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At least 505 records · Page 28

Machine learning enabled measurements of astrophysical (p,n) reactions with the SECAR recoil separator

he synthesis of heavy elements in supernovae is affected by low-energy (n,p) and (p,n) reactions on unstable nuclei, yet experimental data on such reaction rates are scarce. The SECAR (SEparator for CApture Reactions) recoil separator at FRIB (Facility for Rare Isotope Beams) was originally designed to measure astrophysical reactions that change the mass of a nucleus significantly. We used a novel approach that integrates machine learning with ion-optical simulations to find an ion-optical solution for the separator that enables the measurement of (p,n) reactions, despite the reaction leaving the mass of the nucleus nearly unchanged. A new measurement of the 58 Fe (p,n)⁢ 58 Co reaction in inverse kinematics with a 3.66 ± 0.12 MeV/nucleon 58 Fe beam (corresponding to 3.69 ± 0.12 MeV proton energy in normal kinematics) yielded a cross-section of 20.3 ± 6.3 mb and served as a proof of principle experiment for the new technique demonstrating its effectiveness in achieving the required performance criteria. This novel approach paves the way for studying astrophysically important (p,n) reactions on unstable nuclei produced at FRIB.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Spectroscopic investigations of beam-plasma interactions in an ion plume

We report the results of spectroscopic investigations of beam-plasma interactions in the plume from a 3 cm ion source operated on argon. Ion-electron, ion-neutral, and electron-neutral scattering are identified by studying the dependence of neutral and ion emission intensities on chamber pressure and mass flow rate, and by analyzing the emission lineshapes at a non-orthogonal angle to the plume axis. Through the Doppler shift, we are able to separate contributions from fast beam ions and fast charge-exchange neutrals on the one hand, and of slow neutrals and slow ions on the other. We discuss the application of this new technique to the characterization of beam plasma interactions in the downstream region of ion thruster engines, and its potential for identifying the processes which lead to grid erosion.

Ruyten, W. M.↗

Advanced Analysis of X-ray Fluorescence Measurements of the Interfacial Density of Eu Ions at Liquid–Liquid Interfaces for Solvent Back-Extraction

X-ray fluorescence near total reflection (XFNTR) is the primary technique used to measure the element-specific interfacial density of ions at liquid−liquid interfaces. Fluorescence from ions in the bulk liquids can complicate the determination of the interfacial density; consequently, measurements have been previously limited to samples without ions in the upper phase and with concentrations on the order of 10 μM or less in the lower phase. We modify the analysis of XFNTR data to account for ions in both bulk phases, then demonstrate its use in the context of rare-earth separations processes. In a model of ion stripping (i.e., back-extraction), dodecane solutions of di(2-ethylhexyl)- phosphoric acid (HDEHP) loaded with Eu(III) at the 1 mM level are placed in contact with either pure water or aqueous solutions of nitric or citric acid at pH 3. XFNTR measurements of equilibrated, quiescent samples reveal that citric acid solutions produce a disproportionately large depletion of ions from the interface compared to that from the bulk organic solution, whereas stripping by pure water or nitric acid solutions is negligible. As a result, this advance in the methodology of XFNTR may have broad applicability to the investigation of metal ions in chemical and biological processes at liquid−liquid interfaces.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Rotation Rate of Saturn's Magnetosphere using CAPS Plasma Measurements

