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Material Recovery and Waste Form Development FY 2015 Accomplishments Report

The Material Recovery and Waste Form Development (MRWFD) Campaign under the U.S. Department of Energy (DOE) Fuel Cycle Technologies (FCT) Program 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 FY 2015 Accomplishments Report provides a highlight of the results of the research and development (R&D) efforts performed within the MRWFD Campaign in FY-14. 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 primarily focuses on the many technical accomplishments made during FY-15. The campaign continued to utilize an engineering driven-science-based approach to maintain relevance and focus. There was increased emphasis on development of technologies that support near-term applications that are relevant to the current once-through fuel cycle.

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Low Temperature Waste Form Process Intensification

This study successfully demonstrated process intensification of low temperature waste form production. Modifications were made to the dry blend composition to enable a 50% increase in waste concentration, thus allowing for a significant reduction in disposal volume and associated costs. Properties measurements showed that the advanced waste form can be produced using existing equipment and processes. Performance of the waste form was equivalent or better than the current baseline, with approximately double the amount of waste incorporation. The results demonstrate the feasibility of significantly accelerating low level waste immobilization missions across the DOE complex and at environmental remediation sites worldwide.

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The Effect of Environmental Relative Humidity on Carbonation and Oxidation in a Cementitious Waste Form - 18448

Cementitious material has been developed and used for the nuclear waste disposal. Cast Stone, a type of cementitious waste form, is considered for solidification and immobilization of part of low activity radioactive waste (LAW) at DOE Hanford Site in Richland, WA. During its life cycle, the waste form, which is produced from Portland cement, fly ash, blast furnace slag and liquid waste, is subject to reaction with carbon dioxide and oxygen, both in gaseous and dissolved form. The reactions may alter the physical and chemical properties of the waste form and thus change its retention ability for the radionuclides. Therefore, understanding the rate and the impact of oxidation and carbonation in the material is important for projecting the long-term performance of Cast Stone. However, the rate of carbonation and oxidation in Cast Stone closely depends on the moisture content in the material, which varies largely with the environmental relative humidity (RH). In this study, experiments are carried out to study the effect of environmental relative humidity on the carbonation and oxidation rate as well as the leaching of the constituents from Cast Stone. Cast Stone samples doped with Cr as a reaction indicator are aged for 16 to 32 weeks under N{sub 2}, air, and 2% CO{sub 2} (in nitrogen) environments with various relative humidities (15%, 40%, 68%, 100%). After aging, samples were tested for the pH-dependent leaching (EPA Method 1313) and mass transfer rate under diffusion-controlled leaching (EPA Method 1315) of constituents. The progress of the carbonation was measured for each condition to determine the rate of carbonation front ingress. The results show that environmental relative humidity strongly influences carbonation and oxidation in Cast Stone; however, the impact is different for the rate of reaction and for the extent of reactions. The former refers to the rate at which the reaction front ingresses, while the latter refers to the fraction of the material reacted. For both carbonation and oxidation, the largest impact of the reactions at the exposure surface is observed at intermediate relative humidity (68%). However, for carbonation, the reaction front evolves more rapidly under drier conditions, with the highest rate observed at 15% RH. As a result, carbonation and oxidation have different degree of impact on the leaching behavior of Cast Stone samples aged under various relative humidities. (authors)

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Durability and degradation of HT9 based alloy waste forms with variable Ni and Cr content

Short-term electrochemical and long-term hybrid electrochemical corrosion tests were performed on alloy waste forms in reference aqueous solutions that bound postulated repository conditions. The alloy waste forms investigated represent candidate formulations that can be produced with advanced electrochemical treatment of used nuclear fuel. The studies helped to better understand the alloy waste form durability with differing concentrations of nickel and chromium, species that can be added to alloy waste forms to potentially increase their durability and decrease radionuclide release into the environment.

