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At least 919 records · Page 51
All sourcesNASA NTRSDOE OSTI
NASA NTRS1985

Mass Transport Phenomena Between Bubbles and Dissolved Gases in Liquids Under Reduced Gravity Conditions

The long term objective of the experiment is to observe the dissolution of isolated, immobile gas bubbles of specified size and composition in a solvent liquid of known concentration in the reduced gravity environment of earth orbit. Preliminary bubble dissolution experiment conducted both in the NASA Lewis 2.2 sec drop tower and in normal gravity using SO2 - Toluene system were not completely successful in their objective. The method of gas injection and lack of bubble interface stabiliy experienced due to the extreme solubility of SO in Toluene has the effects of changing the problem from that of bubble dissolution to one of bubble formation stability and subsequent dissolution in a liquid of unknown initial solute concentration. Current work involves further experimentation in order to refine the bubble injection system and to investigate the concept of having a bubble with a critical radius in a state of unstable equilibrium.

Dewitt, K. J.↗
NASA NTRS2007

Coatings on Atacama Desert Basalt: A Possible Analog for Coatings on Gusev Plains Basalt

Surface coatings on Gusev Plains basalt have been observed and may contain hematite and nanophase Fe-oxides along with enrichments in P, S, Cl, and K relative to the underlying rock. The Gusev coatings may be derived from the dissolution of adhering soil and/or parent rock along with the addition of S and Cl from outside sources. Transient water for dissolution could be sourced from melting snow during periods of high obliquity, acid fog, and/or ground water (Haskin et al., 2005). Coatings on basalt in the hyper-arid (less than 2mm y(sup -1)) Atacama Desert may assist in understanding the chemistry, mineralogy and formation mechanisms of the Gusev basalt coatings. The Atacama Desert climate is proposed to be analogous to a paleo-Mars climate that was characterized by limited aqueous activity when the Gusev coatings could have formed. The objectives of this work are to (i) determine the chemical nature and extent of surface coatings on Atacama Desert basalt, and (ii) assess coating formation mechanisms in the Atacama Desert. Preliminary backscattered electron imaging of Atacama basalt thin-sections indicated that the coatings are as thick as 20 m. The boundary between the coating and the basalt labradorite, ilmenite, and augite grains was abrupt indicating that the basalt minerals underwent no chemical dissolution. The Atacama coatings have been added to the basalt instead of being derived from basalt chemical weathering. Semi-quantitative energy dispersive spectroscopy shows the coatings to be chemically homogeneous. The coating is depleted in Ca (0.9 wt% CaO) and enriched in K (1.3 wt.% K2O) and Si (69.1 wt.% SiO2) relative to the augite and labradorite grains. A dust source enriched in Si (e.g., poorly crystalline silica) and K and depleted in Ca appears to have been added to the basalt surface. Unlike the Gusev coatings, no P, S, and Cl enrichment was observed. However, Fe (3.2 wt.% FeO) was present in the Atacama coatings suggesting the present of Fe-oxides. While the chemistry of Atacama coating does not mirror the Gusev coating, the coating formation mechanism may be similar. The Atacama coatings of surface basalt are derived completely from exogenous sources. If surface Mars rocks have experienced limited wetting conditions as in the Atacama, then Mars coatings may be derived only from dissolution of material adhering to rock.

Sutter, B.↗
NASA NTRS2012

Oxidation and the Effects of High Temperature Exposures on Notched Fatigue Life of an Advanced Powder Metallurgy Disk Superalloy

