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DOE OSTI2020

Spatiotemporal flame propagations, combustion and solid particle emissions from lean and stoichiometric gasoline direct injection engine operation

Increased particle number and mass emissions in gasoline direct injection (GDI) engines should require to investigate in-cylinder flame and combustion characteristics associated with primary source of particle emissions. In this article, in-cylinder spatiotemporal flame luminosity is quantitatively characterized to features combustion process and solid particle emissions from a GDI engine operating in two lean and one stoichiometric modes. Low- and high-steady state operating points were used to compare combustion strategies on flame development and emission characteristics. A fiber-optic sensor composed of eight measurement channels detected the flame front and the direction of the flame propagation in the combustion chamber. Solid particle emissions in the exhaust were measured using an engine exhaust particle sizer and a micro soot sensor. Results of the experiments showed that two lean combustion modes by injection strategies resulted in distinct combustion and flame development. Lean combustion modes generated high diffusion flame by burning stratified rich-mixture. Although the lean cases resulted in strong diffusion flames, the lean-homogeneous produced similar particle size distributions with the stoichiometric mode with high ash particles. Piston pool fires on the piston surface in the lean-stratified mode induced a large accumulation mode with high particle mass concentrations.

42 ENGINEERING↗

DOE OSTI2025

Excitons in fractionally filled moiré superlattices

Long-range Coulomb forces give rise to correlated insulating states when charge particles populate a moiré superlattice at certain fractional filling factors. Such behavior is characterized by a broken translation symmetry wherein particles spontaneously form a Wigner crystal. Here, focusing on the experimental findings of Xu et al. [Nature (London) 587, 214 (2020)], we present a theory that captures the correlated insulating state of a fractionally filled moiré superlattice through the energy shift and change in oscillator strength of the exciton absorption resonance. The theory shows that the experimental findings can only be supported if the electrons reside in a charge-ordered state (i.e., electrons are not randomly distributed among the sites of the moiré superlattice). Furthermore, we explain why the energy shifts of exciton resonances are qualitatively different in cases where the superlattice is nearly empty compared with a superlattice whose sites are doubly occupied.

excitons↗

NASA NTRS1984

Plasma and energetic particle structure upstream of a quasi-parallel interplanetary shock

ISEE 1, 2 and 3 data from 1978 on interplanetary magnetic fields, shock waves and particle energetics are examined to characterize a quasi-parallel shock. The intense shock studied exhibited a 640 km/sec velocity. The data covered 1-147 keV protons and electrons and ions with energies exceeding 30 keV in regions both upstream and downstream of the shock, and also the magnitudes of ion-acoustic and MHD waves. The energetic particles and MHD waves began being detected 5 hr before the shock. Intense halo electron fluxes appeared ahead of the shock. A closed magnetic field structure was produced with a front end 700 earth radii from the shock. The energetic protons were cut off from the interior of the magnetic bubble, which contained a markedly increased density of 2-6 keV protons as well as the shock itself.

Kennel, C. F.↗

NASA NTRS1975

Lunar soil and surface processes studies

Glass particles in lunar soil were characterized and compared to terrestrial analogues. In addition, useful information was obtained concerning the nature of lunar surface processes (e.g. volcanism and impact), maturity of soils and chemistry and heterogeneity of lunar surface material. It is felt, however, that the most important result of the study was that it demonstrated that the investigation of glass particles from the regolith of planetary bodies with little or no atmospheres can be a powerful method for learning about the surface processes and chemistry of planetary surfaces. Thus, the return of samples from other planetary bodies (especially the terrestrial planets and asteroids) using unmanned spacecraft is urged.

