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High Level Gap Analysis for Accident Tolerant and Advanced Fuels for Storage and Transportation

This initial gap analysis considers proposed accident tolerant fuel (ATF) options currently being irradiated in commercial reactors, since these are most likely for future batch implementation. Also, advanced fuel (AF) options that may be likely for use in advanced reactors are considered. The cladding technologies considered were chromium-coated zirconium-based alloys, FeCrAl, and both monolithic and matrix composite Silicide carbide (SiC). The fuel technologies considered were chromium-doped uranium dioxide fuel, uranium alloys, uranium nitride, and uranium silicide. Numerous national labs, industry, and countries are performing significant testing and modeling on these proposed technologies to establish performance, but at this time none of the prototypes being irradiated have achieved end-of-life (EOL) burnup. There are some testing results after one burnup cycle to verify in-reactor performance, but little data beyond that. As the ATF prototypes acquire more burnup, data will be produced that is relevant to storage and transportation. The DOE:NE Spent Fuel and Waste Science and Technology (SWFST) Storage and Transportation (ST) Control Account will evaluate the performance data as it becomes available for application to the identified gaps for ST.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Fundamental Studies of Tritium Diffusivity in Pure and Defective Zircaloy-4 Getters (Tritium Science Program FY2020 Report)

Zirconium (Zr) alloys are extensively used as tritium (T) getters in nuclear reactors due to their low absorption cross section to thermal neutron, good mechanical properties at high temperature and resistant to corrosion in different environmental conditions. Zr alloys have better thermal properties than many other refractory alloys including stainless steel. The nuclear characteristic is simulated, and T is produced in tritium-producing burnable absorber rods (TPBAR) by the irradiation of neutron flux in pressurized water reactor (PWR). T thus produced diffuses through the pellets and is captured by the getter where it chemically reacts with Zr to form metal hydride (ZrTx). These hydrides are brittle and affect adversely the mechanical properties of alloys. In addition to that, mismatch in the lattice structures after hydride formation creates a stress which needs to be considered in component design and their life evaluation. Therefore, understanding the behavior of T and its species becomes significant as fuel burnup is increased, which leads to increase in hydrogen pickup and oxide formation. The transport of T and its species in pure Zr alloys, and in alloys with certain alloying elements and defects are important to understand in order to enhance the performance of the materials.

36 MATERIALS SCIENCE↗

Report on Thermal Cycling Testing and Bimaterial Weld Development for a Passively Actuated Materials Surveillance Test Article

This report describes the continuation and conclusion of a thermal cycling test program designed to evaluate a family of passively actuated material surveillance test articles. Additionally, the report details a preliminary study of bimetallic welding between 316 stainless steel and TZM (tungsten-zirconium-molybdenum) alloy. The test program was ultimately successful in demonstrating the basic viability of the passively actuated test article concept as well as specifically validating the procedures developed to size specimens to mimic the mechanical response of operating components. The report discusses and summarizes the results of the complete test program which tested samples for more than 1,000 controlled thermal cycles. The weld development program included both stir friction and electron beam joining. The stir friction welding was ultimately successful, while the electron beam welding would require additional development. Ultimately, these test programs pave the way for implementing a materials surveillance program in future molten salt reactors (MSRs). The report conclusions outline a plan for transforming the research and developed described here into a definite set of practices and procedures for a surveillance program at a future operating reactor.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Fuel Performance Analysis of Chromium-Coated Cladding under Burst Conditions

To reduce the oxidation of zirconium-based alloy cladding at high temperatures, accident tolerant fuel systems have been proposed. Of the concepts identified, chromium-coated cladding has been shown to slow oxidation without greatly impacting the fuel system geometry or neutronic performance. To determine how coated-cladding tubes will perform under high-temperature accident conditions, pressurized-tube burst tests have been performed using the Severe Accident Test Station at Oak Ridge National Laboratory. To begin modeling these tubes to better understand how the coating will impact cladding behavior, these burst tests were simulated with the BISON fuel performance code. Cladding tube surface temperatures for the burst test were developed by fitting thermocouple data into axial and azimuthal profiles, while pressure data were compared until cladding failure. The temperatures at failure and the pressure evolution show relatively good agreement between the simulation and experiment results. This is the first step of a larger effort to simulate the cladding deformation process under high-temperature transient conditions and assess the cladding margin to failure more accurately.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Oxidation-resistant coatings for refractory metals used in inert atmospheres

Test conditions and results are reported for various coatings on a 1 percent zirconium columbium alloy at a temperature of 2000 deg F. Molybdenum silicide over molybdenum is most effective coating, tin-aluminum coating is adequately protective, chromium-molybdenum silicides are not protective.

