Search NASA⌕ Search

SEARCH · Search NASA

Results for “fluoride”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 109 records · Page 6

Morphological Characterization of Uranyl Fluoride Particles via Atomic Force Microscopy

Uranium hexafluoride (UF 6 ) undergoes a rapid hydrolysis reaction when exposed to atmospheric water. In addition to producing hazardous HF gas, the hydrolysis reaction produces uranyl fluoride (UO 2 F 2 ), a radioactive solid phase particulate material. Because of the technological utility of UF 6 in the nuclear fuel cycle, understanding the transport properties of UO 2 F 2 aerosol produced via UF 6 hydrolysis is important for accident scenarios. Moreover, the fundamental chemical and physical properties of the UF 6 hydrolysis reaction are not completely understood. Recently, several experiments on the aerosol phase properties of UO 2 F 2 produced in this way have shown that under most relevant conditions, the particle size distribution (PSD) of UO 2 F 2 can be extremely small, approximately 3 to 5 nm, which is well below the threshold that can be routinely observed via scanning electron microscopy (SEM). Although readily observable in the aerosol phase, observation of nanometer-sized particles in the condensed phase (i.e. deposited on surfaces) remains a challenge. Here, in this study, we have used atomic force microscopy (AFM) to study the PSD and morphological characteristics of UO 2 F 2 deposited at low and high concentrations under different humidity conditions, a primary variable in the hydrolysis reaction. Here, we find strong agreement between PSD measured in the aerosol phase via scanning mobility particle sizing and PSD measured via AFM, with particle sizes peaked below 4 nm for low-humidity conditions. At higher humidity, the distribution is centered around 5 to 10 nm but extends up to 20 nm. These results are in stark contrast to previous measurements using SEM that show PSD on the order of 300- to 1000-nm particle sizes; moreover, these are the first direct measurements of individual particles of UO 2 F 2 having been produced via UF 6 hydrolysis deposited on surfaces. These measurements, therefore, open a new avenue for collecting and detecting UO 2 F 2 in the condensed phase and further refine the PSD, which is critical for environmental transport determinations.

Uranium hexafluoride↗

Spatially Resolved Raman Spectroscopic Investigation of Uranyl Fluoride: A Case Study in the Importance of Instrument Optimization

Raman spectroscopy is an emerging technique for rapid and nondestructive analysis of nuclear materials for forensic and nonproliferation applications as it is a powerful tool for distinguishing multiple chemical forms of materials with similar stoichiometries. Recent developments in spectroscopic software have enabled rapid data collection with high-speed Raman spectroscopic mapping capabilities. However, some uranium-rich materials are susceptible to degradation in humid air and/or laser-induced phase transformations. To mitigate environmental or measurement-related sample degradation of potential samples of interest, we have taken a systematic approach to define optimized data collection parameters for high-throughput measurements of uranyl fluoride (UO 2 F 2 ), which is an important intermediate material in the nuclear fuel cycle. First, we systematically describe the influence of optical magnification (5× to 100×), laser power, and exposure time on obtained signal for identical particles of UO 2 F 2 and find that at low laser power and exposure times, comparable signal is obtained regardless of optical magnification. Second, we ensure sample integrity during data collection, and third, collect spectroscopic maps that employ optimized parameters to reduce the time required to obtain spatially resolved spectroscopic information. Reductions of 90% and 99% in measurement times are discussed as they relate to differences in resolving spectroscopic features of particles in identical mapping areas. Finally, during this work, we found that additional data processing options were needed and thus developed a customized Python script for importing, processing, analyzing, and visualizing Raman spectroscopic map data.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Neutronics and thermal-hydraulics simulation of generic pebble-bed fluoride-salt-cooled high-temperature reactor (gFHR)

