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At least 469 records · Page 26

Multi-Cycle Cesium Ion Exchange Testing Using Spherical Resorcinol-Formaldehyde Resin with Diluted Hanford Tank Waste 241-AP-105

Washington River Protection Solutions requested that at least 4 L of Hanford tank waste collected from tank 241-AP-105 and diluted to approximately 5.6 M Na (AP-105DF) be prepared for use in vitrification studies. Cesium removal was required to meet this objective and the waste pretreatment platform, established at Pacific Northwest National Laboratory, was used to create the vitrification feed. The Test Platform mimicked the Low-Activity Waste Pretreatment System (LAWPS) facility planned to pretreat Hanford tank waste supernate by removing solids in a cross flow filter apparatus and processing the supernate through ion exchange columns to remove cesium. At the time of testing, the ion exchange media was targeted to be spherical resorcinol-formaldehyde (SRF) resin. The SRF resin has been tested with a wide array of simulants and process scales, but column performance testing with actual tank waste had been somewhat limited to two Hanford tank wastes (AP-101 and AN-102) in up to two process cycles. This report describes testing conducted in a total of six load elute cycles with the AP-105DF tank waste. The column system was first tested with simulant and was previously described; this report describes the six process cycle results with the AP-105DF tank waste.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Mark-18A Loading Capacity and Dilute Acid Rinse of DGA Resin

Savannah River National Laboratory is developing a separations flowsheet for the recovery of valuable elements from irradiated 242 Pu targets. The primary impetus for this effort is to recover the rich amount of 244 Pu contained in the targets, however, the targets also contain other valuable isotopes such as heavy Cm and 241,243 Am. DGA Resin, developed by Eichrom Technologies Inc., was selected to recover these materials from the 7 – 9 M HNO 3 matrix raffinate of the anion exchange process used to separate Pu. The resin has a high affinity for trivalent actinides and rare earth elements (REEs) in moderate to strong nitric acid. After loading the resin, the extracted materials (including Cm and Am) are to be recovered as oxides in a two-step process by thermally drying and reducing the mass and volume of the resin in the process column followed by calcination of the resultant residue. It is desirable to reduce the amount of residual HNO 3 in the resin bed prior to these furnace operations, but the reduced acid concentration is known to lower the distribution coefficients of the components of interest to the extractant. The purpose of this study was to validate the loading capacity of the resin and determine losses to be expected from rinsing the loaded resin with dilute HNO 3 .

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Metallic Phase-Free Zn-Al Mixed Oxide Dual Function Materials Enable High Co Selectivity in Reactive Carbon Capture From Dilute Streams

Scaling conventional carbon capture and utilization methods can be limited by cost and permitting issues associated with transportation of captured CO2. Reactive carbon capture (RCC), in which a single solid-phase dual function material (DFM) is used to both capture CO2 from dilute streams (e.g., flue gas) and catalytically convert the bound species to products in a single unit operation, has the potential to reduce energy and capital costs by over 50% relative to separate capture and conversion. To incentivize adoption, high-value products such as methanol and CO should be targeted. Appealingly, CO can be produced at atmospheric pressure, thereby lowering overall H2 demand; however, high reaction temperatures (> 600 degrees C) and the use of oxidizable transition metals, such as Ni, are often necessary to drive the reverse water-gas shift (RWGS) during reactive desorption of the bound CO2. The sensitivity of these transition metals to oxygen undercuts their utility in point source RCC. To further derisk RCC, it is essential to develop metallic-phase free DFMs that are insensitive to residual oxygen in flue gas and can achieve selective reactive desorption to CO at moderate pressures (< 400 degrees C). To this end, we have developed K-modified Zn-Al mixed oxides (K/ZnAlOx) to convert captured CO2 to CO with > 97% selectivity and yields up to 53% of captured CO2 at 400 degrees C. Complementary in situ spectroscopy studies revealed the role of K-modification in improving RCC performance of unmodified ZnAlOx. The top performing DFM was also subjected to extended RCC cycling with oxygen co-fed with CO2 during the capture test to assess durability under simulated flue gas.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of Dilute Magnetism in a Topological Insulator

Three-dimensional (3D) topological insulator (TI) has emerged as a unique state of quantum matter and generated enormous interests in condensed matter physics. The surfaces of a 3D TI consist of a massless Dirac cone, which is characterized by the Z 2 topological invariant. Introduction of magnetism on the surface of a TI is essential to realize the quantum anomalous Hall effect and other novel magneto-electric phenomena. Here, by using a combination of first-principles calculations, magneto-transport and angle-resolved photoemission spectroscopy (ARPES), we study the electronic properties of gadolinium (Gd)-doped Sb 2 Te 3 . Our study shows that Gd doped Sb 2 Te 3 is a spin-orbit-induced bulk band-gap material, whose surface is characterized by a single topological surface state. Our results provide a new platform to investigate the interactions between dilute magnetism and topology in magnetic doped topological materials.

