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At least 1,315 records · Page 73

Impact of electrode porosity architecture on electrochemical performances of 1 mm-thick LiFePO4 binder-free Li-ion electrodes fabricated by Spark Plasma Sintering

Thick electrodes with high active material loadings have been intensively studied over the last couple of decades in pursuit of achieving high energy density systems. To optimize and enhance the electrochemical performance of such electrodes, one has to control the pore morphology by, for example, varying the pore size and shape, and the level of porosity. In the present work, the fabrication of thick binder-free LiFePO4 (LFP) electrodes with two different pore sizes (12 and 20 mu m) and porosities (21 vol% and 44 vol%) using Spark Plasma Sintering (SPS) and templating approach is reported. The well-controlled porous architecture inside the thick electrodes is realized by fine-tuning experimental parameters. The impact of porosity architecture on electrochemical performance is quantified and correlated with the 3D tortuosity values determined from both micro-computed tomography and electrochemical impedance-based experimental methods. Based on the micro-computed tomography data analysis, estimated tortuosity values along X, Y, and Z axes reveal an anisotropic effect perpendicularly to the SPS compression axis (Z-direction). This is particularly profoundly observed in the samples with larger pores (20 mu m). The correlation between morphological properties and the rate capability performance is established indicating that the capacity loss happens mainly due to the Li-ion diffusion limitations.

Cathode material↗

Mapping 3D grain and precipitate structure during in situ mechanical testing of open-cell metal foam using micro-computed tomography and high-energy X-ray diffraction microscopy

Open-cell metal foams are ultra-low-density cellular metals with complex hierarchical structures that span bulk, cell, ligament, and sub-ligament scales and give rise to desirable properties such as high strength-to-weight ratio and excellent energy absorption. Although literature suggests that intrinsic material structures at sub-ligament length scales (e.g., grains and precipitates) play an important role in mechanical behavior of open-cell metal foams, there are very few experimental measurements of such structures in three dimensions and for meaningful volumes of foam. This study seeks to map and track the three-dimensional (3D) grain and precipitate structures of an intact volume of open-cell aluminum foam by advancing microstructural characterization techniques that leverage X-ray micro-computed tomography (μCT) and far-field high-energy X-ray diffraction microscopy (FF-HEDM). A 6%-relative-density aluminum foam sample was mechanically tested in compression while μCT and FF-HEDM measurements were collected at interrupted loading states at beamline 1-ID of the Advanced Photon Source. Further, a new scanning strategy and reconstruction algorithm were established to enable characterization of a foam volume with diameter approximately four times wider than the nominal width of the X-ray beam. The result is a set of maps that detail both the 3D grain and precipitate structures throughout the foam volume at successive strain steps. A novel grain tracking procedure was developed to track individual grains within the foam volume by accounting for the large rigid-body motions that individual ligaments can undergo during mechanical loading. The ability to track grains and precipitate structures in three dimensions throughout large bulk deformation of ultra-low-density polycrystalline materials enables new possibilities for validating numerical models and investigating local failure mechanisms. Furthermore, the methods and procedures developed in this study could be applied to other ultra-low-density structures, such as additively manufactured lattices.

36 MATERIALS SCIENCE↗

Catalysts by pyrolysis: Direct observation of chemical and morphological transformations leading to transition metal-nitrogen-carbon materials

