Investigation of physical and chemical properties for upgraded SAP (SiO2Al2O3P2O5) waste form to immobilize radioactive waste salt
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l ‐asparaginases from mesophilic bacteria (ASNases), including two enzymes very successfully used in the treatment of leukaemia, have been consistently described as homotetramers. On the contrary, structural studies show that homodimers of these enzymes should be sufficient to carry out the catalytic reaction. In this report, we investigated whether the type I Yersinia pestis asparaginase (YpAI) is active in a dimeric form or whether the tetrameric quaternary structure is critical for its activity. Using multiple biophysical techniques that investigate enzymatic properties and quaternary structure at either high or low protein concentration, we found that dimeric YpAI is fully active, suggesting that the tetrameric form of this subfamily of enzymes does not bear significant enzymatic relevance. In this process, we extensively characterized YpAI, showing that it is a cooperative enzyme, although the mechanism of allostery is still not definitely established. We showed that, like most type I ASNases, the substrate affinity of YpAI is low and this enzyme is very similar in terms of both the structure and enzymatic properties to homologous type I ASNase from Escherichia coli (EcAI). We extended these studies to more medically relevant type II ASNases, used as anti‐leukaemia drugs. We confirmed that type II ASNases are not allosteric, and that they might also be functional in a dimeric form. However, the determination of the accurate tetramer⇆dimer dissociation constants of these enzymes that most likely lie in the picomolar range is not possible with currently available biophysical techniques.
The research conducted in this work package is aimed at taking advantage of the long term thermodynamic stability of crystalline ceramics to create more durable waste forms (as compared to high level waste glass) in order to reduce the reliance on engineered and natural barrier systems. Durable ceramic waste forms that incorporate a wide range of radionuclides have the potential to broaden the available disposal options and to lower the storage and disposal costs associated with advanced fuel cycles. Assemblages of several titanate phases have been successfully demonstrated to incorporate radioactive waste elements, and the multiphase nature of these materials allows them to accommodate variation in the waste composition. Recent work has shown that they can be produced from a melting and crystallization process. The objective of this report is to explore the phase formation and microstructural differences between lab scale melt processing in varying gas environments with alternative densification processes such as Hot Pressing (HP) and Spark Plasma Sintering (SPS). The waste stream used as the basis for the development and testing is a simulant derived from a combination of the projected Cs/Sr separated stream, the Trivalent Actinide - Lanthanide Separation by Phosphorous reagent Extraction from Aqueous Komplexes (TALSPEAK) waste stream consisting of lanthanide fission products, the transition metal fission product waste stream resulting from the transuranic extraction (TRUEX) process, and a high molybdenum concentration with relatively low noble metal concentrations. Melt processing as well as solid state sintering routes SPS and HP demonstrated the formation of the targeted phases; however differences in microstructure and elemental partitioning were observed. In SPS and HP samples, hollandite, pervoskite/pyrochlore, zirconolite, metallic alloy and TiO 2 and Al 2 O 3 were observed distributed in a network of fine grains with small residual pores. The titanate phases that incorporate M +3 rare earth elements were observed to be distinct phases (ex. Nd 2 Ti 2 O 7 with less degree of substitution as compared to the more homogeneous melt processed samples where a high degree of substitution and variation of composition within grains was observed. Liquid phase sintering was enhanced in reducing gas environments and resulted in large (10-200 microns) irregular shaped grains along with large voids associated with the melt process; SPS and HP samples exhibited finer grain size with smaller voids. Metallic alloys were observed in the bulk of the sample for SPS and HP samples, but were found at the bottom of the crucible in melt processed trials. These results indicate that for a first melter trial, the targeted phases can be formed in air by utilizing Ti/TiO 2 additives which aid phase formation and improve the electrical conductivity. Ultimately, a melter run in reducing gas environments would be beneficial to study differences in phase formation and elemental partitioning.
A method includes forming one or more oxide barrier layers on one or more protected portions of a magnetic, metallic body, and converting one or more unprotected portions of the magnetic, metallic body to a less magnetic material by exposing the magnetic metallic body having the one or more oxide barrier layers formed thereon to nitrogen. One or more protected portions of the magnetic, metallic body that are beneath the one or more oxide barrier layers are not converted to the less magnetic material. The method can be used to form one or more layers of a laminated electric motor.
