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Laboratory-Scale Melter Systems for Simulated and Real AP-107 Tank Waste - 20483

The Hanford Waste Treatment and Immobilization Plant (WTP) will process and stabilize waste that is stored in underground tanks on the Hanford Site. At the WTP, the tank waste will be combined with glass-forming and modifying additives to form an aqueous and solid mixture called melter feed, which will then be vitrified in joule-heated melters. A small-scale melter system, the continuous laboratory-scale melter (CLSM), is designed to operate with a continuous feeding process while periodically pouring glass product and collecting off-gas. Two CLSMs were constructed: one in a non-radioactive environment for processing waste simulants and another in a fume hood capable of handling radioactive material for processing actual Hanford tank waste. The waste sample received for vitrification in the CLSM was from Hanford tank 241-AP-107. Approximately 12 liters of melter-feed slurry was vitrified into 7 kilograms of glass product over the course of 10 hours of charging to the CLSM. The partitioning of technetium-99 in the product streams was used to calculate the technetium-99 recovery and help determine when the vitrification process had reached a steady state. The average single-pass retention of technetium-99 in the glass product was then calculated for the processing of AP-107 waste in the CLSM system. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Low Count and Background Radionuclides Analysis - 20488

The US Department of Energy (DOE) is often faced with the need to evaluate radionuclides at low concentrations. When site sample data are likely to be close to threshold activity concentrations of interest, then the means by which the radiochemical analysis is performed and reported is critical. This situation can occur when differentiating from zero (presence/absence) for radionuclides that do not occur naturally, close comparison with environmental background for naturally occurring radionuclides, close comparison with a risk- or dose-based threshold concentrations of interest, or even comparisons across studies. There are several analytical issues that are of concern, but the two that appear to cause incorrect decisions to be made most often involve establishing detection limits and subtracting ambient background conditions in the laboratory. These issues are not critical when radionuclide activity concentrations are large relative to thresholds of concern, but they seem to be poorly understood when it matters. When the comparisons are important and are likely to be close to a threshold of interest, then the general contract with the analytical laboratories needs to be changed so that the right or appropriate data are obtained. The concern is that important decisions are made incorrectly more often as greater scrutiny is placed on DoE's radionuclide cleanup or monitoring decisions by the public and other stakeholders. Examples are presented of problems that have been observed for different projects, both within and outside the realm of DOE and NRC remediation and radioactive waste disposal problems, and solutions are offered that should lead to better data from which important decisions need to be made. The first example is from Los Alamos National Laboratory (LANL) and involves radionuclide concentrations in soil and rock beneath LANL's Material Disposal Area (MDA) G. An initial review of the data led to a conclusion that americium and plutonium are a long way present beneath MDA G. A more thorough review of the data that accounted properly for ambient background and the detection limits that had been established led to the opposite conclusion. Another example is from the Nevada National Security Site where tritium results from one of the wells were unexpectedly high. Proper understanding and analysis of ambient background led to the conclusion that the increased concentrations were not so obvious, and that a different contract with the analytical laboratory was needed to provide more appropriate data to support a better determination. Other examples are used from regulatory review of projects in Nevada, where background levels and secular equilibrium for naturally occurring radionuclides are not established correctly because of analytical issues. The same basic issues have also been found to create difficulties analyzing historical data from the West Valley Demonstration Project. There is evidence in the data that the apparent lack of secular equilibrium where it is expected to exist is related to ambient background subtraction or other analytical issues. A final example is presented for analysis of Tc-99 in samples of depleted uranium. In this case, two different studies that were performed only three months apart provide quite different results. The US Environmental Protection Agency (EPA) established the data quality objectives (DQO) process in the mid-1980's to establish decision performance criteria for data collection. EPA guidance (EPA G-4, for example) clearly distinguishes between DQOs and measurement performance objectives (MQOs) that should be addressed for laboratory analysis of samples. The language of DQOs and MQOs has become confused over time it seems, and the subsequent effects seem to include a lack of attention to decision performance and a routine approach to measurement quality. In order to better address radionuclide sample analysis when the concentrations are close to thresholds of concern, which might be zero for some radionuclides, background for others, and risk-based thresholds for yet others, it is important that routine laboratory analysis methods are adjusted, and that the project team and the laboratory work closely together to ensure that the data meets the MQO requirements of laboratory analysis and reporting of results, and that the MQOs effectively support project-specific DQOs. This basic approach will be applied in Los Alamos in the coming year to the collection of moisture data from underneath MDA T that will be analyzed for americium and neptunium isotopes. Proper understanding of the radiochemistry methods and reporting, and of appropriate statistical methods is critical to the success of such projects, ensuring that the right decisions are made. (authors)

