TIME-TEMPERATURE-TRANSFORMATION DIAGRAMS FOR THE SLUDGE BATCH 3 - FRIT 418 GLASS SYSTEM

Abstract

As a part of the Waste Acceptance Product Specifications (WAPS) for Vitrified High-Level Waste Forms defined by the Department of Energy - Office of Environmental Management, the phase stability must be determined for each of the projected high-level waste (HLW) types at the Savannah River Site (SRS). Specifically, WAPS 1.4.1 requires the glass transition temperature (Tg) to be defined and time-temperature-transformation (TTT) diagrams to be developed. The Tg of a glass is an indicator of the approximate temperature where the supercooled liquid converts to a solid on cooling or conversely, where the solid begins to behave as a viscoelastic solid on heating. A TTT diagram identifies the crystalline phases that can form as a function of time and temperature for a given waste type or more specifically, the borosilicate glass waste form. In order to assess durability, the Product Consistency Test (PCT) was used and the durability results compared to the Environmental Assessment (EA) glass. The measurement of glass transition temperature and the development of TTT diagrams have already been performed for the seven Defense Waste Processing Facility (DWPF) projected compositions as defined in the Waste Form Compliance Plan (WCP). These measurements were performed before DWPF start-up and the results were incorporated in Volume 7 of the Waste Form Qualification Report (WQR). Additional information exists for other projected compositions, but overall these compositions did not consider some of the processing scenarios now envisioned for DWPF to accelerate throughput. Changes in DWPF processing strategy have required this WAPS specification to be revisited to ensure that the resulting phases have been bounded. Frit 418 was primarily used to process HLW Sludge Batch 3 (SB3) at 38% waste loading (WL) through the DWPF. The Savannah River National Laboratory (SRNL) fabricated a cache of glass from reagent grade oxides to simulate the SB3-Frit 418 system at a 38 wt % WL for glass transition temperature measurement and TTT diagram development. The glass transition temperature (Tg) was measured using differential scanning calorimetry (DSC) and was recorded to be 443 {+-} 3 C. Using the previous TTT diagrams as guidance, subsamples of the glass were isothermally heat treated for 0.5 to 768 hours at temperatures between 400 C to 1100 C. Each of the 56 heat treated samples, along with quenched and centerline canister cooled (CCC) treated samples, were analyzed using Xray diffraction (XRD) and the PCT. Crystallization was detected only in samples treated at 600 C for more than 192 hours, and 700, 800, and 900 C for more than 48 hours. Phases crystallized were similar in composition if not the same as those found in the previous TTT studies. Six different crystalline phases were detected, including nepheline, acmite, lithium silicate, trevorite, krinovite, and albite. Overall, phases were spinel (iron) based, lithium metasilicate, sodium aluminosilicate or sodium transition metal silicate in composition. No new crystalline families were detected. Durability, as measured by the PCT, decreased when lithium silicate or nepheline crystals were present. Only one heat treated sample had a measured PCT response exceeding the benchmark EA glass, which was a sample treated at 600 C for 768 hours. During normal processing at the DWPF these conditions would be highly unlikely to occur, even in an extreme accident scenario. In order to continue to meet the requirements of the WCP, a simplified strategy is suggested for the generation of future TTT diagrams. A strategy has been developed that would require completing two more TTT diagrams for two averaged, future, predicted waste types. By creating diagrams for the resulting glass compositions of encompassing waste types, it will give insight to the crystallization regions possible for those averages. As discussed in the report, 'Initial MAR Assessments to Access the Impact of Al-Dissolution on DWPF Operating Windows' (WSRC-STI 2007-00688), the majority of waste compositions could be grouped into two future flowsheet scenarios, with and without Al-dissolution. Compositions Cluster 2 and Cluster 4 represent these waste projections. MAR assessments were completed on the two clusters and possible frits and windows of operation were selected for each projected waste type. It is recommended that a TTT diagram be developed for the following: (1) Cluster 2 combined with Frit-510 at a 34 wt % WL; and (2) Cluster 4 combined with Frit-418 at a 38 wt % WL. Given the results of the current study showed little change in the types of crystalline phases formed after heat treatment as compared to the TTT diagrams for the WCP glasses, it is unlikely that extreme differences will occur in the TTT diagram for future waste forms, as long as extreme waste stream changes or new frit components are not introduced.