Transition metal-nitrogen-carbon materials (M-N-C catalysts) are promising electrocatalysts in polymer electrolyte fuel cells (PEFCs) and electrolyzer applications. High temperature treatment in inert atmosphere (pyrolysis) is the essential, most common method for the synthesis of M-N-C catalysts and critical to achieve high electrocatalytic activity and electronic conductivity. To this day, despite many uses and successful implementations in materials manufacturing, pyrolysis has been an entirely empirical technology, with process control and optimization relying exclusively on “Edisonian” approach. The knowledge gap in the mechanism about how the precursor is being transformed into catalysts hinders further development of the M-N-C catalysts regardless of the precursor class and processing protocols. In this work, we probed the morphological evolution and chemical transformation of a nitrogen-containing charge transfer organic salt, mixed with transition metal (iron) salt and amorphous silica powder (precursor) during the pyrolysis process via a combination of in situ synchrotron and laboratory-based diagnostic techniques. The pyrolysis process is found to be divided into three stages. During a controlled temperature ramp, the selected organic N-C precursor (nicarbazin) began melting and decomposing just below 400 °C, forming a certain number of micrometer-scale pores and pathways. With increase in temperature from 400 °C to 900 °C, amorphous carbon domains started forming, and reduced (metallic) iron nanoclusters appeared, being dispersed uniformly throughout the carbonaceous matrix. When temperature advanced above 900 °C, graphitization of carbon commenced, associated with appearance and evolution of atomically dispersed metal-nitrogen moieties in the carbonaceous matrix. As the graphitization advanced further, a secondary process of agglomeration of metal nanoparticles occurred. Multi-analytical technique observations conducted here provide a base for rational design and optimization of M-N-C electrocatalysts via pyrolysis.

36 MATERIALS SCIENCE↗

Fast spark-detection system for GEM detectors

The sPHENIX experiment is currently under commissioning at the Relativistic Heavy Ion Collider (RHIC) at Brookhaven National Lab (BNL). The Time Projection Chamber (TPC) serves as a tracking detector for the experiment. The sPHENIX TPC uses a stack of four Gas Electron Multipliers (GEMs) as a gain stage in a reduced ion back-flow configuration. To mitigate the damaging effects of sparks in the GEMs, an online spark monitoring system was created. Once the system detects a spark in a GEM stack, the voltages across the GEMs in that stack can be lowered to prevent further sparking without affecting the gain and efficiency of the other modules. Spark signals are coupled out of the GEM stack by a pick-off capacitor attached to the bottom of the bottom GEM. Custom PCBs convert the oscillatory spark signal into a mono-polar pulse that is then digitized. The software then saves the waveform in a server and uses experimentally derived thresholds to determine how to react. As a result, the system has so far proven to be effective at improving the stability of the TPC and preventing damaging events while collecting cosmic ray data.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Correcting beam space charge effects in Active-Target Time Projection Chamber

By providing a large gaseous volume for nuclear interactions while simultaneously recording the tracks of resulting reaction products, an active target serves as both a thick target and a detector. Once a reaction occurs, the emitted charged fragments strip electrons from the target gas along their path as they transverse the detector. Collection of these stripped electrons allow for detection of the product tracks. As beam intensity increases, the resulting ionization in the active target can significantly distort this collection of electrons. If left uncorrected, the resulting measurements could be wrong. In this paper, we investigate the impact of the space charge produced by heavy radioactive beams within the Active Target - Time Projection Chamber at Michigan State University. The beams are injected parallel to the electric field of the time projection chamber which is operated without a magnetic field for this experiment. Furthermore, we analyze the rate dependence of the space charge effects and demonstrate that they can be modeled and effectively corrected.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Development of thin-gap GEM- μ RWELL hybrid detectors

Micro Pattern Gaseous Detectors (MPGDs) are used for tracking in High Energy Physics and Nuclear Physics because of their large area, excellent spatial resolution capabilities and low cost. However, for high energy charged particles impacting at a large angle with respect to the axis perpendicular to detector plane, the spatial resolution degrades significantly because of the long trail of ionization charges produced in clusters all along the track in the drift region of the detector. The long ionization charge trail results in registering hits from large number of strips in the readout plane which makes it challenging to precisely reconstruct the particle’s position using simple center of gravity algorithm. As a result, the larger the drift gap, the more severe the deterioration of spatial resolution for inclined tracks. For the same reason, the position resolution is also severely degraded in a large magnetic field, where the Lorentz E x B effect causes the ionization charges to follow a curved and longer path in the detector gas volume. In this paper, we report on the development of thin-gap MPGDs as a way to maintain excellent spatial resolution capabilities of MPGD detectors over a wide angular range of incoming particles. In a thin-gap MPGD, the thickness of the gas volume in the drift region is reduced from typically 3 mm to 1 mm or less. We present preliminary test beam results demonstrating the improvement in spatial resolution from 400 m with a standard 3 mm gap μ RWELL prototype to ~140 μ m with a double amplification GEM- μ RWELL thin-gap hybrid detector. Here, we also discuss the impact of a thin-gap drift volume on other aspects of the performance of MPGD technologies such as the efficiency and detector stability.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Direct local parametrization of nuclear state densities using the back-shifted Bethe formula

