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At least 703 records · Page 39

A high-volume resonator for L-band DNP-NMR

DNP-NMR and EPR experiments that operate at or greater than L-band (i.e., ν 0 (e – ) = 1–2 GHz) are typically limited to maximum sample volumes of several hundred µL. These experiments rely on well-known resonator designs for DNP/EPR irradiation such as the loop-gap resonator and Alderman-Grant coil, where their maximum volumes limit further application to imaging experiments and high-throughput screening beyond L-band. Herein, we demonstrate a birdcage (BC) resonator design that can accommodate several mL of sample while operating around 1.5 GHz. The sample volume is maximized by using two identical BC resonators in a stacked configuration. Simulations are used to optimize the BC design and the performance is validated experimentally with liquid-state Overhauser-DNP-NMR experiments. This BC design exploits just the parasitic capacitance of conductive rings and features no fixed tuning capacitors. An enhancement of –77 is achieved on a 10 mM 4-Amino-TEMPO in H 2 O sample for a 5 mL sample volume. Finally, the associated sample heating is minimal due to the low-E-fields generated and the large sample mass with +3.4 K when driving 100 W for several seconds.

47 OTHER INSTRUMENTATION↗

Topology-driven compressive behavior of Inconel 718 lattice structures with Z-strut reinforcement fabricated by laser powder bed fusion

This study investigates the compressive deformation behavior and mechanical performance of Inconel 718 lattice structures fabricated by laser powder bed fusion (LPBF). Four unit-cell topologies—BCC, FCC, BCCZ, and FCCZ—were designed with a unit-cell size of 3 mm and fabricated under identical process conditions to isolate the effect of topology. Measured relative densities ranged from 14.65% to 17.72%. Compressive testing showed that Z-strut-reinforced topologies (BCCZ: 54.6 MPa; FCCZ: 80.2 MPa) exhibited higher strength than their unreinforced counterparts, which may be associated with mixed-mode deformation behavior enabled by the vertically aligned Z-struts. Finite element simulations and Digital Image Correlation (DIC) analysis support the observation of a transition from node-dominated deformation in BCC/FCC to mixed-mode deformation in BCCZ/FCCZ. These findings suggest that unit-cell topology is a key design variable for tailoring deformation mechanisms in LPBF lattice structures.

36 MATERIALS SCIENCE↗

Machine-learning predictions of the shale wells’ performance

The ultra-low permeability nature of shale reservoirs leads to an extended linear flow and necessitates horizontal wells with multi-stage engineered fractures to efficiently extract hydrocarbons resources. These artificially-generated and naturally-occurring fractures form complex networks that create complex flow regimes which control oil production. These fractures are neither identical nor equally-spaced, which leads to a production profile with a masked onset of the boundary-dominated flow. The combination of the extended linear flow with the indeterminate onset of the boundary-dominated flow challenges the current deterministic analytic approaches to forecast the estimated ultimate recovery (EUR). In this work, we propose a novel machine-learning approach which overcomes these challenges and provides reliable EUR estimates based on field-wide analyses. We implement a novel unsupervised machine learning (ML) methodology, which allows for automatic identification of the optimal number of features (signals) present in the data based on non-negative matrix/tensor factorization coupled with k-means clustering incorporating regularization and physics constraints. In the presented analyses, the input data to the ML algorithm is the available (public) production history from the field collected at existing unconventional reservoirs. We validate our approach through hindcasting of the production data, where we achieved an excellent agreement. In addition, our approach is able to identify the poorly-performing wells, which could benefit from early refracing. Our approach provides fast and accurate estimations of the well performance without presumptions about the state of the well or the flow regime.

