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At least 973 records · Page 54

Simulant Development of Potential 200 West Area Waste Feeds

Preliminary planning for retrieval, qualification, and pretreatment of waste in Hanford’s 200 West Area (200W) has begun as part of the West Area Risk Management project. Experimental studies to technically mature pretreatment process operations will likely be needed because of the uniqueness of 200W waste. Pacific Northwest National Laboratory formulated five simulants to represent 200W-qualified feed based on the preliminary flowsheet provided by Washington River Protection Solutions, LLC. The simulant recipes were devised using applicable historical information as a reference point to support the use of the flowsheet waste vectors, which were combined into five distinct groups. These five groups formed the basis for the liquid composition targets that were adapted into recipes using charged-balanced salt species. The liquid phase recipes were batched in 1-L quantities and analyzed at Pacific Northwest National Laboratory. Once confirmed to be stable, the liquid solutions were tested for compatibility with candidate solid components. Specific solid components were recommended based on cross-examining the proposed solid phases in the flowsheet with relevant data from the literature. Mixtures of solid components were added to aliquots of the liquid batches and sub-sampled to measure particle size distribution. The measured distribution was compared to independently created benchmark distributions appropriate for each simulant. This process was iterated until a solid phase composition that resulted in a representative particle size distribution was found. After the final compositions were confirmed, a suite of chemical and physical characterization data was collected. This report describes the simulant basis, formulation methodology, laboratory measurements, and data collected for the recipes recommended to represent 200W waste feeds.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Blending as an In-Tank Waste Processing Strategy: Year 1 Progress Report

The Hanford Site stores approximately 56 million gallons of radioactive legacy defense waste in underground tanks. Direct feed of southeast quadrant tank waste to a high-level waste treatment facility is currently being explored to accelerate tank treatment activities. This study seeks to de-risk waste transfers by favorably altering the resuspension and critical velocities of wastes through strategic waste blending. Wastes rich in aluminum- and zirconium-bearing solids pose significant risks due to their high settled strength and density. A series of tests explores how solid phase particle size and suspending phase chemistry alter waste transport properties, quantified through the just-suspended mixing speed (NJS), for pure and blended aluminum- and zirconium-bearing waste solid simulants. The study utilizes a range of gibbsites (three sizes spanning 10 to 90 µm) and zirconia solids (three sizes spanning 10 to 100 µm). As expected, the NJS of pure solids largely follows predictions based on literature correlations; blends of gibbsite and zirconium-bearing solids of differing particle sizes exhibit NJS maxima attributed to dense packing of the mixed-size settled solids. The findings of this study will assist in developing strategies to optimize the transport of waste solids for the safe and efficient delivery of tank waste.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Comparison of GOES-Retrieved and In Situ Measurements of Deep Convective Anvil Cloud Microphysical Properties During the Tropical Composition, Cloud and Climate Coupling Experiment (TC(sup 4))

One of the main goals of the Tropical Composition, Cloud and Climate Coupling Experiment (TC(sup 4)) during July and August 2007 was to gain a better understanding of the formation and life cycle of cirrus clouds in the upper troposphere and lower stratosphere and how their presence affects the exchange of water vapor between these layers. Additionally, it is important to compare in situ measurements taken by aircraft instruments with products derived from satellite observations and find a meaningful way to interpret the results. In this study, cloud properties derived using radiance measurements from the Geostationary Operational Environmental Satellite (GOES) imagers are compared to similar quantities from aircraft in situ observations and are examined for meaningful relationships. A new method using dual \angle satellite measurements is used to derive the ice water content (IWC) for the top portion of deep convective clouds and anvils. The results show the in situ and remotely sensed mean microphysical properties agree to within approx.10 microns in the top few kilometers of thick anvils despite the vastly different temporal and spatial resolutions of the aircraft and satellite instruments. Mean particle size and IWC are shown to increase with decreasing altitude in the top few kilometers of the cloud. Given these relationships, it may be possible to derive parameterizations for effective particle size and IWC as a function of altitude from satellite observations

