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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.

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At least 199 records · Page 11
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Direct drive with the argon fluoride laser as a path to high fusion gain with sub-megajoule laser energy

Argon fluoride (ArF) is currently the shortest wavelength laser that can credibly scale to the energy and power required for high gain inertial fusion. ArF's deep ultraviolet light and capability to provide much wider bandwidth than other contemporary inertial confinement fusion (ICF) laser drivers would drastically improve the laser target coupling efficiency and enable substantially higher pressures to drive an implosion. Our radiation hydrodynamics simulations indicate gains greater than 100 are feasible with a sub-megajoule ArF driver. Our laser kinetics simulations indicate that the electron beam-pumped ArF laser can have intrinsic efficiencies of more than 16%, versus about 12% for the next most efficient krypton fluoride excimer laser. We expect at least 10% ‘wall plug' efficiency for delivering ArF light to target should be achievable using solid-state pulsed power and efficient electron beam transport to the laser gas that was demonstrated with the U.S. Naval Research Laboratory's Electra facility. These advantages could enable the development of modest size and lower cost fusion power plant modules. This would drastically change the present view on inertial fusion energy as being too expensive and the power plant size too large.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2015

Hydrogen desorption kinetics for aqueous hydrogen fluoride and remote hydrogen plasma processed silicon (001) surfaces

The desorption kinetics of molecular hydrogen (H{sub 2}) from silicon (001) surfaces exposed to aqueous hydrogen fluoride and remote hydrogen plasmas were examined using temperature programmed desorption. Multiple H{sub 2} desorption states were observed and attributed to surface monohydride (SiH), di/trihydride (SiH{sub 2/3}), and hydroxide (SiOH) species, subsurface hydrogen trapped at defects, and hydrogen evolved during the desorption of surface oxides. The observed surface hydride species were dependent on the surface temperature during hydrogen plasma exposure with mono, di, and trihydride species being observed after low temperature exposure (150 °C), while predominantly monohydride species were observed after higher temperature exposure (450 °C). The ratio of surface versus subsurface H{sub 2} desorption was also found to be dependent on the substrate temperature with 150 °C remote hydrogen plasma exposure generally leading to more H{sub 2} evolved from subsurface states and 450 °C exposure leading to more H{sub 2} desorption from surface SiH{sub x} species. Additional surface desorption states were observed, which were attributed to H{sub 2} desorption from Si (111) facets formed as a result of surface etching by the remote hydrogen plasma or aqueous hydrogen fluoride treatment. The kinetics of surface H{sub 2} desorption were found to be in excellent agreement with prior investigations of silicon surfaces exposed to thermally generated atomic hydrogen.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Electrochemical Sensor Development for Fluoride Molten Salt Redox Control

Fluoride molten salts are proposed for many uses in the near future such as coolant for nuclear fission and fusion applications. This medium is advantageous due to superior heat transfer properties and chemical stability. These advantages result in better safety characteristics, increased output, and lower costs. These molten salts are sensitive to impurities, especially water and oxygen, however. These impurities can react with the fluorides to form hydrofluoric acid which will corrode the containing materials through the following mechanism: 2 HF + M → H{sub 2} + MF{sub 2}. Due to this sensitivity it is necessary to monitor the condition of the molten salt in order to prevent corrosion utilizing redox control. This study investigates the requirements and design of an electrochemical sensor which can perform this real time monitoring of the molten salt's redox potential.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2017

Study of Tritium Transport in Nuclear-Grade Graphite and Molten Fluoride Salt Systems

