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At least 145 records · Page 8

Halogenation of used aluminum matrix test reactor fuel – a bench-scale demonstration with surrogate materials

In this work, experiments with surrogate materials were performed at bench scale to demonstrate a halogenation technique applicable to treatment of used aluminum matrix test reactor fuel. The technique involves dissolution and separation of aluminum from used aluminum matrix test reactor fuel in molten-halide salt systems prior to treatment and disposition of the fuel’s uranium and fission products. Demonstration of the halogenation technique was performed with neodymium metal as a non-radiological surrogate for uranium metal. Experiments involved blending forms of aluminum and neodymium metal with ammonium and lithium chloride or ammonium and lithium bromide, which upon heating decomposed into ammonia gas and the respective hydrogen chloride or bromide gas. The latter reacted with the metals to form the respective aluminum and neodymium halides. At elevated temperatures, aluminum halides gasified away from the respective neodymium halides, which fused with their respective lithium halides. Samples of fused and distillate salts were collected and analyzed, yielding extents of aluminum removal that ranged from 94.5–98.2% for chlorination runs and 91.4–97.8% for bromination runs. No neodymium was detected in the distillate fractions. Some experiments were repeated with excess reactants, and a portion of aluminum chloride distillate was processed into a consolidated waste form.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Standard Characterization Techniques for Inorganic Phase Change Materials

Salt hydrates are promising candidates for phase change materials (PCMs) because of their low cost and high energy storage capacity. However, practical applications of salt hydrate based PCMs are limited due to their poor thermal cycling performance caused by phase separation and supercooling. Various techniques, including differential scanning calorimetry (DSC) and transient plane source (TPS) have been used to characterize salt hydrate based PCMs but may not provide full understanding of the degradation mechanism. In this manuscript, salt hydrate and graphite composites are prepared. Temperature history (T-History) method and X-ray diffraction (XRD) are utilized for measuring melting temperature, energy storage, and latent heat degradation of the PCM composites. Highlighting the importance of each technique and how each technique plays an important role in analyzing salt hydrates performance accurately. Temperature history, and X-ray diffraction are also used in conjunction to precisely predict the cause of degradation in salt hydrate PCMs with thermal cycling, as in most literatures the cause of degradation in salt hydrate are attributed to phase segregation, supercooling, and change in stichometry water concentration without any scientific validation.

Kumar, Navin↗

Influence of Water, Vacuum, and Temperature on Surface Conditions of a Zeolite‐based Molecular Sieve

Molecular sieves such as zeolite-based materials are ubiquitous in industrial separation processes. However, there is a significant gap in understanding the surface properties and adsorption mechanisms for commercial zeolites, as most research focuses on pure zeolite powders rather than industrially relevant forms. Here, this work addresses this gap in understanding by employing advanced characterization techniques, including positron annihilation spectroscopy, X-ray diffraction, scanning electron microscopy, X-ray fluorescence spectroscopy, X-ray photoelectron spectroscopy, liquid nitrogen sorption, and Fourier-transform infrared spectroscopy, to investigate the adsorption and desorption behavior of water in commercial zeolite 13X. Our research reveals insights into the pore-filling mechanisms, the impact of material binders on adsorption properties, and the dynamics of hydration and drying processes for zeolites. Monitoring changes on a minute scale allowed the distinction between fast and slow processes leading to sample drying. The identification of positronium bound to Na + ions indicated that water molecules remain in the vicinity of Na + ions after air-drying zeolite 13X. These findings highlight the importance of various environmental conditions in restoring zeolite properties to baseline after hydration, with significant implications for optimizing industrial processes. This work sets the direction for further research aimed at developing more efficient and robust separation techniques.