Level densities are often parametrized using the back-shifted Bethe formula (BBF) for nuclei that possess experimental data for s-wave neutron resonance average spacings and a complete discrete level sequence at low excitation energies. However, these parametrizations require the additional modeling of the dependence of the spin-cutoff parameter on excitation energy. Here, in this work, we avoid the need to model the spin distribution of level densities by using the experimental data to parametrize directly the state densities, for which the BBF does not depend on the spin-cutoff parameter. This approach allows for a local parameterization of state densities that is independent of the spin-cutoff parameter. We provide these parameters in a tabulated form for applications in nuclear reaction calculations and for testing microscopic approaches to state densities.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Nanopore networks in colloidal silica assemblies characterized by XCT for confined fluid flow modeling

Fluid flow through nanopore structures has exhibited different behavior than that described by Darcy's law, derived from pore networks of micrometer scale. Here, pressure assemblies of colloidal silica spheres of specified diameters from 94 to 620 nanometers were prepared as model nano-porous media. The smaller silica spheres tended to form random packing, but some substantial ordering was found in the packing of the larger silica spheres. X-ray computed tomography (XCT), with a voxel resolution of 16 nm, was used to characterize the nanopore networks. The porosity of the Nano-XCT pore network (34%) was less than the total porosity of the assemblies as determined by X-ray attenuation (52%), possibly due to the limits of voxel resolution during segmentation. Fluid flow in the nanopore networks was simulated using the single-phase Lattice Boltzmann Method, and the simulated permeability was compared with the empirical and experimental values. Based on our characterization, although a well-ordered packing of silica spheres was not achieved, it was found that the nanopore networks in the colloidal silica assemblies had pore size distributions corresponding to the particle sizes. The simulated permeability was less than the experimental measurement for water flow, but the complex packing of silica spheres and surface chemistry issues need to be considered in future research.

02 PETROLEUM↗

Flavor Dependence of Charged Pion Fragmentation Functions

We have measured the flavor dependence of multiplicities for π + and π - production in semi-inclusive deep-inelastic scattering (SIDIS) on proton and deuteron to explore a possible charge symmetry violation in fragmentation functions. The experiment used an electron beam with energies of 10.2 and 10.6 GeV at Jefferson Lab and the Hall-C spectrometers. The electron kinematics spanned the range 0.3 < x < 0.6, 2 < Q 2 < 5.5 GeV2, and 2.2 < W < 3.2 GeV. The pion fractional momentum range was 0.3 < z < 0.7, and the transverse momentum range was 0 < p T < 0.25 GeV/c. Assuming factorization and allowing for isospin breaking, the results can be described by two “favored” and two “unfavored” effective low p T fragmentation functions that are flavor-dependent. We find each pair converges to a common flavor-independent fragmentation function at the highest W, where factorization is most applicable.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Quenching of single-particle strength inferred from nucleon-removal transfer reactions on 15 C

The difference in the proton and neutron separation energies (ΔS) of the weakly bound 15 C ground state is -19.86 MeV, an extreme value. Data from intermediate-energy heavy-ion induced (HI-induced) knockout reactions on nuclei spanning -20 ≲ ΔS ≲ +20 MeV, suggest that the degree to which single-particle strength is quenched, R s , has a negative correlation with ΔS, decreasing from unity around -20 MeV to around 0.2 at +20 MeV. For the 15 C ground state (R s = 0.96 (4) in HI-induced knockout), contrasting results have recently been obtained via the neutron-adding transfer reaction, which reveal a value of R s = 0.64 (15), similar to the value observed at modest and more extreme values of ΔS with reaction probes other than HI knockout. In order to explore the any potential differences between adding and removing processes in transfer reactions at extreme ΔS, single-neutron removal transfer reactions on 15 C were performed at 7.1 MeV/u in inverse kinematics. The removal of a valence neutron in 2s 1/2 orbit using both (p, d) and (d, t) reactions shows consistent quenching factors and agrees with those from the neutron-adding reaction. The present results, which can be compared with neutron knockout reaction, suggest that correlations, represented by the quenching factor, show limited dependence on neutron-proton asymmetry under the most extreme asymmetry conditions so far achieved in transfer reactions.

