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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Matrimid substrates with bicontinuous surface and macrovoids in the bulk: A nearly ideal substrate for composite membranes in CO 2 capture

Scalable fabrication of thin-film composite (TFC) membrane for post-combustion carbon capture is often limited by the availability of high-performance nanoporous substrate. Ideally, the substrate should allow for fast gas transport at the selective layer/substrate interface as well as in the bulk of the substrate. In this study, highly permeable Matrimid substrates were prepared via vapor- and nonsolvent-induced phase separations. The phase separation mechanism of the Matrimid®/N-methyl-2-pyrrolidone casting solution was modulated by the addition of LiCl to control the solution thermodynamic stability, and nanoporous Matrimid substrates were formed with a bicontinuous surface and macrovoids in the bulk. This hierarchically optimized structure resulted in a CO 2 permeance of 2.60 × 10 5 GPU (1 GPU = 1 × 10 –6 cm 3 (STP) cm –2 s –1 cmHg –1 = 3.349 × 10 –10 mol m –2 s –1 Pa –1 ), which was ca. 11 times more permeable than a benchmark polyethersulfone substrate with cellular pores. The benefit of using this new substrate was demonstrated by coating a 170-nm amine-containing polymer to form a TFC facilitated transport membrane. The membrane exhibited a CO 2 permeance of 932 GPU at 57°C, which was 72 GPU higher than the counterpart coated on the benchmark substrate. Meanwhile, the CO 2 /N 2 selectivity was remained at 158. This permeance improvement could be well explained by the resistance-in-series model, where the improved permeance was attributed to the reductions in substrate and lateral diffusion mass transfer resistances. The upper bound (UB) analysis indicates that the Matrimid substrate is nearly ideal for the state-of-the-art polymers for CO 2 /N 2 separation. Here, the substrate improvement could also reduce the parasitic energy associated with the membrane process due to the reduced membrane cost and flue gas compression requirement.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Dynamic Behavior of Natural Seep Vents: Analysis of Field and Laboratory Observations and Modeling (Final Scientific/Technical Report)

In this project, we have analyzed data collected by the U.S. Department of Energy (DOE), National Energy Technology Laboratory (NETL) in a high pressure water tunnel (HPWT) and data from two research cruises to natural seeps in the Gulf of Mexico to adapt and validate a numerical model to predict the dynamics of natural seeps in the deep oceans. The HPWT data include video observations of the shrinkage rate of individual methane and natural gas bubbles under simulated deep-water conditions. Field data were collected during two cruises by the Gulf Integrated Spill Research (GISR) Consortium led by Texas A&M University and funded by the Gulf of Mexico Research Initiative (GoMRI). These data included in situ observations from a remotely operated vehicle (ROV) of gas bubbles at two natural seep sites in the Gulf and acoustic observations of the natural seep bubble flares in the ocean water column. The acoustic data were from multibeam echosounders, one mounted in a forward-looking orientation on the ROV and another mounted down-looking in the haul of the ship. All of these laboratory and field data were focused on the dynamics of natural gas bubbles at temperatures and pressures favorable for clathrate hydrate formation between the gas and water. Our analyses of this data focused on understanding the mechanisms responsible for gas bubble dissolution within the hydrate stability zone (HSZ) of the oceans. Ice-like hydrate shells may form on the bubble-water interface under these conditions, and it was unknown how this might affect the mass transfer of gas into the ocean. We were able to extract bubble shrinkage rates from the HPWT datasets. Using this data we determined that mass transfer coefficients with and without a hydrate shell match empirical values for bubbles in contaminated systems (so-called dirty bubbles contaminated by naturally occurring surfactants). We also showed that free gas, and not gas hydrate, is the dominant dissolving phase when the hydrate sub-cooling is below 11 degree Celsius (temperature difference between hydrate the hydrate formation temperature and ambient temperator) or the pressure is reducing as bubbles rise through the ocean water column. Using this mass transfer model, our numerical model of bubble dissolution matched the over 200 HPWT experiments with an average error of 10% for predicting the bubble size at the end of an experiment. From field data in the literature, we also observed that gas bubbles dissolve faster when they are initially released, following mass transfer coefficients for so-called clean-bubbles (those not yet contaminated by surfactants). Shortly after release within the HSZ, a hydrate shell forms on the bubble-water interface, and the mass transfer reduces to rates matching those of dirty bubbles. We correlated this transition time from clean to dirty bubble behavior with the initial bubble surface area and the hydrate sub-cooling. With this model for hydrate formation time and using the mass transfer coefficients deduced from the HPWT data, we validated our numerical model for predicting the rise heights of natural seep flares in the oceans. Flare heights are commonly observed in haul-mounted acoustic multibeam data. The numerical model predicts bubbles to rise high in the ocean water column owing to the slower mass transfer rates for dirty bubbles that accompany the majority of their rise time. We found that the numerical model predictions matched the observed flare heights within 5% to 10% accuracy when we compared the rise heights of the largest bubbles released from the seafloor with the bubbles acoustically visible in the multibeam data. Bubbles become acoustically transparent as they shrink to sizes of order 1 mm in diameter for the multibeam frequencies used in the field. The forward-looking multibeam on the ROV also provided data on the lateral spreading of bubbles in natural seep flares. Our analysis of this data showed that spreading follows a diffusion process, with the effective diffusivity correlating with the wobbling length scale of these ellipsoidal bubbles. When we apply this diffusivity in a random displacement model of bubble spreading, our numerical simulations match closely the lateral spread observed by the M3 in the ocean water column. Finally, we compared the seep model predictions for the acoustic properties of these natural seep plumes with that observed by the acoustic instruments in the field. The M3 and EM 302 observations were converted to relative values of target strength using a calibration we obtained in the laboratory for the M3 and using an algorithm from the manufacturer for the EM 302. Comparing the numerical seep model to these data, we obtain good agreement over the whole height of rise of these bubble flares. This further validates the numerical model. Overall, our validated seep model captures the key dynamics of gas bubbles released from natural seeps in the oceans and helps to predict the fate of methane in the water column.