Oxidation and the effects of high temperature exposures on notched fatigue life were considered for a powder metallurgy processed supersolvus heat-treated ME3 disk superalloy. The isothermal static oxidation response at 704 C, 760 C, and 815 C was consistent with other chromia forming nickel-based superalloys: a TiO2-Cr2O3 external oxide formed with a branched Al2O3 internal subscale that extended into a recrystallized - dissolution layer. These surface changes can potentially impact disk durability, making layer growth rates important. Growth of the external scales and dissolution layers followed a cubic rate law, while Al2O3 subscales followed a parabolic rate law. Cr- rich M23C6 carbides at the grain boundaries dissolved to help sustain Cr2O3 growth to depths about 12 times thicker than the scale. The effect of prior exposures was examined through notched low cycle fatigue tests performed to failure in air at 704 C. Prior exposures led to pronounced debits of up to 99 % in fatigue life, where fatigue life decreased inversely with exposure time. Exposures that produced roughly equivalent 1 m thick external scales at the various isotherms showed statistically equivalent fatigue lives, establishing that surface damage drives fatigue debit, not exposure temperature. Fractographic evaluation indicated the failure mode for the pre-exposed specimens involved surface crack initiations that shifted with exposure from predominately single intergranular initiations with transgranular propagation to multi-initiations from the cracked external oxide with intergranular propagation. Weakened grain boundaries at the surface resulting from the M23C6 carbide dissolution are partially responsible for the intergranular cracking. Removing the scale and subscale while leaving a layer where M23C6 carbides were dissolved did not lead to a significant fatigue life improvement, however, also removing the M23C6 carbide dissolution layer led to nearly full recovery of life, with a transgranular initiation typical to that observed in unexposed specimens.

Sudbrack, Chantal K.↗
DOE OSTI2016

Corrosion Testing of Carbon Steel Exposed to Sludge Heel Chemical Cleaning Solutions - 16109

As efforts continue to treat and dispose of millions of gallons of legacy radioactive materials from the production of nuclear weapons, non-compliant waste storage tanks will gradually be emptied of the bulk waste volume leaving heel materials requiring removal prior to tank closure. The waste heel slurries are distributed on the floor of large, million gallon tanks, which frequently contain numerous obstructions that limit the effectiveness of mechanical removal methods. As a result, chemical cleaning methods are needed for the effective removal of the heels as well as chemical scales that are present on the tank walls and other interior surfaces. Two tank cleaning technologies have already been implemented at the Savannah River Site (SRS): Low Temperature Aluminum Dissolution (LTAD) and Bulk Oxalic Acid Cleaning (BOAC). Recent chemical cleaning efforts on SRS Tank 12 were very successful with regard to bulk sludge heel (especially for Al, Fe, and U phases) and beta/gamma radionuclide removal. Although chemical cleaning using these technologies has been shown to be effective, no disposition path has been identified for oxalate added during BOAC, and insoluble oxalate salts are accumulating within the SRS tank farm and waste processing facilities (evaporators, etc.). Extensive sludge washing is also required to remove moderately soluble sodium oxalate salts prior to sludge vitrification in the SRS Defense Waste Processing Facility (DWPF). As a result, oxalate additions to the tank farm need to be minimized by the use of supplementary acids to assist sludge removal in OA or the use of other cleaning reagents or processing strategies. Previous SRNL testing revealed the importance of pH control for BOAC and recommended the use of a supplementary acid (dilute HNO{sub 3}) with OA to minimize oxalate additions. Primary drivers in SRS Tank Closure Performance Assessments, which evaluate the fate and impact of tank sludge residuals on a geological timescale, are the removal of alpha emitting radionuclides present at low concentrations such as Pu, Am, and Np, which are not highly soluble in currently utilized chemical cleaning reagents. Scoping studies conducted at SRNL revealed promising methods to dissolve the actinides within the HLW tank heels. Oxidation of the actinides with permanganate in either strong caustic (10 M NaOH) or dilute acidic (0.2 M HNO{sub 3}) solutions was shown to result in dissolution of oxy/hydroxide phases of these metals in the absence of major sludge phases. The waste tanks at SRS and Hanford are constructed of carbon steel. Carbon steel corrodes rapidly in most acidic and/or oxidizing environments. Previous electrochemical corrosion testing indicated that the corrosion rates in dilute HNO{sub 3} with OA may result in manageable corrosion rates, over short exposure periods. Additional corrosion testing was performed to provide data for the nitric acid/OA blend as well as the acid/permanganate and caustic permanganate based chemical cleaning solutions. Corrosion rates from the passive coupon tests for the nitric acid/oxalic acid blend were significantly greater than those observed previously with the electrochemical testing. This result may be due to simultaneous electrochemical and chemical dissolution of the steel. The corrosion rate data from the coupon tests in the nitric acid/oxalic acid blend were evaluated to determine the degree of potential structural damage. The corrosion rates, although relatively high, would not be expected to cause damage that would reduce the capacity of the tank primary wall if the process is completed within a month. The corrosivity of sodium permanganate in four proposed cleaning solutions, 1 nitric acid solution and 3 sodium hydroxide solutions, was studied by electrochemical methods at room temperature. The corrosion rates were significantly less aggressive than in the nitric acid/oxalic acid blend corrosion tests. Passive coupon tests needs to be performed in these solutions to ensure that chemical dissolution of the metal is not occurring simultaneously. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2026

