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Title: Summary Report: Glass-Ceramic Waste Forms for Combined Fission Products

Abstract

Glass-ceramic waste form development began in FY 2010 examining two combined waste stream options: (1) alkaline earth (CS) + lanthanide (Ln), and (2) + transition metal (TM) fission-product waste streams generated by the uranium extraction (UREX+) separations process. Glass-ceramics were successfully developed for both options however; Option 2 was selected over Option 1, at the conclusion of 2010, because Option 2 immobilized all three waste streams with only a minimal decrease in waste loading. During the first year, a series of three glass (Option 2) were fabricated that varied waste loading-WL (42, 45, and 50 mass%) at fixed molar ratios of CaO/MoO{sub 3} and B{sub 2}O{sub 3}/alkali both at 1.75. These glass-ceramics were slow cooled and characterized in terms of phase assemblage and preliminary irradiation stability. This fiscal year, further characterization was performed on the FY 2010 Option 2 glass-ceramics in terms of: static leach testing, phase analysis by transmission electron microscopy (TEM), and irradiation stability (electron and ion). Also, a new series of glass-ceramics were developed for Option 2 that varied the additives: Al{sub 2}O{sub 3} (0-6 mass%), molar ratio of CaO/MoO{sub 3} and B{sub 2}O{sub 3}/alkali (1.75 to 2.25) and waste loading (50, 55, and 60 mass%). Lastly,more » phase pure powellite and oxyapatite were synthesized for irradiation studies. Results of this fiscal year studies showed compositional flexibility, chemical stability, and radiation stability in the current glass-ceramic system. First, the phase assemblages and microstructure of all of the FY 2010 and 2011 glass-ceramics are very similar once subjected to the slow cool heat treatment. The phases identified in these glass-ceramics were oxyapatite, powellite, cerianite, and ln-borosilicate. This shows that variations in waste loading or additives can be accommodated without drastically changing the phase assemblage of the waste form, thus making the processing and performance characteristics of the waste form more predictable/flexible. However, in the future, the glass phase still needs to be accurately characterized to determine the effects of waste loading and additives on the glass structure. Initial investigations show a borosilicate glass phase rich in silica. Second, the normalized concentrations of elements leached from the waste form during static leach testing were all below 0.6 g/L after 28d at 90 C, by the Product Consistency Test (PCT), method B. These normalized concentrations are on par with durable waste glasses such as the Low-Activity Reference Material (LRM) glass. The release rates for the crystalline phases (oxyapatite and powellite) appear to be lower (more durable) than the glass phase based on the relatively low release rates of Mo, Ca, and Ln found in the crystalline phases compared to Na and B that are mainly observed in the glass phase. However, further static leach testing on individual crystalline phases is needed to confirm this statement. Third, Ion irradiation and In situ TEM observations suggest that these crystalline phases (such as oxyapatite, ln-borosilicate, and powellite) in silicate based glass ceramic waste forms exhibit stability to 1000 years at anticipated doses (2 x 10{sup 10}-2 x 10{sup 11} Gy). This is adequate for the short lived isotopes in the waste, which lead to a maximum cumulative dose of {approx}7 x 10{sup 9} Gy, reached after {approx}100 yrs, beyond which the dose contributions are negligible. The cumulate dose calculations are based on a glass-ceramic at WL = 50 mass%, where the fuel has a burn-up of 51GWd/MTIHM, immobilized after 5 yr decay from reactor discharge.« less

Authors:
; ; ; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1031436
Report Number(s):
PNNL-20749
AF5805000; TRN: US1200111
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS; 12 MANAGEMENT OF RADIOACTIVE WASTES, AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES; ADDITIVES; BOROSILICATE GLASS; CERAMICS; DECAY; FISSION PRODUCTS; FLEXIBILITY; GLASS; HEAT TREATMENTS; IRRADIATION; MICROSTRUCTURE; OXIDE MINERALS; RADIATIONS; RARE EARTHS; SILICA; SILICATES; STABILITY; TESTING; THORIUM MINERALS; TRANSITION ELEMENTS; TRANSMISSION ELECTRON MICROSCOPY; URANIUM; WASTE FORMS; WASTES; Glass-ceramic; waste form; nulear waste

