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Title: HIGH-THROUGHPUT FIRST-PRINCIPLES STUDY ON HIGH-ENTROPY ALLOYS
Creator: Zhang, Jie
Date: 2021
Description: This research thesis discusses the current ecosystem surrounding a new type of alloy: high entropy alloys (HEA) or multi-element crystalline...
Show moreThis research thesis discusses the current ecosystem surrounding a new type of alloy: high entropy alloys (HEA) or multi-element crystalline materials and lays out the high-throughput first-principles calculation as a valuable approach to study these materials. The density function theory (DFT) from computational material science prospect was implemented to investigate the HEAs. Using EMTO-CPA algorithm, high-throughput DFT calculations were conducted. A total of 1958 HEA systems including equimolar and non-equimolar systems were studied with respect to the varies properties, including lattice parameters, bulk moduli, elastic constants, and elastic anisotropy. The first-principles HEA dataset was employed as the training set for the DeepSets a machine learning model. DeepSets, in combination with EMTO-CPA high-throughput calculation, successfully predicted the mechanical properties of specific HEA composition. This paves a promising new path of designing, investigating, and validating the HEA system compared to the time-consuming conventional HEA design method. The doping effect of Vanadium (V) and Titanium (Ti) to NbMoTaW HEA, as well as V or Ti as the fifth element with different molar fraction to the NbMoTaW HEA system, were studied. The phase stability of the new systems was discussed and concluded that all proposed systems tend to form single-phase solid solution. Though the addiction of V only slightly enhances the system’s ductility, the addition of Ti not only enhances the quinary system NbMoTaWTiX (X =0.25, 0.5,0.75, 1.0) ductility, but enables the system to be closer to fully isotropic.
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Title: Effects of Microstructure Engineering on Laser Powder Bed Fusion Processed Superalloy IN718 through Inoculant Addition
Creator: Ho, I-Ting
Date: 2023
Description: Additive manufacturing (AM) techniques can now be utilized as innovative tools that provide unlimited design flexibility for the fabrication...
Show moreAdditive manufacturing (AM) techniques can now be utilized as innovative tools that provide unlimited design flexibility for the fabrication of geometrically complex metallic structures. For production of Ni-base superalloy components used in advanced gas turbine engines, laser powder bed fusion (L-PBF), which is one of the AM techniques, is frequently used as it allows good metallurgical bonding of powder feedstock and simultaneously enables development of ultra-efficient power systems for aerospace propulsion, space exploration and power generation. One of the major challenges associated with additively manufactured Ni-base superalloy components is that the extreme temperature gradients encountered during processing negatively impact the underlying microstructure and mechanical properties of the material. Although the macroscopic shape and chemistry of the additively fabricated part may be identical to the conventionally manufactured part, the resulting properties are usually compromised. In an effort to make Ni-base superalloys more amenable for processing via additive manufacturing, varying levels of benign inoculants that promote may heterogeneously grain nucleation were blended into Inconel 718 (IN718) powder feedstock and used for processing via L-PBF to characterize the microstructural evolution. In the first study, 0.2 wt. % of micron-sized CoAl2O4 flakes was found to effectively change the grain morphology during the L-PBF process leading to significant reduction in crystallographic texture and thus resulting elastic anisotropy. Dispersion of nano-oxides resulting from the reduction of CoAl2O4 particles also contributed to improved tensile strength and steady creep strain rate. It should be noted, however, that, the multiple iterations of remelting as the result of deposition of new layers dissolved the Co-rich particles reduced from CoAl2O4 inoculants. Instead of having nucleation events contributed by elemental Co, the oxide agglomerates as a result of Marangoni convection seemed to be the major contribution to facilitating grain refinement by inhibiting the heat transfer in the surroundings. On the other hand, addition CoAl2O4 particles appeared to generally reduce the melt pool width while increase the melt pool depth by inhibiting the degree of heat transfer and Marangoni flow. The changes in melt pool dimension aided in improving the relative density and surface roughness of the bulk samples by generating better metallurgical bonding to the subsequent layers. As the trade-off, however, the changes in