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At least 739 records · Page 41

Literature Review: Crud Formation at the Liquid/Liquid Interface of TBP-Based Solvent-Extraction Processes

This report summarizes the literature reviewed on crud formation at the liquid:liquid interface of solvent extraction processes. The review is focused both on classic PUREX extraction for industrial reprocessing, especially as practiced at the Hanford Site, and for those steps specific to plutonium purification that were used at the Plutonium Reclamation Facility (PRF) within the Plutonium Finishing Plant (PFP) at the Hanford Site.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Final Technical Report: Imaging a Dry Storage Cask with Cosmic Ray Muons

The goal of this project is to build a scaled prototype system for monitoring used nuclear fuel (UNF) dry storage casks (DSCs) through cosmic ray muon imaging. Such a system will have the capability of verifying the content inside a DSC without opening it. Because of the growth of the nuclear power industry in the U.S. and the policy decision to ban reprocessing of commercial UNF, the used fuel inventory at commercial reactor sites has been increasing. Currently, UNF needs to be moved to independent spent fuel storage installations (ISFSIs), as its inventory approaches the limit on capacity of on-site wet storage. Thereafter, the fuel will be placed in shipping containers to be transferred to a final disposal site. The ISFSIs were initially licensed as temporary facilities for ~20-yr periods. Given the cancellation of the Yucca mountain project and no clear path forward, extended dry-cask storage (~100 yr.) at ISFSIs is very likely. From the point of view of nuclear material protection, accountability and control technologies (MPACT) campaign, it is important to ensure that special nuclear material (SNM) in UNF is not stolen or diverted from civilian facilities for other use during the extended storage.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Development and Optimization of Voltammetric Methods for Real Time Analysis of Electrorefiner Salt with High Concentrations of Actinides and Fission Products

This project addresses the problem of achieving accurate material control and accountability (MC&A) around pyroprocessing electrorefiner systems. Spent nuclear fuel pyroprocessing poses a unique challenge with respect to reprocessing technology in that the fuel is never fully dissolved in the process fluid. In this case, the process fluid is molten, anhydrous LiCl-KCl salt. Therefore, there is no traditional input accountability tank. However, electrorefiners (ER) accumulate very large quantities of fissile nuclear material (including plutonium) and should be well safeguarded in a commercial facility. Idaho National Laboratory (INL) currently operates a pyroprocessing facility for treatment of spent fuel from Experimental Breeder Reactor-II with two such ER systems. INL implements MC&A via a mass tracking model in combination with periodic sampling of the salt and other materials followed by destructive analysis. This approach is projected to be insufficient to meet international safeguards timeliness requirements. A real time or near real time monitoring method is, thus, direly needed to support commercialization of pyroprocessing. A variety of approaches to achieving real time monitoring for ER salt have been proposed and studied to date—including a potentiometric actinide sensor for concentration measurements, a double bubbler for salt depth and density measurements, and laser induced breakdown spectroscopy (LIBS) for concentration measurements. While each of these methods shows some promise, each also involves substantial technical complexity that may ultimately limit their implementation. Yet another alternative is voltammetry —a very simple method in theory that has previously been tested for this application to a limited extent. The equipment for a voltammetry system consists of off-the-shelf components (three electrodes and a potentiostat), which results in substantial benefits relative to cost and robustness. Based on prior knowledge of electrochemical reduction potentials for each of the species of interest, voltammetry can be used to quantify concentrations of a variety of elemental species—including uranium, plutonium, minor actinides, and rare earths. Various methods have been tested by other researchers to date—including cyclic voltammetry, square wave voltammetry, normal pulse voltammetry, etc. In most cases, it has been observed that there is a very limited concentration range for which the output can be readily correlated with concentration in the salt. Furthermore, testing to date has been limited to simple ternary salts with only a single element being quantified. While incomplete for application to MC&A for pyroprocessing, these results lead us to believe that voltammetry can be optimized based on salt properties and fundamental electrochemical rate processes to yield a highly accurate and robust method. This project is divided into four tasks jointly executed by three university research groups. This includes experimental measurement of key physical data on the systems of interest, development of a predictive voltammetry model, experimental validation of the voltammetry model, and design/verification of an optimized measurement method. This project supports the goals of the US-ROK Joint Fuel Cycle Study in addition to the NA-24 Office of the National Nuclear Security Agency and the International Atomic Energy Agency (IAEA).

