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Browsing by Author "Bai, Xianming"

Now showing 1 - 20 of 27
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    Anisotropic hydrogen diffusion in alpha-Zr and Zircaloy predicted by accelerated kinetic Monte Carlo simulations
    Zhang, Yongfeng; Jiang, Chao; Bai, Xianming (Springer Nature, 2017-01-20)
    This report presents an accelerated kinetic Monte Carlo (KMC) method to compute the diffusivity of hydrogen in hcp metals and alloys, considering both thermally activated hopping and quantum tunneling. The acceleration is achieved by replacing regular KMC jumps in trapping energy basins formed by neighboring tetrahedral interstitial sites, with analytical solutions for basin exiting time and probability. Parameterized by density functional theory (DFT) calculations, the accelerated KMC method is shown to be capable of efficiently calculating hydrogen diffusivity in alpha-Zr and Zircaloy, without altering the kinetics of long-range diffusion. Above room temperature, hydrogen diffusion in alpha-Zr and Zircaloy is dominated by thermal hopping, with negligible contribution from quantum tunneling. The diffusivity predicted by this DFT + KMC approach agrees well with that from previous independent experiments and theories, without using any data fitting. The diffusivity along < c > is found to be slightly higher than that along < a >, with the anisotropy saturated at about 1.20 at high temperatures, resolving contradictory results in previous experiments. Demonstrated using hydrogen diffusion in alpha-Zr, the same method can be extended for on-lattice diffusion in hcp metals, or systems with similar trapping basins.
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    Atomistic Modeling of Defect Energetics and Kinetics at Interfaces and Surfaces in Metals and Alloys
    Alcocer Seoane, Axel Emanuel (Virginia Tech, 2024-01-02)
    Planar defects such as free surfaces and grain boundaries in metals and alloys play important roles affecting many material properties such as fracture toughness, corrosion resistance, wetting, and catalysis. Their interactions with point defects and solute elements also play critical roles on governing the microstructural evolution and associated property changes in materials. This work seeks to use atomistic modeling to obtain a fundamental understanding of many surface and interface related properties and phenomena, namely: orientation-dependent surface energy of elemental metals and alloys, segregation of solute elements at grain boundaries and their impact on grain boundary cohesive strength, and the controversial sluggish diffusion in both the bulk and grain boundaries of high entropy alloys. First, an analytical formula is derived, which can predict the surface energy of any arbitrary (h k l) crystallographic orientation in both body-centered-cubic (BCC) and face-centered-cubic (FCC) pure metals, using only two or three low-index (e.g., (100), (110), (111)) surface energies as input. This analytical formula is validated against 4357 independent single element surface energies reported in literature or calculated by the present author, and it proves to be highly accurate but easy to use. This formula is then expanded to include the simple-cubic (SC) structure and tested against 4542 surface energies of metallic alloys of different cubic structures, and good agreement is achieved for most cases. Second, the effect of segregation of substitutional solute elements on grain boundary cohesive strength in BCC Fe is studied. It is found that the bulk substitution energy can be used as an effective indicator to predict the embrittlement or strengthening potency induced by the solute segregation at grain boundaries. Third, the controversial vacancy-mediated sluggish diffusion in an equiatomic FeNiCrCoCu FCC high entropy alloy is studied. Many literature studies have postulated that the compositional complexity in high entropy alloys could lead to sluggish diffusion. To test this hypothesis, this work compares the vacancy-mediated self-diffusion in this model high entropy alloy with a hypothetical single-element material (called average-atom material) that has similar average properties as the high entropy alloy but without the compositional complexity. The results show that the self-diffusivities in the two bulk systems are very similar, suggesting that the compositional complexity in the high entropy alloy may not be sufficient to induce sluggish diffusion in bulk high entropy alloys. Based on the knowledge learned from the bulk alloy, the exploration of the possible sluggish diffusion has been extended to grain boundaries, using a similar approach as in the study of self-diffusion in bulk. Interestingly, the results show that sluggish diffusion is evident at a Σ5(210) grain boundary in the high entropy alloy due to the compositional complexity, especially in the low temperature regime, which is different from the bulk diffusion. The underlying mechanisms for the sluggish diffusion at this grain boundary is discussed.
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    Computational and Data-Driven Design of Perturbed Metal Sites for Catalytic Transformations
    Huang, Yang (Virginia Tech, 2024-05-23)
    We integrate theoretical, computational and data-driven approaches for the sake of understanding, design and discovery of metal based catalysts. Firstly, we develop theoretical frameworks for predicting electronic descriptors of transition and noble metal alloys, including a physics model of d-band center, and a tight-binding theory of d-band moments to systematically elucidate the distinct electronic structures of novel catalysts. Within this framework, the hybridization of semi-empirical theories with graph neural network and attribution analysis enables accurate prediction equipped with mechanistic insights. In addition, novel physics effect controlling surface reactivity beyond conventional understanding is uncovered. Secondly, we develop a computational and data-driven framework to model high entropy alloy (HEA) catalysis, incorporating thermodynamic descriptor-based phase stability evaluation, surface segregation modeling by deep learning potential-driven molecular simulation and activity prediction through machine learning-embedded electrokinetic model. With this framework, we successfully elucidate the experimentally observed improved activity of PtPdCuNiCo HEA in oxygen reduction reaction. Thirdly, a Bayesian optimization framework is employed to optimize racemic lactide polymerization by searching for stereoselective aluminum (Al) -complex catalysts. We identified multiple new Al-complex molecules that catalyzed either isoselective or heteroselective polymerization. In addition, feature attribution analysis uncovered mechanistically meaningful ligand descriptors that can access quantitative and predictive models for catalyst development.
