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At least 595 records · Page 33
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Physical, Chemical, and Mineralogical Characterizations of MSWI Ash Product and Recommendations for Downstream Processing

The primary objectives of this project are to (1) systematically characterize MSWI ash, and (2) based on characterization findings, design preliminary flowsheets for downstream processing. To achieve these objectives, a total of ten tasks were completed, including sample collection, physical separation tests, liberation tests, synthetic MSWI ash preparation, elemental composition analysis, sequential chemical extraction, mineralogical characterization, pozzolanic activity characterization, thermal stability characterization, processing flowsheet design, TEA and T2M, and project performance reporting. Many useful findings and conclusions were obtained from the exhaustive efforts of this project from several different aspects, including: a) Valuable Metals in MSWI Ash: MSWI ash contains a diverse array of valuable metals. Based on potential recoverable values, the most valuable metals present in MSWI ash include Fe, Ti, Mn, Cu, Zn, V, Co, Ni, Sr, Sn, Ag, Mo, and Sc. Some of these metals have been identified as critical minerals by DOE and DOI, suggesting that MSWI is a promising feedstock for critical mineral recovery. Noticeable graphical and seasonable variations in the valuable metal content of MSWI ash were observed. Nevertheless, it was challenging to discern any clear, definitive patterns for conclusions from those observations. Compared with bottom ash, fly ash contains more volatile metals, such as Zn and Sn, but less nonvolatile metals, such as Fe, Mn, Cu, Zn, Co, and Ni. Mineralogical analyses showed that MSWI ash contains a substantial amount of calcium minerals, such as portlandite, lime, gypsum, and calcite. In addition, it was found that different types of valuable metals often exist in the same particles. b) Physical Separation of MSWI Ash: Both dry sieving and wet sieving were performed on MSWI ash. A notable disparity in the size distribution of the same material was observed when using the two different sieving methods. The disparity is due to the agglomeration of small particles. For the valuable metals investigated, no significant enrichment in a specific size fraction was observed, suggesting that it is challenging to preconcentrate the valuable metals through size fractionation. Due to the presence of ferromagnetic materials, such as Fe, most of the materials reported to the magnetic products obtained by dry magnetic separation. However, the enrichment effect is minimal due to the existence of particle agglomerates. Density separation at a cut-off density of 2.7 SG or higher led to noticeable enrichment of selected valuable metals, particularly Ti. The unburned carbon present in MSWI ash was effectively removed by flotation using diesel as the collector. A novel reagent scheme, Na2S plus cationic collectors, that can efficiently beneficiate nonferrous metals plus Co was developed. c) Liberation Tests: The particle size of MSWI ash was effectively reduced by grinding, and as a result, the encapsulated valuable metal particles (if any) were liberated to a certain degree. However, particle size reductions did not noticeably enhance the beneficiation performance using the physical separation methods, primarily due to the inefficiency of these methods in processing fine particles and/or a possibility that insufficient liberation is not a limiting factor for achieving satisfactory physical separation performance. Valuable metals were classified into water leachable, ion-exchangeable, acid soluble, reducible, oxidable, and insoluble forms. It was found that the distributions in the different categories, i.e., the occurrence modes of the valuable metals, were not affected by the particle size. d) Leaching Characteristics of Metals from MSWI Ash: Most of the valuable metals were extracted from the fly ash samples when using 1 M HCl or HNO3 as the lixiviant. The leaching reaction is a very fast process, which can reach equilibrium within the first 5 min. The releasing of Co, Ni and Ag are sensitive to leaching temperature, a higher recovery value could be obtained when using relatively higher leaching temperatures. The leachability of the valuable metals present in MSWI bottom ash is relatively lower than that of fly ash. Leaching recoveries increased with elevations in the acid concentration. Relatively high leaching recoveries were obtained for REEs, Mn, Co, Ni, Cu, and Zn using 1 M HCl or HNO3 as the lixiviant. Elevations in the reaction temperature noticeably increased the leachability of the valuable metals, whereas the leachability was barely influenced by oxidizing and reducing agents. Similar to fly ash, leaching valuable metals from bottom ash is a rapid process, with most of the leaching reaction completed within the first 5 minutes. e) Combusted iPhones: The original structure of iPhones was remained after treating at 400 ºC and 600 ºC, while after being treated at 800℃, the screen bent, and the back cover of iPhone melted. Increasing the combustion temperature to 1000℃, the screen scattered, and most of the components turned into ashes. Combustion enhanced the leachability of REEs, while the leachability of the other valuable metals, except for Zn, was barely affected. Most of the REEs present in the original iPhones occurred as oxidizable forms. With elevations in the combustion temperature up to 600 ºC, the oxidizable REEs were transformed to acid soluble forms. However, further elevations in temperature resulted in decreases in the acid soluble fraction and corresponding increases in the reducible and oxidizable forms. Additionally, combustion temperature also significantly altered the occurrence modes of other metals present in the iPhones. f) Synthetic MSWI Ash: It was found that in the absence of hydrogen peroxide, all the elements except for Si were leached to certain degrees. It is noteworthy that approximately 80% of Zn was leached with 1.2 M HCl. When hydrogen peroxide was added to the reaction system, noticeable increases in the leaching recovery of Fe, Mn, Co, Ni, and Cu were observed. The leaching recovery of Al and Si was barely affected by adding hydrogen peroxide. These results suggested that the majority of Zn in the synthetic MSWI ash existed as metal oxide, a portion of Fe, Mn, Co, Ni, and Cu existed as metal oxide, and Al and Si are associated with glasses which are difficult to leach. Additionally, the remaining Fe, Mn, Co, Ni, and Cu in the metallic form were efficiently oxidized in the presence of hydrogen peroxide. g) Pozzolanic Activity and Thermal Stability of MSWI Ash: MSWI fly ash has higher pozzolanic activity compared to the bottom ash sample, which indicates that the fly ash sample consumed more portlandite because of its smaller particle size as reactivity fundamentally relates to reaction surface area. However, after the recovery of valuable elements, the pozzolanic activity of both the valuable elements fraction and the less valuable elements-rich products decreased significantly, which means that the valuable elements recovery lowers the Ca(OH)2 consumption, thus leading to the low activity of SCM. h) Flowsheet Design for Metal Recovery from MSWI Ash: Based on the results of the comprehensive physical separation and acid leaching tests, circuits that enable the beneficiation of the valuable metals were developed. In these circuits, the valuable metals are recovered into nonferrous, ferrous, and other valuable metal concentrates, which are processed separately in the acid leaching step. The subsequent separation and purification steps are simplified due to the physical beneficiation step. In addition, the overall recovery cost is reduced since physical beneficiation is much cheaper compared with chemical processing. Using different technologies, such as selective precipitation and solvent extraction, a comprehensive hydrometallurgical circuit was designed, and compounds of Cu, Zn, Mn, Co, and Ni with a purity close to or even higher than 95% were successfully generated.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Removal of Iron from Pyrite-Rich Coal Refuse by Calcination and Magnetic Separation for Hydrometallurgical Extraction of Rare Earth Elements

