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At least 55 records · Page 3

FWP FEAA149: “Next Generation Environmental Barrier Coatings”

Environmental barrier coatings (EBCs) are required coatings for utilization of SiC/SiC ceramic matrix composite (CMC) components in gas turbines, where the EBC represents the life-limiting factor for such components. EBC/CMC systems have shown success in aero-engine applications with increased turbine inlet temperatures and improved efficiencies, which are achieved through higher temperature stability, lower density, and decreased reliance on cooling air compared to traditional superalloys. While industrial gas turbines (IGTs) do not currently utilize SiC/SiC CMCs, the current shift towards low-carbon or carbon-free fuel sources for power generation could result in a need for EBC/CMC components with higher temperature capabilities. In this work, three tasks were outlined to improve understanding of EBC lifetimes to encourage use in IGTs with carbon-free fuel such as hydrogen: 1. Define the bond coating oxidation kinetics and EBC failure criteria, 2. Measure thermal expansion coefficients of each layered material, and 3. Perform advanced characterization and modeling to assess EBC lifetimes. Cyclic steam oxidation tests were conducted on various EBC/Si/SiC chemistries and EBC/SiC architectures to define substrate oxidation kinetics and EBC failure modes. An open-source code was developed to quantify the undulating thermally grown oxide thickness with thousands of measurements from specimen cross-section images. Bond coating oxidation kinetics were determined and used to develop a kinetic and thermodynamic model for predicting EBC lifetimes. High-temperature Raman spectroscopy was utilized for determining the SiO 2 thermally grown oxide phase transformation as the life-limiting feature for EBCs. Model efforts supported the claim that the SiO 2 phase transformation causes elevated stress during thermal cycling with associated cracking that decreases the adhesion strength of the EBC, eventually resulting in coating spallation. The finite element model subroutine will be made publicly available upon internal review. Further development of an EBC lifetime model for IGTs involves definition of a critical SiO 2 thickness for EBC spallation and must also consider both environmental (gas velocity, pressure, etc.) and specimen (EBC dopants, layer architectures, etc.) effects into predicted bond coating oxidation kinetics for long-lifetime components.

36 MATERIALS SCIENCE↗

High-Temperature SiC Cladding Bowing Irradiation Design and HFIR Readiness

Silicon carbide fiber–reinforced silicon carbide (SiC/SiC) matrix composites are candidate materials for long-term accident-tolerant fuel cladding for use in light water reactors (LWRs). This report documents the design of a dry SiC/SiC composite cladding bowing experiment intended for irradiation in the High Flux Isotope Reactor. The dry experiment allows for testing at representative LWR temperatures for comparison to previous experimental results. This report describes detailed neutronics, thermal, and bowing analyses supporting the irradiation. The design leverages calculations from previous irradiation experiments and production targets for reduced design complexity. The thermal analysis provides a map of SiC thermometer temperatures for comparison during post-irradiation examination to determine the experiment’s irradiation temperatures. Finally, two concepts for introducing localized constraints representative of pressurized water reactor grid spacers are presented.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

High-Temperature SiC Cladding End Plug Irradiation Design and HFIR Readiness

This report documents the design of a High Flux Isotope Reactor (HFIR) irradiation experiment intended to evaluate irradiation effects on the hermeticity of silicon carbide (SiC) end plug specimens under a radial fast neutron flux gradient at representative light-water reactor (LWR) temperatures of approximately 300 °C. The overarching goal of this work is to statistically evaluate SiC end plug hermeticity and mechanical properties following irradiation using the high-throughput irradiation capability discussed here. Each specimen consists of a short section of SiC fiber–reinforced SiC (SiC/SiC) tube with a single monolithic SiC end plug joined to one end. The experiment allows up to 66 specimens to be irradiated in six different stacks within a dry, sealed irradiation capsule derived from the previously developed high-temperature SiC/SiC cladding bowing experiment. The neutronics basis, thermal analysis, and HFIR readiness of the experiment are discussed in this report for two possible design cases. The first design case is based on existing approval documentation and components that are on hand and approved for use, so the experiment insertion would require only specimen receipt, specimen pre-irradiation characterization, experiment assembly, and final fabrication package approval. The second design case provides improved thermal robustness and the preferred end plug geometry but requires fabrication of a modified holder and revisions to the HFIR approval documentation, in addition to the other activities required for the first design case, before insertion.