03 NATURAL GAS↗

Glass transition temperature studies of planetary ball milled glasses: Accessing the rapidly cooled glassy state in Na 4 P 2 S 7-x O x , 0 ≤ x ≤ 7, Oxy-thio phosphate glasses

This paper details the very first in-depth study of the glass transition temperature (T g ) for planetary balled milled (PBM) Na 4 P 2 S 7-x O x (NaPSO), where 0 ≤ x ≤ 7, glasses. For 0 ≤ x ≤ 5, fully amorphous, homogeneous, and chemically reacted compositions can be prepared. For samples with 5 < x ≤ 7, partially amorphous but fully chemically reacted glass-ceramics can be produced. The reproducible, thermally cyclable onset T g and the onset crystallization temperature, T c , were investigated as a function of the composition and of the short-range order (SRO) structures of the glasses. Additionally, we examined the extreme sub-T g exothermic relaxations present due to the high energy milling processing and correspondingly high effective quenching rate. Using a differential scanning calorimeter (DSC) and scanning from well below the onset T g , the glasses are observed to relax exothermally below T g . The integrated relaxation enthalpy, ΔH rel , is ~ 0 for the x = 2 glass, but is significantly exothermic for lower and higher values of x. Once the high fictive state of these glasses has been erased by scanning to above the T g , but below the T c of the glass, the DSC scans of the glasses recover normal behavior for a normally cooled glass without any relaxation exotherm. The T g s of these glasses remain relatively constant for 0 ≤ x ≤ 3, but for glasses with 3 < x ≤ 5, T g increases sharply following the combined effects of the phosphate chain length increasing caused by the formation of bridging oxygens and the increasing concentration of more charge dense non-bridging oxygens (NBOs). For x > 5, both T g and Tc decrease sharply, becoming nearly identical at x = 7 where glass formation essentially ceases. For smaller values of x, T c increases with both chain length and the structural complexity of the composition but decreases sharply for glass-ceramics of x > 5.

36 MATERIALS SCIENCE↗

The S solubility of Cr and Al containing simulated low-activity waste glass

Here, the presence of sulfur-containing molten salt phases during vitrification is a particular problem which can be detrimental to the melter. Borosilicate compositions were designed to explore both the effects of a fixed amount of Cr, as Cr 2 O 3 or Na 2 CrO 4 , and the impact of Al 2 O 3 , on sulfur solubility as determined by progressively adding elemental S. The NABS series (with Al 2 O 3 ) has a higher SO 3 solubility of ~3.5 mol% while the NBS series (without Al 2 O 3 ) has a SO 3 solubility of ~2 mol%. Crystalline Cr 2 O 3 formed in the NABS series upon the addition of S but is not present in the NBS series. At the highest S addition, a separate salt phase always forms, and was identified as Na 2 (S,Cr)O 4 via electron dispersive spectroscopy, ultraviolet-visible spectroscopy, x-ray diffraction, and thermal analysis. Magic angle spinning nuclear magnetic resonance identified no change in the B coordination in either series as S is added, suggesting that the Na is scavenged from other locations, such as the Si sites, to charge compensate sulfate, whether in the glass or in the salt. The Cr precursor identity did not affect the observed overall behavior regarding sulfur, but did impact Cr redox as identified with Raman spectroscopy.

36 MATERIALS SCIENCE↗

Evaluation of the effects of neutron irradiation on first-generation corrosion mitigation coatings on SiC for accident-tolerant fuel cladding

In this work, high purity SiC and SiC/SiC composites coated with commercial TiN, Cr, CrN, or CrN/Cr multilayer coatings were irradiated in Ar or flowing PWR water in the Massachusetts Institute of Technology Nuclear Reactor Laboratory (MITR). Irradiation in Ar was performed in the core. In the water environment, identical samples were placed in one of three different locations: in-core, providing exposure to neutron damage and radiolysis-affected water; above-core, where samples were exposed to radiolysis-affected water but not neutron damage, or outside of the core, where samples were exposed to the coolant water without the effects of radiation. Radiation in Ar revealed significant cracking of all but the TiN coatings, attributed to differential swelling between the coating and substrate. Lattice swelling was not observed in any of the coatings, but 0.2% void swelling was observed in the Cr coating. All of the coatings failed during water exposures in the core. Likewise, CrN/Cr spalled in each condition. Cr was protective, except under radiation damage as a result of cracking, and TiN severely degraded in the core with no coating was found following exposure. A SiC/coating ATF cladding system is anticipated to perform adequately following improvements in coating ductility and purity.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

The influence of nitrogen and nitrides on the structure and properties of proton irradiated ferritic/martensitic steel