In the metallurgical extraction of rare earth elements (REEs), the ratio of contaminant ions to REEs in the leachate dictates the cost and operational efficiency of the downstream processes. The current study investigated the potential iron contamination removal from the feed to the hydrometallurgical process by calcination followed by magnetic separation. The 2.20 specific gravity sink fraction of Baker coal seam coarse refuse was pulverized to finer than 180 μm, calcined at various temperatures, and separated into magnetic and non-magnetic fractions using a wet high-intensity magnetic separator at different field strengths. The untreated feed, calcined products, and their subsequent magnetic and non-magnetic fractions were subjected to acid leaching tests with 1.2 M sulfuric acid at 75 °C and 1% w/v solids concentration. The recovery of light and heavy rare earth elements (LREEs and HREEs, respectively) along with the concentration of common contaminant ions (Al, Ca, and Fe) were measured as output variables. The weight percent of magnetic material was maximized at approximately 29% by calcination at a temperature of 400 °C. Magnetic removal of this fraction using a field strength of 1.15 Tesla resulted in the rejection of 81% of the iron. Leaching of the magnetic fraction provided significantly higher Fe recovery relative to untreated feed material and the non-magnetic fraction. The non-magnetic fraction was subsequently calcined at 600 °C to dehydroxylate the clays and released the REE minerals in the same manner as the treatment of the original coarse refuse material. A comparison of the leachate elemental concentrations resulting from the leaching of both the calcined non-magnetic and original coarse refuse showed only a slight reduction in the iron content from the non-magnetic material. This finding combined with the REE loss in the magnetic fraction resulted in the conclusion that the magnetic removal step was unfavorable.