The fluoride-salt-cooled high-temperature reactor (FHR) is one type of the advanced reactors and has been attracting great interest from the research institutes and commercial companies in the recent years. However, currently the technology is relatively immature. To facilitate the design and safety analysis of FHRs, Kairos Power published the generic FHR (gFHR) benchmark. In this paper, a hybrid method combining the stochastic code and deterministic code is developed to simulate the gFHR benchmark. Serpent 2 is employed as a few-group cross section generator and the cross sections are applied to the finite difference neutron diffusion code AGREE. A good consistency with the gFHR benchmark is achieved. The agreement between the Serpent 2 results and the AGREE results shows that the hybrid method is applicable to FHRs. The thermal-hydraulics are coupled to neutronics for the steady-state calculations and good agreement between AGREE and SAM is achieved. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Use of Nucleating Agent NA11 in the Preparation of Polyvinylidene Fluoride Dual-Layer Hollow Fiber Membranes

Polyvinylidene fluoride (PVDF) dual-layer hollow fiber membranes were simultaneously fabricated by thermally induced phase separation (TIPS) and non-solvent induced phase separation (NIPS) methods using a triple orifice spinneret (TOS) for water treatment application. The support layer was prepared from a TIPS dope solution, which was composed of PVDF, gamma-butyrolactone (GBL), and N-methyl-2-pyrrolidone (NMP). The coating layer was prepared from a NIPS dope solution, which was composed of PVDF, N,N-dimethylacetamide (DMAc), and polyvinylpyrrolidone (PVP). In order to improve the mechanical strength of the dual-layer hollow fiber, a nucleating agent, sodium 2,2'-methylene bis-(4,6-di-tert-butylphenyl) phosphate (NA11), was added to the TIPS dope solution. The performance of the membrane was evaluated by surface and cross-sectional morphology, water flux, mechanical strength, and thermal property. Our results demonstrate that NA11 improved the mechanical strength of the PVDF dual-layer hollow fiber membranes by up to 42%. In addition, the thickness of the coating layer affected the porosity of the membrane and mechanical performance to have high durability in enduring harsh processing conditions.

36 MATERIALS SCIENCE↗

Structure and Stability of Iron Fluoride at High Pressure–Temperature and Implication for a New Reservoir of Fluorine in the Deep Earth

Fluorine (F) is the most abundant halogen in the bulk silicate Earth. F plays an important role in geochemical and biological systems, but its abundance and distribution in the terrestrial mantle are still unclear. Recent studies suggested that F reservoirs in the deep mantle are potentially hosted in terrestrial oxide minerals, especially in aluminous bridgmanite. However, the knowledge about the formation and stability field of fluoride in the Earth’s interior is rare. In this study, we combine in situ laser-heated diamond anvil cell, synchrotron X-ray diffraction, and first-principles structure search to show that a new tetragonal structure of FeF 3 is stable at pressures of 78–130 GPa and temperatures up to ~1900 K. Simulation predicted the tetragonal phase takes a much denser structure due to the rotation of FeF 6 octahedral units. The equations of states of tetragonal FeF3 are determined by experiment and verified by simulation. Our results indicate that FeF 3 can be a potential key phase for storing F in the Earth’s lower mantle and may explain some mantle-derived magma with high F concentration.

58 GEOSCIENCES↗

A Fluoride-Rich Solid-Like Electrolyte Stabilizing Lithium Metal Batteries

To address the problems associated with Li metal anodes, a fluoride-rich solid-like electrolyte (SLE) that combines the benefits of solid-state and liquid electrolytes is presented. Its unique triflate-group-enhanced frame channels facilitate the formation of a functional inorganic-rich solid electrolyte interphase (SEI), which not only improves the reversibility and interfacial charge transfer of Li anodes but also ensures uniform and compact Li deposition. Furthermore, these triflate groups contribute to the decoupling of Li + and provide hopping sites for rapid Li + transport, enabling a high room-temperature ionic conductivity of 1.1 mS cm -1 and a low activation energy of 0.17 eV, making it comparable to conventional liquid electrolytes. Consequently, Li symmetric cells using such SLE achieve extremely stable plating/stripping cycling over 3500 h at 0.5 mA cm -2 and support a high critical current up to 2 mA cm -2 . Here, the assembled Li||LiFePO 4 solid-like batteries exhibit exceptional cyclability for over 1 year and a half, even outperforming liquid cells. Additionally, high-voltage cylindrical cells and high-capacity pouch cells are demonstrated, corroborating much simpler processibility in battery assembly compared to all-solid-state batteries.