High-temperature salts are proposed as coolant in recent reactor technologies including Fluoride Salt-Cooled High Temperature Reactor (FHR) with fluoride salt as primary and secondary loop coolant, Molten Salt Reactors (MSRs) with fuel salt, and high-magnetic-field fusion machines with salt coolant blanket. The baseline coolant is {sup 7}Li{sub 2}BeF{sub 4} (flibe) due to its good thermal-hydraulic and neutronic properties. Tritium produced in flibe due to neutron irradiation makes the issue of tritium transport an area of great interest. In the temperature range of 427- 704 deg. C, tritium readily diffuses through metallic reactor structural materials, which makes tritium control and capture a key technical challenge. It is anticipated that tritium can be captured by graphite, as graphite material showed a high affinity for tritium in the Molten Salt Reactor Experiment (MSRE) due to the porous and irregular crystallite microstructure. Two types of nuclear grade graphite which used as core components for FHR: matrix graphite, which encapsulates the TRISO (Tri-structural-isotropic) fuel particles in FHR, and high purity, isotropic nuclear grade graphite IG-110 which can be used as moderator and reflector in reactor core for both fission and fusion reactor. The microstructure of matrix graphite and IG-110 is different from that of matrix graphite, due to the raw material and manufacturing processes. There are three phenomena important for predicting tritium transport in graphite-salt systems: tritium species diffusion in molten flibe; tritium species transport at the salt-graphite interface; and tritium species transport in graphite. In this summary microstructure characterization of IG-110 and matrix graphite, characterization of graphite-salt interface as well as techniques for trace tritium detection in graphite are discussed.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2017

New Czech R and D Program on Fluoride Salt-cooled Nuclear Reactor Systems

A technology of nuclear reactor systems with liquid molten salt fuel has been investigated in the Czech Republic since 1999. The original effort came from the national Partitioning and Transmutation concept based on the subcritical Accelerator Driven System for incineration of transuranium elements with liquid fluoride fuel and pyrochemical partitioning fuel cycle technology. After 2005, the original R and D intentions were gradually converted to classical Molten Salt Reactor (MSR) technology and to thorium - uranium fuel cycle. The aim of this choice was to contribute to the development of an advanced nuclear technology, which can minimize environmental impact of nuclear power, save the natural resources and which has some potential to be deployed also in a non-superpower country. The basic technological development of selected areas of MSR and Th - U fuel cycle technology was realized in the frame of the SPHINX project solved in 2005 - 2012. In addition to the domestic activities of the MSR technology development, in 2012 the Czech Ministry of Industry and Trade and the US - Department of Energy concluded an agreement about the collaborative R and D on Molten Salt Reactor and Fluoride-salt-cooled High-temperature Reactor (FHR) technologies. These facts and results created the principal background for the present national program on the MSR/FHR technology development which was approved by the Ministry of Industry and Trade in 2016 and is granted by the Technological Agency of the Czech Republic.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2016

Ionic conductivity of binary fluorides of potassium and rare earth elements

The ionic conductivity s of KYF{sub 4} and K{sub 2}RF{sub 5} single crystals (R = Gd, Ho, Er) and KNdF{sub 4} and K{sub 2}RF{sub 5} ceramic samples (R = Dy, Er) has been studied in the temperature range of 340–500°C. A comparative analysis of the σ values for these objects has been performed. Binary fluorides of potassium and rare earth elements were synthesized by the hydrothermal method (temperature 480°C, pressure 100–150 MPa) in the R{sub 2}O{sub 3}–KF–H{sub 2}O systems. The σ values of tetraf luorides are 3 × 10{sup –5} S/cm (KYF{sub 4} single crystal) and 3 × 10{sup –6} S/cm (KNdF{sub 4} ceramics) at 435°C. A K{sub 2}ErF{sub 5} single crystal with σ = 1.2 × 10{sup –4} S/cm at 435°C has the maximum value of ionic conductivity among pentafluorides. The anisotropy of ionic transport was found in K{sub 2}HoF{sub 5} single crystals, σ{sub ∥c}/σ{sub ⊥c} = 2.5, where σ{sub ∥c} and σ{sub ⊥c} are, respectively, the conductivities along the crystallographic c axis and in the perpendicular direction.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