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    Computational Studies of the Mechanical Response of Nano-Structured Materials
    Beets, Nathan James (Virginia Tech, 2020-05-18)
    In this dissertation, simulation techniques are used to understand the role of surfaces, interfaces, and capillary forces on the deformation response of bicontinuous metallic composites and porous materials. This research utilizes atomistic scale modeling to study nanoscale deformation phenomena with time and spatial resolution not available in experimental testing. Molecular dynamics techniques are used to understand plastic deformation of metallic bicontinuous lattices with varying solid volume fraction, connectivity, size, surface stress, loading procedures, and solid density. Strain localization and yield response on nanoporous gold lattices as a function of their solid volume fraction are investigated in axially strained periodic samples with constant average ligament diameter. Simulation stress results revealed that yield response was significantly lower than what can be expected form the Gibson-Ashby formalism for predicting the yield response of macro scale foams. It was found that the number of fully connected ligaments contributing to the overall load bearing structure decreased as a function of solid volume fraction. Correcting for this with a scaling factor that corrects the total volume fraction to "connected, load bearing" solid fraction makes the predictions from the scaling equations more realistic. The effects of ligament diameter in nanoporous lattices on yield and elastic response in both compressive and tensile loading states are reported. Yield response in compression and tension is found to converge for the two deformation modes with increasing ligament diameter, with the samples consistently being stronger in tension, but weaker in compression. The plastic response results are fit to a predictive model that depends on ligament size and surface parameter (f). A modification is made to the model to be in terms of surface area to volume ratio (S/V) rather than ligament diameter (1/d) and the response from capillary forces seems to be more closely modeled with the full surface stress parameter rather than surface energy. Fracture response of a nanoporous gold structure is also studied, using the stress intensity-controlled equations for deformation from linear elastic fracture mechanics in combination with a box of atoms, whose interior is governed by the molecular dynamics formalism. Mechanisms of failure and propagation, propagation rate, and ligament-by-ligament deformation mechanisms such as dislocations and twin boundaries are studied and compared to a corresponding experimental nanoporous gold sample investigated via HRTEM microscopy. Stress state and deformation behavior of individual ligaments are compared to tensile tests of cylinder and hyperboloid nanowires with varying orientations. The information gathered here is used to successfully predict when and how ligaments ahead of the crack tip will fracture. The effects of the addition of silver on the mechanical response of a nanoporous lattice in uniaxial tension and compression is also reported. Samples with identical morphology to the study of the effects of ligament diameter are used, with varying random placement concentrations of silver atoms. A Monte Carlo scheme is used to study the degree of surface segregation after equilibration in a mixed lattice. Dislocation behavior and deformation response for all samples in compression and tension are studied, and yield response specifically is put in the context of a surface effect model. Finally, a novel bicontiuous fully phase separated Cu-Mo structure is investigated, and compared to a morphologically similar experimental sample. Composite interfacial energy and interface orientation structure are studied and compared to corresponding experimental results. The effect of ligament diameter on mechanical response in compressive stress is investigated for a singular morphology, stress distribution by phase is investigated in the context of elastic moduli calculated from the full elastic tensor and pure elemental deformation tests. Dislocation evolution and its effects on strain hardening are put in the context of elastic strain, and plastic response is investigated in the context of a confined layer slip model for emission of a glide loop. The structure is shown to be an excellent, low interface energy model that can arrest slip plane formation while maintaining strength close to the theoretical prediction. Dislocation content in all samples was quantified via the dislocation extraction algorithm. All visualization, phase dependent stress analysis, and structural/property analysis was conducted with the OVITO software package, and its included python editor. All simulations were conducted using the LAMMPS molecular dynamics simulation package. Overall, this dissertation presents insights into plastic deformation phenomena for nano-scale bicontinuous metallic lattices using a combination of experimentation and simulation. A more holistic understanding of the mechanical response of these materials is obtained and an addition to the theory concerning their mechanical response is presented.
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    Computer-Aided Formulation of Magnetic Pastes for Magnetic Components in Power Electronics
    Ding, Chao (Virginia Tech, 2021-05-25)
    Magnetic components are necessary for switch-mode power electronics converters, but they are often the bulkiest and heaviest in the system. Novel magnetic designs with intricate structures lead to the size reduction of power electronics converters but pose challenges to the fabrication process and material availability. Because of their low-temperature and pressure-less process-ability, magnetic pastes would be the material of choice to make magnetic cores with complex geometries. However, most magnetic pastes reported in the literature suffer from low relative permeability (µr < 26) due to the low magnetic fraction limited by viscosity. The conventional approach of developing magnetic pastes involves experimental iterations with trial-and-error efforts to determine the optimal compositions. To shorten the development cycle and take advantage of the computational power in the current age, this work focuses on exploring, validating, and demonstrating a computer-aided methodology to correlate material's processing, microstructure, and property to guide the development of magnetic pastes. The discrete element method (DEM) simulation was explored to create materials' microstructure and the finite element method (FEM) simulation was utilized to study the magnetic permeability based on the microstructure created by DEM or taken from an actual material sample. The combination of DEM and FEM provided the linkage among processing-microstructure-property relations. Then, the methodology was verified and demonstrated by improving a starting formulation. The formulation was modeled with DEM based on multiple variables, e.g., particle shape, size, size distribution, mixing ratio, gap, gap distribution, magnetic volume fraction, etc. The optimal mixing ratio of different powders to achieve the maximum magnetic fraction was determined by DEM. Experimental results confirmed the predicted optimal mixing ratio. To further take advantage of the computational tools, the magnetic permeability of the magnetic pastes was computed by FEM based on the DEM-generated microstructures. The effects of powder mixing ratio and magnetic volume fraction on the magnetic permeability were studied, respectively. Compared with the experimental values, the microstructure-based FEM simulations could predict the magnetic permeability of the formulations with varied powder mixing ratios or magnetic volume fractions with an average error of only 10 %. Another critical aspect of employing magnetic pastes for magnetic components in power electronics is capable of tailoring their magnetic permeability to meet different design needs. The methodology was further verified and demonstrated by guiding the selection of composition parameters for tailorable magnetic permeability of a starting formulation with flaky particles. An FEM model was constructed from a microstructural image and varied parameters were explored (particle permeability, matrix permeability, particle volume fraction, etc.) to tailor the magnetic permeability. To verify the simulated results, a set of magnetic pastes with various volume fractions of flakes was prepared experimentally and characterized for their permeability. Comparing the simulated and measured permeability, the error was found to be less than 10 %. Last, the guideline was demonstrated to predict a material composition to achieve a target relative permeability of 30. From the predicted composition, the magnetic paste was prepared and characterized. The error between experimental permeability and the target was only 5 %. With the guideline, one can formulate magnetic pastes with tailorable permeability with minimal experimental effort and select the composition parameters to achieve a target permeability. After developing a series of magnetic pastes with tailorable permeability and a maximum value of 35, the feasibility of making magnetic components with magnetic pastes was demonstrated. The commonly used magnetic cores – C-core, E-core, toroid core, bar core, and plate core were fabricated by a low-temperature (< 200 °C) and pressure-less molding process. Several innovative magnetic components with intricate core structures were also fabricated to demonstrate the shape-forming flexibility. The magnetic paste can also be used as the feedstock for paste-extrusion-based additive manufacturing, which further enhances the shape-forming capability. For demonstration, a multi-permeability core was fabricated by 3D printing the magnetic pastes with tailored permeability. The feasibility of making high-performance magnetic components by additive manufacturing or low-temperature pressure-less molding of magnetic pastes opens the door to power electronics researchers to explore more innovative magnetic designs to further improve the efficiency and power density of the power electronics converters.
