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At least 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Improving bamboo’s fuel and storage properties with a net energy export through torrefaction paired with catalytic oxidation

Using torrefied char, or biocoal, as solid fuel provides an opportunity to introduce a sustainable feedstock into the energy market. The goals of this study were to investigate how torrefaction improves the energy content and the grindability of a Malaysian bamboo along with understanding the potential for integrated energy recovery from torrefaction gases. The feedstock was torrefied at 250–290 °C for 1 h and the combustion characteristics and grindability of the solid products along with the composition of torrefied gas species were measured. The results showed a beneficial increase in elemental carbon increased from 47 to 63 wt% at 290 °C torrefaction, reflecting an increase in higher heating value from 17.8 to 25.6 MJ/kg. The combustion behavior of all the products appeared to show three distinct combustion zones; however, torrefaction severity leading to higher combustion temperature and time as the fixed carbon augmented with the increase of torrefaction temperature. This increase in severity also lead to more friable and grindable material, and the 290 °C condition required a factor of 2.7 less hold-up time in the mill compared to the raw bamboo, and a factor of 8.5 less energy (938 and 111 kWh/tonne respectively). Through analysis of the gas and volatile formation, a case study showed that catalytic oxidation can convert nearly 100% of the embodied chemical energy into usable thermal energy. These experimental findings were scaled to a 100,000 tonne/y capacity torrefaction plant and in the moderate case of 270 °C operating temperature, the plant has 1.25 GJ/tonne excess energy beyond what the process needs.

09 BIOMASS FUELS↗
DOE OSTI2020

Surface structure of linear nanopores in amorphous silica: Comparison of properties for different pore generation algorithms

In this work, we compare the surface structure of linear nanopores in amorphous silica (a-SiO 2 ) for different versions of “pore drilling” algorithms (where the pores are generated by the removal of atoms from the preformed bulk a-SiO 2 ) and for “cylindrical resist” algorithms (where a-SiO 2 is formed around a cylindrical exclusion region). After adding H to non-bridging O, the former often results in a moderate to high density of surface silanol groups, whereas the latter produces a low density. The silanol surface density for pore drilling can be lowered by a final dehydroxylation step, and that for the cylindrical resist approach can be increased by a final hydroxylation step. In this respect, the two classes of algorithms are complementary. We focus on the characterization of the chemical structure of the pore surface, decomposing the total silanol density into components corresponding to isolated and vicinal mono silanols and geminal silanols. The final dehyroxylation and hydroxylation steps can also be tuned to better align some of these populations with the target experimental values.

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

Catalytic and electrocatalytic performance of Sr(Ti 0.3 Fe 0.7 Ru 0.07 )O 3-δ for applications in solid oxide fuel cells supplied with ethanol steam reforming mixtures

We discuss how direct utilization of alcohols in Solid Oxide Fuel Cells (SOFCs) can improve the conversion efficiency by using excess heat for internal reforming and simplify the system balance of plant. Thanks to their scarce carbon- formation tendency, perovskite oxide anodes are promising alternatives to Ni-based cermets. Here we show that Sr(Ti 0.3 Fe 0.7 Ru 0.07 )O 3-δ (STF-Ru) exsolution anodes provide both catalytic reforming activity and electro- chemical activity with steam/ethanol (S/E) mixtures at 3:1 and 2:1 M ratio between 700 and 800 °C. Electrolyte- supported scandia stabilized zirconia SOFCs with STF-Ru anodes and Sr 0.95 Ti 0.3 Fe 0.7 O 3-δ (STF) cathodes are reasonably stable in the 3:1 S/E mixture over 20 h at 800 °C, with maximum power density of 195 mW/cm 2 and 140 mW/cm 2 at 0.7 V. Deactivation instead occurs with the 2:1 S/E mixture. Comparatively, cells with Ni-YSZ anodes rapidly coke and fail under the same conditions. Ethanol steam reforming experiments in a fixed bed powder reactor reveal that, above 650 °C, gas phase reactions convert ethanol to CO, hydrogen, acetaldehyde and ethylene, while STF-Ru catalyzes steam reforming. Thermogravimetric and Raman characterizations show that a moderate amount of carbon is deposited on the STF-Ru surface, which is more amorphous than the disruptive carbon which degrades Ni-YSZ.