Phillips, W. M.↗

A simplified design procedure for life prediction of rocket thrust chambers

An analytical procedure for predicting thrust chamber life is developed. The hot-gas-wall ligaments separating the coolant and combustion gas are subjected to pressure loading and severe thermal cycling. The resulting stresses interact during plastic straining causing incremental bulging of the ligaments during each firing cycle. This mechanism of plastic ratcheting is analyzed and a method using a yield surface for combined bending and membrane loading developed for determining the incremental permanent deflection and progressive thinning near the center of the ligaments. Fatigue and tensile instability are analyzed as possible failure modes. Results of the simplified analyses compare favorably with available experimental data and finite element analysis results for OFHC (Oxygen Free High Conductivity) copper. They are also in reasonably good agreement with experimental data for NARloy Z, a copper-zirconium-silver alloy developed by the Rocketdyne Division of Rockwell International.

Porowski, J. S.↗

Fabrication and Evaluation of Titanium and Zirconium based Wires for use during Extended, Deep Space, Missions

Novel materials and designs are necessary for transport vessels and propulsion systems to fulfill NASA's vision of easier access to space and the expansion of human exploration beyond low-earth orbit. Spacecraft components must necessarily be lighter and stronger than their predecessors and will likely be required to serve new purposes. Furthermore, they must be resilient to the thermal, vacuum, and radiation environment of space for extended periods of time and may need to perform in the near proximity of a nuclear fuel source. To this end research has been initiated to fabricate novel, composite, wires based on titanium and zirconium pearlitic alloys. It is expected that the fabricated wire will well endure in the space environment with application as tethers, sail components, fasteners, and a myriad of other (including earth-based) uses. A background on pearlitic wire, novel alloy development, microstructural characterization, and initial mechanical testing results will be presented and discussed.

Grugel, Richard N.↗

Fundamental Studies of Tritium Formation and Diffusivity in Pure and Defective Zircaloy-4 Getters

Zirconium (Zr) alloys have excellent mechanical properties at high temperature and are resistant to corrosion in different environmental conditions. These alloys are used as tritium (3H or T) getters in nuclear reactors due to their low absorption cross section to thermal neutrons and excellent thermo-mechanical properties. Zr alloys have better mechanical and thermal properties than many other refractory alloys including stainless steel. After the irradiation of TPBAR by neutron flux, 3H produced during irradiation diffuses though the pellets and is captured by the getter. 3H chemically reacts with Zr metal to form metal hydride (ZrTx). Hydrides thus formed are brittle and adversely affect the mechanical and thermal properties of alloys. The lattice mismatch at the interface of alloy and metal hydrides also creates a stress that significantly reduces the alloy’s performance and operation life. Therefore, understanding the behavior of 3H and its species becomes significant as fuel burnup is increased, which leads to increase in hydrogen pickup and oxide formation.