We present the present status of an investigation of the rotation rate of Saturn 's magnetosphere using a 3D velocity moment technique being developed at Goddard which is similar to the 2D version used by Sittler et al. (2005) [1] for SOI and similar to that used by Thomsen et al. (2010). This technique allows one to nearly cover the full energy range of the CAPS IMS from 1 V less than or equal to E/Q less than 50 kV. Since our technique maps the observations into a local inertial frame, it does work during roll manoeuvres. We have made comparisons with Wilson et al. (2008) [2] (2005-358 and 2005-284) who performs a bi-Maxwellian fit to the ion singles data and our results are nearly identical. We will also make comparisons with results by Thomsen et al. (2010) [3]. Our analysis uses ion composition data to weight the non-compositional data, referred to as singles data, to separate H+, H2+ and water group ions (W+) from each other. The ion data set is especially valuable for measuring flow velocities for protons, which are more difficult to derive using singles data within the inner magnetosphere, where the signal is dominated by heavy ions (i.e., proton peak merges with W+ peak as low energy shoulder). Our technique uses a flux function, which is zero in the proper plasma flow frame, to estimate fluid parameter uncertainties. The comparisons investigate the experimental errors and potential for systematic errors in the analyses, including ours. The rolls provide the best data set when it comes to getting 4PI coverage of the plasma but are more susceptible to time aliasing effects. Since our analysis is a velocity moments technique it will work within the inner magnetosphere where pickup ions are important and velocity distributions are non-Maxwellian. So, we will present results inside Enceladus' L shell and determine if mass loading is important. In the future we plan to make comparisons with magnetic field observations, use Saturn ionosphere conductivities as presently known and the field aligned currents necessary for the planet to enforce corotation of the rotating plasma.

Sittler, E.↗

Transition Metal Blocking Microporous Polymer Separators for Energy-Dense and Long-Lived Li-ion Batteries

A revolution in electric-powered mobility is imminent, catalyzed by breakthroughs in Li-ion battery technology that have dramatically lowered the $/kWh price tag of electrochemical energy storage. Increases in production have also enabled greater penetration in key markets. World-wide registration of new plug-in hybrid electric and battery-only electric vehicles (PHEV and BEV) increased by 70% from 2014 to 2015, and sales of PHEVs and BEVs are predicted to be 35% of all vehicle sales by 2040, reaching 41 million units per year—a 90-fold increase from 2015.1,2 In stride with industry giants such as Tesla, EV manufacturers rely on Li-ion cell Original Equipment Manufacturers (OEMs) for relentless improvements in Li-ion battery technology necessary to drive this bullish market penetration outlook. Advancing energy and power density is critical to alleviating EV-customer range anxiety. Furthermore, strategies to extend battery-pack life beyond 1000 cycles—particularly when operating under aggressive duty cycles—requires fresh perspectives and innovation in cell components.

36 MATERIALS SCIENCE↗

Power balance analysis at the L-H transition in JET-ILW NBI-heated deuterium plasmas

The understanding of the physics underlying the L-H transition has strong implications for ITER experimental reactor and demonstration power plant (DEMO). In many tokamaks, including JET, it has been observed that, at a particular plasma density, n e,min , the power necessary to access H-mode P L-H is minimum. In the present work, L-H transitions of JET deuterium plasmas heated by neutral beam injection (NBI) are studied for the first time by means of a power balance analysis to characterize the main contributions in the transition, through integrated transport modelling. In the pulses analysed, we do observe a minimum of the L-H power threshold in density, indicating the presence of density branches and of n e,min . Electron and ion heat fluxes at the transition are estimated separately. The electron/ion equipartition power results in favour of the ions, as shown by QuaLiKiz quasilinear gyrokinetic simulations, which predict a larger ion transport that causes T e > T i . The resulting edge ion heat flux also shows a clear change of slope below n e,min , similarly to ASDEX-Upgrade (AUG) NBI pulses (Ryter et al 2014 Nucl. Fusion 54 083003). JET NBI data are compared to radio-frequency heated AUG and Alcator C-mod pulses (Schmidtmayr et al 2018 Nucl. Fusion 58 056003), showing a different trend of the power, coupled to ions at the L-H transition with respect to the linearity observed in the radio-frequency heated plasmas. Finally, the presence of n e,min and the role of the ion heat flux is discussed in the paper, although it seems it is not possible to explain the presence of a P L-H minimum in density by a critical ion heat flux and by the equipartition power for the JET NBI-heated plasmas analysed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Argon ions injected parallel and perpendicular to the magnetic field

Preliminary results are reported of measurements obtained with the 0-10-kHz electric-field plasma-wave receivers and single-particle ion detectors of the ARCS-3 sounding-rocket payload over the auroral oval on February 10, 1985, after downward/field-parallel or transverse-spiral injection of Ar ions from the accelerator subpayload (separating itself at 2.3 m/s). The data are presented graphically and briefly characterized. The waves induced by the parallel injections are found to be much weaker than those induced by the perpendicular injections. In addition to the expected response to the Ar beam, an ion flux at pitch angle 90 deg was detected during the second parallel injection.

