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Title: Thermodynamic and Microstructural Mechanisms in the Corrosion of Advanced Ceramic Tc-bearing Waste Forms and Thermophysical Properties

Abstract

Technetium-99 (Tc, t 1/2 = 2.13x10 5 years) is a challenge from a nuclear waste perspective and is one of the most abundant, long-lived radioisotopes found in used nuclear fuel (UNF). Within the Hanford Tank Waste Treatment and Immobilization Plant, technetium volatilizes at typical glass melting temperature, is captured in the off-gas treatment system and recycled back into the feed to eventually increase Tc-loadings of the glass. The aim of this NEUP project was to provide an alternative strategy to immobilize fission technetium as durable ceramic waste form and also to avoid the accumulation of volatile technetium within the off gas melter system in the course of vitrifying radioactive effluents in a ceramic melter. During this project our major attention was turned to the fabrication of chemical durable mineral phases where technetium is structurally bond entirely as tetravalent cation. These mineral phases will act as the primary waste form with optimal waste loading and superior resistance against leaching and corrosion. We have been very successful in fabricating phase-pure micro-gram amounts of lanthanide-technetium pyrochlores by dry-chemical synthesis. However, upscaling to a gram-size synthesis route using either dry- or wet-chemical processing was not always successful, but progress can be reported on amore » variety of aspects. During the course of this 5-year NEUP project (including a 2-year no-cost extension) we have significantly enhanced the existing knowledge on the fabrication and properties of ceramic technetium waste forms.« less

Authors:
 [1]
  1. Univ. of Nevada, Las Vegas, NV (United States). Dept. of Mechanical Engineering
Publication Date:
Research Org.:
Battelle Energy Alliance, LLC, Idaho Falls, ID (United States)
Sponsoring Org.:
USDOE Office of Nuclear Energy (NE)
OSTI Identifier:
1416358
Report Number(s):
12-3445
12-3445
DOE Contract Number:
AC07-05ID14517
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English

Citation Formats

Hartmann, Thomas. Thermodynamic and Microstructural Mechanisms in the Corrosion of Advanced Ceramic Tc-bearing Waste Forms and Thermophysical Properties. United States: N. p., 2017. Web. doi:10.2172/1416358.
Hartmann, Thomas. Thermodynamic and Microstructural Mechanisms in the Corrosion of Advanced Ceramic Tc-bearing Waste Forms and Thermophysical Properties. United States. doi:10.2172/1416358.
Hartmann, Thomas. 2017. "Thermodynamic and Microstructural Mechanisms in the Corrosion of Advanced Ceramic Tc-bearing Waste Forms and Thermophysical Properties". United States. doi:10.2172/1416358. https://www.osti.gov/servlets/purl/1416358.
@article{osti_1416358,
title = {Thermodynamic and Microstructural Mechanisms in the Corrosion of Advanced Ceramic Tc-bearing Waste Forms and Thermophysical Properties},
author = {Hartmann, Thomas},
abstractNote = {Technetium-99 (Tc, t1/2 = 2.13x105 years) is a challenge from a nuclear waste perspective and is one of the most abundant, long-lived radioisotopes found in used nuclear fuel (UNF). Within the Hanford Tank Waste Treatment and Immobilization Plant, technetium volatilizes at typical glass melting temperature, is captured in the off-gas treatment system and recycled back into the feed to eventually increase Tc-loadings of the glass. The aim of this NEUP project was to provide an alternative strategy to immobilize fission technetium as durable ceramic waste form and also to avoid the accumulation of volatile technetium within the off gas melter system in the course of vitrifying radioactive effluents in a ceramic melter. During this project our major attention was turned to the fabrication of chemical durable mineral phases where technetium is structurally bond entirely as tetravalent cation. These mineral phases will act as the primary waste form with optimal waste loading and superior resistance against leaching and corrosion. We have been very successful in fabricating phase-pure micro-gram amounts of lanthanide-technetium pyrochlores by dry-chemical synthesis. However, upscaling to a gram-size synthesis route using either dry- or wet-chemical processing was not always successful, but progress can be reported on a variety of aspects. During the course of this 5-year NEUP project (including a 2-year no-cost extension) we have significantly enhanced the existing knowledge on the fabrication and properties of ceramic technetium waste forms.},
doi = {10.2172/1416358},
journal = {},
number = ,
volume = ,
place = {United States},
year = 2017,
month = 9
}

Technical Report:

