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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 559 records · Page 31
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Testing of Alternative Abrasives for Water-Jet Cutting at C Tank Farm

Legacy waste from defense-related activities at the Hanford Site has predominantly been stored in underground tanks, some of which have leaked; others may be at risk to do so. The U.S. Department of Energy’s goal is to empty the tanks and transform their contents into more stable waste forms. To do so requires breaking up, and creating a slurry from, solid wastes in the bottoms of the tanks. A technology developed for this purpose is the Mobile Arm Retrieval System. This system is being used at some of the older single shell tanks at C tank farm. As originally planned, access ports for the Mobile Arm Retrieval System were to be cut using a high- pressure water-jet cutter. However, water alone was found to be insufficient to allow effective cutting of the steel-reinforced tank lids, especially when cutting the steel reinforcing bar (“rebar”). The abrasive added in cutting the hole in Tank C-107 was garnet, a complex natural aluminosilicate. The hardness of garnet (Mohs hardness ranging from H 6.5 to 7.5) exceeds that of solids currently in the tanks, and was regarded to be a threat to Hanford Waste Treatment and Immobilization Plant systems. Olivine, an iron-magnesium silicate that is nearly as hard as garnet (H 6.5 to 7), has been proposed as an alternative to garnet. Pacific Northwest National Laboratory proposed to test pyrite (FeS 2 ), whose hardness is slightly less (H 6 to 6.5) for 1) cutting effectiveness, and 2) propensity to dissolve (or disintegrate by chemical reaction) in chemical conditions similar to those of tank waste solutions. Cutting experiments were conducted using an air abrader system and a National Institute of Standards and Technology Standard Reference Material (SRM 1767 Low Alloy Steel), which was used as a surrogate for rebar. The cutting efficacy of pyrite was compared with that of garnet and olivine in identical size fractions. Garnet was found to be most effective in removing steel from the target; olivine and pyrite were less effective, but about equal to each other. The reactivity of pyrite, compared to olivine and garnet, was studied in high-pH, simulated tank waste solutions in a series of bench-top experiments. Variations in temperature, degree of agitation, grain size, exposure to air, and presence of nitrate and nitrite were also studied. Olivine and garnet showed no sign of dissolution or other reaction. Pyrite was shown to react with the fluids in even its coarsest variation (150-1000 μm). Projected times to total dissolution for most experiments range from months to ca. 12 years, and the strongest control on reaction rate is the grain size.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2025

CFD modeling and simulation for corrosive wear of refractory in molten slag

The development of high-wear resistant refractories having minimal production costs is facilitated by characterizing the wear mechanisms associated with their corrosive wear. Static cup testing is a commonly used method for comparing the corrosion resistance performance of two or more refractory materials. Although the static cup test conditions are not as severe as dynamic tests, this study shows that the thermal gradient present within the system during heating and cooling stages serves to generate movement of the slag leading to mechanical wear. The thermal gradient within the refractory, and between the slag and the refractory, occurs during the ramp stage of the test and lasts until the soaking stage is reached bringing the system to a thermal equilibrium. Using computational fluid dynamics (CFD) capabilities embedded within ANSYS software, this study modelled and quantified the convection currents within the slag and associated shear stresses generated on the refractory walls due to the thermal gradient. A traditional ladle furnace was employed as a case study to verify the results of the studied CFD model. The corrosion rate of the refractory lining was found to depend on the mass transfer coefficient of the refractory dissolution into the slag, and a velocity term which governs the extent of corrosion at any given location. This velocity term is a function of slag viscosity, as well as the concentration gradient and/or temperature gradient at the triple points. In this study, wall shear stress was used as a reliable proxy for identifying high-velocity regions prone to excessive corrosive wear. Elevated wall shear stress near the slag/air and slag/molten steel interfaces align with observed corrosion grooves, which reflects the intensified corrosive wear at these locations.

