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At least 127 records · Page 7

Conversion degree and heat transfer in the cold cap and their effect on glass production rate in an electric melter

A predictive model of melt rate in waste glass vitrification operations is needed to inform melter operations during normal and off-normal operations. This paper describes the development of a model of the cold cap (the reacting melter feed floating on molten glass in a glass melter) that couples heat transfer with the feed-to-glass conversion kinetics. The model was applied to four melter feeds designed for high-level and low-activity nuclear waste feeds using the material properties, either measured or estimated, to obtain temperature and conversion distribution within the cold cap. The cold cap model, when coupled with a computational fluid dynamics model of a Joule-heated glass melter, allows the prediction of the glass production rate and power consumption. The results show reasonable agreement with the melting rates measured during pilot-scale melter tests.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

(abstract) Undercooling Studies of the Bulk Metallic Glass Forming Zr(sub 41.2)Ti(sub 13.8)Cu(sub 12.5)Ni(sub 10.0)Be(sub 22.5) Alloy During Containerless Electrostatic Levitation Processing

Bulk glass forming metallic alloys have long been desired for technological applications and for investigation into liquid undercooling, solidification processes, and thermophysical properties. A glass forming alloy Zr(sub 41.2)Ti(sub 13.8)Cu(sub 12.5)Ni(sub 10.0)Be(sub 22.5) was used to investigate the thermal treatments affecting undercooling and vitrification. The experiments were performed using the high temperature high vacuum electrostatic levitator at JPL. A sample approximately 3 mm in diameter was melted, superheated, undercooled, and solidified while levitated in high vacuum. The results show that when the sample was held above its melting temperature for a sufficient period of time to dissolve oxides and then cooled faster than a critical cooling rate, it undercooled to the glass transition temperature, T(sub g), and formed a glassy alloy. The required critical cooling rate for metallic glass formation was obtained to be between 0.9 K per second and 1.2 K per second for the 42.4 mg sample.

levitation vitrification↗

Crucible Melter Simulation in Nek5000

Nuclear tank waste at the Hanford site is slated for vitrification in large scale refractory-lined melters to transform it into a stable borosilicate waste form suitable for long-term storage or disposal. Molten glass corrodes the refractory lining over time at a rate correlated to the velocity of molten glass against the refractory-lined wall. To properly design a melter and plan for maintenance, it is necessary to accurately model the glass flow and find the correlation between flow velocity and corrosion rate. This modeling was started in STAR-CCM+ CFD software and is being continued in Nek5000 for its fast-running and quick turnaround code. This poster explains the basic process of reconstructing the geometry, fluid properties, and heating of test melters in Nek5000. The geometry is imported from a mesh file and boundary conditions assigned based on surface IDs. The fluid properties are set in the .par and .usr case files. The heating of the actual crucibles in joule heating with electrodes but simulated in Nek5000 with a volumetric heat source term. This volumetric heat source is fit to the actual heating profile with piecewise polynomials and exponentials. Basic results and verification methods are explained in the poster, as well as further work that must be done to complete modeling.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Mercury Speciation of Hanford 241-AP-107 Tank Waste Samples - 20384

The concentration of key mercury species in the Hanford tank waste has not been previously measured. Based on process knowledge, an estimated inventory of 2,100 kg of mercury is assumed and was distributed in varied amounts across 149 single-shell tanks (SSTs) and 28 double-shell tanks (DSTs). Limited analyses of individual SSTs and DSTs for total mercury were all below detection, yielding upper limits in concentration estimates based solely on instrument detection limits, resulting in an uncertain mercury inventory for Hanford tanks. Accurate and reliable chemical speciation and quantification is desired to anticipate, predict, and abate the mass movements of various mercury species through the Hanford waste processing flowsheet. Highly sensitive separation and quantification methods for total, elemental, and monomethyl mercury species, in tank waste, have been developed at the Pacific Northwest National Laboratory's (PNNL) Radiochemical Processing Laboratory (RPL). A non-radiological environmental method to quantify mercury species has been adapted for application to Hanford tank 241-AP-107 raw supernatant feed, filtered feed, and cesium-decontaminated samples. These samples represent feed inventory and pretreatment process effluents prior to immobilization by vitrification. This method separates and preconcentrates total, elemental, and monomethyl mercury onto selective solid substrates with little-to-no radioactive background. The solid samples can then be released from strict radiological control, allowing for analytical work to be conducted in low-level radiological facilities. Separation of mercury species was demonstrated at PNNL's RPL in Richland, Washington before transport and analytical quantification using cold vapor atomic fluorescence spectrometry (CVAFS) at PNNL's Marine Science Laboratory (MSL) in Sequim, Washington. Additional studies were conducted to assess the stability of monomethyl mercury in distilled matrices and preconcentrated onto the Carbotrap{sup R} solid substrate to assess sample degradation over time during transport. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Field-Scale Lysimeter Studies of Glass and Cementitious Waste Forms at the Hanford Site - 20392

The Hanford site Integrated Disposal Facility (IDF) will receive waste forms from vitrification activities at the Hanford Waste Treatment and Immobilization Plant (WTP). The waste form inventory to be disposed of at the IDF will consist of vitrified low-activity waste (LAW) in glass forms and solidified (or encapsulated) secondary wastes in cementitious forms. The IDF is a near-surface burial facility located near Hanford's Waste Treatment and Immobilization Plant in the 200 East Area of the site's Central Plateau. An extensive set of laboratory experimental data has been collected to support IDF performance assessment calculations of the eventual degradation of waste forms and mobility of contaminants. This paper describes the start of a field experiment to generate waste-form performance data on a larger scale (tens of centimeters), over a longer duration (five years or more), and under field conditions representative of the IDF. Results from this study are expected to improve model descriptions of contaminant mobility, reduce uncertainties about the representativeness of laboratory results in the IDF performance assessment, improve stakeholder confidence in the safe disposal of treated waste at the IDF, and facilitate the adoption of informed facility designs with the potential to reduce operational costs. A lysimeter test facility near Hanford's 200 West Area has been repurposed to carry out long-term assessments of waste forms buried in sediments excavated from the IDF. The waste forms are buried in large drainage lysimeters, open caissons that are two meters in diameter and three meters deep. Waste forms are buried in up to six locations in each lysimeter. Samplers collect pore water and drainage water beneath the waste forms and air from the pore space adjacent to waste forms. Sensors measure temperature, soil water content, soil water tension, and drainage flux. One lysimeter containing cementitious waste forms and one containing glass waste forms have been completed, along with a control lysimeter (without waste forms). The cementitious waste forms are Cast Stone grout formulations using a liquid secondary waste simulant and a generic Hanford high-salt simulant, as well as a hydrated lime-based grout formulation using a liquid secondary waste simulant. Technetium-99 and iodine-127 were added as tracers to monitor contaminant mobility. Glass waste forms were fabricated in two formulations (LAWA44 and ORLEC28), with rhenium and molybdenum tracers to monitor waste form degradation. The predicted performance of the waste forms in the lysimeters was modeled prior to installation to determine waste form size, tracer concentration/activity, and locations of sensors and samplers. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Special Analyses for the Hanford Integrated Disposal Facility Performance Assessment - 20102

In 2014, the Department of Energy (DOE) Office of River Protection and its contractors began to develop a performance assessment for the near-surface disposal of low-level and mixed low-level waste at the Hanford Site's Integrated Disposal Facility (IDF). The IDF is a doubly-lined landfill that was constructed between 2004 and 2006 to be the disposal facility for the vitrified low-activity waste that will be produced at the Waste Treatment and Immobilization Plant (WTP). IDF is also expected to receive solid secondary waste produced at the WTP and other solid wastes from site activities. The IDF has been in a preoperational state awaiting authorization from DOE and a RCRA permit modification from the State of Washington Department of Ecology to receive waste. Both the Disposal Authorization Statement and permit modification require a performance assessment demonstrating that the system of engineered and natural features will limit releases of radionuclides and hazardous chemicals from the IDF and be protective of human health and the environment. The simulated duration is 10,000 years. Based on the analyses presented in the 2017 Integrated Disposal Facility Performance Assessment, DOE issued a conditional Operating Disposal Authorization Statement for the IDF in June 2018. The long-term performance of the IDF to be protective of human health and the environment was evaluated under the requirements of DOE Order 435.1, Radioactive Waste Management. Computer simulations were performed to evaluate whether or not the IDF would comply with DOE requirements. In the time that has passed since the performance assessment was approved by DOE, new information has been discovered that had not been considered in the performance assessment. Since this new information has not been evaluated, the potential impact of the changes have not been taken into consideration in DoE's disposal authorization. DOE and its contractors follow a change control process to screen and, when necessary, evaluate new information that could potentially impact the conclusions of the completed performance assessment. This paper will describe the change control process and provide two examples of evaluations performed following the change control process. The first example evaluates a new waste form for liquid secondary waste that was not evaluated in the performance assessment. In the performance assessment, liquid secondary waste was assumed to be solidified with grout. A new recommendation to dispose of the liquid secondary waste after drying it to a powder was evaluated. The second example evaluates inventory implications from changes to the flow sheet that estimates the feed composition to the low-activity waste vitrification facility. The changes result in higher strontium concentrations in the vitrified waste stream. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Progress towards the POCO of UK Highly Active Storage Tanks - 20112

In the UK Highly Active (HA) waste is stored in stainless steel Highly Active Storage Tanks (HASTs) prior to encapsulation in glass in one of three operating vitrification plants. Significant progress has been made towards the reduction in the volume of HA Liquor (HAL) stored in these HASTs and several tanks currently operate at heel levels. In recent years a strategy has been developed towards the Post Operational Clean Out (POCO) of the tanks and significant progress has been made in confirming this strategy since it was last presented at WMS [1]. For a variety of reasons changes to associated operational assumptions have also been made. This paper will highlight recent progress and changes associated with the strategy, including a description of some of the challenges that have been overcome and associated technical work undertaken. It will also detail current plans to POCO the HASTs, as quickly as possible, while minimising the risk and continuing to support other ongoing reprocessing and clean-up programmes as part of the overall UK clean-up mission. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Oxidation of Glycolate in the Defense Waste Processing Facility (DWPF) Recycle Collection Tank - 20305

The Savannah River Site's Defense Waste Processing Facility (DWPF) operations are being upgraded with the introduction of the Nitric-Glycolic Flowsheet. Glycolic acid has been shown superior to formic acid as the reducing acid used during chemical processing. The new flowsheet improves or maintains necessary parameters such as 1) reduction of mercury, 2) adjustment of feed rheology and 3) adjustment of melter oxidation/reduction potential. Further, the potential for catalytic hydrogen generation in DWPF processing is virtually eliminated. DWPF process condensates are collected and returned to the SRS Concentration, Storage and Transfer Facilities (CSTF). The Recycle Collection Tank (RCT) collects off-gas condensate during chemical processing, vitrification, and other unit operations performed in DWPF and is the singular return vessel delivering recycle effluent back to CSTF. Each batch of recycle may contain a small amount of glycolate from chemical processing and melter off-gas condensates. To avoid potential flammability issues due to thermolysis of glycolate in the CSTF, chemical oxidation within the RCT has been investigated as an option for mitigating the transfer of glycolate. Sodium permanganate has been down-selected as the best option for oxidation of glycolate. Testing was performed using both 2-L and 22-L reactors (16,800:1 and 1,530:1 scale by volume) with non-radioactive waste simulants to approximate the expected RCT compositions. RCT simulants were evaluated at various process pH and temperature conditions. Also, RCT operations, namely the sequence of addition of corrosion inhibitors (NaOH and NaNO{sub 2}) versus a permanganate strike, were evaluated. Glycolate was introduced via a sludge simulant to mimic both expected entrainment and abnormal process foam-over conditions - the range being between 68 and 5100 mg/kg glycolate. Glycolate destruction was monitored by ion chromatography (IC). The corresponding manganese behavior was monitored in real-time using in situ ultraviolet-visible (UV-Vis) spectroscopy. RCT glycolate content can be reduced to below the IC detection limit within 90 minutes for all concentrations investigated. Ion Chromatography analysis revealed that under alkaline conditions, glycolate is primarily oxidized to oxalate with no significant formation of CO{sub 2} or carbonate, and nitrite is not oxidized to nitrate. Initially, complete oxidation of organics species and nitrite was assumed. Determination of the mechanistic chemical reaction has allowed the required amount of permanganate to be more accurately predicted and the total addition to be significantly reduced. UV-Vis measurements reveal that permanganate (Mn{sup 7+}) is reduced to manganate (Mn{sup 6+}) in the RCT. The oxidant stoichiometry is defined by using the initial permanganate to glycolate (P/G) molar ratio. At low initial glycolate concentration (68 and 140 mg/kg), the minimum required initial permanganate to glycolate (P/G) molar ratio was found to be 5-6. With high initial glycolate concentrations (5100 mg/kg) a lower (P/G) molar ratio of ∼2.5 was needed. The final portion of this effort supporting the nitric/glycolic flowsheet will be to test actual (fully radioactive) RCT samples as per the above simulant tests. (authors)