09 BIOMASS FUELS↗
DOE OSTI2020

Advanced sorbents for modular oxygen production for REMS gasifiers

Under a DOE funded effort, Thermosolv LLC has been developing a sorbent-based oxygen production technology for gasification and oxy-combustion applications. The sorbents utilize oxygen-storage properties of certain perovskites to (1) selectively adsorb oxygen at moderate temperature from compressed air and (2) release the adsorbed oxygen into a vacuum or a sweep gas such as CO2 and/or steam. Through cyclic operations of multiple sorbent beds such a process can be made continuous. Pressure drop across the sorbent bed and other similar design considerations dictate that the sorbent be in the form of a high surface-area-to-volume pellet and yet still possess sufficient crush strength and integrity. Process efficiency is determined by the sorption and desorption kinetics and sorbent capacity. Typical process involves cycle times in the order of 100 seconds, a time too short to fully utilize the full volume of the sorbent and the sorption capacity of the sorbent pellets. As a part of this project, Thermosolv LLC undertook the development of oxygen sorbents as a high-surface area supported sorbent on a light-weight inert support to (1) reduce the cost, (2) increase the productivity, and (3) reduce the overall weight of the reactor. Using a previously developed perovskite (LSCF 1991) with its well-characterized performance, composite sorbent pellets each consisting of an inert core coated by a thin layer of the functional perovskite material were produced. Several low-density, inexpensive inert solids supports in the 1/8”-1/4” size were selected to keep the pressure drop across the sorbent bed in the acceptable range. A number of commercial technologies including spray coating, dip coating, incipient impregnation of porous substrate followed by thermal annealing at various temperatures and duration were employed and tested to produce robust composite supported sorbent pellets. A sense of optimum coating thickness was developed by testing sorbent pellets of various increasing diameter pellets. LSCF-1991extrudates ranging in size from 1/32” to 3/16” were tested in a TGA and in a fixed-bed pressure swing test set-up for sorption/desorption cycles of interest. The data show that for the operational conditions of interest the coating thickness for a supported sorbent pellet needs to be approximately 1/32” (about 0.8 mm). Subsequent work thereby concentrated on developing composite pellets of various substrates, shapes and sizes with coating layer of about this size range. Candidate support materials were chosen based on cost, inertness, mechanical strength, thermal expansion and chemical stability with sorbent material, and in a size range to give an acceptable pressure drop in fixed-bad reactor configurations. Coating application methods used for application of the sorbent onto the support included precipitation, spray coating and dip coating from sorbent slurries and sol gels. For all coated supports where we could successfully apply a uniform coating of desired thickness with an acceptable handling performance in terms of exfoliation, TGA-based cyclic sorption/desorption testing was performed to determine cycling capacity of oxygen. Among nearly twenty different support materials tested, best adhesion performance was obtained from stainless saddle supports. In the bench-scale fixed-bad tests stainless steel saddle support composite pellets with a coating thickness in the 0.6 mm or so range, the composite sorbent pellet performance approached up to 95% of that of the 2 mm parent material pellets. In a parallel approach to reducing the cost of the sorbent, alternate sorbent formulations replacing/reducing the amount of cobalt in the LSCF family were also investigated. Successful formulations that could match the performance of LSCF 1991 were identified based on TGA cyclic tests as LSCF 1919 and LSF 1910. In the range of operational envelop of cycle times and other relevant process operating conditions, the reduced Co formulations showed comparable performance in the bench-scale fixed-bad cyclic operations. As a part of this project, we also attempted substitution of La and Sr with Ca and Ba, and Co with Mn, Ni and Cu with little success, but the overall project goal of reducing sorbent cost in terms of raw material and manufacturing expenses was successful.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2024

Examining Graphite Degradation in Molten Salt Environments: A Chemical, Physical, and Material Analysis

Molten-salt reactors (MSRs) are Generation IV nuclear reactors that use liquid salt as a coolant and/or fuel. In several MSR designs, graphite serves as a moderator and/or reflector. However, due to limited experimental data and operational experience, our understanding of graphite behavior in molten salt environments remains incomplete. This report aims to identify the degradation mechanisms of nuclear graphite in MSRs, detail the mechanisms of each factor, and provide an initial assessment of their impact on the structural integrity of graphite components. This assessment is based on an extensive literature review and insights from subject matter experts. Furthermore, given the limited data, a modeling strategy using existing Grizzly software is proposed for a more thorough analysis where appropriate. Additionally, it presents mitigation strategies where applicable. The report covers physical degradation mechanisms such as infiltration, erosion, and abrasion, as well as chemical degradation mechanisms including fluorination, intercalation, corrosion, and oxidation. Molten salt can infiltrate the porous structure of graphite, leading to several detrimental effects. Entrapment of fissile products within the graphite pores can cause radiation damage and could pose challenges in the handling and disposal of contaminated components. The differential thermal expansion between the infiltrated salt and graphite, along with internal stress from pressurized molten salt and volumetric heating, can compromise the structural integrity of graphite. To mitigate these effects, employing ultra-fine graphite grades and applying sealants and coatings are effective strategies. A computational model based on coupled solid mechanics and heat transfer phenomena could be used to predict the internal stresses using Grizzly software. In pebble-bed MSRs, graphite fuel pebbles can cause abrasion against reactor components due to friction and wear. The severity of wear is influenced by various factors such as temperature, environment, and the presence of lubricants. Tribological studies reveal that higher temperatures and molten salt environments, such as FLiBe, significantly reduce wear rates compared to dry conditions. Additionally, the chemical composition of the salt can further optimize graphite's tribological performance. Long-term wear effects can be modeled by incorporating surface defects into the geometry and predict stresses under thermal and radiation effects using Grizzly software. Chemical degradation of graphite in a molten salt environment can occur through fluorination and intercalation. Fluorination can occur via replacement of hydrogen or oxygen atoms, or at the active sites, but does not cause structural degradation. Intercalation, on the other hand, can lead to exfoliation, where layers of graphite separate and peel away, damaging the graphite. Protective coatings can enhance graphite's resistance to intercalation. Graphite generally exhibits good chemical stability in molten salt environments, though it can corrode under specific conditions, particularly in the presence of impurities or oxidants. Studies have shown that protective coatings, such as plasma-sprayed partially stabilized zirconia (PSZ), can effectively prevent such degradation. Corrosion behavior varies significantly with different graphite grades and coating applications, underscoring the need for detailed studies on uncoated and coated graphite to understand and mitigate corrosion mechanisms in MSRs. Research indicates that the presence of oxidants and impurities can accelerate graphite degradation in molten salts, making it essential to explore acceptable impurity limits. Oxidation is another critical degradation mechanism, leading to weight loss and structural damage due to the formation of CO and CO 2 from the reaction of carbon atoms with oxygen. This process creates new porosity and compromises graphite's integrity. While extensive research on graphite oxidation has been conducted for gas-cooled reactors, studies specific to MSRs are limited. Findings from the coal industry suggest that molten alkali metal salts can significantly accelerate graphite oxidation, a hypothesis worth exploring for fluoride salts in MSRs. Understanding oxidation behavior in MSRs is vital for developing protective measures. The analysis of post-irradiated graphite from the MSRE experiment demonstrated exceptional chemical compatibility with molten fluoride salt, suggesting that the extent of chemical attack on graphite largely depends on the salt's infiltration capability. Therefore, the use of ultra-fine grade graphite could help mitigate chemical degradation effects. Existing oxidation modeling capabilities in Grizzly, which use reaction-diffusion equations to model graphite-air interactions, could be adapted to simulate the chemical degradation effects of graphite in molten salt environments.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2023