Glass, B. P.↗

DOE OSTI2018

IgG Antibody 3D Structures and Dynamics

Antibodies are vital for human health because of their ability to function as nature’s drugs by protecting the body from infection. In recent decades, antibodies have been used as pharmaceutics for targeted therapy in patients with cancer, autoimmune diseases, and cardiovascular diseases. Capturing the dynamic structure of antibodies and characterizing antibody fluctuation is critical for gaining a deeper understanding of their structural characteristics and for improving drug development. Current techniques for studying three-dimensional (3D) structural heterogeneity and variability of proteins have limitations in ascertaining the dynamic structural behavior of antibodies and antibody-antigen complexes. Here, we review current techniques used to study antibody structures with a focus on the recently developed individual-particle electron tomography (IPET) technique. IPET, as a particle-by-particle methodology for 3D structural characterization, has shown advantages in studying structural variety and conformational changes of antibodies, providing direct imaging data for biomolecular engineering to improve development and clinical application of synthetic antibodies.

antibody dynamics↗

NASA NTRS1998

Resuspension of Particles by Aerodynamic Deagglomeration

A deagglomerator system was developed, characterized by laboratory tests and flown under low gravity (low-g) microgravity conditions. Requirements for a dry powder deagglomeration system were generated by university and National Aeronautics and Space Administration (NASA) scientists from diverse fields of interest including exobiology, planetary sciences, and atmospheric sciences. Existing deagglomeration methods and devices are reviewed. An aerosol generation method suitable for dry powders over a large range of particles sizes and types at high concentrations with consistent deagglomeration efficiency was evaluated. Development of a pulsed-flow laboratory device and experimental approaches to meet the requirements without being g- dependent are described. Results of laboratory one-g quantitative characterization on one type of dry powder particle generator is discussed. Data from NASA low-g tests are summarized.

Fonda, Mark↗

DOE OSTI2024

Experimental investigation of Multi-Mode heat transfer to a Free-Falling dilute particle cloud in a heated vertical tube

The development of dilute particle heat exchangers and reactors for advanced energy systems requires an understanding of the multi-mode heat transfer from a heated wall to falling particles. This study presents experimental results of the overall heat transfer coefficient for a free-falling, dilute flow of particles with solid volume fraction from 0.0005 to 0.006 corresponding to feed rates from 3.7 kg s -1 m -2 to 44 kg s -1 m -2 in a vertical, heated tube containing quiescent air at atmospheric pressure. Tube wall temperatures are varied between 300°C to 900°C while keeping the particle inlet temperature constant. The experimental results show that the overall heat transfer coefficient is a strong function of particle feed rate and surface temperature. Good agreement was obtained with prior studies conducted at comparable temperatures but lower particle feed rates (< 4 kg m -2 s -1 ). The established correlations for particle-to-wall radiation and particle-to-gas convection were used to estimate the wall-to-gas convective contribution from the measured overall heat transfer coefficient. The experimental results indicated a 4 to 6 times improvement in the wall convection in the solid-gas mixture compared to that expected from natural convection in a single-phase gas. Furthermore, the data presented here are applicable to characterize heat transfer in dilute particle heat exchangers, furnaces, and solar receivers.

14 SOLAR ENERGY↗

DOE OSTI2023

Vertical distribution of boundary layer new particle formation and implications for nanoparticle growth mechanisms (Final Report)

New particles can form high above ground in the atmosphere before such formation events are observed by ground-based instruments. Once formed, these particles can take up significant amounts of water vapor, which has implications on the mechanisms by which nanoparticles grow and, ultimately, impact cloud formation processes. These observations motivated the research performed in this project using a combination of modeling, laboratory experiments, and the analysis of field observations. We hypothesized is that ground-based measurements do not always accurately represent the location and timing of new particle formation events, nor do they adequately characterize the dominant physical and chemical processes that are responsible for the subsequent growth of newly formed particles. Essentially, we wanted to study the new particle formation process under conditions that we expect may be more relevant to the actual location in the atmosphere where such events take place, which are often characterized by higher relative humidities, lower temperatures, and a broader range of precursors and oxidants compared to those observed at ground level. This project had two main objectives, each of which directly addressed our hypothesis. Our first is to investigate the timing, distribution, meteorological conditions, and nanoparticle properties associated with boundary layer new particle formation through the analysis of ARM field campaigns such as HI-SCALE and long-term observations and observations performed in other locales such as in China and India where atmospheric conditions could play a crucial role in determining the mechanisms of new particle formation. This activity provided a comprehensive description, both in time and in space, of the gases and nanoparticle properties that are responsible for these events. We also performed modeling studies to explore the vertical profile and timing of new particle formation events from these campaigns. Our second objective was to perform laboratory and process-level modeling studies to investigate the role that conditions such as low ambient temperature, high relative humidity, and different oxidants such as nitrate radical play in determining unique chemical pathways for nanoparticle growth. In doing so, we revisited the representation of nanoparticle growth in global models and updated assumptions of formation and growth based on the findings of the field, laboratory, and process-level-model work. Our research provides crucial insights into the most important regions of the atmospheric boundary layer for future observational and modeling studies. It also identifies the most relevant environmental conditions, precursors, and oxidants that are responsible for nanoparticle growth, which will aid in the design of laboratory studies and process-level model experiments. The unique pathways that we discovered can be incorporated into regional and global models, thereby improving predictions and attribution of the role of new particle formation in, e.g., air pollution formation and cloud properties.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2023

