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At least 73 records · Page 4

Engineering-Scale Batch Purification of Ternary MgCl 2 -KCl-NaCl Salt Using Thermal and Magnesium Contact Treatment

High-temperature molten chloride salts are a desirable heat transfer and energy storage media. The NaCl-KCl-MgCl 2 is of particular interest because of its low melting point and relatively inexpensive constituents. Moisture and hydroxides must be removed from the salt to control corrosion at high temperatures. Previous studies have developed and demonstrated various techniques for bench-scale salt purifications. This paper details the system, process, and insight gained in the purification of a 200 kg scale batch of NaCl-KCl-MgCl 2 salt at Oak Ridge National Laboratory.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Sludge Batch 11 Assembly: Tank 35

Savannah River Mission Completion Nuclear Safety and Engineering Integration (SRMC-E) has requested that Savannah River National Laboratory (SRNL) perform Tank 35 characterization analyses in support of Sludge Batch 11 (SB11) assembly. Two Tank 35 samples were delivered to SRNL and composited into a single sample in April 2023. The composite sample was analyzed for the following: density, weight percent solids, chemical composition, radionuclides, supernate corrosion control tests, and x-ray diffraction for burkeite, gibbsite, and boehmite.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Sludge Batch 11 Assembly: Tank 15

Savannah River Mission Completion Nuclear Safety and Engineering Integration (SRMC-E) has requested that Savannah River National Laboratory (SRNL) perform Tank 15 characterization analyses in support of Sludge Batch 11 (SB11) assembly. This report provides important characterization of the slurry in Tank 15 prior to transfer from Tank 15 to Tank 13 (prior to sending to Tank 51) in order to demonstrate that the transfer is "Low Rem" and ensure the sludge concurs with the estimated transfer mass for the SB11 recipe. A total of 3 sets of Tank 15 samples were delivered to SRNL from December 2022 to August 2023. The individual sets of composite samples were analyzed for density, weight percent solids, chemical composition, radionuclides, and/or supernate corrosion control tests.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Sludge Batch 11 Assembly: Tank 26

Savannah River Mission Completion Nuclear Safety and Engineering Integration (SRMC-E) has requested that Savannah River National Laboratory (SRNL) perform Tank 26 characterization analyses in support of Sludge Batch 11 (SB11) assembly. This report provides important characterization of the slurry in Tank 26 prior to transfer from Tank 26 to Tank 51 that confirms the transfer is "Low Rem" and ensures the sludge concurs with the estimated transfer mass for the SB11 recipe. Two Tank 26 samples were delivered to SRNL and composited into a single sample in September 2023. The composite sample was analyzed for the following: density, weight percent solids, chemical composition, radionuclides, supernate corrosion control tests, and x-ray diffraction for burkeite, gibbsite, and boehmite. The slurry was also evaluated for sulfate washing behavior in order to provide knowledge on insoluble sulfate dissolution during Tank 51 sludge washing similar to a previous washing study performed in 2019. The Tank 26 sample results are consistent with and representative of PUREX sludge and the prior usage of Tank 26 as a feed tank for the 1F and 2F Evaporators.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Sludge Batch 11 Assembly: Tank 35

Savannah River Mission Completion Nuclear Safety and Engineering Integration (SRMC-E) has requested that Savannah River National Laboratory (SRNL) perform Tank 35 characterization analyses in support of Sludge Batch 11 (SB11) assembly. Two Tank 35 samples were delivered to SRNL and composited into a single sample in April 2023. The composite sample was analyzed for the following: density, weight percent solids, chemical composition, radionuclides, supernate corrosion control tests, and x-ray diffraction for burkeite, gibbsite, and boehmite.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Sludge Batch 11 Assembly: Tank 26 (Rev.1)

Savannah River Mission Completion Nuclear Safety and Engineering Integration (SRMC-E) has requested that Savannah River National Laboratory (SRNL) perform Tank 26 characterization analyses in support of Sludge Batch 11 (SB11) assembly. This report provides important characterization of the slurry in Tank 26 prior to transfer from Tank 26 to Tank 51 that confirms the transfer is "Low Rem" and ensures the sludge concurs with the estimated transfer mass for the SB11 recipe. Two Tank 26 samples were delivered to SRNL and composited into a single sample in September 2023. The composite sample was analyzed for the following: density, weight percent solids, chemical composition, radionuclides, supernate corrosion control tests, and x-ray diffraction for burkeite, gibbsite, and boehmite. The slurry was also evaluated for sulfate washing behavior in order to provide knowledge on insoluble sulfate dissolution during Tank 51 sludge washing similar to a previous washing study performed in 2019. The Tank 26 sample results are consistent with and representative of PUREX sludge and the prior usage of Tank 26 as a feed tank for the 1F and 2F Evaporators.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Sludge Batch 11 Assembly: Tank 51