58 GEOSCIENCES↗
DOE OSTI2022

Momentum transfer and plasma rotation caused by destabilized eigenmodes in tokamaks

In this work, the influence of magnetohydrodynamic eigenmodes destabilized by energetic ions on the momentum of these ions and concomitant sheared plasma rotation are studied. Two mechanisms affecting rotation are revealed: (i) spatial channelling (SC) – radially separated emission and absorption of the momentum; (ii) mode induced redistribution (MIR) across the magnetic field of the momentum of energetic ions. Forces arising during SC and MIR produce both toroidal and poloidal rotations. In addition, the momentum emission during SC leads to a radial flux of fast ions and generation of a radial electric field. Using the developed theory, estimates were made for the ITER (International Thermonuclear Experimental Reactor) 15 MA baseline scenario. They show that a global toroidicity-induced Alfvén eigenmode destabilized by alpha particles and neutral beam injection can result in significant radial electric field and forces applied to plasma. However, available data are not sufficient for a reliable prediction of the effects of SC and MIR in ITER. In general, one can expect that sheared rotation arising after destabilization of Alfvén modes and fast magnetoacoustic modes by energetic ions will tend to suppress the turbulence and improve plasma performance. The importance of plasma rotation is supported, in particular, by the fact that during the JET DTE1 experimental campaign the best parameters were achieved in a deuterium–tritium discharge where the rotation frequency was largest.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Assessment of DFT methods for the prediction of detachment energies and electronic structures of complex and multiply charged anions

Here, in this work, we assess the ability of different density functional theory methods to reproduce the vertical/adiabatic detachment energies (VDEs/ADEs) of a series of 40 anions, including monoanion versus multiply charged anions (MCAs) and covalent versus noncovalent interaction. The statistical analysis of errors is firstly performed by comparing the theoretical values with the experimental benchmark data obtained from the negative ion photoelectron spectroscopy (NIPES). The proposed optimally tuned range-separated (OTRS) functionals are proved to not only well reproduce the experimental VDEs/ADEs, but also simulate experimental NIPES. The result implies a more serious issue of delocalization error for MCAs and a balanced description of electron-rich/- deficient region of anions is necessary. The radius of the spherically symmetric average electron localization function (ELF) region is demonstrated as a useful descriptor for the characterization of electronic structure of anionic systems and a quasilinear fitting model is proposed to efficiently obtain their OTRS parameters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Root carbon interation with soil minerals is dynamic, leaving a legacy of microbially derived residues

Minerals preserve the oldest most persistent soil carbon, and mineral characteristics appear to play a critical role in the formation of soil organic matter (SOM) associations. To test the hypothesis that carbon source and soil microorganisms also influence mineral-SOM associations, we incubated permeable minerals bags in soil microcosms with and without plants, in a 13CO2 labelling chamber. Mineral bags contained quartz, ferrihydrite, kaolinite, or native soil minerals isolated via density separation. Using 13C-NMR, FTICR-MS, and lipidomics, we traced plant-derived carbon onto minerals harvested from microcosms at three plant growth stages, characterizing total carbon, 13C enrichment, and SOM chemistry. While C accumulation was rapid and mineral-dependent, the accumulated amount was not significantly affected by the presence of plant roots. However, the rhizosphere did shape the chemistry of mineral-associated SOM. Minerals incubated in the rhizosphere were associated with a more diverse array of compounds with different C functional groups (carbonyl, aromatics, carbohydrates, lipids) than minerals incubated in a bulk soil control. These diverse rhizosphere-derived compounds may represent a “transient fraction” of mineral SOM, rapidly exchanging with mineral surfaces. Our results also suggest that many of the lipids which persist on minerals are microbially-derived with a large fraction of fungal lipids.