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Cementitious Waste Form Development for Treatment of EMF Evaporator Bottoms - 18611

Direct Feed Low-Activity Waste operations at the Hanford Site (Washington State, USA) involve concentrating the Hanford low-activity waste (LAW) melter off-gas condensate waste stream by evaporation at the Effluent Management Facility (EMF) followed by recycle back to the melter feed. The EMF evaporator bottoms waste stream is expected to contain variable, high levels of halides and sulfate that could strain LAW melter performance and co-mingled radionuclides, technetium-99 ({sup 99}Tc) and iodine-129 ({sup 129}I), that readily volatilize in the LAW melter and are expected to accumulate during recycle. To this end, there is a need for alternative disposition paths for the EMF evaporator bottoms waste stream that bypass recycling to the LAW melter. One such alternative is solidification in low-temperature cementitious waste forms (CWFs) that meet disposal facility acceptance criteria. The work herein addresses recent waste form development and testing performed to identify CWF candidates that meet off-site disposal acceptance criteria and/or on-site Hanford Integrated Disposal Facility waste acceptance criteria. Phase one testing activities included the production and evaporation of simulated EMF evaporator feed from the Hanford Waste Treatment and Immobilization Plant melter offgas effluent liquid secondary waste stream, which was then analyzed to demonstrate the behavior and fate of contaminants of concern (COCs). Based on analyses from these preliminary tests, a simulant for the EMF evaporator bottoms waste stream was formulated and used to evaluate several dry material compositions proposed for CWF development and testing. In particular, dry ingredient recipes used in early testing efforts contained a combination of ordinary Portland cement (OPC), Class F fly ash (FA), blast furnace slag (BFS), Aquaset{sup R} II-H, and/or Aquaset{sup R} II-GH to generate CWFs at various water-to-dry material ratios. CWFs were then tested according to the Toxicity Characteristic Leaching Procedure (TCLP) for COCs, such as Cr, Zn, As, and Se, to determine which specimens comply with land disposal restrictions (40 CFR 268). The results of TCLP testing showed that chromium leaching was a persistent challenge, except when using the original Cast Stone dry ingredient recipe (8% OPC, 47% BFS, 45% FA) to immobilize the EMF evaporator bottoms simulant. Improving Cr immobilization and evaluating leaching behavior for COC Hg were identified as objectives for the second phase of testing. During second phase testing efforts, a screening test was performed to determine whether the bulk EMF waste composition is a factor in producing an acceptable solidified waste form. A series of eight simulants with varying concentrations of major salts of boron, chloride, nitrite, and sulfate were prepared and immobilized using three dry ingredient recipes. Each dry ingredient recipe contained two to three of the following: BFS, OPC, FA, and Aquaset{sup R} II-GH. All eight simulants were spiked with Zn, Cr, As, Se, and Hg prior to production of the CWFs, similar to previous tests, and used to test for residual free liquids and TCLP analysis. The TCLP results indicate that all phase two formulated CWFs meet land disposal requirements when compared to Universal Treatment Standards (40 CFR 268) for hazardous wastes, regardless of simulant composition. Furthermore, re-absorption of residual free liquids is most quickly achieved for nearly all simulant compositions using the original Cast Stone recipe; however, replicas analysis is required to corroborate these findings. (authors)

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Single-component-at-a-time variation study for glass-ceramic waste forms

Here, a 51-sample composition variation study was performed on glass-ceramic waste forms for a raffinate waste stream from aqueous reprocessing of used nuclear fuel containing high fractions of Mo, alkalis, alkaline earths (AEs), and rare earths (REs). The study was designed with a single-component-at-a-time variation approach off a centroid composition. The components that were varied included Al, B, Ca, Li, Mo, Na, REs, Si, Zr, and Others (containing minor components). Data analysis included crystallization curves, microstructure, and phase compositions. A number of components (i.e., Li 2 O, B 2 O 3 , REO x , MoO 3 , Na 2 O, and ZrO 2 ) significantly impacted the concentration and chemistry of phases, especially the primary phases of oxyapatite [i.e., Ca 2 RE 8 (SiO 4 ) 6 O 2 ] and powellite (i.e., AEMoO 4 ), precipitated in the slow-cool heat-treated waste forms; minor phases included cerianite [i.e., Ce x Zr (1-x) O 2 ], Ba-molybdate [i.e., Ba(Gd 0.67 Mo 0.33 O 3 ], noble metals, pollucite (i.e., CsAlSiO 4 ), and RE-borosilicate (i.e., RE 3 BSi 2 O 10 ).