Beads Binder↗

Development of Mixed Matrix Membranes by Using NH 2 ‐Functionalized UiO‐66 and [APTMS][AC] Ionic Liquid for the Separation of CO 2

The ever‐escalating CO 2 concentration in the atmosphere calls for accelerated development and deployment of carbon capture processes to reduce emissions. Mixed matrix membranes (MMMs), which are fabricated by incorporating the beneficial properties of highly selective inorganic fillers into a polymer matrix, have exhibited significant progress and the ability to enhance the performance of a membrane for gas separation. In this research, an amine‐based ionic liquid (IL) [APTMS][AC] was prepared, which has greater CO 2 affinity and greater solubility due to its amine moiety. The metal–organic framework (MOF) UiO‐66 with a multidimensional crystalline structure was used as a filler due to its appropriate porosity and tunable properties, and it was functionalized with NH 2 . MOFs were further modified with an IL to prepare UiO‐66@IL and UiO‐66‐NH 2 @IL, and MMMs incorporating each MOF were fabricated with the polymer Pebax‐1657. All the prepared membranes and MOFs were characterized to predict their separation efficiency. Several characterization techniques, namely, FTIR spectroscopy, XRD, and SEM, were used to successfully synthesize UiO‐66@IL and UiO‐66‐NH 2 @IL composites and confirmed proper dispersion and excellent polymer‒filler compatibility at filler loadings ranging from 0 to 30 wt.%. The separation performances were investigated, and the results showed that the incorporation of RTIL with the highly crystalline structure and large surface area of UiO‐66 enhanced the separation efficiency of the membrane. The permeability of CO 2 for all fabricated membranes continuously increased with increasing filler concentration, wherein the permeability was comparatively high for the UiO‐66‐NH 2 MMMs. The CO 2 /CH 4 selectivity improved by 35%, 54%, and 60%, respectively, for UiO‐66@IL, UiO‐66‐NH 2 , and UiO‐66‐NH 2 @IL MMMs compared to simple UiO‐66 for CO 2 /CH 4 and by 28%, 36%, and 63%, respectively, for CO 2 /N 2 , with an increase in filler loading in the MMMs.

Khalid, Hafiza Mamoona (ORCID:0009000135165855)↗

Impacts of stochastic coalescence variability on warm rain initiation using Lagrangian microphysics in box and large-eddy simulations

Various coalescence methods for Lagrangian microphysics schemes are tested in box and large-eddy simulation (LES) models, including the stochastic all-or-nothing super-droplet method (SDM) and a version of SDM (dSDM) that applies a fractional approach similar to the average impact method. In LES, variabilities driven by microphysics and by flow realizations are separated using the “piggybacking” technique. Rain initiation averaged over many realizations of the box model is delayed and rain variability increases as the number of super-drops per collision volume ( N SD ) is decreased using SDM. In contrast, rain initiation time using SDM in LES is insensitive to N SD for 32 ≤ N SD ≤ 512. This is explained through the interaction between LES grid boxes, each acting as a separate collision volume. Variability across the ensemble of LES collision volumes using SDM results in rain quickly initiating in some of the LES grid cells at low N SD and leading to a similar overall timing of rain initiation from the cloud compared to simulations with high N SD . There is a ~20% decrease in the total rain mass and mean rain flux as N SD is increased from 32 to 256, with little additional change as N SD is increased from 256 to 512. The fractional coalescence approach in dSDM leads to reduced microphysical variability and a 15-18 min delay in rain initiation compared to SDM. Finally, an additional LES ensemble with microphysical variability feeding back to the dynamics shows that flow variability dominates the impact of microphysical variability on rain properties. Thus, flow variability must be constrained to isolate impacts of microphysical variability.