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Thermally and chemically responsive nanoporous materials for efficient capture of fission product gases.

The objective of this project was to develop robust, high-efficiency materials for capture of fission product gases such as He, Xe and Kr in scenarios relevant for both reactor fuels and reprocessing operations. The relevant environments are extremely harsh, encompassing temperatures up to 1500 °C, high levels of radiation, as well as potential exposures to highly-reactive chemicals such as nitric acid and organic solvents such as kerosene. The requirement for nanostructured capture materials is driven in part by the very short (few micron) diffusion distances for product gases in nuclear fuel. We achieved synthesis, characterization and detailed modeling of the materials. Although not all materials reviewed in this report will be feasible for the ultimate goal of integration in nuclear fuel, nevertheless each material studied has particular properties which will enable an optimized material to be efficiently developed and characterized.

36 MATERIALS SCIENCE↗

First ARM Aerosol Chemical Speciation Monitor Users’ Meeting Report

The first U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) user facility aerosol chemical speciation monitor (ACSM) users’ meeting was held on April 11-13, 2017, at Aerodyne Research, Inc. in Billerica, Massachusetts, to discuss the Southern Great Plains (SGP) atmospheric observatory ACSM data quality and establish best practices for data collection and processing. The participants examined six years of calibration and processed data. Specific issues raised by data users were addressed and case studies from two field experiments were examined. The most recent data from the ACSM installed in the newly commissioned SGP ARM Mobile Facility 7 (AMF7) were also evaluated. The participants recommended that the SGP ACSM data be reprocessed using calibration values averaged over the history of SGP ACSM calibrations. They also recommended that the data quality be evaluated by comparing (1) observed versus predicted particulate ammonium (NH4+) mass loadings, and (2) ACSM mass loadings versus mass loadings calculated from particle size and light scattering data. The contents of the datastreams from the ACSM were defined based on ARM requirements and the necessary tasks to implement these recommendations were assigned to the mentor and the instrument manufacturer. Some of the recommendations were implemented for the SGP data and are presented in this report. Data from two ARM sites located in marine environments were also analyzed. These analyses as well as instrument intercomparisons have led to further questions about data treatment. These will be addresses in the second users’ meeting scheduled for the summer of 2018.

54 ENVIRONMENTAL SCIENCES↗

First ARM Aerosol Chemical Speciation Monitor Users’ Meeting Report

The first U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) user facility aerosol chemical speciation monitor (ACSM) users’ meeting was held on April 11-13, 2017, at Aerodyne Research, Inc. in Billerica, Massachusetts, to discuss the Southern Great Plains (SGP) atmospheric observatory ACSM data quality and establish best practices for data collection and processing. The participants examined six years of calibration and processed data. Specific issues raised by data users were addressed and case studies from two field experiments were examined. The most recent data from the ACSM installed in the newly commissioned SGP ARM Mobile Facility 7 (AMF7) were also evaluated. The participants recommended that the SGP ACSM data be reprocessed using calibration values averaged over the history of SGP ACSM calibrations. They also recommended that the data quality be evaluated by comparing (1) observed versus predicted particulate ammonium (NH 4 + ) mass loadings, and (2) ACSM mass loadings versus mass loadings calculated from particle size and light scattering data. The contents of the datastreams from the ACSM were defined based on ARM requirements and the necessary tasks to implement these recommendations were assigned to the mentor and the instrument manufacturer. Some of the recommendations were implemented for the SGP data and are presented in this report. Data from two ARM sites located in marine environments were also analyzed. These analyses as well as instrument intercomparisons have led to further questions about data treatment. These will be addresses in the second users’ meeting scheduled for the summer of 2018.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Initial Evaluation of CaSDB MOF Xe and Kr Capacities