Ramteke, Rajat Rajat Durgesh Ramteke [University o↗
DOE OSTI2016

Reactive Transport Models with Geomechanics to Mitigate Risks of CO2 Utilization and Storage

Reactivity of carbon dioxide (CO 2 ), rocks and brine is important in a number of practical situations in carbon dioxide sequestration. Injectivity of CO 2 will be affected by near wellbore dissolution or precipitation. Natural fractures or faults containing specific minerals may reactivate leading to induced seismicity. In this project, we first examined if the reactions between CO 2 , brine and rocks affect the nature of the porous medium and properties including petrophysical properties in the timeframe of the injection operations. This was done by carrying out experiments at sequestration conditions (2000 psi for corefloods and 2400 psi for batch experiments, and 600°C) with three different types of rocks – sandstone, limestone and dolomite. Experiments were performed in batch mode and corefloods were conducted over a two-week period. Batch experiments were performed with samples of differing surface area to understand the impact of surface area on overall reaction rates. Toughreact, a reactive transport model was used to interpret and understand the experimental results. The role of iron in dissolution and precipitation reactions was observed to be significant. Iron containing minerals – siderite and ankerite dissolved resulting in changes in porosity and permeability. Corefloods and batch experiments revealed similar patterns. With the right cationic balance, there is a possibility of precipitation of iron bearing carbonates. The results indicate that during injection operations mineralogical changes may lead to injectivity enhancements near the wellbore and petrophysical changes elsewhere in the system. Limestone and dolomite cores showed consistent dissolution at the entrance of the core. The dissolution led to formation of wormholes and interconnected dissolution zones. Results indicate that near wellbore dissolution in these rock-types may lead to rock failure. Micro-CT images of the cores before and after the experiments revealed that an initial high-permeability pathway facilitated the formation of wormholes. The peak cation concentrations and general trends were matched using Toughreact. Batch reactor modeling showed that the geometric factors obtained using powder data that related effective surface area to the BET surface area had to be reduced for fractured samples and cores. This indicates that the available surface area in consolidated samples is lower than that deduced from powder experiments. Field-scale modeling of reactive transport and geomechanics was developed in parallel at Idaho National Laboratory. The model is able to take into account complex chemistry, and consider interactions of natural fractures and faults. Poroelastic geomechanical considerations are also included in the model.

01 COAL, LIGNITE, AND PEAT↗
DOE OSTI2018

THERMAL ANNEALING OF IRRADIATED PREHYDRIDED ZIRCALOY-4 MATERIALS

Hydrogen-assisted irradiation growth is an important issue for reliability and performance of nuclear materials in nuclear fuel cladding and fuel assembly components. The mechanisms of irradiation growth are not entirely clear and the role of hydrogen and hydrides are less so. There is evidence that breakaway irradiation growth is strongly influenced by the formation and dynamics of dislocation loops that vary with alloy composition, heat treatment and hydrogen content. Thermal annealing of eight Zircaloy-4 specimens irradiated in the Advanced Test Reactor (ATR) at the Idaho National Laboratory as part of the joint EPRI Nuclear Fuels Industry Research (NFIR) and Fuel Reliability Program (FRP) AsTeR irradiation growth study were performed by hot-stage transmission electron microscopy (TEM), differential scanning calorimetry (DSC), and dilatometry via NSUF RTE 17-1093. Two fluence levels (6.7 and 12.3 dpa) and three hydrogen contents (~10, 40, 120 ppm) were investigated. TEM with a hot stage was used for the quantification of "a" and "c" dislocation loop population densities and size distributions at a range of temperatures from 25 to 800oC. DSC and dilatometry were performed by dynamically heating and cooling from 30 to 750ºC at rates of 5, 10, and 20 oC/min to determine the behavior of dislocation loop annealing. Dynamic temperature DSC tests were able to detect the temperature ranges and enthalpies of "a" and "c" loop annihilation, hydride dissolution and precipitation, secondary particle precipitation, and a?a + ß phase transformations upon heating and cooling. Dilatometry tests showed that all of the test showed initial linear expansion followed by a decrease in expansion rate from about 400 to 600 ºC associated with annihilation of "a" and "c" loops and showed evidence for the thermal stabilizing effect of hydrogen on dislocation loops. The results are discussed in the context of the larger AsTeR program that will include higher exposure (~20 dpa) and different alloys when they become available in 2021.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2017

Experimental study of dissolution of minerals and CO{sub 2} sequestration in steel slag

