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At least 163 records · Page 9

The local ordering of polar solvents around crystalline carbon nitride nanosheets in solution

The crystalline graphitic carbon nitride, poly-triazine imide (PTI) is highly unusual among layered materials since it is spontaneously soluble in aprotic, polar solvents including dimethylformamide (DMF). The PTI material consists of layers of carbon nitride intercalated with LiBr. When dissolved, the resulting solutions consist of dissolved, luminescent single to multilayer nanosheets of around 60–125 nm in diameter and Li+ and Br- ions originating from the intercalating salt. To understand this unique solubility, the structure of these solutions has been investigated by high-energy X-ray and neutron diffraction. Although the diffraction patterns are dominated by inter-solvent correlations there are clear differences between the X-ray diffraction data of the PTI solution and the solvent in the 4–6 Å -1 range, with real space differences persisting to at least 10 Å. Structural modelling using both neutron and X-ray datasets as a constraint reveal the formation of distinct, dense solvation shells surrounding the nanoparticles with a layer of Br - close to the PTI-solvent interface. This solvent ordering provides a configuration that is energetically favourable underpinning thermodynamically driven PTI dissolution.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Generalized Analysis of Dynamic Flow Fouling on Heat Transfer Surfaces

Several energy applications involve flow of untreated heat transfer fluids that contain trace amounts of mineral salts, such as calcium carbonate and calcium sulfate, which show reverse solubility with temperature. The gradual accretion of these salts onto the heat transfer surfaces causes fouling that degrades thermal performance over time. While fouling of bare surfaces has been extensively studied, fouling of nonwetting superhydrophobic or liquid-infused surfaces is less understood, especially under dynamic flow conditions. This study presents a systematic experimental analysis to elucidate dynamic flow fouling of calcium carbonate and calcium sulfate on smooth, superhydrophobic and liquid-infused surfaces in a generalized manner. Here, copper tubes with modified inner surface wettability are fabricated and subjected to forced convection at different flow rates and fouling salt concentrations. Fouling characteristics of the two salts on the different surfaces are examined through microstructural analysis, and quantified in terms of asymptotic fouling resistance that measures the total extent of fouling, and a threshold time, which correlates to the onset of significant fouling. Using Taguchi design of experiments, the study reports, for the first time, closed-form analytical relationships for the asymptotic fouling thermal resistance and threshold time on the Reynolds number, dimensionless concentration of fouling agent and dimensionless infused liquid viscosity that represents the different surface types in a unified manner. It is shown that the analytical model accurately predicts the fouling characteristics in up to about 97% of the data, based on which contour maps of optimum surface designs for minimizing fouling resistance are presented. The results provide information on designing surfaces for reduced fouling or for estimating the fouling characteristics for a given surface in applications.

36 MATERIALS SCIENCE↗

Effect of Soluble Corrosion Products on Electrical Double Layer in LiCl-KCl Molten Salts

Corrosion in molten salts greatly hampers the application for renewable energy applications like molten salt reactors. To develop effective strategies for corrosion mitigation, understanding the interfacial structures and properties such as specific ion adsorption and electrical double layer capacitance are crucial. Using cyclic voltammetry and electrochemical impedance spectroscopy, we systematically studied the interfaces on various model electrodes including W (solid), Bi (liquid), and the stainless steel 316 in LiCl-KCl eutectic molten salts with the addition of corrosion species CrCl 2 and FeCl 2 . Both Cr 2+ and Fe 2+ ions increased electrical double layer capacitance, with Cr 2+ showing specific adsorption behavior and shifting the potential of zero charge, while Fe 2+ had minimal effect on point of zero charge. Two-working electrode measurements revealed increasing open-circuit potential and electrical double layer capacitance during the exposure of stainless steel 316, indicating its progressive corrosion and ion accumulation at the interface. X-ray photoelectron spectroscopy and Raman confirmed Cr enrichment at the interface. This work highlights the strong correlation between electrical double layer behavior and corrosion dynamics in molten salts and suggests electrical double layer capacitance as a sensitive, in situ indicator for corrosion monitoring.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Small-scale Assessment of Simplified Ceramic Waste Form Processing

