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DOE OSTI2014

A method for preparation and cleaning of uniformly sized arsenopyrite particles

The oxidative dissolution of sulfide minerals, such as arsenopyrite (FeAsS), is of critical importance in many geochemical systems. A comprehensive understanding of their dissolution rates entails careful preparation of the mineral surface. Measurements of dissolution rates of arsenic from arsenopyrite are dependent on the size and degree of oxidation of its particles, among other factors. In this work, a method was developed for preparation and cleaning of arsenopyrite particles with size range of 150–250 μm. Four different cleaning methods were evaluated for effectiveness based on the removal of oxidized species of iron (Fe), arsenic (As) and sulfur (S) from the surface. The percentage oxidation of the surface was determined using X-ray photoelectron spectroscopy (XPS), and surface stoichiometry was measured using scanning electron microscopy – energy dispersive X-ray spectroscopy (SEM-EDS). Results indicate that sonicating the arsenopyrite particles and then cleaning them with 12N HCl followed by 50% ethanol, and drying in nitrogen was the most effective method. This method was successful in greatly reducing the oxide species of Fe while completely removing oxides of As and S from the arsenopyrite surface. Although sonication and acid cleaning have been widely used for mineral preparation, the method described in this study can significantly reduce grain size heterogeneity as well as surface oxidation, which enables greater control in surface and dissolution experiments.

58 GEOSCIENCES↗

DOE OSTI2021

Novel Geochemistry Determined from High Pressure, High Temperature Simulation Experiments of Hydraulic Fracture Test Site 2

A standard method in unconventional oil and gas production is the process of hydraulic fracturing followed by a shut-in period, during which the fracture fluid remains pressurized in the reservoir for up to three weeks before production begins. Despite this widely used process, very little is known about what occurs in the reservoir during this shut-in process. In order to properly delineate potential reservoir reactions that may occur during shut-in that would lead to corrosion and scaling events, experiments were conducted in high pressure, high temperature reactors to simulate conditions of the Wolfcamp Formation in the Delaware Basin. Experimental design allowed the assessment of the effect of proppant, microbiology, and time on the mineralogy and fluid chemistry in the reservoir. Results suggest the biggest impact on fluid chemistry and shale mineralogy during shut-in is time. Analyses demonstrate dissolution of the shale material, with maximum dissolved ions occurring after 7 days of the shut-in period. After 21 days, results suggest precipitation occurs. The Delaware Basin is demonstrated to be high in sulfate content, which further increases in the fluid due to dissolution reactions during shut-in. The pressure vessel experiments suggest there was no significant contribution to reactions from microbiology during the shut-in period. Furthermore, early production samples demonstrate a significant selection of the microorganism Caminicella, a genus of which has previously been correlated to corrosion and sulfide production. Results suggest shut-in conditions may provide high sulfate concentrations that could later be utilized by a shifted microbial community to drive potential well infrastructure failure. This is the first study to incorporate microbiology, mineralogy, and fluid chemistry to investigate the fundamental geochemical reactions that occur during shut-in and early phase production of the Delaware Downloaded from http://onepetro.org/URTECONF/proceedings-pdf/21URTC/2-21URTC/D021S032R001/2477425/urtec-2021-5219-ms.pdf/1 by Carol Worster on 28 February 2022 Basin. Results from this study can complement observations from the Hydraulic Fracture Test Site 2 observations

58 GEOSCIENCES↗

DOE OSTI2025

Geochemical Impact of Acid Spearhead and Slickwater Stimulation on Wolfcamp Shale from the Hydraulic Fracturing Test Site

The Hydraulic Fracturing Test Site 1 (HFTS-1) was a field study performed in the Wolfcamp Formation in the West Texas Permian (Midland) Basin, USA, with a focus on improving the efficiency of hydraulic fracturing. Investigating site-specific rock-fluid geochemical interactions during hydraulic fracturing is an important step to understanding the impact on formation shale porosity, permeability, and long-term shale gas production. During field operations in this region, hydraulic fracturing fluid (HFF) injection usually starts with a concentrated acid spearhead for rapid rock dissolution, followed by the injection of near-neutral pH slickwater containing chemicals and proppants. A multistep sequential injection approach was used to investigate different stages of rock-fluid interactions. The carbonate content in the host rock is important when acid spearhead is considered, as carbonate mineral dissolution is rapid and can result in porosity and permeability changes in the shale matrix. Here, in this study, we designed flow-through experiments using fractured carbonate-rich and clay-rich Wolfcamp shale cores with (1) a short-time acid soaking step and (2) a long-term slickwater flow-through step to simulate the injection method used at HFTS-1. The fluid chemistry was analyzed. A thorough mineralogical progression [e.g., Calcium (Ca) dissolution and iron (Fe) redox progression] in the cores during HFF injection was also characterized and imaged by synchrotron microprobe. Reactive transport modeling was performed based on the experimental setup. The results showed that the acid spearhead is a crucial step in creating a reaction front by mineral dissolution, especially in carbonate-rich shales. A slight layer of ferrihydrite precipitated during the slickwater flow-through period. This study provides insights into potential geochemical impact due to hydraulic fracturing operations in the Permian Basin.

