Rheological Characterization of Unusual DWPF Slurry Samples (U)

A study was undertaken to identify and clarify examples of unusual rheological behavior in Defense Waste Processing Facility (DWPF) simulant slurry samples. Identification was accomplished by reviewing sludge, Sludge Receipt and Adjustment Tank (SRAT) product, and Slurry Mix Evaporator (SME) product simulant rheological results from the prior year. Clarification of unusual rheological behavior was achieved by developing and implementing new measurement techniques. Development of these new methods is covered in a separate report, WSRC-TR-2004-00334. This report includes a review of recent literature on unusual rheological behavior, followed by a summary of the rheological measurement results obtained on a set of unusual simulant samples. Shifts in rheological behavior of slurries as the wt. % total solids changed have been observed in numerous systems. The main finding of the experimental work was that the various unusual DWPF simulant slurry samples exhibit some degree of time dependent behavior. When a given shear rate is applied to a sample, the apparent viscosity of the slurry changes with time rather than remaining constant. These unusual simulant samples are more rheologically complex than Newtonian liquids or more simple slurries, neither of which shows significant time dependence. The study concludes that the unusual rheological behavior that has been observed is being caused by time dependent rheological properties in the slurries being measured. Most of the changes are due to the effect of time under shear, but SB3 SME products were also changing properties while stored in sample bottles. The most likely source of this shear-related time dependence for sludge is in the simulant preparation. More than a single source of time dependence was inferred for the simulant SME product slurries based on the range of phenomena observed. Rheological property changes were observed on the time-scale of a single measurement (minutes) as well as on a time scale of hours to weeks. The unusual shape of the slurry flow curves was not an artifact of the rheometric measurement. Adjusting the user-specified parameters in the rheometer measurement jobs can alter the shape of the flow curve of these time dependent samples, but this was not causing the unusual behavior. Variations in the measurement parameters caused the time dependence of a given slurry to manifest at different rates. The premise of the controlled shear rate flow curve measurement is that the dynamic response of the sample to a change in shear rate is nearly instantaneous. When this is the case, the data can be fitted to a time independent rheological equation, such as the Bingham plastic model. In those cases where this does not happen, interpretation of the data is difficult. Fitting time dependent data to time independent rheological equations, such as the Bingham plastic model, is also not appropriate