Idaho National Laboratory (INL) and Pacific Northwest National Laboratory (PNNL) have been conducting parallel research, as part of the off-Gas Sigma Team, producing and testing sorbents for the selective capture of xenon and krypton from surrogate nuclear fuel reprocessing off-gas streams. Sorbents promising on a laboratory scale are tested further at INL in a system designed to emulate anticipated plant process conditions. This report summarizes INL’s initial testing of CaSDB MOF developed and produced at PNNL. Previous testing of the same base CaSDB MOF material, conducted at INL in 2016, indicated good saturation capacity for xenon, but a low xenon capacity at initial breakthrough. Additionally, the material displayed a propensity to break down into fine powder during use and handling. The current test series looks at the same base material, but with refinements to production and activation techniques. A series of ambient temperature tests were conducted to determine capacities of CaSDB MOF for krypton and xenon at initial breakthrough as well as at saturation. Adsorption tests were run in triplicate at superficial velocities of 21 and 53 cm/min, along with a single test at 373 cm/min. Saturation capacity across all tests was 30 mmol/kg +/- 2, with capacity at initial breakthrough of 8 mmol/kg +/- 1. It should be noted that while the usable portion of the material has a much tighter size distribution than that previously tested, propensity to physically break down into very fine powder with use and handling continues to be problematic. An improved engineered form is recommended prior to further testing

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Cooperative self-assembly for structure and morphology control of energetic materials

The performance of energetic materials (EM) varies significantly across production lots due to the inability of current production methods to yield consistent morphology and size. Lot-to-lot variations and the inability to remake the needed characteristics that meet specification is costly, increases uncertainty, and creates additional risk in programs using these materials. There is thus a pressing need to more reliably formulate EMs with greater control of morphology. The goal of this project is to use the surfactant-assisted self-assembly to generate EM particles with welldefined size and external morphologies using triaminotrinitrobenzene (TATB) and hexanitrohexaazaisowurtzitane (CL-20) as these EMs are both prevalent in the stockpile and present interesting/urgent reprocessing challenges. We intend to understand fundamental science on how molecular packing influences EM morphology. We develop scale up fabrication of EM particles with controlled morphology, promising to eliminate inconsistent performance by providing a trusted and reproducible method to improve EMs for NW applications.

36 MATERIALS SCIENCE↗

First ARM Aerosol Chemical Speciation Monitor Users’ Meeting Report

The first U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) user facility aerosol chemical speciation monitor (ACSM) users’ meeting was held on April 11-13, 2017, at Aerodyne Research, Inc. in Billerica, Massachusetts, to discuss the Southern Great Plains (SGP) atmospheric observatory ACSM data quality and establish best practices for data collection and processing. The participants examined six years of calibration and processed data. Specific issues raised by data users were addressed and case studies from two field experiments were examined. The most recent data from the ACSM installed in the newly commissioned SGP ARM Mobile Facility 7 (AMF7) were also evaluated. The participants recommended that the SGP ACSM data be reprocessed using calibration values averaged over the history of SGP ACSM calibrations. They also recommended that the data quality be evaluated by comparing (1) observed versus predicted particulate ammonium (NH 4 + ) mass loadings, and (2) ACSM mass loadings versus mass loadings calculated from particle size and light scattering data. The contents of the datastreams from the ACSM were defined based on ARM requirements and the necessary tasks to implement these recommendations were assigned to the mentor and the instrument manufacturer. Some of the recommendations were implemented for the SGP data and are presented in this report. Data from two ARM sites located in marine environments were also analyzed. These analyses as well as instrument intercomparisons have led to further questions about data treatment. These will be addresses in the second users’ meeting scheduled for the summer of 2018.