03 NATURAL GAS↗
DOE OSTI2021

Dy adsorption on and intercalation under graphene on 6 H -SiC(0001) surface from first-principles calculations

Previous experimental observations motivate clarification of configuration stabilities and kinetic processes for intercalation of guest atoms into a layered van der Waals material such as a graphene-SiC system. From our first-principles density functional theory (DFT) calculations, we analyze Dy adsorption and intercalation for graphene on a 6H-SiC(0001) surface, where the system includes two single-atom-thick graphene layers: the top-layer graphene (TLG) and the underling buffer-layer graphene (BLG) above the terminal Si layer. Our chemical potential analysis shows that intercalation of a single Dy atom into the gallery between TLG and BLG is more favorable than adsorption on TLG but that intercalation into the gallery underneath BLG is highly unfavorable. We obtain diffusion barriers of ~0.45 and 0.54 eV for a Dy atom diffusing on and under TLG, respectively. We find that the direct penetration of a Dy atom from the graphene top into the gallery under TLG is almost inhibited below a temperature of ~1400 K due to a large global barrier of at least ~3.5 eV. Instead, we find that a single Dy atom on TLG can easily intercalate by crossing a TLG step (e.g., a zigzag step presaturated by a Dy chain or a reconstructed zigzag step zz57). Additionally, we also perform DFT calculations for different Dy coverages to demonstrate how the favorability of Dy intercalation, as well as the corresponding interlayer spacings, depend on the coverage. Consequently, we can provide general insight and guidance for extensively studied systems involving intercalation of foreign atoms into graphene on a SiC substrate.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Fundamental Investigations into the Properties and Performance of Advanced Materials

Intelligent engineering designs require an accurate understanding of material behavior, since any uncertainties or gaps in knowledge must be counterbalanced with heightened factors of safety, leading to overdesign. Therefore, building better structures and pushing the performance of new components requires an improved understanding of the thermomechanical response of advanced materials under service conditions. This dissertation provides fundamental investigations of several advanced materials: thermoset polymers, a common matrix material for fiber-reinforced composites and nanocomposites; aluminum alloy 7075-T6 (AA7075-T6), a high-performance aerospace material; and ceramic matrix composites (CMCs), an advanced composite for extreme-temperature applications. To understand matrix interactions with various interfaces and nanoinclusions at their fundamental scale, the properties of thermoset polymers are studied at the atomistic scale. An improved proximity-based molecular dynamics (MD) technique for modeling the crosslinking of thermoset polymers is carefully established, enabling realistic curing simulations through its ability to dynamically and probabilistically perform complex topology transformations. The proximity-based MD curing methodology is then used to explore damage initiation and the local anisotropic evolution of mechanical properties in thermoset polymers under uniaxial tension with an emphasis on changes in stiffness through a series of tensile loading, unloading, and reloading experiments. Aluminum alloys in aerospace applications often require a fatigue life of over 109 cycles, which is well over ii the number of cycles that can be practically tested using conventional fatigue testing equipment. In order to study these high-life regimes, a detailed ultrasonic cycle fatigue study is presented for AA7075-T6 under fully reversed tension-compression loading. The geometric sensitivity, frequency effects, size effects, surface roughness effects, and the corresponding failure mechanisms for ultrasonic fatigue across different fatigue regimes are investigated. Finally, because CMCs are utilized in extreme environments, oxidation plays an important role in their degradation. A multiphysics modeling methodology is thus developed to address the complex coupling between oxidation, mechanical stress, and oxygen diffusion in heterogeneous carbon fiber-reinforced CMC microstructures.

