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At least 325 records · Page 18

Topological response of the anomalous Hall effect in MnBi 2 Te 4 due to magnetic canting

Three-dimensional (3D) compensated MnBi 2 Te 4 is antiferromagnetic, but undergoes a spin-flop transition at intermediate fields, resulting in a canted phase before saturation. In this work, we experimentally show that the anomalous Hall effect (AHE) in MnBi 2 Te 4 originates from a topological response that is sensitive to the perpendicular magnetic moment and to its canting angle. Synthesis by molecular beam epitaxy allows us to obtain a large-area quasi-3D 24-layer MnBi 2 Te 4 with near-perfect compensation that hosts the phase diagram observed in bulk which we utilize to probe the AHE. This AHE is seen to exhibit an antiferromagnetic response at low magnetic fields, and a clear evolution at intermediate fields through surface and bulk spin-flop transitions into saturation. Throughout this evolution, the AHE is super-linear versus magnetization rather than the expected linear relationship. We reveal that this discrepancy is related to the canting angle, consistent with the symmetry of the crystal. Our findings bring to light a topological anomalous Hall response that can be found in non-collinear ferromagnetic, and antiferromagnetic phases.

36 MATERIALS SCIENCE↗

Observation of Seeded Mn K β Stimulated X-Ray Emission Using Two-Color X-Ray Free-Electron Laser Pulses

Kβ x-ray emission spectroscopy is a powerful probe for electronic structure analysis of 3d transition metal systems and their ultrafast dynamics. Selectively enhancing specific spectral regions would increase this sensitivity and provide fundamentally new insights. Recently we reported the observation and analysis of Kα amplified spontaneous x-ray emission from Mn solutions using an x-ray free-electron laser to create the 1s core-hole population inversion [Kroll et al., Phys. Rev. Lett. 120, 133203 (2018)]. To apply this new approach to the chemically more sensitive but much weaker Kβ x-ray emission lines requires a mechanism to outcompete the dominant amplification of the Kα emission. Here we report the observation of seeded amplified Kβ x-ray emission from a NaMnO 4 solution using two colors of x-ray free-electron laser pulses, one to create the 1s core-hole population inversion and the other to seed the amplified Kβ emission. Comparing the observed seeded amplified Kβ emission signal with that from conventional Kβ emission into the same solid angle, we obtain a signal enhancement of more than 10 5 . Finally, our findings are the first important step of enhancing and controlling the emission of selected final states of the Kβ spectrum with applications in chemical and materials science.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Optical Control of Adaptive Nanoscale Domain Networks

Adaptive networks can sense and adjust to dynamic environments to optimize their performance. Understanding their nanoscale responses to external stimuli is essential for applications in nanodevices and neuromorphic computing. However, it is challenging to image such responses on the nanoscale with crystallographic sensitivity. Here, the evolution of nanodomain networks in (PbTiO 3 ) n /(SrTiO 3 ) n superlattices (SLs) is directly visualized in real space as the system adapts to ultrafast repetitive optical excitations that emulate controlled neural inputs. The adaptive response allows the system to explore a wealth of metastable states that are previously inaccessible. Their reconfiguration and competition are quantitatively measured by scanning x-ray nanodiffraction as a function of the number of applied pulses, in which crystallographic characteristics are quantitatively assessed by assorted diffraction patterns using unsupervised machine-learning methods. The corresponding domain boundaries and their connectivity are drastically altered by light, holding promise for light-programable nanocircuits in analogy to neuroplasticity. Phase-field simulations elucidate that the reconfiguration of the domain networks is a result of the interplay between photocarriers and transient lattice temperature. The demonstrated optical control scheme and the uncovered nanoscopic insights open opportunities for the remote control of adaptive nanoscale domain networks.

