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At least 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Impact of Irradiation-induced Lattice Defects and Dopants on Thermal Transport in Oxide Nuclear Fuels

Advanced nuclear reactor concepts aim to use fuels that must withstand unprecedented temperature and radiation extremes. In these fuels, thermal energy transport under irradiation is directly related to fuel longevity, reactor safety, and is arguably one of the most important performance metrics. Here we provide a comprehensive, first-principles-informed treatment of phonon mediated thermal transport in a defect-bearing actinide oxide with direct comparison to experimental measurements. Pristine and proton irradiated thorium dioxide was chosen as a model system to treat the complexity of thermal transport in the presence of lattice defects. A thermal transport model is implemented using the linearized Boltzmann transport equation (LBTE) with input from first principles calculations and defect evolution models. The output of the LBTE is compared directly to mesoscopic measurements of thermal conductivity on length scales commensurate with defect accumulation. Parametric measurements of conductivity with irradiation dose and temperature reveal a monotonic decrease in conductivity with irradiation dose, in the range of 0.001 dpa to 0.1 dpa. Besides radiation-induced defects, doping the thorium dioxide crystal with small quantities of uranium atoms also results in a drastic reduction in thermal conductivity. Temperature-dependent measurements of thermal conductivity in uranium-doped thorium dioxide single crystals suggests a resonant scattering mechanism is responsible for the observed reduction. This comprehensive, atomistic- to meso-scale treatment provides the necessary basis to investigate thermal transport under irradiation in more complex systems that exhibit strong electron correlation. This is a poster presentation.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2016

Large scale accelerator production of 225Ac: Effective cross sections for 78–192 MeV protons incident on 232Th targets

Actinium-225 and 213 Bi have been used successfully in targeted alpha therapy (TAT) in preclinical and clinical research. This paper is a continuation of research activities aiming to expand the availability of 225 Ac. The high energy proton spallation reaction on natural thorium metal target has been utilized to produce millicurie quantities of 225 Ac. The results of sixteen irradiation experiments of Th metal at beam energies between 78 and 200 MeV are summarized in this work. Irradiations have been conducted at Brookhaven National Laboratory (BNL) and Los Alamos National Laboratory (LANL), while target dissolution and processing was carried out at Oak Ridge National Laboratory (ORNL). Excitation functions for actinium and thorium isotopes as well as for some of the fission products are presented. The cross sections for production of 225 Ac range from 3.6 to 16.7 mb in the incident proton energy range of 78 to 192 MeV. Based on these data, production of Curie quantities of 225Ac is possible by irradiating a 5.0 g cm -2232 Th target for 10 days in either BNL or LANL proton irradiation facilities.

139Ce↗
DOE OSTI2012

Preliminary results of calculations for heavy-water nuclear-power-plant reactors employing {sup 235}U, {sup 233}U, and {sup 232}Th as a fuel and meeting requirements of a nonproliferation of nuclear weapons

A physical design is developed for a gas-cooled heavy-water nuclear reactor intended for a project of a nuclear power plant. As a fuel, the reactor would employ thorium with a small admixture of enriched uranium that contains not more than 20% of {sup 235}U. It operates in the open-cycle mode involving {sup 233}U production from thorium and its subsequent burnup. The reactor meets the conditions of a nonproliferation of nuclear weapons: the content of fissionable isotopes in uranium at all stages of the process, including the final one, is below the threshold for constructing an atomic bomb, the amount of product plutonium being extremely small.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2019

Decommissioning, Decontamination, and Disposal of LLW-LL, and ILW-LL at a Former Rare Earths Processing Facility in Malaysia - 19087