Erlandson, R. E.↗

Extraction, Characterization, and Stability Studies of Bistriazinyl-Derived Carboxylic Acids

Separation of An(III) and Ln(III) ions will benefit the recycling of used nuclear fuel (UNF). For this purpose, many ligands have been tested over the years, and several separation processes have been successfully demonstrated on the laboratory scale. Current research aims at the development of new ligands that are built only with carbon, hydrogen, oxygen, and nitrogen (CHON), as they can be incinerated completely without secondary waste production. Here, we tested a new class of water-soluble ligands, the bistriazinyl-octa-carboxylic acids. One member, in particular, 2,6-bis-[5,6-di(3,4-dicarboxyphenyl)-1,2,4- triazin-3-yl]-pyridine (BTPOA), was found to be suitable for the selective separation of Am(III) and Cm(III) ions from Ln(III) ions and may act as a CHON alternative to its sulfonated analogue (SO 3 -Ph-BTP). BTPOA exhibited good extraction results and a high selectivity for Am(III) over Eu(III) ions. This ligand’s complexation of metal ions was further studied using potentiometric spectroscopy, as well as time-resolved laser-induced spectroscopy with Cm(III) and Eu(III) in aqueous HClO 4 and HNO 3 media. Conditional stability constants of each formed species were determined. In the HClO 4 system, Cm(III) formed three species (1:1, 1:2, and 1:3) through the stepwise addition of a single BTPOA molecule. On the other hand, in HNO 3 , Cm(III) formed two 1:2 complexes and one 1:3 complex, while the stepwise formation of three species was observed for Eu(III). The stability constants are comparable to the values for SO 3 -Ph-BTP. The radiolytic behavior of BTPOA was also investigated using electron pulse irradiation measurements to determine absolute rate coefficients (k) under ambient temperature conditions for the reaction of BTPOA with typical UNF reprocessing radical radiolysis products the hydrated electron (e aq − , k = (1.60 ± 0.02) × 10 10 M −1 s −1 ), the hydrogen atom (H • , k = (2.17 ± 0.03) × 10 9 M −1 s −1 ), and hydroxyl ( • OH, k = (6.95 ± 0.06) × 10 9 M −1 s −1 ) and nitrate (NO 3 • , k = (0.37 ± 0.02) × 10 7 M −1 s−1) radicals. These rate coefficients indicate that the radiolytic longevity of BTPOA should increase with HNO 3 concentration, owing to the consumption of e aq − /H • , by nitrate anions, and the replacement of • OH by the less reactive NO 3 • .

Diaz Gomez, Laura [Forschungszentrum Juelich (Germ↗

Small Mercury Ion Clock for On-board Spacecraft Navigation

I.Small Ion Clock Approach and Heritage: a) No lasers, uwave cavities, cryogenics, atomic beams, etc. b) Ions are electrically shuttled between separate optical and microwave traps. II. Each trap is optimized for its task: quadrupole for optical state selection; multi-pole for microwave clock. a) Very good stability shown in USNO. Timescale running "open loop." III. "Open loop" operation means no self-measurements of frequency offsets: (Zeeman, ion temperature,... etc.) a) Fewer parts and procedures, produces stable output continuously. IV. Ion clock is not so sensitive to temperature fluctuations a) Measured u:nshielded temperature coefficient of few 10(exp -15) per C. b) No bulky temperature isolation needed.