Yost, Christoher R.↗

The Effect of Solution Chemistries and Freezing Temperatures on the Morphology of Cryogenic Opal-A (COA): Implications for Past Climates on Mars

Cryogenic opal-A (COA) is a type of hydrated amorphous silica that forms when silica-rich geothermal fluids erupt sub-aerially and are exposed to air temperatures below 0 °C. As the fluid cools and water-ice forms, the solution increases in ionic strength and reaches saturation of opal-A. This results in the precipitation of opal-A between water ice crystals. Natural COA is found embedded within frozen fluids near hydrothermal sources, and has been shown to preserve signs of biological activity. In this study, two solution chemistries (hydrochloric acid (HCl) and sulfuric acid (H2SO4)) and three freezing temperatures (-20, -80, -196 ºC) were used to synthesize COA in the lab. SEM analyses showed that COA frozen at -20 ºC in HCl solutions produced smooth silica branches similar to what was observed in previous studies. COA precipitated at lower freezing temperatures demonstrated progressively smaller particle sizes and unique morphologies such as halite dendrites within silica, desiccation cracks, and pores. COA made in H2SO4 solutions was more angular and fragmented than COA made in HCl solutions. Particle size also decreased with decreasing freezing temperature. COA textures have implications for terrestrial samples as well as future samples returned from Mars because they can provide information about past climate and fluid chemistry.

J V Hogancamp↗

A simplified integrated framework for predicting the economic impacts of feedstock variations in a catalytic fast pyrolysis conversion process

Feedstock attributes of lignocellulosic biomass, such as particle size, compositional makeup, and moisture content, can vary substantially even within pre-processed materials and have a significant effect on conversion in fast pyrolysis-based processes. However, the economic impacts of these attributes are not well understood. To address this, biomass deconstruction phenomena captured with a versatile particle-scale simulation were linked to techno-economic impacts via reduced-order models. Parametric analysis of the particle-scale model, which was validated using literature data, was used in combination with multiple linear regression models to develop correlations between feedstock attributes and yields of pyrolysis oil, gas, and char. Yields were then correlated with the minimum fuel selling price (MFSP) using a techno-economic model, bridging the gap between physics-based biomass conversion simulations and predictions of MFSP for a catalytic fast-pyrolysis process. Empirical correlations derived from the literature regarding the impact of mineral matter (ash) on oil yield were also considered. The model correlations deployed in the integrated framework capture the impacts of variation in feedstock attributes on the MFSP. Variations in ash were shown to have the biggest impact, varying MFSP by -13%/+22% due to catalytic effects and lower relative amounts of convertible lignocellulosic material. It was also found that, if ash can be controlled to low levels, the increased extractives in forest residues can help compensate for some yield losses associated with increased ash. As a result, other inputs considered (particle size, moisture content, and reactor temperature) had relatively negligible effects on process economics within the ranges analyzed considering particle-scale effects alone.

BIOMASS FUELS↗

Design of Modular Test Facility for Particle/sCO2 Heat Exchanger Evaluation

Heliogen has designed a 1.3 MW particle and supercritical carbon dioxide (sCO2) test loop to retire technical and manufacturing risks. The data from this facility will be used to validate near commercial-scale particle heat exchanger modules. The heat exchanger is scaled to capture all features of the full-scale modules. Testing will be conducted with CARBOBEAD HSP 16/30, a larger particle size than other recent testing. The system was designed to ASME codes with the constraint that sCO2 piping and other major components are stainless steels.

14 SOLAR ENERGY↗

Analysis of spectrophotometric observations of Venus in the 3-4 micron region

Spectrophotometric data of Venus in the 3-4 micron region are analyzed in the context of current ideas concerning cloud properties. The results show that a homogeneous cloud model, using a unimodal particle size distribution compatible with the results of previous polarization studies, cannot satisfactorily explain the infrared observations. Assuming a composition of 75% H2SO4, agreement is possible if an upper layer of smaller particles is added to the homogeneous cloud. This inhomogeneous cloud structure, however, is not in agreement with the polarization results. Other models, involving bimodal particle size distributions, were also unsuccessful in explaining both sets of observations in a consistent manner.

