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At least 811 records · Page 45
All sourcesNASA NTRSDOE OSTI
DOE OSTI2016

New insights into the hydration of slag in alkaline media using a micro-reactor approach

A micro-reactor approach, developed previously, is used to study the reactions of slag in alkaline media. Micron-sized gaps are milled in slag grains using a focused ion beam (FIB) and subsequently filled with alkaline solutions, leading to dissolution and hydration of the slag. After the hydration is stopped, a scanning electron microscope (SEM) is used to image the gaps. We present the effect of pH and nature of the alkaline solution on the slag dissolution and the hydrate morphology. The results obtained in this study confirm that the presence of aluminum and calcium in solution has a strong retarding effect on the slag dissolution. A major implication of these results is that in blended cements, the reactivity of slag probably suffers from the ions released by cement into solution. We show that strongly adsorbing superplasticizers inhibit the dissolution of slag, but only at lower alkali concentrations and C–S–H seeds may also inhibit the dissolution of slag under certain experimental conditions. The obtained results are compared and contrasted with results obtained for alite and tricalcium silicate previously reported in the literature.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Solubility of pyromorphite Pb 5 (PO 4 ) 3 Cl at 5–65°C and its experimentally determined thermodynamic parameters

Here, the solubility of synthetic pyromorphite Pb 5 (PO 4 ) 3 Cl was determined in a series of dissolution experiments conducted at 5–65 °C and at pH = 2.0. The equilibrium was established within 4 months. The dissolution of pyromorphite was congruent at all the temperatures, and the measured solubility product log K sp,298 for the dissolution reaction: Pb 5 (PO 4 ) 3 Cl ⇌ 5Pb 2+ + 3PO 4 3- + Cl - was determined to be –79.6 ± 0.15. The equilibrium ion activity product of pyromorphite increased with temperature, indicating a positive enthalpy of the dissolution reaction in the temperature range from 5 to 65 °C. The temperature dependence of the log K sp was nonlinear: log K sp = A – B/T + D log(T), where A = 478.77 ± 136.62, B = 29,378 ± 6215, and D = –185.81 ± 46.77. This allowed for calculation of ΔG° r = 454.0 ± 1.7 kJ·mol –1 , ΔH° r = 101.8 ± 6.0 J·mol –1 ·K –1 , ΔC° p,r = –1545 ± 388.9 J·mol –1 ·K –1 , and ΔS° r = –1181 ± 382 J·mol –1 ·K –1 of the dissolution reaction. Using these values and the published standard state quantities for constituent ions, the values of ΔG° f = –3764.3 ± 3.5 kJ·mol –1 , ΔH° f = –4108.4 ± 7.9 J·mol –1 ·K –1 , S° f = 622 ± 382 J·mol –1 ·K –1 , and C° pf = 402 ± 398 J·mol –1 ·K –1 were calculated for synthetic pyromorphite Pb 5 (PO 4 ) 3 Cl.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2025

Ab Initio Structures and Energetics of Hydrated Flat and Terrace-Step Surfaces of Forsterite (Mg 2 SiO 4 )

Forsterite (Mg 2 SiO 4 ), a model divalent metal silicate mineral, has been extensively studied in the context of mineral carbonation. Although dissolution is a key step in this process, the mechanisms by which forsterite dissolves under high CO 2 conditions remain poorly understood. Atomistic simulations could aid in exploring these mechanisms, but it is essential first to understand the structures and energetics of the relevant forsterite surfaces. We present an ab initio study of the structure and surface energy at 0 K of the flat $(010), (110), (001), (111), (021), (101)$ and $(120)$ faces of forsterite using the density functional PBE Hamiltonian and a plane-wave basis set. Dry surfaces became stabilized upon hydration through the formation of bonds between surface Mg and O from water, as well as by the formation of hydrogen bonds. According to surface energy values, the stability order of the hydrated forsterite faces was found to be $(120) < (101) < (021) < (111) < (001) < (110) < (010)$. We also investigated the energetics of the terrace-step $(0\bar{41})$ surface as a model site for forsterite dissolution. Among all the facets, the $(0\bar{41})$ surface is the least stable termination in water. Hydration of Mg atoms on the $(0\bar{41})$ surface increases their susceptibility to dissolution. The presence of a step and its hydration destabilizes the terraces, making step retreat more likely than a dissolution front advancing along the [010] direction. This research will support future simulations to investigate forsterite dissolution in water under CO 2 -rich conditions.

