum of the TEM. In high-resolution TEM (HRTEM) images, smectite basal spacings vary from 1 nm up to 1.5 nm, while micas show 1 or 2 nm basal spacings. Not only is it difficult to differentiate smectites from micas, but there is no way of identifying different classes of smectites in meteorites and IDP's. To differentiate smectites from micas and also to recognize the charge differences among smectites, an alkylammonium method can be employed because the basal spacings of alkylammonium saturated smectites expand as a function of alkylamine chain length and the layer-charge density of the 2:1 expanding phyllosilicate, and the final product is significantly more stable under electron beam examination. Such a method was tested on standard clays and several meteorite samples using four alkylammonium salts.

Golden, D. C.↗

Thermally Conductive Metal-Tube/Carbon-Composite Joints

An improved method of fabricating joints between metal and carbon-fiber-based composite materials in lightweight radiators and heat sinks has been devised. Carbon-fiber-based composite materials have been used in such heat-transfer devices because they offer a combination of high thermal conductivity and low mass density. Metal tubes are typically used to carry heat-transfer fluids to and from such heat-transfer devices. The present fabrication method helps to ensure that the joints between the metal tubes and the composite-material parts in such heat-transfer devices have both (1) the relatively high thermal conductances needed for efficient transfer of heat and (2) the flexibility needed to accommodate differences among thermal expansions of dissimilar materials in operation over wide temperature ranges. Techniques used previously to join metal tubes with carbon-fiber-based composite parts have included press fitting and bonding with epoxy. Both of these prior techniques have been found to yield joints characterized by relatively high thermal resistances. The present method involves the use of a solder (63 percent Sn, 37 percent Pb) to form a highly thermally conductive joint between a metal tube and a carbon-fiber-based composite structure. Ordinarily, the large differences among the coefficients of thermal expansion of the metal tube, solder, and carbon-fiber-based composite would cause the solder to pull away from the composite upon post-fabrication cooldown from the molten state. In the present method, the structure of the solder is modified (see figure) to enable it to deform readily to accommodate the differential thermal expansion.

Copeland, Robert J.↗

In Situ Prediction of Microstructure and Mechanical Properties in Laser-Remelted Al-Si Alloys: Towards Enhanced Additive Manufacturing

Laser surface remelting of aluminum alloys has emerged as a promising technique to enhance mechanical properties through refined microstructures. This process involves rapid cooling rates ranging from 10 3 to 10 8 °C/s, which increase solid solubility within aluminum alloys, shifting their eutectic composition to a larger value of silicon content. Consequently, the resulting microstructure combines a strengthened aluminum matrix with silicon fibers. This study focuses on the laser scanning of Al-Si aluminum alloy to reduce the size of aluminum matrix spacings and transform fibrous silicon particles from micrometer to nanometer dimensions. Analysis revealed that the eutectic structure contained 17.55% silicon by weight, surpassing the equilibrium eutectic composition of 12.6% silicon. Microstructure dimensions within the molten zones, termed ‘melt pools’, were extensively examined using Scanning Electron Microscopy (SEM) at intervals of approximately 20 μm from the surface. A notable increase in hardness, exceeding 50% compared to the base plate, was observed in the melt pool regions. Thus, it is exemplified that laser surface remelting introduces a novel strengthening mechanism in the alloy. Moreover, this study develops an in situ method for predicting melt pool properties and dimensions. A predictive model is proposed, correlating energy density and spectral signals emitted during laser remelting with mechanical properties and melt pool dimensions. This method significantly reduces characterization time from days to seconds, offering a streamlined approach for future studies in additive manufacturing.

36 MATERIALS SCIENCE↗

A TEOM (tm) particulate monitor for comet dust, near Earth space, and planetary atmospheres

Scientific missions to comets, near earth space, and planetary atmospheres require particulate and mass accumulation instrumentation for both scientific and navigation purposes. The Rupprecht & Patashnick tapered element oscillating microbalance can accurately measure both mass flux and mass distribution of particulates over a wide range of particle sizes and loadings. Individual particles of milligram size down to a few picograms can be resolved and counted, and the accumulation of smaller particles or molecular deposition can be accurately measured using the sensors perfected and toughened under this contract. No other sensor has the dynamic range or sensitivity attained by these picogram direct mass measurement sensors. The purpose of this contract was to develop and implement reliable and repeatable manufacturing methods; build and test prototype sensors; and outline a quality control program. A dust 'thrower' was to be designed and built, and used to verify performance. Characterization and improvement of the optical motion detection system and drive feedback circuitry was to be undertaken, with emphasis on reliability, low noise, and low power consumption. All the goals of the contract were met or exceeded. An automated glass puller was built and used to make repeatable tapered elements. Materials and assembly methods were standardized, and controllers and calibrated fixtures were developed and used in all phases of preparing, coating and assembling the sensors. Quality control and reliability resulted from the use of calibrated manufacturing equipment with measurable working parameters. Thermal and vibration testing of completed prototypes showed low temperature sensitivity and high vibration tolerance. An electrostatic dust thrower was used in vacuum to throw particles from 2 x 10(exp 6) g to 7 x 10(exp -12) g in size. Using long averaging times, particles as small as 0.7 to 4 x 10(exp 11) g were weighted to resolutions in the 5 to 9 x 10(exp -13) g range. The drive circuit and optics systems were developed beyond what was anticipated in the contract, and are now virtually flight prototypes. There is already commercial interest in the developed capability of measuring picogram mass losses and gains. One area is contamination and outgassing research, both measuring picogram losses from samples and collecting products of outgassing.

