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At least 973 records · Page 54

Spatiotemporal and Statistical Mapping of Transition Metal Equilibria in Alkaline Media

Transition metal dissolution and redeposition (D/R) kinetics in alkaline media play a critical role in various chemical and electrochemical processes. Competitive reaction kinetics between different transition metals can modulate individual metal behavior in these processes. To date, these phenomena have remained largely unmeasured, and even when captured, they are difficult to statistically characterize due to their dynamic nature, simultaneous occurrence, and spatially heterogeneous nature. Here, in this study, we develop a statistical analysis framework based on in situ and operando X-ray fluorescence microscopy (XFM) to investigate the relative D/R kinetics of multiple transition metals in alkaline media. By employing statistical analysis, we quantify the spatial distribution of D/R species and assess the rate at which the system reaches equilibrium under varying reaction conditions. We show that pH does not simply change the rate of dissolution and redeposition, but reorganizes the cross-element kinetic correlations among Ni, Fe, and Mn and accelerates the spatial equilibration of D/R events, as quantified through correlation analysis, reaction-rate estimation, probability function distributions, and texture-based monitoring statistics. Additionally, we demonstrate how modifying the solvent environment can influence D/R kinetics, providing a pathway for tuning materials synthesis and process optimization. Our study offers valuable insights into the complex interplay between different transition metals and provides a reliable statistical framework for spatial analysis of diverse imaging data sets, enabling deeper extraction of latent information across multiple modalities.

36 MATERIALS SCIENCE↗

Morphological Control of Chromophore Spin State in Zinc Porphyrin–Peptide Assemblies

Self-assembled peptide micelles and fibers demonstrate unique control over the photophysical properties of the bound, light-activated chromophore, zinc protoporphyrin IX, (PPIX)Zn. Micelles encapsulate either a mixture of uncoordinated and coordinated (PPIX)Zn or all coordinated depending on the ratio of peptide/porphyrin. As the ratio increases toward a 1:1 micelle/porphyrin ratio, providing the chromophore with a discrete coordination environment reminiscent of unstructured proteins, the micelles favor triplet formation. Fibers, however, promote a linear array of porphyrin molecules that dictates exciton hopping and excimer formation at ratios as high as 60:1, peptide/porphyrin. However, even in fibers, the formation of the triplet species increases with increasing peptide/porphyrin ratio due to increased spatial separation between neighboring chromophores facilitating intersystem crossing. Full characterization of the micelles structures and comparison to the fibers lead to the comparison with natural systems and the ability to control the excited populations that have utility in photocatalytic processes. In addition, the incorporation of a second chromophore, heme, yields an electron transfer pathway in both micelles and fibers that highlights the utility of the peptide assemblies when engineering multichromophore arrays as inspired by natural, photosynthetic proteins.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

macroMS: Image-Guided Analysis of Random Objects by Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometry

Mass spectrometry imaging is well-suited to characterizing sample surfaces for their chemical content in a spatially resolved manner. However, when the surface contains small objects with significant empty spaces between them, more efficient approaches to sample acquisition are possible. Image-guided mass spectrometry (MS) enables high-throughput analysis of a diverse range of sample types, such as microbial colonies, liquid microdroplets, and others, by recognizing and analyzing selected location targets in an image. Here, we describe an imaging protocol and macroMS, an online software suite that can be used to enhance MS measurements of macroscopic samples that are imaged by a camera or a flatbed scanner. Furthermore, the web-based tool enables users to find and filter targets from the optical images, correct optical distortion issues for improved spatial location of selected targets, input the custom geometry files into an MS device to acquire spectra at the selected locations, and finally, perform limited data analysis and use visualization tools to aid locating samples containing compounds of interest. Using the macroMS suite, an enzyme mutant library of Saccharomyces cerevisiae and nL droplet arrays of Escherichia coli and Pseudomonas fluorescens have been assayed at a rate of ~2 s/sample.