Hott, Daniel [Oak Ridge National Laboratory (ORNL)↗

High Temperature Mechanical Behavior of Refractory Alloys with Digital Image Correlation

Gas turbine efficiency is typically limited by the maximum allowable temperature for components at the inlet side and in the hot gas flow. Refractory alloys and SiC/SiC ceramic-matrix composites (CMCs) are promising candidates for advancing operating temperatures beyond those of Ni-based alloys (>1200 °C). Refractory alloys are more suitable than SiC/SiC CMCs for dynamic components, due to the latter's low toughness and ductility. However, it is well known that refractory alloys suffer from poor oxidation behavior under service lifetimes and conditions, leading to embrittlement concerns. The ARPA-E ULTIMATE program has set out to combine new alloys with advanced coatings to mitigate oxidation/embrittlement effects, while increasing the mechanical performance benefits of refractory materials. Low oxygen (inert gas) or vacuum systems are needed to assess high temperature mechanical performance of developed alloys. To investigate the environmental sensitivity of candidate alloys and develop high temperature testing capabilities, four argon tensile frames were upgraded as well as a single vacuum system at Oak Ridge National Laboratory. Digital image correlation was incorporated into the vacuum frame allowing for surface strain determination and refined insight into thermomechanical response. Creep testing was performed at 1300 °C on two alloys, C-103 and MHC in vacuum and high purity argon environments. The Mo-based alloy showed less sensitivity to oxygen, indicating that testing in well-controlled argon environments may be suitable. The C-103 alloy demonstrated a stronger sensitivity to oxygen in the well-controlled argon environment, illustrating the need for the developed vacuum testing capabilities. “Small” 25 mm and “large” 76 mm MHC specimens showed comparable results in terms of strain rate during creep testing and ultimate tensile strength during tensile testing, suggesting the viability of smaller geometries that use less material of advanced developmental alloys.

Bell, Sam↗

Corrosion characteristics of silicon carbide fiber-reinforced composites in beryllium-bearing molten fluoride salt

Corrosion of SiC-fiber reinforced SiC matrix composites in 2LiF-BeF 2 molten salt was examined following static molten salt exposure for 1000 h at 650 and 750 °C. Composites were fabricated with either Tyranno SA3 or Hi-Nicalon type-S fibers and a chemical vapor infiltration SiC matrix. Both composites showed minimal weight loss after salt exposure and maintained shape. Corrosion was characterized by comprehensive electron microscopy and Raman spectroscopy. In conclusion, based on the results of experimental and thermodynamic analysis, a corrosion mechanism for SiC/SiC is proposed where both the salt and SiC materials play a key role in the phase stability of the composite.

36 MATERIALS SCIENCE↗

Neutronic Consideration of TREAT Facility Fuel SiC Recladding

The Transient Reactor Test (TREAT) Facility is an air-cooled reactor composed of graphite-urania fuel encapsulated in zirconium alloy canisters and surrounded by ~2 ft (~61 cm) of nuclear grade graphite. The primary role of TREAT is to provide in-pile nuclear-heated safety research via transient testing [1]. Benchmark efforts have demonstrated sensitivity of TREAT neutronics models to graphite cross section data and key neutron poisons found in the fuel assemblies [2]. During fabrication of TREAT fuel assemblies, a small concentration of boron was inadvertently introduced with variable concentration into the aggregate of fuel blocks prepared for TREAT use. The concentration of boron, and its respective uncertainty, represent the most sensitive component in a neutronics study; unfortunately, nothing can be done to reduce or otherwise mitigate its impact. Hydrogen in the fuel blocks reduces the mean free path of the core and its true quantity and uncertainty is approximated. The hydrogen remains from pitch binder used in the fuel fabrication process and was not completely released due to incomplete fuel graphitization. Destructive fuel testing is necessary to quantify the actual hydrogen content and to improve benchmark model quality. A third neutron poison of some significance is the hafnium impurity in the Zircaloy-3 (Zry-3) assembly cladding. The quantity of hafnium is expected to be within nominal manufacturing limits for nuclear grade zircaloy. Recladding the fuel assemblies with material that is less neutron absorbing is expected to benefit reactor neutron economy. Moreover, TREAT’s total transient energy is restricted based on the rate of Zry-3 oxidation in TREAT’s air coolant environment. Hence, cladding with more benign air reaction kinetics could dramatically uprate the facility’s experimental capability. Silicon carbide (SiC) has been proposed as a candidate material for recladding TREAT assemblies, as SiC/SiC demonstrate favorable properties within nuclear environments [3]. The current operational limits of TREAT are restricted by the oxidation of Zry-3. Change of the cladding to SiC could feasibly double the current temperature limitation. Recladding opportunities allow for previously damaged fuel assemblies to be returned to service, as Zry-3 is not commercially available. The initial effort required to consider proceeding with any recladding effort is to neutronically characterize key reactor parameters while replacing Zry-3 with SiC. A characterization summary, with respective results, is provided herein.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Characterization of SiO 2 Thermally Grown Oxide Stress Evolution of EBCs with Al-Containing Dopants