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    Corrosion and Tribocorrosion Kinetics of Al-based Concentrated Alloys in Aqueous Sodium Chloride Solution
    Chen, Jia (Virginia Tech, 2021-11-30)
    Commercial aluminum (Al) alloys are often precipitation strengthened to improve strength and wear resistance. However, localized corrosion due to the galvanic coupling between the precipitates and Al matrix often leads to degraded performance when these alloys are exposed to corrosive environment. In this work, Al-based solid solution was synthesized to simultaneously improve the strength and corrosion resistance of Al alloys, which ultimately led to high tribocorrosion resistance. Specifically, the effects of testing condition (e.g. sliding frequency) and alloying effects (e.g. Mn and Mo) on the corrosion and tribocorrosion behavior of Al-based binary and ternary solid solutions were studied. To understand the effects of wear condition on the depassivation-repassivation kinetics during tribocorrosion, in the first study, the tribocorrosion behaviors of Al-20 at.%Mn alloys were investigated in simulated seawater by changing the sliding frequency from 0.05 to 1 Hz in reciprocal motion. The results show that the depassivation rate of passive film increased with increasing sliding frequency. Mechanical wear also increased with increasing sliding frequency, which was mainly related to the increase of coefficient of friction and real contact area. Chemical wear tended to increase with scratching frequency, most likely due to faster repassivation kinetics at lower frequency. The surface layer was analyzed by cross-sectional transmission electron microscopy, indicating the passive film was primarily consisted of aluminum oxide where manganese was selectively dissolved. Despite extensive past research, the fundamental understanding of the alloying effects on the atomistic structure, composition, and chemical state of the passive layer of Al alloys and their formation mechanism is still not well understood. In the second study, the effects of Mn on the aqueous corrosion of Al-Mn alloys were investigated. It was confirmed that Mn alloying could enhance the corrosion resistance of Al without participating in the surface oxidation. Atom probe tomography analysis confirmed the absence of Mn in the anodized and corroded surface of Al-Mn alloys. The selective dissolution of Mn in these alloys was believed to increase the free volume at the metal/oxide interface to facilitate the formation of a denser, thinner oxide layer with closer to stoichiometry composition, leading to its enhanced corrosion resistance than pure Al. Lastly, to better understand the corrosion and tribocorrosion resistance of Al-based lightweight concentrated alloys and the effects of alloying concentrations on the structure and property of the passive layer, the third study investigated the effects of a passive element (Mo) and non-passive element (Mn) on the corrosion and tribocorrosion behavior of Al-Mn-Mo alloys. Specifically, Al80Mn8Mo12 exhibited higher corrosion resistance than Al80Mn20 due to the formation of a more compact and less defective passive film, as explained by the roles Mo played in both the substrate and the passive film. It was found that the pitting potential and corrosion current density of Al-Mn-Mo increased with Mo%. The effect of Mo alloying concentration on the tribocorrosion behavior of Al-Mn-Mo alloys was investigated as well. Adding Mo to Al-Mn alloys led to a lower wear and tribocorroison resistance of Al-Mn-Mo alloys. In addition, decreasing Mn and Mo concentrations resulted in a reduction of the tribocorrosion resistance in the ternary alloy, which was mainly dominated by the mechanical response under the selected testing conditions.
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    Defect and structural evolution under high-energy ion irradiation informs battery materials design for extreme environments
    Rahman, Muhammad Mominur; Chen, Wei-Ying; Mu, Linqin; Xu, Zhengrui; Xiao, Ziqi; Li, Meimei; Bai, Xianming; Lin, Feng (Nature Research, 2020-09-11)
    Understanding defect evolution and structural transformations constitutes a prominent research frontier for ultimately controlling the electrochemical properties of advanced battery materials. Herein, for the first time, we utilize in situ high-energy Kr ion irradiation with transmission electron microscopy to monitor how defects and microstructures evolve in Na- and Li-layered cathodes with 3d transition metals. Our experimental and theoretical analyses reveal that Li-layered cathodes are more resistant to radiation-induced structural transformations, such as amorphization than Na-layered cathodes. The underlying mechanism is the facile formation of Li-transition metal antisite defects in Li-layered cathodes. The quantitative mathematical analysis of the dynamic bright-field imaging shows that defect clusters preferentially align along the Na/Li ion diffusion channels (a-b planes), which is likely governed by the formation of dislocation loops. Our study provides critical insights into designing battery materials for extreme irradiation environments and understanding fundamental defect dynamics in layered oxides.
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    Development of Metallic Fuel Additives and Alloys for Sodium-cooled Fast Reactors
    Zhuo, Weiqian (Virginia Tech, 2022-07-11)
    The major goal of the work is to develop effective additives for U-10Zr (wt.%) metallic fuel to mitigate the fuel-cladding chemical interactions (FCCIs) due to fission product lanthanides and to optimize the fuel phase mainly by lowering the gamma-onset temperature. The additives Sb, Mo, Nb, and Ti have been investigated. Metallic fuels with one or two of the additives and with or without lanthanide fission products were fabricated. In this study, Ce was selected as the representative lanthanide fission product. A series of tests and characterizations were carried out on the additive-bearing fuels, including annealing, diffusion coupling, scanning electron microscopy (SEM), X-ray powder diffraction (XRD), and differential scanning calorimetry (DSC). Sb was investigated to mitigate FCCIs because available studies show its potential as a lanthanide immobilizer. This work extends the knowledge of Sb in U-10Zr, including its effect in the Zr-free region. Sb forms precipitates with fuel constituents, either U or Zr. However, it combines with the lanthanide fission product Ce when Ce is present. Those Sb-precipitates are found to be stable upon annealing, and are compatible with the cladding. The additive does not change the phase transition of U-10Zr. Mo, Nb, and Ti have been investigated for phase optimization based on the known characteristics shown in the binary phase diagrams. The quaternary alloys, i.e., two Mo-bearing alloys and two Nb-bearing alloys, were investigated. Compared to U-10Zr, a few weight percentages of Zr are replaced by those additives in the quarternary alloys. The solid-state phase transitions were determined (alpha and U2Ti transfer into gamma). The transition temperature varies depending on the compositions. The Mo-bearing alloys have lower -onset temperatures than the Nb-bearing alloys. All of them have lower gamma-onset temperatures than that of U-10Zr. Since low gamma-onset temperature is favorable, the results indicate that the fuel phase can be optimized by the replacement of a few weight percentages of Zr into those additives. All the experiments were out-of-pile tests. Therefore, in-pile experiments will be necessary to fully evaluate the performance of the additives in the future.