Geosyntec Consultants, Inc. (Geosyntec) was the design-build Contractor for a project involving the remediation and disposal of low level (LLW-LL and ILW-LL) NORM and TENORM wastes at a former rare earth processing facility in Malaysia. These sites were associated with a plant that extracted rare earth elements from local tin ores. Because of the naturally occurring radioactivity contained in the raw materials, these productions resulted in by-products and residues containing LLW-LL and ILW-LL thorium hydroxide and uranium hydroxide. The total mass of uranium (∼120 tons) and thorium (∼1,200 tons) managed in a single repository required the project design incorporate requirements related to inventory, security and safeguards around nuclear precursor materials. The requirement to consider a performance over a period of more than 10,000 years led to significant challenges in design and modeling of the disposal facility as this disposal facility was purposely designed and permitted as a final disposal for the LLW-LL and ILW-LL. The first phase of the project was the decommissioning, decontamination, and demolition of the 14- acre former rare earth processing plant and excavation of contaminated soils, construction of an engineered cell at the repository for waste disposal, and transportation and disposal of the waste materials into the cell. Final status surveys were carried out to allow the site to be successfully released by the Malaysian regulatory authorities as a clean site for re-development as common industrial use. Over 11,000 loads of material, including approximately 75,000 cubic meters of excavated soils and plant debris, were transported in specially designed steel transport boxes on public roads for disposal in the engineered cell. The second phase of the project included the design and construction of a second engineered cell, enhanced with protective barrier systems and a final cover system constructed of natural materials. Ancillary facilities such as substations, offices, processing buildings, and wastewater treatment plants were constructed to support retrieval and processing of the materials from more than 87,000 individual drums using a semi-automated process. The drums, waste packages, and other materials in the storage facility were systematically extracted, sorted, inventoried, solidified using Portland cement, transported, and disposed in the cell. All temporary facilities were decontaminated, demolished, and disposed in the cell. Radiological inventory and radiation safety programs were implemented to quantify the waste activity and to control exposure to workers and the public during the project. The total mass of radioactive contaminated waste disposed in the two projects is nearly 200,000 tons. The projects were carried out under a high level of scrutiny from Malaysian and international regulatory bodies. Between 2014 and 2017, performance monitoring and modeling activities were carried out to demonstrate that the disposal facility was performing in accordance with design requirements established by regulatory agencies. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2016

fuel cycle cost analysis of Th/U MOX fuel in a block-type HTR - 18619

With a rapid development of nuclear energy in these years, the supply of nuclear fuel is becoming more and more important. Thorium regains attention because of its abundant reserves and excellent physical properties. As a next generation reactor, the high temperature reactor (HTR) is a promising choice for thorium utilization because of its deeper burnup, harder spectrum and better inherent safety. Therefore, a 600 MWth 108-column modular high temperature reactor (MHR) core model with 20%UO{sub 2}-80%ThO{sub 2}; MOX fuel is adapted. A traditional two-step calculation scheme, lattice calculation then core calculation, is used to get the neutronic performance of equilibrium cycle including uranium enrichment and mass of fuel. Using these data, the fuel cycle cost of HTR can be calculated by the levelized lifetime cost method. In order to take into account the variation of unit price, a well-established, standard statistical analysis technique is used by Monte Carlo simulation, (thus, the probability distribution of fuel cycle cost can be obtained. Furthermore, sensitivity calculations are made to analyze the impact on the fuel cycle cost of variations in the unit prices for each fuel cycle component. The result shows that the most influential parameters are unit price of natural uranium, enrichment and discount rate. Finally a comparison of fuel cycle cost between 100%UO{sub 2} and 20%UO{sub 2}-80%ThO{sub 2} MOX fuel is made. The latter is 11% cheaper than the former. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2016