SuFEx‐Based Polysulfonate Formation from Ethenesulfonyl Fluoride–Amine Adducts

Abstract The SuFEx‐based polycondensation between bisalkylsulfonyl fluorides (AA monomers) and bisphenol bis( t ‐butyldimethylsilyl) ethers (BB monomers) using [Ph 3 P=N−PPh 3 ] + [HF 2 ] − as the catalyst is described. The AA monomers were prepared via the highly reliable Michael addition of ethenesulfonyl fluoride and amines/anilines while the BB monomers were obtained from silylation of bisphenols by t ‐butyldimethylsilyl chloride. With these reactions, a remarkable diversity of monomeric building blocks was achieved by exploiting readily available amines, anilines, and bisphenols as starting materials. The SuFEx‐based polysulfonate formation reaction exhibited excellent efficiency and functional group tolerance, producing polysulfonates with a variety of side chain functionalities in >99 % conversion within 10 min to 1 h. When bearing an orthogonal group on the side chain, the polysulfonates can be further functionalized via click‐chemistry‐based post‐polymerization modification.

Wang, Hua↗
DOE OSTI2018

Efficient Removal of Fluoride Using Polypyrrole-Modified Biochar Derived from Slow Pyrolysis of Pomelo Peel: Sorption Capacity and Mechanism

In this study, a novel adsorbent was developed by loading polypyrrole (PPy) onto biochar (BC) prepared by slow pyrolysis of pomelo peel. This PPy-grafted BC mainly exhibited anion-exchange behavior, which dramatically increased fluoride adsorption capacity. The effects of various factors (adsorbent dosage, pyrrole concentration, initial solution pH, co-existing anions and temperature) on the fluoride adsorption were investigated. The adsorbent was characterized by scanning electronic microscopy (SEM), X-ray photoelectron spectroscopy (XPS) and automatic titration methods. Results showed that the optimized adsorbent (BP-0.1) performed excellently at pH 2.8–10.0, and possessed positive charge at pH < 8.6. The adsorption isotherm data were fitted well by the Langmuir model and the maximum adsorption capacity was 18.52 mg/g at 25 ± 2 °C. The adsorption kinetics followed the pseudo-second-order model and adsorption equilibrium was achieved at 24 h. Although both HCO{sub 3}{sup −} and CO{sub 3}{sup 2−} had great influence on F{sup −} adsorption, there was no significant impact in the presence of Cl{sup −}, NO{sub 3}{sup −} and SO{sub 4}{sup 2−}. Real groundwater study showed that 2.5 g/L of BP-0.1 could effectively reduce F{sup −} from 10.0 to 1.4 mg/L at pH 5.0. Thermodynamic parameters confirmed the spontaneous and endothermic nature of the adsorption process. Effect of pH, XPS analysis and the change of amount between Cl{sup −} and F{sup −} in the adsorption process revealed that ion exchange and electrostatic attraction were involved in the adsorption process and ion exchange was the main adsorption mechanism.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2018

Carburization effects on the corrosion of Cr, Fe, Ni, W, and Mo in fluoride-salt cooled high temperature reactor (FHR) coolant

Corrosion of structural alloys in fluoride salt cooled high temperature reactors (FHRs) is affected by the presence of carbon. The stability of the carbides of alloying elements augments their corrosion, however the same property can be useful if these stable carbides are used to protect materials. Exposure tests of pure elements Cr, Fe, Ni, W, and Mo in graphite crucibles at 700 °C were conducted in molten FLiNaK salt for 100 h. Carbide particles were detected on the surfaces of Cr, Mo, and W samples after exposure. The ranking of these elements, from least to greatest corrosion resistance by mass loss per unit area was Cr < Fe < W < Mo < Ni. The stability of chromium carbides was further investigated using chromium samples which were pre-carburized in a reducing hydrocarbon environment at 800 °C prior to exposure tests in molten FLiNaK. In conclusion, the chromium carbide layer produced by pre-carburization was resistant to attack by molten fluoride and slowed corrosion of the underlying chromium metal.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2020