Martonchik, J. V.↗

Earthquake-triggered submarine canyon flushing transfers young terrestrial and marine organic carbon into the deep sea

Submarine canyons transfer substantial amounts of sediment and organic carbon (OC) into the deep ocean, nourishing deep-sea ecosystems and contributing to the global carbon cycle through OC burial and sequestration. Tracking lateral OC transport through submarine canyon systems is challenged by the deep-ocean setting, difficulties with constraining episodic depositional events, and the need to assess the composition and age of marine and terrestrial organic matter. We apply innovative parallel ramped pyrolysis oxidation accelerator mass spectrometry and pyrolysis-gas chromatography-mass spectrometry with isotope analyses to track OC age and sources in the 2016 Kaikoura earthquake-triggered, canyon-flushing event that deposited along >1300 km of a submarine canyon-channel system, offshore Aotearoa New Zealand. Specifically, these techniques allow us to determine the ages, sources, and partitioning of OC within the Kaikoura turbidite deposit and test hypotheses of how submarine canyon systems contribute to lateral OC flux and burial. Our results show that, despite considerable canyon floor erosion, substantial amounts of young OC were flushed into the deep sea, with relatively little (~2%) pre-Holocene OC contributions. Even without a direct connection between rivers and submarine canyons, most (~55%) of the OC in the Kaikoura event bed is from terrestrial sources. However, the deposit also contains substantial amounts (~22%) of marine-derived OC and ~23% of the material is of unassignable origin. Particle sorting imparts variability on the age and composition of OC within turbidite deposits and along the turbidity current flow path. Terrestrial-derived OC is preferentially older than marine-derived OC and concentrated in coarser particle sizes found more commonly at the deposit base and in proximal settings. Young, marine-derived OC is concentrated at the surface of the deposits and tends to be enriched in finer particle sizes. Such OC partitioning in turbidites supports the relevance of depositional models for predicting and quantifying distribution of OC in deep-sea deposits. Earthquake-triggered, canyon flushing events and resulting turbidites enhance OC burial efficiency and can sequester OC effectively, contributing an important carbon sink to the sedimentary carbon cycle.

54 ENVIRONMENTAL SCIENCES↗

Surface thermodynamics of yttrium titanate pyrochlore nanomaterials

Critical particle size can be determined with known surface energy. The surface enthalpy of yttrium titanate pyrochlores was determined to be 4.07 ± 0.32 J m −2 by calorimetry, and the lower limit of critical particle size for this is around 5.0 nm.

Reece, Margaret E.↗

Computer Modeling of Non-Isothermal Crystallization

A realistic computer model for simulating isothermal and non-isothermal phase transformations proceeding by homogeneous and heterogeneous nucleation and interface-limited growth is presented. A new treatment for particle size effects on the crystallization kinetics is developed and is incorporated into the numerical model. Time-dependent nucleation rates, size-dependent growth rates, and surface crystallization are also included. Model predictions are compared with experimental measurements of DSC/DTA peak parameters for the crystallization of lithium disilicate glass as a function of particle size, Pt doping levels, and water content. The quantitative agreement that is demonstrated indicates that the numerical model can be used to extract key kinetic data from easily obtained calorimetric data. The model can also be used to probe nucleation and growth behavior in regimes that are otherwise inaccessible. Based on a fit to data, an earlier prediction that the time-dependent nucleation rate in a DSC/DTA scan can rise above the steady-state value at a temperature higher than the peak in the steady-state rate is demonstrated.