Determining the Solubility Behavior of Kogarkoite in Simulated Nuclear Waste

Kogarkoite (Na 3 FSO 4 ) is a sparingly soluble fluoride–sulfate double salt that has been identified in high level nuclear waste sludge at the Hanford Site and, more recently, in sludge batch compilation samples at the Savannah River Site (SRS). Due to its complex dissolution behavior, which exhibits an inverse dependence on sodium ion activity, the presence of this mineral poses significant challenges to waste retrieval and processing. Incomplete dissolution during sludge washing can lead to the retention of fluoride and sulfate in the high-level waste feed, potentially causing the formation of corrosive, immiscible molten salt layers, known as "glass gall,” in vitrification melters. Current efforts to optimize flowsheet parameters and wash-water volumes are hindered by the absence of a commercially available, certified reference material, which prevents the accurate calibration of analytical methods and the verification of dissolution kinetics. To address this critical gap, this research focuses on the laboratory synthesis of pure Kogarkoite to serve as a standard for comprehensive solubility and washing performance testing. A coupled synthesis and simulant campaign was executed using an evaporative crystallization protocol designed to replicate the dynamic concentration effects observed in tank farm operations. Thirteen simulant matrices were prepared by dissolving systematically varied ratios of sodium fluoride (NaF) and sodium sulfate (Na 2 SO 4 ) in deionized water under three distinct caustic regimes: 0.0 g (control), 4.0 g (~1 M), and 12.0 g (~3 M) sodium hydroxide (NaOH). While thermodynamic equilibrium models suggest that high-caustic environments should favor the stability of the double salt7, results from this evaporative study at 25 0 C revealed a distinct kinetic divergence. Simulants with high hydroxide loading predominantly yielded large, blocky crystals of sodium sulfate decahydrate (Na 2 SO 4 .10H 2 O). Successful synthesis of pure Kogarkoite was achieved exclusively in specific NaOH-free compositional windows, where the precipitate manifested as fine, opaque granular aggregates. Ion chromatography (IC) analysis confirmed phase purity through the simultaneous stoichiometric depletion of both fluoride and sulfate from the supernatant. This successful synthesis establishes a reproducible route to generate bulk Kogarkoite, enabling the subsequent phase of quantitative dissolution testing using inhibited water to optimize sludge-batch assembly.

Sarker, Md Sharif [Florida International Univ. (FI↗
DOE OSTI2023

Dose and dose rate effects on the microstructural and mechanical stability of long-range ordered precipitates in Inconel 718

Nickel-based alloys offer exceptional mechanical properties and corrosion resistance for various applications in extreme environments such as high neutron flux, temperature, and stress. Precipitates, resulting from thermal treatments, increase the strength and creep resistance of these alloys. Here, heavy ion irradiation is shown to destabilize the γ' and γ" precipitates in Inconel 718 nickel-based alloy by disordering and dissolution processes. Transmission electron microscopy and atom probe tomography reveal that the disordering and dissolution rates of the precipitates are proportional to both irradiation dose and dose rate. Irradiation induced disordering occurs at a higher rate than the dissolution. From analyzing the hardening contributions, microscale mechanical results suggest radiation-induced disordering is responsible for the majority of the softening response at low dose. In addition, low dose radiation-induced disordering results in strain localization and is believed to be the primary cause for the drastic degradation of uniform elongation and toughness in irradiated Inconel 718.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Employing the Dynamics of the Electrochemical Interface in Aqueous Zinc-Ion Battery Cathodes