melt pool physics also enhanced the tendency for epitaxial growth and hence retarded the columnar-to-equiaxed transition unless oxide agglomerates are present. In addition to CoAl2O4, candidates including Co, TaCr2, TiB2, and CeO2 particles were also considered to be blended with the powder feedstock of IN718. After the L-PBF process, different degree of microstructural evolution was characterized with the addition of Co, TaCr2, TiB2, or CeO2 particles. It was found that the physical presence of inoculants may change the melt pool geometries that accounted for a comparatively more columnar-grained structure with <101> texture in samples containing Co and TaCr2 particles while a relatively equiaxed-grained structure with <001> texture in samples containing TiB2. The comparison between samples containing TiB2 and CeO2 further indicates that the phase transformation induced agglomeration will also reduce the effectiveness of inoculants due to decreasing nuclei density. Findings from this investigation demonstrate the resulting grain structure upon L-PBF can be profoundly impacted by both chemistry and physical properties of the inoculants. These effects may potentially be harnessed to effectively engineer the microstructure and optimize the properties of L-PBF processed Ni-base superalloys.
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Title: Melt Growth of Indium-Iodide on Earth and in Microgravity
Creator: Riabov, Vladimir
Date: 2023
Description: Indium Iodide is a heavy metal halide and a wide band-gap semiconductor which has a potential for application in room temperature γ- and X-ray...
Show moreIndium Iodide is a heavy metal halide and a wide band-gap semiconductor which has a potential for application in room temperature γ- and X-ray detectors. Its physical properties are similar to those of other materials used as room temperature radiation detectors. Over the years the technology of purification and crystal growth of InI was developed. Significant advances were made to improve purity, crystal structure and resulting electronic properties of the material. Nevertheless, the desired detector performance has not been achieved yet. Stress-induced crystal lattice defects resulting from solidification in contact with crucible are suspected to be responsible for the limited performance. Microgravity environment was previously used to study its effects on the process of crystal growth from the melt applied to semiconductors. It was observed that unlike on Earth materials can solidify without contact with the wall, when the sample is confined by the crucible. It was also shown that such detached solidification can drastically reduce stress-induced defects of the crystal lattice and improve electronic properties of the material. In this study crystal growth of InI was studied in microgravity, attempting to achieve detached solidification, and observe it in a transparent zone of a furnace. Partially detached solidification (a large free surface) has occurred in one of the samples. The resulting crystals were characterized by measuring their electronic properties and estimating the radiation detector performance of the devices manufactured using the crystals.
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Title: Functionalized 2D Materials as Enablers of High Energy and High Power Energy Storage Devices
Creator: Radhakrishnan, Sivaviswa
Date: 2023
Description: The present Thesis concerns with the synthesis of novel functionalized 2D materials for applications as cathodes in lithium-ion batteries. It...
Show moreThe present Thesis concerns with the synthesis of novel functionalized 2D materials for applications as cathodes in lithium-ion batteries. It further concerns with the role of porosity in these novel cathode materials to achieve simultaneously high energy and power density. Examples of the novel cathode materials synthesized here include several functionalized hexagonal boron nitride (hBN) and graphene (G) species. hBN was functionalized with Li₂C₂O₄, LiBF₄, -OBF₂ groups, NOBF₄, etc. The color of the functionalized hBN species ranges from white through brown to black indicating drastic changes in the band structure of hBN due to functionalization. Functionalized G species include Li₂C₂O₄ and -OBF₃ functionalized ones. Preliminary electrochemical tests were carried out for an initial assessment of the properties of these materials. Additionally, the role of the DOL solvent was also investigated in high power CFx batteries
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Title: New Insights to Thermoelectrics from Fundamental Transport Properties to Potential Materials and Device Design
Creator: Pan, Zhenyu
Date: 2022
Description: Thermoelectric (TE) materials have been widely studied as their ability to make direct energy conversion between heat and electricity. However...
