Advanced synchrotron characterization techniques for fusion materials science
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99 GENERAL AND MISCELLANEOUS↗
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Quantification of solution annealing effects on microstructure and property in a laser powder bed fusion 316H stainless steel
Solution annealing (SA) is an effective way to mitigate microstructural heterogeneity and to optimize mechanical performance of alloys manufactured by laser powder bed fusion (LPBF). In this study, a comprehensive and quantitative understanding of the recovery and recrystallization processes in the SA temperature range of LPBF 316H stainless steel is provided using results from analytical electron microscopy and in-situ high-energy synchrotron x-ray scattering. The profound effect of dislocation structures and secondary phase particles on mechanical performance, particularly under tension and creep conditions, is rationalized using deformation models that incorporate microstructural inputs. This study, for the first time, quantifies the broad effect of nano oxide inclusions on dislocation recovery kinetics, on grain growth and recrystallization kinetics, and on tension strength and creep resistance. The fundamental differences between the LPBF and the conventional wrought materials are revealed. The findings address critical questions in post-build processing of AM materials and pave the way for their rapid qualification for high temperature applications.
In-situ X-ray diffraction↗
Irradiation-induced amorphization of Fe-Y-based second phase particles in accident-tolerant FeCrAl alloys
Here, second phase intermetallic particles in an advanced accident-tolerant FeCrAl (Fe-13Cr-5Al-2Mo) alloy are formed in the α-Fe matrix during processing. These particles are prominently related to the added Y. Neutron irradiation to ~7 displacements per atom (dpa) with a dose rate of ~8.16 × 10 -7 dpa/s at 282 °C resulted in the amorphization of these precipitates which could degrade the mechanical properties of the FeCrAl alloys. Analytical electron microscopy and diffraction analysis combined with structural freedom analysis have been used to investigate the radiation resistance of the second phase particles. Radiation tolerance is closely linked to the particle Fe-Y content and can be tailored using the structure freedom value.
36 MATERIALS SCIENCE↗
Utilizing a Dynamic Segmentation Convolutional Neural Network for Microstructure Analysis of Additively Manufactured Superalloy 718
Additive manufacturing (AM) is revolutionizing almost all industries through the production of intricate geometries previously prohibited by cost or machinability. Ni-based superalloys form a primary alloy class for high temperature applications in the petrochemical, aerospace, and nuclear industries because of their intrinsic resistance to creep and the ability to heat treat the superalloy for high strength. Despite these attractive properties, the extreme work hardening of Ni-based superalloys makes traditional manufacturing of complex shapes difficult and thus, these alloys are an attractive target for AM. Superalloy 718 was chosen as an example superalloy because of the wide variety of precipitates that can form within its composition space from the repetitive heating and cooling cycles of the AM process. The precipitates and other microstructure features, such as grain boundaries and dislocations, will dictate the mechanical properties and thus, there is an extensive challenge to characterize the size, number density, composition, and volume fraction of each microstructural feature from AM fabrication using analytical electron microscopy. This work focused on the application of a pixel-wise classification machine learning (ML) model called a dynamic segmentation convolutional neural network (DSCNN) to identify the microstructural features of an as-fabricated additively manufactured superalloy 718.
Taller, Stephen↗
Metal Ion Fluxes Controlling Amphibian Fertilization
Mammalian oocytes undergo major changes in zinc content and localization to be fertilized, the most striking being the rapid exocytosis of over 10 billion zinc ions in what are known as zinc sparks. Here, we report that fertilization of amphibian Xenopus laevis eggs also initiates a zinc spark that progresses across the cell surface in coordination with dynamic calcium waves. This zinc exocytosis is accompanied by a newly recognized loss of intracellular manganese. Synchrotron-based X-ray fluorescence and analytical electron microscopy reveal that zinc and manganese are sequestered in a system of cortical granules that are abundant at the animal pole. Through electron-nuclear double-resonance studies, we rule out Mn2+ complexation with phosphate or nitrogenous ligands in intact eggs, but the data are consistent with a carboxylate coordination environment. Our observations suggest that zinc and manganese fluxes are a conserved feature of fertilization in vertebrates and that they function as part of a physiological block to polyspermy.