Duan, Yuhua↗

Identifying Challenges in Safeguards for Metallic Fuel Fabrication Facilities

As new advanced reactors gain popularity, there is an increasing interest in metallic fuel fabrication for fast reactors. While metallic fuels themselves are not a new idea, as many of the first reactors employed metallic fuels, new designs, compositions, and fabrication methods are appearing throughout the nuclear community. As the interest grows and facilities are constructed, both domestic and international safeguards will need to be heavily involved to support safeguards-by-design (SBD) measures from the start. This work compiles a review of historical and modern fuel types and fabrication methods, fabrication processes, safeguards gaps, and potential safeguards solutions. Metallic nuclear fuel types have been around for many decades and were included in some of the first reactors including the Experimental Breeder Reactor (EBR)-I and -II, the Fermi 1 reactor, the Integral Fast Reactor (IFR), and the Dounreay Fast Reactor (DFR). These reactors used various compositions including pure uranium (U) metal, U-zirconium (Zr) alloys, plutonium (Pu)-aluminum (Al) alloys, U-fissium (Fs) alloys, U-Pu-Zr alloys, and U-molybdenum (Mo) alloys [1, 2, 3, 4, 5]. These small alloying additions are included to improve the material properties of the pure U metal. The alpha-phase U (stable below 661C) suffers elongation in one direction causing grain boundary cracking and increasing creep rate due to irradiation growth, thermal cycling, and preferential crystal orientation. It is ideal to utilize the gamma-phase U (typically stable above 769C) by adding small amounts of alloying elements such as Zr or Mo to stabilize this phase down to room temperature [3]. Additionally, some research has been focused on U with transuranic (TRU) elements present, typically coming from the used fuel recycling process. Including these elements in fast reactor fuel can aid in the reduction of nuclear waste by burning minor long-lived actinides. However, the additions of TRU elements can cause concerns to arise when trying to fabrication or safeguard metallic fuels. A typical metallic fuel element is shown in Figure 1. Sodium is added into the cladding to create a thermal bond between the fuel slug and cladding wall. The fuel slug is then inserted and the end plug is welded on to the top of the fuel element. A gas plenum is left to create a headspace for gaseous fission products to escape rather than continue to build in the fuel itself [1, 5]. Other fuel element geometries exist as well, such as the Lightbridge twisted cruciform geometry shown in Figure 2 [6]. This design allows for better cooling performance and provides room for fuel rod swelling without impacting the fuel rod diameter. There are many different fabrication methods for metallic fuels, which is one of the many benefits of these fuel types. Many of these fabrication methods are relatively easy and cost-efficient. The most popular fabrication method is injection casting, sometimes called vacuum induction melting (VIM), shown in Figure 3 [4, 8, 9, 7, 10]. This method was largely used for EBR-II fuel fabrication. The injection casting system is contained inside of a vessel consisting of a Y2O3-coated graphite crucible surrounded by an induction coil with ZrO2-coated quartz molds suspended above the crucible. The fuel feedstock is placed inside of the graphite crucible and melted using the induction furnace. The induction furnace utilizes a dual frequency with the high frequency melting the feedstock and the low frequency causing stirring of the melted feedstock to form a homogeneous mixture. The mixture is heated to approximately 1600C in an argon environment. The vessel is evacuated and then the quartz molds are lowered into the graphite crucible containing the molten metal and the vessel is repressurized to inject the metal fuel upwards into the molds. The molds are removed and then shattered to release the fuel slugs. This fabrication method was used to fabricate 39,000 metallic fuel pins for EBR-II. While injection casting has been the most common metallic fuel fabrication method throughout the decades, many other methods have been explored including low-pressure gravity casting, microwave casting, continuous casting, centrifugal casting, coextrusion, and many others [11, 12, 8, 13, 14, 15]. Some of these methods aim to mitigate challenges that arise with americium (Am) volatilization during the casting process for TRU-containing fuel feedstocks, an issue with injection casting. Coextrusion is one of the methods explored at the Idaho National Laboratory (INL) and has been utilized for the initial fabrication tests of Lightbridge's unique fuels, as well as other metallic fuels with cladding coextruded. In this process, large billets are formed and machined and then inserted into a molten salt bath for approximately 30 minutes. The billets are then loaded into the extrusion press and extruded. This process can be seen in Figure 4 [15].

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

A simple spectrophotometric method for determination of zirconium or hafnium in selected molybdenum-base alloys

A simple analytical procedure is described for accurately and precisely determining the zirconium or hafnium content of molybdenum-base alloys. The procedure is based on the reaction of the reagent Arsenazo III with zirconium or hafnium in strong hydrochloric acid solution. The colored complexes of zirconium or hafnium are formed in the presence of molybdenum. Titanium or rhenium in the alloy have no adverse effect on the zirconium or hafnium complex at the following levels in the selected aliquot: Mo, 10 mg; Re, 10 mg; Ti, 1 mg. The spectrophotometric measurement of the zirconium or hafnium complex is accomplished without prior separation with a relative standard deviation of 1.3 to 2.7 percent.

Dupraw, W. A.↗

Rapid Quench in an Electrostatic Levitator

The Electrostatic Levitation (ESL) Laboratory at the NASA Marshall Space Flight Center (MSFC) is a unique facility for investigators studying high-temperature materials. The ESL laboratory's main chamber has been upgraded with the addition of a rapid quench system. This system allows samples to be dropped into a quench vessel that can be filled with a low melting point material, such as a gallium or indium alloy, as a quench medium. Thereby allowing rapid quenching of undercooled liquid metals. Up to eight quench vessels can be loaded into a wheel inside the chamber that is indexed with control software. The system has been tested successfully with samples of zirconium, iron-cobalt alloys, titanium-zirconium-nickel alloys, and a silicon-cobalt alloy. This new rapid quench system will allow materials science studies of undercooled materials and new materials development. In this presentation, the system is described and some initial results are presented.

SanSoucie, Michael P.↗

An exploratory study of a zirconium-modified, precipitation-strengthened nickel-30 copper alloy

A precipitation-strengthened alloy has been produced through minor additions of zirconium to a base Ni-30Cu alloy. The results of this exploratory study indicate that thermomechanical processing of a solution-treated Ni-30Cu-0.2Zr alloy produced a dispersion of precipitates. The precipitates have been tentatively identified as a Ni5Zr compound. Comparison of the mechanical properties, as determined by testing in air, of the Zr-modified alloy to those of a Ni-30Cu alloy reveals that the precipitation-strengthened alloy has improved tensile properties to 1200 K and improved stress-rupture properties to 1100 K. The oxidation characteristics of the modified alloy appeared to be equivalent to those of the base Ni-30Cu alloy.