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    Heterogeneous Redox Chemistries in Layered Oxide Materials for Lithium-Ion Batteries
    Xu, Zhengrui (Virginia Tech, 2022-01-05)
    The invention of the lithium-ion battery has revolutionized the passenger transportation field in recent years, and it has emerged as one of the state-of-the-art solutions to address greenhouse gases emission and air pollution issues. Layered oxide lithium-ion battery cathode materials have become commercially successful in the past few decades due to their high energy density, high power density, long cycle life, and low cost. Yet, with the increasing demand for battery performance, it is crucial to understand the material fading mechanisms further to improve layered oxide materials' performance. A heterogeneous redox reaction is a dominant fading mechanism, which limits the utilization percentage of a battery materials' redox capability and leads to adverse effects such as detrimental interfacial reactions, lattice oxygen release, and chemomechanical breakdown. Crystallographic defects, such as dislocations and grain boundaries, are rich in battery materials. These crystallographic defects change the local lithium-ion diffusivity and have a dramatic effect on the redox reactions. To date, there is still a knowledge gap on how various crystallographic defects affect electrochemistry at the microscopic scale. Herein, we adopted synchrotron-based diffraction, imaging, and spectroscopic techniques to systematically study the correlation between crystallographic defects and redox chemistries in the nanodomain. Our studies shed light on design principles of next-generation battery materials. In Chapter 1, we first provide a comprehensive background introduction on the battery chemistry at various length scales. We then introduce the heterogeneous redox reactions in layered oxide cathode materials, including a discussion on the impacts of heterogeneous redox reactions. Finally, we present the different categories of crystallographic defects in layered oxide materials and how these crystallographic defects affect electrochemical performance. In Chapter 2, we use LiCoO2, a representative layered oxide cathode material, as the material platform to quantify the categories and densities of various crystallographic defects. We then focus on geometrically necessary dislocations as they represent a major class of crystallographic defects in LiCoO2. Combining synchrotron-based X-ray fluorescence mapping, micro-diffraction, and spectroscopic techniques, we reveal that geometrically necessary dislocations can facilitate the charging reactions in LiCoO2 grains. Our study illustrates that the heterogeneous redox chemistries can be potentially mitigated by precisely controlling the defects. In Chapter 3, we systematically investigated how grain boundaries affect redox reactions. We reveal that grain boundaries can guide redox reactions in LiNixMnyCo1-x-yO2 (NMC) materials. Specifically, NMC materials with radially aligned grains have a more uniform charge distribution, less stress mismatch, and better cycling performance. NMC materials with randomly orientated grains have a more heterogeneous redox reaction. These heterogeneous redox reactions are related to the lattice strain mismatch and worse cycling performance. Our study emphasizes the importance of tuning grain orientations to achieve improved performance. Chapter 4 systematically investigated how the grain boundaries and crystallographic orientations affect the thermal stability of layered oxide cathode materials. Combining diffraction, spectroscopic, and imaging techniques, we reveal that a cathode materials' microstructure plays a significant role in determining the lattice oxygen release behavior and, therefore, determines cathode materials' thermal stability. Our study provides a fundamental understanding of how the grain boundaries and crystallographic orientations can be tuned to develop better cathode materials for the next-generation Li-ion batteries. Chapter 5 summarizes the contributions of our work and provides our perspective on future research directions.
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    Kinetic Property and SS 316/Alloy 617 Corrosion Study in Molten Chloride and Fluoride Salts
    Yang, Qiufeng (Virginia Tech, 2022-10-04)
    This study focused on the kinetic data measurements, such as diffusion coefficient D and exchange current density i_0 of the electrochemical reactions of corrosion products (Fe, Cr and Ni ions) and corrosive species (OH-), and corrosion studies of structural materials (SS 316H and Alloy 617), including static corrosion and galvanic corrosion, in molten MgCl2-NaCl-KCl and/or NaF-KF-UF4-UF3 salts in a temperature range of 600 to 800C. The study applied the semi-differential (SD) analysis method and innovative fitting method for the kinetic property data measurements in the multicomponent system of NaF-KF-UF4-UF3 salts. In molten MgCl2-NaCl-KCl salts, the measured D_(OH^- ) has the largest value followed by D_(〖Cr〗^(2+) ), D_(〖Fe〗^(2+) ), D_(〖Cr〗^(3+) ) and D_(〖Ni〗^(2+) ) at the studied temperatures, and none of the diffusion coefficients depends on the ion concentration in the studied concentration range and all of them followed the Arrhenius law. At the same temperature, the measured D_(Fe^(2+) ) and D_(〖Cr〗^(2+) ) values in molten NaF-KF-UF4-UF3 salts were slightly smaller than those obtained in molten MgCl2-NaCl-KCl salts. The non-linear curve fitting technique was applied to determine the exchange current density i_0, charge transfer coefficient α, limiting current density i_L and standard rate constant k^0 values. i_0 and k^0 followed the Arrhenius law. The obtained fundamental data can be applied to corrosion models which make the corrosion rate prediction possible in a static system from the experimental kinetic data. Corrosion studies of SS 316H and Alloy 617 in thermal purified molten NaF-KF-UF4-UF3 salts were performed for 120 hours. Based on the post-test analysis, the major metal species corrosion products were Cr, Fe and Mn in SS 316H tests, and Cr, Co, Ni in Alloy 617 tests. The measured UF4/UF3 ratio increased after corrosion tests because some of the U3+ was oxidized to U4+ by corrosive impurities and corrosion products during tests. Cr depletion and salt penetration were observed at grain boundaries (GBs) for both SS 316H and Alloy 617. For Alloy 617 specimens, the corroded area could be divided into two parts: the first part (near the surface) where Cr was completely depleted, and the second part (underneath the first part) where Cr was partially depleted. For SS 316H specimens, the average attack depth was larger than that of Alloy 617. Mo segregation was observed in the matrix of SS 316H specimens but was found to be enriched at GBs in the second part of Alloy 617 specimens. The corrosion study of Alloy 617 with time was also conducted for 72 hours and 32 hours, respectively. A thin layer composed of Fe, Co, Ni and Mo was found on the surface of the specimen, which was different from the previous 120-hour tests. In the salt, the concentration of Cr kept increasing with time, while for the other identified corroded elements, i.e., Fe, Co, Ni and Mo, their concentrations increased first, then decreased until becoming zero or stable. In the galvanic corrosion study of Alloy 617/graphite in molten NaF-KF-UF4-UF3 salts, the galvanic corrosion rate of Alloy 617 at 750C was about four times of that at 650C in the 2-hour tests, which indicated that temperature has a significant effect on the galvanic effect. In the 120-hour galvanic corrosion test, the galvanic corrosion rate became slightly larger with time in the studied system. Similar to the previous 120-hour Alloy 617 corrosion test, the corroded area of the post-test specimen was divided into two parts. The measured attack depth in both parts were much smaller compared with that in the 120-hour Alloy 617 test. This was because of the lower corrosive impurity concentrations in the salt used in the test. The salt in the galvanic corrosion test has been used in the previous corrosion test, during which the corrosive impurities were consumed, which made the salt less corrosive. Finally, it is necessary to point out that all the salts used in the present work were only thermally purified, which is effective in the removal of moisture but not in the removal of oxide impurities. Therefore, further studies are needed to understand the oxides' impacts on the corrosion behavior, especially on the salt penetration.
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    Material Corrosion by Nuclear Reactor Coolants
    Leong, Amanda (Virginia Tech, 2022-09-19)
    This work investigated material corrosion by nuclear reactor coolants, including pressurized water reactor (PWR) coolant, boiling water reactor (BWR) coolant, high-temperature steam, lead-bismuth eutectic (LBE), and molten salt. Novel cladding materials for accident tolerant fuel (ATF) and additive manufacture (AM) Ni-based alloy were studied in water coolants. Similarly, the ATF material and Ni-based alloys were also examined under high-temperature steam to understand the corrosion behavior in beyond design basis accident (BDBA) scenarios. In addition to isothermal corrosion, stress corrosion cracking (SCC) and oxide layer in situ measurements were also conducted. Unlike conventional studies in liquid LBE that focused on Fe-based alloys, the present studies also investigated Ni-based alloys to explore the Ni content effects on the corrosion by LBE at high temperatures under saturated oxygen conditions. In molten salt environments, the corrosion behaviors of both Ni-based and Fe-based alloys were investigated. This study developed a redox potential range for mitigating corrosion by using a redox couple of UF4 /UF3 and a novel approach of potential measurements against F2/ F- potential experimentally.