Rhizosphere, soil organic matter, grassland, 13C-N↗
DOE OSTI2021

Nonlinear kinetic simulation study of the ion–ion streaming instability in single- and multi-ion species plasmas

The nonlinear evolution of the ion–ion streaming instability (IISI) is studied using numerical techniques novel to this problem that afford direct insight into the evolution of the particle distributions of each species. Here, during the linear phase of the instability, we demonstrate quantitative agreement with linear kinetic theory. Subsequently, the electrostatic field generated by the IISI causes ring-like velocity distributions of ions to form that are both heated and slowed to varying degrees relative to their initial flows. Due to variation in the trapping conditions for ion species of differing charge-to-mass ratio, when flows of multiple species interact, the nonlinear evolution of each species can be starkly different: we show a case where a lighter ion species is completely stopped by a heavier ion species via the IISI alone (i.e., without collisions) and, for the first time, demonstrate how the IISI can introduce a relative flow between ion species that initially have the same flow velocities, thereby separating them.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

NENCI-2021. I. A large benchmark database of non-equilibrium non-covalent interactions emphasizing close intermolecular contacts

In this work, we present NENCI-2021, a benchmark database of ~8000 Non-Equilibirum Non-Covalent Interaction energies for a large and diverse selection of intermolecular complexes of biological and chemical relevance. To meet the growing demand for large and high-quality quantum mechanical data in the chemical sciences, NENCI-2021 starts with the 101 molecular dimers in the widely used S66 and S101 databases and extends the scope of these works by (i) including 40 cation–π and anion–π complexes, a fundamentally important class of non-covalent interactions that are found throughout nature and pose a substantial challenge to theory, and (ii) systematically sampling all 141 intermolecular potential energy surfaces (PESs) by simultaneously varying the intermolecular distance and intermolecular angle in each dimer. Designed with an emphasis on close contacts, the complexes in NENCI-2021 were generated by sampling seven intermolecular distances along each PES (ranging from 0.7× to 1.1× the equilibrium separation) and nine intermolecular angles per distance (five for each ion–π complex), yielding an extensive database of 7763 benchmark intermolecular interaction energies (E int ) obtained at the coupled-cluster with singles, doubles, and perturbative triples/complete basis set [CCSD(T)/CBS] level of theory. The E int values in NENCI-2021 span a total of 225.3 kcal/mol, ranging from -38.5 to +186.8 kcal/mol, with a mean (median) E int value of -1.06 kcal/mol (-2.39 kcal/mol). In addition, a wide range of intermolecular atom-pair distances are also present in NENCI-2021, where close intermolecular contacts involving atoms that are located within the so-called van der Waals envelope are prevalent—these interactions, in particular, pose an enormous challenge for molecular modeling and are observed in many important chemical and biological systems. A detailed symmetry-adapted perturbation theory (SAPT)- based energy decomposition analysis also confirms the diverse and comprehensive nature of the intermolecular binding motifs present in NENCI-2021, which now includes a significant number of primarily induction-bound dimers (e.g., cation–π complexes). NENCI-2021 thus spans all regions of the SAPT ternary diagram, thereby warranting a new four-category classification scheme that includes complexes primarily bound by electrostatics (3499), induction (700), dispersion (1372), or mixtures thereof (2192). A critical error analysis performed on a representative set of intermolecular complexes in NENCI-2021 demonstrates that the E int values provided herein have an average error of ±0.1 kcal/mol, even for complexes with strongly repulsive E int values, and maximum errors of ±0.2–0.3 kcal/mol (i.e., ~±1.0 kJ/mol) for the most challenging cases. For these reasons, we expect that NENCI-2021 will play an important role in the testing, training, and development of next-generation classical and polarizable force fields, density functional theory approximations, wavefunction theory methods, and machine learning based intra- and inter-molecular potentials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Long-lived isomeric states and quasiparticle band structures in neutron-rich 162,164 Gd nuclei from β decay