Schichtel, Jacob J.↗
DOE OSTI2021

Symmetry in Seeded Metal Nanocrystal Growth

Symmetry underpins the structure and function of the world around us and is also captured in modern nanomaterials, where changing the symmetry of a nanocrystal or the interparticle spacing and orientation of nanocrystal building blocks in a superlattice can give new function. However, the synthesis and assembly of nanocrystals have been limited largely to simple compositions and structures. It remains a grand challenge to achieve nanocrystals with compositional and structural complexity while maintaining the monodispersity required for their use. This Account will illustrate through recent examples that seeded methods enable the synthesis of compositionally and structurally complex multimetallic crystals with defined and predictable symmetries for applications in plasmonics and catalysis. This outcome arises because the barrier for heterogeneous nucleation (i.e., seeded) is lower than that of homogeneous nucleation, where seeds can serve as preferential sites for the growth of complex structures and crystal phases. Our analysis begins by considering metal overgrowth from single-crystalline seeds of different shapes and symmetries, where the kinetics of adatom addition to seeds relative to their diffusion across seeds accounts for the expressed nanocrystal shapes. These results are then compared to overgrowth from seeds with different internal structures (i.e., planar defects), where the relationships between nanocrystal size and volumetric strain energy and surface energy are discussed. A major finding from this analysis is that often the underlying symmetry of seeds can be predictably transferred to the final crystals during overgrowth processes. Consequences of this finding are the predictable syntheses of crystals with different hierarchies akin to snowcrystals as well as nanocrystals with complex compositions (e.g., quaternary nanoparticles). Yet, there are subtle aspects to seeded growth that pave a path toward examples where nanocrystal symmetry has been reduced compared to the original seeds in a controlled manner. As we found, both the concentrations of metal precursors and capping agents can impact whether symmetry is transferred or reduced during overgrowth. Examples from our laboratory will be placed in context to other reported strategies for symmetry breaking. As will be argued, understanding what conditions favor symmetry preservation versus symmetry reduction during seeded crystal growth is central to accessing next-generation crystal forms. The Account concludes by outlining synthetic challenges associated with forming nanoscale heterostructures with precise 3-D placement of different materials within a given nanocrystal as well as facet control within different material domain and interface engineering. Furthermore, we envision meeting these challenges through regioselective and chemoselective seeded syntheses for which a foundation is outlined herein.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Prediction of Performance Variation Caused by Manufacturing Tolerances and Defects in Gas Diffusion Electrodes of Phosphoric Acid (PA)–Doped Polybenzimidazole (PBI)-Based High-Temperature Proton Exchange Membrane Fuel Cells

The automated process of coating catalyst layers on gas diffusion electrodes (GDEs) for high-temperature proton exchange membrane fuel cells results inherently into a number of defects. These defects consist of agglomerates in which the platinum sites cannot be accessed by phosphoric acid and which are the consequence of an inconsistent coating, uncoated regions, scratches, knots, blemishes, folds, or attached fine particles—all ranging from μm to mm size. These electrochemically inactive spots cause a reduction of the effective catalyst area per unit volume (cm2/cm3) and determine a drop in fuel cell performance. A computational fluid dynamics (CFD) model is presented that predicts performance variation caused by manufacturing tolerances and defects of the GDE and which enables the creation of a six-sigma product specification for Advent phosphoric acid (PA)-doped polybenzimidazole (PBI)-based membrane electrode assemblies (MEAs). The model was used to predict the total volume of defects that would cause a 10% drop in performance. It was found that a 10% performance drop at the nominal operating regime would be caused by uniformly distributed defects totaling 39% of the catalyst layer volume (~0.5 defects/μm2). The study provides an upper bound for the estimation of the impact of the defect location on performance drop. It was found that the impact on the local current density is higher when the defect is located closer to the interface with the membrane. The local current density decays less than 2% in the presence of an isolated defect, regardless of its location along the active area of the catalyst layer.

