Randall D. Scheele

Dissolution Kinetics of Pyrochlore Ceramics for the Disposition of Plutonium.

Abstract Single-pass β ow-through (SPFT) experiments were conducted on a set of non-radioactive Ti-based ceramics at 90 °C and pH = 2 to 12. The specimens contained 27.9 to 35.8 wt%CeO2 as a surrogate for UO2 and PuO2. Compositions were formulated as TiO2-saturated pyrochlore (CeP1) and pyrochlorerich baseline (CePB1) ceramic waste forms. Pyrochlore + Hf-rutile and pyrochlore + perovskite + Hf-rutile constituted the major phases in the CeP1 and CePB1 ceramics, respectively. Results from dissolution experiments between pH = 2 to 12 indicate a shallow pH-dependence with an ill-defined minimum. Element release rates determined from experiments over a range of sample surface areas (S) and β ow rates (q) indicate that dissolution rates become independent of q/S values at 10.8 to 10.7 m/s. Dissolution rates dropped sharply at lower values of q/S, indicating rates that are subject to solution saturation effects as dissolved constituents become concentrated. Forward dissolution rates were 1.3(0.30) x 10-3 and 5.5(1.3) x 10-3 g/m2·d for CeP1 and CePB1 ceramics, respectively. Dissolution rates obtained in other laboratories compare well to the findings of this study, once the rate data are placed in the context of solution saturation state. These results make progress toward an evaluation of CeO2 as a surrogate for UO2 and PuO2 as well as establishing a baseline for comparison with radiation- damaged specimens.

High-resolution solid-state nuclear magnetic resonance experiments on highly radioactive ceramics

A triple-containment magic-angle spinning rotor insert system has been developed and a sample handling procedure formulated for safely analyzing highly radioactive solids by high-resolution solid-state NMR. The protocol and containment system have been demonstrated for magic-angle spinning (MAS) experiments on ceramic samples containing 5–10 wt % 239Pu and 238Pu at rotation speeds of 3500 Hz. The technique has been used to demonstrate that MAS NMR experiments can be used to measure amorphous atomic number fractions produced by accelerated internal radiation damage. This will allow incorporated α-emitters with short half-lives to be used to model the long-term radiation tolerance of potential ceramic radioactive waste forms. This is an example of MAS NMR spectroscopy on samples containing fissionable isotopes.

Tc Reductant Chemistry and Crucible Melting Studies with Simulated Hanford Low-Activity Waste

The FY 2003 risk assessment (RA) of bulk vitrification (BV) waste packages used 0.3 wt% of the technetium (Tc) inventory as a leachable salt and found it sufficient to create a significant peak in the groundwater concentration in a 100-meter down-gradient well. Although this peak met regulatory limits, considering uncertainty in the actual Tc salt fraction, peak concentrations could exceed the maximum concentration limit (MCL) under some scenarios so reducing the leachable salt inventory is desirable. The main objective of this study was to reduce the mobile Tc species available within a BV disposal package by reducing the oxidation state of the Tc in the waste feed and/or during melting because Tc in its reduced form of Tc(IV) has a much lower volatility than Tc(VII). Reduced Tc volatility has a secondary benefit of increasing the Tc retention in glass.

Review of Potential Candidate Stabilization Technologies for Liquid and Solid Secondary Waste Streams

Pacific Northwest National Laboratory has initiated a waste form testing program to support the long-term durability evaluation of a waste form for secondary wastes generated from the treatment and immobilization of Hanford radioactive tank wastes. The purpose of the work discussed in this report is to identify candidate stabilization technologies and getters that have the potential to successfully treat the secondary waste stream liquid effluent, mainly from off-gas scrubbers and spent solids, produced by the Hanford Tank Waste Treatment and Immobilization Plant (WTP). Down-selection to the most promising stabilization processes/waste forms is needed to support the design of a solidification treatment unit (STU) to be added to the Effluent Treatment Facility (ETF). To support key decision processes, an initial screening of the secondary liquid waste forms must be completed by February 2010.

Preparation and Characterization of {sup 238}Pu-Ceramics for Radiation Damage Experiments