Overview of the Salt at Wall Thermal Exchanges (SWATH) Experiment

Molten Salt Reactors have attracted increased attention in recent years because of the design and safety possibilities offered by the use of a liquid fuel. The European project SAMOFAR1 (2015-2019) is currently coordinating the research efforts on the Molten Fast Salt Reactor (MSFR) concept in Europe. The MSFR is a fast-spectrum breeder reactor with a large negative power coefficient that can be operated in a Thorium fuel cycle. The fast spectrum allows the reduction of the reprocessing requirements and a better reactor breeding ratio. Other advantages of the MSFR design are the possibility for actinide burning and extending fuel resources, on-line fuel loading and reprocessing and the use of novel passive safety systems such as the fuel salt draining system. The reference MSFR concept is a 3000 MW(th) reactor with three different circuits: the fuel circuit, the intermediate circuit and the power conversion system. The main components of the fuel circuit are the fuel salt which serves as fuel and coolant, the core cavity, the inlet and outlet pipes, the gas injection system (not shown in the figure), the salt-bubble separators, the fuel heat exchangers and the pumps. A lithium fluoride salt has been selected as the fuel matrix. The initial composition (non-irradiated) of the MSFR fuel salt is a mixture of a lithium fluoride, thorium fluoride salts and actinides fluoride (LiF-ThF{sub 4}-{sup 233}UF{sub 4} or LiF-ThF{sub 4}- {sup enr}UF{sub 4}-(Pu-MA)F{sub 3}), with the proportion of LiF fixed at about Development of accurate numerical models for the MSFR can only be accomplished by the use of a multiphysics approach which allows taking into account the coupling between relevant neutronics, thermal hydraulics and thermomechanics phenomena. As it is discussed in the next section, such a reactor model requires further progress on the knowledge of molten salt thermal hydraulics, in particular regarding the accuracy of the fuel salt Computational Fluid Dynamics (CFD) models. The Salt at Wall: Thermal Exchanges (SWATH) experiment is being designed to contribute to this particular point. SWATH is one of the experimental activities of the European H2020 SAMOFAR project and includes both experimental and numerical developments. The main objectives of SWATH are to: (i) Improve molten salt numerical models used for design and safety studies and (ii) Demonstrate the working principles of the cold plug device. The cold plug device is a key safety component of the salt draining system of the MSFR. The cold plug is intended to passively melt during accidental conditions thus allowing the flow of the nuclear fuel from the core cavity to the fuel salt draining tanks by gravity forces. The fuel salt draining tanks are designed to ensure that adequate margins are obtained regarding the fuel cooling capabilities and the reactivity control. The next sections provide an overview of the current challenges in molten salt thermal hydraulics modeling and the SWATH experiment design. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2020

ThH 5 : An Actinide–Containing Superhalogen Molecule

Thorium and its compounds have been widely investigated as important nuclear materials. Previous research focused on the potential use of thorium hydrides, such as ThH 2 , ThH 4 , and Th 4 H 15 , as nuclear fuels. Here, we report studies of the anion, ThH 5 , by anion photoelectron spectroscopy and computations. The resulting experimental and theoretical vertical detachment energies (VDE) for ThH 5 are 4.09 eV and 4.11 eV, respectively. These values and the agreement between theory and experiment facilitated the characterization of the structure of the ThH 5 anion and showed its neutral counterpart, ThH 5 to be a superhalogen. ThH 5 , which exhibits a C 4v structure with five Th–H single bonds, possesses the largest known H/M ratio among the actinide elements, M. Here, the adaptive natural density partitioning (AdNDP) method was used to further analyze the chemical bonding of ThH 5 – and to confirm the existence of five Th–H single bonds in the ThH 5 – molecular anion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Separation of zirconium and hafnium from early actinides and rare earth elements with eichrom’s pb resin in HCl

The separation of zirconium and hafnium isotopes from the early actinides and rare earth elements (REE) with Eichrom’s Pb resin has been studied. Batch studies were performed to characterize the behavior of actinium, thorium, zirconium, hafnium, lutetium, and yttrium on Pb resin from HCl solutions (0.001 M to 11 M). The early actinides and REE had no affinity for the resin at any concentration of HCl, but zirconium and hafnium showed a moderate uptake at high concentrations of HCl with a maximum extraction at 11 M HCl. Several column separations were tested, including with only tracer isotopes and with mass. Rapid, simple separations of zirconium from actinium, thorium, protactinium, and the REE with high yields and low elution volumes are presented with applications for tracer isotope production and fission product separations. Furthermore, the resin is less suitable for hafnium separations as hafnium tends to bleed off the resin even at high concentrations of HCl.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗
DOE OSTI2019

Production of 230 Pa by proton irradiation of 232 Th at the LANL isotope production facility: Precursor of 230 U for targeted alpha therapy

Uranium-230 ( t 1/2 = 20.8 d) is an alpha-emitting radionuclide that has potential application in targeted alpha therapy (TAT) of cancer. Its parent isotope 230 Pa ( t 1/2 = 17.4 d), can be produced by proton irradiation of thorium metal targets. Preliminary 230 Pa production runs were performed at the Los Alamos National Laboratory Isotope Production Facility (LANL-IPF) using thin thorium metal targets and a proton beam energy of 15–30 MeV, followed by radiochemical separation of 230 Pa from the irradiated target matrix. The measured 230 Pa production yields were found to exceed the predicted values in most of the experiments that were performed. Furthermore, this data will inform further production efforts for providing 230 Pa/ 230 U for clinical trials.

07 ISOTOPE AND RADIATION SOURCES↗
DOE OSTI2018

Separation of Protactinium Employing Sulfur-Based Extraction Chromatographic Resins

Protactinium-230 (t 1/2 = 17.4 d) is the parent isotope of 230 U (t 1/2 = 20.8 d), a radionuclide of interest for targeted alpha therapy (TAT). Column chromatographic methods have been developed to separate no-carrier-added 230 Pa from proton irradiated thorium targets and accompanying fission products. Results reported within this paper demonstrate the use of novel sulfur bearing chromatographic extraction resins for the selective separation of protactinium. The recovery yield of 230 Pa was 93 ± 4% employing a R 3 P=S type commercially available resin and 88 ± 4% employing a DGTA (diglycothioamide) containing custom synthesized extraction chromatographic resin. The radiochemical purity of the recovered 230 Pa was measured via high purity germanium γ-ray spectroscopy to be >99.5% with the remaining radioactive contaminant being 95 Nb due to its similar chemistry to protactinium. Finally, measured equilibrium distribution coefficients for protactinium, thorium, uranium, niobium, radium, and actinium on both the R 3 P=S type and the DGTA resin in hydrochloric acid media are reported, to the best of our knowledge, for the first time.

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

Sequential Bond Dissociation Energies of Th + (CO) x , x = 3–6: Guided Ion Beam Collision-Induced Dissociation and Quantum Computational Studies

Collision-induced dissociation (CID) of [Th,xC,xO] + , x = 3–6, with Xe is performed using a guided ion beam tandem mass spectrometer (GIBMS). Products are formed exclusively by the loss of CO ligands. Analyses of the kinetic energy-dependent CID product cross sections yield bond dissociation energies (BDEs) of (CO) x–1 Th + –CO at 0 K as 1.09 ± 0.05, 0.82 ± 0.07, 0.63 ± 0.05, and 0.70 ± 0.05 eV, respectively. Different structures of [Th,xC,xO] + were explored using various electronic structure methods, and BDEs for CO ligand loss from precursor [Th,xC,xO] + complexes were computed. Both experimental and theoretical results corroborate that the structures of [Th,xC,xO] + , x = 3–6, formed experimentally are homoleptic thorium cation carbonyl complexes, Th + (CO) x . The nonmonotonic trend in experimental BDEs is reproduced theoretically, although ambiguities in the spin states of the x = 4–6 complexes (doublet or quartet) remain. BDEs calculated at the coupled cluster with single, double, and perturbative triple excitations (CCSD(T))/cc-pVXZ//B3LYP/cc-PVXZ (X = T and Q) level and a complete basis set (CBS) extrapolation agree reasonably well with the experimental values for all complexes. Thorium oxide ketenylidene carbonyl cations, OTh + CCO(CO) y , y = 1–4, were calculated to be the most stable structures of [Th,xC,xO] + , x = 3–6, respectively; however, these are not observed in our experiment. Potential energy profiles (PEPs) having either quartet or doublet spin calculated at the B3LYP/cc-pVQZ level suggest that the failure to observe OTh + CCO(CO) y , y = 1–4, is the result of a barrier corresponding to the C–C bond formation, making the formation of OTh + CCO(CO) y inaccessible kinetically under the present experimental conditions.

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

Mining for Metal–Organic Systems: Chemistry Frontiers of Th-, U-, and Zr-Materials

The conceptual framework presented in this Perspective overviews the design principles of innovative thorium-based materials that could address urgent needs of the medicinal, nuclear energy, and waste remediation sectors from the lens of zirconium and uranium analogs. We survey the intersections of Zr, Th, and U chemistry with a focus on how the intrinsic behavior of each metal translates to broader material properties, including, but not limited to, structural and topological diversity, preferential metal–ligand binding, and reactivity. On the example of several classes of materials, including organometallic complexes, polyoxometalates, and the primary focus of this Perspective, metal–organic frameworks (MOFs), the design principles that govern the preparation of Zr-, Th-, and U-compounds, including oxophilicity, variation in oxidation states, and stable coordination environments have been considered. Further, we highlight how the impact of the mentioned variables may shift throughout the progression from discrete molecular systems to extended structures. We discuss the common assumption that zirconium-organic materials are typically considered a close analog of thorium-based congeners in areas such as material design and preparation. Through consideration of fundamental chemistry principles, we shed light on the relationships between Zr-, Th-, and U-based materials and highlight how a critical analysis of their distinct properties can be used to target a desired material performance. Finally, we provide a detailed understanding of Th-based materials chemistry by anchoring their fundamental properties between two well-studied reference points, zirconium- and uranium-containing analogs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

An assessment of natural radionuclides in water of Langat River estuary, Selangor

An estuary is an area that has a free connection with the open sea and it is a dynamic semi-enclosed coastal bodies. Ex-mining, aquaculture and industrial areas in Selangor are the sources of pollutants discharged into the estuary water. Radionuclides are considered as pollutants to the estuary water. Gamma radiations emitted by natural radionuclides through their decaying process may give impact to human. The radiological effect of natural radionuclides which are {sup 226}Ra, {sup 228}Ra, {sup 40}K, {sup 238}U and {sup 232}Th, were explored by determining the respective activity concentrations in filtered water along the Langat estuary, Selangor. Meanwhile, in- situ water quality parameters such as temperature, dissolve oxygen (DO), salinity, total suspended solid (TSS), pH and turbidity were measured by using YSI portable multi probes meter. The activity concentration of {sup 226}Ra, {sup 228}Ra and {sup 40}K were determined by using gamma-ray spectrometry with high-purity germanium (HPGe) detector. The activity concentrations of {sup 226}Ra, {sup 228}Ra and {sup 40}K in samples are in the range of 0.17 - 0.67 Bq/L, 0.16 - 0.97 Bq/L and 1.22 - 5.57 Bq/L respectively. On the other hand, the concentrations of uranium-238 and thorium-232 were determined by using Energy Dispersive X-ray Fluorescence Spectrometry (EDXRF). The thorium concentrations are between 0.17 ppm to 0.28 ppm and uranium concentrations were 0.25 ppm to 0.31 ppm. The results show activity concentrations of radionuclides are slightly high near the river estuary. The Radium Equivalent, Absorbed Dose Rate, External Hazard Index, and Annual Effective Dose of {sup 226}Ra, {sup 228}Ra and {sup 40}K are also studied.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2019

Band-to-band transitions and critical points in the near-infrared to vacuum ultraviolet dielectric functions of single crystal urania and thoria

Band-to-band transition energy parameters for single-crystal actinide samples of uranium oxide and thorium oxide were determined and compared using spectroscopic ellipsometry and critical-point dielectric function analyses. Spectroscopic ellipsometry measurements from the near-infrared to the vacuum ultraviolet spectral region were used to determine the dielectric functions of uranium oxide and thorium oxide. Furthermore, the critical-point structure is similar between UO 2 and ThO 2 but strongly blue shifted for ThO 2 . We find bandgap energies of 2.1 eV and 5.4 eV for UO2 and ThO2, respectively.

42 ENGINEERING↗
DOE OSTI2011

Proposal for a Nuclear Gamma-Ray Laser of Optical Range

A possibility of the amplification of the 7.6 eV {gamma} radiation by the stimulated {gamma} emission of the ensemble of the {sup 229m}Th isomeric nuclei in a host dielectric crystal is proved theoretically. This amplification is a result of (1) the excitation of a large number of {sup 229m}Th isomers by laser radiation, (2) the creation of the inverse population of nuclear levels in a cooled sample owing to the interaction of thorium nuclei with the crystal electric field or with an external magnetic field, (3) the emission or absorption of the optical photons by thorium nuclei in the crystal without recoil, and (4) the nuclear spin relaxation through the conduction electrons of the metallic covering.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Oxidation State of 229 Th Recoils Implanted into MgF 2 Crystals

A solid-state nuclear clock based on the low-lying isomeric state in 229 Th has attracted growing interest. One potential problem for the solid-state nuclear clock approach is the suitability of the doped environment for photon emission of the nuclear isomeric state. Specifically, Th n+ n < 4 ions could open non-radiative decay routes for deexcitation, hindering the photon emission. Here we have used time-resolved photoluminescence (TRPL) and density functional theory (DFT) calculations to characterize MgF 2 crystals that have been implanted with 229 Th recoils via a-decay from a 233 U source with the goal of determining the charge state of the implanted thorium atoms. The DFT calculations predicted Th4+ to be the lowest energy oxidation state with Th3+ the next lowest in the MgF2 crystal environment. The DFT calculations also show Th4+:MgF 2 system has a band gap large enough so that the internal electron conversion decay channel is suppressed. Experimentally, we found no evidence for thorium in oxidations state other than +4 using TRPL spectroscopy that has a detection limit for Thn+ n < 4 ions several orders of magnitude smaller than the number of implanted 229Th recoils. This work shows that the solid-state approach is a viable option for a nuclear clock.

229Th Isomeric State↗
DOE OSTI2011

IMPACTS OF SMALL COLUMN ION EXCHANGE STREAMS ON DWPF GLASS FORMULATION: KT08, KT09, AND KT10-SERIES GLASS COMPOSITIONS

This report is the fourth in a series of studies of the impacts of the addition of Crystalline Silicotitanate (CST) and Monosodium Titanate (MST) from the Small Column Ion Exchange (SCIX) process on the Defense Waste Processing Facility (DWPF) glass waste form and the applicability of the DWPF process control models. MST from the Salt Waste Processing Facility (SWPF) is also considered in the study. The KT08-series of glasses was designed to evaluate any impacts of the inclusion of uranium and thorium in glasses containing the SCIX components. The KT09-series of glasses was designed to study the effect of increasing Al{sub 2}O{sub 3} and K{sub 2}O concentrations on the propensity for crystallization of titanium containing phases in high TiO{sub 2} concentration glasses. Earlier work on the KT05-series glasses recommended that the impact of these two components be studied further. Increased Al{sub 2}O{sub 3} concentrations have been shown to improve the properties and performance of high waste loading glasses, and K{sub 2}O has been reported to improve the retention of TiO{sub 2} in silicate glasses. The KT10-series of compositions was designed to evaluate any impacts of the SCIX components at concentrations 50% higher than currently projected.a The glasses were fabricated in the laboratory and characterized to identify crystallization, to verify chemical compositions, to measure viscosity, and to measure durability. Liquidus temperature measurements for the KT10-series glasses are underway and will be reported separately. All but one of the KT08-series glasses were found to be amorphous by X-ray diffraction (XRD). One of the slowly cooled glasses contained a small amount of trevorite, which had no practical impact on the durability of the glass and is typically found in DWPF-type glasses. The measured Product Consistency Test (PCT) responses for the KT08-series glasses are well predicted by the DWPF models. The viscosities of the KT08-series glasses were generally well predicted by the DWPF model. No unexpected issues were encountered when uranium and thorium were added to the glasses with SCIX components. Increased Al{sub 2}O{sub 3} concentrations were not successful in preventing the formation of iron titanate crystals in the KT09-series glasses. Increased K{sub 2}O concentrations were successful in hindering the formation of iron titanates in some of the glasses after the canister centerline cooled (CCC) heat treatment. However, this result did not apply to all of the CCC versions of the glasses, indicating a compositional dependence of this effect. In addition, high concentrations of K{sub 2}O have been shown to hinder the ability of the DWPF durability and viscosity models to predict the performance of these glasses. The usefulness of increased K{sub 2}O concentrations in preventing the formation of iron titanates may therefore be limited. Further characterization was not performed for the KT09-series glasses since the type of crystallization formed was the characteristic of interest for these compositions. All of the KT10-series glasses were XRD amorphous, regardless of heat treatment. Chemical composition measurements showed that the glasses met the targeted concentrations for each oxide. In general, the measured PCT responses of the KT10-series glasses were well predicted by the DWPF models. The measured, normalized release values for silicon for some of the glasses fell above the 95% confidence interval for the predicted values; however, the PCT responses for these glasses remain considerably lower than that of the benchmark Environmental Assessment (EA) glass. The viscosities of the KT10-series glasses were generally well predicted by the DWPF model. The next step in this study will be to compile all of the data developed and further compare the measured properties and performance with those predicted by the current DWPF Product Composition Control System (PCCS) models. Recommendations will then be made as to which models, if any, may need to be modified in order to accommodate the material from SCIX into DWPF glass production.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2010

SLUDGE BATCH VARIABILITY STUDY WITH FRIT 418

The Defense Waste Processing Facility (DWPF) initiated processing Sludge Batch 6 (SB6) in the summer of 2010. In support of processing, the Savannah River National Laboratory (SRNL) provided a recommendation to utilize Frit 418 to process SB6. This recommendation was based on assessments of the compositional projections for SB6 available at the time from the Liquid Waste Organization (LWO) and SRNL (using a model-based approach). To support qualification of SB6, SRNL executed a variability study to assess the applicability of the current durability models for SB6. The durability models were assessed over the expected Frit 418-SB6 composition range. Seventeen glasses were selected for the variability study based on the sludge projections used in the frit recommendation. Five of the glasses are based on the centroid of the compositional region, spanning a waste loading (WL) range of 32 to 40%. The remaining twelve glasses are extreme vertices (EVs) of the sludge region of interest for SB6 combined with Frit 418 and are all at 36% WL. These glasses were fabricated and characterized using chemical composition analysis, X-ray diffraction (XRD) and the Product Consistency Test (PCT). After initiating the SB6 variability study, the measured composition of the SB6 Tank 51 qualification glass produced at the SRNL Shielded Cells Facility indicated that thorium was present in the glass at an appreciable concentration (1.03 wt%), which made it a reportable element for SB6. This concentration of ThO{sub 2} resulted in a second phase of experimental studies. Five glasses were formulated that were based on the centroid of the new sludge compositional region combined with Frit 418, spanning a WL range of 32 to 40%. These glasses were fabricated and characterized using chemical composition analysis and the PCT. Based on the measured PCT response, all of the glasses (with and without thorium) were acceptable with respect to the Environmental Assessment (EA) reference glass regardless of thermal history. All of the normalized boron releases were less than 1 g/L. While all of the targeted glass compositions were predictable with respect to the Product Composition Control System (PCCS) models for durability, a small number of the measured glass compositions were located outside of the lower prediction limit indicating poorer durability than what was actually measured. These unpredictable glasses were in the same lithium metaborate (LM) preparation block during the chemical analyses, which resulted in measured compositions that were not representative of the target compositions. A review of the data did not indicate a clear cause for the problem. Re-digestion and re-measurement of three glasses from this preparation block yielded glass compositions closer to the target values and predicted PCT responses within the PCCS model uncertainty. Therefore, it is believed that the glasses were correctly fabricated and the targeted compositions are closer representations of the true compositions. Per the requirements of the DWPF Glass Product Control Program, the PCCS durability models have been shown to be applicable for the SB6/Frit 418 glass system. PCT results from the glasses fabricated as part of the variability study were shown to be predictable and/or acceptable with respect to the DWPF PCCS models. In addition, the inclusion of ThO{sub 2} was shown to have minimal impact on the acceptability and predictability of the variability study glasses.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