<p dir="ltr">Irradiation-assisted stress corrosion cracking (IASCC) of austenitic stainless steels (SSs) remains one of the most critical material degradation issues in light water reactors (LWRs). This study presents new alloy design strategies and mechanisms to develop IASCC-resistant stainless steels. Additive manufacturing provides not only new mechanisms to suppress IASCC but also high-throughput means to support alloy exploration. New SS design concepts are demonstrated to significantly enhance IASCC resistance, and mechanistic insights are proposed.</p><p dir="ltr">In the first part of this study, we systematically explored the root cause of the superior IASCC resistance of additively manufactured 316L SS after the hot isostatic pressing (HIP) in high-temperature water, compared to 316L SS in other forms. It was found that the overall radiation hardening was not an accurate measure of IASCC susceptibility. A decreased strain localization along grain boundaries, caused by dislocation channel broadening, was identified as the main reason for the IASCC resistance. The phenomenon was further confirmed through <i>in situ</i> straining tests under the TEM. The second part developed a high-throughput approach utilizing directed energy deposition (DED) to accelerate alloy design and testing for improving IASCC resistance. We explored the effects of reactive elements (REs), such as Hf, Ti, and Y, on the IASCC of 316L SS. All of these REs suppressed the radiation hardening, radiation damage, and IASCC of 316L SS, although their contributions varied with concentrations. It is suggested that radiation-induced segregation is not necessary to cause IASCC, while hardness and strain localization exhibited a stronger correlation to the IASCC. Finally, based on the roles of these reactive elements, a new type of SS was developed, which exhibited superior resistance to stress corrosion cracking (SCC) and IASCC. The low level of radiation damage and high corrosion resistance were considered the primary factor.</p>

The objective of this dissertation is to demonstrate the use of in situ TEM mechanical testing to find mechanical properties of as received, self-ion, and proton irradiated Fe-9%Cr ODS. The desire to work at small scale in the characterization of irradiated materials to reduce costs and improve throughput, require the development of novel methods to assess mechanical properties in volume-limited irradiation damage layers. Yet at these micrometer or nanometer scales, the mechanical properties can begin to be impacted by size effects. In this work micropillar compression, cantilever bending, lamellae indentation, and clamped beam fracture testing is conducted on ion-irradiated Fe-9%Cr ODS to find yield stress, elastic modulus, flow stress, and fracture toughness. Micropillars in compression allow us to define a minimum sample dimension, which approaches the obstacle spacing of the material, at which size effects are observed. This relationship between sample dimension and obstacle spacing defined through micropillar compression is extended to a new testing geometry, cantilever bending, and material property, flow stress. Lessons learned during the cantilever bending informed the clamped beam design for conducting fracture testing on a ductile engineering alloy at micrometer scales. Finally, lamellae indentation was conducted to link qualitative observations of the microstructure under load with literature strength of obstacle values. By combining an understanding of the microstructure of irradiated Fe-9%Cr ODS and the in situ TEM technique, one can find the bulk-like mechanical properties of ion irradiated Fe-9%Cr ODS.

<p>Shape memory alloys (SMAs) belong to an important class of active materials. Beyond shape memory, these alloys exhibit super-elasticity and pseudo-plasticity, all originating from a reversible phase transformation from a high-temperature austenitic phase to a low temperature martensitic phase. Their unique thermo-mechanical properties make these SMAs desirable for a wide range of applications in automobiles, robotics, aerospace, construction, and medicine. Only a fraction of the known metallic alloys exhibits martensitic transformations, and a relatively small subset exhibits shape memory. Given this limited pool of SMAs, tunability of this martensitic transformation and, hence, thermo-mechanical properties is a way to move forward for effectively designing the next-generation SMAs for specific applications. The modification in composition has always been at the heart of designing new SMAs for future applications. However, a relatively recent discovery of incorporating a second non-transforming phase in base martensitic materials to tune martensitic transformation to achieve unprecedented thermo-mechanical properties has shown great promise.</p><p><br></p><p>The objective of this work is to utilize the second phase to provide design guidelines for next-generation SMAs and to understand the detailed physics behind the experimentally observed unprecedented thermo-mechanical properties in SMAs as a result of the incorporation of coherent second phases. We first investigate Mg-Sc shape memory alloys that are attractive for a wide range of applications due to their low density. Unfortunately, the use of these alloys is hindered by a low martensitic transformation temperature (173 K). We observe from first-principles calculations that epitaxial strains arising from appropriate substrate or coherent second phase selection increase the martensitic transformation and operational temperature to room temperature. Next, we develop a novel approach to induce martensitic transformation in composite systems of two non-transforming materials. While we demonstrate this approach for the technologically relevant ultra-lightweight Mg/MgLi superlattices, however, our approach is general and will open a wide material space for the discovery and design of next-generation SMAs.</p><p><br></p><p>Finally, to bridge the gap between computationally studied single-crystalline materials and experimentally studied polycrystalline systems, we characterize the role of nanoscale precipitates on temperature- and stress-induced martensitic phase transformation in nanocrystalline Ni63Al37 SMAs using multi-million-atoms molecular dynamics simulations. Simulations provide the understanding of underlying atomistic mechanisms of experimentally observed unprecedented thermo-mechanical properties and the guidelines to design low-fatigue ultra-fine grain shape memory alloys. As a result of the exploration of novel thermomechanical properties in SMAs via coherent second phases, we also published a software package</p><p>to discover coherent precipitates within a base multi-component system by coupling highthroughput equilibrium thermodynamics calculations with strain-based lattice matching.</p>