47 OTHER INSTRUMENTATION↗

Gas Transfer Across Air‐Water Interfaces in Inland Waters: From Micro‐Eddies to Super‐Statistics

In inland water covering lakes, reservoirs, and ponds, the gas exchange of slightly soluble gases such as carbon dioxide, dimethyl sulfide, methane, or oxygen across a clean and nearly flat air‐water interface is routinely described using a water‐side mean gas transfer velocity $\overline{k_{L}}$, where overline indicates time or ensemble averaging. The micro‐eddy surface renewal model predicts $\overline{k_{L}}$ = α o Sc -1/2 ($v\bar{ϵ}$) 1/4 , where Sc is the molecular Schmidt number, $v$ is the water kinematic viscosity, and $\bar{ϵ}$ is the waterside mean turbulent kinetic energy dissipation rate at or near the interface. While α o = 0.39 - 0.46 has been reported across a number of data sets, others report large scatter or variability around this value range. It is shown here that this scatter can be partly explained by high temporal variability in instantaneous ϵ around $\bar{ϵ}$, a mechanism that was not previously considered. As the coefficient of variation (CV e ) in ϵ increases, α o must be adjusted by a multiplier (1 = CV e 2 ) -3/32 that was derived from a log‐normal model for the probability density function of ϵ. Reported variations in α o with a macro‐scale Reynolds number can also be partly attributed to intermittency effects in ϵ. Such intermittency is characterized by the long‐range (i.e., power‐law decay) spatial auto‐correlation function of ϵ. That α o varies with a macro‐scale Reynolds number does not necessarily violate the micro‐eddy model. Instead, it points to a coordination between the macro‐ and micro‐scales arising from the transfer of energy across scales in the energy cascade.

Batchelor scale↗

Unsupervised data mining in nanoscale x-ray spectro-microscopic study of NdFeB magnet

Novel developments in X-ray based spectro-microscopic characterization techniques have increased the rate of acquisition of spatially resolved spectroscopic data by several orders of magnitude over what was possible a few years ago. This accelerated data acquisition, with high spatial resolution at nanoscale and sensitivity to subtle differences in chemistry and atomic structure, provides a unique opportunity to investigate hierarchically complex and structurally heterogeneous systems found in functional devices and materials systems. However, handling and analyzing the large volume data generated poses significant challenges. Here we apply an unsupervised data-mining algorithm known as DBSCAN to study a rare-earth element based permanent magnet material, Nd 2 Fe 14 B. We are able to reduce a large spectro-microscopic dataset of over 300,000 spectra to 3, preserving much of the underlying information. Scientists can easily and quickly analyze in detail three characteristic spectra. Our approach can rapidly provide a concise representation of a large and complex dataset to materials scientists and chemists. For instance, it shows that the surface of common Nd 2 Fe 14 B magnet is chemically and structurally very different from the bulk, suggesting a possible surface alteration effect possibly due to the corrosion, which could affect the material’s overall properties.

36 MATERIALS SCIENCE↗

Shock drive capabilities of a 30-Joule laser at the matter in extreme conditions hutch of the Linac Coherent Light Source

In this paper, we measure the shock drive capabilities of a 30 J, nanosecond, 527 nm laser system at the matter in extreme conditions hutch of the Linac Coherent Light Source. Using a velocity interferometer system for any reflector, we ascertain the maximum instantaneous ablation pressure and characterize its dependence on a drive laser spot size, spatial profile, and temporal profile. We also examine the effects of these parameters on shock spatial and temporal uniformity. Our analysis shows the drive laser capable of generating instantaneous ablation pressures exceeding 160 GPa while maintaining a 1D shock profile. We find that slope pulses provide higher instantaneous ablation pressures than plateau pulses. Our results show instantaneous ablation pressures comparable to those measured at the Omega Laser Facility in Rochester, NY under similar optical drive parameters. In conclusion, we analyze how optical laser ablation pressures are compare with known scaling relations, accounting for variable laser wavelengths.

