REFINEMENT OF THE NEPHELINE DISCRIMINATOR: RESULTS OF A PHASE I STUDY

The performance of a glass used for immobilization of high-level nuclear waste (HLW) is generally quantified by its resistance to chemical degradation, or durability. The durability of a HLW glass is dependent on its composition. If crystalline phases form within a glass during cooling, the composition of the residual glass network is altered, therefore affecting the durability of the glass. Crystallization of nepheline (NaAlSiO{sub 4}) has been shown to adversely impact the durability of HLW glasses since it removes glass forming species (in this case, Al and Si) from the glass network. The propensity for nepheline crystallization in a HLW glass increases with increasing concentrations of Al{sub 2}O{sub 3} and Na{sub 2}O in the glass. Nepheline crystallization is therefore of concern for processing of HLW at the Defense Waste Processing Facility (DWPF) since the sludge waste streams at the Savannah River Site (SRS) can contain high concentrations of Al{sub 2}O{sub 3} and Na{sub 2}O. Currently, a 'nepheline discriminator' is included as a process control constraint at the DWPF. The nepheline discriminator relates the concentrations of SiO{sub 2}, Na{sub 2}O and Al{sub 2}O{sub 3} (as weight percentages in glass) to a critical value of 0.62. The discriminator defines a boundary line on the SiO{sub 2}-Na{sub 2}O-Al{sub 2}O{sub 3} ternary diagram above which (or toward the SiO{sub 2} corner of the ternary) nepheline is not predicted to crystallize in the glass upon quenching or slow cooling. The current equation uses only the concentrations of the SiO{sub 2}, Na{sub 2}O and Al{sub 2}O{sub 3} components in the glass in predicting whether or not nepheline is likely to crystallize. However, several other components have been shown to impact the propensity for nepheline crystallization, including B{sub 2}O{sub 3} and CaO among others. Therefore, the potential exists to further refine the nepheline discriminator to include these components. In addition, recently studied HLW glasses with relatively high Al{sub 2}O{sub 3} compositions of 25 wt % or greater and nepheline discriminator values well below 0.62 have been shown to be free of nepheline crystallization upon quenching and slow cooling. Thus, the current nepheline discriminator equation also appears to be conservative for some HLW glass compositions. Refining the nepheline discriminator to include other important components and to reduce conservatism may provide access to high Al{sub 2}O{sub 3} concentration glass compositions for the DWPF, which could in turn allow access to higher waste loadings, decreased washing and improved waste throughput. The objective of this study was to develop and characterize a series of HLW glass compositions based on a projected composition of Sludge Batch 5 (SB5), the next sludge batch to be processed in the DWPF. The selected glass compositions all had nepheline discriminator values below the current limit of 0.62. They cover a range of locations on the SiO{sub 2}-Na{sub 2}O-Al{sub 2}O{sub 3} diagram. They also include varying amounts of B{sub 2}O{sub 3} and CaO to support an evaluation of the impact of these components on the propensity for nepheline crystallization. The results described in this report confirm that some conservatism exists in the current nepheline discriminator. Several glass compositions, particularly compositions that target higher Al{sub 2}O{sub 3} concentrations, were shown to be very durable (i.e., PCT responses that were more than an order of magnitude better than that of the Environmental Assessment benchmark glass) while their nepheline discriminator values were well below the current nepheline discriminator limit of 0.62. Increased concentrations of B{sub 2}O{sub 3} and increased concentrations of CaO were shown to improve durability responses and suppress the formation of nepheline. This provides incentive to revise the nepheline discriminator to reduce some of this conservatism and incorporate the influence of B{sub 2}O{sub 3}. The revised nepheline discriminator could potentially change from a constant line on the SiO{sub 2}-Na{sub 2}O-Al{sub 2}O{sub 3} ternary diagram to a sloped line, where the slope varies with B{sub 2}O{sub 3} concentration, thus allowing access to higher concentrations of Al{sub 2}O{sub 3} in glass. Additional data will be required to support development and possible implementation of this revision. A Phase II study will be required to provide the necessary data, and recommendations for a Phase II study are included at the end of this report