The 12Cr1MoWV (wt%) ferritic/martensitic steel HT9 is a candidate material for fuel cladding in advanced nuclear reactors, such as the Versatile Test Reactor currently under development. As such, understanding the relationship between microstructure and mechanical properties in the context of irradiation environments for these steels is critical. N content, and more specifically interstitial N, has been hypothesized to be detrimental to irradiated properties at lower temperatures (less than 0.3T m ) to a total of 6 dpa; however, in this work at a dose of 1 dpa the irradiated microstructure was improved with added N, leading to less irradiation hardening. Three variants of HT9 were irradiated with 1.5 MeV protons to a dose of 1 dpa at 300°C. The HT9 variants included Low (10 ppm), Mid (190 ppm), and High (440 ppm) N alloys that were otherwise nearly identical. Changing the N content had a variety of effects on the irradiated defect structures. As N content increased, the average dislocation loop diameter decreased, while the number density of loops increased. Additionally, extensive Ni clustering was observed on dislocations and interfaces. The Mid and High N specimens exhibited significantly less hardening (ΔHV≃100) relative to the Low N specimen (ΔHV≃160). The decrease in hardening is attributed to vanadium carbonitride acting as a sink for Ni clusters that would otherwise form on dislocations. Under the irradiation conditions used, these results suggest increasing the N content in HT9 may have a desirable effect on the irradiated structure and properties at the dose studied, as well as the swelling resistance at higher doses. In other words, N content appears to be a powerful tool for tailoring the self-interstitial atom cluster mobility in F/M steels for different temperature and dose applications.

36 MATERIALS SCIENCE↗

Mechanical and Thermophysical properties of low enriched uranium-10wt% molybdenum rolled foils

In this study, low-enriched (~19.75% 235 U) U-10Mo(wt%) foils were evaluated for both mechanical and thermophysical properties to establish baseline characteristics prior to irradiation testing. Cast U-10Mo ingots were sequentially hot and cold rolled to two different final foil thicknesses, resulting in different levels of cold work being present in the finished foils. The mechanical response of the U-10Mo foils was evaluated in the temperature range of 293–623 K. Increasing test temperatures resulted in decreases of both yield and ultimate tensile strength. Comparison of results to earlier work performed on depleted U-10Mo rolled foils indicates that the material in this study has lower strength and increased ductility. However, a comparison of the two different foil thicknesses in this study found that they were nearly identical in yield and ultimate tensile strength, differing by only 10–20 MPa (<2%). Thermal conductivity was calculated from the measurements of specific heat, linear thermal expansion, and thermal diffusivity from 323 to 1273 K on both thicknesses of the foils. These data were approximately 5–10% lower than previously published data above 573 K and were similar to data for temperature ranges below 573 K. Differences are likely related to differences in grain size and/or impurity content and variation in fabrication history.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Measuring thermal diffusivity and gap conductance in uranium nitride and Zircaloy relevant for microreactor applications

Heat transfer across nuclear fuels and structural interfaces is an important factor for evaluating the performance of nuclear power systems. Specifically, heat generated as nuclear fuel fissions must be transported through the cladding material and through the reactor to reach the steam turbine for power generation. As new microreactor designs emerge, maximizing the efficiency of this heat transfer process becomes crucial to make them commercially viable. This article examines thermal diffusivity and gap conductance in uranium nitride (UN) fuel and Zircaloy-4 (Zry4) cladding using light flash analysis (LFA). Thermal diffusivity measurements were made on monolithic UN pellets and Zry4 exposed to carbon at peak operating temperatures of microreactors and show that carbon ingress has a minimal effect on thermal diffusivity when compared with identical materials not exposed to carbon. Evaluation of gap conductance at the UN-Zry4 interface was done using one-dimensional two-layer thermal transport models as a function of applied pressure. Here the results show that increasing pressure on the UN-Zry4 interface leads to gains in gap conductance per unit area in fuel-cladding assemblies at microreactor operating temperatures. While many other variables are expected to influence UN-Zry4 interfacial gap conductance (e.g. contact surface roughness, porosity, localized heating, environmental gas pressure), the work offers a demonstration of using a conventional LFA apparatus to determine this parameter at elevated temperatures.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Computational insights into the structure of anhydrous Pu(III) oxalate

