55 Search Results

The growing demand for critical minerals and materials requires atom- and energy-efficient, selective separations to overcome the challenges posed by the similar chemical and physical properties of the rare earth elements (REEs) and their low concentrations in unconventional domestic feedstocks. Here, in this study, we developed diethylenetriamine-functionalized graphene oxide (DETA-GO) as a membrane material for REE adsorption and separation. Synthesis conditions were optimized to maximize nitrogen incorporation while also preserving GO dispersibility for facile membrane fabrication. We investigated the mechanism of amine functionalization, the nitrogen-bonding configurations, the organization of the interlayer transport channels, and the resulting effects on ion andmore » water transport for REE separations. Neat-GO and DETA-GO multilayer laminate membranes were fabricated by vacuum filtration onto polymer supports. To investigate the effects of amine functionalization, the membranes were characterized using scanning electron microscopy, Raman, Fourier transform infrared, and X-ray photoelectron spectroscopy, as well as grazing-incidence X-ray diffraction measurements. Ion permeation experiments with representative lanthanum (La³⁺) and ytterbium (Yb³⁺) solutions revealed enhanced ion adsorption and water transport through DETA-GO membranes compared to neat-GO. The strong affinity of the membranes for multivalent REEs was also validated with conductivity and inductively coupled plasma mass spectrometry measurements. Atomistic insight into the role of amine functionalization in modulating nanochannel architecture and long-term stability, optimizing adsorption sites, and regulating REE and water transport was obtained using classical molecular dynamics simulations. Collectively, our joint experimental and theoretical study demonstrates the potential of DETA-GO membranes for selective REE separations, offering insights into ion-binding mechanisms, water-transport properties, and nanochannel optimization for the recovery of critical materials from aqueous feedstocks.« less

Collinear laser spectroscopy experiments on fast, neutral beams have been extensively used for studies on short-lived radioactive nuclei, taking advantage of its high sensitivity. The resulting resonance line-shape is known to show significant distortion, due to the energy exchange during the charge-exchange neutralization process, which can cause large systematic uncertainty in the determined centroid. A model for the line shape was constructed and simulated to be compared to measured Al, Si, and Ni hyperfine spectra. It is shown that the distortion is caused mainly by the transfer of electron into many different energy levels in the projectile atom and subsequentmore » decays, rather than secondary inelastic collisions, which were often assumed in the line shape analysis before. Furthermore, the model can also be applied to other projectile–alkali pairs, providing a reliable line-shape with less fitting parameters than conventional phenomenological models.« less

Sulfonated polysulfone is a promising membrane material for separation and energy generation processes that rely on membranes to control the rates of small-molecule (e.g., water and ions) transport. The interactions among water molecules, ions, and the sulfonate groups in these polymers play a key role in controlling these rates of transport, but much remains unknown about these fundamental interactions in sulfonated polymers. In this study, we used dielectric relaxation spectroscopy to characterize water molecule dynamics in sulfonated polysulfone and Nafion. We found that the charged sulfonate groups contribute to a restriction of water molecule dynamics (i.e., a reduction in themore » characteristic time scale of dipolar motions) in a manner that is governed by the concentration and nature (i.e., conjugate base strength) of the sulfonate group. Additionally, we develop strategies to use these data to aid in modeling ion transport in sulfonated polysulfone. These results may be useful to guide engineering strategies for polymeric membranes.« less

Membrane-based separations are widely used for wastewater treatment due to their low cost and efficiency. However, membrane fouling, which is the unwanted deposition or attachment of contaminants on membrane surfaces and/or within membrane pores, remains a major challenge as it increases the mass transfer resistance and reduces membrane productivity. Membrane fouling is typically probed by macroscopic performance metrics, such as flux decline, and ex situ characterization. However, this does not capture the membrane and fouling layer evolution under operating conditions, potentially masking important mechanisms and nonequilibrium pathways that impact fouling. Here, we present a remotely controlled crossflow membrane system andmore » a custom membrane cell for operando fouling characterization using transmission small/wide angle x-ray scattering (SAXS/WAXS). This approach allows direct observation of the nanoscale changes occurring at the membrane surface during pressurized water treatment processes, enabling a new way to understand the connections between dynamic fouling behaviors and membrane performance. Nanoparticle fouling of porous membranes during ultrafiltration was investigated using operando SAXS, and mineral scaling of reverse osmosis membranes was investigated using operando WAXS. Furthermore, this system allows for tracking membrane fouling in real time and under realistic conditions, providing fundamental physical insights into how water chemistry and operating conditions affect macroscopic membrane performance. Moreover, this system opens the door for future in situ and operando studies, and it serves as a testbed for evaluating novel materials/processes for membrane-based separations.« less