54 ENVIRONMENTAL SCIENCES↗

Electrolytic Oxide Reduction of Plutonium Oxide Surrogates

Our research team has investigated electrolytic oxide reduction (EOR) as an improved metal production process versus the currently employed multiple cycle direct oxide reduction (MCDOR) process for the conversion of plutonium oxide to plutonium metal. Inherent advantages in safety, waste generation, efficiency, and operational ease make EOR an attractive alternative to traditional metal production practices. Phase I of the project consisted of the construction of a prototype electrochemical cell, and proof of concept experiments towards the reduction of SnO 2 and CeO 2 compounds. Phase II of the project was focused on the optimization of the cerium system in preparation for future plutonium EOR experiments. We observed the electrolytic reduction of cerium oxide resulting in mixed degrees of success, and discovered this was a result of parasitic side reactions and partial reduction. We employed cyclic voltammetry (CV) to identify the products of these side reactions and characterize partially reduced species. We also observed that, when metal was successfully produced by EOR, a large amount of passed charge was required. We concluded that this observation was due to several inefficiencies of the process relating to the reduction mechanism (e.g. inefficient use of cathodically produced calcium). We used our CV results to guide our optimization of the EOR of CeO 2 by refining our electrochemical method, cell geometry, and materials of construction. Finally, we developed a next generation cell, worked to establish a new molten salt electrochemical capability in the Plutonium Facility, and completed a strategy for plutonium experiments. Our electrochemical method to produce plutonium metal clearly supports the core mission of the laboratory. Furthermore, this project has allowed for the development of capabilities that will provide valuable data to programs interested in characterization and detection, as well as science of signatures. Additionally, establishing this capability in the plutonium facility will facilitate future safeguard studies that can assist with safeguard development in molten salt reprocessing flowsheets, and molten salt reactor designs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dissolution of Used Nuclear Fuel using a TBP/n-paraffin Solvent

The complete recycle of used nuclear fuel (UNF) is desirable to recover the energy value from the remaining U and the higher actinides produced during fuel irradiation; however, the construction of a large-scale reprocessing facility is prohibitively expensive. A simplified flowsheet with a reduced equipment footprint is needed to improve the economic viability. To address this issue, we evaluated a hybrid process which combines the dissolution of UNF pretreated (oxidized) for tritium removal in a tributyl phosphate (TBP) solvent with the solvent extraction cycles required for recovery of the actinide and lanthanide elements. To demonstrate the feasibility of the hybrid process, we prepared actinide solid solutions containing selected fission product elements as surrogates for pretreated, irradiated light water reactor fuel. The distribution of the actinide and fission product elements was measured between the solvent and residual solids to determine dissolution efficiencies. Dissolution of the solid solutions in the TBP solvent was effective for the recovery of both the actinide and lanthanide elements. An increase in the TBP concentration and temperature improved the dissolution efficiencies for these elements. Two-stage dissolutions were successfully used to recover nearly all the actinides and most of the lanthanides from the solid solutions. Our data indicate that most of the fission products generated during fuel irradiation except for the lanthanides and Tc (based on data for Re) would remain in the undissolved solids. The Am/Cm, lanthanides, and other fission product are easily scrubbed from the solvent by contact with nitric acid generating a pure U/Np/Pu stream.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Steam Oxidation and Burst Testing in the Severe Accident Test Station

Within six months of the March 2011 nuclear accident at Fukushima Daiichi, research began at Oak Ridge National Laboratory (ORNL) to simulate the high temperature steam oxidation accident conditions and identify potential accident tolerant fuel (ATF) cladding [1-14]. The ORNL laboratory equipment for steam oxidation equipment was expanded and made available to the entire ATF research community as the Severe Accident Test Station (SATS) in 2012 [5,1 5], including the capability to conduct the standard integral loss of coolant accident (LOCA) experiment [9]. A second SATS has now been deployed in an ORNL hot cell for handling irradiated specimens including reprocessed UO 2 /Zr fuel [16].