Despite the plutonium oxalate method's wide use in plutonium reprocessing, the method's mechanistic details remain unclear, particularly the identity of the plutonium oxidation state during conversion from an oxalate hydrate to the oxide. Recently, the optical vibrational spectra of Pu(III) oxalate during calcination were measured, providing an experimental reference for computational studies aimed at elucidating the oxalate structure. Here, in this work, we compare the vibrational and electronic properties of two candidate anhydrous Pu(III) oxalate structures calculated using density functional theory with recent experiments. We find that both structures are plausible and may coexist at experimental temperatures, providing insights into the broad features measured in the Raman and infrared spectra.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

High-temperature nanoindentation creep studies on castable and sintered nanostructured low-activation ferritic-martensitic alloys

In this article, we present the creep characteristics of two reduced activation ferritic-martensitic steels of identical starting compositions formed by different fabrication routes: a nanostructured ferritic alloy commonly referred to as a castable nanostructured alloy (CNA) and a sintered nanostructured alloy (SNA) variant. Through a series of nanoindentation experiments spanning a temperature range of 25 °C to 650 °C, with a maximum load of 100 mN, we find creep behaviors in the cast and sintered materials to be remarkably similar. The creep stress exponent (n) for CNA and SNA were found to be in the range of 8–35 and the activation volume was ∼14–42b 3 , underscoring a dominance of dislocation-mediated mechanisms in both alloys. Notably, we observed a decline in the creep stress exponent with increasing temperature, attributable to the heightened influence of thermally activated dislocations. This phenomenon suggests a potential transition in the deformation mechanism towards a thermally activated dislocation climb process, significantly impacting the observed creep behavior.

36 MATERIALS SCIENCE↗

Understanding the structural and morphological effects of synthesis route on NpO 2

The availability of actinide standard materials for use in nuclear safeguard applications is critical, as is thorough characterization thereof. Although accurate trace element compositions and isotopic considerations are paramount for deployment of reference standards, structural characterization is also essential towards accurately describing the chemical form and potential matrix effects in candidate materials. Here, to this end, samples of NpO 2 were synthesized via a direct denitration (DD) method and probed with powder X-ray diffraction (PXRD), Raman spectroscopy, and scanning electron microscopy (SEM) for structural and morphological characterization and comparison with NpO 2 materials produced via modified direct denitration (MDD). PXRD confirmed the bulk identity of NpO 2 , and no additional phases were identified using this method. Analysis of Raman data collected using a 532 nm excitation wavelength indicates that samples are mostly phase pure; however, some variability in spectral features is observed. Analysis of additional spectroscopic data collected with a 785 nm excitation wavelength revealed variability in the relative intensity of spectral features. Raman spectroscopy indicates that the sample is primarily NpO 2 ; however, additional signals indicate possible structural disorder, oxidized species, or potential contributions from other Np phases. To further investigate the possibility of additional phase contributions within the sample of NpO 2 , Raman spectroscopic mapping was employed to examine the homogeneity of the sample produced via DD. From this analysis, we determined that despite variability in the intensity of Raman-active vibrational modes, consistent spectra are obtained throughout the area of the sample investigated. SEM images show aggregates with variable sizes and shapes, with rounded, primary particles possessing an average diameter of approximately 100 nm. Comparison of the results of these multimodal analyses to the literature indicates that the crystal chemical, spectroscopic, and microstructural properties of NpO 2 vary based on synthesis method, even if X-ray diffraction data indicate that the bulk phase is NpO 2 .

Direct denitration↗

In situ study on radiation response of tungsten manufactured by laser powder bed fusion

Tungsten (W) produced by laser powder bed fusion (LPBF) was examined by in situ Krypton (Kr) ion irradiation at 400 °C up to 2.52 displacements per atom (dpa) to investigate its radiation response. Dislocation loops with identical Burgers vectors form aligned raft structures, inducing significant grain misorientation accumulation. Defect saturation was observed beyond 0.36 dpa, marked by constant loop density and raft spacing. WO 3 nanoparticles are found in the as-printed matrix and served as efficient defect sinks. Dislocation loops were absorbed at the W/WO 3 interface, facilitating defect annihilation and suppressing defect accumulation. In conclusion, these findings highlight the role of LPBF microstructure and oxide interfaces in mediating radiation-induced defect evolution, offering insights for designing radiation tolerant W-based materials.

