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At least 19 records

Progress Report on Graphite-Salt Intrusion Studies

The document reports on the design, construction, testing and initial operation of the ORNL graphite intrusion system with pressurized molten salts. This technical memorandum is responsive to work package AT-20OR04060203, “Graphite-Salt Studies” —ORNL”, and fulfills Milestone M3AT20OR040602035 “Report on graphite-salt intrusion studies”.The report outlines the procedure of graphite intrusion experiments, which follows the ASTM standard guidance, and the procedures of other characterization measurements of graphite physical properties, also based on ASTM standard methods. A set of 12 graphite grades of various origin and properties went through preliminary characterizations, and six of them were further selected for intrusion experiments with molten FLiNaK. The results are discussed in the context of graphite physical properties and are compared with a several results from literature. The correlation between molten salt impregnation and mercury intrusion, first proposed by MSRE scientists, is discussed in detail. Pending collection of more data, the mercury intrusion porosimetry technique may possibly be used as a rapid method for screening and down selection of graphite grades with extremely low salt intrusion, as required for operation in molten salt reactors. This new system will generate data non only on intrusion behavior, but will also generate a wide range of salt- impregnated graphite samples that will be further analyzed with advanced characterization techniques for better understanding of the effect of salt intrusion on the properties of nuclear graphite. It expected that these results and future results obtained with this system will help advance our understanding of the factors controlling the extent of salt penetration in graphite and of the relationship with intrinsic structural properties of various grades. Together, correlating direct measurements results and graphite structural properties should allow development of a predictable model that could be used for selection and qualification of optimal graphite grades, tailored to design operation conditions and molten salt properties.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Response of salt intrusion in a tidal estuary to regional climatic forcing

Abstract Salinity distribution in a large tidal estuary is subject to estuarine adjustment under the influences of multiple physical drivers such as freshwater pulses and sea level rise, and is crucial to upstream water quality, aquaculture, and ecosystem functions of the estuary. To better understand the estuarine salinity response to climate change, the unstructured-grid Finite Volume Community Ocean Model was implemented to simulate the salt intrusion in the Delaware Bay Estuary. The model was first validated by multiple observational data sets and subsequently applied in an idealized setting to examine the response of salt front to freshwater pulses in high flow conditions, followed by a long-term drought condition supported by a multi-decadal streamflow drought analysis in the estuary. The model results showed that after the freshwater pulses the salt front location moved further upstream with sea level rise. Under the simulated long-term drought condition, the adjustment timescale of salt intrusion varies nonlinearly with sea level rise. With a significant increase in sea level rise, the adjustment timescale starts to decrease. This shift suggests a transition into a different regime where the estuary becomes more stratified, as indicated by an increasing bulk Simpson number with rising sea levels.

54 ENVIRONMENTAL SCIENCES↗

Response Of Salt Intrusion In A Tidal Estuary To Regional Climatic Forcing (FVCOM Output for the baseline scenario)

Salinity distribution in a large tidal estuary is subject to estuarine adjustment under the influences of multiple physical drivers such as freshwater pulses and sea level rise, and is crucial to upstream water quality, aquaculture, and ecosystem functions of the estuary. To better understand the estuarine salinity response to climate change, the unstructured-grid Finite Volume Community Ocean Model was implemented to simulate the salt intrusion in the Delaware Bay Estuary. The model was first validated by multiple observational data sets and subsequently applied in an idealized setting to examine the response of salt front to freshwater pulses in high flow conditions, followed by a long-term drought condition supported by a multi-decadal streamflow drought analysis in the estuary. The model results showed that after the freshwater pulses the salt front location moved further upstream with sea level rise. Under the simulated long-term drought condition, the adjustment timescale of salt intrusion varies nonlinearly with sea level rise. With a significant increase in sea level rise, the adjustment timescale starts to decrease. This shift suggests a transition into a different regime where the estuary becomes more stratified, as indicated by an increasing bulk Simpson number with rising sea levels. These findings have been summarized into a journal manuscript. The data included in this information release request are FVCOM model output associated with the numerical simulations described in the journal manuscript.