Savannah River Mission Completion (SRMC) Nuclear Safety and Engineering Integration has requested that Savannah River National Laboratory (SRNL) perform Tank 51 characterization analyses in support of Sludge Batch 11 (SB11) assembly. This report provides important characterization of the slurry in Tank 51 after transfers from Tank 22, Tank 35, and Tank 13 (post Tank 15 to Tank 13 transfer) to Tank 51 that demonstrates the sludge concurs with the estimated transfer mass for the SB11 recipe. A total of 3 sets of Tank 51 samples were delivered to SRNL from March 2023 to February 2024. The composite sample was analyzed for the following: density, weight percent solids, chemical composition, radionuclides, and supernate corrosion control analyses. The results of the Tank 51 samples are consistent with and representative of expected sludge projections for Sludge Batch 11.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Steady state radiolysis–polyhalide accumulation products [Poster]

The study of steady-state radiolysis of polyhalides is crucial as it simulates the prolonged radiation exposure that materials (e.g., alloys, molten salts) experience in reactor environments. This research provides valuable insights into the long-term effects on material properties, chemical stability, and structural integrity. It is closely linked with fundamental radiation chemistry, which aids in predicting the chemical behavior of accumulation products. Understanding the initial speciation, yield, and chemical evolution of radiolysis products is essential for managing material degradation, controlling corrosion, and ensuring reactor safety.

36 - MATERIALS SCIENCE↗

Novel Mode of Molybdate Inhibition of Desulfovibrio vulgaris Hildenborough

Sulfate-reducing microorganisms (SRM) are found in multiple environments and play a major role in global carbon and sulfur cycling. Because of their growth capabilities and association with metal corrosion, controlling the growth of SRM has become of increased interest. One such mechanism of control has been the use of molybdate (MoO 4 2− ), which is thought to be a specific inhibitor of SRM. The way in which molybdate inhibits the growth of SRM has been enigmatic. It has been reported that molybdate is involved in a futile energy cycle with the sulfate-activating enzyme, sulfate adenylyl transferase (Sat), which results in loss of cellular ATP. However, we show here that a deletion of this enzyme in the model SRM, Desulfovibrio vulgaris Hildenborough, remained sensitive to molybdate. We performed several subcultures of the ∆ sat strain in the presence of increasing concentrations of molybdate and obtained a culture with increased resistance to the inhibitor (up to 3 mM). The culture was re-sequenced and three single nucleotide polymorphisms (SNPs) were identified that were not present in the parental strain. Two of the SNPs seemed unlikely candidates for molybdate resistance due to a lack of conservation of the mutated residues in homologous genes of closely related strains. The remaining SNP was located in DVU2210, a protein containing two domains: a YcaO-like domain and a tetratricopeptide-repeat domain. The SNP resulted in a change of a serine residue to arginine in the ATP-hydrolyzing motif of the YcaO-like domain. Deletion mutants of each of the three genes apparently enriched with SNPs in the presence of inhibitory molybdate and combinations of these genes were generated in the Δ sat and wild-type strains. Strains lacking both sat and DVU2210 became more resistant to molybdate. Deletions of the other two genes in which SNPs were observed did not result in increased resistance to molybdate. YcaO-like proteins are distributed across the bacterial and archaeal domains, though the function of these proteins is largely unknown. The role of this protein in D. vulgaris is unknown. Due to the distribution of YcaO-like proteins in prokaryotes, the veracity of molybdate as a specific SRM inhibitor should be reconsidered.