Neutron-rich nuclei 162,164 Eu were produced by bombarding a proton beam on a 238 U target at the Holifield Radioactive Ion Beam Facility at Oak Ridge National Laboratory and mass separating the 162,164 Eu products. New level schemes and new γ-ray transitions of the daughters 162,164 Gd were identified from β-decay spectroscopy studies. Additionally, half-lives of the 162,164 Eu were remeasured to clarify the previous ambiguous results. Two quasiparticle band structures were built and compared with neighboring nuclei. The β and γ bands were extended in 162 Gd and a γ band was extended in 164 Gd. Half-lives of the isomeric states at (6 - ) 1449 keV in 162 Gd and (4 - ) 1096 keV in 164 Gd were measured to be 99(3) μs and 0.56(3) μs, respectively. Projected shell model calculations were performed and found to be in good agreement with all of the experimental data.

150 ≤ A ≤ 189↗
DOE OSTI2025

Nonequilibrium effects in high-gain inertial confinement fusion

Recent experimental demonstrations of ignition and target gain in inertial confinement fusion (ICF) have stimulated interest in exploring the fundamental physics of violent deuterium-tritium (DT) burn in high-gain ICF targets. A significant DT-burn fraction is a necessary condition for high energy gain and large neutron yields (>100MJ). Using classical molecular-dynamics (MD) simulations and a hybrid fluid-kinetic model, we examine how a large fraction of low-energy 𝛼 particles can kick D and T ions out of equilibrium in high-gain ICF targets. The MD results suggest that (1) temperatures of 𝑇 𝐷 and 𝑇 𝑇 can differ by as much as ∼20% of their mean temperature and (2) the deviation of the DT energy distribution from the Maxwell-Boltzmann function can exceed ∼30%. Some of these MD observations, such as the preferential heating of D ions by low-energy 𝛼 particles and the temperature separation, can be explained by a proposed hybrid fluid-kinetic model. Furthermore, the implication of such nonequilibrium effects on the DT reactivity is also discussed.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

Title Coherent X-ray Studies of Surface Growth and Patterning Processes

X-ray Photon Correlation Spectroscopy (XPCS) is being developed as a tool to study nanoscale dynamics of fluctuations during thin film growth and surface patterning. XPCS examines the evolution of the X-ray scattering speckle pattern in reciprocal space to reveal dynamics information not accessible through any other means. Unlike low-coherence conventional X-ray scattering, which incoherently averages over different regions of a sample, coherent X-ray scattering is sensitive to the detailed structure of a given sample at that moment in time. In thin film growth processes, heterodyning, which occurs due to coherent mixing of two scattered signals, can be used to investigate the relationship between surface growth velocity and defect propagation. And, for polycrystalline thin film growth, the spatial coherence of the X-ray beam can substitute for the missing spatial coherence of the growth process to track layered growth in detail, even in a growth regime in which there are no conventional growth oscillations of the X-ray intensity. This has opened the door for detailed dynamics studies of individual atomic layers during real-world growth and patterning, not just in perfect single-crystal growth cases, which greatly expands the applicability of in-situ X-ray scattering methods. Step-flow dynamics in mounded polycrystalline growth has been studied separately for two thin film organic semiconductors deposited by thermal deposition in a vacuum environment, C60 and diindenoperylene (DIP). Highly oriented polycrystalline thin films are readily obtained in both systems, where mounds are composed of crystalline monolayer-height steps and terraces in a so-called wedding cake morphology. The formation of mounds is understood to be due to significant Ehrlich-Schwoebel step edge barriers that inhibit molecules from hopping down from one layer to the one below. The mounds exhibit local step flow, which can be monitored using coherent X-ray scattering. This is made possible due to heterodyning between scattering from the average mounds and the moving steps, which becomes visible in XPCS analysis. The effect of desorption, i.e. re-evaporation of deposited molecules is found to be important for understanding these processes. The impact of this work is to enable testing of models of step dynamics, the shape of mounds, and merging of mounds to form continuous thin films. Highly ordered polycrystalline thin films deposited on inexpensive substrates have applications in thin film solar cells and other organic electronic devices. In a separate set of experiments, speckle analysis during self-organized ion beam nanopatterning reveals memory stretching back to the beginning of patterning in the early stages and enables measurement of the velocity of self-organized patterns across surfaces providing the possibility of stringent new tests of the theory of pattern formation and motion.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Inverse Compton Cooling in the Coronae of Simulated Black Hole Accretion Flows

