Yutai Katoh

The Advanced Fuels Campaign within the Fuel Cycle Research and Development program of the Department of Energy (DOE) Office of Nuclear Energy is currently investigating a number of advanced nuclear fuel cladding concepts to improve the accident tolerance of light water reactors (LWRs). Some of the leading candidates to replace traditional zirconium-based cladding are aluminaforming ferritic alloys (e.g., FeCrAl) and silicon carbide (SiC) composites. Oak Ridge National Laboratory has developed experimental designs to irradiate thin-walled cladding tubes with representative geometry in the High Flux Isotope Reactor (HFIR) under relevant LWR temperatures and in some cases under prototypic heat flux. These designs allow for post-irradiation examination (PIE) of cladding which closely resembles expected commercially viable geometries and microstructures. PIE will include studies of dimensional change, microstructure variation, mechanical performance, etc. The experiments were designed using relatively inexpensive rabbit capsules for the irradiation vehicle. The simplistic designs combined with the extremely high neutron flux in the HFIR allow for rapid testing of a large test matrix, thus reducing the time and cost for moving advanced cladding materials closer to commercialization. This work describes the capsule designs that have been developed at ORNL, some initial results, and plans for future irradiations.

Ceramic fiber–matrix composites (CFMCs) are exciting materials for engineering applications in extreme environments. By integrating ceramic fibers within a ceramic matrix, CFMCs allow an intrinsically brittle material to exhibit sufficient structural toughness for use in gas turbines and nuclear reactors. Chemical stability under high temperature and irradiation coupled with high specific strength make these materials unique and increasingly popular in extreme settings. This paper first offers a review of the importance and growing body of research on fiber–matrix interfaces as they relate to composite toughening mechanisms. Second, micropillar compression is explored experimentally as a high-fidelity method for extracting interface properties compared with traditional fiber push-out testing. Three significant interface properties that govern composite toughening were extracted. For a 50-nm-pyrolytic carbon interface, the following were observed: a fracture energy release rate of ~2.5 J/m2, an internal friction coefficient of 0.25 ± 0.04, and a debond shear strength of 266 ± 24 MPa. This research supports micromechanical evaluations as a unique bridge between theoretical physics models for microcrack propagation and empirically driven finite element models for bulk CFMCs.

This document outlines the irradiation of silicon carbide cladding tube specimens in the High Flux Isotope Reactor at Oak Ridge National Laboratory. The cladding tube specimens consisted of monolithic, composite, and coated SiC specimens in order to test the effect of these various materials on the overall cladding performance during irradiation. A total of 18 specimens were irradiated for one cycle, with 9 specimens irradiated at low heat flux conditions and 9 specimens at high heat flux conditions. The specimens were inserted in cycle 475 in September 2017 and reached an average irradiation dose of approximately 2.6 dpa.

Swelling, or volumetric expansion, is an inevitable consequence of the atomic displacement damage in crystalline silicon carbide (SiC) caused by energetic neutron irradiation. Because of its steep temperature and dose dependence, understanding swelling is essential for designing SiC-based components for nuclear applications. In this study, swelling behaviors of monolithic CVD SiC and nuclear grade SiC fiber – SiC matrix (SiC/SiC) composites were accurately determined, supported by the irradiation temperature determination for individual samples, following neutron irradiation within the lower transition swelling temperature regime. Slightly anisotropic swelling behaviors were found for the SiC/SiC samples and attributed primarily to the combined effects of the pre-existing microcracking, fiber architecture, and specimen dimension. A semi-empirical model of SiC swelling was calibrated and presented. Finally, implications of the refined model to selected swelling-related issues for SiC-based nuclar reactor components are discussed.

The initial results of a post-irradiation examination study conducted on a SiC-SiC tubular specimen irradiated under a high radial heat flux are presented herein. The elastic properties of the specimen were evaluated before and after the irradiation using the resonant ultrasound spectroscopy (RUS) technique. The composite tubular specimen was considered as an orthotropic elastic with nine elastic constants (Young's moduli, shear moduli and Poisson's ratios—three components of each) for representing its full elastic deformation behavior. All the elastic moduli decreased after irradiation; the reduction was as high as 35% in one of the moduli. The significant decrease in the moduli indicates the presence of microcracks. The results from a computational study show significant stress development in the specimen due to irradiation, primarily caused by differential swelling across the thickness of the specimen. The evaluated stresses exceed the proportional limit stress of the material, indicating the likelihood of matrix microcracking, and thus corroborating the results obtained from RUS. X-ray Computed Tomography (XCT) study confirmed the presence of cracks in the irradiated specimen. These cracks occurred at the inner region of the specimen and propagated in axial and hoop directions. These XCT results are in agreement with the RUS results and stress distribution results from the computational study.