PBE Hamiltonian↗
DOE OSTI2025

Flowsheet Development for the University of Tokyo YAYOI (UTY) Fuel

The Savannah River National Laboratory (SRNL) was requested by H-Canyon Engineering to determine the flowsheet parameters needed to dissolve and store the YAYOI Material Test Reactor (MTR) uranium fuel safely and efficiently. In response to this request, a literature review of existing SRNL MTR dissolution flowsheets and general fuel dissolution literature in the nuclear fuel processing industry was performed to evaluate chemical dissolution parameters required to dissolve the YAYOI fuel and the tin-plated carbon steel product cans (PC). Based on past dissolutions of similar fuel in the H-Canyon and open literature reviews on chemical dissolution of spent nuclear fuel (SNF), the following conclusions and flowsheet recommendations were made.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2017

Ammonia gas Treatment for Uranium Immobilization at DOE Hanford Site - 17067

Ammonia gas is a potential uranium (U) remediation technique for the vadose zone at the Department of Energy's (DOE) Hanford Site in Washington State via pH manipulation. The objective of this work was to investigate U removal from the aqueous phase and mineral dissolution with either NaOH or NH{sub 4}OH in order to understand ammonia as a remediation technique for the vadose zone. Batch experiments were designed to investigate the fate of U and mineral dissolution upon treatment with either NaOH or NH{sub 4}OH. These experiments investigated mineral dissolution and U partitioning in the presence of pure minerals (quartz, kaolinite, illite, montmorillonite, muscovite) and sediments relevant to the Hanford site in either NaCl or synthetic groundwater formulated based on the Hanford site groundwater components. Analysis of mineral dissolution via measurement of major cations has demonstrated that there is a significant increase in dissolution of minerals with basic treatment and likely greater secondary precipitation for the NH{sub 4}OH as compared to NaOH treatment for clay minerals and Hanford sediments. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2015

Rapid fusion method for the determination of refractory thorium and uranium isotopes in soil samples

Recently, approximately 80% of participating laboratories failed to accurately determine uranium isotopes in soil samples in the U.S Department of Energy Mixed Analyte Performance Evaluation Program (MAPEP) Session 30, due to incomplete dissolution of refractory particles in the samples. Failing laboratories employed acid dissolution methods, including hydrofluoric acid, to recover uranium from the soil matrix. The failures illustrate the importance of rugged soil dissolution methods for the accurate measurement of analytes in the sample matrix. A new rapid fusion method has been developed by the Savannah River National Laboratory (SRNL) to prepare 1-2 g soil sample aliquots very quickly, with total dissolution of refractory particles. Soil samples are fused with sodium hydroxide at 600 ºC in zirconium crucibles to enable complete dissolution of the sample. Uranium and thorium are separated on stacked TEVA and TRU extraction chromatographic resin cartridges, prior to isotopic measurements by alpha spectrometry on cerium fluoride microprecipitation sources. Plutonium can also be separated and measured using this method. Batches of 12 samples can be prepared for measurement in <5 hours.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2014

Experiments and modeling of variably permeable carbonate reservoir samples in contact with CO₂-acidified brines

Reactive experiments were performed to expose sample cores from the Arbuckle carbonate reservoir to CO₂-acidified brine under reservoir temperature and pressure conditions. The samples consisted of dolomite with varying quantities of calcite and silica/chert. The timescales of monitored pressure decline across each sample in response to CO₂ exposure, as well as the amount of and nature of dissolution features, varied widely among these three experiments. For all samples cores, the experimentally measured initial permeability was at least one order of magnitude or more lower than the values estimated from downhole methods. Nondestructive X-ray computed tomography (XRCT) imaging revealed dissolution features including “wormholes,” removal of fracture-filling crystals, and widening of pre-existing pore spaces. In the injection zone sample, multiple fractures may have contributed to the high initial permeability of this core and restricted the distribution of CO₂-induced mineral dissolution. In contrast, the pre-existing porosity of the baffle zone sample was much lower and less connected, leading to a lower initial permeability and contributing to the development of a single dissolution channel. While calcite may make up only a small percentage of the overall sample composition, its location and the effects of its dissolution have an outsized effect on permeability responses to CO₂ exposure. The XRCT data presented here are informative for building the model domain for numerical simulations of these experiments but require calibration by higher resolution means to confidently evaluate different porosity-permeability relationships.