Seeler, John F.↗
Microstructural Characterization of the Second High Fluence Baffle-Former Bolt Retrieved from a Westinghouse Two-loop Downflow Type PWR
As one of the pressurized water reactor (PWR) internal components, baffle-former bolts (BFBs) are subjected to significant mechanical stress and neutron irradiation from the reactor core during the plant operation. Over the long operation period, these conditions lead to potential degradation and reduced load-carrying capacity of the bolts. In support of evaluating long-term operational performance of materials used in core internal components, the Oak Ridge National Laboratory (ORNL), through the Department of Energy (DOE), Light Water Reactor Sustainability (LWRS) Program, Materials Research Pathway (MRP) has harvested two high fluence BFBs from a commercial Westinghouse two-loop downflow type PWR. The two bolts of interest, i.e. bolts # 4412 and 4416, were withdrawn from service in 2011 as part of a preventative replacement plan. No identification of cracking or potential damage was found for these bolts during their removal in 2011. However, the bolts required a lower torque for removal from the baffle structure than the original torque specified during installation. Irradiation displacement damage levels in the bolts range from 15 to 41 displacements per atom. The goal of this project is to perform detailed microstructural and mechanical property characterization of BFBs following in-service exposures. The information from these bolts will be integral to the LWRS program initiatives in evaluating end of life microstructure and properties. Furthermore, valuable data will be obtained that can be incorporated into model predictions of long-term irradiation behavior and compared to results obtained in high flux experimental reactor conditions. In this report, we present our latest study in FY22 on microstructural characterizations of the second high fluence baffle-former bolt, i.e., bolt # 4412. Analytical electron microscopy and atom probe tomography characterization were performed. The radiation-induced defects in the material add to the large wealth of knowledge for neutron-induced defects in 304/316 grades of stainless steels, specifically for radiation-induced precipitation after high fluence commercial PWR irradiation. The main findings are summarized as follows: 1) The cavity size was considerably larger in the bolt thread section than in the bolt head, with the bolt thread section having a bimodal distribution of cavities greater than ~6 nm in diameter and less than ~3 nm in diameter. The bolt head only had the small-sized cavities. In addition, there was a denuded zone of large cavities near grain boundaries in the thread section of the bolt. 2) Radiation-induced precipitation in the BFB #4412 was highly complex, with the volume fraction, size, and number density of Ni/Si and Cu-rich precipitates depending strongly on the radiation temperature/dose. In many cases, co-precipitates of adjoined clusters were found with Ni/Si-rich precipitates sandwiched between Cu-rich clusters and Mo/Cr/P-rich clusters. 3) Solute segregation out of solution was highest for most solutes in the thread section of the bolt #4412 with the exception of Cu, which experienced more separation out of solution into Curich clusters in the bolt head section. This highlights the difference in the mechanisms for precipitation of Ni/Si clusters, which have the Ni 3 Si phase composition, and precipitation of Cu-rich clusters. 4) There appear to be multiple simultaneous influences that affect the microstructural variation along the length of the bolt that overcomes the ~2X difference in irradiation dose between the bolt head and the bolt thread. The irradiation temperature, thermal/fast neutron ratio variation, potential strain gradient, and exposure to PWR coolant water that each section of the bolt sees may have more influence on the microstructural evolution than the total irradiation dose. The bolt thread and shank, with higher temperature, higher relative fast neutron flux, higher strain, and exposure to coolant but lower dose, underwent more enhanced cavity formation, precipitation, and solute segregation than the bolt head section.
21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
Fundamental Superconductivity of Nb films for Quantum Computing Application
Niobium is a widely accepted material for quantum computing device as well as superconducting radio frequency (SRF) technology. Superconducting niobium is a marginal type II superconductor which has a very narrow gap (~20-30 mT) of the mixed state at 2K, even showing the intermediate state (IMS) at the early stage of magnetic vortex penetration. Tremendous progress has been made in understanding the impact of the Nb surface and bulk superconductivities on SRF resonator performance. However, the effect of thin superconducting Nb films for quantum computing applications requires further examination. In this study, we explore the fundamental superconducting properties of various thin Nb films and compare them with respect to the energy relaxation time, T1, measured from superconducting qubit fabricated with these films. The Nb films are fabricated both with or without a surface protective layer that prevents the formation of lossy Nb2O5. Electromagnetic properties are characterized by means of bulk magnetization, electromagnetic transport, and dynamics of surface superconductivity. In addition, analytical electron microscopy is implemented to further connect the superconducting properties to microstructure.