Laser-direct-drive fusion target design with a high- Z gradient-density pusher shell

Laser-direct-drive fusion target designs with solid deuterium-tritium (DT) fuel, a high-Z gradient-density pusher shell (GDPS), and a Au-coated foam layer have been investigated through both 1D and 2D radiation-hydrodynamic simulations. Compared with conventional low-Z ablators and DT-push-on-DT targets, these GDPS targets possess certain advantages of being instability-resistant implosions that can be high adiabat (α ≥ 8) and low hot-spot and pusher-shell convergence (CR hs ≈ 22 and CR PS ≈ 17), and have a low implosion velocity (v imp < 3 × 10 7 cm/s). Using symmetric drive with laser energies of 1.9 to 2.5 MJ, 1D LILAC simulations of these GDPS implosions can result in neutron yields corresponding to >~50–MJ energy, even with reduced laser absorption due to the cross-beam energy transfer (CBET) effect. Two-dimensional DRACO simulations show that these GDPS targets can still ignite and deliver neutron yields from 4 to ~10 MJ even if CBET is present, while traditional DT-push-on-DT targets normally fail due to the CBET-induced reduction of ablation pressure. If CBET is mitigated, these GDPS targets are expected to produce neutron yields of >20 MJ at a driven laser energy of ~2 MJ. Here are the key factors behind the robust ignition and moderate energy gain of such GDPS implosions are as follows: (1) The high initial density of the high-Z pusher shell can be placed at a very high adiabat while the DT fuel is maintained at a relatively low-entropy state; therefore, such implosions can still provide enough compression ρR >1 g/cm 2 for sufficient confinement; (2) the high-Z layer significantly reduces heat-conduction loss from the hot spot since thermal conductivity scales as ~1/Z; and (3) possible radiation trapping may offer an additional advantage for reducing energy loss from such high-Z targets.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2024

Pathway to High Rate Capability in Interconnected Composite Electrolytes: A Case Study with a Single-Ion-Conducting Polymer

In a three-dimensional interconnected polymer/ceramic composite electrolyte (3D composite), both the polymer and ceramic electrolyte phases are individually connected with a polymer-rich surface layer to provide conformal contact with the electrodes. This work investigates how the transference number of the polymer phase affects the electrochemical properties of the 3D composite. Here, we fabricate a 3D composite using a “single-ion” conducting polymer electrolyte (PE), Li 1+x+y Al x Ti 2–x Si y P 3–y O 12 (LICGC) ceramic, and compare its electrochemical properties with the neat polymer, and with a 3D composite made with a dual-ion-conducting PE (we reported previously). Our results reveal that changing the polymer phase from a dual-ion-conducting PE to a single-ion-conducting PE results in a 9-fold increase in the limiting current density, although the interfacial impedance between the polymer and LICGC ceramic remains high (and contributes significantly to the total impedance of the 3D composite). Further, the limiting current density of the 3D composite is dictated by the PE and minimally affected by the ceramic scaffold. The ceramic scaffold, however, helps to ease the concentration gradient buildup within the PE and moderately improves the overall transference number. The LICGC scaffold does not provide any additional Li dendrite resistance due to its high reactivity with Li.