Predicting future CNS risks for astronauts during deep-space missions will rely substantially on ground-based rodent data with space-relevant ions and behaviors. For rats, the accumulated evidence indicates that less densely ionizing radiation, such as ⁴He and ¹²C ions, induce behavior deficits at lower doses than densely ionizing ions, such as ⁴⁸Ti and ⁵⁶Fe. However, this observation conflicts with standard somatic radiobiology, in which densely ionizing ions are generally more effective than less densely ionizing ions, and where the DNA/nucleus is the accepted target for radiation-induced tumorigenesis, cytogenetic aberrations, genetic mutations, and reproductive cell death. To gain deeper insight into themore » subcellular nature of the radiation targets for behavior risks, we compared the effects of dose, fluence, and linear energy transfer (LET) of ⁴He and ⁵⁶Fe particles using existing datasets for four distinct behavioral outcomes in rats: elevated plus maze (EPM-anxiety), novel object recognition (NOR-memory), operant responding (OR-response to environmental stimuli), and attentional set-shifting (ATSET-cognitive flexibility). We confirmed that less densely ionizing particles (except protons) showed ~100-fold lower threshold doses than densely ionizing particles for behavioral deficits (0.1–1 cGy for ⁴He vs. 15–100 cGy for ⁵⁶Fe). However, when analyzed by fluence the behavioral responses converged, indicating that ⁴He and ⁵⁶Fe were equally effective on a per-track basis. When analyzed by LET, there were ~100-fold differences in the LET for maximum effectiveness for behavioral deficits and DNA endpoints (~1 vs ~100 keV/μm, respectively). These unique features of radiation-induced behavioral deficits (high sensitivity to particles in the 1-keV/μm range, insensitivity to protons in the 0.2 keV/μm range, and isofluence dependence for particles with LET>1 keV/μm) provide evidence in support of a new hypothesis of sub-micron sized radiosensitive targets for behavioral effects consistent with the thickness of plasma membranes and/or small subcellular structures, smaller than a whole synapse. Like our behavior findings, mouse immature oocyte killing which is known to have a plasma membrane target was also better explained by fluence, rather than dose. In contrast, fluence analyses for DNA/nuclear endpoints in somatic cells (e.g., tumor induction, chromosome aberrations) showed opposite results, suggesting that behavior targets are not DNA. Our findings raise questions regarding the identity of subcellular targets and the multi-cellular functional unit for behavior risks, low-dose susceptibility, and generalizability from rat to other species and astronauts.« less

The number of displacements per atom (dpa) is widely used as an indicator of irradiation damage of materials in proton accelerator facilities. Experiments have been carried out to validate the dpa of metallic materials for protons with energies below 3 GeV. However, measurements of the displacement cross-sections for high-energy protons above 3 GeV have not been carried out and the calculations have not been validated. To validate the displacement cross section of metals in high-energy region, electrical resistivity changes in wires of aluminum, copper and tungsten at 8 K were measured using protons with energies of 120-GeV. The results show that the Norgett-Robinson-Torrensmore » dpa model of the Particle and Heavy Ion Transport Calculation Code overestimates the experimental data. On the other hand, the calculated results using the athermal recombination corrected dpa model were in agreement with the measured displacement cross sections. In the proton energy region above 1 GeV, the displacement cross section is almost constant, which is due to the fact that the damage energy of the material under 1 GeV proton irradiation is almost the same as under 120 GeV proton irradiation. Damage recovery of defects accumulated in the sample was also measured using isochronal annealing: At 80 K, approximately 60 % and 80 % of the damage remains for copper and tungsten, respectively. These results are the same as those obtained from other experiments on proton and neutron irradiation.« less