SiC/SiC ceramic matrix composites (CMCs) are desired for use in combustion environments to achieve higher turbine operating temperatures. However, CMCs require environmental barrier coatings (EBCs) for protection from the gas environment. EBC systems are known to primarily fail through coating delamination via growth of a thermally grown oxide (TGO) at the EBC—silicon bond coating interface when exposed to steam, which accelerates the TGO growth rate. The TGO undergoes a phase transformation during thermal cycling, which results in stresses that may encourage EBC spallation. Yb-silicate EBCs with mullite and yttrium aluminum garnet (YAG) dopant additions were deposited on SiC substrates with a Si intermediate bond coating and exposed to thermal cycling in steam at 1350 °C. The impact of Al dopant additions on the TGO growth rate and the SiO 2 phase transformation was assessed. Photo-stimulated luminescence spectroscopy (PSLS) was used to characterize the Al-containing phases and to measure stress evolution in the EBC following exposure using the stress-induced peak shift of the R-lines of mullite. Raman microscopy was used to map the stresses in the Si bond coating following exposure. It was found that the TGO phase transformation upon cooling increased compressive stress in the Si bond coating within 15 µm of the TGO.

Building Materials↗

Modeling creep behavior in ceramic matrix composites

Here, in this work, a three-dimensional viscoplasticity formulation with progressive damage is developed and used to investigate the complex time-dependent constituent load transfer and progressive damage behavior in ceramic matrix composites (CMCs) subjected to creep. The viscoplasticity formulation is based on Hill's orthotropic plastic potential, an associative flow rule, and the Norton-Bailey creep power law with Arrhenius temperature dependence. A fracture mechanics-informed isotropic matrix damage model is used to account for CMC brittle matrix damage initiation and propagation, in which two scalar damage variables capture the effects of matrix porosity as well as matrix property degradation due to matrix crack initiation and propagation. The Curtin progressive fiber damage model is utilized to simulate progressive fiber failure. The creep-damage formulation is subsequently implemented as a constitutive model in the generalized method of cells (GMC) micromechanics formulation to simulate time-dependent deformation and material damage under creep loading conditions. The developed framework is used to simulate creep of single fiber SiC/SiC microcomposites. Simulation results are in excellent agreement with experimental and numerical data available in the literature.

36 MATERIALS SCIENCE↗

Environmental barrier coatings on enhanced roughness SiC: Effect of plasma spraying conditions on properties and performance

Environmental barrier coatings for SiC/SiC composites are limited by the melting temperature of the Si bond coating near 1414°C. Systems without a bond coating may be required for future turbine applications where material temperatures go beyond 1350 °C. Here, enhanced roughness SiC substrates were developed to assess coating adhesion without the bond coating. Two EBCs with different YbMS/YbDS ratios were produced via modified plasma spraying parameters. Coating microstructure, thermal expansion, and modulus were measured for comparison of coating properties. Cyclic steam exposures at 1350°C were performed to assess oxidation resistance. The EBC with increased concentration of Yb 2 SiO 5 secondary phase displayed a higher CTE, which is typically expected to decrease adhesion lifetimes due to an increase in stress upon thermal cycling. Yet, the EBC chemistry with increased Yb 2 SiO 5 concentration was able to experience longer cycling times prior to coating delamination, likely due to interface interactions with the substrate and the thermally grown oxide.

36 MATERIALS SCIENCE↗

The effects of neutron and ionizing irradiation on the aqueous corrosion of SiC

Chemical vapor deposited (CVD) SiC and nuclear-grade SiC/SiC composite materials were exposed to light water reactor (LWR) conditions at the MIT Nuclear Reactor (MITR) here. Three sets of samples were exposed within flowing PWR-chemistry-coolant under either 1) neutron and ionizing irradiation with resulting radiolysis products, 2) radiolysis products without neutron flux, 3) loop coolant. Post-irradiation examination (PIE) exhibited an increase in corrosion from radiolysis products (particularly H 2 O 2 ), and potentially a further increase from radiation damage. For CVD SiC, regardless of exposure location, the in-situ observed corrosion rate was less than 1 µm per year, potentially within acceptable limits for LWR application.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Evaluation of the effects of neutron irradiation on first-generation corrosion mitigation coatings on SiC for accident-tolerant fuel cladding

