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Corrosion Tests with Developmental Iron Phosphate Glass Waste Forms

Corrosion tests are in progress to assess the dissolution behavior of developmental iron phosphate waste forms for salt waste from electrochemical separation operations. Specimens cut from materials made at PNNL to represent a range of waste salt loadings in prototype composition DPF-5 and a range of iron oxide loadings in prototype composition DPF-3 were subjected to modified ASTM C1308 tests to assess the compositional effects on the relative durabilities and retention of immobilized salt cations. The materials were composed of different amounts of glass and crystalline phases. The test results show both the intrinsic durability of the material and the salt cation retention decrease as the total amount of salt cations added to the material is increased. The results of ASTM C1220 and ASTM C1285 tests conducted with materials DPF5-280 and DPF5-336, which contained about 28% and 34% salt cations (on a mass oxide basis) and bounded the durabilities of the other materials, show that solution feedback does not attenuate the dissolution rate. This suggests the degradation of iron phosphate waste forms can be modelled by using a constant rate that probably depends on the composition and volume fraction of the glass phase. A reference composition should be formulated and used in tests to determine those dependencies. The ASTM C1220 and ASTM C1285 tests with DPF5-280 and DPF5-336 remain in progress to corrode the specimens enough to distinguish the relative extents of glass and crystalline phase corrosion by microscopic examinations. Those results are expected to provide insights regarding the relative dissolution rates of crystalline and glass phases and impact on durability to inform the formulation of the reference composition.

Ebert, W. L.↗

Characteristics of metal waste forms containing technetium and uranium

2 prototype alloys: RAW-1(Tc) and RAW-2(UTc) suitable for a wide range of waste stream compositions are being evaluated to support development of a waste form degradation model that can be used to calculate radionuclide source terms for a range of waste form compositions and disposal environments. Tests and analyses to support formulation of waste forms and development of the degradation model include detailed characterizations of the constituent phases using SEM/EDS and TEM, electrochemical tests to quantify the oxidation behavior and kinetics of the individual and coupled phases under a wide range of environmental conditions, and corrosion tests to measure the gross release kinetics of radionuclides under aggressive test conditions.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Progress and Technology Assessment of Melt-Cast Ceramic Waste Forms

The Savannah River National Laboratory (SRNL) conducted research from FY2011 – FY2020 to develop ceramic waste forms to treat High-Level Waste (HLW) resulting from reprocessing of commercial Used Nuclear Fuel (UNF) as part of the Department of Energy (DOE) office of Nuclear Energy (NE) Fuel Cycle Technologies (FCT) research program. The objective of the research was to develop a reference ceramic waste form and process technology needed to immobilize the combined HLW raffinate stream, including undissolved solids and soluble technetium, and potentially the TRU waste stream resulting from reprocessing processes. This report compiles the relevant literature produced under, and pertinent to, the program objectives and provides a perspective on the technology development as well as prospects for future.

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Separations and Waste Forms Research and Development FY 2013 Accomplishments Report

The Separations and Waste Form Campaign (SWFC) under the U.S. Department of Energy (DOE) Fuel Cycle Research and Development Program (FCRD) is responsible for developing advanced separation and waste form technologies to support the various fuel cycle options defined in the DOE Nuclear Energy Research and Development Roadmap, Report to Congress, April 2010. The fiscal year (FY) 2013 accomplishments report provides a highlight of the results of the research and development (R&D) efforts performed within SWFC in FY 2013. Each section contains a high-level overview of the activities, results, technical point of contact, applicable references, and documents produced during the fiscal year. This report briefly outlines campaign management and integration activities, but the intent of the report is to highlight the many technical accomplishments made during FY 2013.

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Thermal properties and Thermodynamic Equilibrium Modeling of Cementitious Waste Forms

INTRODUCTION Cementitious matrices are used in the US DOE complex and worldwide to solidify aqueous radioactive, hazardous, mixed salt solutions, and sludges to meet low-level radioactive waste (LLW) disposal requirements. Blended formulations are used for most waste form mix designs. Substitution of pozzolans for Class F fly ash has the potential to alter the processing properties and stabilization properties of the resulting waste forms because they add chemical and mineralogical complexity to the final material. The Savannah River Site saltstone waste form was selected as the test case material. CemGEMS software was chosen as the model for predicting hydrated cementitious phases assemblages and phase evolution. Isothermal calorimetry was used as the method for evaluating processing and properties of fresh, uncured waste forms. The test cases consisted of reference case saltstone, and five natural pozzolan substituted saltstone mixes.

