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1,678 records · Page 75

Super-resolution imaging reveals resistance to mass transfer in functionalized stationary phases

Chemical separations are costly in terms of energy, time, and money. Separation methods are optimized with inefficient trial-and-error approaches that lack insight into the molecular dynamics that lead to the success or failure of a separation and, hence, ways to improve the process. We perform super-resolution imaging of fluorescent analytes in five different commercial liquid chromatography materials. Unexpectedly, we observe that chemical functionalization can block more than 50% of the material’s porous interior, rendering it inaccessible to small-molecule analytes. Only in situ imaging unveils the inaccessibility when compared to the industry-accepted ex situ characterization methods. Selectively removing some of the functionalization with solvent restores pore access without substantially altering the single-molecule kinetics that underlie the separation and agree with bulk chromatography measurements. Our molecular results determine that commercial “fully porous” stationary phases are over-functionalized and provide an alternative avenue to characterize and direct separation material design from the bottom-up.

Science & Technology - Other Topics

Maximizing Free Energy Gain

Maximizing the amount of work harvested from an environment is important for a wide variety of biological and technological processes, from energy-harvesting processes such as photosynthesis to energy storage systems such as fuels and batteries. Here, we consider the maximization of free energy—and by extension, the maximum extractable work—that can be gained by a classical or quantum system that undergoes driving by its environment. We consider how the free energy gain depends on the initial state of the system while also accounting for the cost of preparing the system. We provide simple necessary and sufficient conditions for increasing the gain of free energy by varying the initial state. We also derive simple formulae that relate the free energy gained using the optimal initial state rather than another suboptimal initial state. Finally, we demonstrate that the problem of finding the optimal initial state may have two distinct regimes, one easy and one difficult, depending on the temperatures used for preparation and work extraction. We illustrate our results on a simple model of an information engine.

Physics

Software Validation Work With The ZPPR-15 Data

The analysis activities for fast reactors involve using many different pieces of software that are relied upon for their predictive capabilities. For this software to be considered reliable, documented proof that the predictions of the software are accurate is required. In this manuscript, the validation work that covers some of the Argonne software used in fast reactor design activities is discussed and displayed. This validation work includes neutron and gamma flux distributions, reaction rate distributions, and reactivity worth. In an ideal world, a reactor development program would have access to a comprehensive set of experimental facilities to help inform the design aspects of the reactor itself. While thermal-hydraulics experiments, and to a limited degree mechanical experiments, can be carried out today for validation needs, neutronics related experimental facilities are rather impractical because of the lack of experimental facilities. Given the desired time table for construction of new reactors, the reconstitution or creation of new neutronic experimental facilities is untenable and thus those reactor development programs must rely upon any available experimental measurements that are qualitatively similar to the design. While a methodology has been proposed to assess the similarity between the past experimental measurements and the reactor itself, that aspect is beyond the scope of this manuscript. In this manuscript, the focus is entirely placed on the analysis results for a series of experiments carried out at the ZPPR facility in Idaho in the mid-1980s. In this regard, this manuscript only shows the validation of the stated neutronics software for specific loadings of the ZPPR reactor. Because of the fuel form, its proposed enrichment, and the material content of the reactor core, the ZPPR-15 experiments were identified as potential validation data for the reactor. The ZPPR-15 experiments were intended as mockups of a 330 MWe Integral Fast Reactor program which was a follow on program to the Clinch River Breeder Reactor. In the ZPPR-15 series of experiments, measurements of the neutron spectrum, control rod worth, sodium void worth, foil reaction rate distributions, Doppler worth of heated samples, gamma dose, and axial expansion worth were all carried out and published. In many cases, these reactivity coefficients are good candidates to validate the reactivity coefficient calculation scheme used by the analysis software and included in the safety analysis activities of fast reactor development projects today. This manuscript discusses the modeling methodology and accuracy of the calculated experimental results using the LANL software MCNP and the ANL software package ARC (Argonne Reactor Codes). As will be shown, for many of the experimental measurements, the two software packages are found to be good predictive analysis tools for those experiments. In other cases, problems with the analysis methodology or underlying cross section data are exposed which indicates where predictive analysis is not as reliable. Finally, in some of the measurements the conclusion is reached that the experimental measurement cannot be reproduced with the analysis software as it is simply too difficult.