Resolving protein-mineral interfacial interactions during in vitro mineralization by atom probe tomography

Organic macromolecules exert remarkable control over the nucleation and growth of inorganic crystallites during (bio)mineralization, as exemplified during enamel formation where the protein amelogenin regulates the formation of hydroxyapatite (HAP). However, it is poorly understood how fundamental processes at the organic-inorganic interface, such as protein adsorption and/or incorporation into minerals, regulates nucleation and crystal growth due to technical challenges in observing and characterizing mineral-bound organics at high-resolution. Here, atom probe tomography techniques were developed and applied to characterize amelogenin-mineralized HAP particles in vitro, revealing distinct organic-inorganic interfacial structures and processes at the nanoscale. Specifically, visualization of amelogenin across the mineralized particulate demonstrates protein can become entrapped during HAP crystal aggregation and fusion. Identification of protein signatures and structural interpretations were further supported by standards analyses, i.e., defined HAP surfaces with and without amelogenin adsorbed. These findings represent a significant advance in the characterization of interfacial structures and, more so, interpretation of fundamental organic-inorganic processes and mechanisms influencing crystal growth. Ultimately, this approach can be broadly applied to inform how potentially unique and diverse organic-inorganic interactions at different stages regulates the growth and evolution of various biominerals.

36 MATERIALS SCIENCE↗

DOE OSTI2025

Materials Signatures of Metallic Phases (Final Report)

This report summarizes key accomplishments from a 2 year Laboratory Directed Research and Development (LDRD) project focused on advancing nanoscale characterization of metallic particulates and synthesis of laboratory-scale analogs. We successfully developed and refined nanoscale crystallography techniques with significantly improved spatial resolution and throughput compared to traditional transmission electron microscopy. We also established nanotomography capabilities for 3D particle reconstruction and began optimizing throughput for broader application. Additionally, we demonstrated the ability to relocate and characterize individual particles using atomic force microscopy (AFM), providing insights into hardness, conductivity, and magnetic behavior. On the synthesis front, we leveraged controlled and combustion-based methods to investigate annealing effects and rapid oxidation behavior of U–Fe–Ni compounds. These efforts collectively enhance our ability to characterize and interpret particulate formation and transformation under relevant conditions.