The equilibrium shape of 6H-SiC nanostructures and their surfaces were studied by analyzing nano-void (10 nm) shapes, which were introduced in monocrystalline 6H-SiC by hightemperature neutron irradiation, using transmission electron microscopy. The nano-voids were determined to be irregular icosahedrons truncated with six {1100}, twelve f1103}, one smaller top-basal, and one larger bottom-basal planes, which suggests that {1100} and f1103} are the next stable surface class after the basal planes. The relatively frequent absence of the {1100} surface in the nano-voids indicated that the (1103Þ surface type is energetically rather stable. These non-basal surfaces were found not to be atomically flat due to the creation of nanofacets with half unit-cell height in the c-axis. The {1100} and f1103} surfaces were classified as two and four face types according to their possible nanofacets and surface termination, respectively. We also discuss the surface energy difference between the (1103) and (1103) face types in relation to the energy balance within the equilibrium, but irregular, polyhedron, in which the (1103) surface had double the surface energy of the (1103Þ surface (3900 erg/cm2)

The initial results of a post-irradiation examination study conducted on CVD SiC tubular specimens irradiated under a high radial heat flux are presented herein. The elastic moduli were found to decrease more than that estimated based on previous studies. The significant decreases in modulus are attributed to the cracks present in the specimens. The stresses in the specimens, calculated through finite element analyses, were found to be greater than the expected strength of irradiated specimens, indicating that the irradiation-induced stresses caused these cracks. The optical microscopy images and predicted stress distributions indicate that the cracks initiated at the inner surface and propagated outward.

The purpose of this work is to design an irradiation vehicle for testing silicon carbide (SiC) fiber-reinforced SiC matrix composite cladding materials under conditions representative of a light water reactor in order to validate thermo-mechanical models of stress states in these materials due to irradiation swelling and differential thermal expansion. The design allows for a constant tube outer surface temperature in the range of 300–350 °C under a representative high heat flux (~0.66 MW/m2) during one cycle of irradiation in an un-instrumented “rabbit” capsule in the High Flux Isotope Reactor. An engineered aluminum foil was developed to absorb the expansion of the cladding tubes, due to irradiation swelling, without changing the thermal resistance of the gap between the cladding and irradiation capsule. Finite-element analyses of the capsule were performed, and the models used to calculate thermal contact resistance were validated by out-of-pile testing and post-irradiation examination of the foils and passive SiC thermometry. Six irradiated cladding tubes (both monoliths and composites) were irradiated and subsequently disassembled in a hot cell. The calculated temperatures of passive SiC thermometry inside the capsules showed good agreement with temperatures measured post-irradiation, with two calculated temperatures falling within 10 °C of experimental measurements. The success of this design could lead to new opportunities for irradiation applications with materials that suffer from irradiation swelling, creep, or other dimensional changes that can affect the specimen temperature during irradiation.

We irradiated four ferritic alloys with energetic Fe and He ions: one castable nanostructured alloy (CNA) containing Ti-W-Ta-carbides, and three nanostructured ferritic alloys (NFAs). The NFAs were: 9Cr containing Y-Ti-O nanoclusters, and two Fe-12Cr-5Al NFAs containing Y-Zr-O or Y-Hf-O clusters. All four were subjected to simultaneous dual-beam Fe + He ion implantation (650 °C, ~50 dpa, ~15 appm He/dpa), simulating fusion-reactor conditions. Examination using scanning/transmission electron microscopy (STEM) revealed high-number-density helium bubbles of ~8 nm, ~1021 m-3 (CNA), and of ~3 nm, 1023 m-3 (NFAs). STEM combined with multivariate statistical analysis data mining suggests that the precipitate-matrix interfaces in all alloys survived ~50 dpa at 650 °C and serve as effective helium trapping sites. All alloys appear viable structural material candidates for fusion or advanced fission energy systems. Among these developmental alloys the NFAs appear to sequester the helium into smaller bubbles and away from the grain boundaries more effectively than the early-generation CNA.