Aliberti, Gerardo

Effect of Preparation Conditions of Fe@SiO2 Catalyst on Its Structure Using High-Pressure Activity Studies in a 3D-Printed SS Microreactor

Fischer–Tropsch synthesis (FTS) in a 3D-printed stainless steel (SS) microchannel microreactor was investigated using Fe@SiO2 catalysts. The catalysts were prepared by two different techniques: one pot (OP) and autoclave (AC). The mesoporous structure of the two catalysts, Fe@SiO2 (OP) and Fe@SiO2 (AC), ensured a large contact area between the reactants and the catalyst. They were characterized by N2 physisorption, H2 temperature-programmed reduction (H2-TPR), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), X-ray photoelectron microscopy (XPS), and thermogravimetric analysis–differential scanning calorimetry (TGA-DSC) techniques. The AC catalyst had a clear core–shell structure and showed a much greater surface area than that prepared by the OP method. The activities of the catalysts in terms of FTS were studied in the 200–350 °C temperature range at 20-bar pressure with a H2/CO molar ratio of 2:1. The Fe@SiO2 (AC) catalyst showed higher selectivity and higher CO conversion to olefins than Fe@SiO2 (OP). Stability studies of both catalysts were carried out for 30 h at 320 °C at 20 bar with a feed gas molar ratio of 2:1. The Fe@SiO2 (AC) catalyst showed higher stability and yielded consistent CO conversion compared to the Fe@SiO2 (OP) catalyst.

Biochemistry & Molecular Biology

Intrinsic even-odd thickness-driven anomalous Hall effect in epitaxial MnBi2⁢Te4 thin films

We demonstrate precise control of magnetism in MnBi2⁢Te4 thin films through careful synthesis by molecular beam epitaxy, achieving minimal defects and accurate layer thickness control. By optimizing Mn-Bi-Te ratios and growth temperatures, we minimize detrimental self-doping effects and accurately target integer-layer films. X-ray diffraction and reflectivity provide quantitative measures of film quality and thickness. When these macroscale probes of structure and thickness are integrated with magnetotransport measurements, a striking even-odd layer dependence of the anomalous Hall effect is revealed. Odd-layer films exhibit a large hysteresis up to the Néel temperature (∼25K), consistent with noncompensated antiferromagnetism, while even-layer films show minimal response, as expected for an antiferromagnet. The sign of the anomalous Hall effect exhibits a sign reversal for intrinsic magnetism versus magnetism associated with defects. This work identifies critical factors for inducing pure, noncompensated ferromagnetism and reveals the characteristics of the intrinsic anomalous Hall effect in MnBi2⁢Te4, which together is a step toward realizing the zero-field quantum anomalous Hall effect in topological materials.

Mallick, Deb [ORNL] (ORCID:000900005806411X)

Modern insights into the mechanisms of neptunium oxalate decomposition

Neptunium oxalate (Np(C 2 O 4 ) 2 ·6H 2 O) is a historically relevant solid phase used in nuclear processing as a precursor for neptunium dioxide (NpO 2 ). Although Np oxalate has been synthesized and used for NpO 2 production for decades, the thermal decomposition mechanism of this phase remains poorly understood and has not been evaluated in over 30 years. Conflicting reports in historical literature suggest either a direct conversion from anhydrous oxalate to NpO 2 or a decomposition that includes the formation of Np carbonate or oxidized Np intermediate phases. In this work, we reexamine the decomposition pathway of Np(C 2 O 4 ) 2 ·6H 2 O using thermal analysis coupled with evolved gas analysis and temperature-dependent Raman spectroscopy to elucidate decomposition mechanisms and intermediate phases using modern analytical techniques. Thermal analysis revealed a three-stage decomposition process, including dehydration below 200 °C, oxalate breakdown between 170 and 370 °C, and NpO 2 formation by 500 °C. However, an unidentified plateau in the thermal data was observed during measurements. Raman spectroscopy confirmed the stages of decomposition, and in the analysis of potential intermediate phases, no carbonate phases or Np 2 O 5 were identified. Raman data suggest that residual oxalate or nonstoichiometric oxide are present during decomposition before pure NpO 2 is formed. These findings clarify aspects of the Np oxalate decomposition mechanism and address longstanding discrepancies in the literature, with a specific focus on Np-specific materials chemistry.