07 ISOTOPE AND RADIATION SOURCES↗

Hydrophobic amine-based binary mixtures of active pharmaceutical and food grade ingredients: characterization and application in indium extraction from aqueous hydrochloric acid media

The wide spread use of hazardous and expensive solvents for the liquid-liquid extraction (LLE) of critical metals has been a growing source of waste in the metal refinement industry. We have developed and characterized room temperature liquid hydrophobic binary mixtures based on common pharmaceutical and food grade compounds as sustainable, cost effective alternatives to both ionic liquids and conventional solvents. Additionally, we introduce liquid mixtures with Proton Sponge® (1,8-bis(dimethylamino)naphthalene), one of the strongest known organic bases. These mixtures have been applied to the LLE of indium(III) ions from hydrochloric acid solutions, displaying an extraction efficiency greater than 99% in some systems. Here, a systematic approach to identifying the underlying mechanism of extraction, in particular relating to the charge, solubility, and complexation of the indium species in the organic phase has been developed.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Syntheses of gold supported on metal oxides and their application in organic transformations

Herein, we report a general and straightforward synthesis method for gold supported on mesoporous and microporous metal oxides. Supported materials, in general, show higher crystallinity compare to unsupported systems as verified through powder X-ray diffraction (XRD). Also, through XRD, most of the metal is observed to be in its oxide form, whereas the gold support was found to be in its metallic state, which has been further confirmed from TEM. In terms of surface area, the catalyst was not found to follow any trend. Morphology wise, there are no changes observed after doping except in few cases. Combined results from XRD, X-ray fluorescence spectroscopy, Auger, and X-ray photoelectron spectroscopy suggest that gold is mainly in the bulk and very little (0.04% in case of gold doped calcium oxide) or non (in case of gold doped mixed manganese-cerium oxide) on the surface. The presence of Au (0) 4f peaks in XPS further confirms the metallic state of the gold. Oxides of indium, magnesium and calcium have been studied for the organic transformation reactions. An enhancement in activity and product selectivity was observed in the case of the gold supported catalysts. Indium serves as a great catalyst for C–C coupling and electrophilic aromatic substitution reactions and gives >99% conversion. Interestingly, 88% selectivity for C–C coupling and >99% selectivity for aromatic substitution have been achieved at 100 °C and room temperature respectively. Magnesium and calcium give Knoevenagel condensation products. At room temperature with very low catalyst loading, >99% conversion and selectivity were observed for the Knoevenagel reaction with as high as 35.30 TOF. Finally, a mechanism for the C–C coupling reaction has been proposed based on these results.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

jasonSWIR Calibration of Spectralon Reflectance Factor

Satellite instruments operating in the reflective solar wavelength region require accurate and precise determination of the Bidirectional Reflectance Factor (BRF) of laboratory-based diffusers used in their pre-flight and on-orbit radiometric calibrations. BRF measurements are required throughout the reflected-solar spectrum from the ultraviolet through the shortwave infrared. Spectralon diffusers are commonly used as a reflectance standard for bidirectional and hemispherical geometries. The Diffuser Calibration Laboratory (DCaL) at NASA's Goddard Space Flight Center is a secondary calibration facility with reflectance measurements traceable to those made by the Spectral Tri-function Automated Reference Reflectometer (STARR) facility at the National Institute of Standards and Technology (NIST). For more than two decades, the DCaL has provided numerous NASA projects with BRF data in the ultraviolet (UV), visible (VIS) and the Near infraRed (NIR) spectral regions. Presented in this paper are measurements of BRF from 1475nm to 1625nm obtained using an indium gallium arsenide detector and a tunable coherent light source. The sample was a 2 inch diameter, 99% white Spectralon target. The BRF results are discussed and compared to empirically generated data from a model based on NIST certified values of 6deg directional/hemispherical spectral reflectance factors from 900nm to 2500nm. Employing a new NIST capability for measuring bidirectional reflectance using a cooled, extended InGaAs detector, BRF calibration measurements of the same sample were also made using NIST's STARR from 1475nm to 1625nm at an incident angle of 0deg and at viewing angles of 40deg, 45deg, and 50deg. The total combined uncertainty for BRF in this ShortWave Infrared (SWIR) range is less than 1%. This measurement capability will evolve into a BRF calibration service in SWIR region in support of NASA remote sensing missions. Keywords: BRF, BRDF, Calibration, Spectralon, Reflectance, Remote Sensing.