Prestage, John D.↗

Solvent Phase Optimizations Improve Correlations with Experimental Stability Constants for Aqueous Lanthanide Complexes

Stability constants provide insight into ion complexation in water. While computational studies have been shown to model the energy of the complexation successfully using a thermodynamic cycle approach, it does not extend to calculating the stability constants for 1:1 lanthanide to ligand complexes in solution. Using B3LYP and 6-31+G* Pople basis with small core effective core potential (ECP) on the lanthanum ion, and a solvent model based on the full solute electron density (SMD) solvation model we computed and compared with previously published stability constants of the ligands: acetate, acetohydroximate, acetylacetonate, methanoate, tropolonate, hydroxide, catecholate, malonate, oxalate, phthalate, and sulfate. The best R 2 values for the thermodynamic cycle can only be determined by separating the mono and divalent ions to achieve an R 2 value of 0.86 and 0.74 for mono and divalent ions, respectively. We show that by optimizing the lanthanide-ligand structures in implicit solvent, we achieve an improved correlation between experimental and computed stability constants of R 2 value of 0.89 for the combined mono and divalent ions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Novel Polyimide Battery Separator Imbibed with Room-Temperature Ionic Liquids

The journey to Mars will require advancements in many existing technologies, including space power and energy storage systems. According to the 2015 NASA Technology Roadmaps, energy storage is a critical technology area to develop for both terrestrial as well as future long-term space missions. Currently, batteries represent one of the major areas in need of advancement, both in terms of energy density as well as safety. Recently, concerns regarding the fire safety of commercial lithium-ion batteries have prompted efforts to produce nonflammable battery components, namely the electrolyte and separator. Commercial lithium-ion batteries utilize polyolefin separators imbibed with a lithium salt dissolved in cyclic carbonates. This separator/electrolyte combination imparts good ionic conductivities in the range of 10(exp -2) to 10(exp -3) S/cm. However, the cyclic carbonates and polyolefin separator are inherently flammable. Room-temperature ionic liquids (RTILs) appear to be a safer alternative to cyclic carbonates. They offer good ionic conductivities, similar to those observed in cyclic carbonates, but are inherently nonvolatile and nonflammable giving them a safety advantage. Many promising RTILs for battery electrolytes are not compatible with commercial polyolefin separator materials. Polyimide aerogels possess an open-porous, fibrillar network architecture which offers a high degree of porosity (typically greater than 85 porous), required for lithium ion conduction, as well as good mechanical properties. Furthermore, these materials are compatible with all tested RTILs. By creating a polyimide gel and imbibing the gel with a RTIL containing a lithium salt instead of super critically drying them to form aerogels, a nonflammable separator/electrolyte system with conductivities in the range of 1x10(exp -3) S/cm has been demonstrated.

Polyimide↗

Ultrafiltration separation of Am(VI)-polyoxometalate from lanthanides

Partitioning of americium from lanthanides (Ln) present in used nuclear fuel plays a key role in the sustainable development of nuclear energy. This task is extremely challenging because thermodynamically stable Am(III) and Ln(III) ions have nearly identical ionic radii and coordination chemistry. Oxidization of Am(III) to Am(VI) produces AmO 2 2+ ions distinct with Ln(III) ions, which has the potential to facilitate separations in principle. However, the rapid reduction of Am(VI) back to Am(III) by radiolysis products and organic reagents required for the traditional separation protocols including solvent and solid extractions hampers practical redox-based separations. Herein, we report a nanoscale polyoxometalate (POM) cluster with a vacancy site compatible with the selective coordination of hexavalent actinides ( 238 U, 237 Np, 242 Pu and 243 Am) over trivalent lanthanides in nitric acid media. To our knowledge, this cluster is the most stable Am(VI) species in aqueous media observed so far. Ultrafiltration-based separation of nanoscale Am(VI)-POM clusters from hydrated lanthanide ions by commercially available, fine-pored membranes enables the development of a once-through americium/lanthanide separation strategy that is highly efficient and rapid, does not involve any organic components and requires minimal energy input.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Mechanically Resilient Polymeric Films Doped with a Lithium Compound

This invention is a series of mechanically resilient polymeric films, comprising rod-coil block polyimide copolymers, which are doped with a lithium compound providing lithium ion conductivity, that are easy to fabricate into mechanically resilient films with acceptable ionic or protonic conductivity at a variety of temperatures. The copolymers consists of short-rigid polyimide rod segments alternating with polyether coil segments. The rods and coil segments can be linear, branched or mixtures of linear and branched segments. The highly incompatible rods and coil segments phase separate, providing nanoscale channels for ion conduction. The polyimide segments provide dimensional and mechanical stability and can be functionalized in a number of ways to provide specialized functions for a given application. These rod-coil black polyimide copolymers are particularly useful in the preparation of ion conductive membranes for use in the manufacture of fuel cells and lithium based polymer batteries.

