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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2011

Cosmic Ray Interactions in Shielding Materials

This document provides a detailed study of materials used to shield against the hadronic particles from cosmic ray showers at Earth’s surface. This work was motivated by the need for a shield that minimizes activation of the enriched germanium during transport for the MAJORANA collaboration. The materials suitable for cosmic-ray shield design are materials such as lead and iron that will stop the primary protons, and materials like polyethylene, borated polyethylene, concrete and water that will stop the induced neutrons. The interaction of the different cosmic-ray components at ground level (protons, neutrons, muons) with their wide energy range (from kilo-electron volts to giga-electron volts) is a complex calculation. Monte Carlo calculations have proven to be a suitable tool for the simulation of nucleon transport, including hadron interactions and radioactive isotope production. The industry standard Monte Carlo simulation tool, Geant4, was used for this study. The result of this study is the assertion that activation at Earth’s surface is a result of the neutronic and protonic components of the cosmic-ray shower. The best material to shield against these cosmic-ray components is iron, which has the best combination of primary shielding and minimal secondary neutron production.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2013

Uniform and Half‐Space Models for Magnetic Dipole Sources in a Conducting Medium: I. Theory and Results

Underground nuclear events result in electromagnetic signals near the event location. Of particular interest, because its signal can be potentially enhanced by the use of large cavities to decouple the seismic signal, is the generation of an EMP signal within the nuclear detonation (NUDET) cavity, from the formation of a bubble in the local magnetic field. This mechanism is equivalent to a buried time varying magnetic dipole. In order to model such signals Los Alamos National Laboratory is developing a detailed model for the propagation of RF signals from buried sources to nearby sensors, with a focus on sources that are magnetic dipole in character. In order to validate this code, models for simple geometries involving magnetic dipole sources have been implemented. These models represent the fields from vertical and horizontal dipoles in cylindrical coordinates, either in a uniform linear isotropic electrical medium, or in a space consisting of two half spaces interfacing at the plane z=0, with the upper half space having the electrical properties of free space and the lower half space having arbitrary linear conductivity and electrical permittivity. While primarily intended for the validation of the more detailed model, the shorter turnaround time of these models facilitates the study of the general properties of geomagnetic bubble signals. This report summarizes the theory and example results for those models. The use of the model for model validation is illustrated with the near and surface fields for dipoles with Gaussian time dependence. Also examined are the surface fields expected for the geomagnetic bubble predicted by the numerical model of Kovalenko et al for a 1 kt nuclear detonation. The model of Kovalenko et al was also rescaled to allow comparison with Zablocki’s electric field observations for Bilby, Event III, and Event V. While the rescaled Kovalenko et al model had approximately the right time scale for the duration of the main peak, and a slower fall than rise also in qualitative agreement with the observations, the predicted signals had very different polarizations, were too low by more than an order of magnitude, and had less temporal structure. A simple comparison with the vertical B field data of Sweeney, where the detailed event geometries and yields are classified, but the sensor range and bounds on the yields are given, suggest that the scaled Kovalenko et al model gives too small a peak field compared to observations for that data set as well, except perhaps for the Borate event. A companion report will give a detailed discussion of the implementation and code.

58 GEOSCIENCES↗
DOE OSTI2012

Reactor Engineering: Experimental Investigation of Alpha Convection

This report summarizes the progress on DE-FG07-07ID14806 project funded by the US Department of Energy under Nuclear Engineering Education Research (NEER) program. During the project a test apparatus was designed and manufactured for experimental investigation of Alpha Convection. Benchmark testing of the new apparatus without the neutron radiation was performed and numerical simulations were conducted to validate the experimental results on natural convection. These results were reported in a journal publication. Subsequently, we conducted the experiment at Missouri S&T research reactor in the beam port to investigate the phenomenon of Alpha Convection. Unfortunately, these experiments were inconclusive. No observable effect of neutron beam was noticed. Insufficient neutron flux as it passes through the borated water is responsible for the unsuccessful experiments. A number of new experiments are designed and manufactured to investigate the phenomenon. A new experiment using shadowgraphy is designed and manufactured to investigate and visualize the natural convection and the impact of neutron on the phenomenon. Moreover, to continue with the original and newly designed experiments a neutron generator was needed to supply a vertical beam of neutrons. This new source of neutron is acquired using DOE NEUP General Scientific Infrastructure number DE-FOA-0000321. The new facility is installed and tested but is yet to be licensed by NRC for regular use and continuation of the experiments.