47 OTHER INSTRUMENTATION↗

Thermoreflectance imaging of electromigration evolution in asymmetric aluminum constrictions

Electromigration (EM) is a phenomenon whereby the flow of current in metal wires moves the underlying atoms, potentially inducing electronic interconnect failures. The continued decrease in commercial lithographically defined feature sizes means that EM presents an increasing risk to the reliability of modern electronics. To mitigate these risks, it is important to look for novel mechanisms to extend lifetime without forfeiting miniaturization. Typically, only the overall increase in the interconnect resistance and failure voltage are characterized. However, if the current flows non-uniformly, spatially resolving the resulting hot spots during electromigration aging experiments may provide better insights into the fundamental mechanisms of this process. Here in this study, we focus on aluminum interconnects containing asymmetric reservoir and void pairs with contact pads on each end. Such reservoirs are potential candidates for self-healing. Thermoreflectance imaging was used to detect hot spots in electrical interconnects at risk of failure as the voltage was gradually increased. It reveals differential heating with increasing voltage for each polarity. We find that while current flow going from a constriction to a reservoir causes a break at the void, the identical structure with the opposite polarity can sustain higher current (J = 21 × 10 6 A/cm 2 ) and more localized joule heating and yet is more stable. Ultimately, a break takes place at the contact pad where the current flows from narrow interconnect to larger pads. In summary, thermoreflectance imaging with submicron spatial resolution provides valuable information about localized electromigration evolution and the potential role of reservoirs to create more robust interconnects.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Flow field characteristics of a 127-pin rod bundle with hexagonal spacer grids

A determination of nominal flow phenomena in liquid metal fast reactor (LMFR) fuel assemblies is critical toward generation-IV reactor development. Axially positioned spacer grids are used to maintain the geometry of hexagonal rod bundles and simultaneously introduce perturbations in the flow. Three-dimensional (3D) printed asymmetric honeycomb spacer grids were installed in a prototypical 127-pin LMFR fuel assembly model to study complex fluid dynamics interactions induced by the spacer grid and rods. To characterize flow dynamics in this intricate geometry, time-resolved particle image velocimetry (TR-PIV) using the matched-index-of-refraction method was employed to obtain non-intrusive velocity measurements for three axial planes (one near-wall and two interior planes) at a Reynolds number of 6000. The statistical TR-PIV results compared sub-channel-dependent normalized time-averaged velocity, velocity fluctuations, Reynolds stress, vorticity, and turbulence kinetic energy distributions. TR-PIV line profiles characterized downstream spacer grid flow dynamics. Two-point spatial and spatial–temporal cross-correlation fields revealed local coherent structures and quantified convection velocities of traveling vortices. Spatial–temporal decomposition using dynamic mode decomposition (DMD) applied to the near-wall vorticity fields extracted turbulent structures and flow instabilities in the wake region of the spacer grid, along with their decay and frequency rates. Reduced-order velocity fields from DMD reconstructions identified the most energy-containing coherent structures persistent in the near-wall region. This research provides experimental data sets and analyses of flow behavior in rod bundles with hexagonal spacer grids. In conclusion, the results are critical toward LMFR design and geometry optimization, crucial for the validation of computational fluid dynamics and reduced-order flow models.

42 ENGINEERING↗

Scanning Josephson spectroscopy on the atomic scale

The Josephson effect provides a direct method to probe the strength of the pairing interaction in superconductors. By measuring the phase fluctuating Josephson current between a superconducting tip of a scanning tunneling microscope and a BCS superconductor with isolated magnetic adatoms on its surface, we demonstrate that the spatial variation of the pairing order parameter can be characterized on the atomic scale. This system provides an example where the local pairing potential suppression is not directly reflected in the spectra measured via quasiparticle tunneling. Spectroscopy with such superconducting tips also shows signatures of previously unexplored Andreev processes through individual impurity-bound Shiba states. Furthermore, the atomic resolution achieved here establishes scanning Josephson spectroscopy as a promising technique for the study of novel superconducting phases.