25 ENERGY STORAGE↗
DOE OSTI2022

In Situ High-Temperature TEM Observation of Inconel Corrosion by Molten Chloride Salts with N 2 , O 2 , or H 2 O

Here, in situ transmission electron microscopy (TEM) diffraction and imaging techniques are used to monitor and quantify corrosion of Inconel-625 by pure molten chloride salts (MgCl 2 – NaCl – KCl) at 500 °C–800 °C in 1.0 atm inert N 2 or pure O2, or by salts which are controllably hydrated in a high vacuum chamber. The isothermal corrosion rate R in inert N 2 increases from 203 ± 30 μ m year –1 at 700 °C to 463 ± 30 μ m year –1 at 800 °C. An oxygen ambient causes a six-fold increase to R = 1261 ± 170 μ m year –1 at 700 °C. Salt hydration dramatically accelerates corrosion to R > 3 × 10 5 μ m year –1 at 700 °C while it leads to a more moderate R = 95 ± 20 and 486 ± 30 μ m year –1 at 500 °C and 600 °C, respectively. These isothermal corrosion rates indicate that the molten chloride corrosion is significantly accelerated by salt hydration at temperatures above 600 °C, where corrosion is aggravated by increased generation and solubility of corrosive HCl gases. Hence, to reduce rate of corrosion it is important to both avoid incorporation of H 2 O into the system at each stage and ensure proper flushing of the system before increasing the temperature beyond 600 °C. Compositional analysis of the corroded cells indicate that corrosion in O 2 ambient is dominated by oxidation of metals by O 2 gas dissolved in the chloride melt, but corrosion in H 2 O ambients is caused by chlorination of metals by dissolved HCl gas and MgOH + ions. So, to reduce rate of corrosion, steps should be taken to tailor chloride melt compositions that has low solubility for HCl and O 2 . All of our corroded samples exhibit passive-protective oxide layers of Cr, Mg, and Ni. In addition, distinct volatile compounds of Ni, Mo and Cr involving NiCl 2 , (Na,K) 2 MoO 4 and CrO 2 (OH) 2 are detected in N 2 , H 2 O, and O 2 ambients, respectively. We believe that corrosion acceleration can be minimized by minimizing formation of volatile by-products or promoting reactions that could convert these volatile compounds to solid phases, as these volatile compounds led to destruction of protective oxide layers.

14 SOLAR ENERGY↗
DOE OSTI2021

Moderate temperature sintering of BaZr 0.8 Y 0.2 O 3-δ protonic ceramics by A novel cold sintering pretreatment

The state-of-the-art protonic ceramic conductor BaZr 0.8 Y 0.2 O 3-δ (BZY20) requires an extremely high sintering temperature (≥1700 °C) to achieve the desired relative density and microstructure necessary to function as a proton conducting electrolyte. In this work, we developed a cold sintering pretreatment assisted moderate-temperature sintering method for the fabrication of high-quality pure BZY20 pellets. BZY20 pellets with high relative density of ~94% were fabricated with a final sintering temperature of 1500 °C (200 °C lower than the traditional sintering temperature). A comparison with BZY20 control samples indicated that the proper amount of BaCO 3 introduced on the BZY20 particle surface and the high green density achieved by cold sintering pretreatment were the main drivers for lowering the sintering temperature. The electrical conductivity measurement by electrochemical impedance spectroscopy showed that the as-prepared BZY20 pellets have a proton conductivity comparable to the state-of-the-art values. The cold sintering pretreatment outlined in this work has the potential to lower the sintering temperatures for similar types of protonic ceramic materials under consideration for a wide range of energy conversion and storage applications.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Using Low-Cost Measurement Systems to Investigate Air Quality: A Case Study in Palapye, Botswana

Exposure to particulate air pollution is a major cause of mortality and morbidity worldwide. In developing countries, the combustion of solid fuels is widely used as a source of energy, and this process can produce exposure to harmful levels of particulate matter with diameters smaller than 2.5 microns (PM 2.5 ). However, as countries develop, solid fuel may be replaced by centralized coal combustion, and vehicles burning diesel and gasoline may become common, changing the concentration and composition of PM 2.5 , which ultimately changes the population health effects. Therefore, there is a continuous need for in-situ monitoring of air pollution in developing nations, both to estimate human exposure and to monitor changes in air quality. In this study, we present measurements from a 5-week field experiment in Palapye, Botswana. We used a low-cost, highly portable instrument package to measure surface-based aerosol optical depth (AOD), real-time surface PM 2.5 concentrations using a third-party optical sensor, and time-integrated PM 2.5 concentration and composition by collecting PM 2.5 onto Teflon filters. Furthermore, we employed other low-cost measurements of real-time black carbon and time-integrated ammonia to help interpret the observed PM 2.5 composition and concentration information during the field experiment. We found that the average PM 2.5 concentration (9.5 μg∙m –3 ) was below the World Health Organization (WHO) annual limit, and this concentration closely agrees with estimates from the Global Burden of Disease (GBD) report estimates for this region. Sulfate aerosol and carbonaceous aerosol, likely from coal combustion and biomass burning, respectively, were the main contributors to PM 2.5 by mass (33% and 27% of total PM 2.5 mass, respectively). While these observed concentrations were on average below WHO guidelines, we found that the measurement site experienced higher concentrations of aerosol during first half our measurement period (14.5 μg∙m –3 ), which is classified as "moderately unhealthy" according to the WHO standard.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Quarterly Research Performance Progress Report (Q8)