clastic rock↗

DOE OSTI2014

Geo-Chemo-Mechanical Studies for Permanent CO 2 Storage in Geologic Reservoirs

This two-pronged study investigated the rates and mechanisms of formation of Ca and Mg carbonate minerals via reaction of aqueous fluids with silicate minerals and rocks, and the geomechanical effects of such reactions. The kinetic studies focused on the separation of variables, following from previous studies demonstrating rapid formation of carbonates via reaction of the mineral olivine with aqueous fluids rich in NaHCO 3 (plus KHCO 3 and RbHCO 3 ) and NaCl at a high partial pressure of CO 2 . We wished to separate and quantify the effects of NaHCO 3 and NaCl, and to investigate whether bicarbonate-rich, aqueous fluids would also cause rapid formation of carbonates via reaction with other minerals and rocks. Further, we wished to improve upon previous work by adding precise characterization of grain size distributions and surface area, and their changes as a result of reaction. We confirmed previous reports of very rapid olivine carbonation. We found that at a given temperature and CO 2 partial pressure the previously observed rate enhancement in olivine carbonation is due mainly to NaHCO 3 , and not to dissolved NaCl. Further, though reaction of the mineral plagioclase, and two rock compositions, were all faster in the presence of NaHCO 3 -rich fluids, compared with saline and de-ionized water, they were all much slower than reaction of olivine. In the experiments showing the fastest reaction rate, average grain size tended to increase during experiments, presumably due to dissolution of small reactant grains plus growth of product phases on reactant surfaces. Porosity/surface area of grains tended to change with reaction progress, due to the formation of dissolution pits and irregular growth of product phases on reactant grain surfaces. Development of a passivating phase (e.g., a layer of silica) due to incongruent dissolution of solid reactants and/or precipitation of solid products was detected, but was relatively minor and did not have a discernable effect on reaction progress. Geomechanical experiments did not identify pressure-temperature-composition conditions under which porous olivine aggregates undergo reaction driven cracking. Little carbonate formed in these experiments. Though we fulfilled the milestones for this project, a variety of reasons for this remain to be investigated in the future. Reaction of porous olivine aggregates with brines rich in NaHCO 3 caused substantial weakening of samples in compression, due to formation of dissolution pits along olivine-olivine grain boundaries, reducing the solid-solid surface area. A preliminary modeling study funded in part by this grant emphasized potential rate enhancements due to reaction-driven cracking. In related research, not funded by this grant, several additional experimental and modeling studies of reaction-driven cracking are underway.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2014

Chemical Composition and PCT Data for the Initial Set of Hanford Enhanced Waste Loading Glasses