36 MATERIALS SCIENCE↗

Assessment of Existing Transportation Packages for Use with HALEU

Commercial light water reactor operators and fuel vendors in the United States are pursuing changes to fuel that include increased 235 U enrichment. Economic studies generally anticipate maximum near-term fuel assembly designs with up to 8 wt.% 235 U. Many next-generation nuclear reactor designs require high-assay low-enriched uranium (HALEU) (19.75 wt.% > 235 U > 5 wt.%) fuel. One necessary element for the commercial-scale use of HALEU is the ability to safely transport large quantities of enriched fuel material in multiple forms. However, there is uncertainty as to whether subcriticality requirements can be satisfied with existing package designs and whether existing critical benchmark experiment data are sufficient to support criticality safety code validation for HALEU transportation applications. This study assesses the potential to use currently licensed transportation packages for the transportation of increased enrichment unirradiated U fuel forms. The assessment uses selected package designs that represent the five categories of fuel form-boiling water reactor pins and assemblies, pressurized water reactor pins and assemblies, UF 6 , U-metal and tristructural isotropic (TRISO) particles, and UO 2 pellets or powder-and focuses on demonstrating subcriticality and identifying benchmark critical experiments appropriate for use in criticality computer code validation. Key quantities of interest that relate to subcriticality are limiting conditions (e.g., optimum moderation), package or package array k eff , package capacity, and package transportation array size. The SCALE TSUNAMI-3D and TSUNAMI Indices and Parameters codes are used for sensitivity and uncertainty calculations and for identification of candidate critical benchmark experiments for code validation. The primary metric for identifying candidate benchmarks is the similarity coefficient, c k . For each fuel form category, a representative package is evaluated. Results provided for each package evaluation include enrichment and packaging limits (e.g., maximum transportation array size as a function of enrichment) and benchmark critical experiment similarity coefficients. Results indicate that there are viable means for increasing enrichments into the HALEU range across the spectrum of fuel forms with differing increase amounts available for different packages. Sources of subcriticality margin to offset increased enrichment reactivity include reduced transportation array size, reduced fissile mass, burnable absorber credit, and safety analysis margin harvesting. For all packages except the DN-30, numerous critical benchmark experiment candidates for validation were identified.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Structural Phase Separation and Enhanced Superconductivity in La 1.875 Ba 0.125 CuO 4 Under Uniaxial Strain

Strain engineering has attracted significant attention in recent years due to its capability in tuning lattice and electronic structures of quantum materials. Using moderate uniaxial compressive strain, structural phase separation is induced in the low-temperature phase of x = 1/8 La 2-x Ba x CuO 4 (LBCO) single crystals. These structures are low temperature tetragonal (LTT), low temperature less orthorhombic (LTLO), and a plastically deformed nano-domain structure (PDNS), comprised of few-nanometer-sized orthorhombic domains within an amorphous matrix. These three structures exhibit distinct superconducting behaviors. The volume fraction of the LTT structure is suppressed with increasing strain, while its superconducting transition temperature increases and broadens. The LTLO structure exhibits a sharp superconducting transition above 32 K, which increases up to ≈ 36 K at maximum strain. The PDNS phase exhibits a very broad superconducting transition and persists even after removing the strain. This study illustrates the sensitivity of superconductivity to the structure of the LBCO sample near its stripe instability.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Resolving local structural motifs across the phase evolution of zinc titanates with computational x-ray absorption spectroscopy

Resolving the local structure motifs that characterize phase evolution as a function of composition is a key challenge in structure characterization of complex materials. Here, in this study, we combine first-principles simulations and x-ray absorption near-edge structures (XANES) analysis to gain insights into the structure evolution revealed by measurements across a combinatorial zinc titanate thin film, which was grown with smoothly varying composition over a wide range of the Ti:Zn ratio. Specifically, we propose a cluster blind-signal-separation (cBSS) method for XANES spectral analysis based on a library of the structures and spectra of representative local motifs. In addition to motifs from zinc titanate crystals, two types of Ti-defect models constructed in this study are key to the understanding of the structure characteristics in the Zn-rich region. The cBSS method makes use of both spectral clustering of the simulated site-XANES spectra library and the BSS procedure to construct high-fidelity spectral basis functions from an experimental spectral sequence. The method provides a rigorous measure of the spectral sensitivity and basis completeness. The results of the XANES analysis are corroborated with other experimental modalities, including x-ray diffraction and spectroscopic ellipsometry, to validate the cBSS method. The calculated motif weights resulting from fitting the XANES spectra with the cBSS basis probe the atomic structure characteristics of both crystalline and amorphous phases as a function of the Ti/Zn composition. The insights of the local structure motif evolution are pivotal to the understanding of the nonmonotonic trend in the optical gap, which may lead to potential applications through tuning the optical properties of zinc titanate. The workflow of the XANES spectral analysis developed in this work can be generalized to construct the structure-property relationship in a broad material space.