Carburization of metals by a chemical mechanism of carbon transport through molten fluoride salts

Carburization of structural alloys used in Fluoride Cooled High Temperature Reactors (FHR) can result from the interaction between the metal and graphite components and cause changes in alloy properties. However, carburization requires transport of carbon from graphite to alloy surfaces through the molten fluoride coolant. This work introduces an alternative to previously proposed carbon transport mechanisms. The new mechanism is based on the generation of carbonate ions (CO 3 2- ) by oxide impurities in the salt reacting with graphite. CO 3 2- is then reduced on metal surfaces to deposit carbon. This work demonstrates the reduction of dissolved CO 3 2- on pure Fe, Ni, Cr, Mo, and W surfaces without an applied potential in molten FLiNaK at 700 °C. Finally, we also demonstrate that the interaction between oxide and graphite in molten FLiNaK media produces CO 3 2- .

36 MATERIALS SCIENCE↗
DOE OSTI2021

Validating modern methods for impurity analysis in fluoride salts

Salt impurities directly affect degradation of structural materials in molten salt environments, so impurity quantification and analysis of salts is important for the deployment of next generation molten salt nuclear reactors. Despite the importance of moisture and other oxygen containing impurities, reliable methods of measuring these impurities are not well qualified or commonly used. Herein, we present two methods for analysis of oxygen content and one method for analysis of hydrogen content in fluoride salts demonstrated on two batches of LiF-NaF-KF (FLiNaK) salt with differing purity levels. The intentional addition of varying amounts of oxygen and hydrogen to the FLiNaK salt as internal standards produced a linear response using a commercial combustion analysis instrument, and measured amounts were consistent with the standards. Overall, these results indicate the technique is a valid method for measuring oxygen and hydrogen content in fluoride salts. Corrosion studies of 316H in FLiNaK revealed 5 times more mass loss in the salt containing more impurities including hydrogen and transition metals.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Production of anhydrous ƒ-element fluorides through the ionothermal treatment of ƒ-element oxalates

The pivotal role of uranium and plutonium fluorides in the nuclear fuel cycle, particularly in the pyrochemical reduction process, is well recognized. Traditionally, the fluorination of uranium and plutonium materials relies on the use of highly toxic and corrosive gases (e.g., HF (g) , F 2(g) ). Herein, we present an alternative approach using the ionic liquid 1‑butyl‑3-methylimidazolium hexafluorophosphate ([Bmim][PF 6 ] (l) ) and/or hexafluorophosphoric acid (HPF 6(aq) ) as fluorinating agents for the ƒ-element oxalates M$^{III}_{2}$(C 2 O 4 ) 3 ∙ 9H 2 O (s) M$^{III}_{2}$(C 2 O 4 ) 3 ∙ 9H 2 O (s) (M III = Ce, Pu) and M IV (C 2 O 4 ) 2 ∙ 6H 2 O (s) (M IV = Th, U). Our findings demonstrate that [Bmim][PF 6 ] (l) and HPF 6(aq) enable the ionothermal fluorination of ƒ-element oxalates, resulting in the formation of anhydrous CeF 3(s) , ThF 4(s) , and UF 4(s) within 2 hours at 200 °C. This method also facilitates the partial fluorination of plutonium(III) oxalate, yielding a mixture of anhydrous PuF 3(s) and an unidentified phase. Overall, the ionothermal treatment approach offers a safer and more efficient means of producing anhydrous ƒ-element fluorides than conventional methods involving hazardous gases. In addition, we describe the morphology of UF 4(s) materials as a function of production route and demonstrate the presence of morphological signatures that could be used during a nuclear forensic investigation.