A selective oxide-forming alloy, a coating formed from, and a machine component including the coating are provided. The selective oxide-forming alloy includes between atomic percent and 26 atomic percent silicon (Si), between 21 atomic percent and 27 atomic percent titanium (Ti), between 30 atomic percent and 39 atomic percent aluminum (Al), between 2 atomic percent and 10 atomic percent hafnium (Hf), and a balance of niobium (Nb).
Crystals of goethite were synthesized with reduced technetium [{sup 99}Tc(IV)] incorporated within the solid lattice. The presence of {sup 99}Tc(IV) as a substituting cation in the matrix and 'armoring' by an additional layer of precipitated goethite isolated the reduced {sup 99}Tc(IV) from oxidizing agents. These products were used to make monolithic pellets to quantify an effective diffusion coefficient for {sup 99}Tc from goethite waste form contacted with a synthetic Hanford IDF (integrated disposal facility) pore water solution (pH = 7.2, I = 0.05 M) at room temperature for up to 120 days in static reactors. XANES analysis of the goethite solids recovered post-run demonstrated that the {sup 99}Tc in the goethite crystals remains in the reduced {sup 99}Tc(IV) state. The slow release of pertechnetate concentration with time in the static experiments with the monolith followed a square root of time dependence, consistent with diffusion control for {sup 99}Tc release. An apparent diffusion coefficient of 6.15 x 10{sup -11} cm{sup 2}/s was calculated for the {sup 99}Tc-goethite pellet sample and the corresponding leaching index (LI) was 10.2. The results of this study indicate that technetium can be immobilized in a stable, low-cost Fe oxide matrix that is easy to fabricate and these findings can be useful in designing long-term solutions for nuclear waste disposal.
In the effective theory of isoscalar and isovector dark matter-nucleon interactions mediated by a heavy spin-1 or spin-0 particle, 8 isotope-dependent nuclear response functions can be generated in the dark matter scattering by nuclei. We compute the 8 nuclear response functions for the 16 most abundant elements in the Sun, i.e. H, {sup 3}He, {sup 4}He, {sup 12}C, {sup 14}N, {sup 16}O, {sup 20}Ne, {sup 23}Na, {sup 24}Mg, {sup 27}Al, {sup 28}Si, {sup 32}S, {sup 40}Ar, {sup 40}Ca, {sup 56}Fe, and {sup 59}Ni, through numerical shell model calculations. We use our response functions to compute the rate of dark matter capture by the Sun for all isoscalar and isovector dark matter-nucleon effective interactions, including several operators previously considered for dark matter direct detection only. We study in detail the dependence of the capture rate on specific dark matter-nucleon interaction operators, and on the different elements in the Sun. We find that a so far neglected momentum dependent dark matter coupling to the nuclear vector charge gives a larger contribution to the capture rate than the constant spin-dependent interaction commonly included in dark matter searches at neutrino telescopes. Our investigation lays the foundations for model independent analyses of dark matter induced neutrino signals from the Sun. The nuclear response functions obtained in this study are listed in analytic form in an appendix, ready to be used in other projects.
The upward adoption trend of renewable generation not only means cleaner energy integrated into modern power grids, but also that most new generation sources are based on front-end inverter bridges, used as interfaces to most wind generation and all the solar PV. It is well known that due to their power electronics-based construction rather than rotational shafts, these sources do not provide inertia inherently, nor substantial amounts of short-circuit currents. However, stable energy such as what can be stored in energy storage systems, although interfaced via inverters, can be controlled to respond to system disturbances in a manner that emulates inertial behavior. This paper focuses on the application of such energy storage systems to augment inertia in the island of Puerto Rico. To do so, a user defined inverter model that contains grid forming capabilities and fast frequency response is modeled and integrated into the real transmission system in power flow and dynamics software. Energy storage is then connected to two selected areas so that it not only provides frequency regulation to avoid widespread load shedding events, but also other tangible benefits. The simulated cases suggest that even relatively small energy storage systems can avert load shedding events if adequately placed in the transmission network.