The feasibility of directly processing glass-bonded sodalite ceramic waste form materials by heating a mixture of Zeolite 4A, chloride salt, and sodium borosilicate binder glass was demonstrated by generating laboratory-scale materials. This direct processing method eliminates pre-setting the moisture content of the Zeolite 4A, eliminates the step of occluding salt in the prepared Zeolite 4A prior to processing, and can be conducted using larger particle sizes of crushed Zeolite 4A and crushed borosilicate glass than those called for in the current method. These simplifications are expected to facilitate material transfer and handling in a hot cell or controlled atmosphere environment and be more readily implemented at large scale than the current method. Most materials made to assess these simplifications were directly processed at 925 °C for two hours in an argon atmosphere glovebox, but one material was processed at 925 °C for four hours and one material was processed at 880 °C for two hours. Sodalite was generated and became microencapsulated by the binder glass in all materials. The microstructures were uniform throughout each product, were similar in all products, and were similar to the microstructures of materials made previously using the pressureless consolidation or hot isostatic pressing methods. Various formulations showed the efficiency of sodalite generation was not sensitive to the salt-to-Zeolite 4A ratio or salt-to-glass mass ratio, although a greater relative mass of glass is required to encapsulate sodalite generated from large particles of aggregated Zeolite 4A. The upper limit of salt loadings that can be effectively processed remains to be determined. The effectiveness of direct processing provided new insights into the conversion mechanism. The salt was likely dissolved into the glass that transported NaCl into the Zeolite 4A aggregates and sodalite was generated in situ as NaCl migrated from the outside of the aggregate inward. Other salt cations (e.g., potassium, strontium, cesium, and probably lithium) remain dissolved in the glass encapsulating the zeolite/sodalite domains. When the glass solidifies during cooling, small halite inclusion phases form in glass within sodalite domains and large mixed salt inclusions form in glass surrounding the sodalite due to the low solubility of chloride in the (solid) glass. Other salt cations were oxidized during processing and formed inclusions in the bulk glass (e.g., neodymium). Initial degradation tests show the dissolution behavior of directly processed CWF (SCWF) materials is similar to CWF materials made using different methods.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Crystallization of proteins by dynamic control of supersaturation

The growth of protein crystals is known to be the limiting factor in the determination of the three-dimensional structures of most proteins. It is expected that the kinetics of supersaturation, which is directly related to solvent evaporation, will affect protein crystal growth and nucleation and accordingly determine the quality, number, size, and morphology of the crystals. With a technique that controls the evaporation of solvent from a protein solution with N2(g) it is possible to determine the effect of different evaporation profiles on hen egg white lysozyme crystals. Hen egg white lysozyme was chosen as the model protein because it crystallizes easily and has solubility data available for most salt, pH, and temperature ranges. Commercially available lysozyme was further purified by a number of methods. Crystals grown with the purified lysozyme and with the unpurified lysozyme in citrate buffer were different shapes but were found to be of the same symmetry space group by precession photos. Differences were seen in the lysozyme crystals grown using different evaporation rates. At three of the four initial conditions for lysozyme crystal growth, longer evaporation times yielded better crystals. The evaporation times required to see a change in the appearance of the crystals was much longer than expected. The number of rates studied so far represent only a small fraction of the ones now available with the gas evaporation device. The technique also provides for control of both solution pH and temperature which are related to the solubilities of proteins.

Wilson, Lori June↗

Atomistic Simulations for Thermophysical Properties of Uranium-Containing Halide Molten Salts

Characterizing the thermophysical properties in both fuel and coolant salts are critical in modeling, developing, process optimizing and utilizing molten salt reactors (MSRs), as these properties directly relate to operation metrics and can inform on the selection of candidate salts. The demand for consistent, accurate and publicly available thermophysical property data has become more apparent in recent years as interests have increased from molten salt reactor developers. There are a number of challenges in experimentally measuring properties such as thermal conductivity, viscosity, density and heat capacity , which have led to sparse and often times conflicting data points or molten salts in general. Additionally, there are a number of hazards to consider when synthesizing, storing, using, treating and disposing of molten salts. With the advances in computational capabilities over the last 10 years, the use of atomistic simulations can be implemented to support these efforts. The primary objective of this work is characterize the thermophysical transport properties in a number of molten chloride salts, and in particular NaCl-UCl 3 using ab-initio molecular dynamic (AIMD) simulations. In this binary salt the UCl 3 acts as the primary fissile material and NaCl acts as a carrier salt due with its’ high solubility for actinides A number of studies on the thermophysical properties of NaCl-UCl 3 have been published but there is not a vast amount of viscosity data for this system. In 1975, Desyatnik, et al published a study reporting dynamic viscosities that were calculated from kinematic viscosity measurements, and using the coefficients provided the viscosity in a 70:30 NaCl:UCl 3 mixture is 2.29 cP and 2.88 for a 60:40 mixture. Termini et al. recently reported viscosities in the range of 2.75 – 3 cP for the 63:37 NaCl-UCl 3 mixture in the same temperature range using rolling ball viscosity measurements. Computational viscosity of a similar mixture (64:36) can be obtained from the work Andersson et al. using the reported diffusion coefficients, and the hydrodynamic radius from the pair-radial distribution functions (RDFs). Using Eq (1) (vida infra), the viscosity would be 2.50 cP at 1100K. This is not to say that these values are incorrect due to the varying reported values, but aims to highlight the necessity of this work. The data reported in this ongoing work are computations on a 64:36 mixture of NaCl-UCl 3 at 987K. This work is likely to be expanded into varying concentrations of this mixture along with the inclusion of other salt candidate mixtures.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Copper-Doped Tin Oxides Supported on Mesoporous Carbon Xerogel for Boosting the Electrochemical Reduction of CO 2 to Formate in Bicarbonate Solution Coupled with CO 2

