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At least 73 records · Page 4
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Modeling simultaneous particle shrinkage, dissolution and breakage using the modified moving grid technique

Simultaneous shrinkage, dissolution and breakage are important particle size reduction phenomena that characterize processes like the reactive degradation of solid chemicals. The dynamics of the particle size distribution (PSD) for such processes are non-trivial to model due to the number expending processes brought about by the eventual dissolution of particles. To this end, Population Balance Model (PBM) resolved through the sectional techniques is the natural approach. Here, we introduce a modified Moving Grid technique (m-MGT) to accurately resolve the particle size reduction phenomena. Our technique mimics the perpetual particle shrinkage through a continuously left-moving size grid and incorporates a strategic grid removal routine to capture the disappearance of particles. Coupled with the Fixed Pivot (FP) discretization for breakage, our m-MGT not only preserves the moment-related properties, but also benchmarked very well against the analytical number densities and exhibited a minimum of first-order convergence in all assessed case studies.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2020

Investigation of Thermolytic Hydrogen Generation Rate in Tank 44 Dissolved Saltcake Samples

Saltcake core samples collected from Tank 44 in 2006 were dissolved to provide material for HGR measurements applicable to F-Area dissolved saltcake material. Additionally, characterization was performed on the Tank 44 saltcake material. The following are key results from the Tank 44 saltcake characterization. The Tank 44 Upper Saltcake Composite, corresponding to the 171 to 285 inch tank level, contained by mass approximately 69% sodium nitrate, 11% sodium carbonate, 8% sodium nitrite, smaller amounts of other salts and components, and 9% unquantified (which includes water, water of hydration, oxygen/hydrogen content of oxides and hydroxides, and uncertainty). The Tank 44 Lower Saltcake Composite, corresponding to the 76 to 114 inch tank level, contained by mass approximately 49% sodium carbonate, 18% sodium nitrate, smaller amounts of other salts, at least 8% sludge, and 9% unquantified (see above). The dissolved saltcake contained free hydroxide less than quantifiable (<0.01 M) due to the limited quantity of material that could be removed from the Shielded Cells based on the sample radioactivity. Measurement by pH paper provided an approximate pH of 12. The following are key results from the Tank 44 HGR testing. During boiling at 106.7 °C, HGR for Tank 44 dissolved saltcake without added glycolate was 7.2×10 -8 ft 3 h -1 ga l-1 . During boiling at 106.9 °C, HGR for Tank 44 dissolved saltcake with 1000 mg/L of added glycolate was 8.2×10 -8 ft 3 h -1 gal -1 . ∙ For the test without added glycolate, the first several HGR measurements at 70, 85, and 100 °C gave indication of the release of dissolved hydrogen and should not be used to represent the sustained thermolytic HGR for those temperatures. The measurements at boiling are the best representation of thermolysis in this testing. Carbon dioxide was observed at concentrations up to 6 vol% in the flow-system offgas for the test at boiling. ∙ Methane generation was observed at 100 °C and boiling. Methane concentration in the total gas generated during testing remained well below the lower flammability limit for methane in air. The addition of 1000 mg/L of glycolate did not have a significant impact on the hydrogen generation rates measured during this testing. The low hydroxide concentration in the Tank 44 dissolved saltcake likely influenced the relatively low thermolytic HGR and high carbon dioxide release observations in this testing. Based on the observation that methane was generated or released upon heating SRS radioactive Tank 44 waste samples to 100 °C and above, we recommend gaining a greater understanding of the cause and mechanism of its generation. First, the applicable literature should be reviewed to reveal the thermolytic methane generation mechanisms of possible methane generating species in the SRS CSTF. If warranted, a plan should be developed for simulant tests with methylated siloxanes and other applicable compounds in order to gain a better mechanistic understanding of methane generation in the SRS CSTF.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

Investigation of Thermolytic Hydrogen Generation Rate in Tank 44 Dissolved Saltcake Samples