As part of Task 1, we have started by testing our modeling capabilities by reproducing isothermal DFIT simulations presented in the literature. Once satisfied with the results we have started by targeting the modeling of the DFITs at conducted at well 58-32. We have a identified a specific test (cycle 4 in zone 2) as the most interesting to be model with GEOS hydraulic fracturing module. Thus, we have first produced results with an isothermal model and adjusted model parameters to get a satisfying match with field pressure data. The, we have added thermal effects and compared the modeling results with and without thermal effects to estimate how thermal effects may influence test interpretation. Models seem to suggest that, for small volumes of fluid, thermal effects are moderate. In Task 2, we have adapted GEOS phase-field formulation to be able to simulate near-wellbore hydraulic fracture nucleation and propagation. We have devised a novel formulation that, compared to other existing ones, incorporates rock strengths. We have submitted a journal publication about our work. We are currently employing this phase-field formulation to model the experiments taking place at U Pitt and help us understand the effect of various parameters. In Task 3, we have built a model of the region surround well 16A and have started modeling stage 3 stimulation because of its simpler planar geometry. After calibrating simulation parameters using known analytical solutions, we have simulated the stage 3 stimulation using our isothermal hydraulic fracturing module, varying the permeability field, the stress conditions including different physics to get a better understanding of the numerical challenges and of the effects of varying these parameters on the simulation results. In Task 4 laboratory experimentation, a set of specialized drilling and injection tools has been customized and constructed to accommodate an inclined well with an orientation of up to 30 degrees relative to material anisotropy or principal stress axes. These inclined samples have also undergone thermal stress and hydraulic fracturing at a temperature of 190 degrees Celsius. Furthermore, both vertical and deviated sampling testing setups enable an extended analysis of post-peak pressure behaviors, facilitating post-test pressure analyses such as the G-function, step rate, and fracture reopening measurements. Thus, the key components of in-situ stress estimation can be extracted and validated through our experiment, providing a solid foundation for validating existing in-situ stress estimation theories or proposing new ones. Simultaneously, we are integrating computer vision techniques with traditional experimental fracture observation methods such as multi-overcore/slicing and water-penetration fracture observation. This combination will prove beneficial in populating the hydraulic fracture patterns database, generated under challenging EGS conditions. This approach aims to deepen our understanding of the complexities in EGS reservoirs and pave the way for future data-driven investigations. Additionally, PITT has also equipped the ELE International compression machine, which is now prepared for conducting indirect tensile and fracture toughness tests. These tests will aid in characterizing how rock fabrics influence the resulting fracture patterns. Additionally, we have completed the required personnel training and gained access to Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) for conducting more detailed characterization and analysis of rock fabrics, as well as the examination of thermal and hydraulically induced fracture patterns. Thus, the PITT team has effectively demonstrated the capabilities of our experimental apparatuses in exploring the thermal effects, well deviation angles, material anisotropy, and operational choices (such as circulation rate, injection fluid viscosity, and injection rate) and their impact on pressure responses and fracture trajectories under the Utah FORGE conditions.

15 GEOTHERMAL ENERGY↗
DOE OSTI2022

Integration of Omics into a New Comprehensive Rate Law for Competitive Terminal Electron-Accepting Processes in Reactive Transport Models: Application to N, Fe, S, and Contaminant Transformations in Stream and Wetland Sediments

