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At least 1,495 records · Page 83

Thermophysical properties and reversible phase transitions in yttrium hydride

In this study, the thermophysical properties of yttrium hydrides were investigated as a function of temperature (room temperature [RT] to 700°C) and hydrogen concentration (H/Y ratio ranges from 1.52 to 1.93). The results indicate that at the temperatures below 300°C, the hydrogen content did not have a significant influence on the thermal expansion, while the specific heat capacity, the thermal diffusivity, and the calculated thermal conductivity were slightly higher for the larger H/Y ratio. Between 300°C and 700°C, a reversible second-order endothermic transition in all measured thermal properties was observed. It was also found that the onset temperatures of the observed transition varied, with the composition having inverse dependence on the hydrogen content. The phase transition from ( α - Y + δ -YH x ) mixed phase to the δ -YH x single phase was excluded from the main contributors to the observed transition. An attempt was made to explain the behavior of the thermophysical properties at higher temperatures by considering the order–disorder transition as a result of hydrogen redistribution.

36 MATERIALS SCIENCE↗

Characterization of mechanical properties and deformation behavior of highly irradiated 316L stainless steel from target modules at the Spallation Neutron Source using digital image correlation analysis

Tensile specimens with irradiation doses ranging from approximately 0.7 to 7.6 displacements per atom (dpa) were fabricated from 316L samples removed from Spallation Neutron Source (SNS) target vessels after service. Tensile tests were performed in conjunction with digital image correlation (DIC) characterization, which permitted detailed analysis of the strain distribution and deformation behavior of the specimen gauge sections during testing. The results show, while considerable hardening (500–700 MPa increase in yield strength) occurred in the 316L SNS target material with increasing dose, appreciable ductility (19–23% total elongation) remained in the material after irradiation to 7.6 dpa in the mixed neutron/proton environment of the SNS target region. The DIC data showed the strain distribution and deformation behavior of all irradiated specimens were nonuniform during testing. Strain localization in the form of deformation bands or “hotspots” was observed during testing, and in some specimens, the bands propagated as deformation waves along the gauge section. The “traveling wave” deformation behavior affected the amount of elongation each specimen achieved, and the scatter in the elongation data was attributed to the large variation in deformation behavior observed among different specimens. Bands of localized strain, or deformation bands, oriented at specific angles were observed in two-dimensional plots of the strain distribution in the gauge sections of some specimens. Overall, this paper describes the experimental procedures, results, and deformation behavior of tensile specimens from SNS targets after service and illustrates the value of DIC characterization during tensile testing of irradiated materials.

36 MATERIALS SCIENCE↗

Influence of high-strain-rate compression and subsequent heat treatment on (TiNbZr) 89 (AlTa) 11 refractory high-entropy alloys: Dynamic-mechanical behavior and microstructural changes

This study explored the dynamic-mechanical behavior of a novel low-density (TiNbZr) 89 (AlTa) 11 refractory high-entropy alloy (RHEA) across strain rates ranging from 1.0×10 3 to 3.5×10 3 s –1 . A significant increase in the yield and ultimate compressive strengths with rising strain rates up to 3.0×10 3 s –1 was observed and attributed to enhanced dislocation activities and stress-induced microstructural transformations. The formation of the B2 phase and Zr 5 Al 3 precipitates was found to be crucial in bolstering the alloy strength at high strain rates. Beyond strain rates of 3.0×10 3 s –1 , a decrease in strength occurred due to thermal softening and strain localization. Microstructural analyses at 3.5×10 3 s –1 revealed grain refinement, the development of micro shear bands, and dislocation tangles, which were indicative of dynamic recrystallization. Besides, the findings also revealed that the post-dynamic compression heat treatment further enhanced the hardness and microstructural stability of the alloy. These results highlight the potential of the (TiNbZr) 89 (AlTa) 11 RHEA for applications requiring materials with high strength-to-weight ratios, particularly in dynamically loaded environments. It is expected that the results of this study will further advance our fundamental understanding of the behavior of RHEAs under extreme conditions, thereby opening new avenues for material innovation.