Georgiev, Georgi T.↗

Electrospray Thruster Performance with Microfabricated Emitter Arrays and Indium Propellant

The feasibility of a microfabricated indium-fueled electrospray thruster with excellent performance was demonstrated. High efficiency electrospray thrusters with microfabricated components are under development for very compact, distributable propulsion systems that can be employed on both very small and large spacecraft with 10X improvement over SOA in mass, volume and specific impulse The critical components of this technology are the microfabricated emitter arrays and the capillary force driven indium feed system. Grey scale electron-beam lithography patterning and reactive ion dry etching provided the required micron-scale etch precision and uniformity across an array of 400 emitters in 1 cm2. Initial tests of single microfabricated silicon emitters demonstrated better performance than industry standard single emitters and the performance required to achieve 200 micronewtons when scaled up to a thruster with 400 emitters in 1 cm2. Arrays of emitters tested in a preliminary prototype Microfluidic Electrospray Propulsion (MEP) thruster assembly demonstrated stable performance at estimated thrust levels of 5, 50, and 120 µN at extraction voltages less than 4 kV. Current stability was within 0.15 % at 120 µN with only 1.5% of the emitter current collected by the extractor electrode. Post-test inspections revealed that more than 99% of the 400 emitters were electrospraying during the test. Specific impulse was estimated to be >3100 s from measurements of total charge and consumed indium mass at an emitter voltage of 1470 V. The results of this investigation suggest that microfabricated indium electrospray thruster technology is both feasible and capable of excellent performance as a highly compact microthruster.

Marrese-Reading, Colleen M.↗

Combined Stress Testing of Perovskite Solar Cells for Stable Operation in Space

Perovskite solar cells (PSCs) could provide new low-cost opportunities for powering spacecraft. Here we are designing a PSC resilient to lunar surface conditions, focusing on contact/barrier layers combinations that maximize stability. Thermal vacuum stress shows cells with gold back-contacts and SiOx protection retain >90% of initial efficiency and indium tin oxide (ITO)-contacted cells retain ~100% of initial efficiency after five months of stress. SiO x mitigates mechanical aspects of contact stress, retaining 99% of initial efficiency, whereas cells with silicone/cover glass decreased 27%. We further exposed cells to combined illumination, 75 °C heat, and 10 -6 Torr vacuum for 24 h and found that ITO-contacted cells outperformed Au-contacted cells.

14 SOLAR ENERGY↗

12.3% Efficient Lifted-Off and Reconstructed As-Doped CdTe Thin Film Solar Cell

CdTe:As devices grown by MOCVD in the superstrate configuration have been reconfigured to a substrate structure, by employing a cleaving and reconstruction technique. Indium and aluminium doped Zinc oxide (IZO and AZO) layers were used as the transparent front interface without a metal grid. A substrate efficiency of 12.3% was realized with AZO front contact, retaining 80% of the superstrate device efficiency and an impressive approximately 99% of the open-circuit voltage. The IZO-based substrate device on the other hand performed at approximately 69 % retained efficiency. The crucial role of front interfaces is highlighted by the two contacts used here. The results in this work show promise for the development of highly efficient substrate CdTe:As devices.

II-VI semiconductor materials↗

Spectralon BRDF and DHR Measurements in Support of Satellite Instruments Operating Through Shortwave Infrared