Highlights: • CO{sub 2} sequestration potential of steel slag under aqueous medium without the usage of any additive chemicals. • Formation of residue and product layers on the surface of slag particles. • Stabilization of steel slags by carbonation process. •Determining the impact of carbonation of slag on environment. - Abstract: This study strives to achieve a substantial amount of steel slag carbonation without using any harmful chemicals. For this purpose, experiments were performed in an aqueous medium, in a semi-batch reactor, to investigate the effect of varying reaction conditions during the steel slag CO{sub 2} sequestration process. Further, studying the effect of dissolution on carbonation reactions and the mineralogical changes that subsequently occur within the slag helps provide insight into the parameters that ultimately have an impact on the carbonation rate as well the magnitude of the impact.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2023

Free‐Standing α‐MoO 3 / Ti 3 C 2 MXene Hybrid Electrode in Water‐in‐Salt Electrolytes

While transition‐metal oxides such as α‐MoO 3 provide high capacity, their use is limited by modest electronic conductivity and electrochemical instability in aqueous electrolytes. Two‐dimensional (2D) MXenes, offer metallic conductivity, but their capacitance is limited in aqueous electrolytes. Insertion of partially solvated cations into Ti 3 C 2 MXene from lithium‐based water‐in‐salt (WIS) electrolytes enables charge storage at positive potentials, allowing a wider potential window and higher capacitance. Herein, we demonstrate that α‐MoO 3 /Ti 3 C 2 hybrids combine the high capacity of α‐MoO 3 and conductivity of Ti 3 C 2 in WIS (19.8 m LiCl) electrolyte in a wide 1.8 V voltage window. Cyclic voltammograms reveal multiple redox peaks from α‐MoO 3 in addition to the well‐separated peaks of Ti 3 C 2 in the hybrid electrode. This leads to a higher specific charge and a higher rate capability compared to a carbon and binder containing α‐MoO 3 electrode. These results demonstrate that the addition of MXene to less conductive oxides eliminates the need for conductive carbon additives and binders, leads to a larger amount of charge stored, and increases redox capacity at higher rates. In addition, MXene encapsulated α‐MoO 3 showed improved electrochemical stability, which was attributed to the suppressed dissolution of α‐MoO 3 . The work suggests that oxide/MXene hybrids are promising for energy storage.

36 MATERIALS SCIENCE↗
DOE OSTI2021

High Temperature Oxidation Behavior of Fe- and Ni-Based Alloy Foils in Water Vapor at 850 °C

Operating temperatures above 700°C are desired to improve the efficiency of power generation systems such as microturbines. Therefore, the use of creep-resistant Ni-based or Fe-based alloys, which can form protective Cr2O3 and Al2O3 scales, is required. In this paper, Fe- and Ni-based alloy foils were oxidized in air + 10 % H2O for up to 3,000 h at 850°C to identify the most promising alloys. The thickness and chemical composition of the spinel oxide formed on top of the Cr2O3 scale varied between S3100, N08120 and N06230 alloy foils. In addition, the rate of Cr and Mn loss (spinel and Cr2O3 oxidation and volatilization) or Al loss (oxidation) and the dissolution of strengthening precipitates, were found to be a function of the nature of the formed oxide (Fe or Ni-rich spinel, Cr2O3, Al2O3). Alloys N06230 and alumina-forming austenitic (AFA) steels were found to be well-suited for the applications as microturbine recuperator foil materials up to 850°C.

Romedenne, Marie↗
DOE OSTI2019

Influence of Al{sub 2}O{sub 3} Level in CaO-SiO{sub 2}-MgO-Al{sub 2}O{sub 3} Refining Slags on Slag/Magnesia-Doloma Refractory Interactions

The influence of the Al{sub 2}O{sub 3} level in CaO-SiO{sub 2}-MgO-Al{sub 2}O{sub 3} (CSMA) stainless steel refining slags on the degradation of magnesia-doloma refractories was investigated through static refractory finger corrosion tests. The tests were performed at 1620 °C under Ar atmosphere, using slags with Al{sub 2}O{sub 3} contents of 5, 10, and 20 wt pct, respectively. The results indicate that the formation of 2CaO·SiO{sub 2} at the slag/refractory interface was suppressed by increasing the Al{sub 2}O{sub 3} content to 20 wt pct, thereby changing the corrosion mechanism from an indirect dissolution to a direct dissolution of CaO and MgO from the refractories. The increased solubility limit of MgO by the Al{sub 2}O{sub 3}-rich CSMA slags results in an overall higher corrosion rate of the MgO-doloma refractory.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Effect of Welding Parameters on the Corrosion Behavior of Dissimilar Alloy Welds of T6 AA6061 Al-Galvanized Mild Steel