Whittenberger, J. D.↗

Acoustic emission characteristics of copper alloys under low-cycle fatigue conditions

The acoustic emission (AE) characteristics of pure copper, zirconium-copper, and several copper alloys were determined to develop nondestructive evaluation schemes of thrust chambers through AE techniques. The AE counts rms voltages, frequency spectrum, and amplitude distribution analysis evaluated AE behavior under fatigue loading conditions. The results were interpreted with the evaluation of wave forms, crack propagation characteristics, as well as scanning electron fractographs of fatigue-tested samples. AE signals at the beginning of a fatigue test were produced by a sample of annealed alloys. A sample of zirconium-containing alloys annealed repeatedly after each fatigue loading cycle showed numerous surface cracks during the subsequent fatigue cycle, emitting strong-burst AE signals. Amplitude distribution analysis exhibits responses that are characteristic of certain types of AE signals.

Krampfner, Y.↗

NbZr_BCC_SolidSolution_128atoms_VASP6

We performed density functional theory (DFT) calculations for body-centered-cubic (BCC) structures with 128 lattices sites of solid solution binary alloys niobium-zirconium (Nb-Zr). The electronic structures of alloys have been calculated using Vienna Ab initio Simulation Package (VASP). Within this package the DFT approach is used to reduce many-body Schrodinger equation to set of single particle Kohn-Sham (KS) equations. The generalized electronic exchange-correlation functional is described by generalized gradient approximation with the Perdew-Burke-Ernzerhof parametrization. The electron-ion interactions is described by pseudopotentials developed within the plane-wave basis projector augmented-wave (PAW) approach \cite{PAW}. These pseudopotentials are available at the VASP portal (http://cms.mpi.univie.ac.at/vasp/). Our calculations have been run with the pseudopotentials treating s and p semi-core states as valence in case for the elements Nb and Zr. The electronic densities and potentials are expanded over plane-waves with energy cutoff of 350 eV. 2x2x2 k-mesh and normal precision were used. The alloys were modeled by supercell containing 128 randomly distributed atoms. At initial step the atoms occupy perfect bcc lattice cites. This initial structure was optimized until energy changes less than 1e-6 eV, while forces acting on atoms don't exceed 1e-2 eV/angstrom. The electron-ion interaction is described by PAW pseudopotentials. The calculations have been collected by sampling chemical compositions across the entire compositional range. The chemical compositions have been sampled by progressively changing the number of atoms per constituent by 4. For each chemical composition of binaries and ternaries, the first-principle calculations have been run for 100 randomized arrangements of the constituents on the BCC lattice sites. We collected data for a total of 3,100 randomized atomic structures over 31 chemical compositions. The calculations have been collected on NERSC-Perlmutter and OLCF-Summit using the VASP 6.3.2. The VASP calculations for every atomic structure have been performed in 2 main steps: 1. Starting from an ideal body-centered-cubic (BCC) structure, geometry optimization with low precision has been executed to perform a preliminary optimization of the atomic structure. The output for this calculations is available in the files 0.CONTCAR, 0.OUTCAR, rlx1.out. 2. Using the atomic structure resulting from the preliminary geometry optimization, a second geometry optimization has been performed using normal precision. The output for this calculations is available in the files CONTCAR, OUTCAR, rlx2.out, vaspout.h5, and vasprun.xml. Cases 1-10 have been run without generating the file 'vaspout.h5'. Every chemical composition sampled across the composition range in the dataset has its own directory. The convention used to name the directories for binary alloys is AXBY, where A and B refer to the constituents, whereas X and Y are positive integers that represent the number of atoms for each constituent and their values still sum up to 128. Each atomic structure associated with a specific chemical composition has its own sub-directory within the directory of the corresponding chemical composition. The sub-directories for each atomic structure for each chemical composition are named 'case-*', where * is a positive integer that spans all the values from 1 through 100, extremes included. The files contained in each sub-directory 'case-*' for each atomic structure are as follows: FILES contained in each subdirectory with name "case-N" where N ranges between 11 and 100, extremes included: 1. INCAR: input file that contains various parameters and settings for controlling the behavior of the electronic structure calculations 2. KPOINTS: input file that specifies the Bloch vectors (k points) used to sample the Brillouin zone 3. 0.POSCAR: input file that defines the atomic structure of a system 4. 0.CONTCAR: output file that provides the atomic positions and cell parameters after the first geometry optimization has been run with the precision variable set to PREC=Low in the INCAR file 5. 