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At least 55 records · Page 3

A Facile, One-Step Synthesis for Core–Shell Perovskite Materials via Molten Salt

Core–shell La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3 (LSCF)–La 0.8 Sr 0.2 MnO 3 (LSM) heterostructure crystalline materials have been synthesized in a simple, one-step feeding method via a KNO 3 molten salt solvent. Two-phase perovskite composites can be synthesized in times as short as 10 minutes and is demonstrated for the first time in a molten salt. Further, a combination of X-ray diffraction and S/TEM energy dispersive X-ray spectroscopy has been utilized to confirm the formation of an LSM shell on LSCF cores in all samples when adjusting dwell time, core size, weight ratio between core and shell precursors, and weight ratio of powder to salt. Specifically, decreasing the LSCF core size increases core–shell yield. Smaller cores introduce a greater density of facets on the crystal surface and provide more favorable sites for LSM heterogeneous nucleation.

36 MATERIALS SCIENCE↗

Facile Oxidation of Ce(III) to Ce(IV) Using Cu(I) Salts

The synthesis, luminescence, and electrochemical properties of the Ce(III) compound, [(C 5 Me 5 )2(2,6- i Pr 2 C 6 H 3 O)Ce(THF)], 1, were investigated. Based on the electrochemical data, treatment of 1 with CuX (X = Cl, Br, I) results in the formation of the corresponding Ce(IV) complexes, [(C 5 Me 5 ) 2 (2,6- i Pr 2 C 6 H 3 O)Ce(X)]. Each complex has been characterized using NMR, IR, and UV−vis spectroscopy as well as structurally determined using X-ray crystallography. Additionally, the treatment of [(C 5 Me 5 ) 2 (2,6- i Pr 2 C 6 H 3 O)Ce(Br)] with AgF results in the formation of the putative [(C 5 Me 5 ) 2 (2,6- i Pr 2 C 6 H 3 O)Ce(F)]. Furthermore, the electronic structure of these Ce(IV)−X complexes was investigated by bond analyses and the Ce(IV)−F moiety using quantum chemistry NMR calculations.

Aromatic compounds↗

Facile diamond synthesis from lower diamondoids

Carbon-based nanomaterials have exceptional properties that make them attractive for a variety of technological applications. Here, we report on the use of diamondoids (diamond-like, saturated hydrocarbons) as promising precursors for laser-induced high-pressure, high-temperature diamond synthesis. The lowest pressure and temperature $(P-T)$ conditions that yielded diamond were 12 GPa (at ~2000 K) and 900 K (at ~20 GPa), respectively. This represents a substantially reduced transformation barrier compared with diamond synthesis from conventional (hydro)carbon allotropes, owing to the similarities in the structure and full sp 3 hybridization of diamondoids and bulk diamond. At 20 GPa, diamondoid-to-diamond conversion occurs rapidly within <19 μs. Molecular dynamics simulations indicate that once dehydrogenated, the remaining diamondoid carbon cages reconstruct themselves into diamond-like structures at high $P-T$. This study is the first successful mapping of the $P-T$ conditions and onset timing of the diamondoid-to-diamond conversion and elucidates the physical and chemical factors that facilitate diamond synthesis.

36 MATERIALS SCIENCE↗

Expedited Walkdowns and Preparation of Cost Estimates for Decontamination and Demolition of Excess Facilities - 20335