Satellite instruments operating in the reflective solar wavelength region require accurate and precise determination of the Bidirectional Reflectance Distribution Functions (BRDFs) of the laboratory and flight diffusers used in their pre-flight and on-orbit calibrations. This paper advances that initial work and presents a comparison of spectral Bidirectional Reflectance Distribution Function (BRDF) and Directional Hemispherical Reflectance (DHR) of Spectralon*, a common material for laboratory and onorbit flight diffusers. A new measurement setup for BRDF measurements from 900 nm to 2500 nm located at NASA Goddard Space Flight Center (GSFC) is described. The GSFC setup employs an extended indium gallium arsenide detector, bandpass filters, and a supercontinuum light source. Comparisons of the GSFC BRDF measurements in the ShortWave InfraRed (SWIR) with those made by the NIST Spectral Trifunction Automated Reference Reflectometer (STARR) are presented. The Spectralon sample used in this study was 2 inch diameter, 99% white pressed and sintered Polytetrafluoroethylene (PTFE) target. The NASA/NIST BRDF comparison measurements were made at an incident angle of 0 deg and viewing angle of 45 deg. Additional BRDF data not compared to NIST were measured at additional incident and viewing angle geometries and are not presented here The total combined uncertainty for the measurement of BRDF in the SWIR range made by the GSFC scatterometer is less than 1% (k=1). This study is in support of the calibration of the Joint Polar Satellite System (JPSS) Radiation Budget Instrument (RBI) and Visible Infrared Imaging Radiometer Suite (VIIRS) of and other current and future NASA remote sensing missions operating across the reflected solar wavelength region.

Georgiev, Georgi T.↗

History and Flight Devleopment of the Electrodynamic Dust Shield

The surfaces of the moon, Mars, and that of some asteroids are covered with a layer of dust that may hinder robotic and human exploration missions. During the Apollo missions, for example, lunar dust caused a number of issues including vision obscuration, false instrument readings, contamination, and elevated temperatures. In fact, some equipment neared failure after only 75 hours on the lunar surface due to effects of lunar dust. NASA's Kennedy Space Center has developed an active technology to remove dust from surfaces during exploration missions. The Electrodynamic Dust Shield (EDS), which consists of a series of embedded electrodes in a high dielectric strength substrate, uses a low power, low frequency signal that produces an electric field wave that travels across the surface. This non-uniform electric field generates dielectrophoretic and electrostatic forces capable of moving dust out of these surfaces. Implementations of the EDS have been developed for solar radiators, optical systems, camera lenses, visors, windows, thermal radiators, and fabrics The EDS implementation for transparent applications (solar panels, optical systems, windows, etc.) uses transparent indium tin oxide electrodes on glass or transparent lm. Extensive testing was performed in a roughly simulated lunar environment (one-sixth gravity at 1 mPa atmospheric pressure) with lunar simulant dust. EDS panels over solar radiators showed dust removal that restored solar panel output reaching values very close to their initial output. EDS implementations for thermal radiator protection (metallic spacecraft surfaces with white thermal paint and reflective films) were also extensively tested at similar high vacuum conditions. Reflectance spectra for these types of implementations showed dust removal efficiencies in the 96% to 99% range. These tests indicate that the EDS technology is now at a Technology Readiness Level of 4 to 5. As part of EDS development, a flight version is being prepared for several flight opportunities. The flight version of the EDS will incorporate significantly smaller electronics, with an expected mass and volume of 500 g and 350 cm(exp. 3) respectively. One of the opportunities is an International Space Station (ISS) experiment: Materials for International Space Station Experiment 10 (MISSE-10). This experiment aims to verify the EDS can withstand the harsh environment of space and will look to closely replicate the solar environment experienced on the moon. A second flight opportunity exists to provide an EDS to several companies as part of NASA's Lunar CATALYST program. The current mission concept would fly the EDS on the footpad of one of the Lunar CATALYST vehicles. Dust will likely deposit on the footpad through normal surface rover activities, but also upon landing where lunar dust is expected to be uplifted. To analyze the e effectiveness of the EDS system, photographs of the footpad with one of the spacecrafts onboard cameras are anticipated. If successful in these test flights, the EDS technology will be ready to be used in the protection of actual mission equipment for future NASA and commercial missions to the moon, asteroids, and Mars.

Lunar↗

Impact of Host Flexibility on Selectivity in a Supramolecular Host-Catalyzed Enantioselective aza-Darzens Reaction

A highly enantioselective aza-Darzens reaction (up to 99% ee) catalyzed by an enantiopure supramolecular host has been discovered. To understand the role of host structure on reaction outcome, nine new gallium(III)-based enantiopure supramolecular assemblies were prepared via substitution of the external chiral amide. Despite the distal nature of the substitution in these catalysts, changes in enantioselectivity (61 to 90% ee) in the aziridine product were observed. The enantioselectivities were correlated to the flexibility of the supramolecular host scaffold as measured by the kinetics of exchange of a model cationic guest. Finally, this correlation led to the development of a best-in-class catalyst by substituting the gallium(III)-based host with one based on indium(III), which generated the most flexible and selective catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