0.OUTCAR: output file that contains detailed information about the progress of a calculation after the first geometry optimization has been run with the precision variable set to PREC=Low in the INCAR file 6. rlx1.out: file with diagnostic information about the execution of the first geometry optimization with precision variable set to PREC=Low in the INCAR file 7. POSCAR: input file that defines the atomic structure of a system after the first geometry optimization has been run at low precision. This represents the input for the second geometry optimization run with the precision variable set to PREC=Normal in the INCAR file 8. CONTCAR: output file that provides the atomic positions and cell parameters after the second geometry optimization has been run with the precision variable set to PREC=Normal in the INCAR file 9. OUTCAR: output file that contains detailed information about the progress of a calculation after the second geometry optimization has been run with the precision variable set to PREC=Normal in the INCAR file 10. rlx2.out: file with diagnostic information about the execution of the second geometry optimization with precision variable set to PREC=Normal in the INCAR file 11. vaspout.h5: hierarchical HDF5 file containing the inputs and outputs of a VASP calculation. To analyze the data in this file we recommend using py4vasp. This file is only produced if the VASP version used is compiled with HDF5 support 12. vasprun.xml: contains similar information to OUTCAR, but in an xml format. 13. CHGCAR: contains the charge density data of a system. This data is crucial for analyzing electronic structures, calculating electrostatic potential, and studying the distribution of charge in a crystal or molecular system FILES contained in each subdirectory with name "case-N" where N ranges between 1 and 10, extremes included: 1. INCAR: input file that contains various parameters and settings for controlling the behavior of the electronic structure calculations 2. KPOINTS: input file that specifies the Bloch vectors (k points) used to sample the Brillouin zone 3. {ID}.POSCAR: input file that defines the atomic structure of a system at the beginning of ID execution of geometry optimization with PREC=LOW 4. {ID}.CONTCAR: output file that provides the atomic positions and cell parameters at the end of ID execution of geometry optimization with PREC=LOW in the INCAR file 5. {ID}.OUTCAR: output file that contains detailed information about the progress of a calculation after the ID execution of geometry optimization that has been run with the precision variable set to PREC=Low in the INCAR file 6. rlx1.{ID}.out: file with diagnostic information about the execution of the ID execution of the geometry optimization with precision variable set to PREC=Low in the INCAR file 7. N{ID}.POSCAR: input file that defines the atomic structure of a system after the geometry optimization run at low precision. This represents the input for the ID execution of the second geometry optimization run with the precision variable set to PREC=Normal in the INCAR file 8. N{ID}.CONTCAR: output file that provides the atomic positions and cell parameters after the ID execution of the geometry optimization run with the precision variable set to PREC=Normal in the INCAR file 9. N{ID}.OUTCAR: output file that contains detailed information about the progress of a calculation after the ID execution of the geometry optimization run with the precision variable set to PREC=Normal in the INCAR file 10. rlx2.{ID}.out: file with diagnostic information about the ID execution of geometry optimization with precision variable set to PREC=Normal in the INCAR file 11. vaspout.h5: hierarchical HDF5 file containing the inputs and outputs of a VASP calculation. To analyze the data in this file we recommend using py4vasp. This file is only produced if the VASP version used is compiled with HDF5 support 12. vasprun.xml: contains similar information to OUTCAR, but in an xml format. 13. CHGCAR: contains the charge density data of a system. This data is crucial for analyzing electronic structures, calculating electrostatic potential, and studying the distribution of charge in a crystal or molecular system This research is sponsored by the Artificial Intelligence Initiative as part of the Laboratory Directed Research and Development (LDRD) Program of Oak Ridge National Laboratory, managed by UT-Battelle, LLC, for the US Department of Energy under contract DE-AC05-00OR22725. This work used resources of the Oak Ridge Leadership Computing Facility, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC05-00OR22725, under Directorate Discretionary awards MAT025 (Materials Science) and LRN026 (Machine Learning), and INCITE award MAT201. This work also used resources of the National Energy Research Scientific Computing Center, which is supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231, under award ERCAP0025216. REFERENCES (1) Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. Phys. review B 47, 558 (1993). (2) Kresse, G. & Hafner, J. Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium. Phys. Rev. B 49, 14251 (1994) (3) Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. materials science 6, 15–50 (1996) (4) Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. review B 54, 11169 (1996) (5) Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. review b 59, 1758 (1999)

36 MATERIALS SCIENCE↗