The electrochemical reduction of CO 2 into valuable products at mild reaction conditions and using cheap renewable electrical energy are goals to sustain a low-carbon economy. Among the various CO 2 reduction reaction products, formic acid (FA) has received significant attention because of its low Gibbs free energy input requirement and the simple reduction reaction involving the transfer of 2 electrons and 2 protons. In this work, a copper-doped tin oxide catalyst supported on a mesoporous carbon xerogel was shown to enhance the electrochemical reduction of CO 2 to formate in a bicarbonate solution coupled with CO 2 . We observed that the synergistic SnCu oxides enhance the selectivity toward formate from 58.6% for Sn oxide and 28.7% for Cu oxide to over 71.2% for the SnCu oxides. The observed rate of formate production with SnCu oxide was 2.8 times higher compared to the rate of Cu oxide and about 1.5 times higher than with the Sn oxide catalyst. Our results reveal that selectivity for formate comes partly from the electrolysis of the bicarbonate solution and partly from continuous CO 2 gas purged into the solution. The contribution from the electrolysis of bicarbonate solution ranges from 15% to 40% when the concentration of bicarbonate solution ranges from 100 mM to 1 M. Chronoamperometric measurements for stability revealed that Cu oxide and Sn oxide showed stable current density for less than 30 h while under the same conditions, the stable current density was observed for more than 50 h with SnCu oxide catalyst. Additionally, the selectivity toward formate increased by 6% when the reactor pressure was increased from near ambient pressure to 4 psig. Our lab-scale electrochemical cell with SnCu oxide supported on the mesoporous carbon xerogel enhances the CO 2 solubility, minimizes the precipitation of salts that can degrade the catalytic performance, and suppresses the competitive hydrogen evolution reaction, demonstrating the feasibility of using our catalyst and system for the electrochemical conversion of CO 2 into formate with high selectivity, productivity, and stability. Furthermore, this could have significant implications for the mitigation of CO 2 emissions and the development of a sustainable chemical industry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular dynamics simulations of uranyl and plutonyl cations in a task-specific ionic liquid

Ionic liquids (ILs) are a unique class of solvents with potential applications in advanced separation technologies relevant to the nuclear industry. ILs are salts with low melting points and a wide range of tunable physical properties, such as viscosity, hydrophobiciy, conductivity, and liquidus range. ILs have negligible vapor pressure, are often non-flammable, and can have high thermal stability and a wide electrochemical window, making them attractive for use in separations processes relevant to the nuclear industry. Metal salts generally have a low solubility in ILs; however, by incorporating new functional groups into the IL cation or anion that promote complexation with the metal, the solubility can be greatly increased. One such task-specific ionic liquid (TSIL) is 1-carboxy-N, N, N-trimethylglycine bis(trifluoromethylsulfonyl)imide ([Hbet][Tf 2 N]). Water, which is detrimental for electrochemical separations, is a common impurity in ILs and can coordinate with actinyl cations, particularly in ILs containing only weakly coordinating components. Understanding the behavior of actinides in TSIL/water mixtures on a molecular level is vital for designing improved separations processes. Classical molecular dynamics simulations of uranyl(VI) and plutonyl(VI) in 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][Tf 2 N]) with deprotonated Hbet (betaine) and water have been performed to understand the coordination and dynamics of the actinyl cations. We find that betaine is a much stronger ligand than water and prefers to coordinate the metal in a bidentate manner. Potential of mean force simulations yield a relative free energy for betaine coordination of approximately -120 to -90 kJ/mol in mixtures with water. As the amount of betaine coordinated to the actinide increases, the diffusion coefficient of the actinyl cation decreases. Moreover, the betaine ligand is able to bridge between two metal centers, resulting in dimeric complexes with actinide–actinide distances of ~5 Å. Potential of mean force simulations show that these structures are stable, with relative free energies of up to -40 kJ/mol. The crystal structure for [(UO 2 ) 2 (bet) 6 (H 2 O) 2 ][Tf 2 N] 4 shows that the betaine bridges between two uranium atoms to form dimeric complexes similar to those found in our simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Water and acid soluble trace metals in atmospheric particles