36 MATERIALS SCIENCE↗

NASA NTRS2003

Sheet Flows, Avalanches, and Dune Evolution on Earth and Mars

This investigation is a collaboration between researchers at Cornell University, the University of Florida, and the University of Rennes 1, France. Flow modeling at Cornell University focused on mechanisms for the suspension and transport of wind-blown sand that are important in both terrestrial and Martian environments. These mechanisms include the saltation (or jumping) of grains, collisions between grains, and the interaction of grains with the velocity fluctuations of the turbulent wind. Of particular interest are sheet flows; these are relatively thin, highly concentrated regions of grains flowing near the ground under the influence of a strong turbulent wind. In them, the grains are suspended by interparticle collisions. Sheet flows may be relatively rare events, but they have the capacity to move great amounts of sand. In order to describe sheet flows, a turbulent mixture theory was formulated for particles in a fluid in which fluctuations in the volume fiaction of the particles take place on the scale of the turbulent eddies. Ensemble averaged equations for particle and fluid mass, momentum, and energy and fluid rate of dissipation were expressed in terms of Farve (concentration) averaged velocities and the associated velocity fluctuations. Correlations that describe the turbulent suspension of particles and dissipation of turbulent energy of both phases due to fluid particle interactions were modeled and boundary conditions at the bed and at the upper surface of the collisional flow were formulated. The boundary conditions at the upper surface were tested in a numerical simulation developed at the University of Florida. Steady and unsteady solutions for steady and unsteady fully-developed flows were obtained over a range of wind speeds fiom the lowest for which collisional between particles occurred to at which turbulent suspension is found to dominate collisional suspension. Below the value of the wind speed at which collisions between particles were unimportant, numerical solutions were obtained for the velocity distribution function and the resulting fields of concentration, particle and gas mean velocity, and particle shear stress for the steady two-dimensional saltation of spherical sand particles driven by a turbulent wind over a bed characterized by a simple relationship (the splash function) between the properties of incoming particles and those of the rebounding particles and other particles ejected fiom the bed. At the University of Rennes 1, experiments devoted to the characterization of the splash function for beds consisting of either random or ordered arrays of spheres in two- dimensions were completed. These indicated the role played by the packing geometry in the rebound and ejection of grains. Preliminary experiments on response of a three- dimensional collision bed to a collision with a single particle were performed. Data was taken with a single camera focused on the plane of collision. Here, for example, the decrease of the effective coefficient of restitution of the bed with an increase of the angle of incidence of the incoming particle has been measured. Other experiments on avalanches at Rennes studied the properties of the flows of particles that are responsible for the motion of the leeward side of a dune. In these, the dependence of the initiation of avalanches on the packing and depth of the particles was measured. Particle migration was studied in inclined flows of a binary mixture of disks and the mechanisms of diffision and segregation were isolated and characterized. The influence of side wall on dense, rapid inclined flows was measured and shown to be the reason why the angle of the free surface in such flows can exceed the static angle of repose. Future research will be devoted to a better understanding the transition between saltating (collisionless) and collisional flows as the wind speed the increases. This will involve the understanding of the evolution of the splash function as clisions with the bed become more numerous, more frequent, and more violent.

Source record↗

DOE OSTI2018

Coupling of organic and inorganic aerosol systems and the effect on gas–particle partitioning in the southeastern US

Abstract. Several models were used to describe the partitioning of ammonia, water, and organic compounds between the gas and particle phases for conditions in the southeastern US during summer 2013. Existing equilibrium models and frameworks were found to be sufficient, although additional improvements in terms of estimating pure-species vapor pressures are needed. Thermodynamic model predictions were consistent, to first order, with a molar ratio of ammonium to sulfate of approximately 1.6 to 1.8 (ratio of ammonium to 2 × sulfate, R N/2S ≈ 0.8 to 0.9) with approximately 70 % of total ammonia and ammonium (NH x ) in the particle. Southeastern Aerosol Research and Characterization Network (SEARCH) gas and aerosol and Southern Oxidant and Aerosol Study (SOAS) Monitor for AeRosols and Gases in Ambient air (MARGA) aerosol measurements were consistent with these conditions. CMAQv5.2 regional chemical transport model predictions did not reflect these conditions due to a factor of 3 overestimate of the nonvolatile cations. In addition, gas-phase ammonia was overestimated in the CMAQ model leading to an even lower fraction of total ammonia in the particle. Chemical Speciation Network (CSN) and aerosol mass spectrometer (AMS) measurements indicated less ammonium per sulfate than SEARCH and MARGA measurements and were inconsistent with thermodynamic model predictions. Organic compounds were predicted to be present to some extent in the same phase as inorganic constituents, modifying their activity and resulting in a decrease in [H + ] air (H + in µg m -3 air), increase in ammonia partitioning to the gas phase, and increase in pH compared to complete organic vs. inorganic liquid–liquid phase separation. In addition, accounting for nonideal mixing modified the pH such that a fully interactive inorganic–organic system had a pH roughly 0.7 units higher than predicted using traditional methods (pH = 1.5 vs. 0.7). Particle-phase interactions of organic and inorganic compounds were found to increase partitioning towards the particle phase (vs. gas phase) for highly oxygenated (O : C ≥ 0.6) compounds including several isoprene-derived tracers as well as levoglucosan but decrease particle-phase partitioning for low O : C, monoterpene-derived species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1991

Dust particles from comets and asteroids collected at the Earth's orbit: Parent-daughter relationships