Intrinsically stable materials are desirable for constructing energy storage devices, which aim to demonstrate durability under the harsh electrochemical conditions that are detrimental to their lifespan. However, in this study it is demonstrated that the intrinsic instability of an electrochemical interface can be converted from an obstacle into an advantage. In aqueous zinc-ion batteries, manganese oxide (MnO 2 ) exhibits considerable dissolution even in electrolyte containing Mn 2+ salt. Balancing with redeposition alleviates the harmful impact of dissolution on performance and alters the trajectory of the active phase. Inclusion of Mn 2+ salt in the electrolyte induces MnO 2 deposition on all conductive surfaces, requiring that distracting side reactions be eliminated to isolate the dynamics of the active phase. Under conditions favoring dissolution, capacity decreases dramatically and a highly crystalline tetragonal ZnMn 2 O 4 phase forms, while redeposition helps maintain capacity and promotes a disordered cubic Zn-rich phase. Ultimately, this work aims to illuminate a path forward to unlock the potential of batteries made with materials that are fundamentally unstable in their operating environment.

25 ENERGY STORAGE↗
DOE OSTI2025

Mitigating Cyclable Li‐Ion Inventory Loss in Full Cells with Mn‐Rich Disordered Rocksalt Cathodes

Lithium (Li)- and manganese (Mn)-rich disordered rock salt (DRX) materials are promising cathode materials for next-generation Li-ion batteries. Although these cathode materials are Li-ions rich in their pristine state, their incorporation into full cells results in challenges with maintaining Li-ion inventory during cycling. Herein, the degradation mechanisms of DRX materials in different DRX||Graphite full cells are reported. It is found that DRX electrodes contain Li impurities, primarily due to the environmental sensitivity of mechanochemically synthesized DRX materials during sample transfer and storage. In addition, the structural instability of DRX triggers Mn dissolution. Dissolved Mn ions react with exposed Li x C y compounds and induce electrolyte decomposition on the anode, further depleting Li-ion inventory. Control experiments involving the pre-addition of Mn 2+ provide clear evidence of the impact of Mn dissolution on Li-ion inventory. The electrochemical activation process can stabilize DRX, alleviate Mn dissolution and thus mitigate the loss of Li-ion inventory. These mechanistic insights inform the development of chemical pre-lithiation and electrolyte additive strategies to collectively passivate interfaces, mitigate the effects of trace dissolved Mn ions, and preserve Li-ion inventory. Ultimately, the DRX||Graphite full cell achieves highly reversible electrochemical reactions with a high capacity retention. This study fills a research gap in DRX-based full cells and provides insights into degradation mechanisms and optimization strategies for their practical use.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Computational Approach for Rapidly Predicting Temperature–Dependent Polymer Solubilities Using Molecular–Scale Models

One promising approach to recycle multicomponent plastic waste (e. g., multilayer plastic films) is selective dissolution. Selective dissolution is a solvent-mediated process in which differences in polymer solubility in a carefully chosen solvent system are exploited to recover a target polymer. Here, a computational approach was developed that rapidly predicts temperature-dependent polymer solubilities to guide the design of solvent systems for solvent-mediated polymer recycling. Polymer conformations were obtained from molecular dynamics simulations by modeling the polymer as a short oligomer and then used as input to the conductor-like screening model for real solvents (COSMO-RS) for solubility predictions. Using polyethylene (PE) and ethylene vinyl alcohol (EVOH) as representative polymers, the effect of simulation parameters was systematically studied, and predicted solubilities were found to be in good agreement with experimental measurements. Furthermore, the applicability of the approach was demonstrated by identifying selective solvents for PE and EVOH dissolution from a library of 524 solvents.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Secondary structure and dynamics study of the intrinsically disordered silica-mineralizing peptide P 5 S 3 during silicic acid condensation and silica decondensation