In this report, the Savannah River National Laboratory provides chemical analyses and Product Consistency Test results for 20 simulated high level waste glasses fabricated by the Pacific Northwest National Laboratory. The results of these analyses will be used as part of efforts to revise or extend the validation ranges of the current Hanford Waste Treatment and Immobilization Plant glass property models to cover a broader span of waste compositions. The measured chemical composition data are reported and compared with the targeted values for each component for each glass. Two components of the study glasses, fluorine and silver, were not measured since each of these species would have required the use of an additional preparation method and their measured values were likely to be near or below analytical detection limits. Some of the glasses were difficult to prepare for chemical analysis. A sodium peroxide fusion dissolution method was successful in completely dissolving the glasses. Components present in the glasses in minor concentrations can be difficult to measure using this dissolution method due to dilution requirements. The use of a lithium metaborate preparation method for the minor components (planned for use since it is typically successful in digesting Defense Waste Processing Facility HLW glasses) resulted in an unacceptable amount of undissolved solids remaining in the sample solutions. An acid dissolution method was used instead, which provided more thorough dissolution of the glasses, although a small amount of undissolved material remained for some of the study glasses. The undissolved material was analyzed to determine those components of the glasses that did not fully dissolve. These components (e.g., calcium and chromium) were present in sufficient quantities to be reported from the measurements resulting from the sodium peroxide fusion preparation method, which did not leave undissolved material. Overall, the analyses resulted in sums of oxides that ranged from about 98 to 101.5 wt % for the study glasses, indicating excellent recovery of all the components in the chemical composition analyses. Comparisons of the targeted and measured chemical compositions indicated that, in general, the measured values for the glasses met the targeted concentrations. Exceptions were Cr 2 O 3 , MgO, and P 2 O 5 . The measured values for Cr 2 O 3 were somewhat low when compared to the targeted values for all of the study glasses targeting Cr 2 O 3 concentrations above 0.5 wt %. Many of the measured MgO and P 2 O 5 values were below the targeted values for those glasses that contained these components. Two of the study glasses exhibited differences from the targeted compositions that may indicate a batching error. Glasses EWG-HAI-Centroid-2 and EWG-OL-1672 had measured values for Al 2 O 3 and SiO 2 that were lower than the targeted values, and measured values for B 2 O 3 that were higher than the targeted values. Glass EWG-HAI-Centroid-2 also had a measured value for Fe 2 O 3 that was lower than the targeted value. A review of the PCT data, including standards and blanks, revealed no issues with the performance of the tests. The PCT results were normalized to both the targeted and measured compositions of the study glasses. Comparisons of the normalized PCT results for both the quenched and Canister Centerline Cooled versions of the study glasses are made with the Environmental Assessment benchmark glass for reference.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2014

Reconstructing paleo-SMT positions on the Casadia margin using magnetic susceptibility

Magnetic susceptibility (κ) is a mixed signal in marine sediments, representing primary depositional and secondary diagenetic processes. Production of hydrogen sulfide via anaerobic oxidation of methane (AOM) at the sulfate-methane transition (SMT) and organoclastic sulfate reduction above the SMT can result in the dissolution of iron oxides, altering κ in sediments in methane gas and gas hydrate bearing regions. We investigated records of κ on the Cascadia margin (ODP Sites 1249 and 1252; IODP Site 1325) using a Zr/Rb heavy mineral proxy from XRF core scanning to identify intervals of primary detrital magnetic susceptibility and intervals and predict intervals affected by magnetite dissolutions. We also measured total sulfur content, grain size distributions, total organic carbon (TOC) content, and magnetic mineral assemblage. The upper 100 m of Site 1252 contains a short interval of κ driven by primary magnetite, with multiple intervals (> 90 m total) of decreased κ correlated with elevated sulfur content, consistent with dissolution of magnetite and re-precipitation of pyrite. In the upper 90 m of Site 1249, κ is almost entirely altered by diagenetic processes, with much of the low κ explained by a high degree of pyritization, and some intervals affected by the precipitation of magnetic iron sulfides. At Site 1325, κ between 0-20 and 51-73 mbsf represents primary mineralogy, and in the interval 24-51 mbsf, κ may be reduced due to pyritization. This integrated approach allows for a prediction of primary κ and the amount of κ loss at each site when compared to actual κ measurements. In the case of magnetite dissolution and full pyritization, these drawdowns in κ are supported by sulfur measurements, and the exposure times of magnetite to hydrogen sulfide can be modeled. The presence of methane and methane hydrates at these sites, as well as large variations in TOC content, suggest that the past migration rates of the SMT and variation in sulfate reduction rates may influence κ alteration along the Cascadia margin.