This thesis aims to reveal the correlation between stress corrosion cracking propagation behavior and Schmid and Taylor factor mismatch using EBSD analysis. <div><br></div><div>Chloride induced stress corrosion cracking (CISCC) is one of the most vulnerable weaknesses for the widely used austenitic stainless steel in many industries. The complex nature of CISCC involves mechanical, electrochemical, and microstructural perspectives. The objective of this thesis is to assess CISCC phenomenon in austenitic stainless steel from the mechanical and crystallographic perspective, specifically on the effect of local strain and stress and anisotropic plastic deformation. Austenitic stainless steel 304L test coupons are bent in four-point bending fixtures to obtain tensile stress for CISCC, followed by corrosion experiment in boiling magnesium chloride solution. Stress state of the sample is evaluated by finite element analysis (FEA) and X-ray Diffraction Crystallography (XRD) prior corrosion test. Cross section of the cracked region are analyzed with Electron Backscatter Diffraction (EBSD) to analyze the relationship between CISCC behaviors and crystallographic features in the sample. Schmid factor and Taylor factor are used to quantitatively evaluate CISCC initiation and propagation behavior. It is learned that in polycrystalline FCC stainless steel, mismatch of Schmid factor and Taylor factor values in adjacent grains along crack path governs CISCC propagation susceptibility and path selection. Crack propagation factor competition model is proposed based on observations from EBSD maps, incorporating Schmid factor and Taylor factor mismatch, electrochemical condition of crack tip, and anisotropic properties. <br></div>

Copper is an essential metal in today’s economy, due to its superior electrical and thermal conductivities, alloying properties, and chemical uses. Most copper is produced viamining and refining, and most copper is found in the earth’s crust as chalcopyrite, CuFeS2. Typically, chalcopyrite is concentrated and fed to a high temperature pyrometallurgical process which produces >99.99% purity copper cathodes. Recently, Freeport-McMoRan Inc. has implemented a hydrometallurgical autoclave-leaching process that takes chalcopyrite concentrate and produces copper cathodes. It is imperative that these pyrometallurgical and hydrometallurgical processes be modeled and compared so that the extraction industry can best decide which technology to apply in the future. This work presents transient, reduced-order models for the comparison of the two processes using exergy balances. Exergy is typically thought of as the maximum work extractable from a system as it spontaneously reacts to the state of the surrounding environment; for extractive processes, it is also helpful to think of exergy as the minimum work required to effect a concentration, e.g. of copper. Exergy balances are thus similar to first law balances, but they comment on the location and magnitude of usefulenergy flows, instead of energy flows in general. For the baseline case, this work found that the pyrometallurgical process up to 99.5% copper anode stored 54% of the fed exergy in product, lost 20% of the fed exergy, and destroyed the remaining 26%. In contrast, the hydrometallurgical process up to 30 grams-per-liter copper pregnant-leach-solution stored 5% of the fed exergy in product, lost 9% of the fed exergy, and destroyed the remaining 86%. The effects of process variations are also looked at. It is recommended that this work be incorporated in whole-plant exergy balances to more precisely examine the tradeoffs between the pyrometallurgical and hydrometallurgical routes of copper extraction from chalcopyrite concentrates.