Surface waters represent important sources of alternate energy and drinking water in the United States, and characterizing the biogeochemical processes that affect surface water quality is relevant to the DOE-BER mission. Sediment biogeochemical processes regulate the release of carbon (C), nutrients, and contaminants to surface waters and thus influence water quality. Sediment biogeochemical processes are dynamic and affected by the deposition and remobilization of solid material and changes in environmental conditions driven by water discharge variations. Wetlands are important natural filters of surface waters which may either trap, metabolize, or mobilize nutrients and contaminants. Despite their importance, biogeochemical processes regulating nutrient and contaminant release and C transformation in stream and wetland sediments cannot be predicted accurately by current mathematical models. These reactive transport models largely rely on detectable changes in geochemical conditions to activate metabolic processes, do not accurately account for the competition between microbial processes, and poorly constrain effects of hydrological perturbations on biogeochemical processes. In this BER-SBR exploratory project, metagenomic and geochemical signatures were combined to identify microbially-mediated redox processes in anaerobic stream and wetland sediments from the Savannah River Site (SRS, ANL SFA) and East Fork Poplar Creek (EFPC, ORNL SFA) that play important roles in C, uranium (U), and mercury (Hg) transformations. In addition, sediment incubations were conducted to examine the competition between anaerobic respiration processes Finally, new rate laws were developed for reactive transport models that rely on complementary metagenomic and geochemical signatures to identify the underlying anaerobic microbial processes in stream and wetland sediments, describe the competition between the dominant metabolic processes involved in nutrient release and U and Hg mobilization, and more accurately quantify carbon transformation and the response of microbial processes to changes in redox conditions associated with hydrological forcing. These rate laws were optimized in batch reactors with SRS wetland sediments, where iron and sulfate reduction dominate. Anaerobic carbon remineralization processes followed the expected thermodynamic sequence of microbial respiration with depth in both sediments, except that geochemical signals indicated that sulfate reduction was inactive in EFPC sediments and moderate in SRS wetland sediments. Estimates indicated that microbial iron reduction contributed to at least half of the production of reduced iron in these sediments. Incubations demonstrated that nitrate reduction, denitrification, and dissimilatory nitrate reduction to ammonium were active in the natural EFPC sediment and activated upon nitrate amendment in these nitrate-rich sediments. In turn, these processes were outcompeted by the addition of either iron oxides or sulfate as alternative terminal electron acceptors. Although geochemical products of sulfate reduction were not detected in the incubations, the abundance of sulfate reduction genes increased with depth in the sediment and was equally more pronounced in treatments amended with either iron oxides or sulfate. Simultaneously, anaerobic sulfide oxidizing bacteria coupling sulfide oxidation to DNRA (and not conventional denitrification) were apparently enriched over time, regardless of the treatments. These findings indicate that sulfate reduction is important in freshwater stream sediments and probably catalyzed by a cryptic sulfur cycle involving nitrogen species, in which the sulfur products from sulfate reduction are immediately removed by side reactions and not detectable by geochemical measurements alone. Similar experiments in SRS sediments, however, demonstrated little interaction between nitrogen and sulfur cycling microorganisms. Sulfate reduction was impacted by the addition of more thermodynamically favorable electron acceptors, suggesting either that iron-reducing microorganisms outcompeted sulfate-reducing microorganisms for organic substrate, depleting the stock of electron donor available for sulfate reduction, or that the cryptic sulfur cycle was shunted by the precipitation of FeS generated as a result of the abiotic reduction of iron oxides by dissolved sulfide. A diagnostic modeling exercise was conducted to further investigate the competition between terminal electron accepting processes. As conventional kinetic models typically do not account for cryptic cycles and used inaccurate formulations to describe competition between microbial communities, new metabolic rate laws were developed that explicitly express the electron acceptor-specific enzyme of each energetically favorable metabolic process based on gene abundance detected in the incubations. The model was tested with the sediment slurry incubation data to determine whether substrate competition could explain the decrease in sulfate reduction observed in the presence of iron oxide competitor. The model was able to reproduce geochemical concentrations really well in each treatment once the model was calibrated with the unamended control, suggesting that microbial competition was indeed driven by thermodynamic considerations. Overall, carbon remineralization processes and rates will be reproduced much more realistically with the new metabolic rate laws.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

Neutron capture-induced nuclear recoils as background for CE$v$⁢NS measurements at reactors

Nuclear reactors represent a promising neutrino source for CE⁢v⁢NS (coherent-elastic neutrino-nucleus scattering) searches. However, reactor sites also come with high ambient neutron flux. Neutron capture-induced nuclear recoils can create a spectrum that strongly overlaps the CEv⁢NS signal for recoils ≲100 eV for nuclear reactor measurements in silicon or germanium detectors. This background can be particularly critical for low-power research reactors providing a moderate neutrino flux. Here, in this work we quantify the impact of this background and show that, for a measurement 10 m from a 1 MW reactor, the effective thermal neutron flux should be kept below ~7 × 10 –4 ⁢n/cm 2 s so that the CE⁢v⁢NS events can be measured at least at a 5⁢σ level with germanium detectors in 100 kg yr exposure time. This flux corresponds to 60% of the sea-level flux but needs to be achieved in a nominally high-flux (reactor) environment. Improved detector resolution can help the measurements, but the thermal flux is the key parameter for the sensitivity of the experiment. For silicon detectors, the constraint is even stronger and thermal neutron fluxes must be near an order of magnitude lower. This constraint highlights the need of an effective thermal neutron mitigation strategy for future low threshold CEv⁢NS searches. In particular, the neutron capture-induced background can be efficiently reduced by active veto systems tagging the deexcitation gamma following the capture.

79 ASTRONOMY AND ASTROPHYSICS↗
DOE OSTI2024

Exploring the Nature of f-Element Soft Donor Interactions Using Electronically Tunable Azolate Ionic Liquids