Monolithic silicon carbide (SiC) to SiC plate joints were fabricated and irradiated with neutrons at 270–310 °C to 8.7 dpa for SiC. The joining methods included solid state diffusion bonding using titanium and molybdenum interlayers, SiC nanopowder sintering, reaction sintering with a Ti-Si-C system, and hybrid processing of polymer pyrolysis and chemical vapor infiltration (CVI). All the irradiated joints exhibited apparent shear strength of more than 84 MPa on average. Significant irradiation-induced cracking was found in the bonding layers of the Ti and Mo diffusion bonds and Ti-Si-C reaction sintered bond. The SiC-based bonding layers of the SiC nanopowder sintered and hybrid polymer pyrolysis and CVI joints all showed stable microstructure following the irradiation.

Five variants of nano-infiltration transient eutectic (NITE) SiC were prepared using nanopowder feedstock and sintering additive contents of <10 wt%. The dense monolithic materials were subsequently irradiated to 2 and 10 dpa in a mixed spectrum fission reactor at nominally 400 and 700 °C. The evolution in swelling, strength, and thermal conductivity of these materials were examined after irradiation, where in all cases properties saturated at < 2dpa, without appreciable change for further irradiation to 10 dpa. Swelling behavior appeared similar to high-purity chemical vapor deposition (CVD) SiC within measurement uncertainty. The strength roughly doubled after irradiation. Thermal resistivity increase as a result of irradiation was ~20% higher when compared to CVD-SiC.

We observed that ß-SiC, neutron irradiated to 9?dpa (displacements per atom) at ˜1440?°C, began transforming to a-SiC, with radiation-induced Frank dislocation loops serving as the apparent nucleation sites. 1440?°C is a far lower temperature than usual ß???a phase transformations in SiC. SiC is considered for applications in advanced nuclear systems, as well as for electronic or spintronic applications requiring ion irradiation processing. ß-SiC, preferred for nuclear applications, is metastable and undergoes a phase transformation at high temperatures (typically 2000?°C and above). Nuclear reactor concepts are not expected to reach the very high temperatures for thermal transformation. However, our results indicate incipient ß???a phase transformation, in the form of small (~5–10?nm) pockets of a-SiC forming in the ß matrix. In service transformation could degrade structural stability and fuel integrity for SiC-based materials operated in this regime. However, engineering this transformation deliberately using ion irradiation could enable new electronic applications.

Silicon carbide (SiC) fiber–reinforced SiC matrix (SiC/SiC) composites are being actively investigated for use in accident-tolerant core structures of light water reactors (LWRs). Owing to the limited number of irradiation studies previously conducted at LWR-coolant temperature, this study examined SiC/SiC composites following neutron irradiation at 230–340 °C to 2.0 and 11.8 dpa in the High Flux Isotope Reactor. The investigated materials were chemical vapor infiltrated (CVI) SiC/SiC composites with three different reinforcement fibers. The fiber materials were monolayer pyrolytic carbon (PyC) -coated Hi-Nicalon™ Type-S (HNS), Tyranno™ SA3 (SA3), and SCS-Ultra™ (SCS) SiC fibers. The irradiation resistance of these composites was investigated based on flexural behavior, dynamic Young's modulus, swelling, and microstructures. There was no notable mechanical properties degradation of the irradiated HNS and SA3 SiC/SiC composites except for reduction of the Young's moduli by up to 18%. The microstructural stability of these composites supported the absence of degradation. In addition, no progressive swelling from 2.0 to 11.8 dpa was confirmed for these composites. On the other hand, the SCS composite showed significant mechanical degradation associated with cracking within the fiber. This study determined that SiC/SiC composites with HNS or SA3 SiC/SiC fibers, a PyC interphase, and a CVI SiC matrix retain their properties beyond the lifetime dose for LWR fuel cladding at the relevant temperature.

SiC-SiC composites exhibit exceptional high temperature strength and oxidation properties making them an advantageous choice for accident tolerant nuclear fuel cladding. In the present work, small scale mechanical testing along with AFM and TEM analysis were employed to evaluate PyC interphase properties that play a key role in the overall mechanical behavior of the composite. The Mohr-Coulomb formulation allowed for the extraction of the internal friction coefficient and debonding shear strength as a function of the PyC layer thickness, an additional parameter. These results have led to re-evaluation of the Mohr-Coulomb failure criterion and adjustment via a new phenomenological equation.SiC-SiC composites exhibit exceptional high temperature strength and oxidation properties making them an advantageous choice for accident tolerant nuclear fuel cladding. In the present work, small scale mechanical testing along with AFM and TEM analysis were employed to evaluate PyC interphase properties that play a key role in the overall mechanical behavior of the composite. The Mohr-Coulomb formulation allowed for the extraction of the internal friction coefficient and debonding shear strength as a function of the PyC layer thickness, an additional parameter. These results have led to re-evaluation of the Mohr-Coulomb failure criterion and adjustment via a new phenomenological equation.

