To mitigate adverse effects from molten corium following a reactor pressure vessel failure (RPVF), some new reactor designs employ a core catcher and a sacrificial material (SM), such as ceramic or concrete, to stabilize the molten corium and avoid containment breach. Existing reactors cannot easily be modified to include these SMs but could be modified to allow injectable cooling materials. Current reactor designs are limited to using water to stabilize the corium, but this can create other issues such as reaction of water with the concrete forming hydrogen gas. The novel SM proposed here is a granular carbonate mineral that can be used in existing light water reactor plants. The granular carbonate will decompose when exposed to heat, inducing an endothermic reaction to quickly solidify the corium in place and producing a mineral oxide and carbon dioxide. Corium spreading is a complex process strongly influenced by coupled chemical reactions, including decay heat from the corium, phase change, and reactions between the concrete containment and available water. A recently completed Sandia National Laboratories laboratory directed research and development (LDRD) project focused on two research areas: experiments to demonstrate the feasibility of the novel SM concept, and modeling activities to determine the potential applications of the concept to actual nuclear plants. Small-scale experiments using lead oxide (PbO) as a surrogate for molten corium demonstrate that the reaction of the SM with molten PbO results in a fast solidification of the melt due to the endothermic carbonate decomposition reaction and the formation of open pore structures in the solidified PbO from CO2 released during the decomposition. A simplified carbonate decomposition model was developed to predict thermal decomposition of carbonate mineral in contact with corium. This model was incorporated into MELCOR, a severe accident nuclear reactor code. A full-plant MELCOR simulation suggests that by the introduction of SM to the reactor cavity prior to RPVF ex-vessel accident progression, e.g., core-concrete interaction and core spreading on the containment floor, could be delayed by at least 15 h; this may be enough for additional accident management to be implemented to alleviate the situation.
Novel materials based on the aluminum oxyhydroxide boehmite phase were prepared using a glycothermal reaction in 1,4-butanediol. Under the synthesis conditions, the atomic structure of the boehmite phase is altered by the glycol solvent in place of the interlayer hydroxyl groups, creating glycoboehmite. The structure of glycoboehmite was examined in detail to determine that glycol molecules are intercalated in a bilayer structure, which would suggest that there is twice the expansion identified previously in the literature. This precursor phase enables synthesis of two new phases that incorporate either polyvinylpyrrolidone or hydroxylpropyl cellulose nonionic polymers. These new materials exhibit changes in morphology, thermal properties, and surface chemistry. All the intercalated phases were investigated using PXRD, HRSTEM, SEM, FT-IR, TGA/DSC, zeta potential titrations, and specific surface area measurement. These intercalation polymers are non-ionic and interact through wetting interactions and hydrogen bonding, rather than by chemisorption or chelation with the aluminum ions in the structure.
This report describes research and development (R&D) activities conducted during fiscal year 2021 (FY21) specifically related to the Engineered Barrier System (EBS) R&D Work Package in the Spent Fuel and Waste Science and Technology (SFWST) Campaign supported by the United States (U.S.) Department of Energy (DOE). The R&D activities focus on understanding EBS component evolution and interactions within the EBS, as well as interactions between the host media and the EBS. A primary goal is to advance the development of process models that can be implemented directly within the Generic Disposal System Analysis (GDSA) platform or that can contribute to the safety case in some manner such as building confidence, providing further insight into the processes being modeled, establishing better constraints on barrier performance, etc.
The DOE R&D program under the Spent Fuel Waste Science Technology (SFWST) campaign has made key progress in modeling and experimental approaches towards the characterization of chemical and physical phenomena that could impact the long-term safety assessment of heatgenerating nuclear waste disposition in deep-seated clay/shale/argillaceous rock. International collaboration activities such as heater tests, continuous field data monitoring, and postmortem analysis of samples recovered from these have elucidated key information regarding changes in the engineered barrier system (EBS) material exposed to years of thermal loads. Chemical and structural analyses of sampled bentonite material from such tests as well as experiments conducted on these are key to the characterization of thermal effects affecting bentonite clay barrier performance and the extent of sacrificial zones in the EBS during the thermal period. Thermal, hydrologic, and chemical data collected from heater tests and laboratory experiments has been used in the development, validation, and calibration of THMC simulators to model near-field coupled processes. This information leads to the development of simulation approaches (e.g., continuum and discrete) to tackle issues related to flow and transport at various scales of the host-rock, its interactions with barrier materials, and EBS design concept.