54 ENVIRONMENTAL SCIENCES↗

Melting and phase relations of Fe-Ni-Si determined by a multi-technique approach

Many studies have suggested silicon as a candidate light element for the cores of Earth and Mercury. However, the effect of silicon on the melting temperatures of core materials and thermal profiles of cores is poorly understood, due to disagreements among melt detection techniques, uncertainties in sample pressure evolution during heating, and sparsity of studies investigating the combined effects of nickel and silicon on the phase diagram of iron. Here, in this study we develop a multi-technique approach for measuring the high-pressure melting and solid phase relations of iron alloys and apply it to Fe 0.8 Ni 0.1 Si 0.1 (Fe-11wt%Ni-5.3wt%Si), a composition compatible with recent estimates for the cores of Earth and Mercury. This approach combines results (20-83 GPa) from two atomic-level techniques: synchrotron Mossbauer spectroscopy (SMS) and synchrotron x-ray diffraction (XRD). Melting is independently detected by the loss of the Mossbauer signal, produced exclusively by solid-bound iron nuclei, and the onset of a liquid diffuse x-ray scattering signal. The use of a burst heating and background updating method for quantifying changes in the reference background during heating facilitates the determination of liquid diffuse signal onsets and leads to strong reproducibility and excellent agreement in melting temperatures determined separately by the two techniques. XRD measurements additionally constrain the hcp-fcc phase boundary and in-situ pressure evolution of the samples during heating. We apply our updated thermal pressure model to published SMS melting data on fcc-Fe and fcc-Fe 0.9 Ni 0.1 to precisely evaluate the effect of silicon on melting temperatures. We find that the addition of 10 mol% Si to Fe 0.9 Ni 0.1 reduces melting temperatures by ~250 K at low pressures (<60 GPa) and flattens the hcp-fcc phase boundary. Extrapolating our results, we constrain the location of the hcp-fcc-liquid quasi-triple point at 147±14 GPa and 3140±90 K, which implies a melting temperature reduction of 500 K compared with Fe 0.9 Ni 0.1 . The results demonstrate the advantages of combining complementary experimental techniques in investigations of melting under extreme conditions.

36 MATERIALS SCIENCE↗

Stabilization of Miscible Aqueous Phases via Diffusion‐Controlled Multifunctional Nanoparticle‐Ligand Complexation

Liquid‐in‐liquid structuring by harnessing miscible aqueous domains can be achieved by inducing thermodynamically defined phase separation using aqueous solutions of incompatible solutes, where immiscibility is dictated by the concentrations of the solutes. For instance, in aqueous two‐phase systems (ATPSs), the interfacial tension between the two different aqueous solutions is so small that it stabilizes the phase‐separated domains, but not their shape, thus falling short of designing tunable, robust structures. Here, we introduce a diffusion‐controlled strategy that enables liquid‐in‐liquid compartmentalization absent a thermodynamically defined interface or bulk liquid‐liquid phase separation using a barrier formed in situ at the initial contact boundary of an aqueous dispersion of multifunctional nanoparticles and a solution of multifunctional ligands in pure water or a water/alcohol mixture. The nanoparticles and ligands are entropically driven to disperse uniformly but interact at the initial contact boundary more rapidly than bulk mixing, forming a layer that establishes a barrier akin to a semi‐permeable membrane and allows the formation of tubular compartments. A wealth of opportunities is enabled by the proposed technique, where examples in separations, soft electronic devices, and ultralight porous electromagnetic shielding materials are shown.

cryogels↗

Highly selective ion separations based on counter-flow electromigration in nanoporous membranes

Highly selective ion separations are vital for recovering important salts, and membrane-based techniques may enable environmentally friendly ion separations that operate continuously. This study demonstrates that simply opposing convective flow with electromigration in track-etched membranes leads to remarkable selectivities among monovalent ions. Because the membrane-pore diameters are orders of magnitude larger than the ion diameters, advection moves all ions at the same velocity, whereas electrophoretic velocities are proportional to ion mobilities. Thus during counter-flow cation electromigration, less mobile cations have lower electromigration velocity components and pass through porous membranes more rapidly than more mobile cations. Using membranes with 400 nm pores, counter-flow electromigration gives Li + /K + selectivities of 100 and Li + /Na + selectivities around 30 in mixed-salt studies. In this work, numerical simulations based on the extended Nernst-Planck equation agree with trends in experimental data and highlight the importance of high Péclet numbers, high current-to-flow ratios, and uniform current distributions for achieving high selectivities. Importantly, experimental separations give high selectivities at 0.3 M ionic strength and low Li + /K + ratios, which suggest these methods may also work in brine solutions. Nevertheless, energy costs for such separations are high.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

R-Matrix Analysis of the Neutron-Induced Cross Sections on 143 Nd and 147,149 Sm Measured at LANSCE [Slides]

