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Published: 2015

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The Savannah River Site Defense Waste Processing Facility (DWPF) melter was recently idled with glass remaining in the melt pool and riser for approximately three months. This situation presented a unique opportunity to collect and analyze glass samples since outages of this duration are uncommon. The objective of this study was to obtain insight into the potential for crystal formation in the glass resulting from an extended idling period. The results will be used to support development of a crystal-tolerant approach for operation of the high level waste melter at the Hanford Tank Waste Treatment and Immobilization Plant (WTP). Two glass pour stream samples were collected from DWPF when the melter was restarted after idling for three months. The samples did not contain crystallization that was detectible by X-ray diffraction. Electron microscopy identified occasional spinel and noble metal crystals of no practical significance. Occasional platinum particles were observed by microscopy as an artifact of the sample collection method. Reduction/oxidation measurements showed that the pour stream glasses were fully oxidized, which was expected after the extended idling period. Chemical analysis of the pour stream glasses revealed slight differences in the concentrations of some oxides relative to analyses of the melter feed composition prior to the idling period. While these differences may be within the analytical error of the laboratories, the trends indicate that there may have been some amount of volatility associated with some of the glass components, and that there may have been interaction of the glass with the refractory components of the melter. These changes in composition, although small, can be attributed to the idling of the melter for an extended period. The changes in glass composition resulted in a 70-100 °C increase in the predicted spinel liquidus temperature (TL) for the pour stream glass samples relative to the analysis of the melter feed prior to the outage. This indicates that the potential for spinel crystallization increased as a result of idling for an extended period. However, the predicted TL of the pour stream glasses remained 150-200 °C below the mean melt pool temperature of about 1125 °C during the idling period. Given the change in predicted TL over the three month outage, the results indicate that it is important to have a thorough understanding of spinel crystallization within the melter for WTP to operate with a volume percent crystallization constraint. This knowledge will enable process control routines to be developed that avoid bulk crystallization in the melter and allow for recovery from off-normal events. The current WTP crystal-tolerant glass program will develop an improved understanding of spinel crystallization in the WTP melter to allow for operation at maximum waste loading in glass composition systems limited by predictions of spinel crystallization.