Partial replacement of steel by Aluminium (Al) alloys is a promising approach adopted by automotive sector to improve fuel efficiency without compromising on the strength. However, this results in the generation of dissimilar welds of Al alloys and steel. Understanding the corrosion behavior of Al alloys–steel welds as a function of welding parameters is critical in the successful application of such alloys. The present study reports the intergranular corrosion behavior of T6 heat-treated AA6061 Al alloy-galvanized mild steel lap joints, welded by metal inert gas welding–brazing technique as a function of different welding parameters, viz. weld speed (4-6 m/min) and wire feed rate (0.8-0.9 m/min), following ASTM G 67-04. Weld characterization was performed by field emission scanning electron microscopy (FESEM), x-ray diffraction and nano-hardness measurement. Results indicate heavy dissolution and metal loss at the interface. A high volume fraction of Al-Fe intermetallics was precipitated at the weld interfaces, resulting in high hardness and higher localized corrosion. The thickness of Al-Fe intermetallic layer increased with increasing wire feed rate and lower weld speed which enhanced the severity of galvanic and intergranular corrosion.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Chemical reactions, porosity, and microfracturing in shale during weathering: The effect of erosion rate

The rate of chemical weathering has been observed to increase with the rate of physical erosion in published comparisons of many catchments, but the mechanisms that couple these processes are not well understood. We investigated this question in our research by examining the chemical weathering and porosity profiles from catchments developed on marine shale located in Pennsylvania, USA (Susquehanna Shale Hills Critical Zone Observatory, SSHCZO); California, USA (Eel River Critical Zone Observatory, ERCZO); and Taiwan (Fushan Experimental Forest). The protolith compositions, protolith porosities, and the depths of regolith at these sites are roughly similar while the catchments are characterized by large differences in erosion rate (1–3 mm yr ₋1 in Fushan &laquo 0.2–0.4 mm yr ₋1 in ERCZO &laquo 0.01–0.025 mm yr ₋1 in SSHCZO). The natural experiment did not totally isolate erosion as a variable: mean annual precipitation varied along the erosion gradient (4.2 m yr ₋1 in Fushan > 1.9 m yr ₋1 in ERCZO > 1.1 m yr ₋1 in SSHCZO), so the fastest eroding site experiences nearly twice the mean annual temperature of the other two. Even though erosion rates varied by about 100×, the depth of pyrite and carbonate depletion (defined here as regolith thickness) is roughly the same, consistent with chemical weathering of those minerals keeping up with erosion at the three sites. These minerals were always observed to be the deepest to react, and they reacted until 100% depletion. In two of three of the catchments where borehole observations were available for ridges, these minerals weathered across narrow reaction fronts. On the other hand, for the rock-forming clay mineral chlorite, the depth interval of weathering was wide and the extent of depletion observed at the land surface decreased with increasing erosion/precipitation. Thus, chemical weathering of the clay did not keep pace with erosion rate. But perhaps the biggest difference among the shales is that in the fast-eroding sites, microfractures account for 30–60% of the total porosity while in the slow-eroding shale, dissolution could be directly related to secondary porosity. We argue that the microfractures increase the influx of oxygen at depth and decrease the size of diffusion-limited internal domains of matrix, accelerating weathering of pyrite and carbonate under high erosion-rate conditions. Thus, microfracturing is a process that can couple physical erosion and chemical weathering in shales.