Cerium↗
DOE OSTI2013

Novel kinds of down/up-conversion luminescent rare earth doped fluoride BaMgF{sub 4}: RE{sup 3+} microcrystals

Graphical abstract: We achieve the liquid phase chemical synthesis of rare earth fluoride system BaMgF4: RE{sup 3+} microphosphors, which realize down/up-conversion luminescence. - Highlights: • Doped BaMgF{sub 4} microphosphors are firstly prepared by hydrothermal process. • Doped BaMgF{sub 4} nanosheets are firstly prepared by high temperature solution reaction. • The down-conversion luminescence is realized in the rare earth doped BaMgF{sub 4}. • The upconversion luminescence is realized in the rare earth doped BaMgF{sub 4}. - Abstract: In this paper, we realize the liquid-phase chemical synthesis of high-quality orthorhombic polycrystalline BaMgF{sub 4}: RE{sup 3+} (RE = Eu, Tb, Sm, Dy, Yb–Er/Tm) compounds with hydrothermal and high-temperature solution methods, respectively. The products from hydrothermal technology show the micrometer size while the products from hydrothermal technology present nanosheet morphology. The rare earth ions doped BaMgF{sub 4} from hydrothermal synthesis are discussed in details, which can realize the downconversion luminescence for doped Eu{sup 3+} or Tb{sup 3+} and upconversion luminescence for Yb{sup 3+}/Er{sup 3+} (Tm{sup 3+}), respectively. To our knowledge, the hydrothermal or high temperature solution synthesis and photoluminescence (Eu{sup 3+}, Tb{sup 3+} or Yb{sup 3+}/Er{sup 3+}(Tm{sup 3+})) of these fluoride systems are firstly reported.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Ab-Initio Simulation Studies of Cr Solvation in Fluoride Molten Salts

Understanding molten salt chemistry is essential in ongoing research of the molten salt nuclear reactor (MSR). In this context, detailed understanding of the mechanisms underlying selective oxidation of metal species, such as Cr, is required to guide the design of effective corrosion mitigation strategies in molten salts. An important starting point for such mechanistic understanding is knowledge of the solvation structure and its role in controlling metal speciation. In this work, we use ab initio molecular dynamics simulations to study the short-range (on the scale of the nearest-neighbor bond lengths) and medium-range (over length scales of several neighbor spacings) structure in three different fluoride melts with and without Cr addition; namely, 2KF-NaF, 2LiF-BeF 2 , and 3LiF-AlF3. We find that Cr 0 ,Cr 2+ ,Cr 3+ can each be coordinated by different numbers of F-, with the variance in coordination number decreasing as oxidation state increases, and that these coordination geometries are largely independent of solvent. The manner by which Cr changes the medium-range structure, however, is found to be solvent-dependent. While 2KF-NaF melts show short and medium range order that is highly dynamic, 2LiF-BeF 2 and 3LiF-AlF 3 are characterized by molecular associates that are relatively long-lived that organize into oligomer structures on larger length scales. Rather than being solvated by F- ions alone, we find that Cr can incorporate into and be solvated within this oligomer structure. Fluoroacidity, alone, may therefore prove too simple a metric for assessing the corrosivity of molten fluorides. As our work suggests, the ability of Cr to solvate must be understood in the context of the short- and medium-range structure of the solvent.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Optical spectroscopy of molten fluorides: Methods, electronic and vibrational data, structural interpretation, and relevance to radiative heat transfer

In this study, to help address the need for predicting radiative heat transfer (RHT) behavior of molten salts, we conducted a comprehensive review of methods and data from optical spectroscopic measurements on molten fluoride salts. Transmittance, reflectance, and trans-reflectance experimental methods are discussed, along with the corresponding data reduction methodology and the limitations of each technique. Optical spectroscopy is a convenient indirect probe for changes in structural parameters with temperature and composition. Electronic and vibrational absorption data for transition-metal, lanthanide, and actinide solutes and vibrational absorption data for alkali and alkaline earth fluoride solvents are compiled, and the corresponding structural interpretation is discussed and compared with other experimental and theoretical work. We find that solvent and solute vibrational absorption can be significant in the mid-infrared, resulting in near-infrared edges of significance to RHT. Extrapolation and averaging of existing edge data leads to estimated gray absorption coefficient values at 700 °C of 546 m —1 for FLiBe and 276 m —1 for FLiNaK, both within the range of 1 – 6000 m —1 identified to be of engineering relevance for radiative heat transfer analysis.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Removing Fluoride from Double Four-Membered Rings Yielding Defect-Free Zeolites under Mild Conditions Using Ozone