Bustamante, Michael E. [Savannah River National La↗

Modeling Activities Related to Waste Form Degradation: Progress Report

This report represents the milestone deliverable M4SF-21SN010309021 “Modeling Activities Related to Waste Form Degradation: Progress Report” that describes the progress of R&D activities of ongoing modeling investigations specifically on nuclear waste glass degradation, Density Functional Theory (DFT) studies on clarkeite structure and stability, and electrochemical modeling of spent nuclear fuel (SNF). These activities are part of the newly-created Waste form Testing, Modeling, and Performance work package at Sandia National Laboratories (SNL). This work package is part of the “Inventory and Waste Form Characteristics and Performance” control account that includes various experimental and modeling activities on nuclear waste degradation conducted at Oak Ridge National Laboratory (ORNL), SNL, Argonne National Laboratory (ANL), and Pacific Northwest National Laboratory (PNNL).

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Modeling Activities Related to Waste Form Degradation: Progress Report

This report represents the milestone deliverable M4SF-22SN010309092 “Modeling Activities Related to Waste Form Degradation: Progress Report” that describes the progress of R&D activities of ongoing modeling investigations specifically on nuclear waste glass degradation, Density Functional Theory (DFT) studies on clarkeite structure and stability, and electrochemical model development of spent nuclear fuel (SNF). These activities are part of the Waste Form Testing, Modeling, and Performance work package at Sandia National Laboratories (SNL). This work package is part of the “Inventory and Waste Form Characteristics and Performance” control account that includes various experimental and modeling activities on nuclear waste degradation conducted at Oak Ridge National Laboratory (ORNL), SNL, Argonne National Laboratory (ANL), and Pacific Northwest National Laboratory (PNNL).

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Chemical durability and degradation mechanisms of HT9 based alloy waste forms with variable Zr content

In Corrosion studies were undertaken on alloy waste forms that can result from advanced electrometallurgical processing techniques to better classify their durability and degradation mechanisms. The waste forms were based on the RAW3-(URe) composition, consisting primarily of HT9 steel and other elemental additions to simulate nuclear fuel reprocessing byproducts. The solution conditions of the corrosion studies were taken from an electrochemical testing protocol, and meant to simulate conditions in a repository. The alloys durability was examined in alkaline and acidic brines.

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Alternative Pozzolans for Replacement of Fly Ash in Grout: Literature Review for Continuous Improvement of Cement Waste Forms

The Department of Energy (DOE) is currently responsible for treating radioactive and mixed waste, performing environmental restoration, and closing contaminated tanks and facilities resulting from nuclear weapons production during the Cold War. Cementitious reagents are the most widely used materials for (1) chemically stabilizing and encapsulating radionuclides and hazardous metals and (2) solidifying radioactive wastewater. Cementitious grouts and flowable concretes are also the most widely used materials for tank and facility closures and are used extensively for physical as well as chemical stabilization in environmental restoration projects. Ambient temperature radioactive waste cementation is a widely used technology for producing waste forms for final disposal. The current practice of designing and testing waste forms is based on a mid to late 20th century technology approach (i.e., materials, characterization, and test methods) for generating parameters for risk assessments. DOE technology development is needed to address both current, long-term, and emerging issues in this area as new waste streams come online and as regulations, performance knowledge, and risk assessment methodology continue to evolve. Consequently, the use of cementation as a means of treating chemically challenging radioactive liquid waste streams and reactive debris requires an enduring effort.

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Innovative Plutonium Waste Forms: Acceptability to Shipp to WIPP

The mission of the Waste Isolation Pilot Plant in New Mexico is the safe and permanent disposition of transuranic radioactive waste from atomic energy defense activities of the United States. The plant consists of an underground repository in a salt formation that is free of flowing water, easily mined, impermeable, and geologically stable. The salt rock naturally seals fractures and closes openings over time. The repository is now anticipated to receive a greater amount of plutonium materials than originally envisioned. An engineered waste form for safe and efficient transport and long-term disposal of plutonium materials is an urgent need. An optimal waste form could also reduce the disposition life cycle and its associated costs to the taxpayer.

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Radiation stability test on multiphase glass ceramic and crystalline ceramic waste forms

A radiation stability study was performed on glass ceramic and crystalline ceramic waste forms. These materials are candidate host materials for immobilizing alkali/alkaline earth (Cs/Sr-CS) + lanthanide (LN) + transition metal (TM) fission product waste streams from nuclear fuel reprocessing. In this study, glass ceramics were fabricated using a borosilicate glass as a matrix in which to incorporate CS/LN/TM combined waste streams. The major phases in these multiphase materials are powellite, oxyaptite, pollucite, celsian, and durable residual glass phases. Al2O3 and TiO2 were combined with these waste components to produce multiphase crystalline ceramics containing hollandite-type phases, perovskites, pyrochlores and other minor metal titanate phases. For the radiation stability test, selected glass ceramic and crystalline ceramic samples were exposed to different irradiation environments including low fluxes of high-energy (~1–5 MeV) protons and alpha particles generated by an ion accelerator, high fluxes of low-energy (hundreds of keV) krypton particles generated by an ion implanter, and in-situ electron irradiations in a transmission electron microscope. These irradiation experiments were performed to simulate self-radiation effects in a waste form. Ion irradiation-induced microstructural modifications were examined using X-ray diffraction and transmission electron microscopy. Our preliminary results reveal different radiation tolerance in different crystalline phases under various radiation damage environments. However, their stability may be rate dependent which may limit the waste loading that can be achieved.