03 NATURAL GAS↗

DOE OSTI2015

Progress Report on FY15 Crystalline Experiments M4FT-15LL0807052

Colloid-facilitated plutonium transport is expected to be the dominant mechanism in its migration through the environment. The forms of Pu colloids (intrinsic versus pseudo-colloid) and their stabilities control temporal and spatial scales of Pu transport in the environment. In the present study, we examine the stability of Pu intrinsic colloids freshly prepared in alkaline solution relative to Pu-montmorillonite pseudo-colloids using a dialysis device and modeling approaches. Intrinsic colloids prepared under alkaline conditions were found to be unstable over a timescale of months. The kinetics of multiple processes, including hydrolysis/precipitation of Pu(IV), dissolution of intrinsic colloids in the absence and presence of the clay colloids, transport of dissolved Pu species across the dialysis membrane, and formation of pseudo-colloids were examined. The dissolution of intrinsic colloids was the rate-limiting process in most cases. The apparent intrinsic colloid dissolution rate constants range from 6×10 -7 to 1×10 - 6 mol·m -2 ·day -1 and 4×10 -6 to 8×10 -6 mol·m -2 ·day -1 at 25 and 80°C, respectively, while the apparent diffusion rate constants for Pu ions crossing the dialysis membrane are >200 times higher. Elevated temperatures enhance dissolution of Pu colloids and the activation energy for the process is estimated to be 28 kJ mol -1 . The sorption of Pu to montmorillonite appears to be endothermic as the affinity of Pu for the clay increases with increasing temperature. Our results provide an in-depth understanding of how intrinsic and pseudo-colloids interact with each other kinetically. Although the fact that intrinsic colloids tend to dissolve in the presence of montmorillonite and transform into pseudo-colloids may limit the migration of intrinsic colloids, the thermodynamically more stable pseudo-colloids may play an important role in Pu transport in the environment over significant temporal and spatial scales.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

DOE OSTI2017

Dealloying, Microstructure and the Corrosion/Protection of Cast Magnesium Alloys

The purpose of this project was to develop a greater understanding of micro-galvanic corrosion effects in cast magnesium alloys using both experimental and computational methods. Experimental accomplishments have been made in the following areas of interest: characterization, aqueous free-corrosion, atmospheric corrosion, ionic liquid dissolution, rate kinetics of oxide dissolution, and coating investigation. Commercial alloys (AZ91D, AM60, and AZ31B), binary-phase alloys (αMg-2at.%Al, αMg-5at.%Al, and Mg-8at.%Al), and component phases (Mg, Al, β-Mg, β-1%Zn, MnAl3) were obtained and characterized using energy dispersive spectroscopy (EDS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Full immersion in aqueous chloride was used to characterize the corrosion behavior of alloys. Rotating disc electrodes (RDEs) were used to observe accelerated long-term corrosion behavior. Al surface redistribution for freely corroded samples was analyzed using SEM, EDS, and lithium underpotential deposition (Li UPD). Atmospheric corrosion was observed using contact angle evolution, overnight pH monitoring, and surface pH evolution studies. Ionic liquid corrosion characterization was performed using linear sweep voltammetry and potentiostatic dissolution in 150° choline chloride-urea (cc-urea). Two surface coatings were investigated: (1) Li-carbonate and (2) cc-urea. Li-carbonate coatings were characterized using X-ray photoelectron spectroscopy (XPS), SEM, and aqueous free corrosion potential monitoring. Hydrophobic cc-urea coatings were characterized using contact angle measurements and electrochemical impedance spectroscopy. Oxide dissolution rate kinetics were studied using inductively coupled plasma mass spectroscopy (ICP-MS). Computational accomplishments have been made through the development of Kinetic Monte Carlo (KMC) simulations which model time- and composition-dependent effects on the microstructure due to spatial redistribution of alloying elements during corrosion.

36 MATERIALS SCIENCE↗

DOE OSTI2018

FY2017 ILAW Glass Corrosion Testing with the Single-Pass Flow-Through Method

The inventory of immobilized low-activity waste (ILAW) produced at the Hanford Tank Waste Treatment and Immobilization Plant (WTP) will be disposed of at the near-surface, on-site Integrated Disposal Facility (IDF). When groundwater comes into contact with the waste form, the glass will corrode and radionuclides will be released into the near-field environment. Because the release of the radionuclides is dependent on the dissolution rate of the glass, it is important that the performance assessment (PA) model accounts for the dissolution rate of the glass as a function of various conditions. To accomplish this, an IDF PA glass dissolution model based on Transition State Theory (TST) can be employed. The model is able to account for changes in temperature, exposed surface area, and pH of the contacting solution as well as the effect of silicon solution concentrations, specifically the activity of orthosilicic acid (H4SiO4), whose concentration is directly linked to the glass dissolution rate. In addition, the IDF PA model accounts for the ion exchange process. The effect of temperature, pH, H4SiO4 activity, and the rate of ion exchange can be parameterized and implemented directly into the PA rate model. The rate model parameters are derived from laboratory tests with the single-pass flow-through (SPFT) method. The provided data can be used by glass researchers to further the understanding of ILAW glass behavior, by IDF PA modelers to use the rate model parameters in PA modeling efforts, and by Department of Energy (DOE) contractors and decision makers as they assess the IDF PA program.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2019

