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At least 145 records · Page 8

Phase Transitions in Organic and Organic/Inorganic Aerosol Particles

The phase state of aerosol particles can impact numerous atmospheric processes, including new particle growth, heterogeneous chemistry, cloud condensation nucleus formation, and ice nucleation. In this article, the phase transitions of inorganic, organic, and organic/inorganic aerosol particles are discussed, with particular focus on liquid-liquid phase separation (LLPS). The physical chemistry that determines whether LLPS occurs, at what relative humidity it occurs, and the resultant particle morphology is explained using both theoretical and experimental methods. The known impacts of LLPS on aerosol processes in the atmosphere are discussed. Finally, potential evidence for LLPS from field and chamber studies is presented. By understanding the physical chemistry of the phase transitions of aerosol particles, we will acquire a better understanding of aerosol processes, which in turn impact human health and climate.

Chemistry↗

Mitigating Scatter in Mechanical Properties in AISI 410 Fabricated via Arc-Based Additive Manufacturing Process

Wire-based metal additive manufacturing utilizes the ability of additive manufacturing to fabricate complex geometries with high deposition rates (above 7 kg/h), thus finding applications in the fabrication of large-scale components, such as stamping dies. Traditionally, the workhorse materials for stamping dies have been martensitic steels. However, the complex thermal gyrations induced during additive manufacturing can cause the evolution of an inhomogeneous microstructure, which leads to a significant scatter in the mechanical properties, especially the toughness. Therefore, to understand these phenomena, arc-based additive AISI 410 samples were fabricated using robotic gas metal arc welding (GMAW) and were subjected to a detailed characterization campaign. The results show significant scatter in the tensile properties as well as Charpy V-notch impact toughness data, which was then correlated to the microstructural heterogeneity and delta (δ) ferrite formation. Post-processing (austenitizing and tempering) treatments were developed and an ~70% reduction in the scatter of tensile data and a four-times improvement in the toughness were obtained. The changes in mechanical properties were rationalized based on the microstructure evolution during additive manufacturing. Based on these, an outline to tailor the composition of “printable” steels for tooling with isotropic and uniform mechanical properties is presented and discussed.

36 MATERIALS SCIENCE↗

Lead isotopic studies of the Samail ophiolite, Oman

The isotopic composition of Pb and the concentrations of U, Th, and Pb are determined for samples from massive sulfides and lithologic units of the Samail ophiolite. It is shown that the magma that formed the ophiolite was probably derived from a depleted mantle, similar in Pb isotopic composition to the source area of mid-ocean ridge basalt. The gross geochemical characteristics of the mantle sources have remained almost unchanged for the last 100 million years. It is also shown that the U-Th-Pb systematics of the Samail formation indicate that local vertical heterogeneity in the oceanic crust can result from crystal fractionation and metasomatism at, and near, an oceanic spreading center.

Chen, J. H.↗

Version 0 EOSDIS - An overview

Attention is given to NASA's Earth Observing System Data and Information System (EOSDIS), which is to be a single, distributed but internally consistent evolutionary system to support the planning and execution of EOS data acquisitions and to process, archive, and distribute EOS data products and selected non-EOS data to enable interdisciplinary studies of the earth. V0 EOSDIS, a logical step in this evolutionary process, is to address both technical and managerial challenges. Technical challenges include developing a multidiscipline, distributed system for searching and ordering data in a heterogeneous environment, and standardizing data formats and distribution techniques among differing communities and organizations. Managerial challenges include establishing and maintaining a structure consisting of geographically distributed entities such that cooperative development is carried out effectively despite organizational differences, maintaining interactions with the scientific community to ensure its close involvement despite its size and diversity, and keeping the expectations for V0 consistent with its schedules and resources.