Kelton, K. F.↗

Creep of plasma-sprayed-ZrO2 thermal-barrier coatings

Specimens of plasma-sprayed-zirconia thermal-barrier coatings with three different porosities and different initial particle sizes were deformed in compression at initial loads of 6900, 13,800, and 24,100 kPa (1000, 2000, and 3500 psi) and temperatures of 1100, 1250, and 1400 C. The coatings were stabilized with lime, MgO, and two different concentrations of Y2O3. Creep began as soon as the load was applied and continued at a constantly decreasing rate until the load was removed. Temperature and stabilization had a pronounced effect on creep rate while the stress, particle size, and porosity had a lesser effect. Creep deformation was due to cracking and particle sliding.

Firestone, R. F.↗

Corrosion-Resistant Non-Carbon Electrocatalyst Supports for PEFCS

Insufficient durability of commercial catalysts is a persistent issue for PEFC applications.1 Herein, Pt on Nb-doped-TiO 2 is reported as a highly durable electrocatalyst on which the direct 4-electron reduction of oxygen to water is more facile compared to Pt/C. All performance metrics are reported comparing Pt/Nb-TiO2 with a 15% Pt loading, against a commercial Pt/C catalyst (46.5% Pt loading, Tanaka, K. K.). Nb-doped-TiO 2 with high surface area and high electronic conductivity was synthesized using the supercritical fluid method. Initially, the durability of the catalyst was characterized using accelerated stability tests (ASTs) involving 10,000 high potential cycles (DOE/FCCJ protocol) and the Pt/Nb-TiO 2 was found to retain 78% of its initial electrochemically active surface area (ECSA) compared to the 57.6 % retained by Pt/C. These observations were in excellent agreement with previous reports that the Pt particle size of Pt/C grew from 2nm to 8nm during the AST protocol along with severe corrosion and amorphization of the carbon surface.2, 3 TEM and XPS studies of the Pt-Nb-doped-TiO 2 catalyst showed that the Pt particle size grew from 3nm to 6nm and the Nb(IV) and Ti(III) in the support were oxidized to Nb(V) and Ti(IV) after the durability test. Thus, the improvement in Pt/Nb-TiO 2 ECSA retention was attributed to the lower extent of particle growth and lack of oxidative support loss upon oxidation as compared to Pt/C. The oxygen reduction reaction (ORR) performance was characterized by linear polarization using a rotating disk electrode (RDE). The electrochemical surface areas of Pt/Nb-TiO 2 and Pt/C were found to be 48m2·g -1 and 83m2·g -1 respectively, and the mass activity for the ORR at 0.9V vs. RHE were found to be 150 mA·mg-1Pt and 124 mA·mg-1Pt respectively. The improved mass activity on Pt/Nb-TiO 2 was attributed to strong metal support interaction (SMSI) between the Nb-TiO 2 support and the Pt catalyst based on the 625 meV decrease in the binding energy of the Pt4f x-ray photo-electron spectroscopy (XPS) peaks of Pt/Nb-TiO 2 compared to Pt/C. To quantify the impact of the SMSI, a kinetic model was applied to calculate the elementary reaction rate constants for the various steps of the ORR on both catalysts. The reaction rate constant (k1) for the direct 4-electron transfer pathway to produce H 2 O was significantly larger in Pt/Nb-TiO 2 as compared to Pt/C. Thus, the reduction in the electron binding energy as observed in the XPS was found to aid the facile filling of the higher energy 2p orbitals of O 2 thereby leading to improved 4-electron transfer kinetics and improved overall activity.

08 HYDROGEN↗

Formation and Destruction Processes of Interstellar Dust: From Organic Molecules to carbonaceous Grains