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Global Nuclear Markets – Market Arrangements and Service Agreements

The U.S. Department of Energy’s Office of Energy Policy and Systems Analysis (EPSA) requested an assessment of global nuclear markets, including the structure of nuclear companies in different countries and the partnerships between reactor vendors and buyers. EPSA was interested in obtaining information on the competitive context of international sales of reactors and fuel services. The Idaho National Laboratory responded to this request with a plan for information gathering and assessment of global markets in several phases. The first phase researched global sources and developed a collection of information to assist in analyses of global market status and trends in services provided in conversion, enrichment, reactor design, construction and operation, and discharged fuel storage and reprocessing. This report summarized this first phase, including analysis conclusions about current global markets. Additional phases will address specific topics that are of particular interest to EPSA.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Performance Evaluation of the CHKED Multi-Elemental Analysis and Software

The Hybrid K-edge Densitometer (HKED) is a high precision safeguards assay system developed by Ottmar and Eberle [1] for quantification of the U and Pu concentrations of dissolver solutions in spent nuclear fuel reprocessing. The HKED measurement supplements traditional destructive assay methods such as Isotope Dilution Mass Spectrometry (IDMS) and is an essential component of the international safeguards program implementation at these facilities. The Canberra Hybrid K-Edge Densitometry (CHKED) software was recently developed by Canberra Industries to better address the changing composition of the nuclear fuel cycle by addition of a multi-elemental analysis capability to the K-Edge transmission measurement. Our evaluation of the CHKED software was performed at the request of the International Atomic Energy Agency (IAEA) to examine the functionality and performance of the CHKED software and algorithms and identify potential areas for improvement of the software. The reader is assumed to be familiar with the HKED technique and its current implementation in safeguards assay of U and Pu in the nuclear fuel cycle. The Canberra Hybrid K-Edge Densitometry CHKED software replicates functionality of the older VMSbased Hybrid K-Edge Densitometer (HKED) software and incorporates additional analysis algorithms and tools. When the traditional HKED analyses are selected, the CHKED software appears to faithfully reproduce the measurement results as reported by the older software. The CHKED software includes a Multi-elemental K-Edge (MEKED) analysis based in part on algorithms devised at Los Alamos National Laboratory. In principle, the MEKED analysis represents a significant advancement over the traditional HKED analysis, providing a capability to analyze the actinide concentrations from complex solutions, such as low U:Pu ratios (e.g., U:Pu = 1:1) including additional minor actinide components such as Np and Am. However, this MEKED analysis is somewhat limited by reliance on a region of interest (ROI) analysis of the spectrum, the need for extensive calibration measurements and a simplistic interpretation of the KED transmission spectrum. Finally, the MEKED algorithm set associated with the CHKED software (V1.0) acquired by Oak Ridge National Laboratory (ORNL) from Canberra Industries does not seem to be “finished” (e.g., the MEKED analysis seems to only determine measurement results for two actinides with while results for the minor actinides appear to be highly dependent on declaration values).

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Design of, and Test Plan for, an Iodine and Tritium Capture System for a NO 2 -Based Tritium Pretreatment Process

The reprocessing of used nuclear fuel would release volatile radionuclides into the off-gas of a processing plant, including 3 H, 14 C, 85 Kr, and 129 I. One potential simplification to the management of the off-gas streams could be achieved through an efficient tritium pretreatment (TPT) step in which the UO 2 fuel is oxidized either by air or by NO2 before dissolution. Oxidation of the UO2 fuel matrix results in the release of tritium contained within. Upfront removal of tritium from the fuel in a pretreatment step, followed by the abatement of tritium, can minimize or eliminate the distribution of tritium throughout the plant, also decreasing or eliminating the need for tritium capture on multiple off-gas streams. The use of NO 2 as the oxidant in an advanced tritium pretreatment (ATPT) allow the oxidation to be performed at lower temperatures and may result in the quantitative release of iodine from the fuel.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Phase separation and crystallization of complex borosilicate melts for glass-ceramic waste forms

