Plutonium dioxide dissolution in glass

In the aftermath of the Cold War, the U.S. Department of Energy`s (DOE) Office of Fissile Materials Disposition (OFMD) is charged with providing technical support for evaluation of disposition options for excess fissile materials manufactured for the nation`s defense. One option being considered for the disposition of excess plutonium (Pu) is immobilization by vitrification. The vitrification option entails immobilizing Pu in a host glass and waste package that are criticality-safe (immune to nuclear criticality), proliferation-resistant, and environmentally acceptable for long-term storage or disposal. To prove the technical and economic feasibility of candidate vitrification options it is necessary to demonstrate that PuO{sub 2} feedstock can be dissolved in glass in sufficient quantity. The OFMD immobilization program has set a Pu solubility goal of 10 wt% in glass. The life cycle cost of the vitrification options are strongly influenced by the rate at which PUO{sub 2} dissolves in glass. The total number of process lines needed for vitrification of 50 t of Pu in 10 years is directly dependent upon the time required for Pu dissolution in glass. The objective of this joint Pacific Northwest National Laboratory (PNNL) - Savannah River Technology Center (SRTC) study was to demonstrate a high Pu solubility in glass and to identify on a rough scale the time required for Pu dissolution in the glass. This study was conducted using a lanthanide borosilicate (LaBS) glass composition designed at the SRTC for the vitrification of actinides

Feed process studies: Research-Scale Melter

In support of a two-phase approach to privatizing the processing of hazardous and radioactive waste at Hanford, research-scale melter (RSM) experiments were conducted to determine feed processing characteristics of two potential privatization Phase 1 high-level waste glass formulations and to determine if increased Ag, Te, and noble metal amounts would have bad effects. Effects of feed compositions and process conditions were examined for processing rate, cold cap behavior, off-gas, and glass properties. The 2 glass formulations used were: NOM-2 with adjusted waste loading (all components except silica and soda) of 25 wt%, and NOM-3 (max waste loaded glass) with adjusted waste loading of 30 wt%. The 25 wt% figure is the minimum required in the privatization Request for Proposal. RSM operated for 19 days (5 runs). 1010 kg feed was processed, producing 362 kg glass. Parts of runs 2 and 3 were run at 10 to 30 degrees above the nominal temperature 1150 C, with the most significant processing rate increase in run 3. Processing observations led to the choice of NOM-3 for noble metal testing in runs 4 and 5. During noble metal testing, processing rates fell 50% from baseline. Destructive analysis showed that a layer of noble metals and noble metal oxides settled on the floor of the melter, leading to current ``channeling`` which allowed the top section to cool, reducing production rates

The initial dissolution rates of simulated UK Magnox-ThORP blend nuclear waste glass as a function of pH, temperature and waste loading

The first comprehensive assessment of the dissolution kinetics of simulant Magnox–ThORP blended UK high-level waste glass, obtained by performing a range of single-pass flow-through experiments, is reported here. Inherent forward rates of glass dissolution were determined over a temperature range of 23 to 70°C and an alkaline pH range of 8.0 to 12.0. Linear regression techniques were applied to the TST kinetic rate law to obtain fundamental parameters necessary to model the dissolution kinetics of UK high-level waste glass (the activation energy (E a), pH power law coefficient (η) and the intrinsic rate constant (k0)), which is of importance to the post-closure safety case for the geological disposal of vitreous products. The activation energies based on B release ranged from 55 ± 3 to 83 ± 9 kJ mol–1, indicating that Magnox–THORP blend glass dissolution has a surface-controlled mechanism, similar to that of other high-level waste simulant glass compositions such as the French SON68 and LAW in the US. Forward dissolution rates, based on Si, B and Na release, suggested that the dissolution mechanism under dilute conditions, and pH and temperature ranges of this study, was not sensitive to composition as defined by HLW-incorporation rate

Modelling the sulfate capacity of simulated radioactive waste borosilicate glasses