36 MATERIALS SCIENCE↗

Investigating the Durability of Iodine Waste Forms in Dilute Conditions

To prevent the release of radioiodine during the reprocessing of used nuclear fuel or in the management of other wastes, many technologies have been developed for iodine capture. The capture is only part of the challenge as a durable waste form is required to ensure safe disposal of the radioiodine. This work presents the first durability studies in dilute conditions of two AgI-containing waste forms: hot-isostatically pressed silver mordenite (AgZ) and spark plasma sintered silver-functionalized silica aerogel (SFA) iodine waste forms (IWF). Using the single-pass flow-through (SPFT) test method, the dissolution rates respective to Si, Al, Ag and I were measured for variants of the IWFs. By combining solution and solid analysis information on the corrosion mechanism neutral-to-alkaline conditions was elucidated. The AgZ samples were observed to have corrosion preferentially occur at secondary phases with higher Al and alkali content. These phases contained a lower proportion of I compared with the matrix. The SFA samples experienced a higher extent of corrosion at Si-rich particles, but an increased addition of Si to the waste led to an improvement in corrosion resistance. The dissolution rates for the IWF types are of similar magnitude to other Si-based waste form materials measured using SPFT.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dilute Combustion Control Using Spiking Neural Networks

Dilute combustion with exhaust gas recirculation (EGR) in spark-ignition engines presents a cost-effective method for achieving higher levels of engine efficiency. At high levels of EGR, however, cycle-to-cycle variability (CCV) of the combustion process is exacerbated by sporadic occurrences of misfires and partial burns. Previous studies have shown that temporal deterministic patterns emerge at such conditions and certain combustion cycles have a significant influence over future events. Due to the complexity of the combustion process and the nature of CCV, harnessing all the deterministic information for control purposes has remained challenging even with physics based 0-D, 1-D, and high-fidelity computational fluid dynamics (CFD) models. In this study, we present a data-driven approach to optimize the combustion process by controlling CCV adjusting the cycle-to-cycle fuel injection quantity. Readily available data from in-cylinder pressure was used to train a spiking neural network (SNN) which learns the optimal way to manage fuel injection in order to reduce CCV while maintaining acceptable levels of fuel consumption. SNNs are particularly well suited for powertrain control applications due to their ability to be deployed on FPGA-based neuromorphic hardware which are small, inexpensive, and have a low power demand. The high-performance computing (HPC) resources of Oak Ridge National Laboratory were used to run an evolutionary-based training approach for choosing the best SNN configuration that minimizes the size of the network while achieving the desired goal. The neuromorphic hardware with the optimized SNN deployed was connected to the rapid prototyping engine control system for real-time control implementation and tested on a single cylinder version of a GM LNF 4-cylinder engine. The results show a significant reduction of CCV with a small percentage of additional fuel used to stabilize the charge.

33 ADVANCED PROPULSION SYSTEMS↗

Refinement of Pitting Factor Basis to Evaluate Minimum Nitrite Requirement in Dilute Waste Chemistries

Considering that chloride concentrations are an order of magnitude lower at SRS than the maximum chloride previously tested to evaluate pitting susceptibility of carbon steel, it has been proposed that the Pitting Factor methodology be refined to determine if a reduction in the minimum nitrite requirement is warranted in more dilute solutions and those with chloride concentrations more indicative of waste tank chemistries at SRS. Through the use of cyclic potentiodynamic polarization, the susceptibility of A537 carbon steel to pitting corrosion was evaluated. The Pitting Factor was shown to accurately predict pitting susceptibility throughout the chemistry envelope evaluated. In addition, it was shown that nitrite is not required for inhibition of pitting corrosion in tank conditions with chloride concentrations observed at SRS and up to 4 M nitrate. Based upon these findings, new control limits were proposed that removed the minimum nitrite requirement within the chemistry envelope evaluated up to 50 °C.

36 MATERIALS SCIENCE↗

Stepwise chemical abrasion–isotope dilution–thermal ionization mass spectrometry with trace element analysis of microfractured Hadean zircon

Abstract. The Hadean Jack Hills zircons represent the oldest known terrestrial material, providing a unique and truly direct record of Hadean Earth history. This zircon population has been extensively studied via high-spatial-resolution high-throughput in situ isotopic and elemental analysis techniques, such as secondary ionization mass spectrometry (SIMS), but not by comparatively destructive, high-temporal-precision (<0.05 % two-sigma) thermal ionization mass spectrometry (TIMS). In order to better understand the lead loss and alteration history of terrestrial Hadean zircons, we conduct stepwise chemical abrasion–isotope dilution–thermal ionization mass spectrometry with trace element analysis (CA-ID-TIMS-TEA) on manually microfractured Hadean Jack Hills zircon fragments previously dated by SIMS. We conducted three successive HF leaching steps on each individual zircon fragment, followed by column chromatography to isolate U–Pb and trace element fractions. Following isotopic and elemental analysis, the result is an independent age and trace element composition for each leachate of each zircon fragment. We observe ~50 Myr of age heterogeneity in concordant residues from a single zircon grain, along with a protracted history of post-Hadean Pb loss with at least two modes circa ~0 and 2–4 Ga. Meanwhile, stepwise leachate trace element chemistry reveals enrichments of light rare earth elements, uranium, thorium, and radiogenic lead in early leached domains relative to the zircon residue. In addition to confirming the efficacy of the LREE-I alteration index and providing new insight into the mechanism of chemical abrasion, the interpretation and reconciliation of these results suggest that Pb loss is largely driven by low-temperature aqueous recrystallization and that regional thermal events may act to halt – not initiate – Pb loss from metamict domains in the Hadean Jack Hills zircons.

Brenhin Keller, C. (ORCID:0000000174009428)↗

Crystallographically aligned 1.508 eV nitrogen pairs in ultra-dilute GaAs:N

Here, we measure polarized photoluminescence emitted from excitons bound to the 1.508 eV N-N impurity pairs in the ultra-dilute semiconductor alloy GaAs:N grown by both metalorganic chemical vapor deposition (MOCVD) and MBE. In MOCVD-grown GaAs:N, the pair orientation is random, with pairs equally distributed over the two equivalent directions in the growth plane. In contrast, MBE results in a highly uniform ensemble of in-plane pairs preferentially aligned in a single < 110 > direction, and the population of out-of-plane pairs reduced. The results are important for quantum control of N pair qubits where observable energy levels depend on pair orientation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