Waste loadings of reprocessed spent nuclear fuel vitrified into borosilicate glass can be increased by precipitating environmentally stable phases concentrated with waste components in a chemically stable glass matrix. The principal objective of this study was to characterize the development of crystalline powellite (CaMoO 4 and related phases) and oxyapatite (Ca 2 LN 8 Si 6 O 26 ) in borosilicate glass-ceramics and to determine how the formation of those phases affected its chemical durability. Borosilicate glasses provided by PNNL were re-melted and quenched at rates from over 300°C/s to ~0.05°C/s. Isothermal heat treatment experiments were conducted by quenching melts in a molten tin bath at various temperatures, holding for periods of time, and then quenching in a water bath. Analytical electron microscopy and x-ray diffraction provided information about the kinetics of the phase separation and crystallization processes responsible for microstructural development. Powellite and oxyapatite crystals formed during slower quench rates and longer isothermal times, and time-temperature-transformation (TTT) diagrams were developed from the latter experiments. A hot thermocouple test (HTT) system was built to rapidly quench melts and hold them at set times to provide supplementary TTT information, but that system was not as sensitive to the phase transformations as other tests. Corrosion tests were performed to understand how the individual phases in the glass-ceramic affect its overall chemical durability. Product consistency tests, performed at Missouri S&T and at Savannah River National Lab, provided release rates of major elements from samples as a function of cooling rate, and atomic force microscopy and profilometry measurements of surface topology determined the relative corrosion rates of the residual glass and oxyapatite phases. Faster dissolution rates were measured from samples cooled more slowly and these were explained by the greater fractions of B 2 O 3 in the residual glass phase after the formation of oxyapatite and powellite. Oxyapatite was found to be more durable than the residual glass.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Solid-liquid Separation Testing for the Remediation of Hanford Waste Treatment Plant Low Activity Waste Melter Off-Gas Condensate

The Low Activity Waste (LAW) vitrification facility at the Hanford Waste Treatment and Immobilization Plant (WTP) will generate an aqueous condensate stream (LAW Off-Gas Condensate) from the off-gas system. The plan for disposition of this stream during Direct Feed LAW operations is to transfer it to the Effluent Management Facility (EMF), where it will be concentrated by evaporation and recycled to the LAW vitrification facility again. The primary reason to recycle this stream is so that the semi-volatile 99Tc isotope eventually becomes incorporated into the glass. However, this stream also contains non-radioactive salt components that are problematic in the melter, so diversion of this stream to another process would eliminate recycling of these salts and would enable simplified operation of the LAW melter and the Pretreatment Facilities. This diversion from recycling this stream within WTP would have the effect of decreasing the quantity of glass waste produced by allowing further increases in waste loading, resulting in a shortened LAW vitrification mission duration. The concept being tested here involves selectively removing the 99 Tc so that the decontaminated aqueous stream, with the problematic salts, can be disposed as a different waste form and avoid reprocessing through vitrification.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Installation and Commissioning of the Netzsch Skimmer

The DOE molten salt reactor (MSR) program has been focusing on the thermochemistry and transport properties of fuel, diluent/carrier, coolant, flush, and reprocessing salts proposed for various molten salt reactor technologies. Data from the chemistry project inform models of salt behavior used in dynamic models of nuclear salt reactors, for both high fidelity and systems simulations. Reactor and salt processing systems operate well above salt melting points (>600°C), so salt behavior can be well described by thermodynamics. However, much is not known about salt systems that contain two, three, or even more components. The Netzsch skimmer (commissioned this year) can be used in several configurations to collect data on molten systems. The skimmer uses mass spectrometry coupled with a thermogravimetric analyzer to accurately analyze systems up to 2000°C. Because the mass analyzer is coupled directly to the furnace through two nested orifices, there are no losses due to condensation. As a thermogravimetric analyzer, the skimmer measures weight loss and reaction energies simultaneously with evolved gas analysis. The mass spectrometry identifies gas phase species, and these volatility measurements can be used to derive vapor pressures. The skimmer was purchased in fiscal year 2018, delivered in April, installed in May 2019, and now is fully operational as verified by the analysis of known standards. The skimmer is unique because it will be available for study of salt systems that contain actinides or beryllium, although the additional work control to accommodate these hazards is still under review.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