Andreev reflection↗

Tracking Aerosol Convective Interactions Experiment (TRACER) Science Plan

Convective clouds play an important role in the Earth’s climate system as a driver of large-scale circulations and a primary mechanism for the transport of heat, moisture, aerosols, and momentum throughout the troposphere. Despite their climatic importance, multi-scale models continue to have persistent biases produced by insufficient representation of convective clouds. This is the result of an incomplete understanding of key processes such as convective initiation, updraft and downdraft dynamics, cloud and precipitation microphysics, and aerosol-convection interactions. The Aerosol-Cloud-Precipitation-Climate Initiative, an international research group dedicated to advancing understanding of aerosol impacts on clouds relevant to climate, has identified the Houston, Texas region as an optimal location for targeted studies of aerosol-convection interactions within frequently developing isolated deep convection. Houston lies within a humid subtropical climate regime, where onshore flow and sea-breeze convection interact with a range of aerosol conditions associated with Houston’s urban and industrial emissions. Pilot studies have suggested that convective clouds in this region are potentially significantly impacted by the varying aerosol conditions. To increase our understanding of convective cloud life cycles and aerosol-convection interactions, the Tracking Aerosol Convection Interactions Experiment (TRACER) aims to collect a comprehensive data set focused on the evolution of convective clouds and the environment (including aerosol, cloud, thermodynamics, and lightning) in which the clouds initiate, grow, and decay. A unique component of TRACER is that a large number of individual, isolated convective cells will be tracked and measured in high spatial and temporal resolution for the purposes of: (i) Characterizing and linking convective cloud kinematic and microphysical life cycles, (ii) Quantifying environmental thermodynamic and kinematic controls on convective life cycle properties, (iii) Isolating and quantifying the impacts of aerosol properties on convective cloud kinematic and microphysical evolution. TRACER includes a one-year deployment of the U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) user facility’s first ARM Mobile Facility (AMF1) and second-generation C-Band Scanning ARM Precipitation Radar (CSAPR2) aimed at collecting statistical data sets of cloud, precipitation, atmospheric state, and aerosol under varying aerosol loading and local circulation (sea breeze and urban heat island) conditions. A four-month intensive operational period (IOP) from June through September will include deployment of an ancillary site with aerosol, atmospheric state, and precipitation measurements at a location rarely impacted by Houston’s anthropogenic emissions, which will be commonplace near the AMF1 site. Convective cell tracking by the CSAPR2 will provide high-resolution polarimetric and velocity observations under a range of environmental (including aerosol loading) conditions. High-frequency radiosonde launches will capture quickly evolving thermodynamic and kinematic conditions near convective cells, a requirement for isolating aerosol effects on clouds. TRACER will additionally leverage a lightning mapping array, surface meteorological networks, and air pollution networks, and proposals will be entered to deploy additional mobile radar and radiosonde assets during the IOP. This unique combination of cloud, precipitation, lightning, aerosol, and atmospheric state measurements associated with tracked convective cells will ultimately improve our understanding of the convective cloud life cycle and its interaction with individual environmental factors such that improved, next-generation cumulus, microphysics, turbulence, and aerosol parameterizations can be designed.

Convective clouds, aerosols, cloud life cycle, atm↗

Echo-Enabled Harmonic Generation Studies for the FERMI Free-Electron Laser

Studying ultrafast processes on the nanoscale with element specificity requires a powerful femtosecond source of tunable extreme-ultraviolet (XUV) or x-ray radiation, such as a free-electron laser (FEL). Current efforts in FEL development are aimed at improving the wavelength tunability and multicolor operation, which will potentially lead to the development of new characterization techniques offering a higher chemical sensitivity and improved spatial resolution. One of the most promising approaches is the echo-enabled harmonic generation (EEHG), where two external seed lasers are used to precisely control the spectro-temporal properties of the FEL pulse. Here, we study the expected performance of EEHG at the FERMI FEL, using numerical simulations. We show that, by employing the existing FERMI layout with minor modifications, the EEHG scheme will be able to produce gigawatt peak-power pulses at wavelengths as short as 5 nm. We discuss some possible detrimental effects that may affect the performance of EEHG and compare the results to the existing double-stage FEL cascade, currently in operation at FERMI. Finally, our simulations show that, after substantial machine upgrades, EEHG has the potential to deliver coherent multicolor pulses reaching wavelengths as short as 3 nm, enabling x-ray pump-x-ray probe experiments in the water window.

