Stainless steels (SS) exhibit intergranular corrosion in hot, strong, nitric acid (HNO 3 ) solutions. The intergranular corrosion rate is infl uenced by the orientation of the microstructure, the highest rates typically being observed on plate, tube, and forging surfaces that are perpendicular to the hot-working direction. This is known as end-grain corrosion. In addition, pit-like tunnels can penetrate deeply beyond the broad front. In this study, a method is presented to deconvolute the corrosion rate obtained from the weight loss of coupons to investigate the differences in end-grain behavior for two austenitic SS, NAG (nitric acid grade) 18/10L (a Type 304L variant) and Uranus 65 (a Type 310L variant). In a corrosion simulant for dissolver liquor, the broad-front end-grain corrosion rate for the former steel was found to be ~2 mm/y, whereas for the latter it was ~1.1 mm/y. In addition, it is shown that measurement of the size and shape of drilled holes can be used to assess the effect of end grain on gross metal loss. For end-grain pits, neither of the above methods was found to be useful. Instead, sectioning or radiography is required. It was found that in the same test conditions, the maximum observed end-grain pitting rates were 7.0 mm/y for NAG 18/10L and 4.5 mm/y for Uranus 65. Uranus 65, however, showed a much smaller number of end-grain pits compared with NAG 18/10L. The cause of enhanced broad-front intergranular corrosion in the end-grain direction, as opposed to the pitting-like attack, is unknown to us.
In the UK, blended high level nuclear waste (HLW) streams from the Magnox and THORP reprocessing plants are currently vitrified using a lithium sodium borosilicate base glass frit. Laboratory and full size non-radioactive simulations (produced on the Vitrification Test Rig at Sellafield [1]) of these compositions have shown that these glasses need to be melted at circa 1050°C to obtain a reasonable viscosity for pouring. Also, at high waste loadings an alkali molybdate phase (termed “yellow phase”) can form in these glasses [e.g. 2, 3]. Vitrification flowsheets are set to avoid yellow phase formation as this phase is highly corrosive to the inconel melter in the molten state and is partially water soluble at ambient temperature and so may challenge product quality.Ca and Zn additions to the base glass frit have been found to reduce viscosity and allow melt homogeneity and pouring at lower temperatures. It was also theorised that Ca additions could increase the solubility of Mo and thus reduce the likelihood of yellow phase formation. The composition of the phase separated material in as-cast and heat treated specimens of Ca and Zn HLW glasses produced at both laboratory and full scale is examined in this work
Sellafield Ltd operates a Waste Vitrification Plant (WVP) to immobilise the arisings from the reprocessing of spent nuclear fuel. Washout of solids from the base of waste storage tanks in preparation for decommissioning is likely to produce feeds enriched in molybdenum to the WVP. Vitrification of such feeds in the borosilicate glass formulation currently used by the WVP for vitrification of reprocessing waste has been investigated to determine the maximum achievable loading of MoO3.The vitrification of molybdenum in the absence and presence of reprocessing waste was studied. A number of glasses were manufactured in the laboratory containing various waste loadings. The resultant glasses were examined both visually and under the scanning electron microscope for the presence of any phase separation. Additional aluminium was added to the glasses manufactured in the absence of reprocessing waste to improve the durability of the glass. In borosilicate glass containing 3.5 wt% Al2O3 the onset of a molybdenum phase separation was observed in glasses containing 2.6 wt% MoO3. In the presence of Magnox reprocessing waste, phase separation was observed when the product contained >3.8 wt% MoO3. Soxhlet durability testing of a selection of the glasses manufactured was carried out. The Soxhlet durability of glasses in the absence of phase separation was good.
Sellafield Ltd operates 3 vitrification lines to convert highly active concentrate liquor arising as a waste product of reprocessing operations into glass for safe interim storage in the Vitrified Product Store (VPS) prior to long term disposal. Highly Active Liquor (HAL) is stored in Highly Active Storage Tanks and transferred to WVP in batches to the liquid stock tank. It is metered in a semi-continuous batch operation to a calciner (rotating tube furnace) where it is converted into an oxide powder (calcine). Glass frit is fed at the lower end of the calciner where it discharges into an Inconel melter vessel controlled at approximately 1100 C. The glass and calcine are melted together and then poured into a container as a batch operation. After two pours the container is allowed to cool, a lid is then fitted to the container, which after further cooling is welded to the container. This container is then cleaned and transferred to the VPS. Platinoid species containing ruthenium, rhodium and palladium present in the HAL form insoluble oxide phases in the glass product. The platinoid concentration in the glass will increase with increasing waste oxide loading to an extent that settling of the platinoids in the glass may occur, leading to heel enrichment, poor melter performance and difficulty in draining the melter. The viscosity will also increase, which may require higher melter temperatures to mix and pour the molten glass and could result in enhanced corrosion of the melter. Inactive laboratory scale experiments with different glass frit formulations have been performed to determine whether product quality could be maintained with higher platinoid concentrations. Operational envelopes with existing formulations were expanded to observe laboratory trial performance and determine any changes to resulting glass qualities. Also, glasses with high waste incorporations have been produced to test process capability and to ascertain any potential phase separation or devitrification issues that could affect either the process or product performance. Physical properties of the different glass formulations were performed to measure changes in viscosity, density and the rates of settling to examine the amount of phase separation that can occur. The results have shown that ruthenium, palladium or rhodium were insoluble in the melt and were not evenly distributed throughout the glass but clustered together. These results will be used as a basis for further development work. This paper presents some findings of these experiments.
At Sellafield, the Post Operational Clean Out (POCO) of solids from the base of the highly active waste storage tanks, in preparation for decommissioning, will result in a high molybdenum stream which will be vitrified using the current Waste Vitrification Plant (WVP). In order to minimise the number of containers required for POCO, the high molybdenum feed could be co-vitrified by addition to reprocessing waste, using the borosilicate glass formulation currently utilised on WVP. Co-vitrification of high molybdenum feeds has been carried out using non-active simulants, both in the laboratory and on the Vitrification Test Rig (VTR) which is a full scale working replica of a WVP processing line.In addition, a new borosilicate glass formulation containing calcium has been developed by NNL which allows a higher incorporation of molybdenum through the formation of a durable CaMoO4 phase, after the solubility limit of molybdenum in the glass has been reached. Vitrification of the high molybdenum feed in the presence of varying quantities of reprocessing waste liquor using the new glass formulation has been carried out in the laboratory. Up to ∼10 wt% MoO3 could be incorporated without any detrimental phase separation in the product glass, but increasing the fraction of reprocessing waste was found to decrease the MoO3 incorporation. Soxhlet and static powder leach tests have been performed to assess the durability of the glass products. This paper discusses the results of the vitrification of high molybdenum feeds in the presence of reprocessing liquor in both the borosilicate glass formulation currently utilised on WVP and the modified formulation which contain calcium.
The solubility of molybdenum in borosilicate glasses is low. The UK National Nuclear Laboratory has developed a new glass formulation containing calcium and zinc for the vitrification of high molybdenum containing waste arising from the Post Operational Clean Out of the Highly Active Storage Tanks at Sellafield that will decrease the number of product containers required, reducing both production and disposal costs. The new formulation increases the quantity of molybdenum that can be vitrified through the formation of a durable CaMoO 4 phase once the solubility limit of molybdenum in the glass has been exceeded. Extensive laboratory trials confirmed the potential to increase the Mo loading significantly. Recently full scale testing has been performed on the Vitrification Test Rig using highly active liquor simulants to determine the maximum MoO 3 loading that can be achieved. This paper explores the full scale testing and product quality of the glass manufactured during this study.
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