Conduction convection transition.↗
DOE OSTI2012

Applying Human Factors Evaluation and Design Guidance to a Nuclear Power Plant Digital Control System

The United States (U.S.) nuclear industry, like similar process control industries, has moved toward upgrading its control rooms. The upgraded control rooms typically feature digital control system (DCS) displays embedded in the panels. These displays gather information from the system and represent that information on a single display surface. In this manner, the DCS combines many previously separate analog indicators and controls into a single digital display, whereby the operators can toggle between multiple windows to monitor and control different aspects of the plant. The design of the DCS depends on the function of the system it monitors, but revolves around presenting the information most germane to an operator at any point in time. DCSs require a carefully designed human system interface. This report centers on redesigning existing DCS displays for an example chemical volume control system (CVCS) at a U.S. nuclear power plant. The crucial nature of the CVCS, which controls coolant levels and boration in the primary system, requires a thorough human factors evaluation of its supporting DCS. The initial digital controls being developed for the DCSs tend to directly mimic the former analog controls. There are, however, unique operator interactions with a digital vs. analog interface, and the differences have not always been carefully factored in the translation of an analog interface to a replacement DCS. To ensure safety, efficiency, and usability of the emerging DCSs, a human factors usability evaluation was conducted on a CVCS DCS currently being used and refined at an existing U.S. nuclear power plant. Subject matter experts from process control engineering, software development, and human factors evaluated the DCS displays to document potential usability issues and propose design recommendations. The evaluation yielded 167 potential usability issues with the DCS. These issues should not be considered operator performance problems but rather opportunities identified by experts to improve upon the design of the DCS. A set of nine design recommendations was developed to address these potential issues. The design principles addressed the following areas: (1) color, (2) pop-up window structure, (3) navigation, (4) alarms, (5) process control diagram, (6) gestalt grouping, (7) typography, (8) terminology, and (9) data entry. Visuals illustrating the improved DCS displays accompany the design recommendations. These nine design principles serve as the starting point to a planned general DCS style guide that can be used across the U.S. nuclear industry to aid in the future design of effective DCS interfaces.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2013

Electrophilic Metal Alkyl Chemistry in New Ligand Environments

The goals of this project were to design new electrophilic metal alkyl complexes and to exploit these systems in fundamental studies of olefin polymerization and other important and new catalytic reactions. A key target reaction is insertion copolymerization of olefins and polar CH 2 =CHX vinyl monomers such as vinyl halides and vinyl ethers. During the period covered by this report we (i) investigated the properties of ortho-alkoxy-arylphosphine ligands in Ni-based olefin polymerization catalysts, (ii) studied the synthesis of double-end-capped polyethylene using group 4 metal catalysts that contain tris-pyrazolylborate ligands, (iii) explored the ethylene insertion reactivity of group 4 metal tris-pyrazolyl-borate complexes, (iv) showed that (α- diimine)PdMe + species undergo multiple insertion of silyl vinyl ethers, (v) synthesized and explored the reactivity of base-free Ni benzyl complexes that contain ortho-phosphino-arene sulfonate ligands, (vi) established the mechanism of the reaction of vinyl chloride with (α- diimine)PdMe + catalysts, (vii) explored the role of cationic polymerization and insertion chemistry in the reactions of vinyl ethers with (α-diimine)PdMe + species, (viii) discovered a new class of self-assembled tetranuclear Pd catalysts that produce high molecular weight linear polyethylene and copolymerize ethylene and vinyl fluoride, and (ix) developed model systems that enabled investigation of cis-trans isomerization of {phosphine-sulfonate}Pd(II) complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Estimating of pulsed electric fields using optical measurements.

We performed optical electric field measurements ion nanosecond time scales using the electro optic crystal beta barium borate (BBO). Tests were based on a preliminary bench top design intended to be a proof of principle stepping stone towards a modular design optical E field diagnostic that has no metal in the interrogated environment. The long term goal is to field a modular version of the diagnostic in experiments on large scale x ray source facilities, or similarly harsh environments.

Flanagan, Timothy McGuire↗
DOE OSTI2014

Materials for Consideration in Standardized Canister Design Activities.