Citation Formats

Crum, Jarrod V., Riley, Brian J., Turo, Laura A., Tang, Ming, and Kossoy, Anna. Summary Report: Glass-Ceramic Waste Forms for Combined Fission Products. United States: N. p., 2011. Web. doi:10.2172/1031436.
Crum, Jarrod V., Riley, Brian J., Turo, Laura A., Tang, Ming, & Kossoy, Anna. Summary Report: Glass-Ceramic Waste Forms for Combined Fission Products. United States. doi:10.2172/1031436.
Crum, Jarrod V., Riley, Brian J., Turo, Laura A., Tang, Ming, and Kossoy, Anna. Fri . "Summary Report: Glass-Ceramic Waste Forms for Combined Fission Products". United States. doi:10.2172/1031436. https://www.osti.gov/servlets/purl/1031436.
@article{osti_1031436,
title = {Summary Report: Glass-Ceramic Waste Forms for Combined Fission Products},
author = {Crum, Jarrod V. and Riley, Brian J. and Turo, Laura A. and Tang, Ming and Kossoy, Anna},
abstractNote = {Glass-ceramic waste form development began in FY 2010 examining two combined waste stream options: (1) alkaline earth (CS) + lanthanide (Ln), and (2) + transition metal (TM) fission-product waste streams generated by the uranium extraction (UREX+) separations process. Glass-ceramics were successfully developed for both options however; Option 2 was selected over Option 1, at the conclusion of 2010, because Option 2 immobilized all three waste streams with only a minimal decrease in waste loading. During the first year, a series of three glass (Option 2) were fabricated that varied waste loading-WL (42, 45, and 50 mass%) at fixed molar ratios of CaO/MoO{sub 3} and B{sub 2}O{sub 3}/alkali both at 1.75. These glass-ceramics were slow cooled and characterized in terms of phase assemblage and preliminary irradiation stability. This fiscal year, further characterization was performed on the FY 2010 Option 2 glass-ceramics in terms of: static leach testing, phase analysis by transmission electron microscopy (TEM), and irradiation stability (electron and ion). Also, a new series of glass-ceramics were developed for Option 2 that varied the additives: Al{sub 2}O{sub 3} (0-6 mass%), molar ratio of CaO/MoO{sub 3} and B{sub 2}O{sub 3}/alkali (1.75 to 2.25) and waste loading (50, 55, and 60 mass%). Lastly, phase pure powellite and oxyapatite were synthesized for irradiation studies. Results of this fiscal year studies showed compositional flexibility, chemical stability, and radiation stability in the current glass-ceramic system. First, the phase assemblages and microstructure of all of the FY 2010 and 2011 glass-ceramics are very similar once subjected to the slow cool heat treatment. The phases identified in these glass-ceramics were oxyapatite, powellite, cerianite, and ln-borosilicate. This shows that variations in waste loading or additives can be accommodated without drastically changing the phase assemblage of the waste form, thus making the processing and performance characteristics of the waste form more predictable/flexible. However, in the future, the glass phase still needs to be accurately characterized to determine the effects of waste loading and additives on the glass structure. Initial investigations show a borosilicate glass phase rich in silica. Second, the normalized concentrations of elements leached from the waste form during static leach testing were all below 0.6 g/L after 28d at 90 C, by the Product Consistency Test (PCT), method B. These normalized concentrations are on par with durable waste glasses such as the Low-Activity Reference Material (LRM) glass. The release rates for the crystalline phases (oxyapatite and powellite) appear to be lower (more durable) than the glass phase based on the relatively low release rates of Mo, Ca, and Ln found in the crystalline phases compared to Na and B that are mainly observed in the glass phase. However, further static leach testing on individual crystalline phases is needed to confirm this statement. Third, Ion irradiation and In situ TEM observations suggest that these crystalline phases (such as oxyapatite, ln-borosilicate, and powellite) in silicate based glass ceramic waste forms exhibit stability to 1000 years at anticipated doses (2 x 10{sup 10}-2 x 10{sup 11} Gy). This is adequate for the short lived isotopes in the waste, which lead to a maximum cumulative dose of {approx}7 x 10{sup 9} Gy, reached after {approx}100 yrs, beyond which the dose contributions are negligible. The cumulate dose calculations are based on a glass-ceramic at WL = 50 mass%, where the fuel has a burn-up of 51GWd/MTIHM, immobilized after 5 yr decay from reactor discharge.},
doi = {10.2172/1031436},
journal = {},
number = ,
volume = ,
place = {United States},
year = {2011},
month = {9}
}

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