The study of the formation and destruction processes of cosmic dust is essential to understand and to quantify the budget of extraterrestrial organic molecules. interstellar dust presents a continuous size distribution from large molecules, radicals and ions to nanometer-sized particles to micron-sized grains. The lower end of the dust size distribution is thought to be responsible for the ubiquitous spectral features that are seen in emission in the IR (UIBs) and in absorption in the visible (DIBs). The higher end of the dust-size distribution is thought to be responsible for the continuum emission plateau that is seen in the IR and for the strong absorption seen in the interstellar UV extinction curve. All these spectral signatures are characteristic of cosmic organic materials that are ubiquitous and present in various forms from gas-phase molecules to solid-state grains. Although dust with all its components plays an important role in the evolution of interstellar chemistry and in the formation of organic molecules, little is known on the formation and destruction processes of dust. Recent space observations in the UV (HST) and in the IR (ISO) help place size constraints on the molecular component of carbonaceous IS dust and indicate that small (ie., subnanometer) PAHs cannot contribute significantly to the IS features in the UV and in the IR. Studies of large molecular and nano-sized IS dust analogs formed from PAH precursors have been performed in our laboratory under conditions that simulate diffuse ISM environments (the particles are cold -100 K vibrational energy, isolated in the gas phase and exposed to a high-energy discharge environment in a cold plasma). The species (molecules, molecular fragments, ions, nanoparticles, etc) formed in the pulsed discharge nozzle (PDN) plasma source are detected with a high-sensitivity cavity ring-down spectrometer (CRDS). We will present new experimental results that indicate that nanoparticles are generated in the plasma. From these unique measurements, we derive information on the nature, the size and the structure of interstellar dust particles, the growth and the destruction processes of IS dust and the resulting budget of extraterrestrial organic molecules.

Salama, F.↗

Droplet and Particle Methods to Investigate Turbulent Particle Laden Jets

The SARS-CoV-2 pandemic has heightened the interest in particle-laden turbulent jets generated by breathing, talking, coughing and sneezing, and how these can contribute to disease transmission. We present quantitative measurement methods for such flows, while exploring and offering improvements for common shortcomings. We generate jets consisting of either liquid droplets or solid particles in an isothermal, quiescent and electrically isopotential experimental chamber that was constructed to control the effects of ambient forcing on jet behavior. For liquid droplets, we find promise in surface deposition analysis based on fluorescent tracer use. For particles, we explore the performance of commercially available adhesive sampling strips and develop conductive grounded carbon tape based sampling strips. We explore ways in which the smallest of thermal gradients or electrostatic charge issues can affect particle dispersion, and suggest practical methods to address these issues. The developed methods are applied to study the simultaneous deposition of (Formula presented.) 25, 50 and 200 μm solid particles from a particle laden turbulent jet with a mean velocity of 33.2 m/s. The deposition location as a function of particle size was compared to results from a simple numerical RANS model, and illustrates ways in which imprecise initial or boundary conditions can lead to a notable deviation from experimental results. The differences in deposition pattern seen in experimental and numerical results despite a carefully controlled environment and characterized particle ejection indicate the need for a more stringent numerical model validation, especially when studying fate and transport of mid-range (neither purely aerosol or ballistic) sized particles.

42 ENGINEERING↗

Designing the Platinum Catalyst Layer for Improved Performance and Durability in Anion Exchange Membrane Water Electrolysis

To lower the cost of hydrogen produced by anion exchange membrane water electrolysis (AEMWE), it is critical to reduce the use of platinum group metal (PGM) catalysts within the device. While iridium has been successfully replaced with PGM-free catalysts at the anode, platinum-based (Pt) cathode catalysts are still required to meet the activity and durability targets. This study investigates the impact of commercial Pt/C catalyst loading, ionomer type and content, and electrode fabrication method on the cathode catalyst layer properties and AEMWE performance with the aim of determining the feasibility of reduced Pt loadings. While increased Pt loading is found to improve beginning-of-life performance, the effects are minimal above 0.6 mg/cm 2 . Ink characterization shows that ionomer type and content affect the ink stability, particle size, and percent of unbound ionomer, which further impact the homogeneity of the sprayed catalyst layers. The 5% PiperION cathode exhibited the highest performance, which may be attributed to a balance between the small particle size and the low proportion of unbound ionomer, minimizing kinetic and transport losses. Theoretical calculations show that the ionomers interact differently with the Pt surface, causing different surface charges and water adsorption strength and activating different mechanisms for hydrogen evolution. Pt-PiperION lowered the enthalpy of water-splitting by 0.1 eV compared to Pt alone and allowed for equal site access between adsorbed H* and OH* (both adsorbed at circa −2.2 eV). Although catalyst-coated membrane (CCM) fabrication techniques are desirable for scale-up, no performance enhancement is observed compared with the catalyst-coated substrate approach. Durability, as measured by degradation rates, Pt loss, and catalyst layer restructuring, was found to improve with increased Pt loadings, higher ionomer content, and CCM architectures. These findings provide important insight into the significant role of the cathode in AEMWE and strategies for maintaining the performance with low Pt loading or PGM-free catalysts.