The relative contributions of comets and asteroids to the reservoir of dust in the interplanetary medium is not well known. There are direct observations of dust released from comets and there is evidence to associate the IRAS dust bands with possible collisions of Asteroids in the main belt. It is believed that one may combine lab analysis of the physics and chemistry of captured particles with orbital data in order to identify comet and asteroid parent bodies. It is possible to use the collected orbits of the dust to connect with its source in two ways. One is to consider the long time orbit evolution of the dust under Poynting-Robertson drag. The other is to look at the prompt orbit change of dust from comets onto trajectories that intersect the earth's orbit. In order to characterize the orbits of dust particles evolved over a long period of time, a study of its orbital evolution was undertaken. Various parameters associated with these dust orbits as they cross the Earth's orbit were considered in order to see if one may discriminate between particles evolved from comets and asteroids. The method was to calculate by a numerical procedure the orbits of dust particles after they left their parent bodies. It appears that as the particles pass the Earth's orbit, asteroidal grains and cometary grains can be differentiated on the basis of their measured orbital eccentricities even after much planetary perturbation. Broad parent daughter associations can be made on this basis from measurement of their trajectories intercepted in earth orbit.

Jackson, A. A.↗

DOE OSTI2018

Ice Nucleating Particle Sources at Oliktok Point Field Campaign Report

The Ice Nucleating Particle Sources at Oliktok Point U.S. Department of Energy (DOE) Atmospheric Radiation Measurement (ARM) facility field campaign focused on chemically characterizing springtime aerosol sources at Oliktok Point, Alaska. This work was completed to improve our understanding of air masses influencing the site and altering ice nucleating particle (INP) concentrations measured by Dr. Jessie Creamean of the National Oceanic and Atmospheric Administration (NOAA) during her coordinated, simultaneous ARM field campaign “Exploratory Ice Nucleation Measurements at Oliktok”. Together these ARM field campaigns comprised INPOP (Ice Nucleating Particles at Oliktok Point). The field campaign took place at the Oliktok Point Third ARM Mobile Facility (AMF3) site from March 1 to May 31, 2017. A Davis rotating uniform motion (DRUM) impactor was deployed to collect particles for offline analysis for single-particle chemical characterization (aerosol mixing state). Barring a few interruptions due to power outages at the site, daily samples (24-h duration) were collected for analysis by computer-controlled scanning electron microscopy with energy dispersive X-ray spectroscopy (CCSEM-EDX). Unfortunately our user facility grant at the Pacific Northwest National Laboratory (PNNL) Environmental Molecular Sciences Laboratory (EMSL) was placed on hold from October 2017 to February 2018, limiting our ability to do CCSEM-EDX, as our access is also limited at the Michigan Center for Materials Characterization. Therefore, only a subset of these samples were chosen in consultation with J. Creamean and analyzed by CCSEM-EDX. We have proposed to analyze additional samples, targeting samples collected during marine air masses, as part of our DOE Atmospheric System Research (ASR) proposal “Investigating marine and terrestrial aerosol processes and cloud ice nucleation during the Alaskan Arctic melt season”. The size-resolved aerosol mixing state data produced from the ARM field campaign represent the first of such observations in the springtime at Oliktok Point. Since this AMF3 site is located within the North Slope of Alaska (NSA) oil fields near Prudhoe Bay, the site is continually influenced by combustion emissions, with natural sources also contributing to the background aerosol population.

