WEIMOS: Shear Behaviors of Bedded Salt Clay Seams and Their Impact on Disposal Room Porosity.
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This presentation is about the recent progress of my LDRD (233082) about modeling-based assessment of multiple salt performance for underground hydrogen storage, and my talk will be at the CouFrac 2024 conference, Kyoto in Japan.
The Supercritical Water Mixture (SCWM) experiment conducted on the International Space Station (ISS) is designed to study a salt-water solution in the vicinity of the critical transition with a test cell filled with Na2SO4 (aq) 0.5-w. This salt is a Type II salt which undergoes a dramatic decrease in solubility past waters critical point. The paper discusses the liquid-vapor-salt distribution in the test cell for subcritical, trans-critical, and supercritical regimes. In 0-g, the vapor-liquid interface manifests itself by the presence of a large single vapor bubble that is flattened between the two windows. In contrast with pure water, the vapor bubble remains centered in the test cell and is stable for temperatures up to Tc - 50 mK. The processes leading to critical transition during heat-up, as marked by the break-up of the vapor bubble, depends on the applied heating rate. For temperature ramps 1 mKmin, the bubble interface begins to breakup with the formation of a large number of smaller bubbles. For larger temperature ramps (10mKmin), temperature gradients arise in the cell pushing the bubble toward a window surface. As the critical threshold is crossed small variations in cell temperature ( 1 mK) cause an observable spatial variation in density. However, this spatial variation is not discernible as the temperature is increased further into the supercritical regime. The salt precipitation in the vicinity of the critical crossing appears to be heterogeneous in nature with precipitates observable on the cell windows. Direct imaging as well as light scattering indicate a hexagonal structure of the precipitated salt crystals in the near critical regime. The salt deposition is not fully reversible as the temperature is reduced due to window corrosion effects which traps some of the precipitated salt. Critical temperatures as high as 1.9 K above the value for pure water (647.25 K) have been measured. Finally, results on the critical transition phenomena in the presence of an imposed temperature gradient, demonstrating the remarkable stability of the central bubble, are also presented.
Evaluation of high gas velocity and static oxidation behavior of fused-salt-aluminided IN 100 between 1038 and 1149 C
A comprehensive review of the current state of knowledge surrounding molten salt aerosol behavior and bubble transport in molten salt systems relevant to mechanistic source term (MST) analyses of molten salt reactors (MSR) and fluoride high temperature reactors (FHR) was provided. Although relatively little experimental work has been carried out on investigating these phenomena in molten salts compared to that for other nuclear fluids of interest (e.g., aqueous, sodium), the amount of work that has been reported still provides a baseline understanding to inform and design future experimental campaigns on these topics. The bulk of this data is derived from the Molten Salt Reactor Program (MSRP) which was carried out at Oak Ridge National Laboratory (ORNL) nearly 50 years ago, leading to the successful operation of the Molten Salt Reactor Experiment (MSRE). Many other related research efforts are also highlighted in this review, such as recent efforts under the DOE:NE Advanced Reactor Technology (ART) MSR Campaign. The goal of this report is to provide a foundation for modelers to base assumptions on, as well as to make recommendations to experimentalists attempting to close information gaps. As such, Section 4 contains recommendations for future experimental work that may be needed to close current information gaps related to MST modeling of MSRs. Additionally, given the flowing fuel nature of MSRs, the relevance of aerosol and bubble transport behavior in molten salts goes beyond just MST modeling, evidenced by experiences with the pump bowl and off-gas system of the MSRE.
The corrosion behavior of a high creep strength carbide-phase strengthened Ni-based alloy in molten FLiNaK (LiF-NaF-KF: 46.5-11.5-42 mol%) salt in the temperature range of 700°C–750°C has been investigated as a part of the development of structural alloys for fluoride salt-based molten salt reactors (MSRs). The alloy composition was designed based on Hastelloy-N, but with the goal of improving creep strength. Cr depletion depth, a measure of corrosion, was observed to be single micrometers after several hundred hours of corrosion testing. Sequential corrosion testing involving testing of pre-tested samples in fresh salt coupled with SEM-EDS, scanning transmission electron microscopy (STEM) examinations and thermodynamic and kinetic modeling, suggest that the corrosion rate at the alloy-salt interface is governed by diffusion of elements from the alloy bulk to the surface. The carbide phases in the corrosion-tested sample microstructure were identified to be largely M 6 C-type Mo-rich carbides and MC-type mixed carbides. Atom probe tomography (APT) showed some partitioning of Cr and Ti to the carbide phase and showed the carbide phases to be stable at the salt-facing surface.
In this study, we formed core–shell-like polyelectrolyte complexes (PECs) from an anionic bottlebrush polymer with poly (acrylic acid) side chains with a cationic linear poly (allylamine hydrochloride). By varying the pH, the number of side chains of the polyanionic BB polymers (Nbb), the charge density of the polyelectrolytes, and the salt concentration, the phase separation behavior and salt resistance of the complexes could be tuned by the conformation of the BBs. By combining the linear/bottlebrush polyelectrolyte complexation with all-liquid 3D printing, flow-through tubular constructs were produced that showed selective transport across the PEC membrane comprising the walls of the tubules. These tubular constructs afford a new platform for flow-through delivery systems.