36 MATERIALS SCIENCE↗

A Novel Dew Point Meter: Application to the Measurement of the Sulfuric Acid Dew Point for Combustion Flue Gas

Accurate knowledge of acid dew point is essential for industrial and applied combustion applications. Sulfur in the fuel or raw materials is converted to sulfur dioxide (SO2) during combustion, and a portion of the SO2 is oxidized to sulfur trioxide (SO3). The SO3 will react to form H2SO4 vapor when in the presence of water vapor. Even with just trace levels of H2SO4 vapor in the gas phase (1-10 ppm), the dew point can reach 100°C and higher. To avoid acid condensation and the resulting corrosion on heat recovery equipment, plant engineers must ensure that surface temperatures are above the acid dew point, but this decreases the efficiency of thermal energy recovery. Thus, there is a trade-off between minimizing equipment corrosion and maximizing thermal energy recovery, and the acid dew point is a key parameter for this optimization. Commercially available acid dew point meters use electric conductivity sensors. These sensors are known to greatly underestimate the dew point due to their low sensitivity. In addition, no validation testing has been reported for these units and they are often expensive. In this work, we analyze the theory of the sulfuric acid condensation and develop a novel dew point meter based on this analysis. The meter consists of a novel optical instrument that is designed to monitor the slightest appearance of condensation on a hydrophobic window surface as the surface temperature of the window is slowly decreased. In this way, an accurate measurement of the dew point is obtained under a wide range of concentrations. The basis of the instrument is that a collimated beam from a diode laser will generate forward scattered light when the beam encounters surface condensate, and a sophisticated array detector is used to sensitively monitor the onset of light scattering. The measurement procedures are established to rapidly find the acid dew point, while minimizing error. Further, to calibrate the dew point meter we developed a calibration system based on a liquid bubbler that can generate a stable gas flow with a known sulfuric acid dew point. Test results show that the dew point meter can accurately measure acid dew point over a wide range. For H2SO4 vapor concentrations as low as 6 ppm the acid dew point is measured with an error of only ~1°C. To demonstrate the versatility of this instrument, the dew point meter was adapted for use with a high-pressure flow cell to allow for measurements of the dew point of flue gas from pressurized oxy-fuel combustion in a 100 kWth pressurized reactor.

Cheng, Mao↗

PolyDODT: a macrocyclic elastomer with unusual properties

The effect of reaction conditions on the structure of poly(3,6-dioxa-1,8-octanedithiol) (polyDODT) made by Reversible Radical Recombination Polymerization (R3P) using triethylamine (TEA), H 2 O 2 and air was investigated. 800 MHz (1 and 2D) NMR was used to investigate the polymer structures. Sensitivity analysis provided direct evidence for high purity cyclic polyDODT up to M n ~ 100 000 g mol –1 . Here, comparative analysis by High Resolution Multidetector Size Exclusion Chromatography (SEC) using integrated data showed that the cycles had lower viscosity and were more compact (both for R g and R h ) than linear samples of similar molecular weight. However, differential data revealed unusual behavior. While lower molecular weight cyclic polymers eluted later and had lower intrinsic viscosity than their linear counterparts at the same molecular weight, at higher molecular weights the polymers showed strange behavior: both the diffusion coefficient measured by Quasielastic Light Scattering (QELS) and Mark–Houwink–Sakurada plots of intrinsic viscosity for linear and cyclic polyDODT were found to converge. R3P, an aqueous based “green” method is capable of producing polymers at the 10–100 g scale in the lab, which will allow more detailed studies of this new class of biodegradable elastomers so further experimentation can be performed to elucidate the reasons for the unusual findings.