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  • A multi-phase ceramic waste form is being developed at the Savannah River National Laboratory (SRNL) for treatment of secondary waste streams generated by reprocessing commercial spent nuclear. The envisioned waste stream contains a mixture of transition, alkali, alkaline earth, and lanthanide metals. Ceramic waste forms are tailored (engineered) to incorporate waste components as part of their crystal structure based on knowledge from naturally found minerals containing radioactive and non-radioactive species similar to the radionuclides of concern in wastes from fuel reprocessing. The ability to tailor ceramics to mimic naturally occurring crystals substantiates the long term stability of such crystals (ceramics)more » over geologic timescales of interest for nuclear waste immobilization [1]. A durable multi-phase ceramic waste form tailored to incorporate all the waste components has the potential to broaden the available disposal options and thus minimize the storage and disposal costs associated with aqueous reprocessing. This report summarizes results from three years of work on the IAEA Coordinated Research Project on “Processing technologies for high level waste, formulation of matrices and characterization of waste forms” (T21027), and specific task “Melt Processed Crystalline Ceramic Waste Forms for Advanced Nuclear Fuel Cycles” (17208).« less
  • A multi-phase ceramic waste form is being developed at the Savannah River National Laboratory (SRNL) for treatment of secondary waste streams generated by reprocessing commercial spent nuclear. The envisioned waste stream contains a mixture of transition, alkali, alkaline earth, and lanthanide metals. Ceramic waste forms are tailored (engineered) to incorporate waste components as part of their crystal structure based on knowledge from naturally found minerals containing radioactive and non-radioactive species similar to the radionuclides of concern in wastes from fuel reprocessing. The ability to tailor ceramics to mimic naturally occurring crystals substantiates the long term stability of such crystals (ceramics)more » over geologic timescales of interest for nuclear waste immobilization [1]. A durable multi-phase ceramic waste form tailored to incorporate all the waste components has the potential to broaden the available disposal options and thus minimize the storage and disposal costs associated with aqueous reprocessing. This report summarizes results from three years of work on the IAEA Coordinated Research Project on “Processing technologies for high level waste, formulation of matrices and characterization of waste forms” (T21027), and specific task “Melt Processed Crystalline Ceramic Waste Forms for Advanced Nuclear Fuel Cycles” (17208).« less
  • This report describes the scientific basis underlying the approach being followed to design and develop “advanced” glass-bonded sodalite ceramic waste form (ACWF) materials that can (1) accommodate higher salt waste loadings than the waste form developed in the 1990s for EBR-II waste salt and (2) provide greater flexibility for immobilizing extreme waste salt compositions. This is accomplished by using a binder glass having a much higher Na 2O content than glass compositions used previously to provide enough Na+ to react with all of the Cl– in the waste salt and generate the maximum amount of sodalite. The phase compositions andmore » degradation behaviors of prototype ACWF products that were made using five new binder glass formulations and with 11-14 mass% representative LiCl/KCl-based salt waste were evaluated and compared with results of similar tests run with CWF products made using the original binder glass with 8 mass% of the same salt to demonstrate the approach and select a composition for further studies. About twice the amount of sodalite was generated in all ACWF materials and the microstructures and degradation behaviors confirmed our understanding of the reactions occurring during waste form production and the efficacy of the approach. However, the porosities of the resulting ACWF materials were higher than is desired. These results indicate the capacity of these ACWF waste forms to accommodate LiCl/KCl-based salt wastes becomes limited by porosity due to the low glass-to-sodalite volume ratio. Three of the new binder glass compositions were acceptable and there is no benefit to further increasing the Na content as initially planned. Instead, further studies are needed to develop and evaluate alternative production methods to decrease the porosity, such as by increasing the amount of binder glass in the formulation or by processing waste forms in a hot isostatic press. Increasing the amount of binder glass to eliminate porosity will decrease the waste loading from about 12% to 10% on a mass basis, but this will not significantly impact the waste loading on a volume basis. It is likely that heat output will limit the amount of waste salt that can be accommodated in a waste canister rather than the salt loading in an ACWF, and that the increase from 8 mass% to about 10 mass% salt loadings in ACWF materials will be sufficient to optimize these waste forms. Although the waste salt composition used in this study contained a moderate amount of NaCl, the test results suggest waste salts with little or no NaCl can be accommodated in ACWF materials by using the new binder glass, albeit at waste loadings lower than 8 mass%. The higher glass contents that will be required for ACWF materials made with salt wastes that do not contain NaCl are expected to result in much lower porosities in those waste forms.« less
  • Tests were conducted with ceramic waste form (CWF) materials that contained small amounts of uranium and plutonium to study their release behavior as the CWF corroded. Materials made using the hot isostatic press (HIP) and pressureless consolidation (PC) methods were examined and tested. Four different materials were made using the HIP method with two salts having different U:Pu mole ratios and two zeolite reagents having different residual water contents. Tests with the four HIP U,Pu-loaded CWF materials were conducted at 90 and 120 C, at CWF-to-water mass ratios of 1:10 and 1:20, and for durations between 7 and 365 days.more » Materials made using two PC processing conditions were also tested. Tests with the two PC U,Pu-loaded CWF materials were conducted at 90 and 120 C, at a CWF-to-water mass ratio of 1:10, and for durations between 7 and 182 days. The releases of matrix elements, U, and Pu in tests conducted under different test conditions and with different materials are compared to evaluate the effects of composition and processing conditions on the release behavior of U and Pu and the chemical durabilities of the different materials. The distributions of released elements among the fractions that were dissolved, in colloidal form in the solution, and fixed to test vessel walls were measured and compared. Characterization of Pu-bearing colloidal particles recovered from the test solutions using solids analysis techniques are also reported. The principal findings from this study are: (1) The release of U and Pu is about 10X less than the release of Si and 50X less than the release of B under all test conditions. This implies that U and Pu are in a phase that is less soluble than the sodalite and binder glass matrix. (2) Almost all of the plutonium that is released from U,Pu-loaded CWF is present either as colloidal-sized particles in the size range between 5 and 100 nm in the test solution (about 15% of the total) or becomes fixed on stainless steel test vessel walls (about 85% of the total). Work is in progress to determine the nature of the material fixed to the steel. (3) The Pu in the colloidal particles is present as the dioxide PuO{sub 2} or a mixed oxide (U,Pu)O{sub 2}. These particles are of dimensions and composition similar to the (U,Pu)O{sub 2} particles that are present as inclusions in the CWF. They are often found associated with larger (100-nm size) aluminosilicate colloids. (4) The degradation behaviors of U,Pu-loaded CWF processed by HIP and PC are the same with regard to the release of Si, U, and Pu. One difference is that B is released faster from the HIP CWF materials than from the PC CWF materials. (5) The presence of U and Pu does not affect the durability of CWF materials.« less