Ramapriyan, H. K.↗

A Review of Spatial and Seasonal Changes in Condensation Clouds Observed During Aerobraking by MGS TES

Successful operation of the Mars Global Surveyor spacecraft beginning in September 1997, has permitted extensive infrared observations of condensation clouds during the martian southern summer and fall seasons (184 deg<L(sub s)<28 deg). Initially, thin (normal optical depth<0.06 at 825/cm) ice clouds and hazes were widespread, showing a latitudinal gradient. With the onset of a regional dust storm at L(sub s) = 224 deg, ice clouds essentially vanished in the southern hemisphere, to reappear gradually after the decay of the storm. The thickest clouds (optical depth approximately 0.6) were associated with major volcanic features. At L(sub s) =318 deg, the cloud at Ascraeus Mons was observed to disappear between 21:30 and 09:30, consistent with historically recorded diurnal behavior for clouds of this type. Limb observations showed extended optically thin (depth<0.04) stratiform clouds at altitudes up to 55 km. A water ice haze was present in the north polar night at altitudes up to 40 km; this probably provided heterogeneous nucleation sites for the formation of CO2 clouds at altitudes below the 1 mbar pressure level, where atmospheric temperatures dropped to the condensation point Of CO2.

Pearl, J. C.↗

A Review of Spatial and Seasonal Changes in Condensation Clouds Observed During Aerobraking by MGS TES

Successful operation of the Mars Global Surveyor spacecraft, beginning in September 1997, has permitted extensive infrared observations of condensation clouds during the martian southern summer and fall seasons (184 deg less than L(sub s) less than 28 deg). Initially, thin (normal optical depth less than 0.06 at 825/ cm) ice clouds and hazes were widespread, showing a latitudinal gradient. With the onset of a regional dust storm at L(sub s) = 224 deg, ice clouds essentially vanished in the southern hemisphere, to reappear gradually after the decay of the storm. The thickest clouds (optical depth approx. 0.6) were associated with major volcanic features. At L(exp s) = 318 deg, the cloud at Ascraeus Mons was observed to disappear between 21:30 and 09:30, consistent with historically recorded diurnal behavior for clouds of this type. Limb observations showed extended optically thin (depth less than 0.04) stratiform clouds at altitudes up to 55 km. A water ice haze was present in the north polar night at altitudes up to 40 km; this probably provided heterogeneous nucleation sites for the formation of CO2 clouds at altitudes below the 1 mbar pressure level, where atmospheric temperatures dropped to the condensation point of CO2.

Pearl, J. C.↗

Science Desk: General Overview

This viewgraph presentation discusses information sharing and other management procedures between related groups of scientists. ScienceOrganizer is an information repository and digital library for use by distributed scientific project teams which enables the storage and retrieval of heterogeneous project information in multiple formats. Over time, usage by persons results in the development of an increasingly information-rich knowledge base and network. Some of the engineering details include the determination of useful navigation hubs by which users can most easily navigate the information management system.

Keller, Richard M.↗

Investigating Type I Polar Stratospheric Cloud Formation Mechanisms with POAM Satellite Observations

Type Ia PSCs are believed to be composed of nitric acid hydrate particles. Recent results from the SOLVE/THESEO 2000 campaign showed evidence that this type of PSC was composed of a small number of very large particles capable of sedimentary denitrification of regions of the stratosphere. It is unknown whether homogeneous or heterogeneous nucleation is responsible for the formation of these PSCs. Arctic winters are tending to be colder in response to global tropospheric warming. The degree to which this influences ozone depletion will depend on the freezing mechanism of nitric acid hydrate particles. If nucleation is homogeneous it implies that the freezing process is an inherent property of the particle, while heterogeneous freezing means that the extent of PSCs will depend in part on the number of nuclei available. The Polar Ozone and Aerosol Measurement (POAM)II and III satellites have been making observations of stratospheric aerosols and Polar Stratospheric Clouds (PSCs) since 1994. Recently, we have developed a technique that can discriminate between Type Ia and Ib PSCs using these observations. A statistical approach is employed to demonstrate the robustness of this approach and results are compared with lidar measurements. The technique is used to analyze observations from POAM II and II during Northern Hemisphere winters where significant PSC formation occurred with the objective of exploring Type I PSC formation mechanisms. The different PSCs identified using this method exhibit different growth curve as expressed as extinction versus temperature.