Lawson, Kathryn M. [Oak Ridge National Laboratory

Wettability of Two-Dimensional Carbon Allotropes from Molecular Simulations

Force-field Monte Carlo and Molecular Dynamics simulations are used to compare wetting behaviors of model carbon sheets mimicking neat graphene, its saturated derivative, graphane, and related planar allotropes penta-graphene, γ-graphyne, and ψ-graphene in contact with aqueous droplets or an aqueous film confined between parallel carbon sheets. Atomistic and area-integrated surface/water potentials are found to be essentially equivalent in capturing moderate differences between the wetting free energies of tested substrates. Despite notable differences in mechanical and electric properties of distinct allotropes, the predicted allotrope/water contact angles span a narrow window of weakly hydrophilic values. Contact angles in the range of 80 ± 10° indicate modest hydration repulsion incapable of competing with van der Waals attraction between carbon particles. Poor dispersibility in neat water is hence a common feature of studied materials.

Biochemistry & Molecular Biology

High-Density Capacitive Energy Storage in Low-Dielectric-Constant Polymer PMMA/2D Mica Nanofillers Heterostructure Composite

The ubiquitous, rising demand for energy storage devices with ultra-high storage capacity and efficiency has drawn tremendous research interest in developing energy storage devices. Dielectric polymers are one of the most suitable materials used to fabricate electrostatic capacitive energy storage devices with thin-film geometry with high power density. In this work, we studied the dielectric properties, electric polarization, and energy density of PMMA/2D Mica nanocomposite capacitors where stratified 2D nanofillers are interfaced between the multiple layers of PMMA thin films using two heterostructure designs of the capacitors, PMMA/2D Mica/PMMA (PMP) and PMMA/2D Mica/PMMA/2D Mica/PMMA (PMPMP). The incorporation of a 2D Mica nanofiller in the low-dielectric-constant PMMA leads to an enhancement in the dielectric constant, with ∆ε ~ 15% and 53% for PMP and PMPMP heterostructures at room temperature. Additionally, a significant improvement in discharged energy density was measured for the PMPMP capacitor (Ud ~ 38 J/cm3 at 825 MV/m) compared to the pristine PMMA (Ud ~ 9.5 J/cm3 at 522 MV/m) and PMP capacitors (Ud ~ 19 J/cm3 at 740 MV/m). This excellent capacitive and energy storage performance of the PMMA/2D Mica heterostructure nanocomposite may inform the fabrication of thin-film, high-density energy storage capacitor devices for potential applications in various platforms.

Biochemistry & Molecular Biology

Manipulating Na/TM Ratio‐Driven Structural Heterogeneity of O3‐NaNi 1/3 Fe 1/3 Mn 1/3 O 2 Cathode for High‐Voltage Sodium‐Ion Batteries

The stability of O3-type NaNi 1/3 Fe 1/3 Mn 1/3 O 2 under high-voltage cycling is dictated by how synthesis encodes lattice strain and redox heterogeneity. Here, in this study, the role of Na:TM stoichiometry is systematically resolved by tuning the NaOH:precursor ratio during solid-state synthesis. The stoichiometric condition (Na:TM = 1.00) yields minimized microstrain, enabling uniform O3–P3 phase evolution and homogeneous multi-metal redox with preserved octahedral symmetry. In contrast, Na-excess compositions inherit disordered intermediates and heterogeneous distortion fields that trigger abrupt multiphase transitions and promote localized charge redistribution. In situ XRD captures the divergence in phase-transition pathways, TXM resolves particle-level redox heterogeneity, and XANES corroborates a stronger and more reversible Fe redox contribution at stoichiometry, shifting to diminished Fe participation and spatially inhomogeneous redox at higher Na content. These results establish Na:TM stoichiometry as a critical synthesis parameter controlling both structural coherence and redox stability. Electrochemically, the stoichiometric composition exhibits smooth voltage profiles with minimal polarization growth and retains nearly 80% of its initial capacity after 100 cycles even at an extended 4.2 V cutoff, whereas Na-excess compositions show significantly reduced initial coulombic efficiency and rapid voltage fade. Precise stoichiometric tuning provides a scalable route to defect-suppressed O3 frameworks, enabling structurally resilient, high-voltage sodium-layered cathodes.