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    Material Degradation Studies in Molten Halide Salts
    Dsouza, Brendan Harry (Virginia Tech, 2021-04-16)
    This study focused on molten salt purification processes to effectively reduce or eliminate the corrosive contaminants without altering the salt's chemistry and properties. The impurity-driven corrosion behavior of HAYNES® 230® alloy in the molten KCl-MgCl2-NaCl salt was studied at 800 ºC for 100 hours with different salt purity conditions. The H230 alloy exhibited better corrosion resistance in the salt with lower concentration of impurities. Furthermore, it was also found that the contaminants along with salt's own vaporization at high temperatures severely corroded even the non-wetted surface of the alloy. The presence of Mg in its metal form in the salt resulted in an even higher mass-loss possibly due to Mg-Ni interaction. The study also investigated the corrosion characteristics of several nickel and ferrous-based alloys in the molten KCl-MgCl2-NaCl salt. The average mass-loss was in the increasing order of C276 < SS316L < 709-RBB* < IN718 < H230 < 709-RBB < 709-4B2. The corrosion process was driven by the outward diffusion of chromium. However, other factors such as the microstructure of the alloy i.e. its manufacturing, refining, and heat-treatment processes have also shown to influence the corrosion process. Lowering the Cr content and introducing W and Mo in the alloy increased its resistance to corrosion but their non-uniform distribution in the alloy restricted its usefulness. To slow-down the corrosion process, and enhance the material properties, selected alloys were boronized and tested for their compatibility in the molten KCl-MgCl2-NaCl salt. The borided alloys exhibited better resistance to molten salt attack, where the boride layer in the exposed alloy was still intact, non-porous, and strongly adhered to the substrate. The alloys also did not show any compensation in their properties (hardness). It was also found that the boride layer always composed of an outermost silicide composite layer, which is also the weakest and undesired layer as it easily cracks, breaks, or depletes under mechanical and thermal stresses. Various different grades of "virgin" nuclear graphites were also tested in the molten KF-UF4-NaF salt to assist in the selection of tolerable or impermeable graphites for the MSR operational purposes. It was found that molten salt wettability with graphite was poor but it still infiltrated at higher pressure. Additionally, the infiltration also depended on the pore-size and porosity of the graphite. The graphite also showed severe degradation or disintegration of its structure because of induced stresses.
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    Modeling of Effect of Alloying Elements on Radiation Damage in Metallic Alloys
    Zhang, Yaxuan (Virginia Tech, 2020-05-26)
    Metallic alloys are important structural and cladding materials for current and future reactors. Understanding radiation-induced damage on metallic alloys is important for maintaining the safety of nuclear reactors. This dissertation mainly focuses on radiation-induced primary damage in iron-based metallic. Systematic molecular dynamics simulations were conducted to study the alloying element effects on the primary damage in Fe-based alloys, including defect production and dislocation loop transformations, and their connections with defect thermodynamics. First, effects of alloying elements on the primary damage in three Fe-based ferritic alloy systems were studied, with a particular focus on the production behaviors of solute interstitials. The production behaviors of solute interstitials include over-production or under-production, compared with their solute concentration in the Fe matrix. The three alloy systems are: (1) a Fe-Cr alloy system; (2) a Fe-Cu alloy system; and (3) an ideal but artificial Fe-Cr alloy system, which is used as a reference system. It is found that the number ratio of solute interstitials to the total interstitials is distinct in these alloys. The solute interstitials are over-produced in the Fe-Cr systems but under-produced in the Fe-Cu system, compared with solute composition in the alloys. The defect formation energies in both dilute and concentrated alloys, interstitial-solute binding energies, liquid diffusivities of Fe and solute atoms, and heat of mixing have been calculated for both Fe-Cr and Fe-Cu alloys. Among these factors, our analysis shows that the relative thermodynamic stability between Fe self-interstitials and solute interstitials plays the most important role on the production behaviors of solute interstitials. Next, to obtain a correlation that can quantitatively estimate the solute interstitial fraction in the Fe-based alloys, molecular dynamics simulations were conducted to simulate the cascade damage in a series of "artificial" Fe-Cr alloys with tunable binding energies between a substitutional solute (Cr) atom and a Fe self-interstitial atom (SIA). To achieve this, the Fe-Cr cross pair interaction in the interatomic potential was modified by multiplying a scaling factor so that the solute-SIA binding energy varies linearly from positive to negative values. It is found that the solute interstitial fraction has a strong correlation with the solute-SIA binding energy, and the correlation can be approximately described by a Fermi-Dirac-Distribution-like equation. The independent defect production results reported in literature are found to align well with this correlation. The correlation may be used to estimate the solute interstitial fraction in a wide range of Fe-based alloys simply based on the solute-SIA binding energy, without conducting laborious cascade simulations. Furthermore, primary damage was further investigated in Fe-tungsten (W) alloys to investigate the atomic size effect. The large difference in atomic size between Fe and W can introduce both global volume expansion and local lattice distortion in the Fe matrix. In order to understand how oversized W influences the defect production behaviors in Fe-based alloys, molecular dynamics simulations were conducted to study the primary damage in three systems at 300 K: (a) unstrained pure Fe, (b) Fe-5at.%W alloy, and (c) strained pure Fe with the same volume expansion as the Fe-5%W. The investigation of defect production behaviors include the production of Frenkel pairs, and cluster formation preference. Based on the total number of Frenkel pairs, it indicates that the global volume expansion introduced by oversized W and external strain can lead to enhanced defect production. Meanwhile, the defect cluster analysis in all three systems indicates that the local lattice distortion induced by oversized W can significantly influence the morphologies and size distributions of defect structures. Defect formation energies were calculated to interpret the different defect production behaviors in these systems. Finally, radiation can produce not only point defects but also both <100> and ½<111> type dislocation loops in pure Fe and Fe-Cr alloys. However, contradictory experimental results have been reported on how the Cr concentration affects the ratio of <100> to ½<111> dislocation loops. In this section, molecular dynamics simulations were conducted to study how Cr concentration affects the formation probability of <100> dislocation loops from overlapping cascades on a pre-existing ½<111> dislocation loop in a series of Fe-Cr alloys with 0 – 15%Cr at 300 K. Our atomistic modeling directly demonstrates that the ratio of <100> to ½<111> dislocation loops decreases with the increasing Cr concentration, which is consistent with many experimental observations. Next, independent molecular statics calculations show that the formation energies of both <100> and ½<111> dislocation loops increase with the increasing of Cr content. However, the former has a much faster increase rate than the latter, indicating that the formation of <100> loops becomes energetically more and more unfavorable than ½<111> loops as the Cr content increases. The results provide a thermodynamics-based explanation for why Cr suppresses the formation of <100> dislocation loops in Fe-Cr alloys, which can be applied to all <100> loop formation mechanisms proposed in literature. The possible effects of other alloying elements on the formation probability of <100> loops in Fe-based alloys are also discussed.