59 BASIC BIOLOGICAL SCIENCES↗

Coupled Thermal-Hydraulic Analysis and Species Mass Transport in a Versatile Experimental Salt Irradiation Loop (VESIL) Using CTF

With the resurgence of interest in molten salt reactors, there is a need for new experiments and modeling capabilities to characterize the unique phenomena present in this fluid fuel system. A Versatile Experimental Salt Irradiation Loop (VESIL) is currently under investigation at Idaho National Laboratory to be placed in the Advanced Test Reactor (ATR). One of the key phenomena this proposed experiment plans to elucidate is fission product speciation in the fuel-salt and the subsequent effects this has on the fuel-salt properties, source term generation, and corrosion control. Specifically, noble gases (Xe & Kr) will bubble out to a plenum or off-gas system, and noble metals (Mo, Tc, Te, etc.) will precipitate and deposit in specific zones in the loop. This work extends the mass transfer and species interaction models in CTF (Coolant-Boiling in Rod Arrays—Two Fluids) and applies these models to give a preliminary estimation of fission product behavior in the proposed VESIL design. A noble metal–helium bubble mass transfer model is coupled with the thermal-hydraulic results from CTF to determine the effectiveness of this insoluble fission product (IFP) extraction method for VESIL. Amounts of IFP species extracted to the off-gas system and species distributions in VESIL after a 60-day ATR cycle are reported.

Walker, Samuel A.↗

Method for identification of redox control parameters for corrosion mitigation in molten fluoride salts

Structural material corrosion is a significant concern for the development of molten salt-cooled reactors (MSR) and redox control was proposed to mitigate the corrosion. This study presents an efficient approach to identify the partial pressure of F 2 gas for fluorine driven corrosion, the concentration ratios of UF 4 /UF 3 and ZrF 4 /ZrF 2 , and the partial pressure ratio of HF/H 2 needed to limit metal corrosion and its subsequent dissolution in molten fluoride salts. The identification procedure is made by simply using auxiliary axes in Ellingham diagrams. This approach greatly simplifies the optimization of redox control methods in studying the material corrosion in molten salts.

36 MATERIALS SCIENCE↗

A systematic study of lanthanide titanates (A 2 Ti 2 O 7 ) chemical durability: corrosion mechanisms and control parameters

Dense lanthanide titanates ranging from La 2 Ti 2 O 7 to Yb 2 Ti 2 O 7 were synthesized by spark plasma sintering with similar micro-sized microstructure, and their chemical durability and degradation mechanisms were investigated by semi-dynamic leaching tests. Different corrosion mechanisms from incongruent to congruent dissolution were observed with preferential elemental releases of lanthanides in A 2 Ti 2 O 7 (A = La to Gd) and Ti in Er 2 Ti 2 O 7 and Yb 2 Ti 2 O 7 . Initial leaching was controlled by surface dissolution and long-term dissolution shifted to a diffusion-controlled mechanism for titanate pyrochlores from Sm 2 Ti 2 O 7 to Yb 2 Ti 2 O 7 . Both short-term and long-term leaching rates decreased from La 2 Ti 2 O 7 to Yb 2 Ti 2 O 7 , and materials became more corrosion resistant with decreasing ionic radius ratios of the rare-earth elements and titanium. Amorphous passivation films of several nm-thick enriched with Ti formed on the surfaces of the corroded materials, and the formation mechanisms were governed either by surface reorganization with preferential release of lanthanides or dissolution-precipitation from saturated bulk solutions with preferential release of titanium. Finally, these results demonstrate that the ionic size plays a dominant role in determining chemical durability of lanthanide titanates and a strong correlation is established among chemical composition/structural variation, passivation film formation and corrosion mechanisms, and materials chemical durability.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Insights into the mechanisms controlling the residual corrosion rate of borosilicate glasses

Borosilicate glasses are widely used to confine high-level radioactive wastes. The lifetime of these materials could reach hundreds of thousands of years if leaching of the glass into groundwater enables the formation of a passivating gel layer. Even in this regime, the glass will never stop corroding as thermodynamic equilibrium between glass and solution cannot be achieved. Therefore, accurate predictions of glass durability including passivation, require a deep understanding of the mechanisms controlling the so-called residual rate. However, despite tremendous efforts, these mechanisms remain poorly understood. Here, focusing on the behavior of the soluble elements of the International Simple Glass (B, Na, and Ca), we show that the residual rate is controlled by the behavior of B, a glass former supposed to dissolve instantaneously when in contact with water and thus widely considered as an ideal tracer. We then demonstrate that B release is controlled by multiple processes highly dependent on the pH. At the beginning of the passivating layer formation, the hydrolysis of B-O-Si linkages is rate-limiting and has an activation energy of ~60 kJ mol –1 , a value slightly lower than that for breaking Si-O-Si linkages. Once the fraction of closed pores resulting from gel restructuring is high enough, then diffusion of both reactants (water molecules) and some products (mainly B aq , Ca aq ) through the growing gel layer becomes rate-limiting. Consequently, B and Ca accumulate in an inner layer referred to as the active zone, with potential feedback on the B-O-Si hydrolysis. A new paradigm, including B as a key element of the system, is proposed to develop a comprehensive model for the corrosion of borosilicate glass.