Crystalline ceramic↗

Ceramic Waste Form Data Package

The purpose of this data package is to provide information about simulated crystalline waste forms that can be used to select an appropriate composition for a Cold Crucible Induction Melter (CCIM) proof of principle demonstration. Melt processing, viscosity, electrical conductivity, and thermal analysis information was collected to assess the ability of two potential candidate ceramic compositions to be processed in the Idaho National Laboratory (INL) CCIM and to guide processing parameters for the CCIM operation. Given uncertainties in the CCIM capabilities to reach certain temperatures throughout the system, one waste form designated 'Fe-MP' was designed towards enabling processing and another, designated 'CAF-5%TM-MP' was designed towards optimized microstructure. Melt processing studies confirmed both compositions could be poured from a crucible at 1600°C although the CAF-5%TM-MP composition froze before pouring was complete due to rapid crystallization (upon cooling). X-ray diffraction measurements confirmed the crystalline nature and phase assemblages of the compositions. The kinetics of melting and crystallization appeared to vary significantly between the compositions. Impedance spectroscopy results indicated the electrical conductivity is acceptable with respect to processing in the CCIM. The success of processing either ceramic composition will depend on the thermal profiles throughout the CCIM. In particular, the working temperature of the pour spout relative to the bulk melter which can approach 1700°C. The Fe-MP composition is recommended to demonstrate proof of principle for crystalline simulated waste forms considering the current configuration of INL's CCIM. If proposed modifications to the CCIM can maintain a nominal temperature of 1600°C throughout the melter, drain, and pour spout, then the CAF-5%TM-MP composition should be considered for a proof of principle demonstration.

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Development and Durability Testing of a Low‐Temperature Sintering Bi–Si–Zn Oxide Glass Composite Material (GCM) 129 I Waste Form

The capture and safe storage of radiological iodine ( 129 I) from nuclear fuel reprocessing is of concern due to its long half‐life and potential mobility in the environment. The development of durable waste forms in which to store captured iodine requires materials that are both compatible with the iodine capture phases and durable to repository environments. To that end, Sandia is developing a low‐temperature sintering Bi–Si–Zn oxide glass composite material (GCM) waste form and herein presents results of durability testing. Furthermore, durability studies were extended to both the occluded iodine capture material Ag‐Zeolite (Mordenite, MOR) as well as the GCM, synthesized with compositional variations including: amount of Ag flake added, AgI‐MOR particle size in the GCM, and mass loading of I within the AgI‐MOR. Product consistency test (PCT‐B), chemical durability (MCC‐1) tests, and single‐pass flow‐through (SPFT) tests, were performed on both the individual components of the GCM and the completed GCMs. Durability tests indicate low GCM dissolution rates (<10 −3 g/m 2 ·d) across wide variable ranges including: pH, AgI‐MOR loading, I loading, and AgI‐MOR particle size. Results indicate that the Bi–Si–Zn oxide glass matrix sharply limits the release of iodine from the otherwise relatively fast degrading AgI‐MOR getter material. Furthermore, the formation of an amorphous AgI phase during sintering of the GCM results in the limitation of iodine release during waste form degradation. Durability of GCM and release rates approximate those of established nuclear waste glasses, or analogues such as basaltic glass. This suggests that the Bi–Si–Zn GCM is a viable candidate as a repository iodine waste form.

Mowry, Curtis D.↗

The role of environmental conditions on the carbonation of an alkali-activated cementitious waste form

Cast Stone is a cementitious waste form being considered for the solidification of low activity waste at the DOE Hanford Site. Under near-surface disposal conditions in an arid environment, Cast Stone is subject to drying and carbonation which may impact retention of waste constituents. Here this study investigates the effects of environmental CO 2 concentration and relative humidity (RH) on the carbonation of Cast Stone. The rate of carbonation front ingress and the extent of carbonation reaction were characterized for samples aged up to 48 weeks at three RH levels and two CO 2 concentrations. While the 68% RH environment allowed the greatest reaction extent, the 15% RH environment yielded the deepest carbonation front ingress. At 68% RH, there was a linear relationship between the ingress rate and CO 2 concentration. Carbonation reactions increased the drying rate of Cast Stone. Redistribution of sodium toward the wetting front was observed under drying and carbonation conditions.