This interim report is an update of ongoing experimental and modeling work on bentonite material described in Jové Colón et al. (2019, 2020) from past international collaboration activities. As noted in Jové Colón et al. (2020), work on international repository science activities such as FEBEX-DP and DECOVALEX19 is either no longer continuing by the international partners. Nevertheless, research activities on the collected sample materials and field data are still ongoing. Descriptions of these underground research laboratory (URL) R&D activities are described elsewhere (Birkholzer et al. 2019; Jové Colón et al. 2020) but will be explained here when needed. The current reports recent reactive-transport modeling on the leaching of sedimentary rock.
The catastrophic nuclear reactor accident at Fukushima damaged public confidence in nuclear energy and a demand for new engineered safety features that could mitigate or prevent radiation releases to the environment in the future. We have developed a novel use of sacrificial material (SM) to prevent the molten corium from breaching containment during accidents as well as a validated, novel, high-fidelity modeling capability to design and optimize the proposed concept. Some new reactor designs employ a core catcher and a SM, such as ceramic or concrete, to slow the molten corium and avoid the breach of the containment. However, existing reactors cannot easily be modified to include these SMs but could be modified to allow injectable cooling materials (current designs are limited to water). The SM proposed in this Laboratory Development Research and Development (LDRD) project is based on granular carbonate minerals that can be used in existing light water reactor plants. This new SM will induce an endothermic reaction to quickly freeze the corium in place, with minimal hydrogen explosion and maximum radionuclide retention. Because corium spreading is a complex process strongly influenced by coupled chemical reactions (with underlying containment material and especially with the proposed SM), decay heat and phase change. No existing tool is available for modeling such a complex process. This LDRD project focused on two research areas: experiments to demonstrate the feasibility of the novel SM concept, and modeling activities to determine the potential applications of the concept to actual nuclear plants. We have demonstrated small-scale to large-scaled experiments using lead oxide (Pb0) as surrogate for molten corium, which showed that the reaction of the SM with molten Pb0 results in a fast solidification of the melt and the formation of open pore structures in the solidified Pb0 because of CO 2 released from the carbonate decomposition. Our modeling simulations show that Sierra Mechanics/Aria code can be used to model a molten corium spreading experiment and the PbO/carbonate experiment. A simplified carbonate decomposition model has been developed to predict thermal decomposition of carbonate mineral in contact with corium. This model has been incorporated into an input model for MELCOR, a severe accident nuclear reactor code developed by Sandia National Laboratories for the U.S. Nuclear Regulatory Commission. A full-plant MELCOR simulation suggests that the ex-vessel accident progression, e.g., core-concrete interaction and core spreading on the containment floor, could be significantly delayed by the introduction of SM to the reactor cavity prior to the reactor pressure vessel failure. Delays of one and half day are suggested with limited SM. Filling the cavity with SM might delay progression by days. Additionally, the modeling suggests that the relative concentration (molar fraction) of hydrogen in containment could be substantially reduced by the non-condensable gas (CO 2 ) generation associated with the SM reaction effectively making the hydrogen concentration below its flammable limit. ACKNOWLEDGEMENTS This research was supported by the Laboratory Directed Research and Development Program of Sandia National Laboratories (Sandia). The authors would like to express thanks to all Sandia staff who helped with this research, including Ms. Denise Bencoe for assisting with the performance of the small-scaled experiments at Advanced Material Laboratories, Ms. Amanda Sanchez and Ms. Lydia Boisvert for grinding all natural carbonate materials and sieving, Dr. Anne Grillet for measuring the microstructure of the samples using X-ray micro CT Scan (SKYSCAN 1272), Dr. Clay Payne for the XRD measurement, Dr. Eric Lindgren for assisting the selection of crucible materials, Dr. Larry Humphries for review this report and Dr. Randall O. Gauntt for reviewing this research, who has retired from Sandia at the time of this publication. The authors like to thank Ms. Laura Sowko for editing this report. Additionally, the authors appreciated the use of the FARO L-26S data information described in Section 4.2.2.1 of this report downloaded from STRESA, Joint Research Centre, European Commission (c) Euratom, 2019.