quenching factor↗

Shape evolution in neutron-rich Rh isotopes: First measurement of negative-parity isomers in 117,119 Rh

The β-delayed γ-ray spectroscopy of neutron-rich 117,119 Rh isotopes has been investigated at the Radioactive Isotope Beam Factory of RIKEN. The 1/2 − isomers in 117,119 Rh have been identified for the first time. The systematics of energy differences between the 9/2 + and 1/2 − states have been extended up to N = 74, which shows a tendency to first increase with the neutron number N, then reach a maximum at N ≈ 68, and subsequently decrease. Self-consistent triaxial relativistic Hartree-Bogoliubov (TRHB) calculations highlight the crucial role of triaxial deformation, particularly in the positive-parity states, in driving the observed evolution of energy differences. A shape transition from axially symmetric to triaxial and back to symmetric deformation is suggested along the Rh isotopic chain. These findings provide new insights into the structure of neutron-rich nuclei in the A ∼ 110 region and motivate further studies of exotic isotopes in this region to explore the interplay between triaxiality and shell evolution.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Nondestructive geochemical characterization of fossil hominin taphonomy and burial history

To date, only three Homo habilis specimens have been discovered that have associated craniodental and postcranial elements, providing a limited fossil record of the ontogeny and morphology of early members of the genus Homo. Recently, a nearly complete dentition, likely attributable to H. habilis, was discovered and excavated from early Pleistocene-age fluvial-lacustrine sediments of the upper Burgi Member of the Koobi Fora Formation at site F25787 in Area 13, near Ileret, Kenya. On the surface less than 15 m away, at site F25966, postcranial elements were found, which, if from the same individual as the nearby dentition, would represent the fourth associated craniodental and postcranial assemblage of this species. We developed a geochemical taphonomic history of these ca. 2 Ma hominin fossils using nondestructive X-ray based microanalytical tools (synchrotron and benchtop X-ray fluorescence chemical imaging and micro- and nano-computed tomography volumetric reconstruction), bulk analyses of sediments and paleosols at the excavation sites, and sedimentologic and stratigraphic observations. We integrate the chemical and physical taphonomic histories to test whether teeth (excavated in situ) and postcranial bones (eroded onto the outcrop surface) derive from a single individual. Minor differences in taphonomic history are attributable to the different biomineral properties of the dental and osseous components and to differences in physical damage during early post-mortem scavenging, dispersal, and burial in adjacent depositional settings. Microscale geochemical mapping enabled the temporal ordination of chemical and physical events in the specimens’ chemical taphonomic histories. Specifically, authigenic Fe- and K-bearing clays and Y, U, and Sr uptake occurred in post-burial fractures in bones and were also incorporated pervasively throughout dentin in teeth. Barite mineralization occurred along the latest fractures in both materials, and as a coating on tooth roots. The stratigraphic, taphonomic, and geochemical evidence supports the interpretation that the hominin fossils represent a single individual. Finally, successful application of these nondestructive sample characterization methods demonstrates capabilities for thorough interrogation of the taphonomic histories of other potential hominin fossil associations, enabling more robust and accurate palaeontologic constraints using those relationships.

36 MATERIALS SCIENCE↗

Groundwater flowpath characteristics drive variability in per- and polyfluoroalkyl substances (PFAS) loading across a stream-wetland system