We have investigated ozone treatment of as-made LTA zeolites under mild temperature conditions (175 °C) using experiments and periodic DFT as a method of energy savings and engineering defects such as silanol nests in comparison with conventional calcination at 550 °C. We have studied ozone treatment on LTA samples synthesized with 1,2-dimethyl-3-(4-methylbenzyl) imidazolium (denoted as “BULKY”) as the primary organic structure-directing agent (OSDA) and with various amounts of tetramethylammonium (TMA) as a secondary OSDA. Ozone treatment of LTA-BULKY at 175 °C was found to give defect-free, pristine LTA materials as determined by 29 Si NMR, 13 C NMR, Raman spectra, and DFT to assign the spectra. This represents a significant and unexpected finding: that fluoride ions can be completely removed from double four-membered rings (D4Rs) under such mild conditions. Furthermore, ozone treatment of LTA-BULKY-TMA samples removed BULKY but left behind TMA/F, giving a new and more diverse structural landscape of Si environments in LTA. Ab initio MetaDynamics calculations provide pathways with relatively low barriers, explaining how fluoride ions can be removed from D4Rs, leaving behind defect-free LTA materials under mild conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Effective Remediation of Groundwater Fluoride with Inexpensively Processed Indian Bauxite

India represents one-third of the world’s fluorosis burden and is the fifth global producer of bauxite ore, which has previously been identified as a potential resource for remediating fluoride-contaminated groundwater in impoverished communities. In this work, we use thermal activation and/or groundwater acidification to enhance fluoride adsorption by Indian bauxite obtained from Visakhapatnam, an area proximate to endemic fluorosis regions. We compare combinatorial water treatment and bauxite-processing scenarios through batch adsorption experiments, material characterization, and detailed cost analyses. Heating Indian bauxite above 300 °C increases available surface area by > 15× (to ~170 m 2 /g) through gibbsite dehydroxylation and reduces the bauxite dose for remediating 10 ppm F – to 1.5 ppm F – by ~93% (to 21 g/L). Additionally, lowering groundwater pH to 6.0 with HCl or CO 2 further reduces the average required bauxite doses by 43–73% for ores heated at 300 °C (~12 g/L) and 100 °C (~77 g/L). Product water in most examined treatment scenarios complies with EPA standards for drinking water (e.g., As, Cd, Pb, etc.) but potential leaching of Al, Mn, and Cr is of concern in some scenarios. Among the defluoridation options explored here, bauxite heated at 300 °C in acidified groundwater has the lowest direct costs ($6.86 per person per year) and material-intensity.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Electronic Structure Predictions of the Energetic Properties of Tellurium Fluorides

The heats of formation, bond dissociation energies (BDEs), fluoride affinities (FA), fluorocation affinities (FCA), electron affinities (EA), and ionization energies (IP) of TeFn (n = 1 - 6) have been predicted using the Feller-Peterson-Dixon (FPD) approach. To benchmark the approach, the bond dissociation energies of Te 2 and TeO, the heats of formation of Te 2 , TeH 2 , TeO and TeO 2 , and the electron affinity for TeO and TeO 2 were calculated as there are experimental thermodynamic data available for these tellurium compounds, which allow confirmation of the heat of formation of Te gas as ΔH f,0K (Te) = 50.7 ± 0.6 kcal/mol. Spin-orbit corrections are required for good results and cannot be ignored. A comparison between fluoride affinities, fluorocation affinities, electron affinities, and ionization energies of TeF n and SeF n is reported.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