47 OTHER INSTRUMENTATION↗

An investigation of the facsimile camera response to object motion

A general analytical model of the facsimile camera response to object motion is derived as an initial step toward characterizing the resulting image degradation. This model expresses the spatial convolution of a time-varying object radiance distribution and camera point-spread function for each picture element in the image. Time variations and these two functions during each convolution account for blurring of small image detail, and variations between, as well as during, successive convolutions account for geometric image distortions. If the object moves beyond the angular extent of several picture elements while it is being imaged, then geometric distortion tends to dominate blurring as the primary cause of image degradation. The extent of distortion depends not only on object size and velocity but also on the direction of object motion, and is therefore difficult to classify in a general sense.

Huck, F. O.↗

A plan for the characterization, calibration, and evaluation of LAPR-2

A new airborne Linear Array Pushbroom Radiometer (LAPR-II) was built. LAPR-II will use linear arrays of silicon detectors to acquire four channels of digital image data for spectral bands within the visible and near infrared portions of the spectrum (0.4 - 1.0 micrometers). The data will be quantized to 10 bits, and spectral filters for each channel will be changeable in flight. The instrument will initially be flown aboard a NASA/Wallops' aircraft, and off nadir pointing of LAPR-II will be possible. Together, the instrument and its platform will provide a flexible readily available source of digital image data for scientific experiments. If LAPR-II is to serve as a precise scientific instrument, the instrument's characteristics must be quantitatively described and the data must be calibrated with respect to absolute radiometric units. The LAPR-II is described and the work required to characterize the instrument's spectral response, radiometric response, and spatial resolution and to calibrate the response from the many detectors per array is outlined.

Ilrons, J. R.↗

Static and dynamic properties of incommensurate smectic-A(IC) liquid crystals

The elasticity, topological defects, and hydrodynamics of the incommensurate smectic A(IC) phase liquid crystals are studied. The phase is characterized by two colinear mass density waves of incommensurate spatial frequency. The elastic free energy is formulated in terms of a displacement field and a phason field. It is found that the topological defects of the system are dislocations with a nonzero phason field and phason field components. A two-dimensional Burgers lattice for these dislocations is introduced. It is shown that the hydrodynamic modes of the phase include first- and second-sound modes whose direction-dependent velocities are identical to those in ordinary smectics.

Lubensky, T. C.↗

The impact of land-surface wetness heterogeneity on mesoscale heat fluxes

Vertical heat fluxes associated with mesoscale circulations generated by land-surface wetness discontinuities are often stronger than turbulent fluxes, especially in the upper part of the atmospheric planetary boundary layer. As a result, they contribute significantly to the subgrid-scale fluxes in large-scale atmospheric models. Yet they are not considered in these models. To provide some insights into the possible parameterization of these fluxes in large-scale models, a state-of-the-art mesoscale numerical model was used to investigate the relationships between mesoscale heat fluxes and atmospheric and land-surface characteristics that play a key role in the generation of mesoscale circulations. The distribution of land-surface wetness, the wavenumber and the wavelength of the land-surface discontinuities, and the large-scale wind speed have a significant impact on the mesoscale heat fluxes. Empirical functions were derived to characterize the relationships between mesoscale heat fluxes and the spatial distribution of land-surface wetness. The strongest mesoscale heat fluxes were obtained for a wavelength of forcing corresponding approximately to the local Rossby deformation radius. The mesoscale heat fluxes are weakened by large-scale background winds but remain significant even with moderate winds.

Chen, Fei↗

Equatorial Density Irregularity Structures at Intermediate Scales and Their Temporal Evolution

We examine high resolution measurements of ion density in the equatorial ionosphere from the AE-E satellite during the years 1977-1981. Structure over spatial scales from 18 km to 200 m is characterized by the spectrum of irregularities at larger and smaller scales and at altitudes above 350 km and below 300 km. In the low-altitude region, only small amplitude large-scale (lambda greater than 5 km) density modulations are often observed, and thus the power spectrum of these density structures exhibits a steep spectral slope at kilometer scales. In the high-altitude region, sinusoidal density fluctuations, characterized by enhanced power near 1-km scale, are frequently observed during 2000-0200 LT. However, such fluctuations are confined to regions at the edges of larger bubble structures where the average background density is high. Small amplitude irregularity structures, observed at early local time hours, grow rapidly to high-intensity structures in about 90 min. Fully developed structures, which are observed at late local time hours, decay very slowly producing only-small differences in spectral characteristics even 4 hours later. The local time evolution of irregularity structure is investigated by using average statistics for low-(1% less than sigma less than 5%) and high-intensity (sigma greater than 10%) structures. At lower altitudes, little chance in the spectral slope is seen as a function of local time, while at higher attitudes the growth and maintenance of structures near 1 km scales dramatically affects the spectral slope.