Defect sink↗

Establishing metrics to quantify spatial similarity in spherical and red blood cell distributions

As computational power increases and systems with millions of red blood cells can be simulated, it is important to note that varying spatial distributions of cells may affect simulation outcomes. Since a single simulation may not represent the ensemble behavior, many different configurations may need to be sampled to adequately assess the entire collection of potential cell arrangements. In order to determine both the number of distributions needed and which ones to run, we must first establish methods to identify well-generated, randomly placed cell distributions and to quantify distinct cell configurations. We utilize metrics to assess (1) the presence of any underlying structure to the initial cell distribution and (2) similarity between cell configurations. We propose the use of the radial distribution function to identify long-range structure in a cell configuration and apply it to a randomly distributed and structured set of red blood cells. To quantify spatial similarity between two configurations, we make use of the Jaccard index, and characterize sets of red blood cell and sphere initializations. As an extension to our work submitted to the International Conference on Computational Science, we significantly increase our data set size from 72 to 1048 cells, include a similar set of studies using spheres, compare the effects of varying sphere size, and utilize the Jaccard index distribution to probe sets of extremely similar configurations. Our results show that the radial distribution function can be used as a metric to determine long-range structure in both distributions of spheres and RBCs. We determine that the ideal case of spheres within a cube versus bi-concave shaped cells within a cylinder affects the shape of the Jaccard index distributions, as well as the range of Jaccard values, showing that both the shape of particle and the domain may play a role. Furthermore, we also find that the distribution is able to capture very similar configurations through Jaccard index values greater than 95% when appending several nearly identical configurations into the data set.

59 BASIC BIOLOGICAL SCIENCES↗

Synthesis and Photophysics of Phenylene Based Triplet Donor–Acceptor Dyads: ortho vs. para Positional Effect on Intramolecular Triplet Energy Transfer

Two phenylene based geometrical/isomeric triplet ortho- and para–dyads (o–3 and p–3, respectively) were synthesized and fully characterized using advanced photophysical tools and computations. In dyad o–3, the through-space donor-acceptor interactions led to simultaneous triplet energy transfer and charge transfer with identical kinetics. On the other hand, in the dyad p–3, it was found that the phenylene spacer favors a fast triplet energy delocalization over the charge transfer process. Furthermore, analysis of the results from the present investigation indicates that the deactivation of the photo-excited species (o–3)* occurs through both the intrinsic channel viz. S0←S1 and charge recombination. In the case of dyad p–3, the results indicate that the primary deactivation pathway is self-quenching or triplet-triplet annihilation involving the acceptor unit(s).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NIRDye 812: A molecular platform tailored for multimodal bioimaging applications of targeted fluorescence- and photoacoustic-guided surgery