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    Modeling of Thermal Transport Properties in Metallic and Oxide Fuels
    Chen, Weiming (Virginia Tech, 2021-08-26)
    Thermal conductivity is a critical fuel performance property not only for current UO2 oxide fuel based light water reactors but also important for next-generation fast reactors that use U-Zr based metallic fuels. In this work, the thermal transport properties of both UO2 based oxide fuels and U-Zr based metallic fuels have been studied. At first, molecular dynamics (MD) simulations were conducted to study the effect of dispersed Xe fission gas atoms on the UO2 thermal conductivity. Numerous studies have demonstrated that xenon (Xe) fission gas plays a major role on fuel thermal conductivity degradation. Even a very low Xe concentration can cause significant thermal conductivity reduction. In this work, the effect of dispersed Xe gas atoms on UO2 thermal conductivity were studied using three different interatomic potentials. It is found that although these potentials result in significant discrepancies in the absolute thermal conductivity values, their normalized values are very similar at a wide range of temperatures and Xe concentrations. By integrating this unified effect into the experimentally measured thermal conductivities, a new analytical model is developed to predict the realistic thermal conductivities of UO2 at different dispersed Xe concentrations and temperatures. Using this new model, the critical Xe concentration that offsets the grain boundary Kapitza resistance effect on the thermal conductivity in a high burnup structure is studied. Next, the mechanisms on how Xe gas bubbles affect the UO2 thermal conductivity have been studied using MD. At a fixed total porosity, the effective thermal conductivity of the bubble-containing UO2 increases with Xe cluster size, then reaches a nearly saturated value at a cluster radius of 0.6 nm, demonstrating that dispersed Xe atoms result in a lower thermal conductivity than clustering them into bubbles. In comparison with empty voids of the same size, Xe-filled bubbles lead to a lower thermal conductivity when the number ratio of Xe atoms to uranium vacancies (Xe:VU ratio) in bubbles is high. Detailed atomic-level analysis shows that the pressure-induced distortion of atoms at bubble surface causes additional phonon scattering and thus further reduces the thermal conductivity. For metallic fuels, temperature gradient and irradiation induced constituent redistribution in U-Zr based fuels cause the variation in fuel composition and the formation of different phases that have different physical properties such as thermal conductivity. In this work, a semi-empirical model is developed to predict the thermal conductivities of U-Zr alloys for the complete composition range and a wide range of temperatures. The model considers the effects of (a) scattering by defects, (b) electron-phonon scattering, and (c) electron-electron scattering. The electronic thermal resistivity models for the two pure components are empirically determined by fitting to the experimental data. A new mixing rule is proposed to predict the average thermal conductivity in U-Zr alloys based on their nominal composition. The thermal conductivity predictions by the new model show good agreement with many available experimental data. In comparison with previous models, the new model has further improvement, in particular for high-U alloys that are relevant to reactor fuel compositions and at the low-temperature regime for the high-Zr alloys. The average thermal conductivity model for the binary U-Zr fuel is also coupled with finite element-based mesoscale modeling technique to calculate the effective thermal conductivities of the U-Zr heterogeneous microstructures. For a U-10wt.%Zr (U-10Zr) fuel at temperatures below the ɑ phase transition temperature, the dominant microstructures are lamellar δ-UZr2 and ɑ-U. Using the mesoscale modeling, the phase boundary thermal resistance R (Kapitza resistance) between δ-UZr2 and ɑ-U has been determined at different temperatures, which shows a T-3 dependence in the temperature range between 300K and 800K. Besides, the Kapitza resistance exhibits a strong dependence on the aspect ratio of the δ-UZr2 phase in the alloying system. An analytical model is therefore developed to correlate the temperature effect and the aspect ratio effect on the Kapitza resistance. Combining the mesoscale modeling with the newly developed Kapitza resistance model, the effective thermal conductivities of many arbitrary δ-UZr2 + ɑ-U heterogeneous systems can be estimated.
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    Molecular Dynamic Simulation of Polysiloxane
    Chaney, Harrison Matthew (Virginia Tech, 2023-04-10)
    Polymer Derived Ceramics are a promising class of Materials that allow for higher levels of tunability and shaping that traditional sintering methods do not allow for. Polysiloxanes are commonly used as a precursor for these types of material because of their highly tunable microstructures by adjusting the side groups on the initial polymer. These Polymers are generally cross linked and pyrolyzed in inert atmospheres to form the final polymer. The microstructures of Polymer Derived Ceramics is complex and hard to observe due to the size of each microstructure region and the proximity in the periodic table that the elements present have. The process of forming phases such as Graphitic Carbon, Amorphous Carbon, Silicon Carbide. Silicon Oxide, and SiliconOxycarbide are not well understood. Simulation provides a route to understanding the phenomenon behind these phase formations. Specifically, Molecular dynamics simulation paired with the Reaxff forcefield provides a framework to simulate the complex processes involved in pyrolysis such as chemical reactions and a combination of thermodynamic and kinetic interactions. This Thesis examines firstly the size effect that a system can have on phase separation and the change in composition. Showing that size plays a major role in how the system develops and limits the occurrence of specific reactions. Secondly, this thesis shows that using polymer precursors with different initial polymer components leads to vastly different microstructures and yield. This provides insights into how the transition from polymer to ceramic takes place on a molecular level.
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    Molecular Dynamics Studies of Anisotropy in Grain Boundary Energy and Mobility in UO₂
    French, Jarin C. (Virginia Tech, 2019-04-25)
    Nuclear energy is a proven large-scale, emission-free, around-the-clock energy source. As part of improving the nuclear energy efficiency and safety, a significant amount of effort is being expended to understand how the microstructural evolution of nuclear fuels affects the overall fuel performance. Grain growth is an important aspect of microstructural evolution in nuclear fuels because grain size can affect many fuel performance properties. In this work, the anisotropy of grain boundary energy and mobility, which are two important properties for grain growth, is examined for the light water reactor fuel uranium dioxide (UO₂) by molecular dynamics simulations. The dependence of these properties on both misorientation angle and rotation axis is studied. The anisotropy in grain boundary energy is found to be insignificant in UO₂. However, grain boundary mobility shows significant anisotropy. For both 20º and 45º misorientation angles, the anisotropy in grain boundary mobility follows a trend of M₁₁₁>M₁₀₀>M₁₁₀, consistent with previous experimental results of face-centered-cubic metals. Evidences of grain rotation during grain growth are presented. The rotation behavior is found to be very complex: counterclockwise, clockwise, and no rotation are all observed.