The silica forming repeat R5 of sil1 from Cylindrotheca fusiformis was the blueprint for the design of P5S3, a 50-residue peptide which can be produced in large amounts by recombinant bacterial expression. It contains five protein kinase A target sites and is highly cationic due to 10 lysine and 10 arginine residues. In the presence of supersaturated ortho silicic acid P5S3 strongly enhances silica-formation whereas it retards the dissolution of amorphous silica (SiO2) at globally undersaturated concentrations. The secondary structure of P5S3 during these different functions was studied by circular dichroism (CD), complemented by nuclear magnetic resonance (NMR) studies of the peptide in the absence of silicate. The NMR studies of dual-labeled (13C, 15N) P5S3 revealed a disordered structure at pH 2.8 and 4.5. Within the pH range of 4.5 to 9.5, the CD data verified the disordered secondary structure but also suggested the presence of some polyproline II character in the absence of silicic acid. Upon silicic acid polymerization and during dissolution of preformed silica, the CD spectrum of P5S3 indicated partial transition into an α-helical conformation which was transient during silica-dissolution. Consequently, the secondary structural changes observed for P5S3 correlate with the presence of oli-gomeric/polymeric silicic acid, presumably due to P5S3-silicic acid interactions. These interactions appear, at least in part, ionic in nature since dodecylsulfate micelles, which are negatively charged, cause similar conformational shifts to P5S3 in the absence of silica while ß-D-dodecyl maltoside micelles, which are neutral, do not. Thus, P5S3 influences both the condensation of silicic acid into silica and its decondensation back to silicic acid. Moreover, the dynamics of these pro-cesses may be indirectly monitored by following structural changes to P5S3 with CD spectroscopy.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2019

Direct Observation of Pure Cu and Cu-Ag Anode Passivation in H{sub 2}SO{sub 4}-CuSO{sub 4} Aqueous Solution by Channel Flow Double Electrode and Optical Microscopy

The dissolution and passivation of pure Cu and Cu-5 wt pct Ag anodes in H{sub 2}SO{sub 4}-CuSO{sub 4} electrolyte were investigated by a direct observation method that combined the techniques of optical microscopy and channel flow double electrode. Linear sweep voltammetry of the anodes showed that the dissolution of Cu transited from the charge transfer-controlled reaction to the mass transfer-controlled reaction, followed by the passivation of the electrodes. The direct observation of the pure Cu anode revealed that Cu particles were generated on the surface and the particles fell away during passivation. On the other hand, a slime layer of Ag particles that adhered to the surface was generated during the dissolution of the Cu-5 wt pct Ag anode. The Cu-5 wt pct Ag anode was passivated with a lower current density than the pure Cu anode, which suggested that the morphology and adhesive characteristics of the slime on the anode affected the passivation. The direct observation method described herein is useful for understanding reactions on electrodes that undergo drastic changes in their surface morphology. Information obtained from this method can help with the development of new processes for the effective utilization of limited natural resources and energy, such as the recycling of Cu by electrorefining.

36 MATERIALS SCIENCE↗
DOE OSTI2019

Thermo-chemical Fluid Flow Simulation in Hot-Dip Galvanizing: The Evaluation of Dross Build-Up Formation

This paper presents a new computational framework to investigate the driving force for the formation of intermetallic dross particles in the zinc bath and dross build-up on the bath hardware. This is a major problem in continuous hot-dip galvanizing lines. The Computational Fluid Dynamics (CFD) model calculates the turbulent thermo-chemical flow conditions within the liquid melt. A detailed modeling of the steel strip–liquid interface enhances this approach, by means of a conjugated heat transfer calculation and a spatially resolved, temperature- and concentration-dependent iron dissolution and aluminum uptake. The heart of the computational framework is a thermodynamic model, which assesses the driving force for the formation or dissolution of dross particles in the bath and dross build-up on stationary and rotating equipment. The simulation results are validated with temperature and species depth profile measurements. The applicability of the CFD model is shown by investigating the locally resolved aluminum uptake and iron dissolution at the steel-strip surface, and the multi-physics conditions in the region near the roll. The novel approach of evaluating the thermodynamic driving force enables the assessment of the formation of dross build-up at the roll surface.