Groundwater dependent ecosystems in areas with industrial and military land use are at risk of direct exposure to a wide range of contaminants, including PFAS chemicals. Glaciated terrain often has mixed high and low permeability sediments coupled with groundwater flow-through lake features. These hydrogeologic attributes create highly complex ‘source to seep’ dynamics that make spatiotemporal contaminant transport patterns difficult to predict. We investigated one such system in detail using a suite of heat-tracing and chemical methods. Numerous (n=57) preferential groundwater discharge zones (vertical flux rates ranging 0.2 to 3.2 m/d) were identified across the upper Quashnet River stream-wetland system in Mashpee, MA, USA, adjacent to an Air Force Base with several known PFAS source areas. Surface-water and groundwater samples were collected and analyzed (n=145) for precursors and terminal PFAS compounds between March and September 2022. Samples were collected at identified seeps along the Quashnet River (n=59), from wells upgradient from the stream-wetland system (n= 44), from contributing flow-through kettle lakes (n=8), and at multiple locations along the Quashnet River (n=34). Samples from seeps and wells had measured PFAS concentrations ranging from non-detect to approximate 3,500 ng/L (mean= 1,650 ng/L), and a range of deuterium excess values (3.2 to 15.9 per mil) indicative of varying degrees of groundwater-lake interaction prior to emergence at the discharge zones. Groundwater-lake interaction along flowpaths that sourced the sampled seeps was farther supported by significant correlations (p < 0.01) between deuterium excess and %PFAS precursors, and between %PFAS precursors and multiple terminal PFAS compounds (e.g., PFPeS, PFBS, PFHxS). However, some sampled seeps contributing groundwater to the stream-wetland system had much higher total PFAS concentrations (>1000 ng/L) than the upgradient kettle lakes, despite showing lake (evaporative) isotopic signatures, indicating the potential for groundwater flowpath convergence at wetland discharge zones and the influence of lakebed PFAS precursor reactions. PFAS compounds and water isotopic composition at sampled multilevel groundwater wells, rivers, lakes, and seeps suggest that a complex mixture of source groundwater and flowpath characteristics are responsible for diverse observed PFAS mixtures at preferential discharge zones across the stream-wetland system. Further, total PFAS loading patterns to the Quashnet River via groundwater discharge remained remarkably similar from winter to summer to fall conditions, despite a regional dry period in late summer 2022 with the upper river channel completely drying. This work addresses gaps in the existing PFAS literature by demonstrating the importance of subsurface fate and transport on PFAS compound concentrations in controlling contaminant mass loading in preferential groundwater discharge zones and presents a transferrable field toolkit for efficient characterization of spatially preferential PFAS transport dynamics.

Contaminant transport↗

Environmental and socio-economic Pareto-front trade-off analysis of U.S. PET packaging material in a circular economy

Various recycling technologies are emerging to implement circular economy in plasticssupply chain systems. However, the environmental and socio-economic trade-offs of in circular economy are not well understood at a systems level. Particularly, quantifying these trade-offs as a function of end-of-life (EOL) management decisions, including transition of recycling technologies, systems level metrics such as circularity, recycled content, and the need for fossil-derived plastics are not well understood. Here, the present study addressed these research gaps by applying a systems analysis modeling approach that utilizes material flow analysis, life cycle assessment, socioeconomic data, and system optimization techniques for polyethylene terephthalate (PET) packaging supply chains in the United States. Pareto-front trade-offs between conflicting environmental and socio-economic impacts as well as those between socioeconomic impacts and circularity were explored using the epsilon constraint method. The Pareto-front trade-off analysis revealed the transition of EOL management strategies for PET packaging systems, including changes in selection of recycling technologies, to aid decision making process by quantifying studied system metrics. Transitioning from environmentally optimal to socio-economically optimal systems led to increased employment (by 17%), wages (by 26%), and revenues (by 6%) but also led to increased global warming potential (GWP; by 65%), energy consumption (by 59%), and reliance on fossil PET in the system (by 78%). Finally, the results show that there is not a unique set of recycling technologies to achieve a sustainable circular economy of PET packaging system, instead it depends on the decision maker’s objectives and targeted metrics of the system.