Liu, Jinliang↗

Understanding FLiNaK Salt Intrusion Behavior on Nuclear-Grade Graphite via Neutron Tomography

Graphite is an essential material as a neutron moderator in molten salt reactors (MSRs). To understand the impact of salt on the graphite structure to develop structural materials for MSRs, molten salt intrusion behavior on nuclear-grade graphite was studied. The graphite samples, IG-110 and PCEA, were tested for infiltration with LiF-NaF-KF (FLiNaK) at 750°C, 5 bar for 12 h, and, after the intrusion experiment, the graphite was analyzed by neutron imaging. The graphite and Li from FLiNaK showed great contrast in the neutron attenuation coefficient. Thus, the salt behavior in the graphite structure has been visualized for the first time without damaging the sample. The 3D image of the graphite was reconstructed after a neutron computed tomography scan, and the average salt coverage distribution of the XY surface in different depths was obtained from the reconstructed 3D images.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

A neutron tomography study to visualize fluoride salt (FLiNaK) intrusion in nuclear-grade graphite

Manufactured graphite is a preferred material for in-core components of molten salt reactors and fluoride salt-cooled high-temperature reactors, which are in permanent contact with liquid salts. However, owing to the porous nature of nuclear graphite, under certain conditions, molten salts may intrude graphite's pores and affect graphite's properties and functionality. Therefore, a better understanding of molten salt intrusion (distribution across sample cross section and penetration depth) is needed to assess its effects. Here, in this work, we have demonstrated the use of neutron imaging (computed tomography) in the evaluation of salt penetration and distribution of a wide range of graphite grades with diverse microstructures that have been subjected to FLiNaK (LiF–NaF–KF) intrusion at 750 °C and 5 bar pressure for 12 h. Because of the great neutron attenuation contrast from scattering and adsorption between Li (from FLiNaK) and the graphite matrix, we have obtained direct visualization of FLiNaK salt distribution in the salt-impregnated graphites for the first time. Three-dimensional reconstructed images and cross-sectional concentration profiles demonstrate that salt penetration and density distribution are greatly dependent on the microstructural properties of the graphite grade.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Viewing is understanding: Graphite microstructure effects on infiltrated molten salt distribution revealed by 3D neutron tomography

Molten salt infiltration in the pore network of nuclear graphite may cause unwanted changes to graphite's local structure and mechanical and thermal properties. A detailed and comprehensive understanding of molten salt intrusion (distribution across sample cross section and penetration depth) is needed to assess its effects. Here, in this work, we report on an improved methodology for the use of neutron imaging (computed tomography) to evaluate salt penetration and distribution of a wide range of graphite grades with diverse microstructures. Neutron tomography data were acquired on the same graphite sample before and after salt intrusion; the 3D reconstructed volumes were digitally co-registered and subtracted. The difference in neutron attenuation coefficient represents direct visualization of FLiNaK (LiF–NaF–KF) salt distribution in the salt-impregnated graphite samples. This improved methodology was applied to investigate the effect of exposure times (12 h and 336 h) and of graphite microstructure when exposed to FLiNaK at 750 °C and 3 bar (gauge) pressure, starting from flowing argon at near atmospheric pressure. The results show that medium-grained and fine-grained graphites evolve to equilibrium at significantly different rates: fast salt uptake in medium-grained graphites produces salt deposits throughout the volume of graphite specimens, whereas salt infiltration in fine-grained graphites is much slower and limited to exposed surfaces.

FLiNaK infiltration↗

GRAPHITE–MOLTEN SALT CONSIDERATIONS FOR COMPONENTS IN NUCLEAR APPLICATIONS

The new High Temperature Reactor (HTR) designs being considered for future Gen IV nuclear reactor deployment include designs utilizing molten salt as the primary coolant. These molten-salt cooled, graphite core designs pose new material compatibility challenges that are not considered within the gas-cooled HTR designs that have been previously built and operated. While the Molten Salt Reactor Experiment (MSRE) demonstrated that the molten salt can be considered chemically inert to graphite the novel physical and thermal interactions that the molten salt poses may be just as impactful as the chemical reactivity. Specifically, molten salt intrusion into the open pore structure of nuclear graphite grades can provide additional internal stresses within the microstructure exacerbating the stress buildup from irradiation induced dimensional change. Additionally, designs using a molten salt containing liquid fuel could provide “hot spots” within graphite structural components causing local thermal stresses. Abrasion and erosion concerns are magnified with molten salt due to the extremely high density of the salts (some have higher densities than the structural graphite components). Finally, the graphite-graphite and fuel pebble-graphite tribological behavior are distinctly difference within the molten salt from the inert gas environments and must be investigated. These topics and others are currently under investigation within the DOE Advanced Reactor Technologies (ART) graphite program and will be discussed in depth.