Saltcake core samples collected from Tank 44 in 2006 were dissolved to provide material for HGR measurements applicable to F-Area dissolved saltcake material. Additionally, characterization was performed on the Tank 44 saltcake material. The following are key results from the Tank 44 saltcake characterization. The Tank 44 Upper Saltcake Composite, corresponding to the 171 to 285 inch tank level, contained by mass approximately 69% sodium nitrate, 11% sodium carbonate, 8% sodium nitrite, smaller amounts of other salts and components, and 9% unquantified (which includes water, water of hydration, oxygen/hydrogen content of oxides and hydroxides, and uncertainty). The Tank 44 Lower Saltcake Composite, corresponding to the 76 to 114 inch tank level, contained by mass approximately 49% sodium carbonate, 18% sodium nitrate, smaller amounts of other salts, at least 8% sludge, and 9% unquantified (see above). The dissolved saltcake contained free hydroxide less than quantifiable (<0.01 M) due to the limited quantity of material that could be removed from the Shielded Cells based on the sample radioactivity. Measurement by pH paper provided an approximate pH of 12. The following are key results from the Tank 44 HGR testing. During boiling at 106.7 °C, HGR for Tank 44 dissolved saltcake without added glycolate was 7.2×10 -8 ft 3 h -1 gal -1 . During boiling at 106.9 °C, HGR for Tank 44 dissolved saltcake with 1000 mg/L of added glycolate was 8.2×10 -8 ft 3 h -1 gal -1 . For the test without added glycolate, the first several HGR measurements at 70, 85, and 100 °C gave indication of the release of dissolved hydrogen and should not be used to represent the sustained thermolytic HGR for those temperatures. The measurements at boiling are the best representation of thermolysis in this testing. Carbon dioxide was observed at concentrations up to 6 vol% in the flow-system offgas for the test at boiling. Methane generation was observed at 100 °C and boiling. Methane concentration in the total gas generated during testing remained well below the lower flammability limit for methane in air. The addition of 1000 mg/L of glycolate did not have a significant impact on the hydrogen generation rates measured during this testing. The low hydroxide concentration in the Tank 44 dissolved saltcake likely influenced the relatively low thermolytic HGR and high carbon dioxide release observations in this testing. Based on the observation that methane was generated or released upon heating SRS radioactive Tank 44 waste samples to 100 °C and above, we recommend gaining a greater understanding of the cause and mechanism of its generation. First, the applicable literature should be reviewed to reveal the thermolytic methane generation mechanisms of possible methane generating species in the SRS CSTF. If warranted, a plan should be developed for simulant tests with methylated siloxanes and other applicable compounds in order to gain a better mechanistic understanding of methane generation in the SRS CSTF.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2021

New insights into the role of fly ash in mitigating alkali-silica reaction (ASR) in concrete

Alkali-silica reaction (ASR) mitigation mechanisms of fly ash in concrete are still being debated and remain an interesting research topic. This study provides new insights into the role of aluminum oxide (Al{sub 2}O{sub 3}) in fly ash particles on ASR mitigation. A comprehensive test program was conducted and included expansion measurements, dissolution model experiments of exposed and embedded borosilicate glass elements, analyses of pore and immersion solutions, quantification of Ca(OH){sub 2} content, and microstructural analyses. It was found that in addition to the traditionally accepted mitigation mechanisms such as alkali binding, diffusion control and reduction in available Ca(OH){sub 2}, dissolution control of reactive aggregates by aluminum discharged from fly ash particles also contributed to the ASR mitigation. Re-introducing alkalis to fly ash-incorporated concrete prisms which exhibited undeleterious expansion under a long-term ASR exposure triggered and significantly increased the subsequent expansion.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Investigating Abiotic and Biotic Mechanisms of Pyrite Reduction