58 GEOSCIENCES↗
DOE OSTI2022

Switching from batch to continuous granulation: A case study of metoprolol succinate ER tablets

Continuous manufacturing (CM) has been used to produce several immediate release drug products. No extended-release (ER) product manufactured employing CM technology has been approved yet. Herein this study investigated the critical aspects of switching from the batch mode of high shear granulation to the continuous operation of twin-screw granulation for extended-release tablets. Metoprolol succinate ER tablets was used as a model ER formulation for this purpose. A central composite design (CCD) was employed to determine the effects of high shear granulator (HSG) parameters, namely impeller speed, granulation time, and binder liquid feeding rate, on the critical granulation characteristics important for product performance. These critical granulation characteristics served as a guide for switching from the batch processing to the continuous operation for achieving the same breaking strength and dissolution for this ER metoprolol tablets. The granulation time was the most critical factor affecting the bulk properties of granules which contributed to tablet dissolution. The higher density and lower compressibility of granules were attained at the longest granulation time of 5.4 min with the fastest liquid feeding rate of 75 g/min. The granules’ density was the primary factor negatively affecting the dissolution of metoprolol tablets. However, the breaking strength of tablets confounded the effect of granules density on metoprolol dissolution. Switching the processing parameters of high shear granulation to twin-screw granulation achieved similar dissolution profiles (F2 greater than 50). The screw speed was not found to affect bulk properties of granules. The root cause of granulation failures in twin-screw granulation, such as premature consolidation, excessive swelling, poor cohesion, inconsistent shearing effects, and formation of deformed agglomerates, were identified. In conclusion, the use of critical granulation characteristics through a performance-based approach of ER tablets facilitated the switching of manufacturing of an ER formulation form batch to continuous operation.

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

Compatibility of Fe-Cr-Al and Fe-Cr-Al-Mo oxide dispersion strengthened steels with static liquid sodium at 700 °C

We report the corrosion behavior and tensile properties of oxide dispersion strengthened (ODS) FeCr, FeCrAl, FeCrAlMo steels and 316H stainless steel were evaluated after 1000 h at 700 °C in static sodium with and without an oxygen getter (Zr foil). Without Zr foil to getter the dissolved oxygen in the liquid sodium, combined oxidation (formation of Cr, Fe-rich or Al-rich oxides) and dissolution of the studied materials was observed. For the ODS FeCr, Cr- and Fe-rich oxide formation and dissolution induced Cr depletion in the underlying alloy and led to the formation of laves phases that were observed to be detrimental to the room temperature tensile properties. For ODS FeCrAlMo and FeCrAl Al-rich oxide formation and dissolution resulted in Al depletion in the underlying alloys but did not impact tensile properties at room temperature. For 316H temperature induced sensitization combined with oxidation decreased room temperature tensile properties. With Zr foil added as oxygen getter, roughened surfaces and Al depletion profiles suggested the dissolution of ODS FeCr and FeCrAl into the liquid sodium while limited dissolution was observed for ODS FeCrAlMo and 316H. For the 316H and ODS FeCrAlMo steels, precipitates were formed at the grain boundaries after exposure. Tensile properties of ODS FeCr, FeCrAl and FeCrAlMo were not affected by the 1000 h corrosion exposure with Zr foil added to the sodium but for 316H temperature-induced grain boundary sensitization negatively affected the tensile properties.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Effect of chromium on corrosion resistance of Ni-Cr-Mo-Gd alloys in seawater

Neutron absorbing materials are being considered within commercial spent nuclear fuel disposal canisters to maintain nuclear subcriticality in storage. To select candidate alloys for the canisters, both neutron absorption and corrosion resistance should be considered. This work examines corrosion resistance of Ni-Cr-Mo-Gd alloys developed specifically for neutron absorption. The addition of Gd results in a secondary gadolinide phase (Ni 5 Gd) that significantly changes the corrosion properties. Testing was performed primarily in seawater at 30°C. Seawater was selected as the most prevalent terrestrial brine and is characterized by a high chloride concentration. Various electrochemical corrosion techniques were carried out to evaluate Ni-Cr-Mo-Gd alloys with different Cr compositions and investigate the role of Ni 5 Gd phase on corrosion behavior. C22 was included as a benchmark material, due to the similarity in composition and the significant corrosion data available. Here, test results showed a tendency to passivate over time which is attributed to dissolution of surface exposed Ni 5 Gd phase. Cross-sectional analysis indicated that dissolution could penetrate hundreds of micrometers deep under aggressive conditions. It was found that higher Cr variant (21.01%) showed much shallower impact, suggesting Cr prevented primary phase corrosion and thus reduced Ni 5 Gd phase dissolution. Acid pickling of the specimens showed much less dissolution for a higher Cr material and suggested some primary phase dissolution for the low Cr specimen. Acid pickled specimens showed positive shifts in the repassivation potential, suggesting increased surface passivation.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Innovative high-temperature ammonium bifluoride fusion and rapid analysis of elements with nuclear forensic value