Here we present a formulation for a local cooling function to be employed in the diffuse, hot corona region of 3D GRMHD simulations of accreting black holes. This new cooling function calculates the cooling rate due to inverse Compton scattering by considering the relevant microphysics in each cell in the corona and approximating the radiation energy density and Compton temperature thereby integrating over the thermal seed photon flux from the disk surface. The method either assumes the ion and electron temperatures are equal (1T) or calculates them separately (2T) using an instantaneous equilibrium approach predicated on the actual relevant rate equations (Coulomb and Compton). The method is shown to be consistent with a more detailed ray-tracing calculation where the bulk of the cooling occurs, but is substantially less costly to perform. As an example, we apply these methods to a harm3d simulation of a 10M⊙, non-spinning black hole, accreting at nominally 1% the Eddington value. This new approach leads to radiative efficiency values sime65% above Novikov–Thorne, with a larger fraction of total cooling in the corona as compared to simulations performed using the original target-temperature cooling function. Time-averaged post-processing reveals that the continuum spectral observations predicted from these simulations are qualitatively similar to actual X-ray binary data, especially so for the 1T approach, which yields a harder power-law component (Γ = 2.25) compared to the 2T version (Γ = 2.53).

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2021

Al 2 O 3 /TiO 2 coated separators: Roll-to-roll processing and implications for improved battery safety and performance

Heat generation is one of the major concerns with lithium-ion batteries (LIB) while charging them at higher currents, which could inadvertently impact the rate performance and reduce the safety of the cell. Polymer separator is one of the least thermal conductive components of a LIB. In addition, commercial separators for LIB are made from polyolefin membranes that tend to shrink and curl at higher temperatures due to their lower melting temperature (~130 °C). Developing separators with improved thermal stability and higher electrolyte uptake is essential for enhancing the safety as well as the performance of the LIB. In this work, a thin layer of ceramic coatings (Al 2 O 3 and TiO 2 ) is applied on propylene (PP) membrane to improve the thermal stability and electrolyte affinity without compromising the rate performance. A slurry with 100% Al 2 O 3 coated on the polypropylene separator exhibited the best improvement in thermal stability ( shrinkage of 0.6% vs 6.0% for uncoated membrane) and excellent rate performance with 92% capacity retention at 2C. The Al 2 O 3 coated separator demonstrated excellent electrolyte wettability compared to the uncoated membrane. The cross-plane thermal conductivity of the ceramic coated separators is analyzed to understand their heat transfer behavior. The thermal conductivity of the separator is improved by ~3.2 times with the Al 2 O 3 coating.

25 ENERGY STORAGE↗
DOE OSTI2025

Investigating event-shape methods in the search for the chiral magnetic effect in relativistic heavy ion collisions

The chiral magnetic effect (CME) is a phenomenon in which electric charge is separated by a strong magnetic field from local domains of chirality imbalance and parity violation in quantum chromodynamics. The CME-sensitive observable, the charge-dependent three-point azimuthal correlator Δ⁢𝛾 , is contaminated by a major physics background proportional to the particle's elliptic flow anisotropy 𝑣 2 . Event-shape engineering (ESE) binning events in dynamical fluctuations of 𝑣 2 and event-shape selection (ESS) binning events in statistical fluctuations of 𝑣 2 are two methods to search for the CME by projecting Δ⁢𝛾 to the measured anisotropy 𝑣 2 = 0 intercept. Here, we conduct a systematic study of these two methods using physics models as well as toy model simulations. It is observed that the ESE method fulfills the general premise of measuring the CME but is statistically hungry. It is found that the intercept from the ESS method depends on the details of the event content, such as the mixtures of background-contributing sources, because of statistical fluctuations of intertwining variables used in the method, and is thus not practically useful to measure the CME.