Pyrite (FeS 2 ) has a very low solubility and therefore has historically been considered a sink for iron (Fe) and sulfur (S) and unavailable to biology in the absence of oxygen and oxidative weathering. Anaerobic methanogens were recently shown to reduce FeS 2 and assimilate Fe and S reduction products to meet nutrient demands. However, the mechanism of FeS 2 mineral reduction and the forms of Fe and S assimilated by methanogens remained unclear. Thermodynamic calculations described herein indicate that H 2 at aqueous concentrations as low as 10 –10 M favors the reduction of FeS 2 , with sulfide (HS – ) and pyrrhotite (Fe 1–x S) as products; abiotic laboratory experiments confirmed the reduction of FeS 2 with dissolved H 2 concentrations greater than 1.98 × 10 –4 M H 2 . Growth studies of Methanosarcina barkeri provided with FeS 2 as the sole source of Fe and S resulted in H 2 production but at concentrations too low to drive abiotic FeS 2 reduction, based on abiotic laboratory experimental data. A strain of M. barkeri with deletions in all [NiFe]-hydrogenases maintained the ability to reduce FeS 2 during growth, providing further evidence that extracellular electron transport (EET) to FeS 2 does not involve H 2 or [NiFe]-hydrogenases. Physical contact between cells and FeS 2 was required for mineral reduction but was not required to obtain Fe and S from dissolution products. The addition of a synthetic electron shuttle, anthraquinone-2,6-disulfonate, allowed for biological reduction of FeS 2 when physical contact between cells and FeS 2 was prohibited, indicating that exogenous electron shuttles can mediate FeS 2 reduction. Here, transcriptomics experiments revealed upregulation of several cytoplasmic oxidoreductases during growth of M. barkeri on FeS 2 , which may indicate involvement in provisioning low potential electrons for EET to FeS 2 . Collectively, the data presented herein indicate that reduction of insoluble FeS 2 by M. barkeri occurred via electron transfer from the cell surface to the mineral surface resulting in the generation of soluble HS – and mineral-associated Fe 1–x S. Solubilized Fe(II), but not HS – , from mineral-associated Fe 1–x S reacts with aqueous HS – yielding aqueous iron sulfur clusters (FeS aq ) that likely serve as the Fe and S source for methanogen growth and activity. FeS aq nucleation and subsequent precipitation on the surface of cells may result in accelerated EET to FeS 2 , resulting in positive feedback between cell activity and FeS 2 reduction.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS1985

Method for growth of crystals by pressure reduction of supercritical or subcritical solution

Crystals of high morphological quality are grown by dissolution of a substance to be grown into the crystal in a suitable solvent under high pressure, and by subsequent slow, time-controlled reduction of the pressure of the resulting solution. During the reduction of the pressure interchange of heat between the solution and the environment is minimized by performing the pressure reduction either under isothermal or adiabatic conditions.

Shlichta, P. J.↗
DOE OSTI2019

Theoretical Calculation Guided Design of Single-Atom Catalysts toward Fast Kinetic and Long-Life Li–S Batteries

Lithium–sulfur (Li–S) batteries are enticing next-generation energy storage technologies due to their high theoretical energy density, environmental friendliness, and low cost. Yet, low conductivity of sulfur species, dissolution of polysulfides, poor conversion from sulfur reduction, and lithium sulfide (Li 2 S) oxidation reactions during discharge–charge processes hinder their practical applications. Herein, under the guidance of density functional theory calculations, we have successfully synthesized large-scale single atom vanadium catalysts seeded on graphene to achieve high sulfur content (80 wt % sulfur), fast kinetic (a capacity of 645 mAh g –1 at 3 C rate), and long-life Li–S batteries. Both forward (sulfur reduction) and reverse reactions (Li 2 S oxidation) are significantly improved by the single atom catalysts. This finding is confirmed by experimental results and consistent with theoretical calculations. The ability of single metal atoms to effectively trap the dissolved lithium polysulfides (LiPSs) and catalytically convert the LiPSs/Li 2 S during cycling significantly improved sulfur utilization, rate capability, and cycling life. Our work demonstrates an efficient design pathway for single atom catalysts and offers solutions for the development of high energy/power density Li–S batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Understanding the TiH (2-x) /TiO y System at Elevated Temperature: A Literature Review