Lawrence Livermore National Security, LLC (LLNS) is the prime contractor responsible for managing and operating Lawrence Livermore National Laboratory (LLNL). The mission of the LLNL is to strengthen security of the United States through development and application of world-class science and technology to enhance the nation's defense, reduce the global threat from terrorism and weapons of mass destruction, and respond with vision, quality, integrity, and technical excellence to scientific issues of national importance. To accomplish its mission, LLNL must plan and manage its campus space and facilities to optimize use of its relatively small one-square-mile footprint. LLNL currently has numerous excess facilities that require decontamination and demolition (D and D). The LLNL Legacy Facility Program is responsible for stewardship and risk reduction programs to effectively manage these excess assets at LLNL. The Legacy Facility Program identified 10 excess facilities at LLNL that were candidates for demolition based on risks from further degradation of the facilities, potential exposure to hazardous materials, or need for removal to make way for new program facilities. The buildings range from a structure built in 1943 to serve as a US Navy drill hall during World War II, to a facility that provided neutrons to study material properties for the fusion energy program. The National Nuclear Security Administration (NNSA) appropriated FY19 funding for the development of Class 3 estimates for these 10 excess facilities that would be used to develop a Program Management Plan for funding consideration. Class 3 estimates are not conceptual, nor overly detailed, but adequate to be used for budget and appropriation purposes. Using existing strategic sourcing agreements, LLNL was able to organize a team of senior subject matter experts (SMEs) with diverse technical backgrounds across the Department of Energy (DOE) Complex to complete extensive process knowledge (PK) reviews and walk-downs of each excess facility and to deliver accurate and complete estimates under an expedited schedule (i.e., within eight weeks). To facilitate the expedited schedule, LLNL was fully prepared for the arrival of the JGMS team, which consisted of the following companies: J.G. Management Systems, Inc. (JGMS); Strata-G, LLC; and Michael Baker International. LLNL provided background and PK information on the excess facilities, pictures, supporting historical documentation, and radiological survey history as well as escorted access to the facilities. The JGMS team has previous experience supporting Program Management Plans for excess facilities at the Y-12 National Security Complex. The team mobilized to LLNL and performed the facility walk-downs from January 22-25, 2019. Using a methodical evaluation process, expertise, and experience, the team was able to deliver walk-down draft reports and estimates to LLNL before their February 8, 2019 deadline. LLNL then in turn reviewed, completed the estimates by adding waste management costs and other LLNL costs, and delivered the estimates to NNSA by February 15, 2019. The completed final reports, including draft D and D estimates, were delivered to LLNL before their March 6, 2019 deadline. The work was successfully completed ahead of the expedited schedule required by LLNL, resulting in a commendation from the client. This paper describes how the partnership and collaboration as a fully integrated team comprised of the prime contractor, LLNS, and the JGMS team successfully met the needs of the US government, resulting in the performance of expedited site walk-downs, the development of summary evaluation reports, and the preparation of draft Class 3 estimates and preliminary schedules for the D and D of 10 excess facilities at LLNL. The efforts of the team will enable the D and D of the first excess facility in the 2020-2021 time frame. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Assessment of Baseline Monitoring Data for the Remote-Handled Low-Level Waste Disposal Facility at Idaho National Laboratory

The purpose of this document is to summarize environmental monitoring data collected at the Remote-Handled Low-Level Waste (RHLLW) Disposal Facility during the first four years of facility operations (FY 2019 through FY 2022). This summary provides a “baseline” condition for the facility, which can be used to distinguish contaminant releases from the RHLLW Disposal Facility from pre existing contamination as well as potential future releases from other sources (i.e., upgradient aquifer sources), as specified in the facility monitoring plan. Sufficient data has been collected over the first four years of operation of the RHLLW Disposal Facility to establish baseline conditions for future compliance monitoring of aquifer wells and performance monitoring of vadose zone lysimeters. Except for seven elevated tritium measurements from lysimeter HFEF-South believed to have been impacted by waste disposals, all data was deemed appropriate for establishing baseline concentrations. Monitoring of the aquifer detected indicator analytes gross alpha and gross beta and target analytes tritium and C-14. There were a few C-14 detections prior to an increase in the required detection level (RDL) after the first round of sampling. I-129 and Tc-99 were not detected above RDLs in aquifer samples. Lysimeter samples detected indicator analytes gross alpha and gross beta and target analyte tritium. Target analytes C-14, I-129, and Tc-99 were not detected above RDLs in lysimeter samples. Except for tritium, baseline concentrations of indicator and target analytes measured during the first four years of RHLLW facility operations are expected to represent conditions through the expected 20 year operating period of the facility. Elevated tritium in the aquifer, a result of past discharges of tritium at upgradient facilities, showed a decline over the first four years of operations, and levels are expected to continue to decline with time as a result of dilution and decay. Current tritium levels in lysimeter samples may be elevated due to tritium in the water applied during construction and infiltration testing of the facility. As a result, tritium concentrations in lysimeters may decline with time as a result of dilution and decay. Statistical measures (i.e., mean, standard deviation, and 99% upper confidence level [UCL]) were calculated for all detected analytes using the four years of concentration data. These measures will be used to evaluate future monitoring results and to demonstrate the facility is performing, or not performing, as established in the facility performance assessment (PA). Future monitoring results will also be combined with the baseline data in this report to further establish temporal trends and natural variability in the measurements. Based on the data collected during the baseline period, it is recommended the gross alpha action level for performance monitoring increase from 10 to 20 pCi/L due to several baseline measurements exceeding the preliminary action level of 10. An action level of 20 pCi/L is slightly greater than the 99% UCL, is protective of the aquifer, and would reduce unnecessary sampling. It is also recommended that tritium be added to the lysimeter analyte list for post-baseline period monitoring. Tritium, while not a dose concern, is a good tracer that can provide valuable information on water flow in and around the RHLLW Disposal Facility. Recommendations for a tritium action level are provided if considered necessary.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Accelerating Nuclear Facility Mission Completion Through an Improved Chemical Hazard Control Strategy - 20460