Gurau, Vladimir (ORCID:0000000327429061)↗
DOE OSTI2023

Controlling product selectivity in hybrid gas/liquid reactors using gas conditions, voltage, and temperature

For the conversion of CO 2 into fuels and chemical feedstocks, hybrid gas/liquid-fed electrochemical flow reactors provide advantages in selectivity and production rates over traditional liquid phase reactors. However, fundamental questions remain about how to optimize conditions to produce desired products. Here, using an alkaline electrolyte to suppress hydrogen formation and a gas diffusion electrode catalyst composed of copper nanoparticles on carbon nanospikes, we investigate how hydrocarbon product selectivity in the CO 2 reduction reaction in hybrid reactors depends on three experimentally controllable parameters: (1) supply of dry or humidified CO 2 gas, (2) applied potential, and (3) electrolyte temperature. Changing from dry to humidified CO 2 dramatically alters product selectivity from C 2 products ethanol and acetic acid to ethylene and C 1 products formic acid and methane. Water vapor evidently influences product selectivity of reactions that occur on the gas-facing side of the catalyst by adding a source of protons that alters reaction pathways and intermediates.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Role of electronic energy loss on defect production and interface stability: Comparison between ceramic materials and high-entropy alloys

High-entropy alloys (HEAs) and some complex alloys exhibit desirable properties and significant structural stability in harsh environments, including possible applications in advanced reactors. Energetic ion irradiation is often used as a surrogate for neutron irradiation; however, the impact of ion electronic energy deposition and dissipation is often neglected. Moreover, differences in recoil energy spectrum and density of cascade events on damage evolution must also be considered. In many chemically complex alloys, the mean free path of electrons is reduced significantly, thus their decreased thermal conductivity and slow dissipation of localized radiation energy can have noticeable effects on displacement cascade evolution that is greatly different from metals with high thermal conductivity. In this work, nanocrystalline HEAs of Ni 20 Fe 20 Co 20 Cr 20 Cu 20 and nonequiatomic (NiFeCoCr) 97 Cu 3 , both having much lower room-temperature thermal conductivity than pure Ni or Fe, are chosen as model HEAs to reveal the role that electronic energy loss during ion irradiation has in complex alloys. The response of nanocrystalline HEAs is investigated under irradiation at room temperature using MeV Ni and Au ions that have different ratios of electronic energy to damage energy, which is the energy dissipated in displacing atoms. Different from previously reported amorphization of nanocrystalline SiC, experimental results on these HEAs show that, similar to the process in nanocrystalline oxide materials, both inelastic thermal spikes via electron–phonon coupling and elastic thermal spikes via collisions among atomic nuclei contribute to the overall grain growth. The growth follows a power law dependence with the total deposited ion energy, and the derived value of the power-exponent suggests that the irradiation-induced instability at and near grain boundaries leads to local rapid atomic rearrangements and consequently grain growth. The high power-exponent value can be attributed to the sluggish diffusion and delayed defect evolution arising from the chemical complexity intrinsic to HEAs. Here, this work calls attention to quantified fundamental understanding of radiation damage processes beyond that of simplified displacement events, especially in simulating neutron environments.

36 MATERIALS SCIENCE↗
NASA NTRS1989

Raman intensity as a probe of concentration near a crystal growing in solution

The feasibility of using Raman spectral scattering signals for measurements of concentration profiles near a crystal interface during growth or dissolution is discussed. With KH2PO4 (KDP) as a test material, optical multichannel analyzer (OMA) detection of a solute Raman vibrational band provided direct quantification of solute concentration with band intensity. The intersection of incident laser and Raman collection optics provided 3-D selective point measurements of the solution concentration field. Unlike many other techniques, the Raman band intensity is not sensitive to the typical temperature variations. Precision calibration of Raman intensity versus KDP concentration with less than 1 pct standard deviation error levels was demonstrated. A fiber optic, which sampled incident laser intensity and coupled it to the OMA, provided a fully synchronized monitor of fluctuations in laser power to correlate with observed Raman signals. With 1 W of laser power at the sample, good data statistics required eight repeated data collections at approximately 2.5 min collection. The accumulated time represents the concentration measurement time at one spatial location. Photomicroscopy documented a 30 micrometer diameter by 200 micrometer of laser Raman scattering region in the solution near the crystal surface. The laser beam was able to approach up to 25 micrometer from the crystal surface. However, a crystal surface reflected intensity contribution was weakly detectable. Nucleated microcrystals were seen in the crystal-growing solution. These microcrystals convect right up to the crystal surface and indicate no quiet diffusion region under normal gravity conditions. Translation of the solution cell with respect to the optics caused systematic intensity errors.