Titanium hydride of varying TiH stoichiometry is used in pyrotechnic compositions. In order to yield consistent performance, manufacturing processes must be developed to ensure precise and reproducible material properties, including composition and morphology. Legacy synthesis protocols are not comprehensive nor are the required apparatuses still available. To guide the development of novel production procedures, this report reviews literature on relevant chemical reactions and diffusion events occurring at elevated temperature in the TiH (2-x) /TiO y system. Titanium hydride exposed to air spontaneously forms a passivating oxide layer. Upon heating, significant hydrogen release, which is accompanied by changes to the surface oxide layer, is noted by 375–400°C. At higher temperatures (above about 500°C) the oxide layer is reported to be essentially nonexistent as a result of oxide-layer dissolution processes and, potentially, oxide-layer reduction due to water formation. Based on the reviewed literature, we hypothesize that, by 500°C, the surface layer consists of an oxyhydride phase, which is a solid solution of oxygen in titanium hydride. We believe that hydrogen release from titanium hydride is controlled by the kinetics of molecular hydrogen desorption on the oxyhydride surface. No literature data is available for corresponding activation energies of the dynamic desorption process, and the equilibrium phase diagram of this three-component system remains largely unexplored as well. These gaps in knowledge might be addressed through coordinated computational modeling and experimental efforts.

36 MATERIALS SCIENCE↗
NASA NTRS1975

Oxide nucleation on thin films of copper during in situ oxidation in an electron microscope

Single-crystal copper thin films were oxidized at an isothermal temperature of 425 C and at an oxygen partial pressure of 0.005 torr. Specimens were prepared by epitaxial vapor deposition onto polished faces of rocksalt and were mounted in a hot stage inside the ultrahigh-vacuum chamber of a high-resolution electron microscope. An induction period of roughly 30 min was established which was independent of the film thickness but depended strongly on the oxygen partial pressure and to exposure to oxygen prior to oxidation. Neither stacking faults nor dislocations were found to be associated with the Cu2O nucleation sites. The experimental data, including results from oxygen dissolution experiments and from repetitive oxidation-reduction-oxidation sequences, fit well into the framework of an oxidation process involving the formation of a surface charge layer, oxygen saturation of the metal with formation of a supersaturated zone near the surface, and nucleation followed by surface diffusion of oxygen and bulk diffusion of copper for lateral and vertical oxide growth, respectively.

Heinemann, K.↗
NASA NTRS1976

Oxidation of metals and alloys in controlled atmospheres using in situ transmission electron microscopy and Auger spectrography

Single-crystalline thin films of copper were oxidized at an isothermal temperature of 425 C and at an oxygen partial pressure of .005 Torr in situ in a high-resolution electron microscope. The specimens were prepared by epitaxial vapor deposition onto polished 100 and 110 faces of rocksalt and mounted in a hot stage inside an ultra-high-vacuum specimen chamber of the microscope. Large amounts of sulfur, carbon, and oxygen were detected by Auger electron spectroscopy on the surface of the as-received films and were removed in situ by ion-sputter etching immediately prior to the oxidation. The nucleation and growth characteristics of Cu2O on Cu were studied. Results show that neither stacking faults nor dislocations are associated with the Cu2O nucleation sites. The growth of Cu2O nuclei is linear with time. The experimental findings, including results from oxygen dissolution experiments and from repetitive oxidation-reduction-oxidation sequences, fit well into the framework of an oxidation process involving (a) the formation of a surface-charge layer, (b) oxygen saturation in the metal and (c) nucleation, followed by surface diffusion of oxygen and bulk diffusion of copper for lateral and vertical oxide growth, respectively.

Rao, D. B.↗
NASA NTRS1971

Research on rechargeable oxygen electrodes

Studies were carried out on a number of factors which may influence the behavior of the platinum electrocatalyst of oxygen electrodes for use in rechargeable metal-oxygen batteries or hydrogen-oxygen fuel cells. The effects of pretreatments for various potentials and added ionic species, which could be present in such systems, were studied with reguard to: (1) the state of surface oxidation, (2) platinum dissolution, (3) the kinetics of oxygen evolution and reduction (including the role of hydrogen peroxide), and (4) changes in porous electrode structure. These studies were carried out on smooth platinum, platinized platinum, and Teflon-bonded platinum black electrodes in carefully purified electrolyte solutions. The main factors which appear to affect rechargeable oxygen electrode performance and life are: (1) the buildup of a refractory anodic layer on extended cycling, and (2) the dissolution of platinum.