Relativistic heavy-ion collisions↗
DOE OSTI2025

Interfacial electroneutrality controls transport of asymmetric salts through charge-patterned mosaic membranes

Membranes that selectively enhance target solute permeation while rejecting competing species are essential for precision separations. This study introduces charge-patterned mosaic membranes (CMMs) that selectively transport divalent asymmetric salts by leveraging a net-neutral membrane–solution interface. This mechanism, dictated by the charge ratio of positive and negative domains on the membrane surface and the balance of cations and anions in the salt, is supported by analytical, numerical, and experimental results. Analytical solutions identified cationic domain coverages (f + ) of 33%, 50%, and 66% as optimal for the selective transport of +2:−1 salts, +1:−1 salts, and +1:−2 salts, respectively, under conditions where the pattern size (L) is significantly larger than the Debye length. Numerical simulations and experiments using CMMs with alternating charged-stripes inkjet-printed onto nanostructure copolymer substrates confirmed these findings. By varying stripe widths to control f + , pressure-driven filtration experiments demonstrated selective enrichment of MgCl 2 and K 2 SO 4 at the predicted f + values, with deviations from these values leading to salt rejection. These results highlight the pivotal role of a net-neutral interface in enabling asymmetric salt enrichment. This study positions CMMs as a versatile platform for tuning ion selectivity, addressing challenges in resource recovery, water treatment, and precision separations.

additive manufacturing↗
DOE OSTI2024

Elucidating the Gas-Phase Behavior of Nitazene Analog Protomers Using Structures for Lossless Ion Manipulations Ion Mobility-Orbitrap Mass Spectrometry

2-benzylbenzimidazoles, or “nitazenes”, are a class of novel synthetic opioids (NSOs) that are increasingly being detected alongside fentanyl analogs and other opioids in drug overdose cases. Nitazenes can be 20x more potent than fentanyl but are not routinely tested for during postmortem or clinical toxicology drug screens; thus, their prevalence in drug overdose cases may be under-reported. Traditional analytical workflows utilizing liquid chromatography-tandem mass spectrometry (LC-MS/MS) often require additional confirmation with authentic reference standards to identify a novel nitazene. However, additional analytical measurements with ion mobility spectrometry (IMS) may provide a path towards reference-free identification, which would greatly accelerate NSO identification rates in toxicology labs. Presented here are the first IMS and collision cross section (CCS) measurements on a set of fourteen nitazene analogs using a Structures for Lossless Ion Manipulations (SLIM)-Orbitrap MS. All nitazenes exhibited two high intensity baseline-separated IMS distributions, which fentanyls and other drug and drug-like compounds also exhibit. Incorporating water into the electrospray ionization (ESI) solution caused the intensities of the higher mobility IMS distributions to increase the intensities of the lower mobility IMS distributions to decrease. Nitazenes lacking a nitro group at the R1 position exhibited the greatest shifts in signal intensities due to water. Furthermore, IMS-MS/MS experiments showed that the higher mobility IMS distributions of all nitazenes produced fragment ions with m/z 72, 100, and other low intensity fragments while the lower mobility IMS distributions only produced fragment ions with m/z 72 and 100. The IMS, solvent, and fragmentation studies provide experimental evidence that nitazenes potentially exhibit three gas-phase protomers. In conclusion, the cyclic IMS capability of SLIM was also employed to partially resolve four sets of structurally similar nitazene isomers (e.g., protonitazene/isotonitazene, butonitazene/isobutonitazene/secbutonitazene), showcasing the potential of using high-resolution IMS separations in MS-based workflows for reference-free identification of emerging nitazenes and other NSOs.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2022