36 MATERIALS SCIENCE↗

Controlled exposure of CuO thin films through corrosion-protecting, ALD-deposited TiO 2 overlayers

Ultra-thin film coatings are used to protect semiconductor photoelectrodes from the harsh chemical environments common to photoelectrochemical energy conversion. These layers add contact transfer resistance to the interface that can result in a reduction of photoelectrochemical energy conversion efficiency of the photoelectrode. Here, we describe the concept of a partial protection layer, which allows for direct chemical access to a small fraction of the semiconductor underlayer for further functionalization by an electrocatalyst. The rest of the interface remains protected by a stable, inert protection layer. CuO is used as a model system for this scheme. Atomic layer deposition (ALD)-prepared TiO 2 layers on CuO thin films prepared from electrodeposited Cu 2 O allow for the control of interfacial morphology to intentionally expose the CuO underlayer. The ALD-TiO 2 overlayer shrinks during crystallization, while Cu 2 O in the underlayer expands during oxidation. As a result, the TiO 2 protection layer cracks to expose the oxidized underlying CuO layer, which can be controlled by preceding thermal oxidation. Furthermore, this work demonstrates a potentially promising strategy for the parallel optimization of photoelectrochemical interfaces for chemical stability and high performance.

14 SOLAR ENERGY↗

Discovering the nanoscale origins of localized corrosion in additive manufactured stainless steel 316L by liquid cell transmission electron microscopy

Here, we use liquid cell scanning transmission electron microscopy (STEM) to directly characterize the nanoscale origins of corrosion initiation in Additive manufacturing (AM) 316 L stainless steel. Under applied anodic potentials, we found that the dislocation cellular boundaries were preferentially corroded and that regions of localize corrosion occurred along the cellular boundaries. We directly observed the earliest stages of corrosion by controlling the biasing parameters to decelerate the corrosion processes. The results show that highly localized corrosion occurs via inclusion dissolution along dislocation cell boundaries. More widespread corrosion initiates at the dislocation cell boundaries and spreads throughout the dislocation networks.

36 MATERIALS SCIENCE↗

Scale up, Field testing, and Optimization of Nontoxic, Durable, Economical Coatings for Control of Biofouling and Corrosion (Abstract Only)

The objective of this project is the technical maturation and demonstration of a durable, economical, and nontoxic coating, Superhydrophobic Lubricant Infused Composite (SLIC), that will prevent fouling organisms from growing on marine and hydrokinetic (MHK) structures and prevent invasive mussels from growing on hydropower structures. SLIC technology was developed and patented by PNNL. It combines multiple antifouling mechanisms to provide excellent antifouling performance, durability, and low hydrodynamic drag without using toxic materials. Advanced proof-of-concept testing and demonstrations completed during a Phase 1 TCF project attracted industry interest and partnerships for this Phase 2 effort focused on maturation of a commercial product. Specific tasks and tests will shift the development emphasis to optimizing formulations, validating antifouling performance to address specific application needs, explore compatibility with other paint systems, develop a product with useful shelf life (in can), and determine curing times and effective applications methodology. Phase 2 efforts will focus upon technology transfer and commercialization of the technology with the industrial team. Industrial partners now include a coatings development specialist (Lorama), hydrophobic material manufacturer and paint developer (Dry Surface Technologies), nontoxic biodegradable lubricants manufacturer (BioBlend), and aquatic applications specialists (Prometheus Innovations, River Connectivity Systems). Engagement with the MHK device developers, the PNNL Marine and Coastal Research Laboratory (MCRL) test site in Sequim WA, Bureau of Reclamation, and Taylor Shellfish throughout the project will provide topical expertise and field test sites that will deliver crucial real-world performance data. Through this Phase 2 effort, SLIC will transition from a Technical Readiness Level (TRL) 5 to TRL 6 and long-term performance data will be acquired through demonstrations. The field test data will allow optimization of SLIC formulation to enhance performance (e.g., durability) and packaging, which are key de-risking activities for technology transfer and ultimately to the production of a viable commercial product.

13 HYDRO ENERGY↗