North Slope of Alaska, Oliktok Point, aerosols, or↗

DOE OSTI2024

Godiva IV Simulated Radiation Field Characterization and Variance Reduction

Godiva IV is a system comprised of highly enriched uranium alloyed with molybdenum in the form of fuel plate rings. The reactor, along with its predecessors, was designed with the unique ability to satisfy interests in the super-prompt-critical reactor operation space. Originally, the reactor was part of the Los Alamos Critical Experiments Facility (LACEF) at Technical Area-18 (TA-18). The radiation field around Godiva at this facility was well characterized and understood. As a fast neutron system, the neutron spectrum in and around Godiva was close to a Watt Fission spectrum. The Kiva where Godiva IV was located at LACEF was made of thin, sheet metal walls which did not contribute significantly to the neutron spectrum. Following the transition of LACEF to the National Critical Experiments and Research Center (NCERC) in Nevada, Godiva-IV was moved from TA-18 to the Device Assembly Facility (DAF) at the Nevada National Security Site (NNSS). Part of this move brought renewed interest in radiation field characterization. The new facility introduced significant changes to the environment surrounding Godiva, and preliminary foil irradiation results suggested that the room contribution to the neutron spectrum was significant. Unlike at TA-18, a large thermal neutron signature was added to the fast spectrum from Godiva due to significant room return. A primary goal due to the additional complexity that the room return adds to the Godiva IV radiation emission spectrum was the development of an efficient Monte Carlo N-Particle (MCNP) calculation capable of characterizing the neutron spectrum anywhere in the room around Godiva. A campaign of activation foil irradiations and analysis were completed to support the validation of the MCNP model. The modeling of these foils in MCNP can be easily done with a standard volumetric neutron flux tally. However, given the multitude of locations and reaction rates to be modeled, further steps must be taken to increase the efficiency of these calculations in MCNP. During this study, a benchmark model currently under development for Godiva IV was used. A qualitative assessment of the thermal neutron contributors was performed using spatial neutron distribution plots. Additional detail was added to the model based on the qualitative results showing the thermal spectrum’s large sensitivity to hydrogenous material. Neutron energy spectra was evaluated at discrete locations in the room around Godiva to quantify the relative contribution of various components. It was discovered that the concrete walls are the largest contributor to the thermal signature, with minor contributions from plastic components surrounding Godiva. Following these results, two different variance reduction techniques were implemented to improve the problem efficiency in these calculations. In the first approach, an F5 point detector tally was implemented in the standard Godiva IV criticality problem. The second approach involved a weight-window generator implementation with an F5 point detector tally in a fixed source problem. The weight window implementation reduced the runtime from 42739.55 minutes to 1803.34 minutes (computer time), compared to the F5 KCODE implementation.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2020

Hollow Silica Particles: Recent Progress and Future Perspectives

Hollow silica particles (or mesoporous hollow silica particles) are sought after for applications across several fields, including drug delivery, battery anodes, catalysis, thermal insulation, and functional coatings. Significant progress has been made in hollow silica particle synthesis and several new methods are being explored to use these particles in real-world applications. This review article presents a brief and critical discussion of synthesis strategies, characterization techniques, and current and possible future applications of these particles.