36 MATERIALS SCIENCE

Observation of deuteron and antideuteron formation from resonance-decay nucleons

High-energy hadronic collisions generate environments characterized by temperatures above 100 MeV (refs.), about 100,000 times hotter than the centre of the Sun. At present, it is therefore unclear how light (anti)nuclei with mass number A of a few units, such as the deuteron, 3 He or 4 He, each bound by only a few MeV, can emerge from these collisions. Here, the ALICE Collaboration reports that deuteron–pion momentum correlations in proton–proton (pp) collisions provide model-independent evidence that about 90% of the observed (anti)deuterons are produced in nuclear reactions following the decay of short-lived resonances, such as the Δ(1232). These findings, obtained by the ALICE Collaboration at the Large Hadron Collider, resolve a gap in our understanding of nucleosynthesis in ultrarelativistic hadronic collisions. Apart from offering insights on how (anti)nuclei are formed in hadronic collisions, the results can be used in the modelling of the production of light and heavy nuclei in cosmic rays and dark-matter decays.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS

Strong gradient neoclassical transport in the plateau regime

Strong gradient regions in tokamaks such as the pedestal or internal transport barriers are regions of reduced turbulence where neoclassical transport can play a dominant role. In pedestals, gradient lengths comparable to the ion poloidal gyroradius have been measured. Standard neoclassical theory can miss important strong gradient effects in these regions because it assumes that the gradient length scales of density, temperature and potential are larger than the ion poloidal gyroradius. We extend plateau regime neoclassical theory into regions of gradients of the order of the ion poloidal gyroradius to capture strong gradient effects on transport processes in the pedestal and internal transport barriers. The fundamental idea behind our new framework is to keep a scale separation between the orbit widths and the gradient length scales by performing a large aspect ratio expansion. In the plateau regime, strong gradients cause poloidal variation that is in–out as well as up–down asymmetric. We study two different test cases assuming either radial force balance or the absence of turbulence and show that strong gradient effects can enhance or reduce standard neoclassical theory predictions in the plateau regime in strong gradient regions.

fusion plasma

Morgana Overview – NCERC Support for Dynamic Subcritical Experiments

The LANL Subcritical Experiments Program (SCE) recently executed the Morgana Subcritical Experiment at the NNSS. This was the first subcritical experiment executed by LANL for several years (since 2021). It was also notably the first that required SCE personnel to have FMH qualifications for a portion of the work conducted under nuclear criticality safety limits.

45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEF

Self-generated electrokinetic flows from active-charged boundary patterns

We develop a hydrodynamic description of self-generated electrolyte flow in capillaries whose bounding walls feature nonuniform distributions of charge nonuniform active ionic fluxes. The hydrodynamic velocity arising in such a system has components that are forbidden by symmetry in the absence of charge and fluxes. However, when these two boundary mechanisms are simultaneously present, they can lead to a symmetry broken state where steady flows with both unidirectional and circulatory components emerge. We show that these flow states arise when modulated boundary patterns of charge and fluxes are offset by a flux-charge phase difference, which is associated with the separation between sites of their peak densities on the wall. Mismatch in diffusivity of cationic and anionic species can modify the flow states and becomes an enhancing factor when fluxes of both ion species are being produced together at the same site. We demonstrate that this mechanism can be realized with a microfluidic generator that is powered by enzyme-coated patches that catalyze reactants in the solution to produce fluxes of ions. The local ionic elevation or depletion, which disrupts a nonuniform double layer, promotes self-induced gradients yielding persistent body forces to generate bulk fluid motion. Our work quantifies a boundary-driven mechanism behind self-sustained electrolyte flow in confined environments that exists without any external bulk-imposed fields or gradients. It provides a theoretical framework for understanding the combined effect of active and charged boundaries that are relevant in biological or soft matter systems, and can be utilized in electrofluidic and iontronic applications.

active matter

Derivation of low-energy Hamiltonians for heavy-fermion materials

Here, by utilizing a multiorbital periodic Anderson model with parameters obtained from ab initio band structure calculations, combined with degenerate perturbation theory, we derive effective Kondo-Heisenberg and spin Hamiltonians that capture the interaction among the effective magnetic moments. This derivation encompasses fluctuations via both nonmagnetic 4⁢𝑓 0 and magnetic 4⁢𝑓 2 virtual states, and its accuracy is confirmed through comparison with experimental data obtained from CeIn 3 . The significant agreement observed between experimental results and theoretical predictions underscores the potential of deriving minimal models from first-principles calculations for achieving a quantitative description of 4⁢𝑓 materials. Moreover, our microscopic derivation unveils the underlying origin of anisotropy in the exchange interaction between Kramers doublets, shedding light on the conditions under which this anisotropy may be weak compared to the isotropic contribution.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND

Selective solid-state isolation of NMR circuit elements using back-to-back field effect transistors

Nuclear Magnetic Resonance (NMR) electronics that employ selective solid-state isolation of circuit elements can include solid-state switches, such as back-to-back Field Effect Transistor (FET) pairs, and isolated gate drive electronics adapted to operate the solid-state switches in order to selectively decouple induction coils from receive electronics. The solid-state switches can be placed in series to achieve higher standoff voltages, and can be configured for low on resistance and short switching times. The gate drive electronics can include electrical isolation components adapted to enhance standoff voltages and reduce electrical noise at the selectively isolated receive electronics.

Walsh, David O.

Theory of the thermionic current beyond the traditional space charge limit enabled by trapped ions in the virtual cathode

We show that trapped ions in virtual cathode potential wells can raise the transmitted current of emitted electrons into a plasma much closer to the full emission than is predicted by cathode sheath theories without trapped ions. The transmitted current is controlled by the well barrier voltage, which must adjust to balance the creation of low-energy ions within the well, and their loss. Our model considers the case of a plasma-facing cathode where trapped ions are created passively via charge-exchange collisions and lost passively via thermal leakage over the well. We quantify these rates and estimate the current in terms of system parameters for thermionic emission into a plasma with several cathode geometries. A general prediction is that the current as a function of emitted flux does not saturate at the traditional space charge limit (the onset of a well) but can reach far higher values until the trapped ion balance breaks down, causing instability. The maximum stable current depends on parameters but in principle can be arbitrarily high if active techniques are used to manipulate the trapped ion balance. We conclude that major improvements in plasma technologies with hot cathodes might be achieved by optimizing the current enhancement enabled by trapped ions.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY

Pinning ångström-size solid ionic channels for rare-earth element separation

High-purity rare-earth elements are essential for modern technologies, yet current solvent extraction processes are energy-intensive and environmentally harmful because of inadequate selectivity and ligand toxicity. Although combining size exclusion and binding affinity can improve lanthanide separation, the role of long-range confinement remains underexplored. Here we report lanthanide separation in aqueous systems using extremely confined manganese oxide solid ionic channels with optimized layer spacing. Different lanthanides induce distinct solid-state phase transformations in manganese oxide, creating a strong driving force for separation. Two lanthanide groups, differing by ~1.4 Å in spacing, were identified and confirmed to be stable by density functional theory. The narrower confinement of heavier Group II lanthanides improves cross-group separation by increasing the dehydration barrier for lighter Group I lanthanides without inducing strong binding. Here, we further developed a strategy to pin the confinement dimensions and enhance same-group separation, increasing enrichment factors for La–Nd and La–Pr pairs from 1.6 ± 0.1 and 1.5 ± 0.1 to 5.4 ± 0.1 and 4.2 ± 0.1, respectively.

Chemical engineering

Multi-modal dynamic radiography using short-pulse laser-generated probe beams

Radiography is an important tool for the interrogation of dynamic experiments in the fields of dynamic properties of materials, and in condensed matter, high explosive, and high-energy-density physics. Multi-modal radiography advances the hypothesis that combining the information delivered by multiple radiographic modalities can lead to more constrained (improved) “reconstruction” of the scene than can be obtained from a single probe. We identify four modalities: multi-probe, time sequence, multi-view, and multi-messenger. Multi-probe radiography is a promising candidate for a next-generation dynamic radiographic facility. High-energy X-rays are the most frequently used probe for dynamic radiography, although recent developments show the utility of proton (pRad), electron (eRad), and neutron probe beams. Because each probing species interacts with material in the radiographic scene through quantitatively different mechanisms, each returns independent information about the scene, which can add extra constraints to the reconstruction process. How to conduct detailed, quantitative “co-analysis” of multiple data streams remains an area of active research. Multi-beam, short-pulse, laser-generated probes offer sufficient dose, an appropriate spectrum, and appropriate spatio-temporal resolution to produce high-quality dynamic radiographs. This paper reports on technology development to advance the state of the art of multi-modal/multi-probe radiography and the pursuit of both deterministic and inferential (AI/ML assisted) co-analysis methodologies to produce more constrained reconstructions from multi-modal data.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY