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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.↗

NASA NTRS1985

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

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

Dewitt, K. J.↗

NASA NTRS2007

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

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

Sutter, B.↗

NASA NTRS2012

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

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

Sudbrack, Chantal K.↗

DOE OSTI2016

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

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

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2026

Determining the Solubility Behavior of Kogarkoite in Simulated Nuclear Waste

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

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

DOE OSTI2023

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

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

36 MATERIALS SCIENCE↗

DOE OSTI2021

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

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

25 ENERGY STORAGE↗

DOE OSTI2025

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

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

36 MATERIALS SCIENCE↗

DOE OSTI2021

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

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

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