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At least 415 records · Page 23

Effect of pretreatment conditions on Fe-ZSM-5 properties and performance for Fischer–Tropsch synthesis

Iron supported on ZSM-5 is a widely studied catalyst for Fischer–Tropsch synthesis (FTS). Iron is activated with H 2 , CO, or a mixture of CO and H 2 prior to FTS, resulting in phase transformations that make it challenging to understand structure–property relationships. Furthermore, in this work, we demonstrate that increasing the pretreatment temperature of Fe–Na-ZSM-5 reduces CO conversion irrespective of the reductant, but the product selectivity, iron particle size, composition, CO adsorption properties, and zeolite structure is dependent on both the pretreatment temperature and reductant. Pretreatment of Fe–Na-ZSM-5 in H 2 induces sintering of iron particles, increasing C 2 –C 4 olefins and C 5+ hydrocarbons selectivity from 19.0% and 14.0% at 350 °C to 28.2% and 25.4% at 770 °C, respectively. Conversely, CO pretreatment facilitates carbide formation, coke deposition, and CH 4 formation.

36 MATERIALS SCIENCE↗

Cost-Effective Thermomechanical Processing of Nanostructured Ferritic Alloys: Microstructure and Mechanical Properties Investigation

Nanostructured ferritic alloys (NFAs), such as oxide-dispersion strengthened (ODS) alloys, play a vital role in advanced fission and fusion reactors, offering superior properties when incorporating nanoparticles under irradiation. Despite their importance, the high cost of mass-producing NFAs through mechanical milling presents a challenge. This study delves into the microstructure-mechanical property correlations of three NFAs produced using a novel, cost-effective approach combining severe plastic deformation (SPD) with the continuous thermomechanical processing (CTMP) method. Analysis using scanning electron microscopy (SEM)-electron backscatter diffraction (EBSD) revealed nano-grain structures and phases, while scanning transmission electron microscopy (STEM)-energy dispersive X-ray spectroscopy (EDS) quantified the size and density of Ti-N, Y-O, and Cr-O fine particles. Atom probe tomography (APT) further confirmed the absence of finer Y-O particles and characterized the chemical composition of the particles, suggesting possible nitride dispersion strengthening. Correlation of microstructure and mechanical testing results revealed that CTMP alloys, despite having lower nanoparticle densities, exhibit strength and ductility comparable to mechanically milled ODS alloys, likely due to their fine grain structure. However, higher nanoparticle densities may be necessary to prevent cavity swelling under high-temperature irradiation and helium gas production. Further enhancements in uniform nanoparticle distribution and increased sink strength are recommended to mitigate cavity swelling, advancing their suitability for nuclear applications.

36 MATERIALS SCIENCE↗

Structural characterizaiton and gas reactions of small metal particles by high-resolution, in-situ TEM and TED

The existing in-situ transmission electron microscopy (TEM) facility was improved by adding a separately pumped mini-specimen chamber. The chamber contains wire-evaporation sources for three metals and a specimen heater for moderate substrate temperatures. A sample introduction device was constructed, installed, and tested, facilitating rapid introduction of a specimen into the mini-chamber while maintaining the background pressure in that chamber in the 10(-9) millibar range. Small particles and clusters of Pd, grown by deposition from the vapor phase in an in-situ TEM facility on amorphous and crystalline support films of alumina and on ultra-thin carbon films, were analyzed by conventional high-resolution TEM and image analysis in terms of detectability, number density, and size distribution. The smallest particles that could be detected and counted contained no more than 6 atoms; size determinations could be made for particles 1 nm in diameter. The influence of various oxygen plasma treatments, annealing treatments, and of increasing the substrate temperature during deposition was investigated. The TEM technique was employed to demonstrate that under otherwise identica l conditions the lattice parameter of Pd particles in the 1 to 2 nm size range and supported in random orientation on ex-situ prepared mica films is expanded by some 3% when compared to 5 nm size particles. It is believed that this expansion is neither a small-particle diffraction effect nor due to pseudomorphism, but that it is due to a annealing-induced transformation of the small as-deposited particles with predominantly composite crystal structures into larger particles with true f.c.c. structure and thus inherently smaller lattice parameter.