Code of Federal Regulation (CFR) 10 CFR 830, Nuclear Safety Management [1], explicitly identifies hazardous materials in addition to radioactive materials when establishing the scope of materials that must be evaluated in Hazard Category (HC) 1, 2, and 3 nuclear facilities. This inclusion has led to a near decade-long progression of more and more rigorous application of chemical hazard controls in these facilities. The progressive addition of more rigorous chemical hazard controls has occurred across the Department of Energy (DOE) Complex, having been driven by contractors and regulators alike. However, chemical hazards in other DOE facilities have been, and continue to be, controlled using traditional industrial safety centered strategies. Thus, identical chemical hazards are controlled using dramatically different approaches based solely on the facility type. Not only are the controls different, the analysis and derivation rigor and requirements are also significantly different. In particular, chemical control derivation and application in non-nuclear facilities are much less onerous than the comprehensive hazard analysis process used in nuclear facilities, even in circumstances in which chemicals are not initiators to, or do not exacerbate a nuclear event. While the derivation and control approaches used in these two types of facilities are disparate, the safety results are similarly effective based on a review of reported chemical events from 2014 through 2018. While both approaches achieve comparable safety outcomes, the approach used in nuclear facilities results in significantly greater preparation costs and implementation costs. Furthermore, the problem with the differing approach is not relegated to the control preparation and implementation burden. The operational impact of potentially unnecessary controls slows mission completion without a corresponding increase in safety, not to mention the dilution of the importance of Technical Safety Requirements. The proposed solution must first include a critical and thorough examination of DOE Complex and top-tier chemical industry chemical hazard control practices, coupled with a similar examination of the driving facility regulatory requirements. Results from the examination can then be used to fuel a bold departure from current chemical control practices in Hazard Category 1, 2, and 3 nuclear facilities. Development of an improved and consistent chemical hazard control process would follow, one that continues to ensure safety while accelerating mission completion and significantly reducing the burden associated with chemical hazard control development and implementation. The improved process must establish a hierarchy where radiological hazards are addressed using safety class and safety significant controls and chemical hazards are addressed using overarching safety management programs (with limited unique exceptions). The improved Hazard Category 1,2, and 3 nuclear facility chemical hazard control strategy, while compliant with 10 CFR 830 [1], would be founded on the requirements in 10 CFR 851, Worker Safety and Health Program [2], and the complementary DOE O 151.1D, Comprehensive Emergency Management System [3]. In this way, the Hazard Category 1, 2, and 3 nuclear facility chemical hazard control strategy would, wherever appropriate, be the same process used at other DOE Complex facilities. Ultimately, the improved process will maintain safety and significantly reduce costs and life cycle risk through faster mission completion. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Survey of U.S. Research Reactor Auxiliary Facilities Used for Material Testing and Basic Neutron Science