36 MATERIALS SCIENCE↗
DOE OSTI2014

In-situ early-age hydration study of sulfobelite cements by synchrotron powder diffraction

Eco-friendly belite calcium sulfoaluminate (BCSA) cement hydration behavior is not yet well understood. Here, we report an in-situ synchrotron X-ray powder diffraction study for the first hours of hydration of BCSA cements. Rietveld quantitative phase analysis has been used to establish the degree of reaction (α). The hydration of a mixture of ye'elimite and gypsum revealed that ettringite formation (α ∼ 70% at 50 h) is limited by ye'elimite dissolution. Two laboratory-prepared BCSA cements were also studied: non-active-BCSA and active-BCSA cements, with β- and α′{sub H}-belite as main phases, respectively. Ye'elimite, in the non-active-BCSA system, dissolves at higher pace (α ∼ 25% at 1 h) than in the active-BCSA one (α ∼ 10% at 1 h), with differences in the crystallization of ettringite (α ∼ 30% and α ∼ 5%, respectively). This behavior has strongly affected subsequent belite and ferrite reactivities, yielding stratlingite and other layered phases in non-active-BCSA. The dissolution and crystallization processes are reported and discussed in detail. -- Highlights: •Belite calcium sulfoaluminate cements early hydration mechanism has been determined. •Belite hydration strongly depends on availability of aluminum hydroxide. •Orthorhombic ye’elimite dissolved at a higher pace than cubic one. •Ye’elimite larger reaction degree yields stratlingite formation by belite reaction. •Rietveld method quantified gypsum, anhydrite and bassanite dissolution rates.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Effect of retarders on the early hydration of calcium-sulpho-aluminate (CSA) type cements

The retardation of calcium-sulpho-aluminate (CSA) type cements by three common retarders—sodium gluconate, sodium–potassium tartrate and borax is investigated at a 2% addition rate. Each of the retarders has a different effect on the early-age hydrate assemblage, as shown by quantitative X-ray diffraction, thermogravimetric analysis, scanning electron microscopy and pore solution analysis. Regardless of the retarder used, the hydration starts with mainly the dissolution of ready soluble (calcium) alkali sulphates and ye'elimite, followed by the formation of ettringite and aluminium hydroxide, whereby the specific clinker mineral dissolution as well as ettringite-forming reaction is delayed in different ways depending on the retarder used. The results showed that the retardation is mainly caused by preventing hydrates formation in the case of tartrate and gluconate. Contrary, borax retards the hydration by preventing to a certain extent the dissolution of ye'elimite and lowers the initial pH. Furthermore, the morphology of ettringite is altered depending on the type of the retarder used.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Modelling of the sulfuric acid attack on different types of cementitious materials

A chemical-reactive transport model is used to simulate the sulfuric acid attack of cement pastes based on ordinary Portland cement (CEM I), blended Portland cements (CEM III, CEM IV, and CEM V), and calcium aluminate cement (CAC). This model accounts for the dissolution of cement hydrates (portlandite, C-S-H, hydrogarnet), and the precipitation of deterioration products (ettringite and gypsum). Moreover, diffusion of the aqueous species in the pore space of the material is considered. With this model, the hydrate contents, the porosity, and the deterioration phase contents throughout a sulfuric acid attack are determined. Two indicators are defined to predict the service life of the cementitious materials: the deterioration depth and the dissolved calcium content. These two indicators show that calcium aluminate cement has a better resistance to sulfuric acid attack than that of Portland cements. This better resistance is mainly due to the partial dissolution of CAC hydrate as opposed to the total dissolutions of CH and C-S-H.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Synchrotron X-ray nanotomographic and spectromicroscopic study of the tricalcium aluminate hydration in the presence of gypsum

