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Title: Glass Macrocracking Determination in Prototypic Canisters Containing Lanthanide Borosilicate Glass

Authors:
Publication Date:
Research Org.:
SRS
Sponsoring Org.:
USDOE
OSTI Identifier:
882729
Report Number(s):
WSRC-TR-2006-00015
DOE Contract Number:
DE-AC09-96SR1850
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English

Citation Formats

JONES, TIMOTHY. Glass Macrocracking Determination in Prototypic Canisters Containing Lanthanide Borosilicate Glass. United States: N. p., 2006. Web. doi:10.2172/882729.
JONES, TIMOTHY. Glass Macrocracking Determination in Prototypic Canisters Containing Lanthanide Borosilicate Glass. United States. doi:10.2172/882729.
JONES, TIMOTHY. Thu . "Glass Macrocracking Determination in Prototypic Canisters Containing Lanthanide Borosilicate Glass". United States. doi:10.2172/882729. https://www.osti.gov/servlets/purl/882729.
@article{osti_882729,
title = {Glass Macrocracking Determination in Prototypic Canisters Containing Lanthanide Borosilicate Glass},
author = {JONES, TIMOTHY},
abstractNote = {},
doi = {10.2172/882729},
journal = {},
number = ,
volume = ,
place = {United States},
year = {Thu Jan 19 00:00:00 EST 2006},
month = {Thu Jan 19 00:00:00 EST 2006}
}

Technical Report:

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  • A ternary diagram showing the homogeneous glass processing region of a base frit, rare earth oxide and thorium oxide has been developed for a residence temperature of 1475 C. Thorium oxide was used as a plutonium surrogate. All ThO2 glasses that were processed included a 1:1 mole ratio of Th to Gd. Gadolinium is added to the glass as a neutron absorber. Forty individual glass compositions were melted at 1475 C for 4 to 6 hours with periodic stirring. Two glasses (B-20-25 and B-25-25) were processed with a ThO2 loading of 25 weight percent (oxide) without amorphous phase separation ormore » crystalline species detected by X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM) or Transmission Electron Microscopy (TEM). These were processed with 55 weight percent frit, 20 weight percent rare earth oxides and 50 percent frit, 25 percent rare earth oxides. Crystalline species that formed outside of the homogeneous glass processing region due to solubility limits or insufficient processing temperature were identified. Amorphous phase separation was detected and examined by TEM at high ThO2 loadings (20 to 30 weight percent oxide). The base frit was able to dissolve up to 65 weight percent rare earth oxides when thorium oxide was not present. Durability testing will be performed on three glasses from three different regions of the homogeneous glass processing region. Product Consistency Test (PCT) results are pending and will be added to this document under a future revision.« less
  • A prototype lanthanide borosilicate (LaBS) glass containing 10 mass % plutonium was reacted with water vapor at 200 C for periods of 14 to 56 days. These tests, while not designed to replicate specific conditions that may be found in a potential geologic repository (e.g., Yucca Mountain), have been shown to accelerate alteration phase formation. The surfaces of the glass samples, along with alteration phases, were examined with a transmission electron microscope (TEM). Tests of 14 days produced macroscopic ({approximately} 20 {micro}m) crystallites of a plutonium-lanthanide silicate. An extensive alteration layer was found on the glass surface containing amorphous aluminosilicatemore » layered with bands of a cryptocrystalline plutonium silicate. After 56 days of testing, additional alteration phases were formed, including a strontium lanthanide oxide phase. One of the options for disposal of surplus plutonium, particularly for impure residues that may be unfit for production of MOX fuel, is vitrification followed by geologic disposal. Since geologic disposal requires a passive system to isolate the radiotoxic elements from the biosphere, it is important to understand the possible corrosion mechanisms of the waste form.« less
  • The Department of Energy Office of Environmental Management (DOE/EM) plans to conduct the Plutonium Disposition Project at the Savannah River Site (SRS) to disposition excess weapons-usable plutonium. A plutonium glass waste form is the preferred option for immobilization of the plutonium for subsequent disposition in a geologic repository. A reference glass composition (Lanthanide Borosilicate (LaBS) Frit B) was developed during the Plutonium Immobilization Program (PIP) to immobilize plutonium in the late 1990's. A limited amount of performance testing was performed on this baseline composition before efforts to further pursue Pu disposition via a glass waste form ceased. Recent FY05 studiesmore » have further investigated the LaBS Frit B formulation as well as development of a newer LaBS formulation denoted as LaBS Frit X. The objectives of this present task were to fabricate plutonium loaded LaBS Frit X glass and perform corrosion testing to provide near-term data that will increase confidence that LaBS glass product is suitable for disposal in the Yucca Mountain Repository. Specifically, testing was conducted in an effort to provide data to Yucca Mountain Project (YMP) personnel for use in performance assessment calculations. Plutonium containing LaBS glass with the Frit X composition with a 9.5 wt% PuO{sub 2} loading was prepared for testing. Glass was prepared to support Product Consistency Testing (PCT) at Savannah River National Laboratory (SRNL). The glass was thoroughly characterized using x-ray diffraction (XRD) and scanning electron microscopy coupled with energy dispersive spectroscopy (SEM/EDS) prior to performance testing. A series of PCTs were conducted at SRNL using quenched Pu Frit X glass with varying exposed surface areas. Effects of isothermal and can-in-canister heat treatments on the Pu Frit X glass were also investigated. Another series of PCTs were performed on these different heat-treated Pu Frit X glasses. Leachates from all these PCTs were analyzed to determine the dissolved concentrations of key elements. Acid stripping of leach vessels was performed to determine the concentration of the glass constituents that may have sorbed on the vessels during leach testing. Additionally, the leachate solutions were ultrafiltered to quantify colloid formation.« less
  • The Department of Energy Office of Environmental Management (DOE/EM) plans to conduct the Plutonium Disposition Project at the Savannah River Site (SRS) to disposition excess weapons-usable plutonium. A plutonium glass waste form is a leading candidate for immobilization of the plutonium for subsequent disposition in a geologic repository. A reference glass composition (Lanthanide Borosilicate (LaBS) Frit B) was developed during the Plutonium Immobilization Program (PIP) to immobilize plutonium. A limited amount of performance testing was performed on this baseline composition before efforts to further pursue Pu disposition via a glass waste form ceased. Therefore, the objectives of this present taskmore » were to fabricate plutonium loaded LaBS Frit B glass and perform additional testing to provide near-term data that will increase confidence that LaBS glass product is suitable for disposal in the Yucca Mountain Repository. Specifically, testing was conducted in an effort to provide data to Yucca Mountain Project (YMP) personnel for use in performance assessment calculations. Plutonium containing LaBS glass with the Frit B composition with a 9.5 wt% PuO{sub 2} loading was prepared for testing. Glass was prepared to support Product Consistency Testing (PCT) at Savannah River National Laboratory (SRNL) and for additional performance testing at Argonne National Laboratory (ANL) and Pacific Northwest National Laboratory (PNNL). The glass was characterized using x-ray diffraction (XRD) and scanning electron microscopy coupled with energy dispersive spectroscopy (SEM/EDS) prior to performance testing. A series of PCTs were conducted at SRNL with varying exposed surface area and test durations. The leachates from these tests were analyzed to determine the dissolved concentrations of key elements. Acid stripping of leach vessels was performed to determine the concentration of the glass constituents that may have sorbed on the vessels during leach testing. Additionally, the leachate solutions were ultrafiltered to quantify colloid formation. The leached solids from select PCTs were examined in an attempt to evaluate the Pu and neutron absorber release behavior from the glass and to identify the formation of alteration phases on the glass surface. Characterization of the glass prior to testing revealed that some undissolved plutonium oxide was present in the glass. The undissolved particles had a disk-like morphology and likely formed via coarsening of particles in areas compositionally enriched in plutonium. Similar disk-like PuO{sub 2} phases were observed in previous LaBS glass testing at PNNL. In that work, researchers concluded that plutonium formed with this morphology as a result of the leaching process. It was more likely that the presence of the plutonium oxide crystals in the PNNL testing was a result of glass fabrication. A series of PCTs were conducted at 90 C in ASTM Type 1 water. The PCT-Method A (PCT-A) was conducted to compare the Pu LaBS Frit B glass durability to current requirements for High Level Waste (HLW) glass in a geologic repository. The PCT-A test has a strict protocol and is designed to specifically be used to evaluate whether the chemical durability and elemental release characteristics of a nuclear waste glass have been consistently controlled during production and, thus, meet the repository acceptance requirements. The PCT-A results on the Pu containing LaBS Frit B glass showed that the glass was very durable with a normalized elemental release value for boron of approximately 0.02 g/L. This boron release value was better than two orders of magnitude better from a boron release standpoint than the current Environmental Assessment (EA) glass used for repository acceptance. The boron release value for EA glass is 16.7 g/L.« less
  • This study focuses on the development of a compositional envelope that describes the retention of various impurities in lanthanide borosilicate (LaBS) glass for vitrification and immobilization of excess, defense-related plutonium. A limited amount of impurity data for the various plutonium sources is available and projections were made through analysis of the available information. These projections were used to define types and concentrations of impurities in the LaBS glass compositions to be fabricated and tested. Sixty surrogate glass compositions were developed through a statistically designed approach to cover the anticipated ranges of concentrations for several impurity species expected in the plutoniummore » feeds. An additional four glass compositions containing actual plutonium oxide were selected based on their targeted concentrations of metals and anions. The glasses were fabricated and characterized in the laboratory and shielded cells facility to determine the degree of retention of the impurity components, the impact of the impurities on the durability of each glass, and the degree of crystallization that occurred, both upon quenching and slow cooling. Overall, the LaBS glass system appears to be very tolerant of most of the impurity types and concentrations projected in the plutonium waste stream. For the surrogate glasses, the measured CuO, Ga{sub 2}O{sub 3}, Na{sub 2}O, NiO, and Ta{sub 2}O{sub 5} concentrations fell very close to their target values across the ranges of concentrations targeted in this study for each of these components. The measured CaO and PbO concentrations were consistently higher than the targeted values. The measured Cr{sub 2}O{sub 3} and Fe{sub 2}O{sub 3} concentrations were very close to the targets except for the one highest targeted value for each of these components. A solubility limit may have been approached in this glass system for K{sub 2}O and MgO. The measured Cl{sup -}, F{sup -}, SeO{sub 2} and SO{sub 4}{sup 2-} concentrations were well below their target values for all of the study glasses. This is likely due to volatilization of these species during melting of the glass batch. Note that the degree of volatilization that occurred in this crucible-scale study may differ from the full-scale melter. The measured HfO{sub 2} concentrations were below their target values for all of the surrogate glasses. It is likely that for HfO{sub 2}, the solubility limit in the glass was exceeded and some of the HfO{sub 2} batch material remained in the bottom of the crucibles after pouring the glasses. X-ray diffraction and scanning electron microscopy (SEM) results indicated that some crystalline HfO2 remained in some of the surrogate glasses with the lowest concentration of impurities. No other crystalline phases were identified. The Product Consistency Test (PCT) results showed that all 60 of the surrogate glass compositions tested were very durable, regardless of thermal history, with the highest normalized release for boron being 0.041 g/L. The pH of the leachate solutions was generally lower than that of conventional waste glasses due to the lack of alkali in the LaBS glass, which likely impacted the PCT results. The normalized release rates for the elements measured were generally too small to attempt to correlate the results with the compositions of the test glasses. The Toxicity Characteristic Leaching Procedure results showed that no hazardous metals were leached from the surrogate glasses in any measurable concentration. A plutonium-containing crystalline phase with a cross-shaped morphology was identified via SEM in the glasses fabricated with plutonium oxide. This phase was identified in a previous study of plutonium-bearing LaBS glasses and may provide an opportunity to intentionally crystallize some of the plutonium oxide into a highly insoluble form with an intrinsic neutron absorber. Additional work is necessary to better characterize the influence that this phase has on durability of the glass. The PCT results for the plutonium-containing LaBS glasses with impurities were similar to previous tests conducted on PuO{sub 2}-containing glasses without impurities added. The highest normalized release for boron was 0.02 g/L, which bounded the highest normalized release for plutonium of 0.01 g/L.« less