Accelerated Testing of Selected Filler Compositions

The fillers R&D program, mostly experimental, is part of a broader R&D program that includes new process modeling and performance assessment of criticality effects and the overall importance of criticality to repository performance (consequence screening). A literature research and consultation effort with experts by Hardin and Brady (2018) identified several potentially effective and workable filler materials including cements (primarily phosphate based), molten-metal alloys, and low-temperature glasses. Filler attributes were defined and the preliminary lists were compared qualitatively. Further comparative analysis will be done (e.g., cost estimates) after experimental screening has narrowed the list of alternatives. The following cement filler compositions were selected for experimental development work and accelerated testing in FY19: Aluminum phosphate cements (APCs); more specifically aluminum oxide / aluminum phosphate (Al 2 O 3 / AlPO 4 ) cements in which Al 2 O 3 serves as the filler material bound by an AlPO 4 binder formed by the reaction of Al 2 O 3 with H 3 PO 4 ; Calcium phosphate cements (CPCs); more specifically composed of pure or nearly pure hydroxyapatite (Ca 5 (PO 4 ) 3 (OH)); Magnesium potassium phosphate cements (MKPs) composed of magnesium oxide / magnesium potassium phosphate (MgO / MgKPO 4 ) cements in which MgO serves as the filler and MgKPO 4 serves as the binder formed by the reaction of MgO with monopotassium phosphate (KH 2 PO 4 ) and tricalcium phosphate ((Ca 3 (PO 4 ) 2 ); Two additional potential cement materials were explored preliminarily as the result of: (1) continued literature investigations into other filler candidates (wollastonite-based phosphate ceramic) and (2) the experimental discovery of a well-consolidated fly ash phosphate cement during the evaluation of fly ash as a potential filler material with Al 2 O 3 in APCs. Fly ash phosphate cements, more specifically in which a fly ash material composed primarily of mullite and quartz serves as the filler and is reacted with H 3 PO 4 to form amorphous phosphate phase(s) as the binder; Wollastonite aluminum phosphate cements (WAPC), specifically wollastonite / aluminum phosphate (CaSiO 3 / AlPO 4 ) in which CaSiO 3 serves as the filler material and AlPO 4 serves as the binder formed by Al(OH) 3 or metakaolin as Al sources and H 3 PO 4 or ammonium dihydrogen phosphate (ADP) (NH 4 H 2 PO 4 ) as phosphate sources. The FY19 effort focused on the optimization of compositions and subsequent processing of these five materials to achieve dense and well-consolidated monolithic samples with relatively low porosity. Once these goals were met basic material properties screening evaluations were performed including an assessment of dissolution resistance in water at elevated temperature (200 °C) and mechanical testing including unconfined compressive strength (UCS) testing. To date, the aluminum phosphate cements (APCs) appear to show the most promise for continued development. They are easily prepared and form smooth pourable slurries that remain stable for days with relatively low viscosities of several thousand centipoise (cP). They are then set at elevated temperatures (e.g., 170 °C) under ambient (0.1 MPa) or elevated pressure (~1MPa). Overall, they demonstrate the best dissolution resistance in water at elevated temperature (200 °C) and good compressive strengths. However, additional effort is required to optimize the APC slurry formulations and the process used for thermal curing these materials. The calcium phosphate cements (CPCs) can be formed at room temperature to produce a well-consolidated body. However, their slurry viscosities are very high (and difficult to measure) and they exhibit relatively short cure times of 2 to 3 hours. Also, dissolution resistance is very poor, the poorest of all the cements examined The same is the case for the small number of MKP cements fabricated; they cure very quickly (10 minutes or less) and disintegrate within a few hours upon immersion in distilled water. Surprisingly, fly ash reacts with phosphoric acid to form dense and well-consolidated cements but the mixture rapidly sets at room temperature (less than 30 minutes) and the subsequent conversion of the binder to an amorphous phosphate phase(s) as a function of temperature is complicated. Finally, the wollastonite aluminum phosphate cements (WAPC) are easily prepared and form smooth pourable slurries that remain stable for several hours. They are then set at 130 °C. A WAPC sample exhibited the highest compressive strengths of all the materials we evaluated but in general their dissolution resistance to water is poor.