Source record↗

Sand and dust issues for the MESUR mission

The presence of particles in the Martian atmosphere increases the rate of erosion of the heat shield during the entry phase of the MESUR mission. Preliminary analysis has shown that under certain conditions particles will penetrate the bow shock of the entry vehicle, impact and erode the heat shield, above the anticipated rate from the ablation process. Knowledge of the distribution, sizes, and composition of particles suspended in the atmosphere will permit the estimation of the heat shield recession both for a nominal Mars atmosphere and in dust storm conditions. On the surface of Mars, sand and dust can effect the operations and design of the science instruments (i.e., imaging) and lander subsystems (i.e., solar arrays). Distribution and deposition of sand and dust on the planet's surface will dictate the feasibility of using solar arrays as a power source for the lander. Furthermore, the potential abrasive nature of blowing particles must be understood in order to properly select suitable materials for lander structure and any components exposed to the environment. The selection of lander material may also be dictated by corrosive and chemically active properties of particles at a potential landing site. Some key interests concerning sand and dust on the surface and in the atmosphere are summarized in a number of questions that are included.

Wercinski, P. F.↗

The Organic Aerosols of Titan's Atmosphere

One of Titan's many characteristics is the presence of a haze that veils its surface. This haze is composed of heavy organic particles and determining the chemical composition of these particles is a primary objective for future probes that would conduct in situ analysis. Meanwhile, solar occultations provide constraints on the optical characteristics of the haze layer. This paper describes solar occultation observations obtained by the Visual and Infrared Mapping Spectrometer (VIMS) onboard the Cassini spacecraft. These observations strongly constrain the optical characteristics of the haze layer. We detail the different steps involved in the processing of these data and apply them to two occultations that were observed at the South Pole and at the equator in order to investigate the latitudinal dependence of optical properties. The light curves obtained in seven atmospheric windows between 0.933-microns to 5-microns allow us to characterize atmospheric layers from 300 km to the surface. Very good fits of the light curves are obtained using a simple profile of number density of aerosols that is characterized by a scale height. The main difference between the South Pole and the equator is that the value of the scale height increases with altitude at the South Pole whereas it decreases at the equator. The vertically integrated amount of aerosols is similar at the two locations. The curve describing the cross-section versus wavelength is identical at the two locations suggesting that the aerosols have similar characteristics. Finally, we find that the two-way vertical transmission at 5-microns is as large as 80% at both locations.

solar occultation↗

Aerogel-Based Insulation Materials for Cryogenic Applications

Many different aerogel-based materials are now being used in thermal insulation systems for cryogenic applications. These materials include flexible composite blankets, bulk-fill particles, and polymer composites in both evacuated and non-evacuated environments. In ambient environments, aerogels provide superior thermal performance compared to conventional polymeric foam and cellular glass insulations while offering unique advantages in avoiding problems with weathering, moisture, and mechanical damage. Aerogels are also used as spacer materials in multilayer insulation systems. These layered systems provide combined structural-thermal capability for cryogenic systems in either vacuum-jacketed or externally-applied insulation designs. Test data (effective thermal conductivity) include a wide range of both commercial and experimental aerogel materials. Testing was performed using laboratory cryostats and standard methods including full range vacuum (from ambient pressure to high vacuum) and boundary temperatures 293 K and 78 K. Examples of aerogel-based insulation systems are given for both evacuated and non-evacuated applications.

heat transfer↗

Aerogel-Based Insulation Materials for Cryogenic Applications

Many different aerogel-based materials are now being used in thermal insulation systems for cryogenic applications. These materials include flexible composite blankets, bulk-fill particles, and polymer composites in both evacuated and non-evacuated environments. In ambient environments, aerogels provide superior thermal performance compared to conventional polymeric foam and cellular glass insulations while offering unique advantages in solving problems with weathering, moisture, and mechanical damage. Aerogels are also used as spacer materials in multilayer insulation systems. These layered systems provide combined structural-thermal capability for cryogenic systems in either vacuum-jacketed or externally-applied insulation designs. Test data (effective thermal conductivity) include a wide range of both commercial and experimental aerogel materials. Testing was performed using laboratory cryostats and standard methods including full range vacuum (from ambient pressure to high vacuum) and boundary temperatures 293 K and 78 K. Examples of aerogel-based insulation systems are given for both evacuated and non-evacuated applications.