Giner, J.↗
DOE OSTI2025

Understanding the Dissolution and Passivation of an Aluminum Electrode during Electrocoagulation of Groundwater Using Neutron and X-ray Reflectometry

An aluminum (Al)-based electrocoagulation (EC) system can effectively remove dissolved silica and hardness in groundwater. The effectiveness of Al-EC in terms of pollutant removal, Faradaic efficiency, and energy consumption depends on the interfacial electrolysis or passivation of the electrode in water. Thus, understanding the electrolysis reaction at the liquid/electrode interface during operation is important for sustainable EC deployment. Here, a continuous flow-through Al-EC system was tested with various groundwater simulants, i.e., chloride (Cl – )-based, sulfate (SO 4 2– )-based, and mixed solutions. High pollutant removal with low energy consumption was observed in Cl – -based groundwater treatment, while low pollutant removal with high energy consumption was observed in SO 4 2– -based groundwater. For example, the required energy per unit mass of Al dosing in SO 4 2– -based groundwater is three times higher than that in Cl – -based groundwater at 10 mA/cm 2 . However, increasing the Cl – concentration significantly reduces this energy demand. In SO 4 2– -based groundwater, the silicate removal efficiency drops from 85.1% to 24.0% compared to that for Cl – -based groundwater, while Mg 2+ and Ca 2+ removal efficiencies decrease to 0.6% from 15.8% and 5.7% from 44.8%, respectively. To better understand this EC performance, we used in situ neutron reflectometry (NR) to examine the interfacial dynamics of Al dissolution and passivation at a 100 nm scale occurring on the surface of the sacrificial Al electrodes during EC. Ex situ X-ray reflectometry (XRR) was also used to support the in situ NR results. Both NR and XRR results revealed that Al dissolution is influenced by the presence of Cl – in the simulants, while a passivating layer forms on the electrode in a SO 4 2– -based solution. In the Cl – -based solution, anodic Al dissolution occurred locally and inhomogeneously across the surface of the Al anode film, resulting in a localized thickness reduction over time. In the SO 4 2– -based solution, no apparent dissolution of the Al anode was identified. Instead, Al underwent oxidation, forming an amorphous Al 2 O 3 surface layer within the Al electrode film that increased in thickness over time. In the mixed solution, both anodic Al dissolution and surface Al 2 O 3 layer formation occurred, indicating that Al dissolution and surface Al 2 O 3 layer formation are attributable to the Cl – and SO 4 2– ions, respectively.

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

Effects of Sodium Exposure on the Tensile Properties of Grade 91 steel

Two heats of G91 steel have been investigated in liquid sodium at 550- 650°C to understand their corrosion behaviour, microstructural evolution, and tensile properties. Sodium exposure experiments of subsized, sheet-type tensile specimens of G91 were performed in Argonne’s forced convection sodium materials testing loops, SMT-1 and SMT-2. Maximum exposure times of ~49,000 h at ~38,000 h, and ~20,000 h have been achieved at 550, 600, and 650°C, respectively. Thermal aging experiments of G91 steel were also conducted in parallel, and the results were compared with those of the sodium-exposed specimens to isolate the effect of thermal aging from the effect of sodium exposure. It was found that the yield stress and ultimate tensile strength of G91 were reduced by more than 50% after sodium exposures at 650°C due to decarburization. The reduction in tensile strength was accompanied by the dissolution of M 23 C 6 carbides and excessive grain growth. The effect of sodium at 550 and 600°C was insignificant for exposure times up to ~49,000 h and ~38,000 h, respectively. The effect of sodium on the microstructural stability and tensile properties of G91 is largely dependent on the carbon mass transfer in the alloy-sodium system.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2020

Calculated Reduction Potentials of Electrolyte Species in Lithium–Sulfur Batteries

In this work, reduction potentials of electrolyte molecules in the lithium–sulfur (Li/S) battery and their variations in several solvent environments are studied using the density functional theory method with Dunning’s triple-ζ correlation consistent basis set. Reliable reduction potential values are key for electrolyte additive design needed for suppressing polysulfide dissolution shuttle mechanism, resulting in poor cycle performance and severe self-discharge of the Li/S battery. Although isolated electrolyte molecules have reduction potentials outside the operating voltage range of the Li/S battery, complexation with other electrolyte species enables the electrolyte molecules to be reduced within the operating voltage range. Among the electrolyte species considered in this study, bis(fluorosulfonyl)imide (FSI – ) and fluoroethylene carbonate (FEC) yield reduction potentials within the expected range, suggesting the development of fluorine-containing additives as a promising line of research.