36 MATERIALS SCIENCE↗

Assessment of CTF for Steady-state and Transient Post-CHF Conditions in Support of Time-at-Temperature Modeling Applications

The US nuclear industry is exploring options to improve operational economics and uprate the current fleet of light-water reactors by investigating transitioning to cladding performance–based safety criteria as opposed to the current limit, which requires complete avoidance of critical heat flux (CHF)/dryout. Past experience has shown that not all events leading to a dryout are severe enough to cause fuel performance degradation. Allowing temporary dryout of the fuel—that is, using a time-at-temperature (TaT) strategy—could allow for economic improvements via large power uprates and enhanced operational flexibility for current plants without compromising fuel integrity. To support this effort, the US Department of Energy is executing a comprehensive program that includes generating cladding material data under TaT conditions, developing new mechanistic models, and demonstrating modeling and simulation capabilities for transients of interest. This paper presents work performed to assess the CTF thermal-hydraulics subchannel code. CTF is a package used in the VERA core simulator, which will ultimately be used for TaT analysis. CTF will provide the thermal-hydraulic boundary conditions that will be needed for fuel performance analysis in the BISON code. Quantifying both the accuracy and uncertainty of post-CHF models will therefore be necessary. This paper outlines the strategy for the assessment of TaT and presents the results of using the steady-state and transient dryout experiments of the Boiling Fine-mesh Bundle Tests for CTF validation. The results show that the current model tends to overpredict steady-state critical power. This behavior translates to the transient tests, in which CTF is unable to capture transient dryout behavior. Some discussion of sensitivity analysis work being performed is provided to indicate which models must be further analyzed to properly model transient dryout and its uncertainty.

Salko Jr, Robert [ORNL] (ORCID:0000000253566679)↗

Mott and generalized Wigner crystal states in WSe 2 /WS 2 moiré superlattices

Moiré superlattices can be used to engineer strongly correlated electronic states in two-dimensional van der Waals heterostructures, as recently demonstrated in the correlated insulating and superconducting states observed in magic-angle twisted-bilayer graphene and ABC trilayer graphene/boron nitride moiré superlattices. Transition metal dichalcogenide moiré heterostructures provide another model system for the study of correlated quantum phenomena because of their strong light–matter interactions and large spin–orbit coupling. However, experimental observation of correlated insulating states in this system is challenging with traditional transport techniques. Here we report the optical detection of strongly correlated phases in semiconducting WSe 2 /WS 2 moiré superlattices. We use a sensitive optical detection technique and reveal a Mott insulator state at one hole per superlattice site and surprising insulating phases at 1/3 and 2/3 filling of the superlattice, which we assign to generalized Wigner crystallization on the underlying lattice. Furthermore, the spin–valley optical selection rules of transition metal dichalcogenide heterostructures allow us to optically create and investigate low-energy excited spin states in the Mott insulator. We measure a very long spin relaxation lifetime of many microseconds in the Mott insulating state, orders of magnitude longer than that of charge excitations. Here, our studies highlight the value of using moiré superlattices beyond graphene to explore correlated physics.

36 MATERIALS SCIENCE↗

Combining Chemistry, Material Science, Inspiration from nature, and Serendipity to Develop Stimuli-responsive Polymeric Materials

Neither of us can remember people talking about stimuli-responsive polymers when we were students. Even though this was still in the last century, it was almost 70 years after Staudinger's seminal paper "uber Polymerisation"![1] By the time we entered graduate school in the early 1990 s, the first papers on polymer light emitting diodes appeared, while research on electrically conducting, nonlinear optical, and other "functional" polymers was already in full swing. Looking back, there were some stimuli-responsive materials that were around at the time, but it took the better part of the last 30 years until the field had developed into what we think is one of the most vibrant areas of polymer science. Before the potential usefulness of this class of materials was recognized, researchers were focused on developing polymeric materials that would not respond to external influences, and in fact maintain (in particular) their mechanical properties in a wide range of environments. This has led to the development of many environmentally robust polymers, which have come to impact basically every aspect of our daily life. Ironically, this long-sought stability now comes back to haunt us in the form of plastic pollution, but this is another story. The concept of materials that adapt their properties in response to changing environmental conditions might appear like a complete reversal with respect to the original goals of creating stable materials. However, eventually a) it was recognized that materials that respond to a specific stimulus in a predictable and useful manner would significantly broaden the potential usefulness of polymers, and b) the field of polymer science had developed to the point where the rational design, preparation, and characterization of such materials became possible. The expression 'stimuli-responsive polymer' had been first used in the 1980's, however its use really only gained popularity a few decades later. In the early days, terms such as environmentally-sensitive or environmentally-responsive polymers, stimuli-reversible or stimuli-sensitive polymers, or polymers with phase transitions have also been used.