Gallego, Nidia↗

Progress Report on Graphite-Salt Interaction Studies (FY21)

This report summarizes the activities performed in FY21 to investigate the interactions between nuclear graphite and molten salts, such as FLiNaK. First, building on last year’s achievements, the team improved the procedure for measurements on pressurized salt intrusion in nuclear graphite and performed new experiments at variable pressures with specimens of different sizes and shapes. Additionally, the team actively provided suggestions and comments for ASTM D8091, Standard Guide for Impregnation of Graphite with Molten Salts , which came up for periodic revision in 2021. Second, the team expanded its capabilities to further characterize salt-impregnated graphite by procuring and installing a laser-induced breakdown spectroscopy (LIBS) instrument capable of producing a 3D chemical composition of a surface and subsurface region of specimens. A methodology for accurately analyzing information was developed, and a manuscript was submitted for publication. The LIBS instrument sample cell is sealed in controlled inert atmosphere, which is an advantage for using humidity-sensitive samples and Be-contaminated samples. This aligns with the team’s effort to expand the capabilities of handling FLiBe and Becontaining materials in two newly installed glovebox units. Third, the team performed preliminary tribology tests for pebble graphite wear in contact with stainless steel in dry state and in molten salt at high temperature. These tests are needed to establish the baseline for the wear of pebble graphite by friction against metallic walls. The friction and wear of pebbles in the fluoride salt-cooled hightemperature reactor are expected to generate dust, which is a concern for other components’ properties and safe reactor operation.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Demonstrate and De-Risk an Internally Lined Tank Design for Molten-Salt Thermal Energy Storage Benefitting CSP and Nuclear-Energy Sectors

The LIMOSA project extends the Gen3 CSP "Liquid Pathway" project to evaluate 720 degrees C thermal energy storage based on molten chloride salts. While SETO selected the Particle Pathway for Gen3 demonstration, LIMOSA was created to resolve a major risk factor with molten chloride salts - the design of the salt storage tank. The project team designed and assembled a test system leveraging experience from Oak Ridge National Lab and the Liquid Pathway Phases 1 and 2. The key innovation in the project is development of a graphite-foil barrier to protect insulation from salt intrusion and wetting.

chloride salt↗

Modeling the microplastic distribution along the Delaware River Estuary: Accumulation patterns and hydrodynamic influences

Microplastic pollution is an escalating environmental concern, particularly in densely populated estuary regions, where it poses significant threats to aquatic life and human health. The dispersion patterns of microplastic particles along estuaries are influenced and complicated by multiple environmental factors such as river flow, tidal mixing, salt intrusion, and estuarine circulation. This study examines the accumulation and dispersion patterns by modeling three typical classes of microplastics in the Delaware River Estuary: synthetic fibers, sinking plastic films, and rising plastic pellets. Our findings reveal specific areas with high microplastic accumulation for each type. Notably, the upper estuary regions exhibit significant retention of rising microplastics, associated with a region with reduced along-thalweg velocities downstream of Trenton, NJ and upstream of Philadelphia, PA. Conversely, synthetic fibers and sinking plastic films accumulate in the flow convergence zone near the bottom salinity front, typically downstream of Philadelphia. All of the microplastic accumulation hot spot locations are controlled by the balance of river discharge and salinity intrusions. During the dry season, microplastic accumulation hot spots shift upstream in the estuary, whereas in the wet season, the strong river discharge pushes them downstream. Furthermore, on the other hand, tidal mixing, settling, and resuspension processes strongly impact the spreading of microplastics along the river.