The rheology of modern Portland cement (PC) concrete critically depends on the correct dosage of gypsum (calcium sulfate hydrate) to control the hydration of the most reactive phase - tricalcium aluminate (C{sub 3}A). The underlying physio-chemical mechanism, however, remains unsolved mainly due to the lack of high-spatial-resolved and chemistry-sensitive characterization of the C{sub 3}A dissolution frontier. Here, we fill this gap by integrating synchrotron-radiation based crystallographic, photon-energy-dependent spectroscopic and high-resolution morphological studies of the C{sub 3}A hydration product layer. We propose that ettringite (6CaO·Al{sub 2}O{sub 3}·SO{sub 3}·32H{sub 2}O) is the only hydration product after the initial reaction period and before complete gypsum dissolution. We quantify the 2D and 3D morphology of the ettringite network, e.g. the packing density of ettringite at various surface locations and the surface dissolution heterogeneity. Our results show no trace of a rate-controlling diffusion barrier. We expect our work to have significant impact on modeling the kinetics and morphological evolution of PC hydration.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Corrosion of 316 L stainless steel under the natural circulation of molten NaCl-MgCl 2 salt

The corrosion behavior of 316 L stainless steel (SS) was studied via the natural circulation of molten eutectic NaCl-MgCl 2 salt through a microloop. The post-corrosion tested 316 L SS microloop sections were characterized with microscopy techniques to determine the microstructural and microchemical changes that occurred at the alloy/salt interface. It was found that 316 L SS showed heterogeneous dissolution at the hot-leg, whereas deposition of corrosion products occurred at the cold-leg. For the first time, experimentally obtained molten salt flow-induced corrosion of 316 L SS results were combined with computational thermodynamic-kinetic models to validate the dissolution and deposition in terms of elemental compositional changes at the alloy/salt interface. The thermodynamic-kinetic modeling predicted that the heterogeneous dissolution of Cr and Fe from the hot-leg section of 316 L SS persisted throughout the salt circulation. The model also estimated that, despite Cr deposition starting earlier than Fe, the total redeposition of Fe is expected to be significantly greater than that of Cr over the circulation of salt. Furthermore, the modeling accurately predicted the subsurface enrichment of Mo which is attributed to the reduced Cr activity and the relatively higher diffusion rate of Mo within the alloy matrix. Here, the agreement between modeling and experimental results confirms that Fe chlorides dissolve at the hot-leg and subsequently deposit at the cold-leg due to activity changes driven by the thermal gradient. By contrast, Cr was not detected in the cold-leg deposits, which is attributed to its weaker temperature dependence on activity, limiting its redeposition under these conditions.

36 - MATERIALS SCIENCE↗
DOE OSTI2023

Mastering the synergy between Na 3 V 2 (PO 4 ) 2 F 3 electrode and electrolyte: A must for Na-ion cells

Sodium-ion batteries are emerging as suitable energy storage devices for special applications such as high-power devices with the advantages of being cheaper and more sustainable than the Li-ion equivalents. The sodium ion cells consisting of polyanionic Na 3 V 2 (PO 4 ) 2 F 3 - hard carbon electrodes exhibit high power rate capabilities but limited cycle life, especially at high temperatures. To circumvent this drawback we herein conducted in-depth analyses of the origins of structural degradations occurring in Na 3 V 2 (PO 4 ) 2 F 3 electrodes upon long cycling. Vanadium dissolution with associated parasitic reactions is identified as one of the major reasons for cell failure. Its amount varies depending on the electrolyte, with NaTFSI-based electrolyte showing the least vanadium dissolution as the TFSI - anion decomposes without producing acidic impurities, in contrast to the NaPF 6 -based electrolyte. The dissolved vanadium species undergoes oxidation and reduction processes at the Na 3 V 2 (PO 4 ) 2 F 3 and HC electrodes, respectively, with the electrochemical signature of these processes being used as a fingerprint to identify state of health of the 18650 cells. Here, having found that surface reactivity is the primary cause of vanadium dissolution we provide methods to mitigate it by combining surface coating and optimized electrolyte formulation.

25 ENERGY STORAGE↗