Source record↗

SSME - Materials and Methods for Addressing High-Pressure Hydrogen Embrittlement

From the humid, corrosion-friendly atmosphere of KSC, to the extreme heat of ascent, to the cold vacuum of space, the Space Shuttle faced one hostile environment after another. One of those harsh environments the hydrogen environment existed within the shuttle itself. Liquid hydrogen was the fuel that powered the shuttle s complex, powerful, and reusable main engine. Hydrogen provided the high specific impulse the bang per pound of fuel needed to perform the shuttle s heavy lifting duties. Hydrogen, however, was also a potential threat to the very metal of the propulsion system that used it. The diffusion of hydrogen atoms into a metal can make it more brittle and prone to cracking a process called hydrogen embrittlement. This effect can reduce the toughness of carefully selected and prepared materials. A concern that exposure to hydrogen might encourage crack growth was present from the beginning of the Space Shuttle Program, but the rationale for using hydrogen was compelling. This paper outlines the material characterization, anomaly resolution, and path to understanding of hydrogen embrittlement on superalloys through the course of the SSME program. Specific examples of nickel alloy turbine housings and single crystal turbine blades are addressed. The evolution of fracture mechanics analytical methods is also addressed.

Matejczk, Daniel↗

Quasi-In-Situ Analysis of Electrode Top Atomic Layers via High-Sensitivity Low-Energy Ion Scattering and Potential-Controlled Sample Transfer

Electrocatalytic reactions involve interfacial interactions between the surfaces of electrodes and reactive species at an electrolyte interface. There are presently no universal or unambiguous methods to directly assay the active top atomic layer composition that influences the reactivity of these electrodes under relevant operating conditions. Low-energy ion scattering (LEIS) spectroscopy is a surface characterization technique that yields compositional analysis of the outermost atomic layer of a material, but it must be performed in ultrahigh vacuum (UHV). Application of LEIS measurements to electrochemical materials that are removed from ambient liquid-phase environments thus leaves an open question as to whether the surface that is transferred to UHV is truly the surface that manifested during the electrochemical reaction. Toward the goal of preserving the active surface state, we developed a sample transfer workflow for LEIS enabling air-free removal and drying of an electrode from an electrochemical cell while maintaining control of the potential using an auxiliary electrode. The potential-controlled emersion method was demonstrated to give distinct potential-dependent surface compositions for a Cu−Pd alloy relative to removal after uncontrolled return to open-circuit potential. A Cu-enriched surface was found at anodic potential and a Pd-enriched surface at cathodic potential, suggesting that the approach can be used to retain representative atomic configurations during transfer. Since adsorbates will often persist from the reaction environment, conventional sample pretreatment methods for removal, including atomic O and atomic H exposure, were also contrasted. Both methods were found to differ with results from incidental low-dose depth profiling by the LEIS primary ion source, which removes adventitious species and surface atoms during the course of repeated measurements. These depth profiles were found to be sensitive to sample history and thus qualitatively informative, despite the possible changes induced by ion damage. The results exhibit (i) the need for complete control over the polarization state of the sample at all times (no excursions to open circuit during transfer) and (ii) the utility of low-dose depth profiling to capture changes in the near-surface composition.

Alloys↗

Design, fabrication and test of graphite/epoxy metering truss structure components, phase 3

The design, materials, tooling, manufacturing processes, quality control, test procedures, and results associated with the fabrication and test of graphite/epoxy metering truss structure components exhibiting a near zero coefficient of thermal expansion are described. Analytical methods were utilized, with the aid of a computer program, to define the most efficient laminate configurations in terms of thermal behavior and structural requirements. This was followed by an extensive material characterization and selection program, conducted for several graphite/graphite/hybrid laminate systems to obtain experimental data in support of the analytical predictions. Mechanical property tests as well as the coefficient of thermal expansion tests were run on each laminate under study, the results of which were used as the selection criteria for the single most promising laminate. Further coefficient of thermal expansion measurement was successfully performed on three subcomponent tubes utilizing the selected laminate.