Microstructures of single-crystal bulk tungsten (W) and polycrystalline W foil with a strong grain texture were investigated using transmission electron microscopy following neutron irradiation at ∼90–800 °C to 0.03–4.6 displacements per atom (dpa) in the High Flux Isotope Reactor with a mixed energy spectrum. The dominant irradiation defects were dislocation loops and small clusters at ∼90 °C. Additional voids were formed in W irradiated at above 460 °C. Voids and precipitates involving transmutation rhenium and osmium were the dominant defects at more than ∼1 dpa. We found a new phenomenon of microstructural evolution in irradiated polycrystalline W: Re- and Os-rich precipitation along grain boundaries. Comparison of results between this study and previous studies using different irradiation facilities revealed that the microstructural evolution of pure W is highly dependent on the neutron energy spectrum in addition to the irradiation temperature and dose.

This work reports the first mechanical properties of Ti3AlC2-Ti5Al2C3 materials neutron irradiated at ∼400, 630 and 700 °C at a fluence of 2 × 1025 n m−2 (E > 0.1 MeV) or a displacement dose of ∼2 dpa. After irradiation at ∼400 °C, anisotropic swelling and loss of 90% flexural strength was observed. After irradiation at ∼630–700 °C, properties were unchanged. Microcracking and kinking-delamination had occurred during irradiation at ∼630–700 °C. Further examination showed no cavities in Ti3AlC2 after irradiation at ∼630 °C, and MX and A lamellae were preserved. However, disturbance of (0004) reflections corresponding to M-A layers was observed, and the number density of line/planar defects was ∼1023 m−3 of size 5–10 nm. HAADF identified these defects as antisite TiAl atoms. Ti3AlC2-Ti5Al2C3 shows abrupt dynamic recovery of A-layers from ∼630 °C, but a higher temperature appears necessary for full recovery.

Raman spectra from polycrystalline beta-silicon carbide (SiC) were collected following neutron irradiation at 380–1180 °C to 0.011–1.87 displacement per atom. The longitudinal optical (LO) peak shifted to a lower frequency and broadened as a result of the irradiation. The changes observed in the LO phonon line shape and position in neutron-irradiated SiC are explained by a combination of changes in the lattice constant and Young's modulus, and the phonon confinement effect. The phonon confinement model reasonably estimates the defect-defect distance in the irradiated SiC, which is consistent with results from previous experimental studies and simulations.

The stability of MX-type precipitates is critical to retain mechanical properties of both reduced activation ferritic–martensitic (RAFM) and conventional FM steels at elevated temperatures above 500 C. The stability of TaC, TaN and VN nanoprecipitates under thermal aging (600 and 700 C), creep (600 C) and ion irradiation (Fe ion, 500 C) conditions was systematically studied in this work. The statistical particle evolution in density and size was characterized using transmission electron microscopy. Nanoprecipitate stability under the studied conditions manifested differently through either dissolution, reprecipitation, growth or fragmentation, with TaC exhibiting the greatest stability followed by VN and TaN in sequence. Nanoprecipitate evolution phenomena and mechanisms and the apparent disagreement of this interpretation with published literature on the subject are discussed. These findings not only help understanding the degradation mechanisms of RAFM and conventional FM steels at elevated temperatures and under stress and irradiation, but should also prove beneficial to the development of advanced RAFM steels.

The stability of MX-type precipitates is critical to retain mechanical properties of both reduced activation ferritic–martensitic (RAFM) and conventional FM steels at elevated temperatures. Radiation resistance of TaC, TaN, and VN nanoprecipitates irradiated up to ~49 dpa at 500 °C using Fe2+ is investigated in this work. Transmission electron microscopy (TEM) utilized in standard and scanning mode (STEM) reveals the non-stoichiometric nature of the nanoprecipitates. Irradiation did not alter their crystalline nature. The radiation resistance of these precipitates, in an order of reduced resistance, is TaC, VN, and TaN. Particle dissolution, growth, and reprecipitation were the modes of irradiation-induced instability. Irradiation also facilitated formation of Fe2W type Laves phase limited to the VN and TaN bearing alloys. This result suggests that nitrogen level should be controlled to a minimal level in alloys to gain greater radiation resistance of the MX-type precipitates at similar temperatures as well as postpone the formation and subsequent coarsening of Laves phase.