Wilkinson, R. Allen↗
NASA NTRS1999

Role of Dynamic Nucleation at Moving Boundaries in Phase and Microstructure Selection

Solidification microstructures that form under steady-state growth conditions (cells, dendrites, regular eutectics, etc.) are reasonably well understood in comparison to other, more complex microstructures, which form under intrinsically non-steady-state growth conditions due to the competition between the nucleation and growth of several phases. Some important practical examples in this latter class include microstructures forming in peritectic systems in highly undercooled droplets, and in strip cast stainless steels. Prediction of phase and microstructure selection in these systems has been traditionally based on (1) heterogeneous nucleation on a static interface, and (2) comparing the relative growth rate of different phase/microstructures under steady-state growth conditions. The formation of new phases, however, occurs via nucleation on, or ahead of, a moving boundary. In addition, the actual selection process is controlled by a complex interaction between the nucleation process and the growth competition between the nuclei and the pre-existing phase under non-steady-state conditions. As a result, it is often difficult to predict which microstructure will form and which phases will be selected under prescribed processing conditions. This research addresses this critical role of nucleation at moving boundaries in the selection of phases and solidification microstructures through quantitative experiments and numerical modeling in peritectic systems. In order to create a well characterized system in which to study this problem, we focus on the directional solidification of hypo- and hyper-peritectic alloys in the two-phase region, imposing a large enough ratio of temperature gradient/growth rate (G/V(sub p)) to suppress the morphological instability of both the parent (alpha) and peritectic (Beta) phases, i.e. each phase alone would grow as a planar front. Our combined experimental and theoretical results show that, already in this simplified case, the growth competition of these two phases leads to a rich variety of microstructures that depend sensitively upon the relative importance of nucleation, diffusion, and convection.

Karma, Alain↗
DOE OSTI2025

Mechanistic Insights into the Surface Instabilities of TiNb 2 O 7, a High‐Power Li‐Ion Anode

TiNb 2 O 7 (TNO) is a promising Li-ion battery anode for high-power applications, such as implantable medical devices and heavy-duty equipment. Hailed as being safe due to its elevated operating potential near 1.6 V, TNO has long been assumed to be highly stable in the carbonate-based electrolytes used in Li-ion batteries. Herein, all mechanisms occurring at the surface of both TNO and Nd-doped TNO are identified, and both materials in fact show significant gassing. CO 2 is even released at open circuit conditions, demonstrating the poor chemical stability of the material in the electrolyte even prior to battery operation. Such extreme instability is a critical safety concern. In addition, it was found that Ti dissolves from the surface of TNO particles at low voltage (below 1.4 V vs Li), and in fact deposits on the counter electrode. Ti further inside TNO particles then diffuses to the Ti-poor surface during discharge. Partial carbon-coating as a mitigating measure has also been tested and found to exacerbate these processes. The findings identify novel reactions occurring within TNO, and clearly highlight the need to stabilize the surfaces of TNO in order to prevent such aggressive deterioration at the surface of the particles.

25 ENERGY STORAGE↗
DOE OSTI2020

Determining the hydration energetics on carbon-supported Ru catalysts: An adsorption calorimetry and density functional theory study

Fundamental knowledge on the energetics at the interface between a water layer and a metal catalyst is essential so as to understand the roles that water can play in the synthesis, activation and regeneration of noble metal-based catalysts. Here, we report the direct measurement of the enthalpy of water adsorption (Δh ads ) on activated carbon (C) and activated C-supported Ru nanoparticles, which are promising catalyst as applied to the hydrogenation/hydrodeoxygenation (HDO) of oxygenates (phenolics, aldehydes, etc.). Specifically, the near-zero coverage enthalpy of water adsorption on a C-supported Ru catalyst is -75.3 ± 0.4 kJ/(mol water), suggesting favorable water–metal binding. This is much more exothermic than that on C, which has an enthalpy of adsorption of -50.3 ± 1.3 kJ/(mol water). Despite the favorable initial binding, the magnitudes of enthalpies of water condensation on C and Ru-C indicate that overall, their surfaces are both hydrophobic. Moreover, the experimentally-measured near-zero coverage water adsorption enthalpy at the Ru sites is in very good agreement with our density functional theory based calculations. At low coverages, we obtain a water binding energy of -61.7 kJ/(mol water), which increases to -78.1 kJ/(mol water) at saturation. Complementary results are also obtained from a thermal analysis, which employed a thermogravimetric analysis–differential scanning calorimetry–mass spectrometry (TG-DSC-MS), a spectroscopic investigation using ex situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and a morphological evaluation with transmission electron microscopy (TEM). We point out that in carbon-supported metal catalysts, such as Ru-C, a strong hydration at near-zero coverage and relative weak water-surface interactions occurs upon saturation. Such heterogeneity is essential and crucial for catalytic hydrogenation/HDO reactions that involve balanced interactions among the water-rich reactant mixture and nonpolar organic products.