A catalogue of and attributes of the Materials Irradiation and Testing facilities (MIF) and the Basic Neutron Science facilities (BSF) of auxiliary (AUX) facilities of research reactors are compiled. The survey of these facilities is drawn from the set of U.S. university and DOE research reactor facilities and should be considered as a reference point when comparing commonalities in international AUX facilities. The size and shielding capabilities of the facilities, the typical characterization equipment used, and the neutron flux and irradiation capabilities of the facilities are listed. Short descriptions of experimental activities and current practices are detailed for MIFs and BSFs. The attributes are important in consideration of the reconfiguration of the facilities for purposes other than stated mission, i.e., for proliferation of weapons-usable nuclear material (WUNM). An evaluation of the capacity for production rate of WUNM from neutron beams-on-targets or a sample that has been placed in an irradiation position for a period is provided. Further evaluation of reconfiguration of these MIF and BSF are recommended to refine the proliferation risks. Specifically, MIF hot cells and potential configurations, additional modeling of facility throughput and development of methods for determining levels of concern for MIF and BSF have all been identified as steps for refinement of determination of the risks associated with these facilities. Future work will focus on: 1. A model of projected throughput for different MIF and BSF configurations that will be used to provide a window of potential operational misuse for a facility and better understand the capability of production and the rate of processing for WUNM in these facilities. 2. A misuse study for various configurations of MIF hot cell layouts detailing capacity, specifications, shielding constraints for MIF operations, identification of a maximum shielding thickness, and reasonable need associated with each activity performed in a MIF. 3. Development of a rule of thumb rating system utilizing data gathered from previous reports to show levels of concern at a given power level, flux, and experiment set.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Contaminant Migration Modeling to Support the In Situ Decommissioning of Hardened Nuclear Facilities - 20215

The decommissioning of hardened nuclear facilities provides a unique challenge in balancing current worker dose with exposure to future receptors and media. In situ decommissioning (ISD) is a cost-effective and safe option for the closure of such facilities but requires a detailed understanding of the threat that radioactive and hazardous constituents remaining in the facilities pose to groundwater and surrounding surface water. The Savannah River Site (SRS) extensively employs contaminant migration models within the decommissioning process to develop site-specific removal, grouting, and monitoring strategies in support of safe and effective final end states of nuclear facilities. This work discusses the use of contaminant migration modeling in the ISD process at SRS, including specific examples from the closure of P-Reactor and R-Reactor, Building 235-F, F-Canyon and F/H Laboratory Complex. Migration models developed during the closure of P-Reactor and R-Reactor were divided into four source areas: the reactor vessel, the process area, the disassembly basin, and the purification wing. Each source area was assigned a specific inventory and migration pathway and was then subject to varying hypothetical removal, capping, and grouting schemes. Modeling indicated that groundwater Maximum Concentration Limits (MCLs) might be exceeded if no action was taken for eleven and ten constituents of concern (COCs) at P-Reactor and R-Reactor, respectively. These exceedances could occur in as few as 200 to 500 years. Alternatively, the migration modeling demonstrated that the selected ISD actions reduced contaminant mobility which allowed for significant radioactive decay and resulted in fewer predicted exceedances of groundwater MCLs (five COCs for P-Reactor; eight COCs for R-Reactor). In response to the modeling results for P-Reactor and R-Reactor, effectiveness monitoring programs were developed to target contaminants, specific to each reactor, that may migrate to groundwater. Contaminant migration modeling also revealed that roof collapse was a large factor in the release of COCs to the environment, giving rise to roof improvements, and an inspection and vegetation control program to ensure roof stability over time. Contaminant migration modeling is also aiding in the closure planning for hardened facilities in F Area. Building 235-F housed the Actinide Billet Line, which produced Np-237 billets for irradiation in SRS reactors, and the Plutonium Fuel Form (PuFF) facility that produced Pu-238 heat sources for the space program. As a result of these missions, areas within Building 235-F contain considerable residual amounts of both Pu-238 and Np-237. Contaminant migration modeling of Building 235-F was originally performed in 2012 to identify the feasibility of ISD and the amount of radioactive material removal required to prevent the exceedance of groundwater MCLs. The original model indicated that a 60% reduction in the PuFF facility Pu-238 inventory could keep groundwater concentrations below standards, while Np-237 did not pose a threat to groundwater. However, updates to the model with an emphasis on source impact pathways revealed that, due to the orientation of the source areas relative to groundwater flow, no amount of reasonable removal of Pu-238 would keep groundwater concentrations below MCLs and that Np-237 could be a large contributor to localized MCL exceedances. With this insight, the refined 2019 model is being used to assist in the development of grouting plans specific to each facility source area, where bentonite may be utilized to slow the migration of Pu-238 and its daughter products from the PuFF facility and a reducing grout may decrease Np-237 transport by ensuring the nuclide remains in the less mobile +IV oxidation state. The beginning phases of contaminant migration modeling are underway for F-Canyon and associated facilities using lessons learned from the Reactors and Building 235-F. A contaminant migration pathway, similar to the pathway used for the reactor vessels, is being developed for the hot and warm canyons. The F-Canyon inventories are being spatially refined to identify specific and localized source zones, comparable to Building 235-F, that may impact groundwater. Contaminant migration modeling provides vital input within the ISD process, from facility investigation to post closure effectiveness monitoring, making it a valuable tool in the development of safe and effective end states for hardened nuclear facilities at SRS. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Findings on subtask 3.3 – applicability of automated brine chemistry determinations for treatment and recovery processes through facility automation/modularization: engineering design study