Continental aerosols are collected above a deciduous forest in eastern Tennessee and subjected to selective extractions to determine the water-soluble and acid-leachable concentrations of Cd, Mn, Pb, and Zn. The combined contributions of these metals to the total aerosol mass is 0.5 percent, with approximately 70 percent of this attributable to Pb alone. A substantial fraction (approximately 50 percent or more) of the acid-leachable metals is soluble in distilled water. In general, this water-soluble fraction increases with decreasing particle size and with increasing frequency of atmospheric water vapor saturation during the sampling period. The pattern of relative solubilities (Zn being greater than Mn, which is approximately equal to Cd, which is greater than Pb) is found to be similar to the general order of the thermodynamic solubilities of the most probable salts of these elements in continental aerosols with mixed fossil fuel and soil sources.

Lindberg, S. E.↗

Implementation of Isotopic Removal Capability in Griffin for Multi-Region MSR Depletion Analysis

This work reports the first step in such an analysis, the verification of isotope removal capability for multi-region MSR depletion in Griffin. Verification studies are performed against SERPENT for chemical species removal from the core to an off-gas system for MSR analysis. A brief review of the Bateman equations including the isotopic removal term is provided along with a description of the example problem used in the verification studies performed in Griffin versus SERPENT. Next, the results of the verification study are presented for isotopic depletion, isotopic depletion with removal, and the specific analysis case of varying the solubility of Iodine in a salt system and how this can affect material buildup in the off-gas system. Lastly, the results are analyzed and future work detailing the fully coupled MSR depletion analysis that incorporates the true multiphysics of the system is discussed.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Direct regeneration of lithium ion cathodes by ionothermal relithiation

A method for relithiating cathode material from spent lithium-based batteries, the method comprising: (i) mixing delithiated cathode material and a lithium salt with an ionic liquid in which the lithium salt is at least partially soluble to form an initial mixture; (ii) heating the initial mixture to a temperature of 100° C. to 300° C. to result in relithiation of the delithiated cathode material; and (iii) separating the ionic liquid from the relithiated cathode material; wherein, in embodiments, the cathode material is a lithium metal oxide, wherein the metal is selected from the group consisting of Ni, Co, Fe, Mn, Al, Zr, Ti, Nb, and combinations thereof, or wherein the cathode material has the formula LiNi x Mn y Co z O 2 , wherein x>0, y>0, z>0, and x+y+z=1; wherein, in some embodiments, the ionic liquid has a nitrogen-containing cationic portion, such as an imidazolium ionic liquid.

Luo, Huimin↗

Solubility of non-polar gases in electrolyte solutions

Solubility theory describes the effects of both concentration and temperature on solute activity coefficients. It predicts the salting-out effect and the decrease in solubility of non-polar gases with increased electrolyte concentration, and can be used to calculate heats of solution, entropies, and partial molal volumes of dissolved gases

Walker, R. L., Jr.↗

Boron and Lithium in Calcium Sulfate Veins: Tracking Precipitation of Diagenetic Materials in Vera Rubin Ridge, Gale Crater

The NASA Curiosity rover's ChemCam instrument suite has detected boron in calcium-sulfate-filled fractures throughout the sedimentary strata of Gale crater including Vera Rubin ridge. The presence of elevated B concentration provides insights into Martian subsurface aqueous processes. Here, we extend the data set of B in Ca-sulfate veins across Gale crater, comparing the detection frequency and relative abundances with Li. We report 33 new detections of B within veins analyzed between Sols 1548 and 2311 where detections increase in Pettegrove Point and Jura members, which form Vera Rubin ridge. The presence of B and Li in the Ca-sulfate veins is possibly due to dissolution of preexisting B in clays of the bedrock by acids or neutral water and redistribution of the elements into the veins. Elevated frequency of B detection in veins of Gale crater correlates with presence of dehydration features such as desiccation cracks, altered clay minerals and detections of evaporites such as Mg-sulfates and chloride salts in the host rocks. The increased observations of B also coincide with decreased Li concentration in the veins (average Li concentration of veins drops by ~15 ppm). Boron and Li have varying solubilities, and Li does not form salts as readily upon dehydration as B, causing it to remain in the solution. So the weak negative correlation between B and Li may reflect the crystallization sequence during dehydration on Vera Rubin ridge.