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Effect Of Oxidation On Chromium Leaching And Redox Capacity Of Slag-Containing Waste Forms

The rate of oxidation is important to the long-term performance of reducing salt waste forms because the solubility of some contaminants, e.g., technetium, is a function of oxidation state. TcO 4 - in the salt solution is reduced to Tc(IV) and has been shown to react with ingredients in the waste form to precipitate low solubility sulfide and/or oxide phases [Shuh, et al., 1994, Shuh, et al., 2000, Shuh, et al., 2003]. Upon exposure to oxygen, the compounds containing Tc(IV) oxidize to the pertechnetate ion, Tc(VII)O 4 - , which is very soluble. Consequently the rate of technetium oxidation front advancement into a monolith and the technetium leaching profile as a function of depth from an exposed surface are important to waste form performance and ground water concentration predictions. An approach for measuring contaminant oxidation rate (effective contaminant specific oxidation rate) based on leaching of select contaminants of concern is described in this report. In addition, the relationship between reduction capacity and contaminant oxidation is addressed. Chromate was used as a non-radioactive surrogate for pertechnetate in simulated waste form samples. Depth discrete subsamples were cut from material exposed to Savannah River Site (SRS) field cured conditions. The subsamples were prepared and analyzed for both reduction capacity and chromium leachability. Results from field-cured samples indicate that the depth at which leachable chromium was detected advanced further into the sample exposed for 302 days compared to the sample exposed to air for 118 days (at least 50 mm compared to at least 20 mm). Data for only two exposure time intervals is currently available. Data for additional exposure times are required to develop an equation for the oxidation front progression. Reduction capacity measurements (per the Angus-Glasser method, which is a measurement of the ability of a material to chemically reduce Ce(IV) to Ce(III) in solution) performed on depth discrete samples could not be correlated with the amount of chromium leached from the depth discrete subsamples or with the oxidation front inferred from soluble chromium (i.e., effective Cr oxidation front). Exposure to oxygen (air or oxygen dissolved in water) results in the release of chromium through oxidation of Cr(III) to highly soluble chromate, Cr(VI). Residual reduction capacity in the oxidized region of the test samples indicates that the remaining reduction capacity is not effective in re-reducing Cr(VI) in the presence of oxygen. Consequently, this method for determining reduction capacity may not be a good indicator of the effective contaminant oxidation rate in a relatively porous solid (40 to 60 volume percent porosity). The chromium extracted in depth discrete samples ranged from a maximum of about 5.8 % at about 5 mm (118 day exposure) to about 4 % at about 10 mm (302 day exposure). The use of reduction capacity as an indicator of long-term performance requires further investigation. The carbonation front was also estimated to have advanced to at least 28 mm in 302 days based on visual observation of gas evolution during acid addition during the reduction capacity measurements. Depth discrete sampling of materials exposed to realistic conditions in combination with short term leaching of crushed samples has potential for advancing the understanding of factors influencing performance and will support conceptual model development.

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Characterization and corrosion behavior test of glass ceramic waste form

The research conducted in this work package is to collect data in support of future development of glass ceramic waste forms and to help develop the next generation high performance waste management technologies. This work package collaborates closely with the work conducted under “Glass Ceramic – Pacific Northwest National Laboratory (PNNL) - (FT-15PN030704)” and “CCIM Test with Glass Ceramic – Idaho National Laboratory (INL) – (FT-15IN030707)”. The Los Alamos National Laboratory (LANL) is focusing on characterization, testing procedures on glass ceramics from the test matrix and melter testing to further develop and mature the glass ceramic waste form for immobilization of high level waste (HLW) raffinate stream. In Fiscal Year 2015, we are mainly working on multi-phase glass ceramic waste forms. Various characterization and testing techniques (including X-ray diffraction, transmission electron microscopy/scanning transmission electron microscopy, scanning electron microscopy, synchrotron X-ray, nano-indentation) were used to characterize and investigate the corrosion behavior of glass ceramics.

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Investigating the Durability of Iodine Waste Forms in Dilute Conditions

To prevent the release of radioiodine during the reprocessing of used nuclear fuel or in the management of other wastes, many technologies have been developed for iodine capture. The capture is only part of the challenge as a durable waste form is required to ensure safe disposal of the radioiodine. This work presents the first durability studies in dilute conditions of two AgI-containing waste forms: hot-isostatically pressed silver mordenite (AgZ) and spark plasma sintered silver-functionalized silica aerogel (SFA) iodine waste forms (IWF). Using the single-pass flow-through (SPFT) test method, the dissolution rates respective to Si, Al, Ag and I were measured for variants of the IWFs. By combining solution and solid analysis information on the corrosion mechanism neutral-to-alkaline conditions was elucidated. The AgZ samples were observed to have corrosion preferentially occur at secondary phases with higher Al and alkali content. These phases contained a lower proportion of I compared with the matrix. The SFA samples experienced a higher extent of corrosion at Si-rich particles, but an increased addition of Si to the waste led to an improvement in corrosion resistance. The dissolution rates for the IWF types are of similar magnitude to other Si-based waste form materials measured using SPFT.