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
Fundamental Superconductivity of Nb films for Quantum Computing Application
Niobium is a widely accepted material for quantum computing device as well as superconducting radio frequency (SRF) technology. Superconducting niobium is a marginal type II superconductor which has a very narrow gap (~20-30 mT) of the mixed state at 2K, even showing the intermediate state (IMS) at the early stage of magnetic vortex penetration. Tremendous progress has been made in understanding the impact of the Nb surface and bulk superconductivities on SRF resonator performance. However, the effect of thin superconducting Nb films for quantum computing applications requires further examination. In this study, we explore the fundamental superconducting properties of various thin Nb films and compare them with respect to the energy relaxation time, T1, measured from superconducting qubit fabricated with these films. The Nb films are fabricated both with or without a surface protective layer that prevents the formation of lossy Nb2O5. Electromagnetic properties are characterized by means of bulk magnetization, electromagnetic transport, and dynamics of surface superconductivity. In addition, analytical electron microscopy is implemented to further connect the superconducting properties to microstructure.
72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
Chemical Environment and Structural Variations in High Entropy Oxide Thin Film Probed with Electron Microscopy
For this work, we employ analytical transmission electron microscopy (TEM) to correlate the structural and chemical environment variations within a stacked epitaxial thin film of the high entropy oxide (HEO) Mg 0.2 Co 0.2 Ni 0.2 Cu 0.2 Zn 0.2 O (J14), with two layers grown at different substrate temperatures (500 and 200 °C) using pulsed laser deposition (PLD). Electron diffraction and atomically resolved STEM imaging reveal the difference in out-of-plane lattice parameters in the stacked thin film, which is further quantified on a larger scale using four-dimensional STEM (4D-STEM). In the layer deposited at a lower temperature, electron energy loss spectroscopy (EELS) mapping indicates drastic changes in the oxidation states and bonding environment for Co ions, and energy-dispersive X-ray spectroscopy (EDX) mapping detects more significant cation deficiency. Ab initio density functional theory (DFT) calculations validate that vacancies on the cation sublattice of J14 result in significant electronic and structural changes. The experimental and computational analyses indicate that low temperatures during film growth result in cation deficiency, an altered chemical environment, and reduced lattice parameters while maintaining a single phase. Our results demonstrate that the complex correlation of configurational entropy, kinetics, and thermodynamics can be utilized for accessing a range of metastable configurations in HEO materials without altering cation proportions, enabling further engineering of functional properties of HEO materials.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Probing individual single atom electrocatalyst sites by advanced analytical scanning transmission electron microscopy
Single atom electrocatalysts (SAEs) are promising next-generation materials for promoting a variety of important reactions, such as the oxygen reduction, nitrogen reduction, and CO 2 reduction reactions. While bulk characterization techniques such as X-ray absorption spectroscopy and Mössbauer spectroscopy have significantly enhanced our understanding of these catalysts, direct probing of individual single metal atom sites at the atomic scale is necessary to understand local variations in the properties of these sites and accelerate design and synthesis of improved SAEs. Aberration-corrected scanning transmission electron microscopy (STEM) has become a powerful tool for providing this type of atomic-scale information about SAE metal sites. These sites are typically unstable under the electron beam, however, which, in combination with conventional acquisition methods and detectors, has limited the type and quantity of information obtainable by spectroscopic STEM techniques. Here, we map multiple individual SAE metal sites in a nitrogen-doped carbon containing atomically dispersed Fe and Re (FeReNC) at the atomic scale by direct electron detection electron energy-loss spectroscopy (EELS). Direct electron detection provides an improved signal-to-noise ratio over conventional scintillator-based detectors and enables detection and real space localization of weak signals. In addition, we demonstrate an automated method for identification of metal atom positions, placement of the probe on these sites, and simultaneous EELS and energy dispersive X-ray spectroscopic (EDS) signal acquisition. This simultaneous acquisition of EELS and EDS provides access to the composition and bonding of a wide range of SAE metal sites. In this study, focusing the probe directly on the metal sites also increases the relevant data acquisition rate by more than an order of magnitude over two-dimensional mapping, enabling improved statistical measurements of site properties. The versatility, sensitivity, and speed that these techniques provide enhances our ability to probe the local elemental and chemical environment of a large number of individual SAE metal site structures at the atomic scale, enabling an improved understanding of the variations in the local properties of these electrocatalysts to be gained. As a result, significantly increased information about individual metal sites will be available to future electrochemical studies through these techniques, accelerating the development of advanced SAEs.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Internal carburization and scale formation on austenitic steels in supercritical carbon dioxide
Direct-fired supercritical CO 2 (sCO 2 ) power cycles are being commercialised to revolutionise fossil energy as a low-emission power source. In order to lower the cost of this technology, less expensive steels are needed in the lower temperature segments of the cycle. However, there are concerns about internal carburisation of steels in sCO 2 . A consistent observation is that thin, Cr-rich oxides appear to reduce C ingress compared to thick Fe-rich oxides formed on 9–12% Cr ferritic-martensitic steels. Advanced austenitic stainless steels (SS) like alloy 709 (20Cr-25Ni) are able to continue to form Cr-rich oxides at 650°C, while a conventional type 316 H SS formed a Fe-rich scale. The C diffusion profiles in SS specimens were quantified at 550°C–650°C using glow discharge optical emission spectroscopy and electron probe microanalysis. Analytical transmission electron microscopy was used to compare the thin protective Cr-rich oxide formed on alloy 709 in sCO 2 at 650°C to that formed in ambient air.