36 MATERIALS SCIENCE↗

Glass-Bonded Monazite Waste Forms for Lanthanide and Actinide Immobilization: From Theoretical Design to Scale-Up Production and Characterization

The development of nuclear waste forms for both existing and future nuclear wastes is critical to ensuring global environmental safety. This study focuses on waste management from molten salt reactors, where fuel exists in a salt form and could be processed in real time for the removal of neutron poisons such as xenon isotopes (e.g., 135 Xe) and rare earth elements (REEs, e.g., 149 Sm). To ensure safe, stable, and long-term disposal in geological repositories, REEs must be incorporated into a durable waste form. Iron-phosphate glasses are a promising candidate due to their low melting points, high chemical durability, and their ability to incorporate high concentrations of REEs. In this study, we successfully prepared iron-phosphate glass waste forms with high Nd loadings (up to 37 mass %) in batch sizes ranging from small (23 g) to large (1600 g). The resulting materials contained up to 75 mass % NdPO 4 , contributing to their mechanical resilience and exceptional chemical durability. These findings highlight the potential of iron-phosphate glasses as high-efficiency, chemically durable waste forms and demonstrate the successful transition from theoretical design to scaled-up production.

amorphous materials↗

Evaluation of Degradation Mechanisms for Solid Secondary Waste Grout Waste Forms

The overall objective of this work is to provide defensibility for the long-term performance of grouted Hanford SSW streams when disposed in a near surface disposal facility, IDF, on the Hanford Site. Providing defensibly for the long-term performance of the grouted waste forms is consistent with the research and development activities identified in the Performance Assessment Maintenance Plan, (Westcott et al. 2019), that are necessary to address the assumptions made in the PA. Specifically, this work addresses two areas identified for further research and development activities in the plan: (1) “Evaluate ongoing research on transport characteristics of cementitious materials using accelerated tests to approximate the effects of aging/alteration/weathering”; and (2) “Evaluate ongoing research on microbial effects on transport processes in cementitious materials.” The assembled subject matter expert team evaluated a list of degradation mechanisms and supporting processes and provided rankings of areas where further research and development (R&D) are needed. From this assessment, high priority R&D areas include: (1) the effects of carbonation, Ca leaching, and SSW dimensional change in grout waste forms; (2) updated model representations of grouted waste forms; and (3) scaled testing demonstrations. Moderate priority items including a paper study on possible microbial influence, reoxidation rates, radionuclide/contaminant dissolution from SSW in the grout and freeze thaw behavior. Other processes evaluated were either deemed unlikely to occur, to have little impact on the SSW waste forms, or to occur at time frames beyond those considered (>10,000 years). The assessments and proposed R&D approaches are expected to support an update to the WRPS SSW roadmap.

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Reassessment of Dose Contributions from the Paducah Cask Special Waste Form Buried in the E-Area Low-Level Waste Facility

During a recent revision to the groundwater and inadvertent human intruder screening analysis report (Aleman and Hamm, 2023), weaknesses within the screening logic were observed resulting in the addition of U-235 being brought back into the list of radionuclides requiring inventory limits within the Paducah Cask special waste form (SWF). In addition, while reviewing the earlier vadose zone transport analysis efforts, an inconsistency was observed in the initial U-235P inventory that was supplied to the Consolidated Waste Tracking System (CWTS) back in 2009.

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Investigation of processing advanced waste forms in Cold Crucible Induction Melter systems

The Cold Crucible Induction Melter (CCIM) technology has been identified in several independent reviews and studies as a potential alternative or supplemental vitrification technology for specific U.S. Department of Energy (DOE) high level radioactive waste (HLW) streams. These inventories have unique chemistries, such as high alumina, high iron, high chromium, etc., that are not amenable to efficient immobilization in conventional borosilicate glass (BSG) matrices. Advanced waste forms, such as iron phosphate glass (FePG), high crystalline BSG (HC-BSG), and alumino-silicate glass-ceramic (GC) have been shown to provide significantly improved immobilization matrices for these challenging waste streams, including dramatically improved waste loadings; however, they are difficult to efficiently process in the baseline joule-heated ceramic melters (JHCMs). The CCIM technology can effectively process these advanced waste forms at the desired high waste loadings. This paper describes the most recent collaborative activities between the DOE Office of Environmental Management (DOE EM) and various Russian institutions in modeling, development and testing of advanced waste forms in CCIMs, including FePG and HC-BSG formulations. Additionally, past interactions with other international partners, including France and Korea, are described. Finally, recent enhancements to CCIM processing related to modeling, draining techniques and automated control, which were collaboratively developed, will be discussed. (authors)

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