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Development of a Performance and Processing Property Acceptance Region for Cementitious Low-Level Waste Forms at Savannah River Site - 13174

The Saltstone Production and Disposal Facilities (SPF and SDF) at the Savannah River Site (SRS) have been treating decontaminated salt solution, a low-level aqueous waste stream (LLW) since facility commissioning in 1990. In 2012, the Saltstone Facilities implemented a new Performance Assessment (PA) that incorporates an alternate design for the disposal facility to ensure that the performance objectives of DOE Order 435.1 and the National Defense Authorization Act (NDAA) of Fiscal Year 2005 Section 3116 are met. The PA performs long term modeling of the waste form, disposal facility, and disposal site hydrogeology to determine the transport history of radionuclides disposed in the LLW. Saltstone has been successfully used to dispose of LLW in a grout waste form for 15 years. Numerous waste form property assumptions directly impact the fate and transport modeling performed in the PA. The extent of process variability and consequence on performance properties are critical to meeting the assumptions of the PA. The SPF has ensured performance property acceptability by way of implementing control strategies that ensure the process operates within the analyzed limits of variability, but efforts continue to improve the understanding of facility performance in relation to the PA analysis. A similar understanding of the impact of variability on processing parameters is important from the standpoint of the operability of the production facility. The fresh grout slurry properties (particularly slurry rheology and the rate of hydration and structure formation) of the waste form directly impact the pressure and flow rates that can be reliably processed. It is thus equally important to quantify the impact of variability on processing parameters to ensure that the design basis assumptions for the production facility are maintained. Savannah River Remediation (SRR) has been pursuing a process that will ultimately establish a property acceptance region (PAR) to incorporate elements important to both processability and long-term performance properties. This process involves characterization of both emplaced product samples from the disposal facility and laboratory-simulated samples to demonstrate the effectiveness of the lab simulation. With that basis confirmed, a comprehensive variability study using non-radioactive simulants will define the acceptable PAR, or 'operating window' for Saltstone production and disposal. This same process will be used in the future to evaluate new waste streams for disposal or changes to the existing process flowsheet. (authors)

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Analysis of Krypton-85 Legacy Waste Forms: Part II

During a removal of legacy materials from one hot cell at the Idaho National Laboratory in 2010, five metal capsules and some loose zeolite material were identified as krypton (Kr) immobilization test specimens produced in the late 1970s under the Airborne Waste Management Program (AWMP). This AWMP research and development effort examined the encapsulation of 85Kr within a collapsed zeolite structure for use as a potential waste form for long-term storage. The recovered capsules appeared to have been placed to the side and remained untouched after the AWMP was halted in the mid-1980s. These reclaimed capsules and loose material presented a unique opportunity to study a potential 85 Kr waste form after three half-lives had elapsed. The first phase of this study included two parts: The first was to assess the physical condition of the capsule walls, and the second was to examine the Kr-containing material within the capsules. The first part of this study was previously reported and noted that substantial corrosion was observed throughout each capsule wall of the two previously breached capsules that were examined. One of these capsules had been hot isostatic pressed (HIPed) and one was not HIPed. The second part of the study examined the materials contained in the two previously breached capsules. There appears to be a relatively uniform distribution of Kr and rubidium throughout the pellets examined. The chemical composition of the pellets appears to be consistent with 5A molecular sieves. The material contained within the HIPed capsules showed ~1 at. % lead (Pb). The origin of the Pb is currently indeterminate. X-ray diffraction analysis shows a significant shift from the 5A structure, most likely due to the Kr encapsulation/sintering process that occurred when the samples were made. Calculations based on the energy dispersive spectrometry elemental analysis show a residual Kr level within the pellets that is within a factor of 2 of the reported Kr capacities for this type of processed material. This provides a clear indication that a significant fraction of the Kr initially encapsulated in the material remained within the waste form even following a significant breach of the capsule wall. As a result, it would appear that this Kr immobilization method, even in non-HIPed form, is very promising as a waste form for long-term storage. The successful analysis of these two breached capsules forms a solid basis for the future analysis of the remaining unbreached capsules, which offers the opportunity to provide an even more complete understanding of the long-term Kr retention performance of this promising waste form.