aerogel layered composites↗

Characterization and Analysis of Aerosol Particle Retention and Re-aerosolization from Hook-and-Loop Fasteners on the International Space Station

The extensive use of hook and loop fasteners aboard the International Space Station warrants careful examination of its contribution to indoor air pollution, as its fine fibers catch aerosol particles then re-aerosolize them upon being pulled apart, often within the breathing zone of astronauts. This problem is expanded by the lack of gravity because airborne particles larger than 1 micrometer do not settle. Instead these aerosols remain in the air until removed by filtration. Aerosol inhalation can have negative health effects, ranging from acute symptoms to long-term consequences, depending on particle sizes, mass and material composition. This study characterizes the size distribution, number concentration, and mass concentration of re-aerosolized debris generated by hook and loop fasteners taken from the stray light cover of the Microgravity Science Glovebox in the U.S. Laboratory of the ISS to understand the extent of its impact on air quality. Transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM), in conjunction with energy dispersive spectroscopy (EDS) were also used to characterize the morphology and composition of the particles.

Boyajian, Barbara↗

The importance of energetic particle precipitation on the chemical composition of the middle atmosphere

The present review deals with the importance of three distinct classes of precipitation which directly deposit energy into the middle atmosphere, viz. galactic cosmic radiation, energetic solar protons and relativistic electron precipitation from the earth's radiation belts. Chemical considerations during particle precipitation are discussed, with special emphasis on the relative production rate of odd nitrogen and odd hydrogen species during ionizing particle precipitation. The long residence time of NO in the upper stratosphere, where catalytic interaction with O3 is most effective, requires that this mechanism be included in future modeling of global distribution of O3. Other situations causing O3 depletion are also identified.

Thorne, R. M.↗

Atmospheric emission of nanoplastics from sewer pipe repairs

Nanoplastic particles are inadequately characterized environmental pollutants with significant adverse effects on aquatic and atmospheric systems, causing drastic impacts on human health through inhalation, ingestion, and skin penetration. At present, it is explicitly assumed that environmental nanoplastics (EnvNP) are weathering fragments of microplastic or larger plastic debris discharged into terrestrial and aquatic environments, while atmospheric occurrence of EnvNP is solely attributed to aerosolization by wind and other mechanical forces. However, sources and emissions of unintended EnvNP are poorly understood and are therefore largely unaccounted for in various risk assessments. In this work, we show that large quantities of EnvNP may be directly emitted into the atmosphere as steam laden waste components discharged from a commonly used technology to repair sewer pipes in urban areas. Comprehensive chemical analysis of the discharged waste condensate reveals abundant presence of insoluble colloids, which after drying form solid organic particles with composition and viscosity consistent with EnvNP. We suggest that airborne emissions of EnvNP from these globally used sewer repair practices may be prevalent in highly populated urban areas. Airborne emissions of these EnvNP particles may have important implications on air quality and toxicological levels in large urban areas that need to be mitigated.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Chemical compositions of primitive solar system particles

Chemical studies of micrometeorites are of fundamental importance primarily because atmospheric entry selection effects (such as destruction of friable objects) are less significant than those for conventional meteorites. As a result, particles that have experienced very little postaccretional processing have a significant chance of surviving the Earth encounter and subsequent collection. Thus, chemical analyses of these relatively unaltered micrometeorites may lead to a better understanding of the compositions of the most primitive materials in the solar system and thereby constrain the conditions (physical and chemical) that existed in the early solar nebula. Micrometeorites have been collected from the stratosphere, polar ices, and ocean sediments, but the stratospheric collection is the best source for the most unaltered material because they are small and are not heated to their melting points. Despite the fact that the stratospheric micrometeorites have masses in the nanogram range, a variety of microanalytical techniques have been applied to bulk chemical analyses with part-per-million sensitivity. In some cases, multi-disciplinary studies (e.g., chemistry and mineralogy) have been performed on individual particles. The first-order conclusion is that the chondrite-like particles are chemically similar to carbonaceous chondrites but in detail are distinct from members of the conventional meteorite collection. The purpose of this paper is to provide an overview of the results to date and identify important areas for further study.