36 MATERIALS SCIENCE↗

DOE OSTI2022

H-Canyon Dissolver Offgas Monitoring Using Raman Spectroscopy

This report describes the development and in facility demonstration of a Raman spectrometer to monitor known aluminum offgas components generated during the dissolution of Spent Nuclear Fuel at the Savannah River Site H-Canyon facility. The presence of these gases is an indicator that material is actively being dissolved. This process monitoring technique, which measures the offgas in real time, has the potential to improve the efficiency of facility operations. If the dissolution time is too short, time is wasted due to extended dissolution periods with additional probing of the dissolver pot to confirm that fragment levels are below the thresholds for continuing to the next charge or moving the dissolvent to a receiving tank. If the dissolution time is too long, time and energy are wasted.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2022

Electrical-Discharge-Machining Contamination Removal from Metal Additively Manufactured Components

The use of an electrochemical dissolution process is shown to remove the recast layer contamination from the surfaces of electrical-discharge-machining cut components, as well as the interior exposed surfaces of the structure. The solution chemistry, cell potential, and exposure time are all relevant interdependent variables. Optimization of the electrode geometry should be made for each type of component. For the case of Cu-Zn recast contamination of 300-series alloy components, surface composition analysis indicates that complete electrochemical dissolution is achieved using a dilute solution of nitric acid (HNO 3 ). For example, electrochemical dissolution of the Cu-Zn recast is accomplished at 1.2 V cell potential using a 20% nitric solution and an exposure time of 4 h. The use of a nitric acid bath was specifically chosen since it’s chemically compatible and will not degrade the host alloy or the component. In sum, an electrochemically driven dissolution process can be tailored to remove of the recast contamination without affecting the integrity of the host component structure and its dimensional tolerances.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Small Punch Testing of Molybdenum-99 Targets

Northstar Medical Radioisotopes is developing an accelerator-based method to produce 99 Mo, which is a parent isotope of the commonly used 99m Tc medical isotope. The Mo targets being designed for the accelerator will be produced from enriched 100 Mo, also known as aMo . Pressed and sintered powder feedstock is used to fabricate aMo targets, producing 29 mm disk-shaped targets. The targets are subjected to 1–6 days in line of an electron beam with subsequent dissolution of the disk to retain the 99 Mo, which decays to 99m Tc at radio-pharmacies. The press and sinter method is advantageous because the inherent porosity produced by this method enables increased surface area and therefore increased flow of dissolution media, decreasing the dissolution time and reducing the need for a highly acidic media. Although porosity aids in dissolution, it reduces the mechanical strength and ductility. Targets require good mechanical integrity when subjected to the conditions in the accelerator. Therefore, Northstar is seeking methods to rapidly test disk samples after fabrication to assure mechanical performance metrics are achieved. This report details the design and testing of a small punch test (SPT) that accommodates the 29 mm disk. Initial data were used to relate the SPT data to tensile properties, such as the yield strength (YS), ultimate tensile strength (UTS), and total elongation to failure. Although the SPT has been established as a somewhat reliable method for testing metallic materials, few studies have applied the SPT to refractory materials such as Mo. Based on tensile testing performed at Oak Ridge National Laboratory on different Mo samples, correlation between the Mo tensile and SPT properties could be performed, establishing a standard calibration that could be applied to other Mo samples. To test the efficacy of the SPT with Mo, multiple different disk batches were fabricated under different conditions (e.g., pressure, lubricant) with commercially available pure Mo powder. Generally, only a UTS could be well defined because the press and sinter disks failed under brittle fracture, making it difficult to determine the YS and elongation. Compared with disks fabricated with aMo powder, the aMo samples underperformed their pure nat Mo counterparts. This report summarizes the current status of the SPT, but further evaluation is needed before it can be applied as a reliable quality assurance tool.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

DOE OSTI2023

Decoding Zeolite Crystallization and Stage III in Nuclear Waste Glasses by Coupled Modeling and Experiments