Rowan, Stuart J.↗

Self-Powered Circularly Polarized Light Detection Enabled by Chiral Two-Dimensional Perovskites with Mixed Chiral–Achiral Organic Cations

Direct detection of circularly polarized light (CPL) holds great promise for the development of various optical technologies. Chiral 2D organic–inorganic halide perovskites make it possible to fabricate CPL-sensitive photodetectors. However, selectively detecting left-handed circularly polarized (LCP) and right-handed circularly polarized (RCP) light remains a significant challenge. Herein, we demonstrate a greatly enhanced distinguishability of photodiode-type CPL photodetectors based on chiral 2D perovskites with mixed chiral aryl (R)-(+),(S)-(–)-α-methylbenzylammonium (R,S-MBA) and achiral alkyl n-butylammonium (nBA) cations. The (R,S-MBA 0.5 nBA 0.5 ) 2 PbI 4 perovskites exhibit a 10-fold increase in circular dichroism signals compared to (R,S-MBA) 2 PbI 4 perovskites. Here, the CPL photodetectors based on the mixed-cation perovskites exhibit self-powered capabilities with a specific detectivity of 2.45 × 10 12 Jones at a o V bias. Notably, these devices show high distinguishability (gres) factors of –0.58 and +0.54 based on (R,S-MBA 0.5 nBA 0.5 ) 2 PbI 4 perovskites, respectively, surpassing the performance of (R-MBA) 2 PbI 4 -based devices by over 3-fold and setting a record for CPL detectors based on chiral 2D n = 1 perovskites.

36 MATERIALS SCIENCE↗

Increasing the Stability of Deep Blue Phosphor‐Sensitized OLEDs Using the Polariton‐Enhanced Purcell Effect

Abstract The stability of efficient, deep blue organic light‐emitting diodes (OLEDs) remains a major challenge in the field of organic electronics. Poor device stability originates from the high probability for destructive non‐radiative triplet exciton annihilation events. Phosphor‐sensitized fluorescence (PSF) is proposed to achieve an efficient, deep blue color by energy transfer from phosphors to fluorophores. Recently, the polariton‐enhanced Purcell (PEP) effect is introduced to decrease the triplet radiative lifetime and density, resulting in an increase in blue phosphorescent OLED lifetime. Here, the PEP effect is introduced to enhance the stability of the PSF‐OLEDs. It is shown that the PEP effect increases all radiative decay rates of the phosphors and fluorophores, leading to a reduction in the triplet annihilation events. Using a Pt‐complex phosphor sensitizer and a so‐called multi‐resonance fluorescent emitter in a PEP cavity, a 3.1‐fold lifetime increase is observed at a current density ofJ= 10 mA cm −2 , reduced EQE roll‐off and deep blue color with Commission Internationale de l'Eclairage coordinates of (0.13, 0.09). The PEP effect maximally extends PSF‐OLED lifetimes in devices with the highest triplet‐to‐singlet energy transfer rates. Moreover, this work suggests that the benefits of PEPs apply to all triplet‐based OLEDs.

Chemistry↗

A comparative study on cubic and tetragonal Ce-ZrO 2 supported Rh catalysts for N 2 O decomposition

Zirconium oxide (ZrO 2 ) exhibits strong synergy with cerium oxide (CeO 2 ), acting as a structural and electronic promoter during catalytic redox reactions. As a result, Ce-ZrO 2 composite oxides are widely used as supports in various catalytic systems. In our previous work, we demonstrated that the incorporation of Zr 4+ into the CeO 2 lattice significantly enhanced Rh dispersion, improved redox ability, and stabilized surface Rh species, which collectively boosted the de-N 2 O activity of Rh/Ce-ZrO 2 catalysts. Building on these findings, the present study emphasizes that the crystallographic phase of Ce-ZrO 2 , governed by the Ce/Zr ratio, plays a decisive role in tuning the physicochemical environment of Rh active sites and thereby optimizing catalytic performance. In conclusion, tailoring the Ce/Zr ratio to favor the cubic fluorite structure emerges as a promising strategy for the rational design of highly active and stable catalysts for N 2 O decomposition and potentially other redox-sensitive environmental applications.