25 ENERGY STORAGE↗

Investigation of Corrosion Behavior of Carbide Phase Strengthened Nickel‐Based Alloy in Molten Fluoride Salt

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.

Gordon, Ryan [Univ. of Wisconsin, Madison, WI (Uni↗

Positron annihilation lifetime spectroscopy study of polyvinylpyrrolidone‐added polyvinylidene fluoride membranes: Investigation of free volume and permeation relationships

ABSTRACT Polyvinylidene fluoride (PVDF) membranes were prepared via the phase inversion method from casting solutions containing PVDF, dimethylformamide (DMF), and polyvinylpyrrolidone (PVP) as pore former. PVP was used in the casting solution in a range of 0–5 wt % and extracted. The effect on membranes of using PVP in the casting process was analyzed by X‐ray diffraction, differential scanning calorimetry, scanning electron microscopy, viscosity, and water permeability techniques. With an increase of PVP from 0 to 5 wt %, the PVDF casting solution viscosities increased from 858 to 1148 cP; the resulting PVDF membrane thickness increased; and the crystallinity of PVDF membranes decreased from 40.0 to 33.3%, which indicates that the addition of PVP inhibits the degree of crystallization in the PVDF membranes. SEM results revealed the shape and size of macropores in the membranes; these macropores changed after PVP addition to the casting solutions. The impact of structural changes on free‐volume properties was evaluated using positron annihilation lifetime spectroscopy (PALS) studies. PALS analysis indicated no effect on the average radius (~3.4 Å) of membrane free‐volume holes from the addition of PVP to the casting solution. However, the percentage of o ‐Ps pick‐off annihilation intensity, I 3 , increased from 1.7 to 5.1% with increased PVP content. Further, increasing the PVP content from 0.5 to 5% resulted in an increased final pure water permeability flux. For instance, the 210 min flux for a 14% PVDF + 0.5% PVP membrane was found to be 3.3 times greater than a control membrane having the same PVDF concentration. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58 , 589–598

Eren, Bilge↗

Assessment of SCALE and MELCOR for a generic pebble bed fluoride high-temperature reactor

This paper presents the development and application of SCALE and MELCOR models for a fluoride salt-cooled high-temperature reactor (FHR) based on publicly available specifications. SCALE version 6.3beta15 was used to generate power distributions and decay heat curves, and MELCOR version 2.2.18019 was used to calculate the thermal hydraulic response of an assumed FHR primary system. Here, an approach was developed for determining the equilibrium state of the core using depletion of a core slice model and blending of fuel compositions at different burnups to provide three-dimensional fuel composition in the core. Results compared between a core with entirely fresh fuel and one with an equilibrium fuel composition revealed that the equilibrium core led to lower steady-state temperatures but slower cooldown during a loss of flow accident (LOFA). A sensitivity study was then conducted to explore the transient response of our FHR system to variations in thermal hydraulic parameters of the system using the equilibrium core. The inlet temperature, graphite thermal conductivity, and SCRAM time all provided significant control over peak fuel and coolant temperatures. Uncertainties in radionuclide decay data in SCALE were used to perform a decay heat sensitivity study, and we found that uncertainties in decay heat led to negligible impact on peak temperatures during the course of the transient. In all cases evaluated, the observed peak fuel temperatures remained approximately 700 K below anticipated failure limits for the LOFA.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

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↗

Application of the Redlich-Kister expansion for estimating the density of molten fluoride psuedo-ternary salt systems of nuclear industry interest

The development of next-generation molten salt reactors relies on accurate knowledge of the thermophysical properties of the candidate coolant and fueled molten salts. These thermophysical properties include density, viscosity, thermal conductivity, and heat capacity. Because of difficulties in measuring thermophysical properties of molten salts, there are many gaps in the current state of thermophysical property knowledge of these salts, particularly those that contain actinides or beryllium. Therefore, leveraging modeling techniques to estimate unknown molten salt thermophysical properties and guide future experimental measurements has high value for the nuclear industry. Here, the densities of molten fluoride pseudo-ternary salt systems, which are of interest to the nuclear industry, were estimated using Redlich-Kister expansion and Muggianu interpolation techniques. The pseudo-ternary systems considered for estimation in this study were NaF-LiF-ZrF 4 , LiF-BeF 2 -ZrF 4 , LiF-BeF 2 -ThF 4 , NaF-LiF-BeF 2 , NaF-KF-BeF 2 , NaF-ZrF 4 -UF 4 , and NaF-BeF 2 -UF 4 . This Redlich-Kister estimation approach accounts for nonideal mixing behavior based on pseudo-binary subsystem interaction parameters determined from experimentally measured pseudo-binary system density data sets. The Redlich-Kister estimation was compared with the method of additive molar volumes, which assumes ideal mixing. Additionally, the Redlich-Kister approach was used to determine previously unknown binary and ternary interaction parameters based on experimentally measured density data sets for select pseudo-ternary salt systems. The results of this study show improvement in density estimation using the Redlich-Kister approach for all systems considered compared with estimation by additive molar volumes. Furthermore, this analysis allowed for the estimation of nonideal density behavior in experimentally unstudied ZrF 4 -UF 4 and BeF 2 -UF 4 , as well as the quantification of ternary interaction in NaF-LiF-ZrF 4 , NaF-BeF 2 -UF 4 , and NaF-ZrF 4 -UF 4 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Novel pyrolytic boron nitride coating to reduce graphite interactions in molten fluoride salt

Future salt reactors like the Fluoride-salt-cooled-High Temperature Reactor require varying material flavors. Graphite is required for neutron moderation and potential fuel forms, while structural metals are required for containment. Studies show graphite/metal interactions exist when both materials share a salt medium. These interactions may accelerate the corrosion of the metal and change the surface of graphite materials. A novel pyrolytic boron nitride coating on graphite is investigated for reducing graphite/metal interactions. Finally, this is the first known application of such a coating, and salt exposure tests reveal the pyrolytic boron nitride coating reduces the interactions between stainless steel and uncoated graphite.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Corrosion characteristics of monolithic SiC materials in beryllium-bearing molten fluoride salt

In this work, chemical vapor deposited SiC single crystal and polycrystals were exposed to a static beryllium-bearing molten fluoride salt, 2LiF–BeF 2 for 500 and 1000 h at 750 °C. Overall, the single crystal and polycrystalline SiC materials experienced slight weight loss and nominal surface etching regardless of the material type. Localized pitting and nonuniform Si removal from surface regions were associated with trace metal impurities and oxygen. Cross-sectional observation revealed minimal subsurface changes in the microstructure. The corrosion damage processes were similar to those reported for molten LiF–KF–NaF salt with trace impurities, indicating that the impurities significantly affect SiC corrosion.

36 MATERIALS SCIENCE↗

Silver diamine fluoride differentially affects dentin and hypomineralized enamel permeabilities

OBJECTIVES: To investigate the physicochemical effect of silver diamine fluoride (SDF) by correlating permeability with mineral density and elemental composition of hypomineralized enamel and carious dentin. METHODS: Enamel and dentin from human carious primary teeth with and without SDF treatment in-vivo, and hypomineralized enamel from permanent molars with and without SDF treatment in-vitro were scanned using micro X-ray computed tomography. Spatial maps of biometals (calcium, zinc), phosphorus, and silver were generated using X-ray fluorescence microprobe. Permeabilities were computed using Porous Microstructure Analysis software. RESULTS: The intrinsic permeability of SDF-treated carious dentin was 14.3 % lower than untreated sound dentin (6.39e-15 ± 3.01e-15 m² vs 7.46e-15 ± 1.82e-15 m²; P < 0.0001), while untreated carious dentin was 98.4 % higher (1.48e-14 ± 7.11e-15 m²; P < 0.0001). SDF-treated and untreated transparent dentin showed similar reduced permeabilities (75.6 % and 78.4 % lower than untreated sound dentin, respectively; P = 0.93). Severely hypomineralized enamel showed permeability reaching 108.1 % of adjacent sound dentin (5.71e-15 ± 2.04e-15 m² vs 5.28e-15 ± 1.30e-15 m²; P = 0.1409) and was significantly higher than mildly hypomineralized enamel (1.39e-15 ± 1.04e-15 m²; P < 0.0001). SDF treatment did not significantly impact the permeability of severely hypomineralized enamel (12.4 % reduction; P = 0.07). Principal component regression identified Zn level as a significant effector of tissue permeabilities in carious primary teeth (P < 0.0001). SIGNIFICANCE: This study introduces a computational method to measure dental tissue permeability, and demonstrates that SDF significantly reduces permeability in carious dentin but not intact hypomineralized enamel. The study reveals biometal Zn localization can alter dentin and enamel permeabilities, providing new insights into pathobiological mechanisms underlying caries and hypomineralization.