Under specific conditions of pH and temperature, nuclear waste immobilization borosilicate glasses may exhibit a sudden acceleration in their corrosion kinetics (stage III)—a behavior that has been associated with the formation of zeolite crystals. Such accelerated dissolution may compromise the integrity of nuclear wasteforms placed in geological depositories. However, thus far, none of the available models is able to predict the thermodynamic propensity and kinetics of zeolite precipitation as a function of the solution conditions due to (i) a lack of fundamental knowledge regarding the nucleation & growth mechanisms of zeolitic phases, (ii) uncertainty regarding the compositions (types) of zeolites that may form and the rate-limiting step in their precipitation as a function of the solution conditions, and (iii) the complexities that arise due to the vast parametric space (i.e., solution chemistry, temperature, number of secondary phases, etc.) that encompass these systems under conditions of environmental exposure. To resolve these challenges, this project aimed to unambiguously identify the thermodynamic propensity for zeolite precipitation and the kinetics thereof as a function of the solution conditions (composition, pH, and temperature). To achieve this goal: 1) We identified the solution conditions and zeolite phases relevant to nuclear glass dissolution. 2) We performed a series of ab initio molecular dynamics (AIMD) simulations to compute the thermodynamic properties of a group of characteristic zeolites that features a large range of compositions, various hydration levels, a wide range of framework structures, and partial atomic site occupancies. 3) We released a first-of-a-kind self-consistent thermodynamic database that can be used to assess the kinetics and the stability fields of zeolitic phases within a Gibbs energy minimization (GEM) framework. 4) We developed a robust geochemical modeling method allowing us to predict the stability of secondary phases (including zeolites, calcium–silicate–hydrate gels, and clays) upon the dissolution of nuclear waste immobilization glasses. 5) We introduced a model that predicts the dissolution kinetics of a series of borosilicate nuclear waste immobilization glasses in terms of the topology of their atomic network. 6) We investigated the roles of the solution composition on the crystallization kinetics of phillipsite zeolites and tobermorite silicate hydrates. Via PNNL’s collaboration and engagement, this project directly supports DOE’s nuclear waste immobilization activities by offering a technical, science-based foundation that will (i) facilitate predictions of the long-term corrosion rates and extents of existing nuclear waste immobilization glasses to help ensure safe and successful vitrification operations, (ii) inform the development of advanced glass formulations with enhanced durability, and, (iii) enable cost-savings that result from making more decisive and hence less conservative predictions while offering higher levels of nuclear waste embedment in smaller, more compact glass volumes.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2025

Plutonium Solubility and Supernate Concentration for Neutralized Fast Critical Assembly Discards to Savannah River Site Tank Waste

The Savannah River Site (SRS) plans to dissolve non-irradiated stainless steel (SS)-clad bundles of Fast Critical Assembly (FCA) materials in eighteen batches.1 FCA dissolution is currently underway in the 6.3D dissolver by simultaneous chemical and electrolytic dissolution, which is required to generate the harsh conditions necessary for dissolution of metal-oxide (MOX) and non-aluminum spent nuclear fuels (NASNFs).2 Nitric acid and potassium fluoride are used to promote chemical dissolution.2 Gadolinium will be added during processing as a thermal neutron poison for criticality control. There are no plans for recovering plutonium from this waste stream. After FCA dissolution, the acidic (HNO3/KF) “discards” containing the dissolved metals will be neutralized by addition of 50 wt% sodium hydroxide to a final free hydroxide concentration of 1.2 M.1 Neutralization will precipitate a slurry of insoluble solids, predominantly metal oxides/hydroxides of plutonium, uranium, and SS components. Small fractions of the SS components, Pu, U, and Gd will remain dissolved in the supernate. The neutralized slurry will be composited to existing radioactive waste storage tanks within the SRS Concentration, Storage, and Transfer Facilities (CSTF) containing other similar sludge batch (SB) materials.1 The fate of soluble plutonium and freshly-precipitated, colloidal plutonium from this process are of concern since the total Pu can challenge the waste acceptance criteria (WAC) at the downstream SRS Liquid Waste (LW) facility. Supernate decants including the neutralized FCA discards (nFCAd) within the CSTF will be composited with salt batch (StB) materials and transferred to the SRS Salt Waste Processing Facility (SWPF), where total plutonium is also of concern.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2020

A Micelle Electrolyte Enabled by Fluorinated Ether Additives for Polysulfide Suppression and Li Metal Stabilization in Li-S Battery

The Li-S battery is a promising next-generation technology due to its high theoretical energy density (2600 Wh kg -1 ) and low active material cost. However, poor cycling stability and coulombic efficiency caused by polysulfide dissolution have proven to be major obstacles for a practical Li-S battery implementation. In this work, we develop a novel strategy to suppress polysulfide dissolution using hydrofluoroethers (HFEs) with bi-functional, amphiphlic surfactant-like design: a polar lithiophilic "head" attached to a fluorinated lithiophobic "tail." A unique solvation mechanism is proposed for these solvents whereby dissociated lithium ions are readily coordinated with lithiophilic "head" to induce self-assembly into micelle-like complex structures. Complex formation is verified experimentally by changing the additive structure and concentration using small angle X-ray scattering (SAXS). These HFE-based electrolytes are found to prevent polysulfide dissolution and to have excellent chemical compatibility with lithium metal: Li||Cu stripping/plating tests reveal high coulombic efficiency (>99.5%), modest polarization, and smooth surface morphology of the uniformly deposited lithium. Li-S cells are demonstrated with 1395 mAh g-1 initial capacity and 71.9% retention over 100 cycles at >99.5% efficiency-evidence that the micelle structure of the amphiphilic additives in HFEs can prohibit polysulfide dissolution while enabling facile Li + transport and anode passivation.