36 MATERIALS SCIENCE↗

New directions and principles for solvent extraction for recovery of lithium from aqueous brines and mineral leachates: A brief review

Increasing demand for lithium for manufacturing of batteries is fueling the unprecedented search for improved recovery and alternative sources. Wider source distribution, lower energy consumption, and greater sustainability make extraction of lithium from brines, both natural and process-derived, an attractive alternative to mineral ores. Solvent extraction, used industrially for production of metals, salts, and pharmaceuticals, has been investigated as a methodology for lithium recovery for several decades. However, industrial application of solvent extraction for lithium recovery has so far been limited. In contrast, direct lithium extraction using adsorbents based on inorganic minerals has rapidly advanced from research to commercialization. A comparison of solvent extraction processes to adsorption highlights these issues and explains the preference for adsorbents. Although the application of solvent extraction has been criticized for use of large amounts of acid, alkali, and organic solvents, steady progress has been made to improve its potential for industrial lithium production, spurred on generally by the advantages of solvent extraction in selectivity and throughput. Previously developed beta-diketone, organophosphate, and crown ether ligands are being adapted and improved. Their novel use with ionic liquids, deep eutectic solvents, and membrane technologies promises to expand capabilities for extraction of lithium from dilute aqueous sources while improving sustainability. Possibilities for further discovery and innovation abound. In this review, we provide a unique perspective from the field of solvent extraction starting with fundamentals such as ion-transfer theory and apply them to understanding lithium selectivity and extraction behavior. In conclusion, the results are cast in the light of the practical realities of developing economical solvent extraction processes.

Brine↗

Emerging roles of circular RNAs in thyroid cancer

As the most common endocrine-related malignant tumor, the prevalence of thyroid cancer (TC) has soared strikingly over the past thirty years then verged to stabilization or even descension temporally. Distributed in a cell-specific manner, circular RNAs (circRNAs) is a novel class of non-coding RNAs characterized by its covalently closed loop without 5′-terminal cap and 3′-terminal poly A tail, which guarantee its distinctive evolutionary conservation and exonucleases resistance. Emerging evidence indicates that circRNA participates in the pathogenesis and carcinogenesis of several cancers including thyroid cancer. In this review, we concentrated on the connection between circRNAs and thyroid cancer so as to obtain a more profound understanding. We aim to discuss this relationship between TC and circRNAs by summarizing the effect of various circRNAs on tumor biological behaviors and clinical application, and systematically outlook the conceivable application of circRNAs in TC diagnosis and therapy.

60 APPLIED LIFE SCIENCES↗

Determining Activity Coefficients of SOA from Isothermal Evaporation in a Laboratory Chamber

Nonideal molecular interactions in aerosol particles influence the partitioning of semivolatile organic compounds (SVOCs). However, few direct measurements exist that determine activity coefficients (γ), which quantify nonideality, for individual organic compounds in different atmospheric mixtures. By measuring the isothermal evaporation of SOA formed from multifunctional SVOCs in an environmental chamber, this study determines the mole-fraction-based γ of the bulk SOA in a variety of pre-existing chemically complex particles, approximated as if the bulk SOA behaved like a single SVOC. These multicomponent mixtures contain molecular structures commonly found in the atmosphere. When treated as a single liquid phase, γ of the bulk SOA tends to increase from ~1 to ~5 as the organic seeds and the SOA have more differing polarities. A high computed γ value of 74 for a wet ammonium sulfate-SOA system indicates phase separation. The γ for some individual species was also quantified based on gas-phase measurements and AIOMFAC model predictions. However, the bulk SOA γ cannot be explained by the simplified speciated SVOC–seed interactions, suggesting incomplete compositional understanding of the bulk SOA. In this work, these results demonstrate a method to quantify nonideal behavior and show that it can occur in multicomponent mixtures and therefore influence OA formation, evolution, and lifetimes.