The capacity of simulated high-level radioactive waste borosilicate glasses to incorporate sulfate has been studied as a function of glass composition. Combined Raman, 57Fe Mössbauer and literature evidence supports the attribution of coordination numbers and oxidation states of constituent cations for the purposes of modelling, and results confirm the validity of correlating sulfate incorporation in multicomponent borosilicate radioactive waste glasses with different models. A strong compositional dependency is observed and this can be described by an inverse linear relationship between incorporated sulfate (mol% SO42−) and total cation field strength index of the glass, Σ(z/a2), with a high goodness-of-fit (R2 ≈ 0.950). Similar relationships are also obtained if theoretical optical basicity, Λth (R2 ≈ 0.930) or non-bridging oxygen per tetrahedron ratio, NBO/T (R2 ≈ 0.919), are used. Results support the application of these models, and in particular Σ(z/a2), as predictive tools to aid the development of new glass compositions with enhanced sulfate capacities

NCAW feed chemistry: Effect of starting chemistry on melter offgas and iron redox

The Pacific Northwest Laboratory (PNL) Vitrification Technology Development (PVTD) program has been established to develop technology to support immobilization of selected Hanford wastes. The effort of the PVTD program is directed by the U.S. Department of Energy (DOE). This report is part of the effort and focuses on the effect of starting waste chemistry on the vitrification process. The objective of the investigation was the evaluation of the effect of starting chemistry on the cold cap behavior in the vitrification of simulated neutralized current acid waste (NCAW). In addition this investigation provides an initial laboratory investigation of the cold cap and method for evaluation of alternate reductants

Development of models and software for liquidus temperatures of glasses of HWVP products. Final report

In an earlier report [92 Pel] was described the development of software and thermodynamic databases for the calculation of liquidus temperatures of glasses of HWVP products containing the components SiO{sub 2}-B{sub 2}O{sub 3}-Na{sub 2}O-Li{sub 2}O-CaO-MgO-Fe{sub 2}O{sub 3}-Al{sub 2}O{sub 3}-ZrO{sub 2}-{open_quotes}others{close_quotes}. The software package developed at that time consisted of the EQUILIB program of the F*A*C*T computer system with special input/output routines. Since then, Battelle has purchased the entire F*A*C*T computer system, and this fully replaces the earlier package. Furthermore, with the entire F*A*C*T system, additional calculations can be performed such as calculations at fixed O{sub 2}, SO{sub 2} etc. pressures, or graphing of output. Furthermore, the public F*A*C*T database of over 5000 gaseous species and condensed phases is now accessible. The private databases for the glass and crystalline phases were developed for Battelle by optimization of thermodynamic and phase diagram data. That is, all available data for 2- and 3-component sub-systems of the 9-component oxide system were collected, and parameters of model equations for the thermodynamic properties were found which best reproduce all the data. For representing the thermodynamic properties of the glass as a function of composition and temperature, the modified quasichemical model was used. This model was described in the earlier report [92 Pel] along with all the optimizations. With the model, it was possible to predict the thermodynamic properties of the 9-component glass, and thereby to calculate liquidus temperatures. Liquidus temperatures measured by Battelle for 123 CVS glass compositions were used to test the model and to refine the model by the addition of further parameters