This paper develops a controller for a grid-forming (GFM) inverter that is capable of operating as either a GFM or grid-feeding source that can improve the operation of a microgrid during on-off grid transitions through use of a novel synchronization approach. Furthermore, this controller avoids use of a phase-locked loop (PLL) and the inverter is able to synchronize with the grid with self-generated voltage and frequency. This prevents the inverter from replicating any grid voltage disturbances in its output—a key disadvantage of many grid-connected inverters that use a PLL. To enable fast synchronization, active synchronization control is adopted both during inverter start-up and microgrid reconnection operation and a method of coordinating synchronization of the inverter with a microgrid controller and grid interconnection circuit breaker is presented. Simulation results for multiple microgrid transition operations and unplanned islanding events demonstrate that the developed non-PLL grid-connected GFM inverter controller and synchronization method are effective in synchronizing the inverter and microgrid to the grid, avoiding phase jump during microgrid transition operation, and improving microgrid islanding transients versus a traditional configuration.
Power systems are transforming with increasing levels of inverter-based resources (IBRs). This transformation requires critical roles of grid-forming (GFM) inverters replacing synchronous generators for bulk power system stabilization and ancillary services, also allowing flexible power system operation, such as microgrid that is operated by multiple GFM IBRs to achieve system resilience against contingencies. To realize the resilient power systems allowing flexible in-and-out operation of GFM IBRs potentially programmed with different primary controls, a synchronization method universally applicable, i.e., independent of control types, would be beneficial to ease the integration process, but it has not been actively studied. To fill the gap, this paper proposes a universal synchronization method that achieves a passive synchronization to enable a smooth transition in a grid with off-nominal system parameters, i.e., voltage and frequency. The logic proposed requires no modification on the primary control, thus applicable to any type of GFMs with a voltage reference input. To validate the concept, a simulation of an IEEE 13-bus benchmark system modified with 3 GFM inverters is presented. It simulates an inverter-driven black start scenario in which GFM inverters autonomously turn on and connect to the grid under heavy loading, using the synchronization logic. The case study demonstrates that GFM inverters can tune their voltage reference to smoothly synchronize without severe transients, and contribute to a seamless black start of the grid under unbalanced load conditions. Two GFM methods - Droop and dispatchable virtual oscillator control - are used for the demo to validate feasibility and interoperability of the passive synchronization.
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This paper discusses the effects of composition and canister centerline cooling (CCC) on the microstructures, phase distribution, and chemical durability of dehalogenated iron phosphate waste forms starting from chloride-based salt simulants including KCl (Simple-1), NdCl3 (Simple-2), SrCl2 (Simple-3), LaCl3 (Simple-4), LiCl (Simple-5), CsCl (Simple-6), as well as a complex simulant containing LiCl, KCl, NaCl, CsI, SrCl2, CeCl3, and NdCl3 called ERV2. The simulants represent salt constituents present in salt wastes from electrorefiners used for electrochemical reprocessing. These salts are reacted with ammonium dihydrogen phosphate (ADP) resulting in a NH4Cl (dechlorination) byproduct that is captured and phosphate product containing oxides of the salt cations. This product is further stabilized using Fe2O3 through vitrification at higher temperatures. The results presented herein describe the properties of CCC-treated materials following dechlorination and vitrification including phase identification and quantification, elemental distributions, and chemical durabilities. The chemical durability in the CCC-cooled samples are lower durability than quenched materials for the ERV2 samples. The phases formed upon CCC cooling are very complex compositionally and microstructurally.
Hollandite-rich multiphase waste form compositions processed by melt-solidification and spark plasma sintering (SPS) were characterized, compared, and validated for nuclear waste incorporation. Phase identification by x-ray diffraction (XRD) and electron back-scattered diffraction (EBSD) confirmed hollandite as the major phase present in these samples along with perovskite, pyrochlore and zirconolite. Distribution of selected elements observed by wavelength dispersive spectroscopy (WDS) maps indicated that Cs formed a secondary phase during SPS processing, which was considered undesirable. On the other hand, Cs partitioned into the hollandite phase in melt-processed samples. Further analysis of hollandite structure in melt-processed composition by selected area electron diffraction (SAED) revealed ordered arrangement of tunnel ions (Ba/Cs) and vacancies, suggesting efficient Cs incorporation into the lattice.