As a result of treaty agreements between Russia and the US, portions of their respective plutonium and nuclear weapons stockpiles have been declared excess. In support of the US Department of Energys 1998 decision to pursue immobilization of a portion of the remaining Pu in a titanate-based ceramic, the authors prepared nearly 200 radiation-damage test specimens of five Pu- and {sup 238}Pu-ceramics containing 10 mass% Pu to determine the effects of irradiation from the contained Pu and U on the ceramic. The five Pu-ceramics were (1) phase-pure pyrochlore [ideally, Ca(U, Pu)Ti{sub 2}O{sub 7}], (2) pyrochlore-rich baseline, (3) pyrochlore-rich baseline with impurities, (4) phase-pure zirconolite [ideally Ca(U, Pu)Ti{sub 2}O{sub 7}], and (5) a zirconolite-rich baseline. These ceramics were prepared with either normal weapons-grade Pu, which is predominantly {sup 239}Pu, or {sup 238}Pu. The {sup 238}Pu accelerates the radiation damage relative to the {sup 239}Pu because of its much higher specific activity. The authors were unsuccessful in preparing phase-pure (Pu, U) brannerite, which is the third crystalline phase present in the baseline immobilization form. Since these materials will contain {approximately}10 mass% Pu and about 20 mass% U, radiation damage to the crystalline structure of these materials will occur overtime. As the material becomes damaged from the decay of the Pu and U, it is possible for the material to swell as both the alpha particles and recoiling atoms rupture chemical bonds within the solid. As the material changes density, cracking, perhaps in the form of microcracks, may occur. If cracking occurs in ceramic that has been placed in a repository, the calculated rate of radionuclide release if the can has corroded would increase proportionately to the increase in surface area. To investigate the effects of radiation damage on the five ceramics prepared, the authors are storing the specimens at 20, 125, and 250 C until the {sup 238}Pu specimens become metamict and the damage saturates. They will characterize and test these specimens every 6 months by (1) monitoring the dimensions, (2) monitoring the geometric and pycnometric densities, (3) monitoring the appearance, (4) determining the normalized amount leached during a 3-day, static, 90 C leach test in high purity water, and (5) monitoring the crystal structure with x-ray diffraction crystallography (XRD). In this paper, the authors document the preparation and initial characterization of the materials that were made in this study. The initial XRD characterizations indicate that the phase assemblages appear to be correct with the exception of the {sup 238}Pu-zirconolite baseline material. They made this latter material using too much Pu, so this material contains unreacted PuO{sub 2}. The characterization of the physical properties of these materials found that the densities for all but three materials appear to be > 94% of theoretical, and only a few of the specimens have significant cracking. Those with cracking were the {sup 239}Pu-zirconolite specimens, which were sintered with a heat-up rate of 5 C/min. They sintered the {sup 238}Pu-zirconolite specimens with a heat-up rate of 2.5 C/min and obtained specimens with only minor surface cracking. Elemental releases during the 3-day MCC leach tests show that the normalized elemental releases depend on (1) whether the Pu is {sup 239}Pu or {sup 238}Pu, (2) the material type, and (3) the identity of the constituent. The effect of the Pu isotope in the ceramic is most dramatic for Pu release, with nominally 50 to 100 times more Pu activity released from the {sup 238}Pu specimens. This is unlikely to be an early indicator of radiation damage, because of the short time between specimen preparation and testing. In contrast greater amounts of Mo are released from the {sup 239}Pu specimens. Of the contained constituents, Ca Al, Pu, and U are the species found at relatively higher levels in the leachates.

Radiation Damage in Titanate Ceramics for Plutonium Immobilization

Results from radiation damage experiments are discussed with respect to the immobilization of Pu declared excess to the weapons programs. The ceramics are titanate-based.

The Status of Radiation Damage Experiments

Experiments have been on-going for about two years to determine the effects that radiation damage have on the physical and chemical properties of candidate titanate ceramics for the immobilization of plutonium. We summarize the results of these experiments in this document.

Nitrogen Trifluoride-Based Fluoride- Volatility Separations Process: Initial Studies

This document describes the results of our investigations on the potential use of nitrogen trifluoride as the fluorinating and oxidizing agent in fluoride volatility-based used nuclear fuel reprocessing. The conceptual process uses differences in reaction temperatures between nitrogen trifluoride and fuel constituents that produce volatile fluorides to achieve separations and recover valuable constituents. We provide results from our thermodynamic evaluations, thermo-analytical experiments, kinetic models, and provide a preliminary process flowsheet. The evaluations found that nitrogen trifluoride can effectively produce volatile fluorides at different temperatures dependent on the fuel constituent.

Calcium Phosphate: A potential host for halide contaminated plutonium wastes.

The presence of significant quantities of fluoride and chloride in four types of legacy wastes from plutonium pyrochemical reprocessing required the development of a new wasteform which could adequately immobilize the halides in addition to the Pu and Am. Using a simulant chloride-based waste (Type I waste) and Sm as the surrogate for the Pu3+ and Am3+ present in the waste, AWE developed a process which utilised Ca3(PO4)2 as the host material. The waste was successfully incorporated into two crystalline phases, chlorapatite, [Ca5(PO4)3Cl], and spodiosite, [Ca2(PO4)Cl]. Radioactive studies performed at PNNL with 239Pu and 241Am confirmed the process. A slightly modified version of the process in which CaHPO4 was used as the host was successful in immobilizing a more complex multi-cation oxide–based waste (Type II) which contained significant concentrations of Cl and F in addition to 239Pu and 241Am. This waste resulted in the formation of cation-doped whitlockite, Ca3-xMgx(PO4)2, β-calcium phosphate, β-Ca2P2O7 and chlor-fluorapatite rather than the chlorapatite and spodiosite formed with Type I waste.

Thermal Stability Studies of Candidate Decontamination Agents for Hanford’s Plutonium Finishing Plant Plutonium-Contaminated Gloveboxes

This report provides the results of PNNLs and Fluors studies of the thermal stabilities of potential wastes arising from decontamination of Hanfords Plutonium Finishing Plants plutonium contaminated gloveboxes. The candidate wastes arising from the decontamination technologies ceric nitrate/nitric acid, RadPro, Glygel, and Aspigel.