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Testing of Crystalline Silicotitanate to Support Tank-Side Cesium Removal System Operations - 20458

The direct feed of waste from the Hanford tank farms to the Low-Activity Waste Facility at the Hanford Waste Treatment and Immobilization Plant requires an intermediate treatment step that prepares the waste for vitrification. Washington River Protection Solutions (WRPS) selected a near-tank treatment system known as the Tank-Side Cesium Removal (TSCR) system to perform the required intermediate treatment functions. The approach in the TSCR system is to filter waste supernatant with a sintered metal dead-end filter and then use a series of ion exchange columns to remove cesium; this system has several similarities to the Tank Closure Cesium Removal system that has been deployed on the Savannah River Site. The ion exchange media proposed for use is crystalline silicotitanate (CST), which is a non-elutable media with a high affinity for cesium. Because the media is non-elutable, loaded columns will be blown down with compressed air, moved into interim storage, and replaced with new columns when cesium capacity is reached. The assumed extent and rate of drying that could be achieved in the TSCR column geometry lacked confirmation by experimental data. In addition, once the columns are loaded with cesium, they generate flammable gases (primarily hydrogen) via radiolysis acting on any resident liquids, i.e., moisture, remaining in the media bed. An assessment of available information on CST concluded that gas generation data that bounds expected operational conditions were needed to support the TSCR system safety basis and planned operations. Working with WRPS, Pacific Northwest National Laboratory (PNNL) designed and conducted testing with CST media to address the need for (a) representative in-column drying data, and (b) bounding flammable gas generation data. Drying testing was performed using a full-height column with a diameter of approximately 2 inches with injected air at temperatures of 18 deg. C and 30 deg. C. Gas generation testing was conducted in an engineered bunker that allowed simultaneous irradiation of up to eight samples at a time. These two experimental approaches used at PNNL for the CST testing are summarized and the major outcomes are presented. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Modeling Marangoni Convection using a Velocity-Time Relationship

The Waste Treatment and Immobilization Plant (WTP) at the U.S. Department of Energy’s (DOE’s) Handford site is designed to treat 56 million gallons of radioactive waste through vitrification. The melting vessels physical and chemical integrity is essential to maintain, as failure has a high safety and financial penalty. Monofrax® K-3 refractory, the material widely used for the melting vessel, undergoes significant corrosion over time, concentrated at the triple-point junction between the gaseous atmosphere, refractory, and glass melt, producing a characteristic neck-like profile that significantly limits refractory service life. Accurate prediction of the corrosion within the melter can be used to prevent this and extend the lifetime of the melters. A computational fluid dynamics (CFD) model was previously developed, and predicted subsurface refractory corrosion, but failed to predict the neck-line profile observed experimentally. To address this limitation, the glass-melt meniscus geometry at the glass-refractory interface was estimated from experimentally measured neck profiles and wettability experiments. A curve was fitted to the neck profile to identify the triple point location, and the meniscus shape was characterized by a contact angle of 1°. A velocity profile accounting for Marangoni convection-driven corrosion was derived from the estimated meniscus geometry. Surface tension measurements from LORPM14R1 glasses of varying composition were coupled with K-3 coupon dissolution rates to establish a surface tension–time relationship. This analytical velocity-time model was integrated into the existing CFD framework to improve prediction of the neck corrosion profile. Work was done in a computational setting with national collaboration, resulting in professional development through presentational and technical writing growth.