<p>A first-principles theory of plasticity in metals currently does not exist. While many plasticity models make reference to rules based on heuristic arguments regarding dislocations (the fundamental mediators of plastic deformation in crystals), the scientific community still does not have a theory of dislocation dynamics which can recover even basic features of plasticity theory. Discrete dislocation dynamics, though a valuable tool for understanding fundamentals topics in dislocation plasticity, becomes unusable beyond ~1.5\% strain due to the line length multiplication inherent in deformation. As a result, it is necessary to develop continuum theories of dislocation dynamics which treat dislocation densities rather than individual dislocations. This thesis examines the foundations of one such continuum theory: line bundle continuum dislocation dynamics, which assumes that dislocations are roughly parallel at every point. First, this assumption is given definite meaning and it is shown from discrete dislocation dynamics data that to be appropriate when modelling dislocation densities on fine length scales (resolving densities on lengths less than 100 nm). Second, it is found that an additional driving force, the correlation stress, emerges from coarse-graining the line bundle dynamics. This correction to the dislocation interactions is dependent on tensorial dislocation correlation functions describing the short-range errors in the products of dislocation densities lying on two slip systems. The full set of these dislocation correlation functions are evaluated from discrete density data with the aid of a novel left-and-right handed classification of slip system interactions in FCC crystals. Lastly, a study of the correlation stress in a representative dislocation system suggests that these stresses are roughly one tenth the magnitude of the mean-field dislocation interaction stress. Taken together, this thesis bridges discrete and continuum models of dislocation dynamics and provides a foundation for future work on a first-principles theory of metal plasticity. </p>

<p>The dissertation offers a Multiphysics perspective in analyzing emerging metallurgical techniques. Heat transfer, structural deformation, and fluid flow associate with one another in phase-changing materials processing methods. To comprehensively analyze these aspects for an optimized final product, the authors have proposed a numerical mathematical model describing the thermal and geometric progression of the binary alloy casting process. The model is further executed in COMSOL Multiphysics, adapted in two metal manufacturing applications, resistance spot welding (RSW) and binder jet printing (BJP). </p><p>Resistance spot welding is a well-adapted metal sheeting joining technique with comparably limited modeling and simulating research. The heat transfer module and geometric deformation module are applied to the simulation of RSW to discuss the thermal gradient development of the welding zone. The model was further calculated and verified through a case study with Python. </p><p>BJP is a rapidly developing additive manufacturing method. The novel 3D printing technique brings challenges in post-processing geometric control and material selection limitations. Multiphysics simulation serves as an excellent tool in process parameters analysis and quality control. This dissertation focuses on the sintering process of BJP of binary alloy powders. Melting and solidification mathematical models were implemented in COMSOL, where the sintering shrinkage rate could be calculated. The shrinkage rate was further verified through experimental analysis of binder jet printed samples. </p><p>Microstructural analysis on sintered binder jet printed parts was performed to assess the validity of BJP to substitute the die casting method for manufacturing of valvebody. Sintering shrinkage and metallurgical analysis have been performed on the green and sintered BJP samples. After sintering, the final part achieved 98% density, and the integrity of the designed channels was preserved. The shrinkage analysis has indicated the effect of printing orientation and sintering orientation on the geometry and metallurgy of the final products. Microstructure analysis on the cross-sections of the sintered products also indicates the various defects induced from biner jet 3D printing. </p><p>The research aims to provide a systematic rheology analysis of the phase transformation process of binary alloys. The dissertation has connected the physical, mathematical modeling with 15 </p><p><br></p><p>simulative modeling through the rheological evaluation of phase-changing manufacturing techniques. The connections were conclusively verified through empirical studies, including case assessment and experimentation. The research aims to offer universally applicable models that can be applied to phase-changing metal processing techniques. </p>