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    Molecular Dynamics Studies of Grain Boundary Mobilities in Metallic and Oxide Fuels
    French, Jarin Collins (Virginia Tech, 2023-08-22)
    Energy needs are projected to continue to increase in the coming decades, and with the drive to use more clean energy to combat climate change, nuclear energy is poised to become an important player in the energy portfolio of the world. Due to the unique nature of nuclear energy, it is always vital to have safe and efficient generation of that energy. In current light water reactors, the most common fuel is uranium dioxide (UO2), an oxide ceramic. There is also ongoing research examining uranium-based based metallic fuels, such as uranium-molybdenum (U-Mo) fuels with low uranium (U) enrichment for research reactors as part of a broader effort to combat nuclear proliferation, and uranium-zirconium-based fuels for Generation IV fast reactors. Each nuclear fuel has weaknesses that need to be addressed for safer and more efficient use. Two major challenges of using UO¬2 are the fission gas (e.g. xenon) release and the decreasing thermal conductivity with increasing burnup. In UMo alloys, the major weakness is the breakaway swelling that occurs at high fission densities. The challenges presented by both fuel types are heavily impacted by microstructure, and several studies have identified that the initial microstructure of the fuel in particular (e.g. initial grain size and grain aspect ratio) plays a large role in determining when and how quickly these processes occur. Thus, knowledge of how such initial microstructures evolve is paramount in having stable and predictable fission gas release and thermal conductivity decrease (in UO2) and fuel swelling (in UMo alloys). Mobility is a critical grain boundary (GB) property that impacts microstructural evolution. Existing literature examines GB mobility for a few specific boundaries but does not (in general) identify the anisotropy relationships that this property has. This work first examined the anisotropy in GB mobility, specifically identifying the anisotropy trend for the low-index rotation axes for tilt GBs in BCC γ U, and fluorite UO2 via molecular dynamics simulation. GB mobility is calculated using the shrinking cylindrical grain method, which uses the capillary effect induced by the GB curvature to drive grain growth. The mobilities are calculated for different rotation axes, misorientation angles, and temperatures in these systems. The results indicated that the density of the atomic plane perpendicular to the (tilt) GB plane (which is also perpendicular to the rotation axis) significantly impacts which GB rotation axis has the fastest boundaries. Specifically, the atomic plane that has a higher density tends to have a faster mobility, because it is more efficient for atoms moving across the GB along such planes. For example, for body-centered cubic materials, the <110> tilt GBs are determined to have the fastest mobilities, while face-centered cubic (FCC) and FCC-like structures such as fluorite have <111> tilt GBs as the fastest. Knowledge of GB mobility and its anisotropy in pure materials is helpful as a baseline, but real materials have solutes or impurities (both intentionally and unintentionally) which are known to affect GB mobility by processes such as solute drag and Zener pinning. Additionally, in reactors, nuclear fission can produce many fission products, each of which acts as an additional impurity that will interact with the GB in some way. Because the initial microstructure and its subsequent evolution are vital for addressing the challenges of using nuclear fuel as described above, knowledge of the impacts of these impurities on GB mobility is required. Therefore, this work examined the impact of solutes and impurities on GB mobility and its anisotropy. In particular, the solute effect was examined using the UMo alloy system, while the impurity effect was examined using Xe (a very common fission product) in the γ U, UMo, and UO2 systems. It is found that both Mo and Xe can cause a solute drag effect on GB mobility in the γ U system, with the effect of Xe being stronger than Mo at the same solute/impurity concentration. Xe also causes a solute drag effect in UO2, though the magnitude of the effect is interatomic-potential-dependent. The mobility anisotropy trend was found to disappear at high solute and impurity concentrations in the metallic U and UMo systems but was largely unaffected in the UO2 system. These results not only increase our fundamental understanding of GB mobility, its anisotropy, and solute/impurity drag effects, but also can be used as inputs for mesoscale simulations to examine polycrystalline grain growth with anisotropic GB mobility and in turn examine how the fuel performance parameters change with these properties.
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    Multiphysics Modelling on the Effects of Composition and Microstructure during Tribocorrosion of Aluminum-based Metals and Structures
    Wang, Kaiwen (Virginia Tech, 2022-08-24)
    Wear and corrosion are two major threats to material integrity in multiple real-life circumstances, including oil and gas pipelines, marine and offshore infrastructures and transportations and biomedical implants. Furthermore, the synergistic effects between the two, named tribocorrosion, could cause, most of the time, severer material degradation to jeopardize materials' long-term sustainability and structural integrity. A representative case is aluminum (Al) and its alloys, which exhibit good corrosion resistance in aqueous solution due to the protection provided by the passive layer. However, these naturally formed layers are thin and delicate, leaving the materials vulnerable to simultaneous mechanical and corrosion damage, which in turn, compromise their resistance to tribocorrosion. Past research in tribocorrosion mainly relies on costly and trial-and-error experimental methods to study the materials' deformation and degradation under simultaneous wear and corrosion. In an attempt to predict tribocorrosion behavior using numerical analysis, this work developed a set of finite-element-based multiphysics models, in combination with experimental methods for parameter input and validation, focusing on different factors influencing the tribocorrosion behavior of materials. The first study developed a model with the coupling between strain and corrosion potential and investigated the effect of bulk material properties on tribocorrosion. This model was validated by existing tribocorrosion experiments of two Al-Mn alloys, to analyze the synergistic effects of mechanical and corrosion properties on the material degradation mechanisms of tribocorrosion. During consecutive passes of the counter body, significant residual stress was found to develop near the edge of the wear track, leading to highly concentrated corrosion current than elsewhere. Such non-uniform surface corrosion and stress-corrosion coupling led to variations of tribocorrosion rate over time, even though testing conditions were kept constant. Tribocorrosion rate maps were generated to predict material loss as a function of different mechanical and electrochemical properties, indicating a hard, complaint metal with high anodic Tafel slope and low exchange current density is most resistant to tribocorrosion. Secondly, the influence of microstructural design on the tribocorrosion behavior of Al-based nanostructured metallic multilayers (NMMs) was investigated computationally. Specifically, this model accounts for elastic-plastic mechanical deformation during wear and galvanic corrosion between exposed inner layers after wear. The effects of individual layer thickness (from 10 to 100 nm) and layer orientation (horizontally and vertically aligned) on the tribocorrosion behavior of Al/Cu NMMs was studied. Both factors were found to affect the subsurface stress and plastic strain distribution and localized surface corrosion kinetics, hence affecting the overall tribocorrosion rate. This model and the obtained understanding could shed light on future design and optimization strategies of NMMs against tribocorrosion. Finally, a combined experimental and computational investigation of the crystallographic effect using Al (100), (110), and (111) single crystals as model systems, to understand the effects of crystallographic orientation on the tribocorrosion kinetics by combining tribocorrosion experiments, materials characterization, and multiphysics modeling. EBSD was exploited to characterize the crystal orientation and dislocation density of the worn samples. The tribocorrosion model was built based on the results of EBSD characterization with the coupling effect of crystal orientation and corrosion. The model successfully predicted the overall tribocorrosion current of single-crystal samples, indicating the important role played by crystal orientation and dislocation density in the acceleration of corrosion.