36 - MATERIALS SCIENCE↗

Kinetics of the Temperature-Dependent e aq - and ·OH Radical Reactions with Cr(III) Ions in Aqueous Solutions

The reactivity of chromium(III) species with the major oxidizing and reducing radiolysis products of water was investigated in aqueous solutions at temperatures up to 150 °C. The reaction between the hydrated electron (e aq - ) and Cr(III) species showed a positive temperature dependence over this temperature range. The reaction was also studied in pH 2.5 and 3.5 solutions for the first time. This work also studied the reaction between acidic Cr(III) species and the hydroxyl radical (·OH). It was found that Cr 3+ did not react significantly with the ·OH radical, but the first hydrolysis species, Cr(OH) 2+ , did with a rate coefficient of k= (7.2±0.3)×10 8 M -1 s -1 at 25 °C. The oxidation of Cr(OH) 2+ by the ·OH radical formed an absorbing product species that ultimately oxidized to give Cr(VI). In conclusion, these newly measured reaction rates allow for the development of improved models of aqueous chromium speciation for the effective remediation of liquid high-level nuclear waste via vitrification processes.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

The evaluation of aluminum and iron metal oxide settling behaviors for Hanford insoluble solids waste preprocessing

The Hanford site is currently one of the largest and most expensive cleanup sites for hazardous, radioactive waste. Over 20% of the waste found at the Hanford site is in the form of a high activity sludge. The insoluble solids in the sludge will need to be concentrated prior to vitrification in the high-level waste (HLW) melter. This will minimize the amount of liquid that will be evaporated during the melting process and expedite the melter processing rate. One proposed option for concentrating the insoluble solids is gravity settling in the storage tanks. Metal oxide compounds containing aluminum and iron make up the majority of the insoluble solids in the sludge, therefore understanding the behavior of these compounds in various tank waste matrices can facilitate sludge pretreatment options. A study of non-radioactive slurry solutions containing Al(OH) 3 (gibbsite), AlO(OH) (boehmite), and Fe 2 O 3 (iron (III) oxide) was conducted to determine the time dependent interface behavior and settling rates of these compounds. Variations in solids loading and sodium concentration were evaluated to represent waste processing conditions and the results of these settling studies were compared with prior tank waste settling tests. Information gathered from these studies can be used to inform future decisions on sludge treatment processes of the insoluble solids processed at the Hanford site.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Enhanced prediction of Cs removal by CST from Hanford tank waste with K accountability

Abstract The treatment of Hanford tank waste is one of the most challenging environmental cleanup activities to date. To expedite the processing of liquid waste stored in underground tanks in Washington State it is necessary to remove the significant dose contributor, 137 Cs. Crystalline silicotitanate ion exchanger is currently used to remove 137 Cs from the aqueous phase of Hanford tank wastes in preparation for vitrification at the Waste Treatment and Immobilization Plant (WTP). Improving the understanding of potassium impacts on ion exchange behavior of Cs will help in the operation of a critical component of one of the most complex treatment processes in the world today. Optimization of this process can result in significant cost savings and less waste production. Toward this effort, a series of batch contact tests varied in potassium concentration were conducted to look at the impact of potassium concentration on Cs distribution. Experimental distribution ratios ( K d ) were compared to the distribution ratios predicted using the ZAM model. A significant underprediction of Cs capacity in the presence of potassium was seen with the existing model. A revision of the equilibrium constants was determined and provided a statistically better fit for determining the Cs K d values in tank waste matrices.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Retention of radionuclides in sol–gel surrogate nuclear explosive debris