Selectivity of Electrochemical Ion Insertion into Manganese Dioxide Polymorphs

The ion insertion redox chemistry of manganese dioxide has diverse applications in energy storage, catalysis, and chemical separations. Unique properties derive from the assembly of Mn–O octahedra into polymorphic structures that can host protons and nonprotonic cations in interstitial sites. Despite many reports on individual ion-polymorph couples, much less is known about the selectivity of electrochemical ion insertion in MnO 2 . In this work, we use density functional theory to holistically compare the electrochemistry of A x MnO 2 (where A = H + , Li + , Na + , K + , Mg 2+ , Ca 2+ , Zn 2+ , Al 3+ ) in aqueous and nonaqueous electrolytes. We develop an efficient computational scheme demonstrating that Hubbard-U correction has a greater impact on calculating accurate redox energetics than choice of exchange-correlation functional. Using PBE+U, we find that for nonprotonic cations, ion selectivity depends on the oxygen coordination environments inside a polymorph. When H + is present, however, the driving force to form hydroxyl bonds is usually stronger. In aqueous electrolytes, only three ion-polymorph pairs are thermodynamically stable within water’s voltage stability window (Na + and K + in α-MnO 2 , and Li + in λ-MnO 2 ), with all other ion insertion being metastable. We find Al 3+ may insert into the δ, R, and λ polymorphs across the full 2-electron redox of MnO 2 at high voltage; however, electrolytes for multivalent ions must be designed to impede the formation of insoluble precipitates and facilitate cation desolvation. We also show that small ions coinsert with water in α-MnO 2 to achieve greater coordination by oxygen, while solvation energies and kinetic effects dictate water coinsertion in δ-MnO 2 . Finally, taken together, these findings explain reports of mixed ion insertion mechanisms in aqueous electrolytes and highlight promising design strategies for safe, high energy density electrochemical energy storage, desalination batteries, and electrocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Holistic Microstructure Control Strategies in Photopolymerization‐Induced Phase Separation of Acrylate Systems

Open porous materials, known for their large surface area and interconnected structures, are essential in various applications, including batteries, ion exchange, catalysis, filtration, and electronic waste recycling. A critical aspect of the functionality of porous membranes is the precise control of pore size and morphology. Photopolymerization-induced phase separation (photo-PIPS) offers a convenient and versatile methods for creating porous structures. However, controlling the porous morphology remains challenging due to the complex interplay between thermodynamics, polymerization kinetics, and monomer structures, which makes it difficult to establish the relationship between processing conditions and resulting morphology in photo-PIPS. Herein, a physics-based phase-field model capable of generating and characterizing the microstructures of porous materials based on both average and localized features is developed. Using the phase-field simulations as test bed, the effects of polarity, light intensity, and curing temperature, as well as the previously unexplored roles of chain transfer agents and substrates, on the morphology of the resulting porous microstructure are investigated. Experiments are performed to verify the results predicted by the simulations. This work lays out a comprehensive guide for designing PIPS-derived porous microstructures and offers practical engineering strategies for tailoring microstructure-level topology and size of pores for application-specific needs.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Co-Assembly of Carbon Nanotube Porins into Biomimetic Peptoid Membranes

Robust and cost-effective membrane-based separations are essential to solving many global crises, such as the lack of clean water. Even though the current polymer-based membranes are widely used for separations, their performance and precision can be enhanced by using a biomimetic membrane architecture that consists of highly permeable and selective channels embedded in a universal membrane matrix. Researchers have shown that artificial water and ion channels, such as carbon nanotube porins (CNTPs), embedded in lipid membranes can deliver strong separation performance. However, their applications are limited by the relative fragility and low stability of the lipid matrix. In this work, we demonstrate that CNTPs can co-assemble into two-dimension (2D) peptoid membrane nanosheets, opening up a way to produce highly programmable synthetic membranes with superior crystallinity and robustness. A combination of molecular dynamics (MD) simulations, Raman spectroscopy, X-ray diffraction (XRD), and atomic force microscopy (AFM) measurements to verify the co-assembly of CNTP and peptoids are used and show that it does not disrupt peptoid monomer packing within the membrane. In conclusion, these results provide a new option for designing affordable artificial membranes and highly robust nanoporous solids.

36 MATERIALS SCIENCE↗