58 GEOSCIENCES↗
DOE OSTI2011

TREATMENT TANK CORROSION STUDIES FOR THE ENHANCED CHEMICAL CLEANING PROCESS

Radioactive waste is stored in high level waste tanks on the Savannah River Site (SRS). Savannah River Remediation (SRR) is aggressively seeking to close the non-compliant Type I and II waste tanks. The removal of sludge (i.e., metal oxide) heels from the tank is the final stage in the waste removal process. The Enhanced Chemical Cleaning (ECC) process is being developed and investigated by SRR to aid in Savannah River Site (SRS) High-Level Waste (HLW) as an option for sludge heel removal. Corrosion rate data for carbon steel exposed to the ECC treatment tank environment was obtained to evaluate the degree of corrosion that occurs. These tests were also designed to determine the effect of various environmental variables such as temperature, agitation and sludge slurry type on the corrosion behavior of carbon steel. Coupon tests were performed to estimate the corrosion rate during the ECC process, as well as determine any susceptibility to localized corrosion. Electrochemical studies were performed to develop a better understanding of the corrosion mechanism. The tests were performed in 1 wt.% and 2.5 wt.% oxalic acid with HM and PUREX sludge simulants. The following results and conclusions were made based on this testing: (1) In 1 wt.% oxalic acid with a sludge simulant, carbon steel corroded at a rate of less than 25 mpy within the temperature and agitation levels of the test. No susceptibility to localized corrosion was observed. (2) In 2.5 wt.% oxalic acid with a sludge simulant, the carbon steel corrosion rates ranged between 15 and 88 mpy. The most severe corrosion was observed at 75 C in the HM/2.5 wt.% oxalic acid simulant. Pitting and general corrosion increased with the agitation level at this condition. No pitting and lower general corrosion rates were observed with the PUREX/2.5 wt.% oxalic acid simulant. The electrochemical and coupon tests both indicated that carbon steel is more susceptible to localized corrosion in the HM/oxalic acid environment than in the PUREX/oxalic acid environment. (3) The corrosion rates for PUREX/8 wt.% oxalic acid were greater than or equal to those observed for the PUREX/2.5 wt.% oxalic acid. No localized corrosion was observed in the tests with the 8 wt.% oxalic acid. Testing with HM/8 wt.% oxalic acid simulant was not performed. Thus, a comparison with the results with 2.5 wt.% oxalic acid, where the corrosion rate was 88 mpy and localized corrosion was observed at 75 C, cannot be made. (4) The corrosion rates in 1 and 2.5 wt.% oxalic acid solutions were temperature dependent: (a) At 50 C, the corrosion rates ranged between 90 to 140 mpy over the 30 day test period. The corrosion rates were higher under stagnant conditions. (b) At 75 C, the initial corrosion rates were as high as 300 mpy during the first day of exposure. The corrosion rates increased with agitation. However, once the passive ferrous oxalate film formed, the corrosion rate decreased dramatically to less than 20 mpy over the 30 day test period. This rate was independent of agitation. (5) Electrochemical testing indicated that for oxalic acid/sludge simulant mixtures the cathodic reaction has transport controlled reaction kinetics. The literature suggests that the dissolution of the sludge produces a di-oxalatoferrate ion that is reduced at the cathodic sites. The cathodic reaction does not appear to involve hydrogen evolution. On the other hand, electrochemical tests demonstrated that the cathodic reaction for corrosion of carbon steel in pure oxalic acid involves hydrogen evolution. (6) Agitation of the oxalic acid/sludge simulant mixtures typically resulted in a higher corrosion rates for both acid concentrations. The transport of the ferrous ion away from the metal surface results in a less protective ferrous oxalate film. (7) A mercury containing species along with aluminum, silicon and iron oxides was observed on the interior of the pits formed in the HM/2.5 wt.% oxalic acid simulant at 75 C. The pitting rates in the agitated and non-agitated solution were 2 mils/day and 1 mil/day, respectively. A mechanism by which the mercury interacts with the aluminum and silicon oxides in this simulant to accelerate corrosion was proposed.

08 HYDROGEN↗
DOE OSTI2024

Catch bond kinetics are instrumental to cohesion of fire ant rafts under load

Dynamic networks composed of constituents that break and reform bonds reversibly are ubiquitous in nature owing to their modular architectures that enable functions like energy dissipation, self-healing, and even activity. While bond breaking depends only on the current configuration of attachment in these networks, reattachment depends also on the proximity of constituents. Therefore, dynamic networks composed of macroscale constituents (not benefited by the secondary interactions cohering analogous networks composed of molecular-scale constituents) must rely on primary bonds for cohesion and self-repair. Toward understanding how such macroscale networks might adaptively achieve this, we explore the uniaxial tensile response of 2D rafts composed of interlinked fire ants ( S. invicta ). Through experiments and discrete numerical modeling, we find that ant rafts adaptively stabilize their bonded ant-to-ant interactions in response to tensile strains, indicating catch bond dynamics. Consequently, low-strain rates that should theoretically induce creep mechanics of these rafts instead induce elastic-like response. Our results suggest that this force-stabilization delays dissolution of the rafts and improves toughness. Nevertheless, above 35 % strain low cohesion and stress localization cause nucleation and growth of voids whose coalescence patterns result from force-stabilization. These voids mitigate structural repair until initial raft densities are restored and ants can reconnect across defects. However mechanical recovery of ant rafts during cyclic loading suggests that—even upon reinstatement of initial densities—ants exhibit slower repair kinetics if they were recently loaded at faster strain rates. These results exemplify fire ants’ status as active agents capable of memory-driven, stimuli-response for potential inspiration of adaptive structural materials.