Sol–gel vitrification can be used to rapidly produce solid, vitreous materials to support nuclear forensics research. Here, this work investigates three sol–gel synthetic approaches’ ability to retain fission products within the glass as a function of drying temperature. Eight of the ten fission products studied were quantitatively retained (less than 5% losses) at temperatures up to 600 °C for glasses prepared using an acidic catalyst and at temperatures up to 300 °C for glasses prepared using a basic catalyst. Both systems show partial loss of ruthenium and complete loss of iodine at temperatures above 300 and 100 °C, respectively.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Hybrid machine learning/physics-based approach for predicting oxide glass-forming ability

Predicting the liquid compositions that will vitrify at experimentally accessible quench rates remains one of the grand challenges in the field of condensed matter physics. This glass-forming ability can be quantified as the critical quench rate needed to suppress crystallization. Knowledge of this critical quench rate also informs which glass composition could be used for new applications. There have been several physical and empirical models presented in the literature to predict the critical quench rate/glass forming ability. These models range from those theoretically derived to those quantified only through experimental characterization. In this work, we instead propose a new method to calculate the critical quench rate using the recently developed toy landscape model combined with machine learning. The toy landscape model accesses the underlying physics that control the vitrification behavior by directly simulating the liquid thermodynamics and kinetics. In conclusion, the results are discussed in terms of industrial impact, physical insights, and how the glass science community can develop improved predictions of glass-forming ability.

Crystallization↗

The S solubility of Cr and Al containing simulated low-activity waste glass

Here, the presence of sulfur-containing molten salt phases during vitrification is a particular problem which can be detrimental to the melter. Borosilicate compositions were designed to explore both the effects of a fixed amount of Cr, as Cr 2 O 3 or Na 2 CrO 4 , and the impact of Al 2 O 3 , on sulfur solubility as determined by progressively adding elemental S. The NABS series (with Al 2 O 3 ) has a higher SO 3 solubility of ~3.5 mol% while the NBS series (without Al 2 O 3 ) has a SO 3 solubility of ~2 mol%. Crystalline Cr 2 O 3 formed in the NABS series upon the addition of S but is not present in the NBS series. At the highest S addition, a separate salt phase always forms, and was identified as Na 2 (S,Cr)O 4 via electron dispersive spectroscopy, ultraviolet-visible spectroscopy, x-ray diffraction, and thermal analysis. Magic angle spinning nuclear magnetic resonance identified no change in the B coordination in either series as S is added, suggesting that the Na is scavenged from other locations, such as the Si sites, to charge compensate sulfate, whether in the glass or in the salt. The Cr precursor identity did not affect the observed overall behavior regarding sulfur, but did impact Cr redox as identified with Raman spectroscopy.

36 MATERIALS SCIENCE↗

Glass Design Using Machine Learning Property Models with Prediction Uncertainties: Nuclear Waste Glass Formulation

The United States Department of Energy is responsible for managing the legacy nuclear waste stored in underground tanks at the Hanford Site. The waste will be separately vitrified as low-activity waste and high-level waste fractions. Waste glass formulation algorithms have been traditionally developed using partial quadratic mixture property-composition models. Recently, machine learning (ML) techniques have been used to predict glass properties and discover new glass materials for nuclear waste vitrification, and these advancements can be utilized to improve waste glass composition design. In this proof-of-principle study, ML algorithms such as Gaussian process regression (GPR) were used to interpolate glass properties (e.g., viscosity, electrical conductivity, chemical durability). After selecting appropriate sets of GPR hyper-parameters for each property, an optimization program was developed to formulate glass compositions to maximize waste loading while simultaneously satisfying property within constraints. The results of the ML-based waste loadings and glass compositions were compared to those obtained using the traditional methods. Comparing to the previous glass design framework, the ML-based optimization methods offer improved glass designs and a streamlined approach to generation of optimally designed data and near real-time updates.

glass formulation, machine learning, constraints, ↗