Strawa, Anthony W.↗

Ionic Liquid Facilitated Solvent‐Phase Polymerization of Ultrasmooth Coatings of Polycatecholamines

Mussel-inspired polycatecholamine coatings and films have proven to be versatile materials for surface modification. However, the progress of chemically modified coatings with tailored properties has been slow due to the lack of definitive evidence of their polymeric structure. Polycatecholamines form aggregates during polymerization, and their formation mechanism has been a subject of debate owing to their insolubility in traditional molecular solvents. Exploiting the capability of ionic liquids (ILs) to exhibit strong electrostatic interactions, herein, the first solution-phase polymerization approach is reported to achieve polymerization of four catecholamines – dopamine (DA), norepinephrine (NE), L-3,4-dihydroxyphenylalanine (L-DOPA), and adrenaline (AD). Kinetic control over the polymerization process in the solution phase enabled it to follow the process with 1 H NMR spectroscopy, revealing the formation of structural features of resulting complex heterogeneous and soluble polymers. The polymers are both covalent and associative in nature. Solution phase polymerization prevented the formation of large aggregates in the solution, thus facilitating the formation of coatings that are ultra-smooth and have root mean square roughness of the order of sub-nm to nm scale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Glass formation - A contemporary view

The process of glass formation is discussed from several perspectives. Particular attention is directed to kinetic treatments of glass formation and to the question of how fast a given liquid must be cooled in order to form a glass. Specific consideration is paid to the calculation of critical cooling rates for glass formation, to the effects of nucleating heterogeneities and transients in nucleation on the critical cooling rates, to crystallization on reheating a glass, to the experimental determination of nucleation rates and barriers to crystal nucleation, and to the characteristics of materials which are most conducive to glass formation.

Uhlmann, D. R.↗

Surface heterogeneity propagation and homogenization for pouch cell-scale Li metal anodes

Li metal anode is a promising candidate for next-generation energy storage systems and is widely explored in Li-ion and solid-state batteries. Despite its potential, Li metal anodes face instabilities during long-term cycling, especially when paired with NMC or sulfur-based cathodes, where Li is cycled at high capacities of 6-8 mAh/cm2, equivalent to a thickness of 30-40 µm. During such extensive utilization, degradation mechanisms such as excessive solid electrolyte interphase (SEI), dendrites, and dead Li emerge, and ultimately lead to sudden failure and reduced cycle life. The origin of the degradation mechanisms stem from surface heterogeneities introduced during Li foil manufacturing and storage [1, 2]. As cycling progresses, the local heterogeneities propagate, resulting in uneven Li utilization and degradation-prone regions across the electrode [3], which consequently induce performance variations at the cell level. This heterogeneity propagation is particularly pronounced in large-format pouch cells in practical applications, where the surface effects are magnified. Without a clear understanding of the multi-scale heterogeneities and the development of surface homogenization methods, the performance consistency will be compromised, hindering the commercialization of Li metal batteries. In this presentation, we investigate the evolution of surface heterogeneity propagation on commercially available Li foils. We discover that inhomogeneous Li utilization appears as early as the first half-cycle of formation, manifesting as localized clusters and pits. In pouch cell configurations, these features exhibit areal density variations across the electrode on a scale of millimeters. To improve Li utilization homogeneity, a scalable mechanical brushing method is introduced to remove the chemically heterogeneous surface passivation layer. Furtherore, the influence of utilization homogeneity on cell-to-cell consistency is evaluated using 32 Li-NMC811 pouch cells divided into as-received and brushed Li groups. On the brushed Li, clusters and pits are no longer observable, and the cells exhibit significantly improved consistency in discharge capacity trajectories and cycle lifetime. Overall, this study highlights the role of Li surface utilization homogeneity on long-term cycling performance. Our research provides a pathway for improving large-area electrode uniformity and establishing evaluation methods for cell-to-cell consistency, both are key steps toward the commercialization of Li metal batteries and beyond. [1] Otto, Svenja-K., et al. "In-depth characterization of lithium-metal surfaces with XPS and ToF-SIMS: toward better understanding of the passivation layer." Chemistry of Materials 33.3 (2021): 859-867. [2] Hatzell, Kelsey, et al. "Aligning lithium metal battery research and development across academia and industry." Joule (2024). [3] Kim, Sangwook, et al. "Calendar life of lithium metal batteries: Accelerated aging and failure analysis." Energy Storage Materials 65 (2024): 103147.