Mary Ann B Meador↗

Local Coordination Environment of Lanthanides Adsorbed onto Cr- and Zr-based Metal–Organic Frameworks

Separating individual lanthanide (Ln) elements in aqueous mixtures is challenging. Ion-selective capture by porous materials, such as metal–organic frameworks (MOFs), is a promising approach. To design ion-selective MOFs, molecular details of the Ln adsorption complexes within the MOFs must be understood. We determine the local coordination environment of lanthanides Nd(III), Gd(III), and Lu(III) adsorbed onto Cr(III)-based terephthalate MOF (Cr-MIL-101) and Zr(IV)-based Universitet in Oslo MOFs (UiO-66 and UiO-68) and their derivatives. In the Cr(III)- and Zr(IV)-based MOFs, Ln adsorb as inner-sphere complexes at the metal oxo clusters, regardless of whether the organic linkers are decorated with amino groups. Missing linkers result in favorable Ln binding sites at oxo clusters; however, Ln can coordinate to metal sites even with linkers in place. Further, MOF functionalization with phosphonate groups led to Ln chemisorption onto these groups, which out-compete metal cluster sites. Ln form monodentate and bidentate and mononuclear and binuclear surface complexes. We conclude that MOFs for ion-selective Ln capture can be designed by a combination of (1) maximizing metal-lanthanide interactions via shared O atoms at the metal oxo cluster sites, where mixed oxo clusters can lead to ion-selective Ln adsorption, and (2) functionalizing MOFs with Ln-selective groups capable of out-completing the metal oxo cluster sites.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Membranes for Lithium Recovery From Conventional and Unconventional Sources

Lithium has been deemed a critical mineral of national importance that finds uses in a wide range of applications, and its demand has been rising significantly in recent years. The urgency of meeting this demand requires lithium extraction from various aqueous sources such as continental brines, geothermal brines, seawater, produced water, and battery waste. While direct lithium extraction (DLE) technologies such as adsorption, ion exchange, and solvent extraction have emerged as possible solutions, membrane technologies are also being investigated for various sources and at different stages of the recovery process. Here, we analyze the application of membranes for pretreatment of lithium source waters, bring management, lithium/magnesium separation, lithium/sodium separation, and lithium hydroxide conversion, and evaluate performance metrics for critical lithium separations from the literature. We explore the potential of membranes at every stage of the recovery process and describe their current status and future prospects. We describe hypothetical process trains with integrated membrane technologies for each source type and address their feasibility and challenges. The potential energy and water impacts of membrane-integrated and conventional DLE processes are also critically considered alongside performance and selectivity metrics, and this is illustrated using examples and calculated from published technical reports. This paper thus provides a comprehensive overview of the application of membranes along every stage of the lithium recovery process, emphasizing the versatility and potential of membrane technologies for critical mineral recovery.

36 MATERIALS SCIENCE↗

Tunable Ion Transport with Freestanding Vermiculite Membranes

Membranes integrating two-dimensional (2D) materials have emerged as a category with unusual ion transport and potentially useful separation applications in both aqueous and nonaqueous systems. The interlayer galleries in these membranes drive separation and selectivity, with specific transport properties determined by the chemical and structural modifications within the inherently different interlayers. Here, in this work, we report an approach to tuning interlayer spacing with a single source material–exfoliated and restacked vermiculite with alkanediamine cross-linkers–to both control the gallery height and enhance the membrane stability. The as-prepared cross-linked 2D vermiculite membranes exhibit ion diffusivities tuned by the length of the selected diamine molecule. The 2D nanochannels in these stabilized vermiculite membranes enable a systematic study of confined ionic transport.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