High-temperature ammonium bifluoride (ABF) fusions were evaluated for potential use in rapid dissolution of post-detonation nuclear debris. The ABF fusion was carried out in a Pt crucible which allowed evaluation of higher fusion and evaporation temperatures. The high-temperature ABF fusion dissolution method was evaluated using geological reference materials: USGS QLO-1a Quartz Latite, USGS SDC-1 Mica Schist, and NIST 278 Obsidian Rock. The optimized dissolution method involved a 10 min fusion at 540 °C, a 5 min reflux in 8 M HNO 3 , an evaporation at 300 °C and final dilution into 45 mL of 2% (v/v) HNO3. The final solution was filtered after heating at 105 °C using a hotblock. This dissolution method was simple, requiring only a hotplate or hotblock, filtered samples were available for ICP-MS analysis or radiochemical separation within 150 min, and was found to have high (>90%) recovery for many isotopes of interest in nuclear forensics applications. U and Pu in the dissolved material was separated using TEVA and UTEVA extraction chromatography columns, a process which resulted in >90% recovery. An irradiated U tracer was spiked into the material prior to dissolution and analyzed for recovery of major fission products and 239Np. The monitored radionuclides had recoveries of greater than 90%, except for the volatile radioiodine isotopes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Real-Time Atomic-Scale Structural Analysis Resolves the Amorphous to Crystalline CaCO 3 Mechanism Controversy

Amorphous calcium carbonate (ACC) occurs as a precursor to geological and biogenic calcium carbonate (CaCO 3 ), yet its transformation pathways and reaction mechanisms remain inconsistent and controversial. In this study, we investigated the transformation of ACC to calcite under both solution and dry conditions, in the presence and absence of impurity ions, utilizing operando time-resolved synchrotron X-ray diffraction (TRXRD) and reactive transport modeling. Results demonstrate that TRXRD techniques allow us to differentiate dissolution-reprecipitation versus solid-state transformation mechanisms for amorphous to crystalline phase transitions. Specifically, we observe that in environments with abundant water, ACC transforms to calcite through a dissolution-reprecipitation mechanism. This features an activation energy of 63 ± 2 kJ/mol and unit cell volume contraction during calcite crystal growth. Conversely, under water-limited conditions, ACC to calcite transformation proceeds via a solid-state transformation mechanism, with an activation energy of 210 ± 2 kJ/mol, three times greater than the dissolution-reprecipitation route, and a unit cell expansion during crystalline calcite growth. Further, to illustrate the magnitude of these effects, the rates of calcite growth were similar during dissolution-reprecipitation at 3 °C [0.00207(35) s –1 ] and solid-state transformation at 280 °C [0.00134(11) s –1 ]. Moreover, the incorporation of an impurity, strontium, significantly retards the rate of calcite growth while expanding its unit cell but whose incorporation is history dependent. Reactive transport modeling of the dissolution–precipitation kinetics suggests that ACC must be dissolving as compact aggregates. These various transformation mechanisms drive diverse geological and biological carbonate formations, impacting their use as paleoenvironmental markers and functional materials synthesis.

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

Integrated Experimental and Modeling Study of Geochemical Reactions of Simple Fracturing Fluids with Caney Shale