25 - ENERGY STORAGE↗

Heterogeneous Chemistry Important in the Polar Stratosphere

Aircraft emissions have been thought to enhance the formation of polar stratospheric clouds in the Arctic winter, and therefore heterogeneous reactions on the surfaces of these clouds may accelerate the polar ozone depletion.

polar stratosphere heterogeneous chemistry ozone d↗

Dynamic crystallization of chondrule melts of porphyritic and radial pyroxene composition

Dynamic crystallization experiments in which heterogeneous nucleation is an important variable have been completed on four melts of chondrule composition. Compositions were chosen to best represent chondrules with porphyritic pyroxene and radial pyroxene textures. Experimental results show that heterogeneous nucleation is essential for the formation of porphyritic textures. Without preexisting nuclei, too much supercooling is established before crystallization is initiated and the textures are more likely to be dendritic or radial. In the near total absence of nuclei, radial textures can form at cooling rates as slow as 5 C/hr in this study. By varying the heterogeneous nucleation conditions and having a melt in which the appropriate phases are stable or metastable, analogs to most of the recognized chondrule textures can be produced in a single melt composition.

Lofgren, G.↗

Prolonged Stability of Pb-Catalyzed CO 2 Electroreduction to Methyl Formate in Acidic Methanol

Electrochemical CO 2 reduction from renewable energy is a promising route to mitigate greenhouse gas emissions from waste sources while generating value-added products. CO 2 electroreduction in methanol is particularly interesting due to the increased CO 2 solubility compared to water and the propensity to form methyl formate, a product absent in aqueous electrolysis. Here, four factors have been identified as critical to achieving prolonged high selectivity for methyl formate production on a Pb cathode in methanol: high pH near the electrode, low bulk pH, low water content, and regeneration of Pb 2+ sites. Increasing concentration of the formic acid product was observed to induce a selectivity shift towards hydrogen, which was mitigated by the in-situ conversion of the formic acid to methyl formate via an esterification reaction. Furthermore, co-electrolysis of CO 2 with dilute molecular oxygen (4% O 2 ) led to Pb catalyst repair through in-situ surface oxidation. Using CO 2 and dilute O 2 along with single-pass catholyte flow to maintain a low formic acid concentration, sustained high selectivity for methyl formate was attained at ~60% faradaic efficiency at -20 mA cm -2 for over 72 hours.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

An overview of the cosmic dust analogue material production in reduced gravity: the STARDUST experience

The formation, properties and chemical dynamics of microparticles are important in a wide variety of technical and scientific fields including synthesis of semiconductor crystals from the vapour, heterogeneous chemistry in the stratosphere and the formation of cosmic dust surrounding the stars. Gravitational effects on particle formation from vapors include gas convection and buoyancy and particle sedimentation. These processes can be significantly reduced by studying condensation and agglomeration of particles in microgravity. In addition, to accurately simulate particle formation near stars, which takes place under low gravity conditions, studies in microgravity are desired. We report here the STARDUST experience, a recent collaborative effort that brings together a successful American program of microgravity experiments on particle formation aboard NASA KC-135 Reduced Gravity Research Aircraft and several Italian research groups with expertise in microgravity research and astrophysical dust formation. The program goal is to study the formation and properties of high temperature particles and gases that are of interest in astrophysics and planetary science. To do so we are developing techniques that are generally applicable to study particle formation and properties, taking advantage of the microgravity environment to allow accurate control of system parameters.