In this work, high purity SiC and SiC/SiC composites coated with commercial TiN, Cr, CrN, or CrN/Cr multilayer coatings were irradiated in Ar or flowing PWR water in the Massachusetts Institute of Technology Nuclear Reactor Laboratory (MITR). Irradiation in Ar was performed in the core. In the water environment, identical samples were placed in one of three different locations: in-core, providing exposure to neutron damage and radiolysis-affected water; above-core, where samples were exposed to radiolysis-affected water but not neutron damage, or outside of the core, where samples were exposed to the coolant water without the effects of radiation. Radiation in Ar revealed significant cracking of all but the TiN coatings, attributed to differential swelling between the coating and substrate. Lattice swelling was not observed in any of the coatings, but 0.2% void swelling was observed in the Cr coating. All of the coatings failed during water exposures in the core. Likewise, CrN/Cr spalled in each condition. Cr was protective, except under radiation damage as a result of cracking, and TiN severely degraded in the core with no coating was found following exposure. A SiC/coating ATF cladding system is anticipated to perform adequately following improvements in coating ductility and purity.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Hydrothermal corrosion of laser printed SiC fibers under extreme environment

We report SiC/SiC fiber composites are proposed cladding materials to improve the accident tolerance of commercial light water nuclear reactor fuel. To evaluate their viability, understanding the kinetics of corrosion under irradiation and high-temperature, high-pressure aqueous environment is critical. In the present work, the microstructure and mechanical properties of novel SiC fibers manufactured by Laser Chemical Vapor Deposition (LCVD) are introduced. The LCVD technology has control over microstructure and stoichiometry while allowing for high purity manufacturing, all key qualities needed in search of an optimum SiC fiber for nuclear energy applications. The isolated hydrothermal corrosion of commercially available carbon-rich Hi-Nicalon Type-S fibers is compared to the LCVD stoichiometric and LCVD silicon-rich fibers. Autoclave testing was carried out at 310°C and 14 MPa in the absence of irradiation. In a separate study, the effect of gamma irradiation on the fibers in the room-temperature environment was analyzed. It was observed from the experiments that the dissolution of the fibers was highly dependent on the stoichiometric ratio, fiber surface morphology and thermal pre-treatment of fibers. Contrary to previous findings, fiber dissolution was also visible under low-temperature gamma irradiation in aqueous environment with LCVD fibers showing lower dissolution.

36 MATERIALS SCIENCE↗

Characterization and qualification of neutron radiation effects – Summary of Japan-USA Joint Projects for 40 years

The Joint Projects under the Japan-USA Fusion Cooperation Program started in 1981 and has continued for more than 40 years. In the Joint Projects, although a wide range of fusion materials and engineering issues were covered, neutron radiation effects on fusion reactor materials have always been the major research emphases, and the neutron irradiation facilities in the US were jointly used by Japanese and US researchers. Japanese test facilities including neutron and charged particle irradiation facilities were complementarily used. Here, the initial focus of the Joint Projects was on fundamental fusion neutron radiation effects and irradiation correlation. Systematic comparison of fission and fusion radiation effects in comparable damage levels and the effects of transmutation-induced helium were investigated. The collaboration was then focused on the effect of dynamic irradiation effects in variable conditions. In addition to the relatively fundamental studies, the Joint Projects contributed largely to development of candidate materials such as RAFM steels, vanadium alloys, SiC/SiC composites, and tungsten alloys, through a mechanism-oriented approach. The Joint Projects also covered issues specific to materials application to fusion blankets and plasma-facing components, including neutron radiation effects such as tritium retention and permeation of neutron-irradiated plasma-facing materials. Various irradiation technologies were developed and applied to the irradiation experiments, including those for in-situ testing.Considering that high energy neutron sources, such as A-FNS and IFMIF-DONES, now have high viability, the research supporting the neutron source programs is essential. The knowledge obtained through the Joint Projects is valuable and should be advanced for this purpose. To this end, it is of urgent necessity to launch an international scientific program accumulating knowledge of fusion neutron radiation effects, including their fundamental aspects.