25 ENERGY STORAGE↗
DOE OSTI2025

Multimodal In Situ Characterization Uncovers Unexpected Stability of a Cobalt Electrocatalyst for Acidic Sustainable Energy Technologies

An accelerated development of durable and affordable sustainable energy technologies is often hindered by a limited understanding of how non-precious materials within these systems degrade. In acidic proton exchange membrane fuel cells and water electrolyzers, metallic cobalt (Co) is considered an unstable component that is often combined with precious metals or other stabilizers. To understand the mechanisms behind Co instability, we employ an experimental platform that quantifies dissolution with on-line inductively coupled plasma mass spectrometry and product formation with electrochemical mass spectrometry during electrochemical testing, along with ex- situ characterization. Under varied conditions (electrocatalysis, time, gas-type saturation, and ion concentration), windows of Co stability are observed that are different than predicted with classical chemical thermodynamics, suggesting new stabilization and degradation mechanisms than previously understood. Notably, Co is active for the hydrogen evolution reaction (HER), with prolonged stability that is ~300 mV different than thermodynamically projected. Additionally, in an oxygenated environment, Co concurrently performs the HER and oxygen reduction reaction (ORR) yet undergoes different morphology changes and dissolution mechanisms. Interestingly, in the absence of electrocatalysis, there is a 22x decrease in dissolution in an oxygen-free environment, proposing a route to decrease Co losses during device shutdown protocols. Lastly, under more extreme operating conditions, Co becomes stable after a substantial amount of dissolution, suggesting that high concentrations of Co 2+ ions in the microenvironment induce the formation of a stable CoHO 2 surface. Altogether, these results can be leveraged to improve the design and development of more robust and cost-effective sustainable energy technologies, as well as promote strategic strategies for prolonged material utilization.

Dissolution↗
DOE OSTI2023

Striking stability of a mixed-valence thallium(III)-thallium(I) complex in some solvents

At the dissolution of solid anhydrous thallium(III) trifluoromethanesulfonate, Tl(CF 3 SO 3 ) 3 , or thallium(III) trifluoroacetate, Tl(CF 3 COO) 3 , in dimethylsulfoxide (dmso) or N,N,N’,N’-tetramethylurea (tmu), intensely red-colored complexes are formed. This red thallium complex is stable for years in dmso, while it is reduced fairly rapidly to thallium(I) in tmu with a half-life time of an hour. At the dissolution of Tl(CF 3 SO 3 ) 3 in N,N-dimethylpropyleneurea (dmpu) an immediate reduction to thallium(I) takes place. A stable colorless aqueous thallium(III) solution is obtained at the dissolution in acidic water. Stable dmso solutions and solid dmso solvates of thallium(III) perchlorate, nitrate and trifluormethanesulfonate can be prepared by adding dmso to concentrated acidic aqueous thallium(III) solutions. These experimental observations conclude that the pure solids Tl(CF 3 SO 3 ) 3 and Tl(CF 3 COO) 3 play an essential role in the formation of the red-colored thallium complexes. 205 Tl NMR data show that the red thallium complex contains equal amounts of thallium(III) and thallium(I). The structure of the red thallium complex in dmso, as determined by EXAFS, has Tl–O bond distances of 2.216(3) and 2.80(2) Å, which are in very close agreement with the bond distances obtained in the pure dmso solvates of the thallium(III) and thallium(I) ions, respectively, and a Tl···Tl distance of 3.49(1) Å bridged by oxygen atoms. From the EXAFS data it is impossible to distinguish if dmso molecules and/or trifluoromethanesulfonate ions act as bridges. DFT calculations could eliminate some structures due to the irrelevant structural parameters or the energetics of the proposed reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