This presentation covers how an established used of R-Matrix codes is being implemented at LANSCE. This presentation displays how there are unique features accessible with detectors at LANSCE that can be used to perform more complete R-Matrix analysis. Additionally discussed is how spin separation is a powerful technique that can be applied in DANCE measurements. Unique method to measure transmission with DICER are discussed. Finally, transmission and capture data are being analyzed in this work. The study can be extended to other channels. The ongoing analysis of the 143 Nd data is presented in this work. The same method is being applied to analyze the 147,149 Sm data. The 143 Nd and 147,149 Sm work started in FY-23 funded by NCSP.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

MUSE adaptive-optics spectroscopy confirms dual active galactic nuclei and strongly lensed systems at sub-arcsec separation

The novel Gaia multi peak (GMP) technique has proven to be able to successfully select dual and lensed active galactic nuclei (AGN) candidates at sub-arcsecond separations. Both populations are important because dual AGN represent one of the central, still largely untested, predictions of ΛCDM cosmology, and compact lensed AGN allow us to probe the central regions of the lensing galaxies. In this work, we present high-spatial-resolution spectroscopy of 12 GMP-selected systems. We used the adaptive-optics assisted integral-field spectrograph MUSE at the VLT to resolve each system and investigate the nature of each component. All targets show the presence of two components confirming the GMP selection. We classify 4 targets as dual AGN, 3 as lensed quasar candidates, and 5 as a chance alignment of a star and an AGN. With separations ranging from 0.30″ to 0.86″, these dual and lensed systems are among the most compact systems discovered to date at z > 0.5. This is the largest sample of distant dual AGN with sub-arcsecond separations ever presented in a single paper.

Scialpi, M. (ORCID:0009000651004986)↗

Ion Mobility Spectrometry-Mass Spectrometry for High-Throughput Analysis

Ion mobility spectrometry is a widely used analytical technique providing gas phase separation of molecules. It has received increasing attention in the recent years with the advancement in technology development and the availability of commercial instruments. In this chapter, we introduced the ion mobility fundamental theory and provided examples of IMS applications, especially for isomer separation, collision cross section database generation, high throughput analysis workflows, software tools for IMS data analysis, and ongoing high resolution SLIM IMS development. While IMS is not yet routinely utilized in drug discovery and pharmaceutical industry, there has been increased interest in high throughput library screening and antibody characterization. With all the ongoing development in IMS technology and informatics, we foresee more and more exciting applications of high throughput IMS analysis in different fields including omics studies, drug discovery and clinical applications in the near future.

Ross, Dylan H.↗

Using Artificial Neural Networks to Predict Physical Properties of Membrane Polymers

Membrane polymers are a promising technology for use in many challenging gas separation applications. Here, the techniques of computer-aided molecular design can be used to search through the massive molecular space of heteropolymers and develop a set of likely candidate repeat units matching specific physical property targets. However, reasonably accurate property prediction algorithms are needed, but these algorithms must be very fast in order to be combined with an optimization framework. Artificial neural networks (ANNs), a branch of machine learning, are applied in this work to predict the physical properties of polymers. All of the physical properties investigated were found to be predicted by ANNs with R 2 scores exceeding 0.82.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular aspects of temperature swing solvent extraction for brine desalination using imidazole-based solvents

Solvent extraction desalination has shown to be a promising energy-efficient technique when compared to separation processes usually employed. Despite the remarkable impact of the organic solvent’s molecular characteristics on this process, few studies have been carried out so far to explicitly ascertain the influence of these characteristics on the solubility of water in the solvent. In this report we assess the viability of four different imidazole-based solvents and compare them to an amine compound for solvent extraction desalination of high salinity brines. All-atom molecular simulations of pure solvent and water-solvent bulk mixtures are used to ascertain the influence of the solvents’ molecular structures on solvent–solvent and solvent–water interaction. Our results show that water solubilization in imidazole-based solvents is an endothermic process, while for a secondary amine (diisopropylamine) it is an exothermic process. We show that imidazole-based solvents can be designed to provide characteristics favorable to brine desalination.