36 MATERIALS SCIENCE↗
A Mechanistic Understanding of Nonclassical Crystal Growth in Hydrothermally Synthesized Sodium Yttrium Fluoride Nanowires
Sodium yttrium fluoride (NaYF 4 ) is an important upconverting material with many potential uses in chemistry, materials science, and biology, which can be synthesized hydrothermally in both cubic (α) and hexagonal (β) crystallographic polymorphs. Understanding the mechanisms underlying the phase conversion between the cubic and hexagonal polymorphs is of great interest to help inform future synthetic efforts, for example in the design of atomically precise quantum materials with well-defined sizes and morphologies. In this work, we use a combination of analytical transmission electron microscopy (TEM), scanning transmission electron microscopy (STEM), powder X-ray diffraction (XRD), in situ liquid cell TEM, atom probe tomography (APT), and extended X-ray absorption fine structure (EXAFS) measurements to show that the hexagonal NaYF 4 nanowires form through a nonclassical crystal growth mechanism involving the formation and subsequent oriented attachment of mesocrystals consisting of cubic (α) phase units. Additionally, EXAFS measurements suggest that substitutional Yb 3+ point defects within NaYF 4 are distributed evenly throughout the crystal lattice without clustering and also that they may exhibit selective substitution into one of the two possible trivalent yttrium sites in the unit cell for hydrothermally synthesized β-NaYF 4 .
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Cluster Analysis of Combined EDS and EBSD Data to Solve Ambiguous Phase Identifications
A common problem in analytical scanning electron microscopy (SEM) using electron backscatter diffraction (EBSD) is the differentiation of phases with distinct chemistry but the same or very similar crystal structure. X-ray energy dispersive spectroscopy (EDS) is useful to help differentiate these phases of similar crystal structures but different elemental makeups. However, open, automated, and unbiased methods of differentiating phases of similar EBSD responses based on their EDS response are lacking. This paper describes a simple data analytics-based method, using a combination of singular value decomposition and cluster analysis, to merge simultaneously acquired EDS + EBSD information and automatically determine phases from both their crystal and elemental data. I use hexagonal TiB 2 ceramic contaminated with multiple crystallographically ambiguous but chemically distinct cubic phases to illustrate the method. Code, in the form of a Python 3 Jupyter Notebook, and the necessary data to replicate the analysis are provided as Supplementary material.
47 OTHER INSTRUMENTATION↗
In-Situ Liquid Cell Transmission Electron Microscopy of Nanoparticles from Spent Nuclear Fuel
Noble Metal Particles (NMP) that are present in SNF play an important role in the Fuel Matrix Degradation (FMD) Model that is being considered for predicting the release rate of radionuclides from a waste package. Previous characterization of chemically separated NMP from SNF showed that these were well-crystallized nanoparticles containing Mo, Tc, Ru, Rh, and Pd with some evidence of actinides. These same chemically separated particles were re-characterized following 10 years of storage as the separated material in water. Scanning Transmission Electron Microscopy (STEM) analysis revealed that significant alteration had occurred in this material during storage, resulting in the almost complete degradation of the NMP. We hypothesized that radiolytic damaged had occurred in the material. To support these concepts, we synthesized a mixed Ru-Pd nanoparticle and subjected it to irradiation in the electron microscope in an in-situ liquid cell. We demonstrated that intense radiation can lead to the decomposition of these metallic particles.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Atomic Structural Features of Stacking Faults and Domain Connections in the Li- and Mn-Rich Cathode
Li- and Mn-rich layered oxides (LMRs), a class of earth-abundant materials for rechargeable Li-ion battery cathodes, crystallize into layered structures of two different symmetries: C2/m represented by Li 2 MnO 3 and R$\overline{3}$m represented by LiMn 0.5 Ni 0.5 O 2 . Fundamental questions about how the C2/m and R$\overline{3}$m domains spatially correlate within the same oxide grain and how the C2/m stacking faults arrange themselves when this happens still remain. Here, by using integrated differential phase contrast imaging in scanning transmission electron microscopy (STEM-iDPC), we probe the structural and compositional details of a prototypical, cobalt-free LMR material, 0.3Li 2 MnO 3 •0.7LiMn 0.5 Ni 0.5 O 2 (Li 1.13 Mn 0.57 Ni 0.3 O 2 ). The connection between the C2/m and R$\overline{3}$m domains is found to be abrupt, facilitated by the small lattice mismatch between the two structures. Stacking faults in the C2/m domains feature atomic plane shifting that accommodates stacking sequence changes, which explains why the stacking faults form in a random manner. Furthermore, a local disordering mechanism was identified to correlate with the C2/m stacking faults. Chemically, it is found that Ni coexists with Mn at the transition metal sites within the nominal Li 2 MnO 3 domain. As a result, this study demonstrates that STEM-iDPC is a very useful tool for capturing all the elements in a single image, revealing atomic details on domain connections and stacking faults in the LMRs.