Kil, Hyosub↗

BOREAS AFM-12 1-km AVHRR Seasonal Land Cover Classification

The Boreal Ecosystem-Atmosphere Study (BOREAS) Airborne Fluxes and Meteorology (AFM)-12 team's efforts focused on regional scale Surface Vegetation and Atmosphere (SVAT) modeling to improve parameterization of the heterogeneous BOREAS landscape for use in larger scale Global Circulation Models (GCMs). This regional land cover data set was developed as part of a multitemporal one-kilometer Advanced Very High Resolution Radiometer (AVHRR) land cover analysis approach that was used as the basis for regional land cover mapping, fire disturbance-regeneration, and multiresolution land cover scaling studies in the boreal forest ecosystem of central Canada. This land cover classification was derived by using regional field observations from ground and low-level aircraft transits to analyze spectral-temporal clusters that were derived from an unsupervised cluster analysis of monthly Normalized Difference Vegetation Index (NDVI) image composites (April-September 1992). This regional data set was developed for use by BOREAS investigators, especially those involved in simulation modeling, remote sensing algorithm development, and aircraft flux studies. Based on regional field data verification, this multitemporal one-kilometer AVHRR land cover mapping approach was effective in characterizing the biome-level land cover structure, embedded spatially heterogeneous landscape patterns, and other types of key land cover information of interest to BOREAS modelers.The land cover mosaics in this classification include: (1) wet conifer mosaic (low, medium, and high tree stand density), (2) mixed coniferous-deciduous forest (80% coniferous, codominant, and 80% deciduous), (3) recent visible bum, vegetation regeneration, or rock outcrops-bare ground-sparsely vegetated slow regeneration bum (four classes), (4) open water and grassland marshes, and (5) general agricultural land use/ grasslands (three classes). This land cover mapping approach did not detect small subpixel-scale landscape features such as fens, bogs, and small water bodies. Field observations and comparisons with Landsat Thematic Mapper (TM) suggest a minimum effective resolution of these land cover classes in the range of three to four kilometers, in part, because of the daily to monthly compositing process. In general, potential accuracy limitations are mitigated by the use of conservative parameterization rules such as aggregation of predominant land cover classes within minimum horizontal grid cell sizes of ten kilometers. The AFM-12 one-kilometer AVHRR seasonal land cover classification data are available from the Earth Observing System Data and Information System (EOSDIS) Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center (DAAC). The data files are available on a CD-ROM (see document number 20010000884).

Steyaert, Lou↗

BOREAS HYD-8 1994 Gravimetric Moss Moisture Data

The Boreal Ecosystem-Atmosphere Study (BOREAS) Hydrology (HYD)-8 team made measurements of surface hydrological processes that were collected at the Northern Study Area-Old Black Spruce (NSA-OBS) Tower Flux site in 1994 and at Joey Lake, Manitoba, to support its research into point hydrological processes and the spatial variation of these processes. The data collected may be useful in characterizing canopy interception, drip, throughfall, moss interception, drainage, evaporation, and capacity during the growing season at daily temporal resolution. This particular data set contains the gravimetric moss moisture measurements from June to September 1994. A nested spatial sampling plan was implemented to support research into spatial variations of the measured hydrological processes and ultimately the impact of these variations on modeled carbon and water budgets. These data are stored in tabular ASCII files. The HYD-08 1994 gravimetric moss moisture data are available from the Earth Observing System Data and Information System (EOSDIS) Oak Ridge National Laboratory (ORNL) Distributed Active Archive Center (DAAC). The data files are available on a CD-ROM (see document number 20010000884).

Wang, Xuewen↗