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    Multiscale Microstructural Investigation of the Ductile Phase Toughening Effect in a Bi-phase Tungsten Heavy Alloy
    Haag IV, James Vincent (Virginia Tech, 2022-06-03)
    A specialty class of alloys known as tungsten heavy alloys (WHAs) possess extremely desirable qualities for adoption in nuclear fusion reactors. Their high temperature stability, improvement in fracture toughness over other brittle candidates, and promising performance in initial experimental trials have demonstrated their utility, and recent advancements have been made in understanding and applying these multiphase materials systems. To that end, Pacific Northwest National Laboratory in collaboration with Virginia Tech have sought to understand and tailor the structure and properties of these materials to optimize them for service in fusion reactor interiors; thereby improving the robustness, efficiency, and longevity of structural materials selected for service in an extremely hostile environment. In this analysis of material viability, a multiscale investigation of the connections between structure-property relationships in these multiphase composite microstructures has been undertaken, employing advanced characterization techniques to bridge the macro, micro, and nanoscales for the purpose of generating a framework for the understanding of the ductile phase toughening effect in these systems. This analysis has yielded evidence suggesting the effectiveness of WHA microstructures in the simultaneous expression of high strength and toughness owes to the intimately bonded nature of the boundary which exists between the dissimilar phases in these bi-phase microstructures. Analytical techniques have been employed to provide added dimensionality to traditional materials characterization techniques, providing the first three-dimensional microstructure reconstructions exhibiting the effects of thermomechanical processing on these dual-phase microstructures, and the first time-resolved approach to the observation of WHA deformation through in-situ uniaxial tension testing. The contributions of purposefully introduced microstructural anisotropy and its contribution to texturing and boundary conformations is discussed, and an emphasis has been placed on the study of the interface between the dissimilar phases and its role in the overall expression of ductile phase toughening. In short, this collective work utilizes multiscale and multidimensional characterization techniques in the in-depth analysis and discussion of WHA systems to connect their structure to the properties which make them excellent candidates for fusion reactor systems.
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    Multiscale Modeling of Effects of Solute Segregation and Oxidation on Grain Boundary Strength in Ni and Fe Based Alloys
    Xiao, Ziqi (Virginia Tech, 2023-01-13)
    Nickel and iron-based alloys are important structure and cladding materials for modern nuclear reactors due to their high mechanical properties and high corrosion resistance. To understand the radiative and corrosive environment influence on the mechanical strength, computer simulation works are conducted. In particular, this dissertation is focused on multiscale modeling of the effects of radiation-induced solute segregation and oxidation on grain boundary (GB) strength in nickel-based and iron-based alloys. Besides the atomistic scale density functional theory (DFT) based calculations of GB strength, continuum-scale cohesive zone model (CZM) is also used to simulate intergranular fracture at the microstructure scale. First, the effects of solute or impurity segregation at GBs on the GB strength are studied. Thermal annealing or radiation induced segregation of solute and impurity elements to GBs in metallic alloys changes GB chemistry and thus can alter the GB cohesive strength. To understand the underlying mechanisms, first principles based DFT calculations are conducted to study how the segregation of substitutional solute and impurity elements (Al, C, Cr, Cu, P, Si, Ti, Fe, which are present in Ni-based X-750 alloys) influences the cohesive strength of Σ3(111),Σ3(112),Σ5(210) and Σ5(310) GBs in Ni. It is found that C and P show strong embrittlement potencies while Cr and Ti can strengthen GBs in most cases. Other solute elements, including Si, have mixed but insignificant effects on GB strength. In terms of GB character effect, these solute and impurity elements modify the GB strength of the Σ5(210) GB most and that of the Σ3(111) least. Detailed analyses of solute-GB chemical interactions are conducted using electron localization function, charge density map, partial density of states, and Bader charge analysis. The results suggest that the bond type and charge transfer between solutes and Ni atoms at GBs may play important roles on affecting the GB strength. For non-metallic solute elements (C, P, Si), their interstitial forms are also studied but the effects are weaker than their substitutional counterparts. Nickel-base alloys are also susceptible to stress corrosion cracking (SCC), in which the fracture mainly propagates along oxidized grain boundaries (GBs). To understand how oxidation degrades GB strength, the next step is to use density functional theory (DFT) calculations to study three types of oxidized interfaces: partially oxidized GBs, fully oxidized GBs, and oxide/metal interface, using Ni as a model system. For partially oxidized GBs, both substitutional and interstitial oxygen atoms of different concentrations are inserted at three Ni GBs: Σ3(111) coherent twin, Σ3(112) incoherent twin, and Σ5(210). Simulation results show that the GB strength decreases almost linearly with the increasing oxygen coverage at all GBs. Typically, substitutional oxygen causes a stronger embrittlement effect than interstitial oxygen, except at the Σ3(111). In addition, the oxygen-induced mechanical distortion has a much smaller contribution to the embrittlement than its chemical effect, except for oxygen interstitials at the Σ3(111). For the fully oxidized GBs, three NiO GBs of the same types are studied. Although the strengths of Σ3(112) and Σ5(210) NiO GBs are much weaker than the Ni counterparts, the Σ3(111) NiO GB has a higher strength than that in Ni, indicating that Σ3(111) GB may be difficult to fracture during SCC. Finally, the strength of a Ni/NiO interface is found to be the weakest among all interfaces studied, suggesting the metal/oxide interface could be a favorable crack initiation site when the tensile stress is low. Furthermore, the effects of co-segregation of oxygen and solute/impurity elements on GB strength are studied by DFT, using the 5(210) GB in an face-centered-cubic (FCC) Fe as a model system. Four elements (Cr, Ni, P, Si) that are commonly present in stainless steels are selected. Regarding the effects of single elements on GB strength, Ni and Cr are found to the increase the GB strength, while both P and Si have embrittlement effects. When each of them is combined with oxygen at the GB, the synergetic effect can be different from the linear sum of individual contributions. The synergetic effect also depends on the spatial arrangement of solute elements and oxygen. If they are aligned on the same plane at the GB, the synergetic effect is similar to the linear sum, although P and Si show stronger embrittlement potencies when they combine with both interstitial and substitutional oxygen. When they are arranged on a trans-plane structure, only nickel combined with oxygen show larger embrittlement potencies than the linear sum in all cases. Crystal Orbital Hamilton Populations analysis of bonding and anti-bonding states is conducted to interpret how the interaction between solutes and oxygen impacts GB strength. Finally, the continuum-scale CZM method, which is based on the bilinear mixed mode traction separation law, is used to model SCC-induced intergranular fracture in polycrystalline Ni and Fe based alloys in the MOOSE framework. The previous DFT results are used to justify the input parameters for the oxidation-induced GB strength degradation. In this study, it is found that the crack path does not always propagate along the weak GBs. As expected, the fracture prefers to occur at the GB orientations perpendicular to the loading direction. In addition, triple junctions can arrest or deflect fracture propagation, which is consistent with experimental observations. Simulation results also indicate that percolated weak GBs will lead to a much lower fracture stress compared to the discontinuous ones.