36 MATERIALS SCIENCE↗

Operation of the Fast Neutron Coincidence Collar (FNCL) with a DD-Neutron Generator

For more than 30 years, the quantitative assay of the 235 U content of light water reactor fresh fuel assemblies relied on measuring coincidence neutrons from fissions induced by an Am(Li) neutron source using 3 He based detectors. The Fast Neutron Collar (FNCL) developed by the International Atomic Energy Agency (IAEA), replaces traditional 3 He proportional counters with an array of liquid scintillator detectors arranged about the fuel assembly to provide improved measurement precision and reduced sensitivity to gadolinium poison rods. The FNCL relies on Am(Li) neutron sources that are no longer commercially available. This work examines the replacement of Am(Li) sources with a commercial off the-shelf deuterium–deuterium (DD) neutron generator. In addition to mitigating supply concerns, the neutron generator offers advantages in measurement precision and potential automation of sequential passive/active neutron measurements. This report presents the initial performance results for both the integrated DD/FNCL and Am(Li)/FNCL assays of compact depleted uranium, low-enriched uranium, and highly enriched uranium standards along with an estimate of the expected performance for fresh fuel assemblies. A discussion of the design and operation of the “FNCL Analysis and Simulation Software” is also provided.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Scalable multiphoton quantum metrology with neither pre- nor post-selected measurements

The quantum statistical fluctuations of electromagnetic fields establish a limit, known as the shot-noise limit, on the sensitivity of optical measurements performed with classical technologies. However, quantum technologies are not constrained by this shot-noise limit. In this regard, the possibility of using every photon produced by quantum sources of light to estimate small physical parameters, beyond the shot-noise limit, constitutes one of the main goals of quantum optics. Here, we experimentally demonstrate a scalable protocol for quantum-enhanced optical phase estimation across a broad range of phases, with neither pre- nor post-selected measurements. This is achieved through the efficient design of a source of spontaneous parametric downconversion in combination with photon-number-resolving detection. The robustness of two-mode squeezed vacuum states against loss allows us to outperform schemes based on N00N states, in which the loss of a single photon is enough to remove all phase information from a quantum state. In contrast to other schemes that rely on N00N states or conditional measurements, the sensitivity of our technique could be improved through the generation and detection of high-order photon pairs. This unique feature of our protocol makes it scalable. Furthermore, our work is important for quantum technologies that rely on multiphoton interference such as quantum imaging, boson sampling, and quantum networks.

36 MATERIALS SCIENCE↗

Rapid quantitative analysis of trace elements in plutonium alloys using a handheld laser-induced breakdown spectroscopy (LIBS) device coupled with chemometrics and machine learning

Here, we present the first reported quantification of trace elements in plutonium via a portable laser-induced breakdown spectroscopy (LIBS) device and demonstrate the use of chemometric analysis to enhance the handheld device's sensitivity and precision. Quantification of trace elements such as iron and nickel in plutonium metal via LIBS is a challenging problem due to the complex nature of the plutonium optical emission spectra. While rapid analysis of plutonium alloys has been demonstrated using portable LIBS devices, such as the SciAps Z300, their detection limits for trace elements are severely constrained by their achievable pulse power and length, light collection optics, and detectors. In this paper, analytical methods are evaluated as a means to circumvent the detection constraints. Three chemometric methods often used in analytical spectroscopy are evaluated; principal component regression, partial least-squares regression, and artificial neural networks. These models are evaluated based on goodness-of-fit metrics, root mean-squared error, and their achievable limits of detection (LoDs). Partial least squares proved superior for determining content of iron and nickel in plutonium metal, yielding LoDs of 15 and 20 ppm, respectively. These results of identifying the undesirable trace elements in plutonium components are critical for applications such as fabricating radioisotope thermoelectric generators or nuclear fuel.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