42 ENGINEERING↗

Defect engineering of porous aromatic frameworks via end capping improves dioxane removal from water

Amorphous porous organic polymers show promise for energy-efficient adsorptive separations, but it is difficult to understand or improve their performance through intentional structural modification. Herein, we report the synthesis of porous aromatic frameworks (PAFs) with pore structures tailored by the incorporation of a monofunctionalized end-capping monomer that disrupts framework topology. Combining experimental characterization with molecular simulations, we show that this defect engineering strategy yields less densely crosslinked networks, which leads to pore collapse and the presence of unique adsorption sites. These defect-engineered PAFs exhibit enhanced removal of 1,4-dioxane, an important environmental pollutant, from water. Increasing the concentration of end-capping monomers produces PAFs with narrower pore size distributions and improved 1,4-dioxane uptake. These results illustrate that defect engineering can effectively modulate polymer connectivity and porosity for applications in selective adsorptive separations. In conclusion, this technique avoids post-synthetic treatments and presents another approach to tailor amorphous polymeric adsorbents.

36 MATERIALS SCIENCE↗

Top-down proteomics

Proteoforms arising from posttranslational modifications, genetic polymorphisms, and RNA splice variants, play a pivotal role as the key drivers in biology. Thus, a comprehensive understanding of proteoforms is essential for unraveling the intricacies of biological systems and bridging the gap between genotype and phenotype. By analyzing whole proteins without digestion, top-down proteomics (TDP) provides a holistic view of the proteome and presents a next-generation approach for deciphering protein function, uncovering disease mechanisms, and advancing precision medicine. This Primer embarks on a journey into the world of TDP by encapsulating its historical context, underlying principles, recent advances, and an outlook on the future of TDP. The experimental section navigates instrumentation, sample preparation, intact protein separation, tandem mass spectrometry techniques, and data collection. Results decipher raw data, visualize intact protein spectra, unravel data analysis, and explain proteoform identification, characterization, and quantitation, as well as statistical analysis. Various applications of TDP spanning the human proteoform project, biomedical, biopharmaceutical, and clinical applications are described. These are complemented by discussions on measurement reproducibility, limitations, and a forward-looking perspective outlining uncharted waters where the field can advance, and potential exciting future applications of TDP.

Roberts, David S.↗

On Alfvénic turbulence of solar wind streams observed by Solar Orbiter during March 2022 perihelion and their source regions

It has been recently accepted that the standard classification of the solar wind solely according to flow speed is outdated, and particular interest has been devoted to the study of the origin and evolution of so-called Alfvénic slow solar wind streams and to what extent such streams resemble or differ from fast wind. In March 2022, Solar Orbiter completed its first nominal phase perihelion passage. During this interval, it observed several Alfvénic streams, allowing for characterization of fluctuations in three slow wind intervals (AS1-AS3) and comparison with a fast wind stream (F) at almost the same heliocentric distance. This work makes use of Solar Orbiter plasma parameters from the Solar Wind Analyzer (SWA) and magnetic field measurements from the magnetometer (MAG). The magnetic connectivity to the solar sources of selected solar wind intervals was reconstructed using a ballistic extrapolation based on measured solar wind speed down to the (spherical) source surface at 2.5 R s below which a potential field extrapolation was used to map back to the Sun. The source regions were identified using SDO/AIA observations. A spectral analysis of in situ measured magnetic field and velocity fluctuations was performed to characterize correlations, Alfvénicity, normalized cross-helicity, and residual energy in the frequency domain as well as intermittency of the fluctuations and spectral energy transfer rate estimated via mixed third-order moments. A machine learning technique was used to separate proton core, proton beam, and alpha particles and to study v − b correlations for the different ion populations in order to evaluate the role played by each population in determining the Alfvénic content of solar wind fluctuations. The comparison between fast wind and Alfvénic slow wind intervals highlights the differences between the two solar wind regimes: The fast wind is characterized by larger amplitude fluctuations, and magnetic and velocity fluctuations are closer to equipartition of energy. In fact the Alfvénic slow wind streams appear to be on a spectrum of wind types, with AS1, originating from open field lines neighboring active regions and displaying similarities with the fast wind in terms of fluctuation amplitude and turbulence characteristics, but not with respect to the alpha particles and proton beams. The other two slow streams differed both in their sources as well as plasma characteristics, with AS2 coming from the expansion of a narrow coronal hole corridor and AS3 from a region straddling a pseudostreamer. The latter displayed the coldest and highest density but the slowest stream with the smallest fluctuation amplitude and greatest magnetic energy excess. It also showed the largest scatter in proton beam speeds and the greatest difference in speed between proton beam and alpha particles. This study shows how the old fast–slow solar wind dichotomy, already called into question by the observations of slower Alfvénic solar wind streams, should further be refined, as the Alfvénic slow wind, originating in different solar wind regions, show significant differences in density, temperature, and proton and alpha-particle properties in the inner heliosphere. The observations presented here provide the starting point for a better understanding of the origin and evolution of different solar wind streams as well as the evolving turbulence contained within.

