INTERNATIONAL STUDY OF ALUMINUM IMPACTS ON CRYSTALLIZATION IN U.S. HIGH LEVEL WASTE GLASS
The objective of this task was to develop glass formulations for (Department of Energy) DOE waste streams with high aluminum concentrations to avoid nepheline formation while maintaining or meeting waste loading and/or waste throughput expectations as well as satisfying critical process and product performance related constraints. Liquidus temperatures and crystallization behavior were carefully characterized to support model development for higher waste loading glasses. The experimental work, characterization, and data interpretation necessary to meet these objectives were performed among three partnering laboratories: the V.G. Khlopin Radium Institute (KRI), Pacific Northwest National Laboratory (PNNL) and Savannah River National Laboratory (SRNL). Projected glass compositional regions that bound anticipated Defense Waste Processing Facility (DWPF) and Hanford high level waste (HLW) glass regions of interest were developed and used to generate glass compositions of interest for meeting the objectives of this study. A thorough statistical analysis was employed to allow for a wide range of waste glass compositions to be examined while minimizing the number of glasses that had to be fabricated and characterized in the laboratory. The glass compositions were divided into two sets, with 45 in the test matrix investigated by the U.S. laboratories and 30 in the test matrix investigated by KRI. Fabrication and characterization of the US and KRI-series glasses were generally handled separately. This report focuses mainly on the US-series glasses. Glasses were fabricated and characterized by SRNL and PNNL. Crystalline phases were identified by X-ray diffraction (XRD) in the quenched and canister centerline cooled (CCC) glasses and were generally iron oxides and spinels, which are not expected to impact durability of the glass. Nepheline was detected in five of the glasses after the CCC heat treatment. Chemical composition measurements for each of the glasses were conducted following an analytical plan. A review of the individual oxides for each glass revealed that there were no errors in batching significant enough to impact the outcome of the study. A comparison of the measured compositions of the replicates indicated an acceptable degree of repeatability as the percent differences for most of the oxides were less than 5% and percent differences for all of the oxides were less than 10 wt%. Chemical durability was measured using the Product Consistency Test (PCT). All but two of the study glasses had normalized leachate for boron (NL [B]) values that were well below that of the Environmental Assessment (EA) reference glass. The two highest NL [B] values were for the CCC versions of glasses US-18 and US-27 (10.498 g/L and 15.962 g/L, respectively). Nepheline crystallization was identified by qualitative XRD in five of the US-series glasses. Each of these five glasses (US-18, US-26, US-27, US-37 and US-43) showed a significant increase in NL [B] values after the CCC heat treatment. This reduction in durability can be attributed to the formation of nepheline during the slow cooling cycle and the removal of glass formers from the residual glass network. The liquidus temperature (T{sub L}) of each glass in the study was determined by both optical microscopy and XRD methods. The correlation coefficient of the measured XRD TL data versus the measured optical TL data was very good (R{sup 2} = 0.9469). Aside from a few outliers, the two datasets aligned very well across the entire temperature range (829 C to 1312 C for optical data and 813 C to 1310 C for XRD crystal fraction data). The data also correlated well with the predictions of a PNNL T{sub L} model. The correlation between the measured and calculated data had a higher degree of merit for the XRD crystal fraction data than for the optical data (higher R{sup 2} value of 0.9089 versus 0.8970 for the optical data). The SEM-EDS analysis of select samples revealed the presence of undissolved RuO{sub 2} in all glasses due to the low solubility of RuO{sub 2} in borosilicate glass. These particles tended to form agglomerates with varying sizes and shapes that were located close to the bottom of crucibles. The results of this study provide further insight into the ability of borosilicate waste glass to incorporate increased (>16 wt %) concentrations of aluminum. The glass composition and properties data will be incorporated into a database of glass composition-property relationships (ComPro) to support further optimization of waste glass compositions at DOE sites.
- Research Organization:
- Savannah River Site (SRS), Aiken, SC (United States)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- DE-AC09-08SR22470
- OSTI ID:
- 938800
- Report Number(s):
- SRNS-STI-2008-00057; TRN: US0806184
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
12 MANAGEMENT OF RADIOACTIVE WASTES, AND NON-RADIOACTIVE WASTES FROM NUCLEAR FACILITIES
ALUMINIUM
CATALYTIC EFFECTS
WASTE FORMS
GLASS
CRYSTALLIZATION
HIGH-LEVEL RADIOACTIVE WASTES
RADIOACTIVE WASTE PROCESSING
CHEMICAL COMPOSITION
CHEMICAL PROPERTIES
PHYSICAL PROPERTIES
LEACHATES