Science & Technology - Other Topics↗
DOE OSTI2016

Where Lower Calcite Abundance Creates More Alteration: Enhanced Rock Matrix Diffusivity Induced by Preferential Dissolution [Where Lower Calcite Abundance Creates More Alteration: Enhanced Rock Matrix Diffusivity Induced by Preferential Carbonate Dissolution]

Fractured rocks are essential for flow, solute transport and energy production in geosystems. Existing studies on mineral reactions in fractured rocks mostly consider single mineral systems where reactions occur at the fracture wall without changing rock matrix properties. This work presents multicomponent reactive transport numerical experiments in a fractured rock from the Brady’s field, a geothermal reservoir at a depth of 1,396 m in the Hot Springs Mountains, Nevada. Initial porosity, permeability, mineral composition (quartz, clay, and calcite), and fracture geometry are based on microscopy characterization and X-ray tomography. The model was calibrated using a CO 2 -saturated water flooding experiment. Three numerical experiments were carried out with the same initial physical properties however different calcite content. Although total dissolved masses are similar among the three cases, abundant calcite (50% (v/v), calcite50) leads to a localized, thick zone of large porosity increase while low calcite content (10% (v/v), calcite10) creates an extended and narrow zone of small porosity increase resulting in surprisingly larger change in effective transport property. After 300 days of dissolution, effective matrix diffusion coefficients increase by 9.9 and 19.6 times in calcite50 and calcite10, respectively, inducing corresponding 2.1 and 3.2 times rise in the slopes of power law tailing, a measure of transport properties. This counterintuitive results suggest that lower abundance of reactive minerals leads to greater alteration in the fractured media. Detailed analysis show that the effective rates of the fast-dissolving calcite are limited by diffusive transport in the altered matrix and the shape of the altered zone. In contrast, the while effective dissolution of slow-dissolving quartz depends on effective diffusion within the entire rock matrix. Calcite dissolution only occurs at the thin altered–unaltered matrix interface of tens of micrometers thickness occupying less than 1% of the total calcite content. In contrast, all quartz are effectively dissolving. Furthermore, this work highlights the importance of mineralogical complexity in determining mineral dissolution and rock matrix property evolution.

58 GEOSCIENCES↗
DOE OSTI2024

Enabling High Stability of Co-Free LiNiO 2 Cathode via a Sulfide-Enriched Cathode Electrolyte Interface

Cobalt-free lithium nickel oxide (LNO) has garnered significant interest as the end member of high-nickel layered oxide cathodes for next-generation batteries. However, its practical performance notably underperforms expectations because of the structural degradation and unstable interfacial chemistry with electrolytes during cycling. Here, in this study, we report that a durable cathode-electrolyte interface (CEI), enriched by in situ formed sulfides and borides, can inhibit LNO structural degradation and suppress Ni ion dissolution. With the CEI protection, the stability of LNO can be remarkably extended, and batteries demonstrate a capacity retention rate of 84% (30 °C) and 79% (50 °C) after 200 cycles at 1C, respectively. These results demonstrate that enriching CEI with sulfur-containing species can effectively stabilize the interfacial chemistry of LNO, particularly at an elevated temperature of 50 °C. This finding provides valuable perspectives on designing electrolytes for cobalt-free LNO and other high-Ni cathodes toward the development of next-generation high-energy-density lithium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Direct visualization of radiation-induced transformations at alkali halide–air interfaces

Radiation driven reactions at mineral/air interfaces are important to the chemistry of the atmosphere, but experimental constraints (e.g. simultaneous irradiation, in situ observation, and environmental control) leave process understanding incomplete. Using a custom atomic force microscope equipped with an integrated X-ray source, transformation of potassium bromide surfaces to potassium nitrate by air radiolysis species was followed directly in situ at the nanoscale. Radiolysis initiates dynamic step edge dissolution, surface composition evolution, and ultimately nucleation and heteroepitaxial growth of potassium nitrate crystallites mediated by surface diffusion at rates controlled by adsorbed water. Finally, in contrast to in situ electron microscopy and synchrotron-based imaging techniques where high radiation doses are intrinsic, our approach illustrates the value of decoupling irradiation and the basis of observation.