Delaware River Estuary↗

A Numerical Study of Hypoxia in Chesapeake Bay Using an Unstructured Grid Model: Validation and Sensitivity to Bathymetry Representation

A three-dimensional unstructured-grid hydrodynamic and water quality model (Semi-implicit Cross-scale Hydroscience Intergrated System Model-Integrated Compartment Model) is applied successfully for Chesapeake Bay. The model is validated with observations of salinity, chlorophyll-a, dissolved oxygen, nutrients, and phytoplankton productions from the year 1991 to 1995 for the mainstem and some major tributaries, based on multiple model skill scores. Model experiments are conducted to test the importance of having (1) an accurate representation of bathymetry to correctly predict hypoxia and other processes and (2) a high-resolution model grid for tributaries to correctly simulate water quality variables. Further, comparison with the model experiment results with bathymetry smoothing indicates that bathymetry smoothing, as commonly used for many systems, changes the stratification and lateral circulation pattern, resulting in more salt intrusion into shallow water regions, and an increase in the freshwater age. Consequently, a model with bathymetry smoothing can lead to an unrealistic prediction of the distribution of hypoxia and phytoplankton production. Local grid refinement shows significant improvement of model simulations on local stratification and water quality variables. Overall, the use of high-resolution unstructured grid model leads to a faithful representation of the complex geometry, and thus a seamless cross-scale capability for simulating water quality processes in the Bay including tributaries and tidal creeks.

54 ENVIRONMENTAL SCIENCES↗

DOE ART Graphite R&D Introduction

Introduction of ART Graphite R&D to include oxidation activities, oxidation resistant graphite, model development, ASME component failure, ASME code development (design rules), ceramic composites, AGC update, molten salt intrusion, split-disk studies, wear testing, and concluding remarks.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Year-around survey and manipulation experiments reveal differential sensitivities of soil prokaryotic and fungal communities to saltwater intrusion in Florida Everglades wetlands

Global sea-level rise is transforming coastal ecosystems, especially freshwater wetlands, in part due to increased episodic or chronic saltwater exposure, leading to shifts in biogeochemistry, plant- and microbial communities, as well as ecological services. Yet, it is still difficult to predict how soil microbial communities respond to the saltwater exposure because of poorly understood microbial sensitivity within complex wetland soil microbial communities, as well as the high spatial and temporal heterogeneity of wetland soils and saltwater exposure. To address this, we first conducted a two-year survey of microbial community structure and bottom water chemistry in submerged surface soils from 14 wetland sites across the Florida Everglades. We identified ecosystem-specific microbial biomarker taxa primarily associated with variation in salinity. Bacterial, archaeal and fungal community composition differed between freshwater, mangrove, and marine seagrass meadow sites, irrespective of soil type or season. Especially, methanogens, putative denitrifying methanotrophs and sulfate reducers shifted in relative abundance and/or composition between wetland types. Methanogens and putative denitrifying methanotrophs declined in relative abundance from freshwater to marine wetlands, whereas sulfate reducers showed the opposite trend. A four-year experimental simulation of salt-water intrusion in a pristine freshwater site and a previously saltwater-impacted site corroborated the highest sensitivity and relative increase of sulfate reducers, as well as taxon-specific sensitivity of methanogens, in response to continuously pulsing of saltwater treatment. Collectively, these results suggest that besides increased salinity, saltwater-mediated increased sulfate availability leads to displacement of methanogens by sulfate reducers even at low or temporal salt exposure. In conclusion, these changes of microbial composition could affect organic matter degradation pathways in coastal freshwater wetlands exposed to sea-level rise, with potential consequences, such as loss of stored soil organic carbon.

54 ENVIRONMENTAL SCIENCES↗

In Situ Spectroscopic Monitoring of MSR Molten Salt and Off-Gas Systems

A significant challenge that must be overcome before commercialization of molten salt reactors is tracking special nuclear material (SNM) through the reactor and subsystems such as fuel chemical processing and off-gas systems. In recent years, several approaches have been explored to track SNM, fission products, and corrosion products in these different subsystems. One such approach is to employ laser and optical spectroscopy to measure the atomic and molecular signals of MSR salts. The advantages of these approaches are that they typically are non-intrusive and offer the capability of process monitoring while still providing low uncertainties. At the Idaho National Laboratory, spectroscopy approaches such as laser-induced breakdown spectroscopy (LIBS) and ultraviolet-visible (UV-Vis) spectroscopy have been utilized to investigate molten salts in an aerosol (LiCl, KCl, RbCl2, NdCl3, and PrCl3) and vapor phases (MgCl5, NdCl5, and ZrCl4) with success. Testing to date has yielded qualitative information on all the above species and quantitative data and analytical figures of merit for species in the vapor phases. These findings, including results from ongoing testing, as well as the experimental conditions and potential applications will be presented.