Our results show that a pseudo-boehmite precursor material can be chemically modified with divalent cationic species, for example, Nickel, to create an effective getter for anionic species. The viability of this novel class of materials is established by a variety of characterization methods, including surface area measurements, scanning electron microscopy, elemental analysis, and sorption capacity measurements. We will present the results of sorption capacity and surface area measurements that show the high sorption capacity of this novel class of getter materials. Our study shows that the divalent cation modification can increase the sorption capacity by as much as a factor of two.
An ongoing Sandia National Laboratories’ (SNL) research study is evaluating a potential design of an injectable sacrificial material (SM) system that could contain and cool corium ejected from a reactor vessel lower head failure during a potential severe accident involving melting fuel at a commercial light water nuclear reactor (LWR). An injectable system could be installed at any existing LWR, without significant modification to the cavity or to the drywell pedestal region of the plant. The conceptual design under consideration is a passive system. The SM is being optimized to quickly cool the corium mixture while creating gas to form porosity in the solid, such that subsequent water flooding can penetrate the structure and provide additional cooling. The SM would form a barrier and limit corium-concrete interactions. This three-year project takes a joint experimental and computational approach. In this paper, we will first discuss the success of our small-scale experiments conducted on the interactions between the surrogate corium material (SCM) and SM, used to evaluate the injectable concept. A larger experimental study, currently underway, will further validate the injectable concept, with a focus on accurately measuring interactions. This paper details the modeling study and its progress, including modeling the experiments on a surrogate system and extending the model to bench-scale corium flow from validation experiments. The project’s modeling studies will use the SNL engineering code suite SIERRA Mechanics to understand the interaction of injectable SM and molten corium and predict corium spreading. Spreading is modeled using a level set method to track the front in conjunction with a pressure-stabilized finite element method on the fully three-dimensional mass, momentum, and energy conservation equations. Using this diffuse-interface method, the corium spreading front can be tracked and an appropriate pseudo-solidification viscosity models can be implemented to accurately model the corium spreading physics. Finally, an injectable SM delivery system is discussed along with its deployment to the six-common commercial LWR designs currently operating in the United States. At the end of this project, a simplified model based on SIERRA simulations will be developed for implementation into MELCOR, a severe reactor analysis code, developed at SNL for the U.S. Nuclear Regulatory Commission. This will allow us to demonstrate the ability of the injectable SM system to mitigate the ex-vessel corium spreading, provide containment and negate the release of radionuclides.
Molecular structures of kerogen control hydrocarbon production in unconventional reservoirs. Significant progress has been made in developing model representations of various kerogen structures. These models have been widely used for the prediction of gas adsorption and migration in shale matrix. However, using density functional perturbation theory (DFPT) calculations and vibrational spectroscopic measurements, we here show that a large gap may still remain between the existing model representations and actual kerogen structures, therefore calling for new model development. Using DFPT, we calculated Fourier transform infrared (FTIR) spectra for six most widely used kerogen structure models. The computed spectra were then systematically compared to the FTIR absorption spectra collected for kerogen samples isolated from Mancos, Woodford and Marcellus formations representing a wide range of kerogen origin and maturation conditions. Limited agreement between the model predictions and the measurements highlights that the existing kerogen models may still miss some key features in structural representation. A combination of DFPT calculations with spectroscopic measurements may provide a useful diagnostic tool for assessing the adequacy of a proposed structural model as well as for future model development. This approach may eventually help develop comprehensive infrared (IR)-fingerprints for tracing kerogen evolution.