Source record↗

Silicon ribbon growth by a capillary action shaping technique

Substantial improvements in ribbon surface quality are achieved with a higher melt meniscus than that attainable with the film-fed (EFG) growth technique. A capillary action shaping method is described in which meniscus shaping for the desired ribbon geometry occurs at the vertex of a wettable die. As ribbon growth depletes the melt meniscus, capillary action supplies replacement material. Topics discussed cover experimental apparatus and growth procedures; die materials investigations, fabrication and evaluation; process development for 25 mm, 38 mm, 50 mm and 100 mm silicon ribbons; and long grain direct solidification of silicon. Methods for the structural and electrical characterization of cast silicon ribbons are assessed as well as silicon ribbon technology for the 1978 to 1986 period.

Schwuttke, G. H.↗

Extreme value statistics analysis of fracture strengths of a sintered silicon nitride failing from pores

Statistical analysis and correlation between pore-size distribution and fracture strength distribution using the theory of extreme-value statistics is presented for a sintered silicon nitride. The pore-size distribution on a polished surface of this material was characterized, using an automatic optical image analyzer. The distribution measured on the two-dimensional plane surface was transformed to a population (volume) distribution, using the Schwartz-Saltykov diameter method. The population pore-size distribution and the distribution of the pore size at the fracture origin were correllated by extreme-value statistics. Fracture strength distribution was then predicted from the extreme-value pore-size distribution, usin a linear elastic fracture mechanics model of annular crack around pore and the fracture toughness of the ceramic. The predicted strength distribution was in good agreement with strength measurements in bending. In particular, the extreme-value statistics analysis explained the nonlinear trend in the linearized Weibull plot of measured strengths without postulating a lower-bound strength.

Chao, Luen-Yuan↗

Update on the NASA GRC Stirling Technology Development Project

The Department of Energy, NASA Glenn Research Center (GRC), and Stirling Technology Company (STC) are developing a free-piston Stirling convertor for a Stirling radioisotope power system (SRPS) to provide spacecraft on-board electric power for NASA deep space missions. The SRPS has recently been identified for potential use on the Europa Orbiter and Solar Probe Space Science missions. Stirling is also now being considered for unmanned Mars rovers. NASA GRC is conducting an in-house project to assist in developing the Stirling convertor for readiness for space qualification and mission implementation. As part of this continuing effort, the Stirling convertor will be further characterized under launch environment random vibration testing, methods to reduce convertor electromagnetic interference (EMI) will be developed, and an independent performance verification will be completed. Convertor life assessment and permanent magnet aging characterization tasks are also underway. Substitute organic materials for the linear alternator and piston bearing coatings for use in a high radiation environment have been identified and have now been incorporated in Stirling convertors built by STC for GRC. Electromagnetic and thermal finite element analyses for the alternator are also being conducted. This paper discusses the recent results and status for this NASA GRC in-house project.

Thieme, Lanny G.↗

Ultrasonic Guided-Wave-Scan System Used to Characterize C-Enhanced Silicon Carbide Composite During Creep- Rupture Tests

Ceramic matrix composites (CMCs) are being developed for advanced aerospace propulsion applications in order to save weight, improve reuse capability, and increase performance. However, mechanical and environmental loads applied to CMCs can cause degradation in the form of discrete flaws and distributed microdamage that can play a significant role in reducing desirable physical properties. Categories of microdamage include fiber/matrix debonding (interface failure), matrix microcracking, fiber fracture and buckling, oxidation, and second-phase formation. Distributed microdamage in CMCs has proven difficult to characterize nondestructively because of the complex microstructure and macrostructure of these materials, and a recent study regarding the durability of a ceramic matrix composite discussed the requirement for improved nondestructive evaluation (NDE) methods for monitoring degradation in these materials.

Roth, Don J.↗

Extraction and Characterization of Lipids from Salicornia virginica and Salicornia europaea

The lipid content from Salicornia virginica and Salicornia europaea is investigated. The plants are leafless halophytes with seeds contained in terminal nodes. The lipids, in the form of cell membranes and oil bodies that come directly from the node cells, are observed using fluorescence microscopy. Two extraction methods as well as the results of extracting from the seeds and from the entire nodes are described. Characterization of the fatty acid components of the lipids using Gas Chromatography in tandem with Mass Spectroscopy is also described. Comparisons are made between the two methods and between the two plant materials as lipid sources.

Kulis,Michael J.↗