This project was undertaken to advance the understanding of how f-elements interact with moderately soft donors, a heavily investigated yet open question which is of prime importance in spent nuclear fuel processing and fundamental inorganic chemistry. During the course of the project, based on exciting results, a stretch goal was developed to study the hydrolysis products of transuranic actinide metals, a somewhat understudied field even with its significance in nuclear fuel cycle and impacts in environmental chemistry. The stretch goal was to take our serendipitous discovery of an easy route to isolation of crystalline multinuclear ƒ-element hydrolysis products, and apply it to gaining a mechanistic understanding of Pu(III/IV) colloid formation. The simplicity of our techniques should lend themselves to the remote handling required for study of many transuranic elements. We developed several methodologies using azolium azolate chemistry to overcome ƒ-element hydrolysis problems that prohibit the isolation of ƒ-element soft donor complexes and to build a crystallographic library of ƒ-element N-donor complexes as a means to understand the fundamental differences between actinide and lanthanide interactions with moderately soft donor ligands. Our next major endeavor will be to transfer this chemistry from 4ƒ elements to transuranic elements, particularly in the study of hydrolysis of Pu(III/IV). While our work is fundamental in nature, applications of the knowledge we are generating should be felt in such diverse fields as catalysis, separations in general, nuclear waste remediation specifically, and many other applications in f-element magnetic and luminescent properties. The potential ramifications of the consistent and robust formation of hydrolysis controlled hexanuclear lanthanide structures are enormous, with future uses being catalyst formation, higher-nuclearity structure synthesis using our hexanuclear motif as a fundamental building block, Pu waste remediation, separations, and many other potential applications resulting from characteristic magnetic and luminescent properties of lanthanide polynuclear structures. Three synthetic methodologies (direct mixing with variable stoichiometries, use of volatile solvent, metathesis) were developed starting with 7 acidic and 6 basic azoles to obtain ionic liquids suitable for f-element coordination. Proton transfer by acidic/basic azole combination led to suitable low melting salts and two cocrystals. Acid/base reaction of azoles with soft-donor permanent cations of ([X 4444 ][OH] (where [X 4444 ] + = tetrabutylammonium [N 4444 ] + or tetrabutylphosphonium [P 4444 ] + ) with weakly acidic azoles including imidazole, 1,2,3-triazole, 1,2,4-triazole, 5-aminotetrazole, 4,5-dicyanoimidazole, and 2-amino-4,5-dicyanoimidazole) revealed several suitable low-melting salts. Metathesis reactions of Na(azolate) were conducted by first using weakly acidic azoles including 4,5-dicyanoimidazole, 2-amino-4,5-dicyanoimidazole, 5-aminotetrazole, and 1,2,4-triazole to form sodium or lithium salts using group(I) hydroxides in methanolic solutions. The best results were obtained by reacting the basic and acidic azoles directly in 1:1 or 3:1 ratios at elevated temperatures. Twenty-two azole mixtures were identified which are either low melting solids or room temperature liquids. Each of the low melting solids was confirmed to be a new solid phase, each of which is being further characterized. The liquids and solids are anticipated to be ILs, eutectics, or partially ionized systems, all of which will be suitable for the dissolution of f-element salts. Five new synthetic methodologies were developed to finding suitable crystallization conditions for f-element complexation with the goal of finding simple one pot reaction syntheses and crystallization strategies that could be used under the demanding conditions of transuranic chemistries. These synthetic methods yield many new crystalline phases which were studied by single crystal X-ray diffraction.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2024

Carbonate Management to Enable Energy- and Carbon-Efficient CO 2 Electrolysis (Final Technical Report)

The rapid growth and plummeting cost of solar energy have spurred growing interest in using CO 2 electrolysis to produce chemicals and fuels as an alternative to conventional petrochemical processes. High-temperature (>800 °C) solid oxide electrolyzers that convert CO 2 into CO and O 2 have recently become commercially available. Low-temperature electrolysis cells offer the prospect of more convenient and flexible operation, which is critical for utilizing intermittent solar energy, and provide access to more valuable C 2+ products such as ethylene, ethanol, and propanol. Over the past 10 years, research in this area has yielded substantial progress in both fundamental understanding of the requisite electrocatalytic reactions and design of prototype devices. Leveraging insights from fuel cells and membrane water electrolyzers, researchers have developed electrolysis cells with gas diffusion electrodes (GDE) that have demonstrated high CO 2 electrolysis current densities (>100 mA cm –2 ) as well as promising selectivity and stability. Despite these advances, the energy efficiency (electrical energy-to-product) and carbon efficiency (CO 2 -to-product) of low-temperature CO 2 electrolysis remain far too low for large-scale deployment. A preponderance of evidence indicates that the principal source of efficiency losses is the rapid and thermodynamically favorable reaction of CO 2 with hydroxide (OH – ) to form carbonate (CO 3 2– ). Carbonate formation imposes steady-state electrolysis conditions that result in large voltage and CO 2 losses for all known (photo)electrochemical CO 2 cells. While much current research remains focused on CO 2 reduction catalyst design, this largely overlooked CO 3 2– problem presents a fundamental scientific barrier to creating a viable electrochemical option for converting solar energy into chemicals and fuels. The project pursues an integrated, multi-PI research effort that establishes a fundamental science of CO 3 2– management. PI Kanan and Co-PI Mani’s contribution to the project is to evaluate strategies to mitigate the CO 3 2– problem by changing the properties of the electrolyte and the environment in which CO 2 reduction catalysis takes place. Experimental studies showed that electrolytes composed of a high concentration of both CO 3 2– and HCO 3 – , which serve as moderately alkaline buffers, improved the cell voltage by compared to all-HCO 3 – electrolytes, but these buffered systems still show substantial CO 2 uptake that reduces pH over time. Computational studies developed a homogenized model of a CO 2 reduction catalyst layer that permits a low-cost exploration of the high-dimensional parameter space associated with catalyst layers on gas diffusion electrodes. The model was validated by accurately reproducing experimental data for the related but simpler reaction of CO reduction and then used to probe the effects of catalyst layer architecture on CO 2 reduction. Minimizing the size of catalyst and hydrophobic domains in the catalyst layer is predicted to mitigate CO 3 2– formation and thereby enable prolonged operation at elevated pH. In support of the CO 2 electrolysis studies, a new method for rapidly prototyping electrochemical cells was developed and validated. The method uses a combination of 3D printing and electroless plating to generate conductive cell components for evaluating new cell designs. The carbonate problem encompasses mass transport processes and acid-base reactions that are relevant to many other electrochemical systems. Investigation of strategies to address the carbonate problem led to an additional line of inquiry into the physicochemical phenomena that determine the efficiency of electrochemical acid-base production, which has numerous applications in the broader field of carbon management. New strategies for using the supporting electrolyte to inhibit H + /OH – recombination in electrochemical acid-base production were evaluated, leading to the development of a novel acid-base producing system that eliminates the need for ion exchange membranes and exhibits promising efficiency and current densities for scalable applications.