25 ENERGY STORAGE↗

DOE OSTI2016

Importance of Heat and Pressure for Solubilization of Recombinant Spider Silk Proteins in Aqueous Solution

The production of recombinant spider silk proteins continues to be a key area of interest for a number of research groups. Several key obstacles exist in their production as well as in their formulation into useable products. The original reported method to solubilize recombinant spider silk proteins (rSSp) in an aqueous solution involved using microwaves to quickly generate heat and pressure inside of a sealed vial containing rSSp and water. Fibers produced from this system are remarkable in their mechanical ability and demonstrate the ability to be stretched and recover 100 times. The microwave method dissolves the rSSPs with dissolution time increasing with higher molecular weight constructs, increasing concentration of rSSPs, protein type, and salt concentration. It has proven successful in solvating a number of different rSSPs including native-like sequences (MaSp1, MaSp2, piriform, and aggregate) as well as chimeric sequences (FlAS) in varied concentrations that have been spun into fibers and formed into films, foams, sponges, gels, coatings, macro and micro spheres and adhesives. The system is effective but inherently unpredictable and difficult to control. Provided that the materials that can be generated from this method of dissolution are impressive, an alternative means of applying heat and pressure that is controllable and predictable has been developed. Results indicate that there are combinations of heat and pressure (135 °C and 140 psi) that result in maximal dissolution without degrading the recombinant MaSp2 protein tested, and that heat and pressure are the key elements to the method of dissolution.

59 BASIC BIOLOGICAL SCIENCES↗

DOE OSTI2022

Fluid Induced Elemental and Mineralogy Alterations of Caney Shale

ABSTRACT: Studies were conducted on cores and rock cuttings recovered from two wells drilled in Caney shale in the Southern Oklahoma. Mineralogical compositions of these samples were obtained by X-Ray Diffraction (XRD) measurements using two methods of sample preparation: conventional powder (by crushing and grinding of rock fragments) and spray-drying of micronized rock powder method. Microstructure and microanalysis were acquired by Scanning Electron Microscopy/Energy Dispersive Spectroscopy (SEM/EDS). Batch experiments were then conducted using selected rock samples and fracturing fluid whilst deionized water was used as control sample for fluid/rock interaction. These were conducted at 95°C and ambient pressure for various time periods to assess the geochemical reactivity of the Caney shale. The rock samples were subsequently recovered from fluid, dried and analysis repeated using identical XRD and SEM/EDS measurements, following the same conditions. Preliminary experimental results show rock mineralogical compositions are predominantly quartz with relatively high clay content. The clay minerals are mainly illite. Carbonate content is less than 10% by weight for most samples, with other non-clay minerals pyrite, albite, dolomite, and some apatite. In general, sprayed samples showed more intense peaks and less full width at half maxima (FWHM) relative to conventional rock-powder samples. Post-experimental mineralogical changes were observed in samples with clay portions breaking down to amorphous entities. As expected, dissolution of carbonates (calcite and dolomite) was observed and newly detected dissolution of biogenic micro quartz resulted in formation of amorphous silica. 1.0 INTRODUCTION Formation of sedimentary rocks involves processes where rock sediments are emplaced with fluids starting interactions that persist over long periods. During the lithification process, sediments and fluids react and attain equilibrium state. This equilibrium is disturbed during drilling, completion, hydraulic fracturing and other operations that involve the introduction of engineered fluids into the subsurface. To return to equilibrium, dissolution and precipitation of minerals may occur. These reactions have implications on the petrophysical properties of the reservoir. Whiles dissolution and precipitation of minerals can enhance porosity and permeability, the reverse can also be true. For example, when acidic fluids are introduced into formations with high carbonate contents, carbonate minerals dissolve into solution thus increasing the porosity and permeability of the formation. In contrast, when alkaline fluids with pH above 11 are introduced into an illite-rich shale formation, the rock-fluid interaction leads to de-flocculation of illite platelets causing substantial increase in clay fines migration, consequently significant reduction in permeability (Salles et al., 2008).

Awejori, G.↗