NASA Discipline Exobiology↗

Heterogeneous Solid Electrolyte Interphase Interactions Dictate Interface Instability in Sodium Metal Electrodes

Sodium (Na) metal batteries have attracted recent attention due to their low cost and high abundance of Na. However, the advancement of Na metal batteries is impeded due to key challenges such as dendrite growth, solid electrolyte interphase (SEI) fracture, and low Coulombic efficiency. This study examines the coupled electro‐chemo‐mechanical interactions governing the electrodeposition stability and morphological evolution at the Na/electrolyte interface. The SEI heterogeneities influence transport and reaction kinetics leading to the formation of current and stress hotspots during Na plating. Further, it is demonstrated that the heterogeneity‐induced Na metal evolution and its influence on the stress distribution critically affect the mechanical overpotential, contributing to a faster SEI failure. The analysis reveals three distinct failure mechanisms—mechanical, transport, and kinetic—that govern the onset of instabilities at the interface. Finally, a comprehensive comparative study of SEI failure in Na and lithium (Li) metal anodes illustrates that the electrochemical and mechanical characteristics of the SEI are crucial in tailoring the anode morphology and interface stability. This work delineates mechanistic stability regimes cognizant of the SEI attributes and underlying failure modes and offers important guidelines for the design of artificial SEI layers for stable Na metal electrodes.

25 ENERGY STORAGE↗

Atomic scale investigation of aluminum incorporation, defects, and phase stability in β -(Al x Ga 1-x ) 2 O 3 films

The development of novel ultra-wide bandgap (UWBG) materials requires precise understanding of the atomic level structural origins that give rise to their important properties. We study the aluminum atom incorporation, defect formation, and their relationships with phase stability in β-(Al x Ga 1-x ) 2 O 3 films, a promising candidate for UWBG applications, to explain atomic scale structural characteristics and properties using a combination of quantitative scanning transmission electron microscopy (STEM) and density functional theory (DFT). Our STEM analysis indicates that ~54% of the incorporated Al substitutes on the octahedrally coordinated Ga 2 site in a series of films grown with different techniques and alloy concentrations. DFT calculations show that, while Al energetically prefers the octahedral site, surface reconstructions and kinetic limitations during the epitaxial growth are responsible for Al occupying both octahedral and tetrahedral sites in (Al x Ga 1-x ) 2 O 3 , ultimately limiting the stability of the β-phase at x < ~50%. Local heterogeneity of composition results in the formation of a planar defect, affecting the stability of the β-phase. The similarity of such inclusions to the metastable γ-phase is discussed.

36 MATERIALS SCIENCE↗

The Nucleosynthetic Heritage of Bennu

The OSIRIS-REx mission sampled the B-type asteroid Bennu and delivered 121.6 g of material to Earth in September 2023. Nucleosynthetic isotope variations are powerful tracers that can be used to establish relationships between different meteorite groups and the returned samples. They can also constrain the samples’ nucleosynthetic heritage, as well as mixing and reservoir formation in the protoplanetary disk. Nucleosynthetic variations reflect the heterogeneous distribution of isotopically distinct dust in the disk, and as such, they provide evidence for the formation of meteorite parent bodies from isotopically distinct dust reservoirs. They are thus also a means to identify exogenous clasts in Bennu materials. Here, we report Ti and Fe isotope data obtained from Bennu samples and carbonaceous chondrites. We also present Ti isotope data for hand-picked matrix from CV and CR chondrites. An isotopic dataset was obtained on aggregate sample OREX-803015-100 consisting of particles typically <500 μm; therefore, its composition represents an average for Bennu materials. A 20.66 mg aliquot was dissolved at Washington University, St. Louis. From this, 5 mg was analysed for Ti and Fe isotopes on a NeptunePlus MC-ICPMS at ETH Zurich; data from a separate aliquot, analysed at Lawrence Livermore National Laboratory, are reported in a companion abstract. Our results demonstrate a close relationship of Bennu to CI and Ryugu samples and therefore a formation outside the snowline, as hypothesized by the mission. Furthermore, the 50 Ti data from the CV and CR matrix fall consistently below the CI and Bennu values, indicating the presence of a uniform matrix mixed with ⁓0.1–0.7% of refractory inclusions in CIs and Bennu.

M. Schönbächler↗