Interactions between rock minerals and hydraulic fluids directly impact the geochemical and geomechanical properties of shale formations. However, the mechanisms of geochemical reactions in shale unconventional reservoirs remain poorly understood. Here, to investigate the geochemical reactions between shale and hydraulic fracturing fluids, a series of batch reactor experiments were undertaken. Three rock samples with different mineralogical compositions and three fluid samples of different compositions (deionized water, deionized water + 2% potassium chloride (KCl), and deionized water + 0.5% choline chloride (C 5 H 14 ClNO) were used. Experiments were undertaken at reservoir temperature and atmospheric pressure. Elemental compositions of effluents after 1, 3, 7, 14, 28 days were analyzed using Inductively Couple Plasma Mass Spectrometry (ICP-MS). Medical Computed Tomography (CT) scan and X-ray Fluorescence (XRF) were conducted on the entire core run to help upscale results obtained from rock-fluid interaction experiments. Geochemical modeling using a reactive simulator, TOUGHREACT, was undertaken to corroborate experimental results. Results show that lower pH triggered high dissolution rates in the rock samples, especially the carbonate components. As pH increased, the rate of dissolution declined significantly, though for most cases dissolution still continued. Observed dissolved silica concentrations were much higher than the quartz solubility, suggesting that much of the silica originates from more soluble silica polymorphs and possibly desorption from clay mineral exchange sites. Concentration of most elemental species in solution increased but aluminium and magnesium concentrations declined rapidly following initial entry into solution. Geochemical modeling corroborated the conclusions regarding mineral dissolution and precipitation observed from experiments, notably; the dissolution of calcite and oxidation of pyrite in reacted shale samples, the likely presence of silica polymorphs such as opal, chalcedony or amorphous silica in these samples, and the reduction of Al and Mg concentrations in solution by precipitation of secondary aluminosilicate phases. The de-flocculation of clay minerals during reaction implies fines migration after hydraulic fracturing. This is detrimental to reservoir productivity as clay fines are displaces and lodged within the micro and nano-fractures created during fracturing. The immediate consumption of aluminium and magnesium also has implications on blockage of hydrocarbon pathways due to precipitation of new minerals in these locations.

04 OIL SHALES AND TAR SANDS↗
DOE OSTI2017

Speciation of CuCl and CuCl 2 Thiol-Amine Solutions and Characterization of Resulting Films: Implications for Semiconductor Device Fabrication

Thiol-amine mixtures are an attractive medium for the solution processing of semiconducting thin films because of their remarkable ability to dissolve a variety of metals, metal chalcogenides, metal salts, and chalcogens. However, very little is known about their dissolution chemistry. Electrospray ionization high-resolution tandem mass spectrometry and X-ray absorption spectroscopy were employed in this study to identify the species formed upon dissolution of CuCl and CuCl 2 in 1-propanethiol and n -butylamine. Copper was found to be present exclusively in the 1+ oxidation state for both solutions. The copper complexes detected include copper chlorides, copper thiolates, and copper thiolate chlorides. No complexes of copper with amines were observed. Additionally, alkylammonium ions and alkylammonium chloride adducts were observed. These findings suggest that the dissolution is initiated by proton transfer from the thiol to the amine, followed by coordination of the thiolate anions with copper cations. Interestingly, the mass and X-ray absorption spectra of the solutions of CuCl and CuCl 2 in thiol-amine were essentially identical. However, dialkyl disulfides were identified by Raman spectroscopy as an oxidation product only for the copper(II) solution, wherein copper(II) had been reduced to copper(I). Analysis of several thiol-amine pairs suggested that the dissolution mechanism is quite general. Finally, analysis of thin films prepared from these solutions revealed persistent chlorine impurities, in agreement with previous studies. These impurities are explained by the mass spectrometric finding that chloride ligands are not completely displaced by thiolates upon dissolution. These results suggest that precursors other than chlorides will likely be preferred for the generation of high-efficiency copper chalcogenide films, despite the reasonable efficiencies that have been obtained for films generated from chloride precursors in the past.

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

Stability limits and defect dynamics in Ag nanoparticles probed by Bragg coherent diffractive imaging

Dissolution is critical to nanomaterial stability, especially for partially dealloyed nanoparticle catalysts. Unfortunately, highly active catalysts are often not stable in their reactive environments, preventing widespread application. Thus, focusing on the structure–stability relationship at the nanoscale is crucial and will likely play an important role in meeting grand challenges. Recent advances in imaging capability have come from electron, X-ray, and other techniques but tend to be limited to specific sample environments and/or two-dimensional images. Here, we report investigations into the defect-stability relationship of silver nanoparticles to voltage-induced electrochemical dissolution imaged in situ in three dimensional detail by Bragg coherent diffractive imaging. We first determine the average dissolution kinetics by stationary probe rotating disk electrode in combination with inductively coupled plasma mass spectrometry, which allows in situ measurement of Ag+ ion formation. We then observe the dissolution and redeposition processes in single nanocrystals, providing unique insight about the role of surface strain, defects, and their coupling to the dissolution chemistry. Finally, the methods developed and the knowledge gained go well beyond a “simple” silver electrochemistry and are applicable to all electrocatalytic reactions where functional links between activity and stability are controlled by structure and defect dynamics.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Super-Resolution Photothermal Patterning in Conductive Polymers Enabled by Thermally Activated Solubility