09 BIOMASS FUELS↗
DOE OSTI2022

Sheath formation around a dielectric droplet in a He atmospheric pressure plasma

Interactions at the interface between atmospheric pressure plasmas and liquids are being investigated to address applications ranging from nanoparticle synthesis to decontamination and fertilizer production. Furthermore, many of these applications involve activation of droplets wherein the droplet is fully immersed in the plasma and synergistically interacts with the plasma. To better understand these interactions, two-dimensional modeling of radio frequency (RF) glow discharges at atmospheric pressure operated in He with an embedded lossy dielectric droplet (tens of microns in size) was performed. The properties of the sheath that forms around the droplet were investigated over the RF cycle. The electric field in the bulk plasma polarizes the dielectric droplet while the electron drift in the external electric field is shadowed by the droplet. The interaction between the bulk and sheath electric fields produces a maximum in E/N (electric field/gas number density) at the equator on one side of the droplet where the bulk and sheath fields are aligned in the same direction and a minimum along the opposite equator. Due to resistive heating, the electron temperature T e is maximum 45° above and below the equator of the droplet where power deposition per electron is the highest. Although the droplet is, on the average, negatively charged, the charge density on the droplet is positive on the poles and negative on the equator, as the electron motion is primarily due to diffusion at the poles but due to drift at the equator.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Realization of a high luminosity muon beam at the Jefferson Lab

The proton is the major component of the visible matter of our universe, so being able to determine its fundamental properties, such as its charge radius, is of vital importance. In recent years, several experiments have been performed for the accurate measurement of the proton radius with different experimental techniques. The main and most common are based on two different techniques: ep scattering and Lamb shift spectroscopy of regular hydrogen atoms. The latter can also be performed on muonic hydrogen atoms with a significant improvement in accuracy. Recent measurements that use this method have highlighted a discrepancy between the results obtained with the diffusion of electrons and those obtained with the spectroscopic technique leading to the so-called ?proton radius puzzle?. The explanation of why this difference between the measured values exists is still a matter of discussion. The last attempt to address the puzzle was the PRad Experiment. It was performed with a unique experimental setup that gave the scientists an excellent control on the systematic errors that are usually present in electron-proton scattering experiments. This has significantly increased the precision of the measurement, bringing it in the same area as the spectroscopic ones done on muonic hydrogen atoms, which are considered the most precise. However, to solve the puzzle once and for all, even more precise electron scattering measurements are needed. Alternatively, new methods can be used, such as eg. muon-proton scattering at low transferred momenta in order to lower the systematic errors that comes with the measurement. This thesis tries to address this problem by studying the set up of an intense muon beam at the Jefferson Laboratory (JLab) that can be used to carry out a high-precision m ? p scattering experiment. Using Montecarlo simulations I studied the muon production resulting from the interaction of the primary electron beam with the beam-dump at JLab Hall-A. The simulations were performed using the FLUKA package via the FLAIR graphical interface. In this study, I modified an existing geometry (built for the ?Beam Dump eXperiment?) and performed several studies in order to optimize the muon beam parameters. In order to estimate the beam intensity, I studied the muon generation and transportation through the concrete bunker surrounding the Hall-A beam-dump. Detailed studies on muon attenuation and dispersion at different depth allowed me to track the beam profile in space and momentum as a function of the distance from the beam-dump. Last, but not least, I studied a possible tagging system for the muon beam. The tagging system will allow us to know with good precision (O(1=1000)) the energy of each muon of the beam. Based on the results obtained, I created an event generator that incorporates the detailed description of the muon beam (energy, position, emittance) useful to define and optimize the experimental setup for a future measurement of the proton radius at the JLab.

