Rachel L. Sell

Final Report - Gas Generation Testing of Uranium Metal in Simulated K Basin Sludge and in Grouted Sludge Waste Forms

The Waste Isolation Pilot Plant (WIPP) is being considered for the disposal of K Basin sludge as RH-TRU. Because the hydrogen gas concentration in the 55-gallon RH-TRU sealed drums to be transported to WIPP is limited by flammability safety, the number of containers and shipments likely will be driven by the rate of hydrogen generated by the uranium metal-water reaction (U + 2 H{sub 2}O {yields} UO{sub 2} + 2 H{sub 2}) in combination with the hydrogen generated from water and organic radiolysis. Gas generation testing was conducted with uranium metal particles of known surface area, in simulated K West (KW) Basin canister sludge and immobilized in candidate grout solidification matrices. This study evaluated potential for Portland cement and magnesium phosphate grouts to inhibit the reaction of water with uranium metal in the sludge and thereby permit higher sludge loading to the disposed waste form. The best of the grouted waste forms decreased the uranium metal-water reaction by a factor of four.

Effects of Self Irradiation from 238Pu on Candidate Ceramics for Plutonium Immobilization

In this document, we describe the results of radiation damage testing and characterization for specimens that were resintered to re-establish crystallinity. The phases in these specimens have become amorphous from radiation induced damage over the 8 months since sintering.

Thermal Decomposition of Neodymium Amide Complexes

The decomposition of NdCl3 L(L = N,N-dimethylformamide [DMF] or N,N-dimethyacetamide [DMA]) compounds has been investigated by thermogravimetric and differential thermal analysis (TGA and DTA) coupled with Fourier transform infrared (FTIR) spectroscopy. When heated in air, the NdCl3L compounds decompose by a mechanism involving oxidation of the amide ligand to CO2 and HCl. Some free armide is also released in the thermal decomposition in air. However, when heated under nitrogen, clean release of DMA or DMF is observed. In both cases, the amide is released two steps. From 30 to 40% of the amide is initially released with little or no associated enthalpy as measured by DTA. As the temperature is increased, the remaining 60 to 70% of the amide is released via an endothermic process. The enthalpy for this release is 53.1 - 3.8 kJ/mole for DMF and 40.9 - 1.1 kJ/mole for DMA, suggesting that DMF binds more strongly to Nd(III) than does DMA. Steric effects caused by the additional methyl group in DMA might be responsible for the weaker binding of this amide compared to DMF.

Polycube oxidation and factors affecting the concentrations of gaseous products

The polycubes stored at the Hanford Plutonium Finishing Plant (PFP) have been identified in a Vulnerability Assessment as material that requires a stabilization process in support of the Defense Nuclear Facility Safety Board Recommendation 94-1. The baseline plan involves a pyrolysis process to separate out the plutonium and uranium oxides before the remaining material is packaged for interim storage, in accordance with the Record of Decision (ROD), issued June 25, 1996, for the Plutonium Finishing Plant Stabilization Final Environmental Impact Statement, DOE/EIS-0244-F. The polycubes were manufactured at Hanford in the 1960s for use in criticality studies to determine the hydrogen-to-fissile atom ratios for neutron moderation. A mixture of plutonium and/or uranium oxides and a polystyrene (vinyl benzene) matrix, cast into the shape of cubes, the polycubes simulated solutions containing high concentrations of fissile materials. The polycubes varied in size, typically 1/2 x 2 x 2 in. up to 2 x 2 x 2 in., and were sealed with a coating of aluminum paint and/or tape (PVC or Shurtape). The estimated 1,600 polycubes (calculated 179,165 grams net weight) stored at PFP were packed in vented food cans with five to eight cubes per can to accommodate gas generation by radiolysis. Some polycube containers are suspected to contain loose material as well, left over from the forming process. With a fairly high {sup 240}Pu content, polycubes present a challenge for handling, as a result of the 7 to 8 R contact dose rate. Significant hazards linked to unstabilized polycubes are associated with the polystyrene matrix, which generates hydrogen gas due to radiolysis. In addition, some cans of polycubes may contain fines. Because of insufficient data, hazards associated with the fines have not been assessed.

Gas Generation Testing of Uranium Metal in Simulated K Basins Sludge and Grouted Sludge Waste Forms

The evolving plan for most of the KE and KW Basin sludges is disposition to WIPP as remote handled (RH) TRU. Because the hydrogen gas concentration in the sealed transportation cask destined for WIPP is limited by flammability safety, the number of containers and shipments to WIPP likely will be driven by the rate of hydrogen generated by the contained uranium metals reaction with water. Therefore, gas generation testing with uranium metal particles of known surface area and immobilized in candidate (grout) solidification matrices was used to identify the effectiveness of various candidate solidification matrices to inhibit the rate of the uranium metal-water reaction.

Effect of Gadolinium Doping on the Air Oxidation of Uranium Dioxide

Researchers at the Pacific Northwest National Laboratory (PNNL) investigated the effects of gadolinia concentration on the air oxidization of gadolinia-doped uranium dioxide using thermogravimetry and differential scanning calorimetry to determine if such doping could improve uranium dioxides stability as a nuclear fuel during potential accident scenarios in a nuclear reactor or during long-term disposal. We undertook this study to determine whether the resistance of the uranium dioxide to oxidation to the orthorhombic U3O8 with its attendant crystal expansion could be prevented by addition of gadolinia. Our studies found that gadolinium has little effect on the thermal initiation of the first step of the reported two-step air oxidation of UO2; however, increasing gadolinia content does stabilize the initial tetragonal or cubic product allowing significant oxidation before the second expansive step to U3O8 begins.

Critical Mass Laboratory Solutions Precipitation, Calcination, and Moisture Uptake Investigations

Laboratory work was conducted at Pacific Northwest National Laboratory and the Plutonium Process Support Laboratory of the Plutonium Finishing Plant (PFP) to study flowsheet conditions to selectively precipitate plutonium oxalate from uranium-bearing Critical Mass Laboratory (CML) solutions in the PFP precipitation apparatus and to dry and calcine the resulting filtercake to generate a stable plutonium oxide bearing powder (as judged by loss-on-ignition measurements) in the ambient humidity of the remote mechanical C (RMC) line in the PFP. Based on these studies with simulated and genuine CML solutions and various constituent materials, process conditions were recommended to the PFP under which the product powders can reasonably be expected to pass the DOE-STD-3013 moisture criterion when packaged in the RMC line at relative humidity up to 80%.