36 MATERIALS SCIENCE↗

NASA NTRS1999

Apollo 17 Soil Characterization for Reflectance Spectroscopy

It is the fine fractions that dominate the observed spectral signatures of bulk lunar soil, and the next to the smallest size fractions are the most similar to the overall properties of the bulk soil. Thus, our Lunar Soil Characterization Consortium has concentrated on understanding the inter-relations of compositional, mineralogical, and optical properties of the <45-micron size fraction and its component sizes (20-44 micron, 10-20 micron, and <10 micron size fractions). To be able to generalize our results beyond the particular sample set studied, it is necessary to quantitatively identify the observed effects of space weathering and evaluate the processes involved. For this, it is necessary to know the chemistry of each size fraction, modal abundances of each phase, average compositions of the minerals and glasses, I(sub s)/FeO values, reflectance spectra, and the physical makeup of the individual particles and their patinas. This characterization includes the important dissection of the pyroxene minerals into four separate populations, with data on both modes and average chemical compositions. Armed with such data, it should be possible to effectively isolate spectral effects of space weathering from spectral properties related to mineral and glass chemistry. Four mare soils from the Apollo 17 site were selected for characterization based upon similarities in bulk composition and their contrasting maturities, ranging from immature to submature to mature. The methodology of our characterization has been discussed previously. Results of the Apollo 17 mare soils, outlined herein, are being prepared for publication in MAPS. As shown, with decreasing grain size, the agglutinitic (impact) glass content profoundly increases. This is the most impressive change for the mare soils. In several soils we have examined, there is an over two-fold increase in the agglutinitic glass contents between the 90-150- micron and the 10-20-micron size fractions. Accompanying this increase in agglutinitic glass is a definite decrease in pyroxenes and to lesser extents, the oxides (ilmenite), volcanic glass, and olivine. Unexpectedly, however, the absolute plagioclase abundances stay relatively constant throughout the different grain sizes, although the abundance of plagioclase relative to the mafic minerals increases with decreasing particle size. These soils were chosen for study based upon their similarities in FeO and Ti02 content, allowing for direct comparisons between evolutions of chemistry between size fractions and among different maturities of soils. The bulk chemistry of these fractions was determined by EMP analyses of fused glass beads. In contrast to the systematic variations in bulk chemistry discussed below, the relatively uniform composition of agglutinitic glass with grain size and soil maturity is illustrated. The composition of the bulk fraction of each size fraction becomes more feldspathic with increasing maturity, with the effect being most pronounced for the finest fractions. The composition of the agglutinitic glass, however, is relatively invariant and more feldspathic (i.e., rich in Al2O3) than even the <10-micron fraction. This relation not only strengthens the "fusion of the finest fraction" (F(sup 3)) hypothesis, but also highlights the important role of plagioclase in the formation of agglutinitic glass. With decreasing grain size, FeO, MgO, and TiO2 contents decrease, whereas CaO, Na2O, and Al2O3 (plag components) increase for all soils. These chemical variations would appear to be coupled with the significant increase in agglutinitic glass and decrease in oxide (ilmenite),pyroxene, and volcanic glass. These changes in chemistry do not appear to be due to distinct changes in the compositions of individual phases but to their abundances. Values of I(sub s)/FeO increase with decreasing grain size, even though the bulk FeO contents decrease. That is, the percentage of the total Fe that is present as nanophase Fe(sup O) has increased substantially in the smaller size fraction. Note that the increase in nanophase FeO in smaller size fractions is significantly greater than the increase in agglutinitic glass content, with its single-domain FeO component. This would seem to indicate that at least some of the FeO is surface correlated. To illustrate this effect, if it is assumed that the nanophase FeO is entirely surface correlated, then equal masses of 15-micron and 6-micron spheres should have about 3x as much FeO in the finer fraction. The recent findings of Kelleret al. of the major role of vapor-deposited, nanophase FeO-containing patinas on most soil particles is a major breakthrough in our understanding of the distribution of FeO within agglutinitic glass and upon grain surfaces. Bidirectional reflectance spectra for a representative Apollo 17 soil (70181) are shown. The size separates all have similar albedo in the blue and follow a regular sequence in which the continuum slope increases, ferrous bands weaken, and albedo, increases with decreasing particle size. The bulk <45-micron soil is typically close to the 10-20 micron spectrum. It is important to note that although the finest fraction (<10 micron) is close in composition to the abundant agglutinitic glass in each size fraction, this size fraction is relatively featureless and does not dominate the spectrum of the bulk <45-micron soil. It has long been suspected that agglutinitic glass, to a large extent, is the product of melting of the finest fraction of the soils, with a dominance of plagioclase. Given the low abundance of pyroxene in the finest fractions of each soil the source of the FeO in these Apollo 17 agglutinitic glasses is not fully identified. We suspect the abundant volcanic glass in these samples may be a significant contributor and this hypothesis will be tested with the suite under study from other Apollo sites.

Taylor, L. A.↗

DOE OSTI2023

Particle size effect of graphite anodes on performance of fast charging Li-ion batteries

Charging energy-dense lithium-ion batteries (LIBs) with thick graphite electrodes at high current densities are typically accompanied by poor performance and safety issues. The root cause is the onset of Li plating at the surface of graphite when lithiated to a high capacity within a short time period. Here, we investigated the behavior of graphite electrodes with various particle sizes under fast charge operations. Results from the electrochemical characterization on graphite electrodes exhibit the superiority of smaller particles over bigger particles in terms of suppressing the onset of Li plating and growth of plated Li particles. Observations from scanning electron microscopy also corroborate the presence of plated Li in electrodes with big graphite particles and its absence in graphite electrodes with small particles, when the cells were lithiated to 90% of the state of charge (SOC). Further, the improved performance of cells with the small particles might be associated with the low Li-ion concentration at the surface of graphite and thus reduced overpotential in graphite electrodes. The simulated results revealed that, compared to bigger particles, smaller particles have lower surface intercalation at any given cell SOC, which may significantly reduce the overpotential in the graphite electrodes and mitigate the onset of Li plating. This agrees well with experimental observations.

25 ENERGY STORAGE↗