Chou, Conrad↗

Kinetic study of hydrogen transport in graphite under molten fluoride salt environment

Here, in this work, a kinetic model, which describes the reactions occurring during the hydrogen charging process on a graphite surface, was optimized on Electrochemical Impedance Spectroscopic (EIS) to study the entry of hydrogen into graphite in high temperature molten FLiNaK salt. The results show that the rate constants of k 1 increases with decreasing applied potential (becoming more negative), and k 2 and k 3 are independent of the applied potential. At the same charging potential, all the three rate constants are independent of the water concentration in the FLiNaK salt. The surface coverage of absorbed hydrogen increases with decreasing the charging potential and increasing the moisture content in the salt. The adsorption efficiency of hydrogen increases with increasingly charging potential and decreases with increasing moisture content of the FLiNaK salt. These results demonstrate that EIS is a promising technique for measuring the kinetic parameters for hydrogen transport in graphite under molten fluoride salt environment.

EIS↗

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↗

Infiltration of molten fluoride salts in graphite: Phenomenology and engineering considerations for reactor operations and waste disposal

The possibility and consequences of salt-infiltration in graphite must be evaluated for graphite used in molten salt reactors (MSRs) and fluoride-salt-cooled high-temperature reactors (FHRs), which can be subjected to salt pressures as high as 500 kPa. The volume of graphite porosity infiltrated by salt can be measured by direct infiltration and it can be predicted from the graphite pore size distribution, the surface tension of the salt, and the contact angle between the graphite and the salt. While these three properties are believed to be insensitive to irradiation, the former can be impacted by chronic or acute oxidation, and the latter two are highly sensitive to the chemistry of the salt and to events such as air ingress. For MSRs, predictions based on nominal properties of salt and graphite reveal that few graphite grades would satisfy the 4 vol% limit set in the Molten Salt Reactor Experiment, and even fewer would satisfy the 0.5 vol% design target. For FHRs, infiltration limits have not been defined and depend on the effect of infiltration on graphite properties, which are discussed. A hypothesis is presented for properties that may be impacted by infiltration and for which future studies are needed.

36 MATERIALS SCIENCE↗

Chemically Tunable Aspect Ratio Control and Laser Refrigeration of Hexagonal Sodium Yttrium Fluoride Upconverting Materials

Hexagonal sodium yttrium fluoride with Na 3x Y 2-x F 6 stoichiometry (β-NaYF) is a promising material for luminescence upconversion applications due to the narrow crystal field splitting of the Yb(III) ion’s lower 2 F 7/2 manifold. However, growing single crystals of β-NaYF remains an outstanding challenge due to thermal expansion stresses that cause cracking during melt growth. Here, we demonstrate a novel hydrothermal synthesis of β-NaYF with the ability to tune the aspect ratio from microplatelets to microrods with aspect ratios that match computationally predicted cavity (Mie) resonances. These crystals have a root-mean-square roughness below 1 nm after calcination, which makes them ideal for optical cavities. The β-NaYF microcrystals are doped with 10% Yb(III) cations and are used to build optomechanical laser-refrigeration devices consisting of a hexagonal β-NaYF crystal located at the end of a cantilever. Laser refrigeration of these devices by >12.5 °C is observed using calibrated measurements of both the cantilever’s fundamental eigenfrequency and a Boltzmann fit to crystal field luminescence from the Yb(III) ions.

36 MATERIALS SCIENCE↗