Sutton, Steve R.↗

Biomass burning and marine aerosol processing over the southeast Atlantic Ocean: a TEM single-particle analysis

This study characterizes single-particle aerosol composition from filters collected during the ObseRvations of Aerosols above CLouds and their intEractionS (ORACLES) and CLoud–Aerosol–Radiation Interaction and Forcing: Year 2017 (CLARIFY-2017) campaigns. In particular the study describes aged biomass burning aerosol (BBA), its interaction with the marine boundary layer and the influence of biomass burning (BB) air on marine aerosol. The study finds evidence of BBA influenced by marine boundary layer processing as well as sea salt influenced by BB air. Secondary chloride aerosols were observed in clean marine air as well as in BB-influenced air in the free troposphere. Higher-volatility organic aerosol appears to be associated with increased age of biomass burning plumes, and photolysis or oxidation may be a mechanism for the apparent increased volatility. Aqueous processing and interaction with the marine boundary layer air may be a mechanism for the presence of sodium on many aged potassium salts. By number, biomass burning potassium salts and modified sea salts are the most observed particles on filter samples. The most commonly observed BC coatings are inorganic salts. These results suggest that atmospheric processes such as photolysis, oxidation and cloud processing are key drivers in the elemental composition and morphology of aged BBA. Fresh BBA inorganic salt content, as it has an important role in the particles' ability to uptake water, may be a key driver in how aqueous processing and atmospheric aging proceed.

54 ENVIRONMENTAL SCIENCES↗

Dynamical Change of Valence States and Structure in NiCu 3 Nanoparticles during Redox Cycling

Alloyed materials are promising candidates to improve catalytic processes. Ni–Cu nanoparticles are used for various reactions, including processes with biomass-derived components. However, dynamical restructuring effects alter the catalytic properties and can deactivate the sample. To understand these structural modifications, a multimodal investigation of NiCu 3 /C was performed to determine compositional and morphological changes during a redox cycle to simulate reduction and oxidation of the catalyst during reaction. We exploit a novel correlative, multimodal approach that combines in situ X-ray absorption spectroscopy (XAS) and in situ scanning transmission electron microscopy and electron energy-loss spectroscopy (STEM-EELS) to describe changes that occur in the sample in realistic conditions. In the fresh sample, there are two morphologies present: core–shell and hollow. Segregation of Cu was observed in both types of particles after synthesis, with Cu being more oxidized in the hollow structures. Upon reduction for 2 h under H 2 at 400 °C, the Cu was reduced, although segregation of Cu and Ni was still observed. Subsequent exposure to O 2 at 400 °C led to a strong reoxidation of Cu with the formation of hollow particles with compositional heterogeneities. The oxidation of metals and segregation phenomena can be related to known catalytic properties of NiCu 3 /C particles, especially regarding the hydrodeoxygenation of 5-hydroxymethylfurfural to 2,5-dimethylfuran.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Influences on Subsurface Plutonium and Americium Migration

Plutonium (Pu) has been released to the environment worldwide, including approximately 1.85 × 1015 Bq (200 kg) of Pu from process waste solutions to unconfined soil structures at the Hanford Site in Washington State. The subsurface mobility of Pu is influenced by complex interactions with sediments, groundwater, and any co-contaminants within the waste stream. Previous investigations at Hanford have shown that Pu exists as discrete PuO 2 particles forming before or after disposal, as secondary solid phases formed from waste interactions with sediments as adsorbed/incorporated species, and/or as dissolved species. In this research, new evidence is presented for the existence of PuO 2 , PuO 2 -Bi 2 O 3 composites, and particles from burnt Pu metal in near-surface sediments where Pu-laden acidic process waste was disposed to sediments. Pu and americium (Am) L3 X-ray absorption spectroscopy and density functional theory suggest that, in larger, more crystalline PuO 2 particles, Am formed from radioactive decay is retained in the Pu IV O 2 structure as Am IV . The Pu and Am that were disposed of in an acidic waste stream have since migrated deeper into the subsurface with detection to at least 37 meters below ground surface. In contrast, Pu deposited near the ground surface from neutral pH waste is found to be homogeneously distributed and relatively immobile. Groundwater extractions performed on contaminated sediments indicate that both Pu and Am are recalcitrant, with Am being fractionally less extractable than Pu on a molar basis. These results suggest that the more mobile fraction of Am has migrated from the near-surface and may be present in the deeper sediments as a different phase than Pu. From these results, it is suggested that Pu and Am deposited from acidic wastes were initially mobile and became significantly less mobile as wastes were neutralized within the soil profile.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