Under the Energy & Environmental Research Center’s (EERC’s) ~$\$$22 million Phase II Brine Extraction and Storage Test (BEST) Program, a multimillion-dollar brine treatment technology test bed facility was established in western North Dakota to provide a platform for evaluating developing technologies and approaches for brine treatment and volume reduction. The initial facility, and associated research effort, was funded by the U.S. Department of Energy (DOE), with in-kind contributions provided by several industry participants and the state of North Dakota. Since its opening, the Brine Technology Test Facility (BTTF) has supported performance evaluations of desalination technologies capable of treating high-salinity produced water (PW) and enabled data collection for multiple approaches of PW management and critical material recovery. As part of the decommissioning process for the original project, facility ownership and liability were transferred to Select Water, which is providing the EERC with a continuing site access option for state or federal research and/or commercial technology development. This report documents the findings from a design study conducted by the EERC and the engineering firm that was originally contracted to design and construct the facility (Advanced Engineering and Environmental Services, LLC [AE2S]) that evaluated the current status of BTTF and its systems and developed a retrofit design to increase the facility’s capabilities through automation and modularization of its PW treatment infrastructure. The proposed retrofit will provide DOE and industry with an expanded range of conditioned PW that can be produced at the facility for evaluating fit-for-purpose water treatment technologies, online instrumentation for brine chemistry determination, and systems that recover critical materials like lithium and magnesium. The current facility consists of an 9600-square-foot facility that includes a 40-foot by 65-foot Class 1, Division 2-rated demonstration area and associated control rooms and lab-ready space capable of sourcing oil and gas PW and wastewater from industrial sources or tailoring brine compositions up to 300,000 mg/L total dissolved solids (TDS) and supplying them at rates up to 25 gpm for extended-duration technology demonstrations. The colocation of the facility with Select Water’s water management facilities allows for access and unloading of more than 10,000 bbl/day of trucked water delivered to site and associated access to on-site Class I and Class II brine disposal wells and nearby hazardous waste landfills operated and/or contracted by Select Water to dispose of concentrate and/or effluents associated with the testing.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Calculating Methane Emissions from Offshore Facilities Using Bottom-Up Methods

With changing demands in regulation, understanding methane emissions from offshore oil and gas production infrastructure has become increasingly important. Reported emissions from facilities in the Gulf of Mexico range from zero to thousands of tons of methane per hour, but these is currently no clear understanding of how this range compares to expected emissions from normally operating facilities. To generate realistic emission estimates, we create two bottom-up models that simulate emissions from facilities operating in the Gulf of Mexico. We estimate type 1 prototypical facilities (typically unmanned, older, lower-producing platforms in shallow water with little processing equipment, compressors, or storage tanks) to emit an average of 13 kg CH 4 h −1 , which corresponds to a loss of 2.7% of the average facility production. Type 2 prototypical facilities (continuously manned, higher production and operate in deeper water with processing equipment, oil storage tanks, compressors and power generation) emit an average of 88 kg CH 4 h −1 , which corresponds to a loss of 2.5% of production. The average measured emission from type 1 facilities was 18 kg CH 4 h −1 with a median production loss estimated at 8%. The average measured emission from type 2 facilities was 36 kg CH 4 h −1 with a median production loss estimated at 2.4%. Using emission factors that consider the long-tail emission distribution partly reconciles the difference between modelled and measured emission estimates, but we suggest the current the fugitive emission estimate may be an underestimate and more data on the number and size of fugitive emissions could explain differences between the modelled and measured emission estimate. We suggest the bottom-up approach described here that uses production data coupled with facility equipment could be used to identify facilities that have abnormally large measured emissions, caused by methodological failure or larger than expected fugitive emissions, which should be targeted for further evaluation resulting in remeasurement or identification of source type so that a more accurate estimates can be made on the absolute emission.

bottom-up↗