VARIABILITY STUDY TO DETERMINE THE SOLUBILITY OF IMPURITIES IN PLUTONIUM-BEARING, LANTHANIDE BOROSILICATE GLASS

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 plutonium 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