98 - NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL↗

Linear and Nonlinear Solvers for Simulating Multiphase Flow within Large-Scale Engineered Subsurface Systems

Simulation of multiphase flow in the subsurface is well-known to be computationally challenging. While there have been many studies that have explored approaches to overcoming these challenges, they often utilize relatively simple case studies. In this paper, we focus on the unique numerical challenges posed by modeling large-scale engineered subsurface systems, characterized by discrete features embedded in a heterogeneous natural subsurface setting. The man-made features such as shafts, tunnels, and barriers often cause multiple challenges in modeling the domain for multiphase porous media flow. This flow scenario can have a wide range of applications such as nuclear waste repositories, enhanced recovery of a petroleum reservoir, geothermal engineering, and carbon sequestration. An example of these severe numerical challenges is the case of performance assessment (PA) for Waste Isolation Pilot Plant (WIPP), the only operating deep geological repository in the US, which simulates extreme material properties of bedded salt rock formation and extreme contrast due to open excavation next to the formation. The models have extremes not only of permeability and porosity but also of the constitutive models needed for multiphase flow; additionally, they have process models like salt creep closure reducing porosity over time, fracturing in clay and anhydrite interbeds of the bedded salt, gas generation from the waste materials, and unintentional human borehole intrusions in some scenarios. Numerical simulations require the solution of coupled systems of nonlinear PDEs; in our work, we use the open-source simulator PFLOTRAN which is based on Finite Volume discretization. The solution of the nonlinear equations requires use of the Newton-Raphson iteration at each time step, which entails the solution of the linearized Jacobian system at each iteration. The effects of all the processes (i.e., large number of unknowns, highly nonlinear constitutive relations, large contrasts in material properties in short distances) lead to an ill-conditioned Jacobian matrix that severely challenges traditional linear solver, i.e., stabilized biconjugate gradient with block Jacobi incomplete LU preconditioner (BCGS-ILU) leading to non-convergence for traditional Newton-Raphson nonlinear solver causing unacceptably long computation time for each model. This paper presents linear solvers such as constrained pressure residual (CPR) two-stage preconditioner with alternate-block-factorization (ABF) and quasi- implicit pressure and explicit saturation (QIMPES) decouplers and flexible generalized residual solver (FGMRES). The new general-purpose nonlinear solver, Newton trust-region dogleg Cauchy (NTRDC), is also introduced to resolve extreme nonlinearities in the models. We demonstrate the effectiveness of each method relative to the default BCGS-Newton solver. The two best cases had nearly 50 times speed-up and achieved completion of a simulation in 14 hours that never completed due to non-convergence with the default solver. We also investigate the strong scalability of each method and discuss some of the deficiencies found for Block Jacobi preconditioner using parallel domain decomposition, and node packing effects of modern processor architecture.

Preconditioner, Nonlinear, Porous media, Multiphas↗

AquaMEND: Reconciling multiple impacts of salinization on soil carbon biogeochemistry

Soil salinization, exacerbated by climate change, poses a global threat to coastal ecosystem function and soil quality. Salinity influences carbon cycling through direct effects on microbial activity and indirect alterations to soil physicochemical properties including cation exchange, pH, and soil organic carbon availability. Current models inadequately represent these complexities, relying on linear reduction functions that overlook specific physicochemical changes induced by salinity. To address this gap, we propose an integrated model framework, AquaMEND, that combines microbial-explicit carbon decomposition and geochemical models. This model allows cation exchange and surface complexation processes to capture solute chemistry and nutrient availability in soils upon saltwater intrusion. Using response functions that capture salinity impacts on both salt-sensitive and salt-resistant microbial processes, AquaMEND simulates how the abiotic and biotic mechanisms work individually and collectively to regulate organic and inorganic pools and fluxes. Here, the parallel structure of aqueous and non-aqueous phases, together with microbial functions, result in a versatile model for solving dynamic coupling of organics, minerals and microbes under various environmental settings.

54 ENVIRONMENTAL SCIENCES↗