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

High Performance Computing to Quantify the Evolution of Microscopic Concentration Gradients During Flash Processing

During the Flash process, the cross section of a plain-carbon or a low-alloy steel is austenitized through rapid heating and transformed on rapid cooling to a predominantly martensite + bainite structure with small amounts of retained austenite. Unlike conventional heat treating, homogeneity is intentionally avoided during Flash processing of steels. The Flash process assembly consists of a pair of rolls that transfer the steel sheets through the heating and cooling stage of the thermal cycle. The initial microstructure of the steel consists of ferrite (body-centered cubic iron) + carbide ((Fe,X)mCn) mixture. The heating rate through the peak temperature is a function of temperature and reaches a peak of about 300-400°C/s and the cooling rate has a maximum value of 3,000-4,000°C/s. The on-heating phase transformations include carbide dissolution, austenite (face-centered cubic iron) nucleation and growth, and diffusion of carbon and other substitutional elements in the steel. The on-cooling phase transformations include formation of martensite (body-centered tetragonal phase containing supersaturated solute) and bainite (ferrite plates with or without fine carbides). In this project, the focus is on Fe-C-Cr steels that are currently Flash processed for armor applications. The modeling effort proposed here will help optimize the Flash thermal cycle for these low alloy steels to achieve the target performance, which is an ongoing effort at SFP Works. A significant feature of Flash processed Fe-C-Cr steels is the presence of scatter in the through-thickness in the sheet. The variability in hardness results from a variability in the bainite + martensite microstructure that is sensitive to the local chemical concentration of C and Cr. Such a chemical inhomogeneity is intentionally obtained in the Flash process. Although such a microstructural gradient is presumably responsible for the exceptional properties of the Flash processed steel, it is very important to quantify the gradients as a function of Flash variabilities in processing parameters and the input microstructure. Understanding the mechanistic pathway that leads to microstructural gradients could be ground-breaking and instrumental for achieving better process control and optimized microstructural state to meet application-specific strength-ductility requirements. Since the final microstructure depends on setting up precise solute concentration gradients through a rapid heating process, and transforming these regions into various phases, it is important to understand how small changes in steel chemistry, input microstructure (carbide size and distribution), and process variables (Flash thermal cycle) will impact the solute concentration gradients.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2018

Chlorophyll-Inspired Red-Region Fluorophores: Building Block Synthesis and Studies in Aqueous Media

Fluorophores that absorb and emit in the red spectral region (600–700 nm) are of great interest in photochemistry and photomedicine. Eight new target chlorins (and 19 new chlorins altogether)—analogues of chlorophyll—of different polarities have been designed and synthesized for various applications; seven of the chlorins are equipped with a bioconjugatable tether. Hydrophobic or amphiphilic chlorins in a non-polar organic solvent (toluene), polar organic solvent (DMF), and aqueous or aqueous micellar media show a sharp emission band in the red region and modest fluorescence quantum yield (Φ f = 0.2–0.3). A Poisson analysis implies most micelles are empty and few contain >1 chlorin. Water-soluble chlorins each bearing three PEG (oligoethyleneglycol) groups exhibit narrow emission bands (full-width-at-half maximum <25 nm). The lifetime of the lowest singlet excited state and the corresponding yields and rate constants for depopulation pathways (fluorescence, intersystem crossing, internal conversion) are generally little affected by the PEG groups or dissolution in aqueous or organic media. A set of chlorin–avidin conjugates revealed a 2-fold increase in Φ f with increased average chlorin/avidin ratio (2.3–12). In summary, the chlorins of various polarities described herein are well suited as red-emitting fluorophores for applications in aqueous or organic media.

59 BASIC BIOLOGICAL SCIENCES↗