This document identifies materials and material mitigation processes that might be used in new designs for standardized canisters for storage, transportation, and disposal of spent nuclear fuel. It also addresses potential corrosion issues with existing dual-purpose canisters (DPCs) that could be addressed in new canister designs. The major potential corrosion risk during storage is stress corrosion cracking of the weld regions on the 304 SS/316 SS canister shell due to deliquescence of chloride salts on the surface. Two approaches are proposed to alleviate this potential risk. First, the existing canister materials (304 and 316 SS) could be used, but the welds mitigated to relieve residual stresses and/or sensitization. Alternatively, more corrosion-resistant steels such as super-austenitic or duplex stainless steels, could be used. Experimental testing is needed to verify that these alternatives would successfully reduce the risk of stress corrosion cracking during fuel storage. For disposal in a geologic repository, the canister will be enclosed in a corrosion-resistant or corrosion-allowance overpack that will provide barrier capability and mechanical strength. The canister shell will no longer have a barrier function and its containment integrity can be ignored. The basket and neutron absorbers within the canister have the important role of limiting the possibility of post-closure criticality. The time period for corrosion is much longer in the post-closure period, and one major unanswered question is whether the basket materials will corrode slowly enough to maintain structural integrity for at least 10,000 years. Whereas there is extensive literature on stainless steels, this evaluation recommends testing of 304 and 316 SS, and more corrosion-resistant steels such as super-austenitic, duplex, and super-duplex stainless steels, at repository-relevant physical and chemical conditions. Both general and localized corrosion testing methods would be used to establish corrosion rates and component lifetimes. Finally, it is unlikely that the aluminum-based neutron absorber materials that are commonly used in existing DPCs would survive for 10,000 years in disposal environments, because the aluminum will act as a sacrificial anode for the steel. We recommend additional testing of borated and Gd-bearing stainless steels, to establish general and localized corrosion resistance in repository-relevant environmental conditions.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2014

Novel Electrolytes for Lithium Ion Batteries

We have been investigating three primary areas related to lithium ion battery electrolytes. First, we have been investigating the thermal stability of novel electrolytes for lithium ion batteries, in particular borate based salts. Second, we have been investigating novel additives to improve the calendar life of lithium ion batteries. Third, we have been investigating the thermal decomposition reactions of electrolytes for lithium-oxygen batteries.

25 ENERGY STORAGE↗
DOE OSTI2014

HFIR Dissolution Nuclear Criticality Analysis Information

H-Canyon Nuclear and Criticality Safety Engineering has completed development of the documentation necessary to complete the September 30, 2014, H-Canyon PBI milestone that states: Complete the analytical work to develop proposed HFIR Criticality Safety Limits associated with receipt and dissolving of HFIR material. Attached to this memorandum are the following: (1) Attachment 1- HFIR Dissolution Nuclear Criticality Analysis; (2) Attachment 2 - SCALE 5/KENO VI sample input As documented in Attachment 1, the safety of HFIR dissolution in H-Canyon has been evaluated. Due to the composition and geometry of the HFIR elements and the chemistry of the dissolution process, there are no credible criticality events associated with HFIR dissolution, with the exception of potential Pu polymerization. There are no mass, concentration, or soluble poison CSLs required for HFIR dissolution in H-Canyon. If SRNL, in the development of the HFIR flow sheet, determines that Pu polymerization is a credible event, a minimum nitric acid PPL and controls will be developed. However, there is no analysis or CSLs needed for this event. The boron in the borated stainless steel posts is not required, and, therefore, blackness testing is not required for criticality safety.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2017

Candidate Low-Temperature Glass Waste Forms for Technetium-99 Recovered from Hanford Effluent Management Facility Evaporator Concentrate

Alternative treatment and disposition options may exist for technetium-99 (99Tc) in secondary liquid waste from the Hanford Direct-Feed Low-Activity Waste (DFLAW) process. One approach includes development of an alternate glass waste form that is suitable for on-site disposition of technetium, including salts and other species recovered by ion exchange or precipitation from the EMF evaporator concentrate. By recovering the Tc content from the stream, and not recycling the treated concentrate, the DFLAW process can potentially be operated in a more efficient manner that lowers the cost to the Department of Energy. This report provides a survey of candidate glass formulations and glass-making processes that can potentially incorporate technetium at temperatures <700 °C to avoid volatilization. Three candidate technetium feed streams are considered: (1) dilute sodium pertechnetate loaded on a non-elutable ion exchange resin; (2) dilute sodium-bearing aqueous eluent from ion exchange recovery of pertechnetate, or (3) technetium(IV) oxide precipitate containing Sn and Cr solids in an aqueous slurry. From the technical literature, promising candidate glasses are identified based on their processing temperatures and chemical durability data. The suitability and technical risk of three low-temperature glass processing routes (vitrification, encapsulation by sintering into a glass composite material, and sol-gel chemical condensation) for the three waste streams was assessed, based on available low-temperature glass data. For a subset of candidate glasses, their long-term thermodynamic behavior with exposure to water and oxygen was modeled using Geochemist’s Workbench, with and without addition of reducing stannous ion. For further evaluation and development, encapsulation of precipitated TcO2/Sn/Cr in a glass composite material based on lead-free sealing glasses is recommended as a high priority. Vitrification of pertechnetate in aqueous anion exchange eluent solution using a high lead content borate glass, or other low melting glass is also recommended for further evaluation and development. Additional laboratory studies of phase behavior and chemical durability of low-temperature glasses is also recommended to provide risk mitigation if one of the primary development paths proves infeasible. This report is a deliverable for the task “Candidate Low-T Glass Waste Forms for EMF Bottoms On-Site Disposition Alternative Option.”

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2019

Novel, Low-Cost, Light-Weight High Efficiency (H*10 Capable) Neutron Detector-Dosimeter

The goal of this project was to design, develop and validate a novel, spectroscopy enabled H*(10) neutron dosimetry system based on the tensioned metastable fluid detector (TMFD) sensor technology. The project team consisted of staff from Oak Ridge National Laboratory (ORNL), Purdue University (PU) and Sagamore Adams Laboratories, LLC (SAL). PU-SAL staff were tasked with the design, development, construction and testing of the H*TMFD hardware and software, along with developing the control and data acquisition software for comparison of predictions from H*TMFD against a commonly accepted and widely used industry standard system; for this project, the Li-I detector coupled to bonner spheres (LiI-BSS) system manufactured by Ludlum, Inc. was utilized as the reference (“gold”) standard – similar in terms of neutron spectroscopy enablement to another industry recognized, albeit, significantly higher cost (est. $300K) system referred to as “ROSPEC” (from BTI, Inc., which was not available for this project). ORNL staff were tasked with providing field-relevant guidance, apparatus and facilities for acquiring data against calibrated neutron sources, and comparing results of H*TMFD against LiI-BSS system predictions in a series of blind-tests conducted at ORNL. Over the course of 12 months, the PU-SAL-ORNL staff successfully accomplished the proposed technical and administrative tasks, inclusive of engaging in outreach to potential users of this technology in the DOE-wide infrastructure. The proposed tasks were successfully accomplished in timely manner; the follow-up type tasks pertaining to SBIR type Phases 2-3 were discussed and are initiated, inclusive of filing for intellectual property (IP) disclosures and possible patent filings by PU’s Office of Technology Commercialization (OTC). Two H*TMFD system architectures (see Exhibits 1 & 2 in the report) were developed and constructed for hand-portability by health-physicists (HPs) – the HP-H*TMFD, and the H*TMFD system which consists of a side-by-side mounted array of 4 TMFDs of 3 different sizes in sensitive volume (including one with borated fluid) that now simultaneously enables neutron energy spectroscopy: single bin for < 0.1 MeV, and 152 energy bins in the 0.1-15.2 MeV range; H*(10) dosimetry from ~5 μRem/h towards 10 R/h ranges. Several experiments were conducted using neutron sources in various configurations (shielded and unshielded). In direct comparison against the LiI-BSS industry standard (acquiring data for 26h each source), the H*TMFD system (acquiring data for ~6h for each source) offered H*(10) dose predictions for the most part accurate to within +/-10% for dose rates in the 100-300 μRem/h range. The LiI-BSS was impractical to use under ultra-low (~10 μRem/h) dose rate space, as also another metering device used at ORNL (Ludlum 4241L non-spectroscopy enabled) for which the lower limit is set by the manufacturer at 100 μRem/h. The enablement for efficient use in timely manner at the 10 μRem/h levels is deemed to be a strong enabling factor for H*TMFD for use in the DOE-nuclear laboratory arena. In terms of weight, the HP-H*TMFD weighs under ~5-7 lb.; the H*TMFD system weighs ~35-lb. As such, it is ~1/4 the weight of an LiI-BSS system weighing ~120 lb (LiI detector with 6 bonner spheres) and, ~1/2 the weight of ROSPEC. As a result of this activity, two involved post-doctoral student staff have now transitioned their knowledge and experiences to DOE’s Pacific Northwest National Laboratory (PNNL). A PU graduate student has also benefited from this project work which formed a principal basis for his Ph.D. dissertation work (in progress).

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2021

Upgrade of the Materials Analysis Particle Probe (MAPP-U) to decipher the impact of lithium-based surfaces on NSTX-U plasma behavior

Understanding the plasma wall interaction (PWI) remains a critical issue for the feasibility of thermonuclear magnetic fusion energy solutions. Key issues with PWI mechanisms in fusion tokamak reactors include: evolution of surface chemistry and its role on hydrogen retention. In particular how low-Z coatings such as lithium can impact the behavior of plasma at the edge and in the core. PMI (plasma-material interactions) are particularly important for strategies that involve low-recycling regimes and the use of lithium PFS (plasma-facing surfaces) to attain them, as in the case of NSTX-U. Recent reports have indicated the importance of access to the evolving plasma-facing surface during and in-between plasma discharges. Changes in surface chemistry and morphology due to ion bombardment and the difficulty of diagnosing plasma-facing surfaces, especially reactive surfaces, complicate the development of a predictive understanding of the wall and its interaction with the plasma. Consequently, this impairs the ability to design advanced PFC materials for future plasma-burning fusion reactors and appropriate PMI code validation. The Materials Analysis Particle Probe (MAPP) is an established and on-going PMI probe diagnostic system compatible with the highly chemically reactive system of lithium and boron coatings adopted by the NSTX-U research program. MAPP is the first PMI diagnostic to capture the surface physics and chemistry in-vacuo in a fusion tokamak system and correlate this data to controlled plasma shots. Currently MAPP captures this information at a fixed radial location at the NSTX-U outboard divertor region. The MAPP diagnostic has enabled understanding of the near-surface and surface chemistry of complex evolving lithiated and borated carbon-based PFC surfaces retention and transport of hydrogen. Coupled to atomistic simulations in collaboration with P. Krstic of Stony Brook U. MAPP has been very successful in achieving high-impact scientific research in its current grant period evidenced by two invited review articles and over 20 peer-reviewed manuscripts and over 40 contributed and invited presentations at both national and international conferences.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2019

Criticality Accident Alarm System Shielding Benchmark: Integral Experiment Request 498, Critical Engineering Decision 1 Report

This report supports Critical/Subcritical Experiment Decision 1 (CED-1) for Integral Experiment Request (IER) 498, a shielding benchmark produced using the Godiva IV critical assembly at the National Critical Experiments Research Center (NCERC). Shielding benchmarks are datasets collected to provide a comparison for computer models that simulate the effect of shielding on radiation transmission from a source to a detector. The purpose of a CED-1 report is to produce a conceptual design for an integral experiment and to identify the long lead-time items. The design presented in this report favors certain detailed design options such as material selections. However, alternative options can be selected as the project evolves. Dimensions are specified only as needed to evaluate feasibility and performance. Development of Criticality Accident Alarm System (CAAS) shielding benchmarks supports two main programmatic needs. The first need is to improve confidence in models of facilities that house nuclear material handling operations. Better models can support effective CAAS detector placement when criticality may result in dose, and it enables more accurate analysis of criticality accident impacts at various locations in a facility. A key quantity that can be verified is the secondary gamma production caused by neutron interactions with various materials. The second programmatic need supported by shielding benchmarks is the ongoing development of methods being integrated into nuclear simulation codes such as the Monte Carlo N-Particle (MCNP) transport code and the SCALE code system used in efforts funded by the Nuclear Criticality Safety Program (NCSP). Previous work performed under the International Criticality Safety Benchmark Experimental Program (ICSBEP) to produce shielding benchmark data is primarily limited to a set of measurements at the SILENE critical assembly at the Valduc facility in France. The experiment used an open configuration and a burst mode operation, which limited detector options to thermoluminescent dosimeters (TLDs) and activation foils. Because TLDs do not record gamma spectra, it was difficult to verify the gamma energy spectrum from the experiment. In this work, the Godiva IV assembly will be used because it is a fast system capable of producing a wide range of source strengths, including super-prompt critical bursts. The room return for the facility is expected to be substantial and challenging to characterize, so a more closed, shielded experimental configuration is considered. Furthermore, because the physics of radiation transport outside the assembly does not change between the burst mode and the delayed critical mode, it is anticipated that most measurements will be made with the Godiva IV assembly in delayed critical mode, operating within a range that will allow electronic counters to collect accurate data. Scoping calculations concluded that a workable room return shield is comprised of 40 cm of 5% borated polyethylene backed by 7 cm of lead. This configuration was shown to produce a ratio of signal–to–room return of over 100 for up to 2 mean free paths of shield sample material, and over 10 for up to 4 mean free paths of shield sample material, ensuring that useful results can be obtained. With no shielding sample in the room return shield, it was shown that the neutron and gamma spectra do not appreciably change with a change in room size. This scoping calculation does not preclude the use of tungsten powder in a binder, some other effective gamma shielding material, or a hybrid design. Dose rates for various source intensities at an unshielded detector are listed herein to inform detector selection during CED-2, and calibration chains are identified. Preliminary estimates of costs and schedules are outlined but remain to be verified. Values could double or triple as estimates become more accurate and are principally included here to demonstrate feasibility. Preliminary estimates indicate that the apparatus can be installed within a feasible schedule and budget. Two measurements per day are assumed. Producing a shielding benchmark at NCERC using the Godiva IV assembly has been shown to be feasible, with manageable uncertainties and risks. A clear, continuing need for shielding benchmark data remains present, and this report identifies and evaluates a method for creating integrated shielding benchmark datasets.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2022

Neptunium (V) Solubility in the Presence and Absence of WIPP Relevant Ligands

CRA (Compliance Recertification Application)-2024 will update the oxidation state specific model used to calculate actinide solubility in the WIPP (Waste Isolation Pilot Plant). The pentavalent Np(V) ion is the most stable ion in solution within the An(V) series. This valence stability of Np(V) in aqueous solution makes Np a useful representative element for studying the aqueous complex chemistry of all An(V), but in the predicted WIPP scenario, this is the only TRU component that increases in the inventory with time as it is the main daughter product of 241 Am decay (alpha, n) so its relative importance increases throughout the 10,000-year performance period of the WIPP, it is only used to represent itself. This work is focused on confirming organic, borate and carbonate effects on solubility of Np(V) in WIPP simulated brines and 5 M NaCl and reassessing the predicted model speciation to strengthen the overall WIPP An(V) model.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Neptunium (V) Solubility in WIPP Brine: Presence and Absence of WIPP-Relevant Organic and Inorganic Ligands

The oxidation state and solubility of neptunium (Np) in 5 M NaCl and high ionic strength synthetic WIPP (Waste Isolation Pilot Plant) brines were systematically investigated as a function of pCH+ (7-11) in the presence and absence of WIPP-relevant organic ligands, including EDTA (Ethylenediaminetetraacetic acid), oxalate, citrate, and acetate, as well as inorganic ligands such as borate and carbonate at a temperature of 23 ± 2°C. This study was conducted through long-term batch solubility experiments spanning approximately 950 days, using an undersaturation approach. A comprehensive set of experimental and spectroscopic techniques, including UV-VIS-NIR spectroscopy and Np L III -edge X-ray Absorption Spectroscopy (XAS), was employed to identify the solubility-controlling Np solid phases and the predominant aqueous Np species present in the samples.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Understanding and Mitigating the Dissolution and Delamination Issues Encountered with High-Voltage LiNi 0.5 Mn 1.5 O 4

In our initial study on the high-voltage 5 V cobalt-free spinel LiNi 0.5 Mn 1.5 O 4 (LNMO) cathode, we discovered a severe delamination issue in the laminates when cycled at a high upper cut-off voltage (UCV) of 4.95 V, especially when a large cell format was used. This delamination problem prompted us to investigate further by studying the transition metal (TM) dissolution mechanism of cobalt-free LNMO cathodes, and as a comparison, some cobalt-containing lithium nickel manganese cobalt oxides (NMC) cathodes, as the leachates from the soaking experiment might be the culprit for the delamination. Unlike other previous reports, we are interested in the intrinsic stability of the cathode in the presence of a baseline Gen2 electrolyte consisting of 1.2 M of LiPF 6 in ethylene carbonate/ethyl methyl carbonate (EC/EMC), similar to a storage condition. The electrode laminates (transition metal oxides, transition metal oxides, TMOs, coated on an Al current collector with a loading level of around 2.5 mAh/cm 2 ) or the TMO powders (pure commercial quality spinel LNMO, NMC, etc.) were stored in the baseline solution, and the transition metal dissolution was studied through nuclear magnetic resonance, such as 1 H NMR, 19 F NMR, scanning electron microscope (SEM), X-ray photoelectron spectroscopy (XPS) and inductively coupled plasma mass spectrometry (ICP-MS). Significant electrolyte decomposition was observed and could be the cause that leads to the TM dissolution of LNMO. To address this TM dissolution, additives were introduced into the baseline electrolyte, effectively alleviating the issue of TM dissolution. The results suggest that the observed delamination is caused by electrolyte decompositions that lead to etching, and additives such as lithium difluorooxalato borate and p-toluenesulfonyl isocyanate can alleviate this issue by forming a firm cathode electrolyte interface. This study provides a new perspective on cell degradation induced by electrode/electrolyte interactions under storage conditions.

25 ENERGY STORAGE↗
DOE OSTI2019

The Effect of Heavy Ion Irradiation on the Forward Dissolution Rate of Borosilicate Glasses Studied In Situ and Real Time by Fluid-Cell Raman Spectroscopy

Borosilicate glasses are the favored material for immobilization of high-level nuclear waste (HLW) from the reprocessing of spent fuel used in nuclear power plants. To assess the long-term stability of nuclear waste glasses, it is crucial to understand how self-irradiation affects the structural state of the glass and influences its dissolution behavior. In this study, we focus on the effect of heavy ion irradiation on the forward dissolution rate of a non-radioactive ternary borosilicate glass. To create extended radiation defects, the glass was subjected to heavy ion irradiation using 197 Au ions that penetrated ~50 µm deep into the glass. The structural damage was characterized by Raman spectroscopy, revealing a significant depolymerization of the silicate and borate network in the irradiated glass and a reduction of the average boron coordination number. Real time, in situ fluid-cell Raman spectroscopic corrosion experiments were performed with the irradiated glass in a silica-undersaturated, 0.5 M NaHCO 3 solution at temperatures between 80 and 85 °C (initial pH = 7.1). The time- and space-resolved in situ Raman data revealed a 3.7 ± 0.5 times increased forward dissolution rate for the irradiated glass compared to the non-irradiated glass, demonstrating a significant impact of irradiation-induced structural damage on the dissolution kinetics.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Improvements in the Sample Space for the Backscattering Silicon Spectrometer (BASIS)

The increase in neutron flux at the Oak Ridge National Laboratory (ORNL) Spallation Neutron Source (SNS), currently operating at 2.0 MW proton beam power, has created new opportunities for higher-throughput neutron scattering experiments while also increasing the importance of minimizing background scattering and optimizing sample-environment operations. To address these challenges on the Backscattering Silicon Spectrometer (BA-SIS), several upgrades were developed and evaluated, including boron carbide (B₄C) masking for flat-plate sample containers, multi-cell sample holders used with a vertically translating sample stick, and an automated helium pump and purge (HPP) system for closed-cycle refrigerators. Neutron diffraction measurements demonstrate that B₄C masks reduce background scattering by 49–67%, outperforming both borated aluminum and boron nitride masks while introducing no additional Bragg reflections within the instrument’s accessible Q-range. Commissioning tests of a double-cell flat-plate sample contain-er showed no measurable crosstalk between adjacent sample compartments and con-firmed stable thermal performance, enabling multiple samples to be measured without re-peated temperature cycling. In addition, the automated HPP system provided reproducible sample-space gas handling with approximately ±1 mbar precision while reducing the need for operator intervention and supporting remote operation. Together, these developments improve signal-to-noise performance, increase experimental throughput, and enhance operational efficiency at BASIS, supporting the instrument’s continued operation under higher neutron flux conditions.

Jalarvo, Niina [ORNL] (ORCID:0000000306446866)↗