Doping induced solubility control (DISC) patterning is a recently developed technique which uses the change in polymer solubility upon doping, along with an optical dedoping process, to achieve high resolution optical patterning. DISC patterning is remarkable because the process resolution exceeds the linear Abbe’s diffraction limit, however, no mechanism has been proposed to explain such high resolution. Here, we use diffraction to spatially modulate the light intensity and determine the dissolution rate, revealing a superlinear dependence on light intensity, which yields features that are sharper than the profile of the writing photomask. This rate law is independent of wavelength, indicating that patterning resolution is not dominated by an optical dedoping reaction, as was previously proposed. Instead we show here that the optical patterning mechanism is primarily controlled by the thermal profile generated by the laser. To quantify this effect, the thermal profile and dissolution rate are modeled using a finite-element model and compared against patterned line cross sections as a function of wavelength, laser intensity, and dwell time. Our model reveals that although the laser-generated thermal profile is broadened considerably beyond the lasers resolution, the highly temperature dependent dissolution rate results in selective dissolution near the peak of the thermal profile. Therefore, the key factor in achieving super-resolution patterning is a strongly temperature dependent dissolution rate|a common feature of many polymers. In addition to suggesting several routes to improved resolution, our model also demonstrates that doping is not required for optical patterning of conjugated polymers, as was previously believed. Instead, we demonstrate that superlinear resolution optical patterning is attainable in any conjugated polymer simply by tuning the solvent quality during patterning, thus extending the applicability of our method to a wide class of materials. Here, we demonstrate the generality of photothermal patterning by writing sub-400 nm features into undoped Pff-BT4T-2OD.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Liquid state properties of SEI components in dimethoxyethane

The solid-electrolyte interphase (SEI) layer is a critical constituent of battery technology, which incorporates the use of lithium metals. Since the formation of the SEI is difficult to avoid, the engineering and harnessing of the SEI are absolutely critical to advancing energy storage. One problem is that much fundamental information about SEI properties is lacking due to the difficulty in probing a chemically complex interfacial system. One such property that is currently unknown is the dissolution of the SEI. This process can have significant effects on the stability of the SEI, which is critical to battery performance but is difficult to probe experimentally. Here, we report the use of ab initio computational chemistry simulations to probe the solution state properties of SEI components LiF, Li 2 O, LiOH, and Li 2 CO 3 in order to study their dissolution and other solution-based characteristics. Ab initio molecular dynamics was used to study the solvation structures of the SEI with a combination of radial distribution functions, discrete solvation structure maps, and vibrational density of states, which allows for the determination of free energies. From the change in free energy of dissolution, we determined that LiOH is the most likely component to dissolve in the electrolyte followed by LiF, Li 2 CO 3 , and Li 2 O although none were favored thermodynamically. Furthermore, this indicates that dissolution is not probable, but Li 2 O would make the most stable SEI with regard to dissolution in the electrolyte.

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

Accelerated Leach Testing of GLASS (ALTGLASS): I. Informatics approach to high level waste glass gel formation and aging

Glass corrosion data from the ALTGLASS™ database were used to determine if gel compositions, which evolve as glass systems corrode, are correlated with the generation of zeolites and subsequent increase in the glass dissolution rate at long times. The gel compositions were estimated based on the difference between the elemental glass starting compositions and the measured elemental leachate concentrations from the long-term product consistency tests (ASTM C1285) at various stages of dissolution, ie, reaction progress. A well-characterized subset of high level waste glasses from the database was selected: these glasses had been leached for 15-20 years at reaction progresses up to ~80%. The gel composition data, at various reaction progresses, were subjected to a step-wise regression, which demonstrated that hydrogel compositions with Si*/Al* ratios of <1.0 did not generate zeolites and maintained low dissolution rates for the duration of the experiments. Glasses that formed hydrogel compositions with Si^*/Al^* ratios ≥1, generated zeolites accompanied by a resumption in the glass dissolution rate. Finally, the role of the gel Si/Al ratio, and the interactions with the leachate, provides the fundamental understanding needed to predict if and when the glass dissolution rate will increase due to zeolitization.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