Frit screening for Rocky Flats ash and sand, slag, and crucible vitrification

Pacific Northwest National Laboratory (PNNL) is developing vitrified waste forms for plutonium-bearing ash and plutonium-bearing sand, slag, and crucible (SS&C) materials from Rocky Flats. Waste forms are to meet product criteria (e.g., safeguard termination limits, storage criteria, and target plutonium loading) and processing constraints (e.g., upper temperature limits, processing time, and equipment compatibility). The target waste form for ash is an agglomerated product, while that for SS&C is a fully encapsulated product. Laboratory scoping studies were conducted on glass formulations from six different glass families: (1) antimony vanadium phosphate, (2) iron vanadium phosphate, (3) tin zinc phosphate, (4) soda-lime silicate, (5) alkali borosilicate, and (6) alkali borate. Glass families were selected due to viscosity behavior in the temperature range of interest (< 800C). Scoping study tests included gradient furnace tests to determine processing range and sintering temperature, thermogravimetric analysis to determine weight loss as a function of temperature, and crucible tests to determine frit compositions tolerance to variations in processing temperature, waste loading, and waste type. The primary screening criterion for the selection of frits for future studies was processing temperature below 400C to minimize the potential for foaming in ash caused by the release of gases (main source of gas is combustion of carbon species) and to minimize processing cycle times. Based on this criterion, glass formulations from the tin zinc phosphate and alkali borosilicate families were selected for future variability testing. Variability testing will include final product evaluation, glass system tolerance to waste loading and composition variation, and identification of parameters impacting time/temperature profiles. Variability testing results will give a final frit formulation for ash and SS&C, and identify key processing parameters. 12 refs., 13 figs., 9 tabs

Effect of composition and temperature on the properties of High-Level Waste (HLW) glasses melting above 1200{degrees}C (Draft)

Increasing the melting temperature of HLW glass allows an increase of waste loading (thus reducing product volume) and the production of more durable glasses at a faster melting rate. However, HLW glasses that melt at high temperatures differ in composition from glasses formulated for low temperature ({approximately}1150{degree}C). Consequently, the composition of high-temperature glasses falls in a region previously not well tested or understood. This report represents a preliminary study of property/composition relationships of high-temperature Hanford HLW glasses using a one-component-at-a-time change approach. A test matrix has been designed to explore a composition region expected for high-temperature high-waste loading HLW glasses to be produced at Hanford. This matrix was designed by varying several key components (SiO{sub 2}, B{sub 2}O{sub 3}, Na{sub 2}O, Li{sub 2}O, Fe{sub 2}O{sub 3}, Al{sub 2}O{sub 3}, ZrO{sub 2}, Bi{sub 2}O{sub 3}, P{sub 2}O{sub 5}, UO{sub 2}, TiO{sub 2}, Cr{sub 2}O{sub 3}, and others) starting from a glass based on a Hanford HLW all-blend waste. Glasses were fabricated and tested for viscosity, glass transition temperature, electrical conductivity, crystallinity, liquidus temperature, and PCT release. The effect of individual components on glass properties was assessed using first- and second- order empirical models. The first-order component effects were compared with those from low-temperature HLW glasses

Frit specification development: Letter report

To specify frit for the Hanford Waste Vitrification Plant (HWVP), the relevant requirements and characterization need to be established. The properties and applicable testing will be incorporated into a specification. Several areas have been identified that require consideration in a frit specification: glass processability and acceptability; frit storage and handling; frit slurry rheology; melter feed rheology; canister decontamination; pumping equipment/pipe erosion; frit cooling rate; and glass melting rate. The listed areas are influenced primarily by frit composition, temperature history, particle morphology, particle size, size distribution. and properties that depend on the primary variables such as hardness and frit density. Frit development proceeds in two steps: the first focuses on the waste glass, and the second on the pre-melt (including cold cap) processing

YBa sub 2 Cu sub (3-x) Co sub x O sub y : A substrate material for YBCO superconductors

The physical properties of the ceramic YBa{sub 2}Cu{sub (3-x)}Co{sub x}O{sub y} have been investigated in order to evaluate its usefulness as a substrate material for YBCO superconductors. YBa{sub 2}Cu{sub (3-x)}Co{sub x}O{sub y} has been found to be thermally and chemically compatible with 123 and displays adequate electrical properties for a substrate material. A material with the nominal composition of YBa{sub 2}Cu{sub 2.2}Co{sub 0.8}O{sub 7} was investigated, extensively. The mechanical properties of this material were found to be poor, e.g., tensile strength was only 60 MPa. A semiconductor-like behavior was observed with a room-temperature resistivity of 70 m{Omega}.cm and a resistivity equal to 4 {times} 10{sup 6} m{Omega}.cm at 77 K