The primary treatment for malignant tumors remains to be surgical removal of the diseased tissue. The presence or absence of residual diseased tissue at the tumor margin is the strongest predictor of postoperative prognosis and recurrence. Accordingly, reliance on the ability of surgeons to visually distinguish diseased tissue from healthy tissue unambiguously in real time is crucial. Near infrared-I (NIRsingle bondI) fluorescence-emitting targeting biomolecular constructs such as anticancer antibody-fluorophore conjugates, namely cetuximab-IRDye® 800CW (CTB-IRDye® 800CW), are FDA-approved for clinical trial usage in the fluorescence-guided resection of diseased tissue due to affording improved direct visualization of tumor tissue when compared to the use of either the unaided eye under standard white light illumination (WLI) surgical techniques or non-targeting fluorophores. Unfortunately, though helpful, CTB-IRDye® 800CW affords limited (i) identification of diseased tissue and (ii) tumor margin delineation, because the immunoconjugate generates suboptimal tumor-to-background ratios (TBRs) as a result of its spectral/photophysical profiles poorly aligning with the fixed optical windows of pre-/clinical setups. As such, CTB-IRDye® 800CW is more prone to affording incomplete resection compared to if TBRs were higher due to otherwise. Here, to aid in accurately identifying deep-seated diseased tissue, photoacoustic (PA) tomography has been implemented alongside CTB-IRDye® 800CW to achieve PA signals that could result in higher TBRs. However, in clinical trial practice, using IRDye® 800CW for PA imaging also yields subpar TBRs due to it affording low PA signals. To overcome such limitations, we developed NIRDye 812, a structurally-modified topological equivalent of IRDye® 800CW, to confer it the capability to yield both higher TBRs and superior PA signal than that of the equivalent CTB-conjugate and fluorophore IRDye® 800CW itself, respectively. To do so, we substituted the oxygen atom at its meso-position with a sulfur atom. CTB-NIRDye 812 demonstrated a red-shifted absorption wavelength at 796 nm and a peak NIR-I fluorescence emission wavelength at 820 nm, which better dovetails with the fixed windows of preinstalled fixed emission filters within commercial pre-/clinical NIR-I fluorescence imaging instruments. Overall, CTB-NIRDye 812 provided a ~ 2-fold increase in TBRs compared to those of CTB-IRDye® 800CW in vivo. Also, NIRDye 812 displayed an ~60% higher PA signal than that of IRDye® 800CW. Collectively, we achieved our goal of improving upon the spectral/photophysical and PA properties of IRDye® 800CW via introducing a subtle modification to its electronic core such that its CTB immunoconjugate could potentially allow for fast track or breakthrough designation by the FDA due to its near-identical structure displaying considerably improved efficacy.

59 BASIC BIOLOGICAL SCIENCES↗

Structural and spectroscopic characterization of photoactive yellow protein and photoswitchable fluorescent protein constructs containing heavy atoms

Photo-induced structural rearrangements of chromophore-containing proteins are essential for various light-dependent signaling pathways and optogenetic applications. Ultrafast structural and spectroscopic methods have offered insights into these structural rearrangements across many timescales. However, questions still remain about exact mechanistic details, especially regarding photoisomerization of the chromophore within these proteins femtoseconds to picoseconds after photoexcitation. Instrumentation advancements for time-resolved crystallography and ultrafast electron diffraction provide a promising opportunity to study these reactions, but achieving enough signal-to-noise is a constant challenge. In this work, we present four new photoactive yellow protein constructs and one new fluorescent protein construct that contain heavy atoms either within or around the chromophore and can be expressed with high yields. Structural characterization of these constructs, most at atomic resolution, show minimal perturbation caused by the heavy atoms compared to wild-type structures. Spectroscopic studies report the effects of the heavy atom identity and location on the chromophore’s photophysical properties. None of the substitutions prevent photoisomerization, although certain rates within the photocycle may be affected. Overall, these new proteins containing heavy atoms are ideal samples for state-of-the-art time-resolved crystallography and electron diffraction experiments to elucidate crucial mechanistic information of photoisomerization.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Use of a segmented cell for the combinatorial development of platinum group metal-free electrodes for polymer electrolyte fuel cells

The development of novel platinum group metal (PGM)-free catalysts is a difficult task, particularly when coupled with the integration into a cathode catalyst layer (CCL). The optimization of such PGM-free electrode structures is often non-linear and iterative, making it a demanding task due to the high number of parameters that affect performance. To accelerate both materials discovery and electrode development, this work demonstrates the application of a high-resolution segmented cell (SC) with 121 segments of 0.413 cm 2 size for combinatorial high-throughput PGM-free catalyst screening and CCL optimization. The approach utilizes three flow-field strips with active areas of 4.45 cm 2 each, distributed over 11 segments. Electrodes with identical catalyst material and fabrication method result in reproducible data with typically less than 10% variation between each segment and match in performance with differential single cell data. High throughput testing of combinatorial sample sets, with varied PGM-free electrocatalyst materials or electrode composition, demonstrated the ability to rapidly discern high performing outliers, and establish or confirm trends in electrode optimization. The results indicated significant performance benefits of electrodes with ionomer content of 45 wt% over lower values, and of water rich inks with 82% water content over those with 50%.

30 DIRECT ENERGY CONVERSION↗