Fulci, Antonino↗
NASA NTRS2002

Smyer H-Chondrite Impact-Melt Breccia and Evidence for Sulfur Vaporization

Smyer is an H-chondrite impact-melt breccia containing approx.20 vol% 0.5- to 13-mm-thick silicate-rich melt veins surrounding unmelted subrounded chondritic clasts up to 7 cm in maximum dimension. At the interface between some of the melt veins and chondritic clasts, there are troilite-rich regions consisting of unmelted. crushed 0.2- to 140-micron-size angular silicate grains and chondrule fragments surrounded by troilite and transected by thin troilite veins. Troilite fills every available fracture in the silicates. including some as thin as 0.1 microns. Little metallic Fe-Ni is present in these regions: the FeS/Fe modal ratio ranges from -25: 1 to approx.500: 1, far higher than the eutectic weight ratio of 7.5: 1. The texture of these regions indicates that the sulfide formed from a fluid of very low viscosity. The moderately high viscosity (0.2 poise) and large surface tension of liquid FeS, its inability to wet silicate grain surfaces at low oxygen fugacities. and the supereutectic FeS/Fe ratios in the troilite-rich regions indicate that the fluid was a vapor. It seems likely that during the shock event that melted Smyer, many silicates adjacent to the melt veins were crushed. Upon release of shock pressure. some of the troilite evaporated and dissociated. Molecules of S2 were transported and condensed into fractures and around tiny silicate grains: there, they combined with Fe from small adjacent metallic Fe-Ni grains to form troilite. The Ni content at the edges of some of these metal grains increased significantly; Co from these Ni-rich grains diffused into nearby kamacite. Impact-induced S volatilization may have played a major role in depleting the surface of 433 Eros (and other chondritic asteroids) in S.

Rubin, Alan E.↗
DOE OSTI2022

Fusion Blanket and Fuel Cycle Research at PNNL: FY22 Year-end Report

During the reporting period, research at PNNL focused on two tasks within the DOE Fusion Blanket and Fuel Cycle Program. Research on Task 1, Tritium Extraction from Pb-Li and He Using a Vacuum Permeator, focused on atomistic modeling to better understand tritium transport in Pd-coated V vacuum permeators. As a lower cost alternative to Pd permeators, thin coatings of Pd (or other noble metals) can be deposited over a substrate like V. However, the permeation performance of composite metal membranes degrades over time, due to the formation of intermetallics at the coating-substrate interface. Computational studies were performed to better understand tritium transport through these Pd-V intermetallics. The results of the FY22 Pd-V modeling study were recently submitted for publication in Computational Materials Science and presented at the Technology of Fusion Energy conference. Future work in this area will focus on interdiffusion barriers to prevent intermetallic formation that is deleterious to tritium transport. There are opportunities for collaboration with researchers at the Colorado School of Mines, who are manufacturing and testing candidate interdiffusion barriers. Research on Task 3, Solid Breeder Materials, included ion irradiation and post-irradiation characterization of lithium orthosilicate (Li 4 SiO 4 ) and lithium metasilicate (Li 2 SiO 3 ) to improve fundamental understanding of irradiation effects, in combination with atomistic modeling focused on the energetics of He clustering in these two ceramic phases. The results of the study suggested that the Li 4 SiO 4 phase, which is more desirable as a solid breeder due to its higher Li density, was amorphized during ion irradiation while the Li 2 SiO 3 phase appeared to be more resistant to irradiation damage. It is possible that Li loss contributed to the poor irradiation performance of the Li 4 SiO 4 , and some thoughts are provided regarding coatings that could be applied to solid breeders like this to prevent Li loss at elevated temperature while not hindering tritium diffusion. The results of the FY22 ion irradiation study were recently submitted for publication in Journal of Nuclear Materials and presented at the 22nd International Conference on Ion Beam Modification of Materials. Future work in this area will focus on Li-rich ceramics such as Li 5 AlO 4 and Li 8 ZrO 6 that have high Li density and should provide rapid tritium release based on previous work with less Li-rich ceramics.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2025

Effects of dose rate on the microstructure and deuterium retention in γ-LiAlO 2 pellets