58 GEOSCIENCES↗

Solubility and Dissolution Rate of LiCl-KCl-NaCl

This work aims to determine the potential risk of directly storing waste salt from the electrorefining process of used nuclear fuel in a geologic repository. To accomplish this, the solubility limit and dissolution rate of four representative chloride salt mixtures (solutes) in water and two brine solutions (solvents) are observed and documented.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Conductivity-Driven Origin of the Limiting Current in Concentrated Electrolytes

Next-generation electrolyte materials are hindered by their ability to support high currents essential for fast-charge and high-power battery applications. The maximum current supported by an electrolyte, the limiting current, is dictated by the formation of concentration gradients across the electrolyte under an electric field. Most of the literature attributes the onset of the limiting current in concentrated electrolytes to the salt concentration at the positive electrode approaching the solubility limit. Here, in this study, we leverage operando X-ray transmission imaging to measure spatiotemporal salt concentration profiles of a polymer electrolyte in a lithium–indium symmetric cell at a current exceeding the limiting current. The measurement of concentration profiles enables mapping the spatiotemporal electric potential, which comprises an ohmic contribution, governed by conductivity, and an overpotential related to maintaining concentration gradients. We find that a precipitous drop in conductivity at the positive electrode drives the divergence of electric potential, rather than a thermodynamic solubility limit.

Abdo, Emily E. [University of California, Berkeley↗

Nitrate and Nitrite Incompatibility with Hydroxide Ions in Concentrated NaOH Solutions: Implications for Hydroxide and Gibbsite Reactivity in Alkaline Nuclear Waste

Electrolyte solutions in alkaline nuclear waste contain aluminate, hydroxide, nitrate and nitrite with sodium as the predominant counterion. The salts of these ions are highly soluble, so the liquids are highly concentrated. This study found that there is a substantial incompatibility between the hydroxide and nitrate and/or nitrate ions. This was determined by the observations that adding just one molal of NaNO2 or NaNO3 to saturated NaOH solution precipitation of 12 moles of NaOH·H2O salt, whereas the common ion effect would have expected only about 1 mole to precipitate. Further analysis indicates that the presence of nitrate and nitrite drastically increases the reactivity of sodium hydroxide ions in solution, which likely influences the reactivity of other hydroxide-mediated reactions. This enhanced reactivity is likely because it disrupts large Na+-OH- ion networks because nitrate and nitrite do not fit in those ion networks similarly to how some ions cannot substitute into a foreign crystal lattice. In contrast, the aluminate ion did not have the same large incompatibility with hydroxide.

Nitrite, Nitrate, Aluminate, NaOH*H2O, Ion-aggrega↗

Efficacy of Stabilizing Calcium Battery Electrolytes through Salt-Directed Coordination Change

Achieving practical, high-energy-density calcium batteries requires controlling the stability of Ca 2+ electrolytes during calcium metal cycling. Because of the highly reactive nature of calcium, most typical electrolyte constituents are unstable, leading to electrode passivation and low Coulombic efficiency. Among various commercially available salts, calcium bis(trifluoromethylsulfonyl)imide (Ca(TFSI) 2 ) is attractive because of its oxidative stability and high solubility in a variety of solvents. However, this salt does not allow for calcium metal plating, and it has been proposed that TFSI – instability induced by Ca 2+ coordination is to blame. In this work, we test the ability of strongly coordinating Ca 2+ cosalts such as halides and borohydrides to displace TFSI – from the first coordination shell of Ca 2+ and thereby stabilize TFSI-based electrolytes to enable calcium plating. Through spectroscopic analysis, we find that the effectiveness of these cosalts at displacing the TFSI – anion is dependent on the solvent’s coordination strength toward Ca 2+ . Surprisingly, electrochemical calcium deposition behavior is not correlated to the population of bound or free TFSI – . Instead, the nature of the coordination interaction between Ca 2+ and the cosalt anion is more important for determining stability. Our findings indicate that TFSI – anions are inherently unstable during calcium deposition even in the nominally free state. Furthermore, strategies aimed at eliminating the interactions of these anions with the electrode surface via interface/interphase design are required.

25 ENERGY STORAGE↗