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Hot Isostatically Pressed Ceramic Waste forms for High Dose Spent Adsorbents - 18129

Decommissioning and clean-up of nuclear facilities requires the development of new technologies to condition radioactive wastes, producing passively safe waste packages of minimal volume, to reduce storage and disposal costs. We have applied hot isostatic pressing to demonstrate conceptual waste forms for high dose spent adsorbents (i.e. ion exchange materials) present on the Sellafield site, UK, and Fukushima Daiichi site, Japan. These radioactive wastes pose several challenges which demand early conditioning to produce a passively safe wasteform, including: a wet and granular nature, and hence dispersible as a result of loss of containment; a very high dose rates as a result of their selectivity for short lived radionuclides (e.g. Sr-90, Cs-137, Co-60); radiogenic self-heating, as a result of the concentration of such lived radio nuclides; hydrogen production as a result of radiolysis of entrained water [1]. Here, we demonstrate the conversion of natural inorganic ion exchange materials into multiphase ceramic waste forms, achieving a waste loading of 100 wt.% and density in excess of 97% theoretical. High resolution thermogravimetric analysis coupled with mass spectroscopy was utilised to characterise the evolution of water and volatiles during the in-can bake out step, prior to the HIP cycle. This allowed optimisation of the bake out parameters (temperature, time and vacuum) to enable complete removal of water and volatiles, affording ceramic bodies with minimal residual porosity by hot isostatic pressing at 1250 deg. C for 4 h in stainless steel canisters. Characterisation of the ceramic waste forms by SEM /EDX and X-ray diffraction revealed the nuclides of concern to be incorporated within well-known natural mineral and synthetic phases, with Cs partitioning into the K-feldspar. (authors)

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Zircaloy Cladding as Starting Precursor for Ceramic Waste-Forms - 15562

Zircaloy cladding of spent fuel is regular waste-stream related to the process of reprocessing. It remains in the apparatus after spent fuel dissolution. The most common technique of zircaloy cladding treatment is cementation and disposal in metallic containers. In view of the high cost of the cladding material (mainly zirconium), there have been a number of proposals for this material to be recovered and re-used. However, the residual contamination of the claddings following the dissolution of the fuel and the chemical stability of the zirconium militate against any proposal for a recycling process that might be economically reasonable. At the same time there is a lot of information available about synthesis of mineral-like materials based on zirconium for immobilization of long-lived radionuclides. The object of this work was to study experimentally electrochemical dissolution of fuel rod cladding for further obtaining starting precursor for the synthesis of ceramic-waste forms. The results of experiments on electrochemical dissolution of zirconium and zirconium alloy (fuel rod cladding) in nitric acid solutions are presented. The peak dissolution rate of specimens is shown to be observed in dilute nitric acid at elevated temperatures. The rate of dissolution rises with temperature, reaching ∼40-70 mg/cm{sup 2}.h at 90 deg. C. The current yield at this point is 0.6-0.7 g/A.h. The results of analysis of the surface oxide film on specimens and residues formed during dissolution are also presented. An electrochemical dissolution of zircaloy claddings is the common technique for preparation of zirconium solutions to be used for ceramic waste form synthesis. (authors)

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Epsilon Metal Waste Form for Immobilization of Noble Metals from Used Nuclear Fuel

Epsilon metal (ε-metal), an alloy of Mo, Pd, Rh, Ru, and Tc, is being developed as a waste form to treat and immobilize the undissolved solids and dissolved noble metals from aqueous reprocessing of commercial used nuclear fuel. Epsilon metal is an attractive waste form for several reasons: increased durability relative to borosilicate glass, it can be fabricated without additives (100% waste loading), and in addition it also benefits borosilicate glass waste loading by eliminating noble metals from the glass and thus the processing problems related there insolubility in glass. This work focused on the processing aspects of the epsilon metal waste form development. Epsilon metal is comprised of refractory metals resulting in high reaction temperatures to form the alloy, expected to be 1500 - 2000°C making it a non-trivial phase to fabricate by traditional methods. Three commercially available advanced technologies were identified: spark-plasma sintering, microwave sintering, and hot isostatic pressing, and investigated as potential methods to fabricate this waste form. Results of these investigations are reported and compared in terms of bulk density, phase assemblage (X-ray diffraction and elemental analysis), and microstructure (scanning electron microscopy).