High-Capacity, High-Voltage Composite Oxide Cathode Materials

This SBIR project integrates theoretical and experimental work to enable a new generation of high-capacity, high-voltage cathode materials that will lead to high-performance, robust energy storage systems. At low operating temperatures, commercially available electrode materials for lithium-ion (Li-ion) batteries do not meet energy and power requirements for NASA's planned exploration activities. NEI Corporation, in partnership with the University of California, San Diego, has developed layered composite cathode materials that increase power and energy densities at temperatures as low as 0 degC and considerably reduce the overall volume and weight of battery packs. In Phase I of the project, through innovations in the structure and morphology of composite electrode particles, the partners successfully demonstrated an energy density exceeding 1,000 Wh/kg at 4 V at room temperature. In Phase II, the team enhanced the kinetics of Li-ion transport and electronic conductivity at 0 degC. An important feature of the composite cathode is that it has at least two components that are structurally integrated. The layered material is electrochemically inactive; however, upon structural integration with a spinel material, the layered material can be electrochemically activated and deliver a large amount of energy with stable cycling.

Hagh, Nader M.↗

Non-local detection of coherent Yu–Shiba–Rusinov quantum projections

Probing spatially confined quantum states from afar—a long-sought goal to minimize external interference—has been proposed to be feasible in condensed-matter systems through the coherent projection of the state. This can be achieved by engineering the eigenstates of the electron sea that surrounds the quantum state using cages built atom by atom, the so-called quantum corrals. However, the demonstration of the coherent nature of the projection and manipulation of its quantum composition are still important goals. Here we show this for the coherent projection of a Yu–Shiba–Rusinov quantum state that is induced by a magnetic impurity, using the eigenmodes of corrals on the surface of a superconductor. This enables us to manipulate the particle–hole composition of the projected state by tuning the corral eigenmodes through the Fermi energy. Our results demonstrate a controlled non-local method for the detection of magnet–superconductor hybrid quantum states.

quantum mechanics↗

ICAN Computer Code Adapted for Building Materials

The NASA Lewis Research Center has been involved in developing composite micromechanics and macromechanics theories over the last three decades. These activities have resulted in several composite mechanics theories and structural analysis codes whose applications range from material behavior design and analysis to structural component response. One of these computer codes, the Integrated Composite Analyzer (ICAN), is designed primarily to address issues related to designing polymer matrix composites and predicting their properties - including hygral, thermal, and mechanical load effects. Recently, under a cost-sharing cooperative agreement with a Fortune 500 corporation, Master Builders Inc., ICAN was adapted to analyze building materials. The high costs and technical difficulties involved with the fabrication of continuous-fiber-reinforced composites sometimes limit their use. Particulate-reinforced composites can be thought of as a viable alternative. They are as easily processed to near-net shape as monolithic materials, yet have the improved stiffness, strength, and fracture toughness that is characteristic of continuous-fiber-reinforced composites. For example, particlereinforced metal-matrix composites show great potential for a variety of automotive applications, such as disk brake rotors, connecting rods, cylinder liners, and other hightemperature applications. Building materials, such as concrete, can be thought of as one of the oldest materials in this category of multiphase, particle-reinforced materials. The adaptation of ICAN to analyze particle-reinforced composite materials involved the development of new micromechanics-based theories. A derivative of the ICAN code, ICAN/PART, was developed and delivered to Master Builders Inc. as a part of the cooperative activity.

Murthy, Pappu L. N.↗