<p> Laser powder bed fusion (LPBF) is a rapidly emerging manufacturing technology capable of producing complex part geometries through the repeated, precise laser melting of metallic powder layers. At present, the process is primarily employed in high-value-added applications which exist in the aerospace, biomedical, and dental industries. As industrial implementation of LPBF has matured, research has focused on established materials for which there are already large bodies of literature and regulatory approval, such as Inconel 718, Inconel 625, Ti-6Al-4V, and 316 stainless steel. However, the rapid solidification process inherent to LPBF leads to vastly different microstructures with improved strength compared to these traditional materials in cast or wrought forms. In general, the high solidification velocity and thermal gradients result in cellular and dendritic solidification structures with finer grain and precipitate sizes than conventionally processed alloys. These microstructure changes warrant the exploration of new alloy systems and reevaluation of historically cast compositions with optimized microstructures, especially considering the tunability of a digitally controlled fabrication process. This work examines laser powder bed fusion of Mar-M 509, a carbide-strengthened cobalt alloy that is typically investment cast directly into complex-shaped components such as nozzle guide vanes (NGVs). NGVs are stationary components in gas turbine engines for propulsion and energy production which require strength under moderate mechanical loading at high temperatures. Investment cast microstructures have porosity defects in slower-cooled regions due to lack of liquid feed to interdendritic regions. As-printed, the cellular and dendritic Mar-M 509 LPBF microstructures lead to the formation of continuous, fiber-like, eutectic carbide structures in the intercellular and interdendritic regions, which limit macroscopic ductility. Thermo-Calc is used for calculation of phase diagrams (CALPHAD) to estimate the equilibrium transformation temperatures of MC, M23C6, and M7C3-type carbides, which informs design of isothermal heat treatments to engineer microstructures with enhanced ductility over the as-printed or cast versions of Mar-M 509 while maintaining tensile strength. Scanning and transmission electron microscopy reveals the composition and distribution of carbide phases as a function of heat treatment temperature. Lastly, heat treatment recommendations for nozzle guide vanes are made.  </p>

<p>    </p> <p>In this thesis, a thermodynamically consistent phase field formulation was developed to identify the physical origin of interfacial transitions that drive macroscopic phenomena, start- ing at the single-particle length scale and building up to the polycrystalline length scale. At the single-particle length scale, the framework identified two interfacial phases that are stable at the surface of Sn nanoparticles: 1) a disordered interfacial phase, i.e., the experimentally observed premelted surface layer; and 2) an ordered surficial phase displaying a remnant de- gree of order in fully melted particles. Regimes of melting behavior as a function of particle size and temperature are discussed. To bridge the gap between single-particle and densified polycrystals, an analytical model was developed to capture the physical driving forces for densification during electric field-assisted sintering. Here, the model acknowledges the struc- tural contributions of particle-particle interfaces to the strength of mechanical, electrical, and surficial driving forces for densification, and shows good agreement with experimental flash sintering data. Finally, the theory was applied to polycrystalline LiCoO₂ (LCO) and shows that the experimentally observed metal-insulator transition is driven by grain bound- ary lithium segregation, the interfacial misorientation, and the size of the abutting grains. A critical misorientation as a function of the macroscopic lithium content exists above which the grain boundaries undergo a metal-insulating transition, suggesting that the fabrication of textured LCO microstructures will delay the metal-insulator transition. </p>

<p>  </p> <p>The next generation of nuclear reactor designs promise to provide clean, safe, and efficient energy to address our current climate crisis. But with these new technologies, nuclear fuel materials must be carefully designed and understood to meet these demands. Candidate oxide and metallic nuclear fuel materials being considered for use in these new reactor technologies, despite their potential, still have significant remaining materials challenges in understanding their long-term performance and integrity under extreme reactor conditions. As such these candidate fuels require extensive materials characterization to understand their long-term performance under reactor conditions. The objective of this study is to evaluate the microstructural evolution of candidate fuels U-50wt%Zr and ThO2 under the following contexts: 1) Investigation of phase stability in candidate metallic fuel U-50wt%Zr under thermal and irradiation treatment; 2) Investigate localized thermal properties of candidate oxide fuel ThO2 under irradiation through a novel correlative microscopy approach. </p> <p>The influence of thermal and irradiation treatment on phase stability in δ-U50wt%Zr was investigated through conventional APT-TEM methodology. U-Zr is a candidate metallic fuel for advanced fast reactor applications. However, there is still work remaining to better understand how these materials evolve under extreme reactor conditions, especially for the δU-50wt%Zr composition. Metallic fuels are susceptible to significant chemical redistribution under extreme conditions resulting in potential degradation of fuel properties and performance. In these experiments, U-50wt%Zr was subjected to thermal annealing and proton irradiation respectively. These treatments produced very different modulated structures in U-50wt%Zr, and the implications of such on phase stability in U-50wt%Zr will be discussed.</p> <p>Additionally, long-term nuclear reactor operation hinges upon efficient thermal transport in nuclear fuels. There is a critical need to understand localized thermal transport in these materials to enable intelligent design of high-performance fuels. A novel correlative atom probe tomography (APT)-transmission electron microscopy (TEM) approach was developed to investigate the influence of irradiation defects on localized thermal diffusivity in ThO2 upon proton irradiation, and implications of such results will be discussed. </p>