54 ENVIRONMENTAL SCIENCES↗

Revisiting Competing Paths in Electrochemical CO 2 Reduction on Copper via Embedded Correlated Wavefunction Theory

We re-evaluate two key steps in the mechanism of CO 2 reduction on copper at a higher level of theory capable of correcting inherent errors in density functional theory (DFT) approximations, namely, embedded correlated wavefunction (ECW) theory. Here, we consider the CO reduction step on Cu(111), which is critical to understanding reaction selectivity. Here, we optimize embedding potentials at the periodic plane-wave DFT level using density functional embedding theory (DFET). All possible adsorption sites (adsites) for each adsorbate then are screened with ECW theory at the catalytically active site to refine the local electronic structure. Unsurprisingly, DFT and ECW theory predict different adsite preferences, largely because of DFT’s inability to properly situate the CO 2π* level. Differing preferred adsites suggest that different reaction pathways could emerge from DFT versus ECW theory. Starting from these preferred ECW theory adsites, we then obtain reaction pathways at the plane-wave DFT level using the climbing-image nudged elastic band method to determine minimum energy paths. Thereafter, we perform ECW calculations at the catalytically active site to correct the energetics at each interpolated structure (image) along the reaction pathways. Via this approach, we confirm that the first step in CO reduction via hydrogen transfer on Cu(111) is to form hydroxymethylidyne (*COH) instead of formyl (*CHO). Although the prediction to preferentially form *COH is consistent with that of DFT, the two theories predict quite different structural and mechanistic behaviors, suggesting that verification is needed for other parts of the mechanism of CO 2 reduction, which is the subject of ongoing work.

30 DIRECT ENERGY CONVERSION↗

Behavior of Water Near Multimodal Chromatography Ligands and Its Consequences for Modulating Protein–Ligand Interactions

Multimodal chromatography is a powerful approach for purifying proteins that uses ligands containing multiple modes of interaction. Recent studies have shown that selectivity in multimodal chromatographic separations is a function of the ligand structure and geometry. Here, we performed molecular dynamics simulations to explore how the ligand structure and geometry affect ligand–water interactions and how these differences in solution affect the nature of protein–ligand interactions. Our investigation focused on three chromatography ligands: Capto MMC, Nuvia cPrime, and Prototype 4, a structural variant of Nuvia cPrime. First, the solvation characteristics of each ligand were quantified via three metrics: average water density, fluctuations, and residence time. We then explored how solvation was perturbed when the ligand was bound to the protein surface and found that the probability of the phenyl ring dewetting followed the order: Capto MMC > Prototype 4 > Nuvia cPrime. To explore how these differences in dewetting affect protein–ligand interactions, we calculated the probability of each ligand binding to different types of residues on the protein surface and found that the probability of binding to a hydrophobic residue followed the same order as the dewetting behavior. This study illustrates the role that wetting and dewetting play in modulating protein–ligand interactions.

59 BASIC BIOLOGICAL SCIENCES↗

Effects of the Grazing Incidence Geometry on X-ray Photon Correlation Spectroscopy Measurements

X-ray photon correlation spectroscopy (XPCS) is a versatile tool to measure dynamics on the nanometer to micrometer scale in bulk samples. XPCS has also been applied in grazing incidence (GI) geometry to examine the dynamics of surface layers. However, considering GI scattering experiments more universally, the GI geometry leads to a superposition of signals due to reflection and refraction effects, also known from the distorted-wave Born approximation (DWBA). In this paper, the impact of these reflection and refraction effects on the correlation analysis is determined experimentally by measuring grazing incidence transmission XPCS (GT-XPCS) and grazing incidence XPCS (GI-XPCS) simultaneously for a thin film sample, showing non-equilibrium dynamics. Here the results of the GI and GT geometry comparisons are combined within the framework of the standardly applied, simplified DWBA. These calculations allow identifying the main contributions of the detected signal from the leading scattering terms along the out-of-plane direction q z , which dominate the measured intensity pattern on the detector. In combination with the calculation of the non-linear effect of refraction in GTSAXS and GISAXS, it is possible to identify experimental conditions that can be chosen to run experiments and data analysis as close as possible to transmission XPCS and to explain which limitations for data interpretations are observed. Consequently, the beam exposure can be significantly reduced by using GI geometry only. Calculations of experimental settings prior to experiments are detailed to determine suitable q z regions for a variety of material systems measured in bulk-sensitive GI-XPCS experiments, allowing us to determine the scaling behavior of typical decay times as a function of q that is comparable to the scaling behavior obtained in distortion-free GT-XPCS or transmission XPCS experiments.