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Secondary Waste Cementitious Waste Form Data Package for the Integrated Disposal Facility Performance Assessment

A review of the most up-to-date and relevant data currently available was conducted to develop a set of recommended values for use in the Integrated Disposal Facility (IDF) performance assessment (PA) to model contaminant release from a cementitious waste form for aqueous wastes treated at the Hanford Effluent Treatment Facility (ETF). This data package relies primarily upon recent data collected on Cast Stone formulations fabricated with simulants of low-activity waste (LAW) and liquid secondary wastes expected to be produced at Hanford. These data were supplemented, when necessary, with data developed for saltstone (a similar grout waste form used at the Savannah River Site). Work is currently underway to collect data on cementitious waste forms that are similar to Cast Stone and saltstone but are tailored to the characteristics of ETF-treated liquid secondary wastes. Recommended values for key parameters to conduct PA modeling of contaminant release from ETF-treated liquid waste are provided.

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Ni and Cr addition to alloy waste forms to reduce radionuclide environmental releases

Reference alloy waste forms (RAW) were fabricated and underwent hybrid corrosion/immersion testing to parameterize the ANL analytical oxidative-dissolution model to enable the calculation of fractional release rates and to determine the effectiveness of Ni and Cr trim additions in reducing release rates of radionuclide surrogates. Figure 1 shows the prototypical multiphase microstructure of the alloys with each phase type contributing about equally to the exposed surface area. The waste forms tested at SRNL were variations of the RAW-6 formulation that uses HT9 as the main alloy component, and are meant to enable evaluation of the impact of Ni and Cr trim additions on the release rates of actinides and Tc-99. The test solutions were deaerated alkaline and acidic brines, ranging in pH 3 to pH 10, representing potential repositories with those conditions. The testing approach consisted of 4 major steps; 1) bare surface corrosion measurements at pH values of 3, 5, 8, and 10, 2) hybrid potentiostatic hold/exposure measurements at pH 3, 3) measurement of radionuclide concentrations and relations to anodic current from potentiostatic holds, and 4) identification of corroding phases using SEM/EDS of electrodes.

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The Thermodynamics of Crystallization and Phase-Separation in Melt-Derived Nuclear Waste Forms

This project aimed to gain detailed and fundamental understanding of the stability of glass waste forms to be used for safe and reliable encapsulation of nuclear waste. The focus was to understand thermodynamic and structural properties involved in crystallization and phase separation in melt-derived waste form glasses and glass-ceramics by studying a baseline glass composition with varying additives. This was achieved by combining neutron total scattering, advanced calorimetric measurements, and extensive modeling study. This project harnessed diverse and complementary approaches and expertise from four collaborating interdisciplinary institutions (two universities, one national laboratory, and one UK university partner). Samples were prepared at the national laboratory and exchanged with the two university institutions. The thermodynamic data obtained by various advanced calorimetry techniques were linked to the underlying short-range structure of waste forms measured by state-of-the-art neutron total scattering experiments. An important element of this project was extensive modeling to interpret and fundamentally understand the experimental results.

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Corrosion mechanisms for metal alloy waste forms: experiment and theory Level 4 Milestone M4FT-14LA0804024 Fuel Cycle Research & Development

This document meets Level 4 Milestone: Corrosion mechanisms for metal alloy waste forms - experiment and theory. A multiphysics model is introduces that will provide the framework for the quantitative prediction of corrosion rates of metallic waste forms incorporating the fission product Tc. The model requires a knowledge of the properties of not only the metallic waste form, but also the passive oxide films that will be generated on the waste form, and the chemistry of the metal/oxide and oxide/environment interfaces. in collaboration with experimental work, the focus of this work is on obtaining these properties from fundamental atomistic models. herein we describe the overall multiphysics model, which is based on MacDonald's point-defect model for passivity. We then present the results of detailed electronic-structure calculations for the determination of the compatibility and properties of Tc when incorporated into intermetallic oxide phases. This work is relevant to the formation of multi-component oxides on metal surfaces that will incorporate Tc, and provide a kinetic barrier to corrosion (i.e. the release of Tc to the environment). Atomistic models that build upon the electronic structure calculations are then described using the modified embedded atom method to simulate metallic dissolution, and Buckingham potentials to perform classical molecular dynamics and statics simulations of the technetium (and, later, iron-technetium) oxide phases. Electrochemical methods were then applied to provide some benchmark information of the corrosion and electrochemical properties of Technetium metal. The results indicate that published information on Tc passivity is not complete and that further investigation is warranted.

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