Calculations were performed to assess how uncertainties in molten salt property values impact the results of behavior models of molten salt reactor systems under steady-state conditions. The thermophysical and thermochemical properties of salt mixtures being considered for use in molten salt reactors are not yet well characterized and methods used to measure property values to molten salts are not yet well established. The limited property data for salts of interest that are available in the literature are inconsistent and unreliable. Many methods used to measure property values remain developmental in the sense that not all variables affecting measured values have been identified or controlled during the measurement and not all aspects of the measurements affecting data quality are calibrated. A prior report described the repeatability of measurements made at Argonne and the reproducibility of measurements made with the same salts at several institutions is being evaluated. There is significant uncertainty in measured property values due to instrumental limitations and the effects of contaminants in the salts used to make the measurements that impacts predictions of salt behavior in a reactor. Most salts of interest are multicomponent eutectic or near-eutectic mixtures and both uncertainty in the salt composition and uncertainty in measured values. Furthermore, the salt composition evolves over time due to the uptake of impurities from the atmosphere and corrosion of containment vessels. More significantly, fission products will accumulate during operation that change the salt compositions and property values. MSR developers need to understand how this uncertainty in the basic property data of the fuel will impact modeling predictions for normal reactor operation as well was in transient scenarios that will impact the safety basis. The calculations and analyses in this report address the impact of uncertainty in measured property values under steady-state conditions through a generalized parametric study. The pooled uncertainty from contributions by a number of factors were considered and quantified, including varying composition due to impurities and fission products, imprecision in the measured values, and uncontrolled aspects of the measurement. In this way, we can begin to gain an understanding of the magnitude of the impact uncertainty will have in modeling MSR systems.
Remote sensing of the surface of Europa with near-infrared instruments has suggested the presence of hydrated materials, including sulfate salts. Attention has been focused on these salts for the information they might yield regarding the evolution of a putative interior ocean, and the evaluation of its astrobiological potential. These materials exhibit distinct infrared absorption features due to bound water. The interactions of this water with the host molecules lead to fine structure that can be used to discriminate among these materials on the basis of their spectral behavior. This fine structure is even more pronounced at the low temperatures prevalent on icy satellites. Examination of hydrated sulfate salt spectra measured under cryogenic temperature conditions provides realistic constraints for future remote-sensing missions to Europa. In particular, it suggests that a spectrometer system capable of 2-5 nm spectral resolution or better, with a spatial resolution approaching 100 m, would be able to differentiate among proposed hydrated surface materials, if present, and constrain their distributions across the surface. Such information would provide valuable insights into the evolutionary history of Europa.
The corrosion behavior of structural alloys SS304 and IN617 when exposed to vapors of MgCl 2 molten salt at 764 °C for 100 h in an argon atmosphere was investigated as a function of the level of oxidizing impurities (e.g., NaOH) present in the salt. Increasing the concentration of oxidizing impurities in the salt caused an increase in corrosion in both structural alloys, as measured by Cr depletion layers. A poorly adhered oxide scale layer containing Mg, Al, and Cr was observed on the surface of the metals, and local attack was observed as well. The Ni-based IN617 showed lower Cr depletion and less scale formation than the Fe-based SS304. These results demonstrate that oxidizing impurities in the molten salt will impact the vapor phase corrosion for structural members exposed to the molten salt headspace. This finding is highly relevant for understanding the effects of the vapor phase in molten salt applications, including molten salt thermal energy storage, molten salt nuclear reactors, and molten salt electrochemistry.
The influence of the microstructure on the corrosion rate of three monolithic SiC samples in FLiNaK salt at 900 °C for 250 h was studied. The SiC samples, labeled as SiC-1, SiC-2, and SiC-3, had corrosion rates of 0.137, 0.020, and 0.043 mg/cm 2 h, respectively. Compared with grain size and the presence of special grain boundaries (i.e., Σ3), the content of high-angle grain boundaries (HAGBs) appeared to have the strongest influence on the corrosion rate of SiC in FLiNaK salt, since the corrosion rate increased six times as the concentration of high-angle grain boundaries increased from 19 to 32% for SiC-2 and SiC-1, respectively. The results here stress the importance of controlling the content of HAGBs during the production process of SiC.
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Underground caverns in salt formations are promising geologic features to store hydrogen (H2) because of salt’s extremely low permeability and self-healing behavior. Successful salt-cavern H2 storage schemes must maximize the efficiency of cyclic injection-production while minimizing H2 loss through adjacent damaged salt. The salt cavern storage community, however, has not fully understood the geomechanical behaviors of salt rocks driven by quick operation cycles of H2 injection-production, whic
To address the need for physics-based models to predict corrosion behavior of materials in molten salts, here we propose potential methods to aid in selection of optimum materials for structural components in molten salt powered technologies. In the present work, the role of alloy thermodynamics and kinetics on governing corrosion rates of Ni-based alloys will be discussed combining experimental and computational methods. A few strategies are presented to quantify corrosion rates of Ni-based materials isothermally exposed in purified KCl-MgCl 2 salts at 600° C-800° C. The influence of capsule material, potential corrosion products and role of alloy composition on the observed corrosion rates was discussed with coupled thermodynamic-kinetic models. Larger depths of corrosion attack were observed in alloy 230 specimens compared to other alloys under similar conditions was attributed to the much higher chemical activity of Cr in the alloy that results in a larger Cr chemical potential gradient.