36 MATERIALS SCIENCE↗

Role of Bottlebrush Additives on the Structure of Block Copolymers in the Bulk and Thin Films

Blending block copolymers (BCP) with additives is a useful approach for controlling BCP morphology and properties. In athermal systems, blends of BCPs with polymer additives having very high molecular (M n ) mass generally result in macrophase separation. Bottlebrush polymers, which consist of a linear backbone and grafted side chains, present an interesting alternative where the overall M n of the system can be very large but the low M n side chains may drive miscibility with the BCP. Here, in this study, a bottlebrush with a polynorbornene backbone and polystyrene (PS) side chains is blended with PS-b-poly(methyl methacrylate) (PS-b-PMMA) of varying M n , and the resulting morphologies are examined in both the bulk and thin films. Two different M n of PS-b-PMMA were used in the bulk study, and the analysis of small-angle X-ray scattering data shows that the blends were miscible and lamellar at all concentrations. This deviates from reference series of both low and high M n linear polymer additives, which either showed morphological transitions from lamellae to cylinders (low M n ) or were immiscible at all mass fractions studied (high M n ). The relative molecular mass of the side chain (N SC ) and the corresponding component in the BCP (N A ) dictate the distribution of the bottlebrush throughout the BCP, analogous to BCP/linear blends or grafted nanoparticles in a homopolymer matrix. The studies on thin films show a thickness dependence for bottlebrush mass fractions at or above 0.17, a behavior which may be driven by conformational changes of the bottlebrush upon confinement.

36 MATERIALS SCIENCE↗

Robust evaluation of ENSO in climate models: How many ensemble members are needed?

Large ensembles of model simulations require considerable resources, and thus defining an appropriate ensemble size for a particular application is an important experimental design criterion. We estimate the ensemble size (N) needed to assess a model's ability to capture observed El Niño-Southern Oscillation (ENSO) behavior by utilizing the recently developed International CLIVAR ENSO Metrics Package (Planton et al., 2021). Using the larger ensembles available from CMIP6 and the US CLIVAR Large Ensemble Working Group, we find that larger ensembles are needed to robustly capture baseline ENSO characteristics (N > 50) and physical processes (N > 50) than the background climatology (N ≥ 12) and remote ENSO teleconnections (N ≥ 6). While these results vary somewhat across metrics and models, our study quantifies how larger ensembles are required to robustly evaluate simulated ENSO behavior, thereby providing some guidance for the design of model ensembles.

54 ENVIRONMENTAL SCIENCES↗

Curvature-controlled geometrical lensing behavior in self-propelled colloidal particle systems

In many biological systems, the curvature of the surfaces cells live on influences their collective properties. Curvature should likewise influence the behavior of active colloidal particles. We show using molecular simulation of self-propelled active particles on surfaces of Gaussian curvature (both positive and negative) how curvature sign and magnitude can alter the system's collective behavior. Curvature acts as a geometrical lens and shifts the critical density of motility-induced phase separation (MIPS) to lower values for positive curvature and higher values for negative curvature, which we explain theoretically by the nature of parallel lines in spherical and hyperbolic space. Curvature also fluidizes dense MIPS clusters due to the emergence of defect patterns disrupting the crystalline order inside the clusters. Using our findings, we engineer three confining surfaces that strategically combine regions of different curvature to produce a host of novel dynamical behaviors, including cyclic MIPS on spherocylinders, directionally biased cyclic MIPS on spherocones, and position dependent cluster fluctuations on metaballs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Molecular recognition of a host protein by NS1 of pandemic and seasonal influenza A viruses