25 ENERGY STORAGE↗
DOE OSTI2024

Real-Time Observation of Nanoscale Kink Band Mediated Plasticity in Ion-Irradiated Graphite: An In Situ TEM Study

Graphite IG-110 is a synthetic polycrystalline material used as a neutron moderator in reactors. Graphite is inherently brittle and is known to exhibit a further increase in brittleness due to radiation damage at room temperature. To understand the irradiation effects on pre-existing defects and their overall influence on external load, micropillar compression tests were performed using in situ nanoindentation in the Transmission Electron Microscopy (TEM) for both pristine and ion-irradiated samples. While pristine specimens showed brittle and subsequent catastrophic failure, the 2.8 MeV Au2+ ion (fluence of 4.378 × 1014 cm−2) irradiated specimens sustained extensive plasticity at room temperature without failure. In situ TEM characterization showed nucleation of nanoscale kink band structures at numerous sites, where the localized plasticity appeared to close the defects and cracks while allowing large average strain. We propose that compressive mechanical stress due to dimensional change during ion irradiation transforms buckled basal layers in graphite into kink bands. The externally applied load during the micropillar tests proliferates the nucleation and motion of kink bands to accommodate the large plastic strain. The inherent non-uniformity of graphite microstructure promotes such strain localization, making kink bands the predominant mechanism behind unprecedented toughness in an otherwise brittle material.

36 MATERIALS SCIENCE↗
DOE OSTI2026

A compact, low-power epithermal neutron counter for lunar water detection

The detection and characterization of lunar water are critical for enabling sustainable human and robotic exploration of the Moon. Orbital neutron spectrometers, such as instruments on Lunar Prospector and the Lunar Reconnaissance Orbiter, have revealed hydrogen-rich regions near the poles but are limited by coarse spatial resolution and low counting efficiency. We present a compact, lightweight, and low-power epithermal neutron detector based on boron-coated silicon imagers, designed to probe subsurface hydrogen at decimeter scales from mobile platforms such as lunar rovers. This instrument leverages the high neutron capture cross-section of 10 B to convert epithermal neutrons into detectable α and 7 Li ions in a fully-depleted silicon imager, providing a unique event topology to identify neutrons while suppressing backgrounds. Monte Carlo simulations demonstrate that a 3 μm boron layer achieves optimal neutron detection efficiency, further enhanced with polyethylene moderation to improve sensitivity to the 0.4 eV–500 keV epithermal energy range. For a 10 cm 2 active area, the detector achieves sensitivity to H 2 O weight fractions as low as 0.01 wt% in a 15 minute measurement. This scalable, portable, low-mass design is well-suited for integration into upcoming Artemis and commercial lunar rovers, providing a transformative capability for in-situ resource prospecting and ground-truth validation of orbital measurements.

Detector modelling and simulations I (interaction ↗
DOE OSTI2025

Measured gain suppression in FBK LGADs with different active thicknesses

In recent years, the gain suppression mechanism has been studied for large localized charge deposits in Low-Gain Avalanche Detectors (LGADs). LGADs are a thin silicon detector with a highly doped gain layer that provides moderate internal signal amplification. Using the CENPA Tandem accelerator at the University of Washington, the response of LGADs with different thicknesses to MeV-range energy deposits from a proton beam were studied. Three LGAD prototypes of 50 μm, 100 μm, and 150 μm were characterized. The devices' gain was determined as a function of bias voltage, incidence beam angle, and proton energy. This study was conducted in the scope of the PIONEER experiment, an experiment proposed at the Paul Scherrer Institute to perform high-precision measurements of rare pion decays. LGADs are considered for the active target (ATAR), and energy linearity is an important property for particle ID capabilities.

Particle tracking detectors↗