The design and development of fully functional Molten-Salt Reactors (MSR) require detailed knowledge of the molten salt properties in order to understand and predict the salt’s behavior. Fundamental properties of interest include molecular structure, speciation, and dynamics (such as diffusion coefficients) of salt components and dissolved corrosion and fission products. Computer modeling is necessary to predict changes in physical and chemical properties due to irradiation, burning of dissolved fuel, and corrosion. The modeling requires experimental data, and advanced neutron and x-ray scattering and spectroscopy provide the most reliable and direct determination of the structure (Pair-Distribution Functions, PDF), and dynamics of ions in the melt. This project dealt with both fluoride and chloride salts. The PDFs have been measured by a combination of neutron and x-ray diffraction. We utilized the techniques of isotope substitutions, a very powerful tool available for neutron-scattering, to extract the details of the liquid structure. Although similar measurements have been done before, modern advanced neutron and x-ray-scattering techniques allow collecting the data at much higher resolution and in a wider range of temperatures. Importantly, we were among the first to study fluoride salts by neutron scattering. The importance of impurities and their effects on salt properties have become apparent recently and so new methods of salt purification were developed. We took advantage of these developments to produce reliable data, which have been used for computer simulations of both clean salts and those with added fission and corrosion products most relevant for MSRs. Ab initio molecular dynamics simulations have been performed to understand the multi-component liquid solution, in particular solubility of impurities and thermodynamic interactions in relation to the ionic-cluster structure of the fluid. We applied machine learning to regress from the simulation and experimental data in order to develop a fast-acting model that can handle molten salt with an arbitrary (≥ 10) number of chemical elements and be able to predict chemical potential as a function of composition and temperature. This project resulted in a number of experimental and computer-simulation publications, a patent application, and numerous conference presentations (American Physical Society, American Chemical Society, and The Electrochemical Society among others). Multiple students and postdocs participated and collaborated on aspects of this project. This project seeded new collaborations between MIT and other institutions, such as the University of Massachusetts Lowell, the University of Illinois Urbana-Champaign, the University of California Berkeley, and Oak Ridge and Los Alamos National Labs. As such, this project has had a broad and lasting impact beyond its original scientific scope.
Tritium, a radionuclide produced through neutron capture by lithium and other elements (beryllium and fluoride) in molten salts, presents unique challenges to radionuclide release. This is true for both fusion energy breeder blankets and molten salt fission reactors. The fundamental understanding of tritium transport is crucial to the safe design and operation of these reactors. The Molten Salt Tritium Transport Experiment (MSTTE), currently under construction at Idaho National Laboratory, aims to investigate tritium transport phenomena using a forced-convection fluoride salt loop. This loop is designed to study various transport mechanisms, such as permeation through metals and gas-liquid interactions, and is intended to support future research on tritium extraction units. A critical aspect of the MSTTE loop design is ensuring a fully developed velocity profile before the fluid reaches the permeation test section where measurements are made. This study employs computational fluid dynamics to model the salt flow behavior within the MSTTE permeation test section. A realizable k-ε turbulent model with enhanced wall treatment is used to simulate the single-phase, vertical upward flow of molten salt FLiNaK under isothermal conditions. The simulation results indicated flow distortion and underdeveloped profiles at all planned flow rates within the test section due to the 85-deg sharp bend. To address this issue, a reduced diameter with a reducer and expander and a flow conditioner are investigated to achieve fully developed flow. The analysis showed that the flow conditioner successfully corrected the flow profile, achieving fully developed behavior at a flow rate of 50 liters per minute (LPM). In conclusion, this research enhances our understanding of flow dynamics in molten salt systems and contributes to optimizing tritium transport control technologies.
This report updates the estimated values of the baseline available drawdowns for the caverns at the Big Hill storage facility, and an updated table listing the available drawdowns. An updated finite element numerical analysis model, which included a fault in the caprock layers, was constructed and the daily data of actual wellhead pressures and oil-brine interfaces was used. The number of available drawdowns for each of the Big Hill SPR caverns is estimated using the new model. All caverns are predicted to have five available drawdowns remaining from a geomechanical perspective. BH-101 and 105 have a region of concern at the floor edge and/or sloping floor, where tensile and dilatant stresses are predicted to occur during each workover. The tensile state is predicted to occur because of the geometries of the edge and floor. Therefore, geomechanical examination for two caverns would be recommended after a drawdown leach. The well integrity of each cavern is not investigated in this report. The estimates for the number of baseline available drawdowns are subject to change in the future as the knowledge of physical phenomena at the sites, and the further development of the models of geomechanical behavior at the sites, evolve over time.