The 1918 influenza A virus (IAV) caused the most severe flu pandemic in recorded human history. Nonstructural protein 1 (NS1) is an important virulence factor of the 1918 IAV. NS1 antagonizes host defense mechanisms through interactions with multiple host factors. One pathway by which NS1 increases virulence is through the activation of phosphoinositide 3-kinase (PI3K) by binding to its p85β subunit. Here we present the mechanism underlying the molecular recognition of the p85β subunit by 1918 NS1. Using X-ray crystallography, we determine the structure of 1918 NS1 complexed with p85β of human PI3K. We find that the 1918 NS1 effector domain (1918 NS1 ED ) undergoes a conformational change to bind p85β. Using NMR relaxation dispersion and molecular dynamics simulation, we identify that free 1918 NS1 ED exists in a dynamic equilibrium between p85β-binding–competent and –incompetent conformations in the submillisecond timescale. Moreover, we discover that NS1 ED proteins of 1918 (H1N1) and Udorn (H3N2) strains exhibit drastically different conformational dynamics and binding kinetics to p85β. These results provide evidence of strain-dependent conformational dynamics of NS1. Using kinetic modeling based on the experimental data, we demonstrate that 1918 NS1 ED can result in the faster hijacking of p85β compared to Ud NS1 ED , although the former has a lower affinity to p85β than the latter. Our results suggest that the difference in binding kinetics may impact the competition with cellular antiviral responses for the activation of PI3K. We anticipate that our findings will increase the understanding of the strain-dependent behaviors of influenza NS1 proteins.

59 BASIC BIOLOGICAL SCIENCES↗

Integrating plant physiology into simulation of fire behavior and effects

Summary Wildfires are a global crisis, but current fire models fail to capture vegetation response to changing climate. With drought and elevated temperature increasing the importance of vegetation dynamics to fire behavior, and the advent of next generation models capable of capturing increasingly complex physical processes, we provide a renewed focus on representation of woody vegetation in fire models. Currently, the most advanced representations of fire behavior and biophysical fire effects are found in distinct classes of fine‐scale models and do not capture variation in live fuel (i.e. living plant) properties. We demonstrate that plant water and carbon dynamics, which influence combustion and heat transfer into the plant and often dictate plant survival, provide the mechanistic linkage between fire behavior and effects. Our conceptual framework linking remotely sensed estimates of plant water and carbon to fine‐scale models of fire behavior and effects could be a critical first step toward improving the fidelity of the coarse scale models that are now relied upon for global fire forecasting. This process‐based approach will be essential to capturing the influence of physiological responses to drought and warming on live fuel conditions, strengthening the science needed to guide fire managers in an uncertain future.

54 ENVIRONMENTAL SCIENCES↗

Universal phase dynamics in VO 2 switches revealed by ultrafast operando diffraction

Understanding the pathways and time scales underlying electrically driven insulator-metal transitions is crucial for uncovering the fundamental limits of device operation. Using stroboscopic electron diffraction, we perform synchronized time-resolved measurements of atomic motions and electronic transport in operating vanadium dioxide (VO 2 ) switches. We discover an electrically triggered, isostructural state that forms transiently on microsecond time scales, which is shown by phase-field simulations to be stabilized by local heterogeneities and interfacial interactions between the equilibrium phases. This metastable phase is similar to that formed under photoexcitation within picoseconds, suggesting a universal transformation pathway. Our results establish electrical excitation as a route for uncovering nonequilibrium and metastable phases in correlated materials, opening avenues for engineering dynamical behavior in nanoelectronics.

36 MATERIALS SCIENCE↗

The promise of metal-halide-perovskite solar photovoltaics: A brief review

Solar photovoltaics (PVs) based on metal-halide perovskites (MHPs) have taken the renewable-energy world by storm. The excitement stems from the promise of a high-efficiency, low-cost, and low “carbon-footprint” new PV technology. Here, a brief overview of the important topics pertaining to MHPs, perovskite solar cells (PSCs) and perovskite solar modules (PSMs) is presented. The topics include: (1) PSC architectures, (2) MHPs, (3) synthesis and processing of MHP thin films, (4) MHP thin-film microstructures, (5) PSC functional layers, (6) interfacial engineering in PSCs, (7) PSC performance, (8) PSC stability, (9) PSMs, (10) lead toxicity, and (11) mechanical behavior and reliability. The significant challenges in the path toward commercialization of this burgeoning PV technology are also highlighted. Chief among them are scalability, stability, reliability, and safety, while achieving high efficiency, low cost, and low “carbon-footprint.” Furthermore, the promise of this new PV technology and the fascinating underlying science make it a worthwhile endeavor to address these challenges.