Li-rich and Mn-rich oxides↗
Grain boundary segregation in BCC vanadium-based alloys: Quantum-accurate computed segregation spectra and targeted experimental validations
Grain boundaries are critically important to the material performance of fusion reactor materials such as vanadium, particularly mechanical properties and irradiation resistance. A key challenge to the design and control of grain boundaries in vanadium alloys is the lack of quantitative data on grain boundary segregation. In this study, we combine computational and experimental methods to address this gap. Furthermore, using a machine learning-accelerated quantum mechanics/molecular mechanics approach, we calculated the segregation spectra for 28 transition metal elements in polycrystalline vanadium, and validated these predictions experimentally for a subset of solutes that sample a range of segregation behavior, specifically zirconium, titanium, and tungsten, using analytical transmission electron microscopy. Furthermore, the agreement between experiment and theory highlights the predictive capability of our approach. Critically, this work provides a comprehensive database of quantum-accurate solute segregation enthalpies in vanadium, enabling the development of advanced alloys for fusion reactors applications.
Fusion materials↗
Deformation band corrosion as a result of applied stress and cold-work in 304 stainless steel in simulated pressurized water reactor primary water conditions
Stainless steels like 304SS are commonly used in pressurized water reactor primary water environments due to their excellent resistance to stress corrosion cracking (SCC). However, SCC susceptibility has been observed in cold-worked 304SS. Cold-rolling introduces a high density of defects, such as deformation bands or dislocations, into the microstructure; applied stress, even if macroscopically below the yield stress, can result in regions with high localized stresses. Cold-worked and non-cold-worked samples were exposed to 360 °C simulated PWR primary water for 1500 h with and without active loading. Corrosion susceptibility of dislocations and deformation bands induced by cold-rolling and/or applied stress was studied using high-resolution (analytical) transmission electron microscopy. Deformation bands were generated in all specimens examined in the study. Penetrative oxidation was observed in some deformation bands in each specimen. The depth of penetrative deformation band oxidation frequently exceeded the depth of grain boundary oxidation in all specimens. However, deformation band oxides generally were narrowly confined to the deformation band plane. Highly Ni-rich regions were observed beyond all oxidation fronts. Surface oxides were thicker in the specimens exposed under active loading. In conclusion, the implications of these findings at surfaces for deformation bands intersecting stress corrosion crack paths are discussed.
EFTEM↗
Effect of Applied Stress on the Selective Oxidation of Alloy 600 Exposed to PWR Primary Water and Rhines Pack Environments
A mechanistic understanding of corrosion and oxidation processes is crucial to ensure long-term resistance to stress corrosion cracking of Ni-base structural alloys in pressurized water reactor (PWR) primary and secondary systems. Aqueous corrosion of Ni-base alloys under PWR primary water conditions was previously compared to gaseous oxidation with comparable oxygen potentials. However, those studies considered only stress-free conditions, which removes a critical parameter for understanding stress corrosion behaviors. A significant knowledge gap exists for the role of applied stresses on selective internal oxidation in gaseous environments. A micro-4-point-bend jig was designed to facilitate stress in a Rhines Pack set-up. Selective oxidation at different stress and strain conditions was investigated in a series of Rhines Pack experiments for Alloy 600. Focused ion beam milling enabled the extraction of site-specific specimens containing selected high-energy grain boundaries from tensile and compressive stress regions. Analytical transmission electron microscopy was employed to analyze the microstructure and chemical composition of the resulting oxides. Protective surface oxide films and selective intergranular oxides were observed at different conditions. The implications of these fundamental differences are discussed relative to intergranular attack and stress corrosion cracking mechanisms in PWR primary water.
stress, 4-point-bend, selective oxidation, Alloy 6↗