08 HYDROGEN↗

Characterizing Deposits Emplaced by Cryovolcanic Plumes on Europa

In the absence of direct observations of Europa’s particle plumes, deposits left behind during eruptive events would provide the best evidence for recent geological activity, and would serve as indicators of the best places to search for ongoing activity on the icy moon. Here, we model the morphological and spectral signatures of europan plume deposits, utilizing constraints from recent Hubble Space Telescope observations as model inputs. We consider deposits emplaced by plumes that are 1 km to 300 km tall, and find that in the time between the Galileo Mission and the arrival of the Europa Clipper spacecraft, plumes that are < 7 km tall are most likely to emplace deposits that could be detected by spacecraft cameras. Deposits emplaced by larger plumes could be detected by cameras operating at visible wavelengths provided that their average particle size is sufficiently large, their porosity is high, and/or they are salt-rich. Conversely, deposits emplaced by large plumes could be easily detected by near-IR imagers regardless of porosity, or individual particle size or composition. If low-albedo deposits flanking lineated features on Europa are indeed cryoclastic mantlings, they were likely emplaced by plumes that were less than 4 km tall, and deposition could be ongoing today. Comparisons of the sizes and albedos of these deposits between the Galileo and Europa Clipper missions could shed light on the size and frequency of cryovolcanic eruptions on Europa.

Lynnae C Quick↗

Characterizing Deposits Emplaced by Cryovolcanic Plumes on Europa

In the absence of direct observations of Europa’s particle plumes, deposits left behind during eruptive events would provide the best evidence for recent geological activity, and would serve as indicators of the best places to search for ongoing activity on the icy moon. Here, we model the morphological and spectral signatures of europan plume deposits, utilizing constraints from recent Hubble Space Telescope observations as model inputs. We consider deposits emplaced by plumes that are 1 km to 300 km tall, and find that in the time between the Galileo Mission and the arrival of the Europa Clipper spacecraft, plumes that are <7 km tall are most likely to emplace deposits that could be detected by spacecraft cameras. Deposits emplaced by larger plumes could be detected by cameras operating at visible wavelengths provided that their average particle size is sufficiently large, their porosity is high, and/or they are salt-rich. Conversely, deposits emplaced by large plumes could be easily detected by near-IR imagers regardless of porosity, or individual particle size or composition. If low-albedo deposits flanking lineated features on Europa are indeed cryoclastic mantlings, they were likely emplaced by plumes that were <4 km tall, and deposition could be ongoing today. Comparisons of the sizes and albedos of these deposits between the Galileo and Europa Clipper missions could shed light on the size and frequency of cryovolcanic eruptions on Europa.

Lynnae C Quick↗

Analysis of cloud polarization measurements

The polarization of sunlight reflected by various cloud types was measured in the near-infrared with a polarimeter flown aboard the NASA Convair 990. The data reduction has been completed and detailed comparisons have been made between the observations and theoretical computations. The analysis presented shows that the polarization in the near-infrared can be used on a routine basis to reliably yield the cloud particle phase (water or ice) and the average particle size in the top part of water clouds (usually within + or - 25%). In some cases the polarization also yields the cloud optical thickness (or a lower limit) and a measure of the width of the particle size distribution in the top of the water clouds.

Hansen, J. E.↗