54 - ENVIRONMENTAL SCIENCES/GLOBAL CLIMATE CHANGE ↗

Covalent Adaptable Networks: Reprocessable Cross-Linked Polymers

Thermoset polymers have desirable properties, such as excellent thermal and mechanical stability, but their covalent cross-links typically prevent repair or recycling. By enabling and controlling dynamic exchange reactions within polymer networks, their covalent bonds rearrange and allow the polymer to be reshaped. These viscoelastic polymer networks, now known as covalent adaptable networks (CANs), are an important frontier for improving plastic circularity, as well as for designing valuable stimuli-responsive materials. This Review describes the history of CANs, dating back to the early days of polymer science, and the evolution of their classification and nomenclature. A comprehensive survey of dynamic reactions and linkage chemistries is provided, as well as methods to characterize and reprocess CANs. Beyond straightforward reprocessing, many advanced applications of CANs and their composites are now emerging. Lastly, we provide perspective on how the development of new chemistries, strategies to control stimuli-responsive bond exchange and mechanical properties, and a deep understanding of exchange reactions will advance this field toward scalable, sustainable, and high-value materials.

Sun, Molly [Northwestern University, Evanston, IL ↗

Quantifying and Modeling the Impact of Phase State on the Ice Nucleation Abilities of 2-Methyltetrols as a Key Component of Secondary Organic Aerosol Derived from Isoprene Epoxydiols

Organic aerosols (OAs) may serve as ice-nucleating particles (INPs), impacting the formation and properties of cirrus clouds when their phase state and viscosity are in the semisolid to glassy range. However, there is a lack of direct parameterization between aerosol viscosity and their ice nucleation capabilities. In this study, we experimentally measured the ice nucleation rate of 2-methyltetrols (2-MT) aerosols, a key component of isoprene-epoxydiol-derived secondary organic aerosols (IEPOX-SOA), at different viscosities. These results demonstrate that the phase state has a significant impact on the ice nucleation abilities of OA under typical cirrus cloud conditions, with the ice nucleation rate increasing by 2 to 3 orders of magnitude when the phase state changes from liquid to semisolid. An innovative parametric model based on classical nucleation theory was developed to directly quantify the impact of viscosity on the heterogeneous nucleation rate. This model accurately represents our laboratory measurement and can be implemented into climate models due to its simple, equation-based form. Based on data collected from the ACRIDICON-CHUVA field campaign, our model predicts that the INP concentration from IEPOX-SOA can reach the magnitude of 1 to tens per liter in the cirrus cloud region impacted by the Amazon rainforest, consistent with recent field observations and estimations. This novel parameterization framework can also be applied in regional and global climate models to further improve representations of cirrus cloud formation and associated climate impacts.

2-methyltetrol↗

The Value of Reversible Carbon Storage in a Zero-Emissions World

Atmospheric carbon dioxide removal (CDR) is required to stabilize global temperature. CDR can be achieved via ecosystem-based approaches that are cost-effective but reversible (e.g., soil and forest management) or by more durable but expensive approaches (e.g., direct air capture coupled with geologic storage). Here, we examine trade-offs between these approaches, focusing on timing, climate impacts, and cost. We simulated reversible carbon accrual for a range of CDR contract structures using a general minimalist model of ecosystem carbon cycling, and parameterized it to simulate US agricultural soil management─specifically cover cropping─as a case study. We then quantified the resulting impact on atmospheric carbon and global temperature using a climate model emulator. We find that maintaining a patchwork of reversible CDR projects by replacing lapsed projects with new projects can reduce warming by 22–195 μ°C in 2100 and that the magnitude of this cooling effect depends on how effectively the patchwork is maintained. Long-term maintenance of reversible CDR projects requires institutional stability that cannot be guaranteed over multiple decades. Consequently, effective CDR ultimately requires replacing reversible projects with durable projects. To address this problem, we modeled the cost of replacing reversible agricultural soil CDR with geologic CDR. We found that using reversible CDR as a bridge to durable CDR is potentially more cost-effective as a global cooling strategy (0.20–0.81 billion USD per μ°C avoided) than perpetual maintenance of reversible CDR (0.32–1.31 billion USD per μ°C avoided) or an immediate transition to durable CDR (1.37–2.19 billion USD per μ°C avoided). However, we emphasize that institutional commitments to maintain reversible CDR projects cannot be guaranteed. Reliance on reversible CDR as a bridge to durable CDR therefore carries an unknown amount of risk and will only function if efforts to maintain reversible CDR are robust.

carbon capture and storage↗