14 SOLAR ENERGY↗

Detection and Perception of Sound by Eagles and Surrogate Raptors

One overarching objective of this program of study was the accumulation of objective, scientifically valid information relating to auditory performance of bald and golden eagles that may be used to guide the development of acoustic alerting/deterrence technologies intended to discourage encroachment into wind energy air spaces. To that end, analyses aimed at the characterization of sensitivity to sound in bald and golden eagles, along with findings in the supra-threshold, dynamic frequency spaces related to response latencies and amplitudes, leads us to conclude that bald, and golden eagles navigate the same basic working auditory space, as in other known and thus far characterized members of the diurnal raptor family. Specifically, bald and golden eagles, along with other raptor species within the group, operate in an auditory space characterized by a frequency band at least four octaves wide and centered on 2 kHz, with an upper frequency limit between 6 and 10 kHz at 80 dB SPL and a lower frequency limit that almost certainly extends below 0.2 kHz. Consequently, we recommend that signal designers use these data as a guideline in efforts to design effective and efficient acoustic alerting/deterrent systems. It is important to note that signal energy broadcast outside of this frequency band at moderate levels will not contribute to the efficacy of a deterrent but will add an unnecessary fraction to the overall acoustic pollution budget. The importance of this consideration is heightened by contemporaneous concerns related to the transmission of noise broadcast by wind energy farms. In addition, based on analyses of data acquired from red-tailed hawks using the same experimental paradigm and data acquisition system, we conclude that auditory function in the red-tailed hawk is sufficiently like that observed in bald and golden eagles to permit its use as a surrogate species. Response waveforms, threshold-frequency curves, and input-output characteristics match those of eagles closely. It should be noted however, that differences in sensitivity and slightly extended high-frequency limits of hearing should be taken into account when extrapolating findings from one species to the others. Although the inclusion of behavioral tests of red-tailed hawks to acoustic stimuli was beyond the scope of this investigation, future efforts to assess response parameters like signal-type preference and habituation rate will further elucidate their suitability to serve as eagle surrogates in behavioral studies; nonetheless, the species in question are well matched with respect to basic auditory performance. A second essential objective of this program of study was the acoustic characterization of a subset of calls comprising the vocal repertoires of bald and golden eagles that may be used to supplement auditory performance findings in the effort to guide the development of acoustic alerting signals. With regard to that objective, the vocal repertoires of both bald and golden eagle species are rich and varied. While similar in spectrographic structure, distinctive differences are also clear. Generally, golden eagles produce some calls with shorter durations, and similar “sounding” calls exhibit distinctively different spectrographic patterns than those of bald eagles. Both species produce calls that contain a wide variety of nonlinear elements that operate to enhance the rich and varied nature of commonly observed vocal products. Comparison of the average power spectra of commonly observed bald and golden eagle calls with threshold-frequency curves leads to the conclusion that call energies fall within the frequency bounds of hearing. Further, the acoustic energy of calls considered in this report tend to fall into overlapping, but different frequency ranges of the acoustic sensitivity curve. This condition may encourage signal designers to vary the frequency content of acoustic deterrence signals in the field. Finally, preliminary observations relating to the tendencies and proclivities of bald eagles to attend to the acoustic landscape lead to the conclusion that eagles monitor their immediate sound environment assiduously. Individuals respond to a variety of natural and synthetic sound signals reliably and, perhaps most relevant in the context of the engineering of acoustic alerting/deterrence technologies, habituation to most sounds considered in this effort was minimal. These preliminary results, while calling for extended behavioral testing, are promising and set the stage for the exportation of behavioral studies into real world scenarios.

17 WIND ENERGY↗

FY21 Status Report on Creep Rupture Testing at ANL to Support the Development of Alloy 709 Code Case

This report provides an update on the status of the creep rupture testing on the first commercial heat of Alloy 709 in support of the Alloy 709 Code Case development. Creep tests were performed in air on the lever-arm load frames in the Mechanical and Environmental Testing Laboratory at Argonne National Laboratory (ANL). In FY21, the focus was on the age-hardened ESR-1150°C material. Twenty two tests were initiated, among which ten were completed. This report presents the data from the completed tests. Metallographic characterization of the fractured specimens were performed and the results are included. The creep data enabled the preliminary analysis of the creep behavior of this material. The characterization showed the effect of test temperature and stress on the deformation microstructure.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