This report presents experimental findings obtained from November 2024 to September 2025. Defect accumulation and microstructural evolution during ion irradiation at elevated temperatures are governed by two competing processes: defect production, driven by dose rate, and defect recovery, controlled by defect diffusion, interaction, and annihilation. At a given dose, the resulting microstructural evolution depends on both the dose rate and irradiation temperature. As a continuation of our FY24 tritium science project, which investigated temperature effects at a fixed dose rate, this study focuses on dose-rate effects at a fixed temperature to provide deeper insights into the irradiated microstructure and compositional changes in γ-LiAlO 2 pellets. The study aims to elucidate the impact of dose rate on microstructure, precipitate morphology, deuterium retention, and lithium volatility in γ-LiAlO 2 pellets under sequential 120 keV He + and 80 keV D 2 + ion irradiation. Three dose rates of 7.3×10 4 , 2.9×10 4 and 6.8×10 5 dpa/s were applied to achieve the same total ion fluence of 2×10 17 (He + +D + )/cm 2 at 500 °C, corresponding to a maximum combined dose of 7.55 dpa at ~255 nm. The irradiated pellets were subsequently characterized using scanning transmission electron microscopy (STEM) and time-of-flight secondary ion mass spectrometry (ToF-SIMS). The microstructural response of γ-LiAlO 2 to ion irradiation was found to be strongly dose-rate dependent. At medium and high dose rates, irradiation produced a surface amorphized layer and an underlying crystalline layer containing LiAl 5 O 8 precipitates, with implanted gases accumulating and forming blisters at the crystalline-amorphous interface. It remains to be investigated whether the amorphized layer was produced by He + ion irradiation prior to D 2 + ion irradiation. In contrast, at low dose rates, the material remained crystalline, with cavities, likely gas-filled, distributed around precipitates, within the γ-LiAlO 2 matrix, and along grain boundaries. While precipitate morphology exhibited anisotropy, their size showed little sensitivity to dose rate in the applied range of this study. This result, however, does not rule out the possibility that further reductions in dose rate could influence precipitate size. High dose-rate irradiation enhanced protonium–deuterium isotopic exchange and lithium depletion in the amorphized region. Collectively, the results show that dose rate governs amorphization, gas redistribution, isotopic exchange, and lithium depletion, providing important insights into the mechanisms underlying structural evolution in γ-LiAlO 2 pellets under reactor-relevant irradiation conditions.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2025

Development of a Robust Reference Electrode in Aggressive Chemical and Radiation Environments in the Hanford Waste Tanks

The Hanford site stores more than 200 million liters of radioactive and chemically hazardous wastes from the production of weapons materials. The wastes are stored in 177 underground carbon-steel storage tanks, separated between 149 single shell tanks (SSTs) and 28 double shell tanks (DSTs). The DSTs provide critical retrieval and interim storage before the waste is vitrified in the Waste Treatment and Isolation Plant (WTP). The tanks will need to remain in-service far beyond the initial 40-year design life, and effective corrosion control practices must remain in force to extend the tanks’ lifespans. This effort includes direct measurements of corrosion rate (e.g., ultrasonic measurements and corrosion coupons) and electrochemical processes (e.g., linear polarization measurements and open circuit potential measurements). The Hanford site began monitoring the corrosion potential in select DSTs in 2008. Of the 45 reference electrodes that have been installed, 29 have failed and 6 others provided unreliable results. DOE-EM is supporting a 3-year program to develop a chemical and radiation resistant reference electrode for application in the Hanford tanks. The first year of the program focused on understanding the failure mechanism for the reference electrodes and identification of candidate construction materials that would mitigate degradation of the electrodes in the waste environment. During the second year of the program, the objectives were to: 1) test candidate materials under simulated waste conditions, 2) design components that will extend the service life of the electrode, 3) fabricate materials for prototype reference electrodes, and 4) assemble prototype reference electrodes for accelerated testing. The reference electrode is constructed of four principal parts: 1) junction, 2) casing, 3) inner chamber backfill materials, and 4) the sensing wire. Principally, improvements of the junction, casing, and inner chamber backfill materials are being pursued. The junction material at the interface between the waste and the inner chamber of the reference electrode was identified as a critical component in the failure of the reference electrodes. Nine candidate replacement junction materials were tested under simulated waste conditions to evaluate permeation rate. These materials included a variety of polymeric and ceramic materials, some of which were 3-D printed. Thus far, porous polyvinylidene fluoride materials have performed satisfactorily and are being considered for prototype development. The commercial electrode casing materials in general have performed well. Additionally, 3-D printing of chemically and mechanically stable materials is being investigated as a means for further improvement in fabrication consistency. SRNL has also investigated altering the reference electrode design to extend the service life. The new design of the interior of the reference electrode casing creates a longer, more tortuous path between the junction material and the electrode sensing wire. A finite element model was used to optimize the design without adversely impacting the circuit resistance of the electrode during the measurements, thus preserving the measurement accuracy while enhancing the service life. The inner chamber back fill materials are also critical to the performance of the reference electrode. Materials that are resistant to intruding tank waste and provide a conductive path to the sensing wire were investigated. Gel and powder materials that are interspersed with a conductive chloride bearing material were tested for their influence on diffusion and electrode resistance. All the investigated materials and components will be assembled, with collaboration from commercial vendors, to fabricate the initial prototypes. Accelerated testing of the prototypes will be initiated in Year 2 of the program and will be completed in Year 3. A recommendation on the materials of construction and the design of the new robust reference electrode will be presented to the Hanford tank farm facility.

Sykes, Kiana [Savannah River National Laboratory (↗