36 MATERIALS SCIENCE↗

Development of hydrothermal corrosion model and BWR metal coating for CVD SiC in light water reactors

SiC/SiC fiber composites with CVD SiC overcoats are potential candidates for light water reactor advanced accident tolerant cladding materials. Understanding its corrosion kinetics in Light Water Reactor (LWR) conditions is essential to evaluate the concept's viability. Existing models only account for the temperature and oxygen concentration effect on the hydrothermal corrosion behavior applicable to LWR operating conditions. However, the development of a general corrosion rate for CVD SiC that accounts for the impact of irradiated microstructure, flow rate, electrical resistivity, pH, and surface roughness is critical for the practical realization of SiC/SiC-based cladding concepts. After a rigorous experimental campaign, this work updates the existing hydrothermal corrosion model to predict hydrothermal corrosion in LWRs. Numerical radiation and coolant chemistry analysis for LWRs conducted based on the updated corrosion kinetic models suggests that CVD SiC is likely a viable environmental barrier coating for Pressurized Water Reactors while questionable for Boiling Water Reactors (BWR) when the effect of irradiation damage on SiC corrosion is considered. An effective mitigation strategy for the double-layer metal coating is proposed for BWR applications. The double-layer metal coating comprising a FeCrAl overcoat with an intermediate Cr bond coating was observed to provide a stable protective barrier against SiC dissolution in BWR conditions. Finally, the proposed metal coating was also fully adherent following quench and burst tests.

36 MATERIALS SCIENCE↗

FLiBe compatibility of fusion-relevant materials

There is current interest in a 2LiF-BeF2 (FLiBe) molten salt blanket for fusion applications, however, very little compatibility data are available for fusion relevant materials. Initial static capsule testing results for 500 h at 550°-750 °C are presented for V-4Cr-4Ti, Fe-8Cr-2W (alloy F82H) compared to type 316H stainless steel and monolithic SiC as a surrogate for SiC/SiC composites. In addition, sintered Be12Ti specimens with varying additions of Be (0–20%) and a Be2C specimen were exposed with F82H coupons at 650 °C in individual Mo capsules. The V-4Cr-4Ti and SiC specimens exposed at 650 °C had small mass changes. Steel specimens showed increasing mass losses with increasing exposure temperature. However, when Be12Ti-Be specimens were included in a capsule with an F82H coupon, increasing F82H mass gains were observed with increasing Be content due to the formation of a Fe-Be surface layer. No layer and no mass gain were observed for the F82H specimen tested with Be2C.

Pint, Bruce [Oak Ridge National Laboratory (ORNL) ↗

Chemical vapor infiltration of additively manufactured preforms: Pore-resolved simulations and experimental validation

The densification of additively manufactured porous preforms by chemical vapor infiltration (CVI) is studied using pore-resolved simulations and experiments. Experimentally, 3D printed silicon carbide (SiC) preforms are subject to CVI synthesis using methyltrichlorosilane (MTS) precursor to obtain high purity SiC/SiC composites. Optical images of the cross sections of the processed preforms are analyzed to obtain the spatial porosity distribution. The numerical method is based on a level set formulation to capture the spatial distribution and time evolution of the pore scale microstructural characteristics. The coupled transport and kinetic effects are represented using a dimensionless Thiele modulus. Simulations are initialized using representative synthetic preform geometries comprising of packed particles based on the size distribution of the powder used for 3D printing. The simulation results are validated against the experimental observations in terms of total density and the distribution of residual porosity. The densification characteristics, porosity classification, concentration profiles, and structure functions are analyzed as functions of processing temperature and Thiele modulus.

36 MATERIALS SCIENCE↗

Predicting EBC Temperature Limits for Industrial Gas Turbines

Higher turbine inlet temperatures may require the use of ceramic matrix composites (CMC) such as SiC/SIC, which require environmental barrier coatings (EBCs) to protect them against the detrimental effect of water vapor. Here, the goal of this project is to determine the maximum bond coating temperature for EBCs for land-based turbines, where the minimum coating lifetime is 25,000 h. If the temperature exceeds the 1414°C melting point of the Si bond coating, then coatings without a bond coating also need to be evaluated. Thus, current Yb 2 Si 2 O 7 EBCs with a Si bond coating and next-generation EBCs without a Si bond coating are being evaluated in laboratory testing using 1-h cycles in air+90%H 2 O. For this initial work, coatings were deposited on CVD SiC coupons. Reaction kinetics at 1250°, 1300° and 1350°C have been evaluated by measuring the thickness of the thermally grown silica scale after 100–500 h exposures. For comparison, scale growth rates for uncoated SiC and Si specimens in dry and wet environments were included as minimum and maximum values, respectively. Based on a critical scale thickness failure criteria, estimated maximum temperatures were calculated for both EBC systems using this initial data.

42 ENGINEERING↗

A Graphene Enhanced SiC-SiC Ceramic Composite Bonding Solution for Generation IV Nuclear Reactors

The feasibility of an effective bonding methodology for SiC/SiC Ceramic Matrix composites using a graphene base brazing compound was established under pressure less conditions. The feasibility demonstration during this program identified the further need to improve the composition of the brazing compound and the processing conditions to enhance the joint strength.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