magnetohydrodynamics (MHD)↗

Probing specific ion effects at air-aqueous dibutyl phosphate interfaces using vibrational sum frequency generation spectroscopy

Molecular properties at air–liquid and liquid–liquid interface hold the key to many processes involving molecular transport across phase boundaries from aerosol formation to carbon cycling and material separation using solvent extraction techniques. Using dibutyl phosphate (DBP) as a representative for partially aqueous soluble surfactants, the specific ion effect (SIE) of the Hofmeister series cations Cs + , Na + , Li + , and Mg 2+ on the partition and interaction between surfactant molecules and water molecules in the air–aqueous interface are investigated using vibrational sum frequency generation spectroscopy and surface tension measurements. In the presence of 1 mM and 1M bulk aqueous phase ionic strength salt concentrations, fundamental qualitative relationships are observed for the salting out of DBP relative to bulk aqueous phase nitrate salt concentrations and the specific cations species. At 1 mM ionic strength, the interfacial charge and hence the interfacial potential modulates the electrostatic interactions; in particular, the counter cations partially screen the negatively charged interface induced by the DBP in a direct Hofmeister order. At 1M ionic strength, the electric field at the interface or interfacial potential is effectively neutralized, and the counter cations promote the partitioning of DBP to the interface depending on their specific interaction with the DBP head group and metal ion hydration properties. The present results lay a foundation to study SIEs of heavier metals on hydrophobic-aqueous DBP interfaces.

Louie, Christina [Washington State University, Pul↗

Gallium oxide (Ga2O3) as a radiation detector distinguishing neutrons and gammas

Gallium oxide (Ga2O3) is a promising ultrawide bandgap semiconductor for radiation detection with the potential of integrating electronic and scintillation functions within a single crystal device. This study establishes the scintillation response of β-Ga2O3 gamma irradiation from yttrium-88 (88Y). Then, californium-252 (252Cf) is used as a spontaneous fission source of mixed neutron and gamma radiation field to measure scintillation signals. Pulse shape discrimination and constant fraction discrimination techniques were used to separate neutron and gamma interaction events. Further investigation indicates that the prompt temporal responses of β-Ga2O3 for gammas and neutrons may enable discrimination of the two by prompt pulse fitting methods, focused around the initial peak. For gamma irradiation, we observed a rise time (τr) of 2.1 ns, decay time (τd) of 9.5 ns, and a full width at half maximum (FWHM) of 6.2 ns. For neutrons, it showed a τr of 2.3 ns, a τd of 12.1 ns, 9.4 ns FWHM, and reduced peak intensity. A diamond detector exhibited a more symmetrical τr and τd for both gamma and neutron signals and therefore is less effective at discriminating between the two by this method. This draws attention to β-Ga2O3’s ability to distinguish neutron and gamma particles. These findings showcase Ga2O3’s potential as a next-generation semiconductor for applications in nuclear safety and medical imaging, where precise discrimination between neutron and gamma interactions is essential.

Valdes, D. J. (ORCID:0000000304373720)↗