FLUKA is a fully integrated particle physics MonteCarlo simulation package which has many applications in high energy experimental physics and engineering. When using a cyclotron for medical radionuclide production, it is important to know that the beam energy is suitable to cause the intended nuclear reaction and minimize unwanted impurities. Here, this work focuses on the comparison of FLUKA as a tool to measure the beam energy of a cyclotron with experimental results using the method of stacked copper foils interspaced by an aluminum degrader. We compared two methods to determine the activity ratio: determining the activity in each foilmore » using the experimentally measured cross-sections from the National Nuclear Data Center (NNDC) cross-section data and calculating the activity in the two Cu foils using the FLUKA program. These results were compared to those reported by Gagnon et al., 2011. The FLUKA results gave energy measurements that were different than the true energy by a percentage in the range of 2.4% to 13%, suggesting that FLUKA is not recommended for pre-calculating the cyclotron beam energy using these low Z materials without experimental confirmation. It also confirms that the experimental cross-section data from the NNDC database is superior for this application giving energy values that ranged from 0.1% to 1.6% from the true energy.« less

Beyond its fascinating chemistry as the first element in the Periodic Table, hydrogen is of high societal importance in energy technologies and of growing importance in energy-efficient computing. In energy, hydrogen has reemerged as a potential solution to long-term energy storage and as a carbon-free input for materials manufacturing. Its utilization and production rely on the availability of proton-conducting electrolytes and mixed proton–electron conductors for the components in fuel cells and electrolyzers. In computing, proton mediation of electronic properties has garnered attention for electrochemically controlled energy-efficient neuromorphic computing. Incorporation of substitutional and interstitial hydride ions in oxides, though only recentlymore » established, enables tuning of electronic and magnetic properties, inviting a range of possible exotic applications. This article addresses common themes in the fundamental science of hydrogen incorporation and transport in oxides as relevant to pressing technological needs. The content covers (1) lattice (or bulk) mechanisms of hydrogen transport, primarily addressing proton transport, but also touching on hydride ion transport; (2) interfacial transport; (3) exploitation of extreme external drivers to achieve unusual response; and (4) advances in methods to probe the hydrogen environment and transport pathway. The snapshot of research activities in the field of hydrogen-laden materials described here underscores exciting recent breakthroughs, remaining open questions, and breathtaking experimental tools now available for unveiling the nature of hydrogen in solid-state matter.« less

Biogas upgrading via CO₂ conversion to CH₄ is an emerging technology for renewable natural gas production and carbon management, but its development is limited by the low H₂ gas to liquid phase transfer. Herein, an innovative biogas upgrading system employing a three-phase design was studied for CO₂ conversion with H₂ supply via gas-permeable membrane. The system produced biogas consisted of 74.1 ± 7.1 % CH₄ and 25.9 ± 7.1 % CO₂ with intermittent injection of H₂. When H₂ supply was continuous, the CH₄ content increased to 91.6 ± 2.2 % at a H₂:CO₂ ratio of 4.4. Although a higher ratiomore » of 5.5 could result in a higher CH₄ percentage of 95.2 ± 2.5 %, biogas production rate started to decrease. The removal efficiency of organic contents remained above 90 % throughout the experiment. Microbial community analysis corroborated the findings, showing that hydrogenotrophic Methanobacteriaceae was more prevalent in the biofilm (71.9 %) compared to that in anaerobic digestion (15.8 %) and effluent (14.1 %).« less

A new detector design has been fielded on the Omega-60 laser facility using a D³ He backlighter capsule to radiograph a magnetized experiment. D³ He capsules produce a low flux (~ 10⁸ total yield in 4π) of protons requiring detectors with close-to single-particle sensitivity to be employed. The new detector stack consisted of both imaging plate (IP) and CR-39 to detect 14.7 MeV protons where, historically, only CR-39 has been used. IP is sensitive to significant contributions in signal from both x-rays and protons so additional filtering has to be added to attenuate the x-rays. Here, the signals and featuresmore » observed from a single shot are detected by both IP and CR-39, giving confirmation that it is protons creating the signatures on the IP. Measurements of PSL/pixel are used to calculate approximate on-shot proton yields and agree with commonly measured yields. A second IP is used at the rear of the stack to measure, and subsequently remove, a background signal. The spatial resolution at the IP is limited, primarily, by a range of proton energies with varying deflections being recorded at the detector, causing potential ‘blurring’ of features. We find for this setup that the blurring effect is less than the smallest identifiable features observed at the detector, and therefore of minimal impact. A large benefit to this new stack design is that IP can be scanned and processed on much faster timescales than CR-39 allowing for prompt shot feedback. Future designs and modifications to the stack design fielded on this experiment could help improve the contrast of the radiograph on IP, as well as detecting protons produced at alternative energies.« less