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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. Fri . "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 = {Fri Sep 01 00:00:00 EDT 2017},
month = {Fri Sep 01 00:00:00 EDT 2017}
}

Technical Report:

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  • The objective of this senior student project is to design and build a prototype construction of a machine that simultaneously provides the proper pressure and temperature parameters to sinter ceramic powders in-situ to create pellets of rather high densities of above 90% (theoretical). This ROHUP (Remote Operated Hot Uniaxial Press) device is designed specifically to fabricate advanced ceramic Tc-99 bearing waste forms and therefore radiological barriers have been included in the system. The HUP features electronic control and feedback systems to set and monitor pressure, load, and temperature parameters. This device operates wirelessly via portable computer using Bluetooth{sup R} technology.more » The HUP device is designed to fit in a standard atmosphere controlled glove box to further allow sintering under inert conditions (e.g. under Ar, He, N{sub 2}). This will further allow utilizing this HUP for other potential applications, including radioactive samples, novel ceramic waste forms, advanced oxide fuels, air-sensitive samples, metallic systems, advanced powder metallurgy, diffusion experiments and more. (authors)« 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
  • 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
  • The DOE Fuel Cycle Research & Development (FCR&D) Program is developing aqueous and electrochemical approaches to the processing of used nuclear fuel that will generate technetium-bearing waste streams. This final report presents Pacific Northwest National Laboratory (PNNL) research in FY10 to evaluate an iron-based alloy waste form for Tc that provides high waste loading within waste form processing limitations, meets waste form performance requirements for durability and the long-term retention of radionuclides and can be produced with consistent physical, chemical, and radiological properties that meet regulatory acceptance requirements for disposal.