Show moreThermoelectric (TE) materials have been widely studied as their ability to make direct energy conversion between heat and electricity. However, the conversion efficiency is still low compared with conventional devices no matter in power generation or electrical cooling. Therefore, most efforts have been made to improve the zT of TE materials, which is the commonly accepted metric for determining the performance of TE materials. But the progress is slow as the key parameters governing the zT is interrelated to each other which makes improving one often at the cost of the others leading to a narrow use of TE applications. Thus this thesis does not confine itself only in searching for high zT TE materials but also exploring useful things which are buried or ignored in previous thermoelectric researches from fundamental transport properties to TE device design. Firstly, we reevaluated the photo-Seebeck effect, which has been known for decades, and demonstrated that it is a powerful tool for semiconductor study as it allows the determination of mobilities, photo-carrier densities, even weighed mobilities (hence effective masses) of both electrons and holes and impact of defects all from a single sample. We then investigated a newly discovered low dimensional material, 2D tellurene, which has the potential to decouple the interrelated parameters to achieve a high zT. Lastly, we reconsidered the question that whether zT is the only merit index determining TE device performance. We hope this thesis can shed some light on thermoelectrics both from fundamental transport properties to device design.
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Title: A Functionalized 2D Boron Nitride Electrode for Rechargeable Batteries
Creator: Tatagari, Vignyatha Reddy
Date: 2021
Description: Motivated by the great performance of the graphene oxide battery and its poor safety, in the present work, an attempt is made to fabricate an...
Show moreMotivated by the great performance of the graphene oxide battery and its poor safety, in the present work, an attempt is made to fabricate an alternative battery from functionalized 2-dimensional (2D) boron nitride. The expectation is that functionalized boron nitride can exhibit the same great electrochemical performance as graphene oxide while it would be much more thermally stable. Toward this goal, synthetic opportunities were explored to realize -OBF3 functionalized hexagonal boron nitride. Both top-down and bottom-up synthetic approaches were considered and implemented. In the top-down methods, commercially available bulk hexagonal boron nitride (h-BN) is reacted with functionalization agents such as LiOBF3 and LiOH.BF3. Synthesis of these functionalization agents and their reactions with h-BN were carried out in several different ways. Bottom-up synthetic approach using Boric Acid and Urea was utilized to synthesize turbostratic boron nitride (t-BN), which is an intermedier in the commercial synthesis of hexagonal boron nitride. Turbostratic boron nitride contains exfoliated and -OH functionalized monolayers of boron nitride. An attempt is made to esterify the -OH groups of turbostratic boron nitride to obtain the desired -OBF3 functionalized monolayers of h-BN. Initial electrochemical tests on turbostratic boron nitride and its esterified form are carried out along with ionic conductivity measurements. Only a very limited electrochemical activity was observed due to a low degree of functionalization in these materials, indicating the need for improved synthetic procedures to achieve the desired target materials.
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Title: MICROSTRUCTURE AND MECHANICAL PROPERTIES OF DISCONTINUOUSLY PRECIPITATED NI-CO-AL ALLOYS
Creator: Ho, Kathy
Date: 2022
Description: The study of high temperature structural materials has been one of great interest and immense focus in recent years of research and...
Show moreThe study of high temperature structural materials has been one of great interest and immense focus in recent years of research and development. With the capability of catering to specific needs and applications while being commercially cost-effective, these materials can be synthesized using various types of methods and materials for a large range of applications. In order to implement the advantageous properties of these materials for practical use in service, empirical data relating to the material and mechanical properties of these high temperature structural alloys must first be obtained. This can be achieved through numerous processing methods. One particular method involves precipitation strengthening. Two types of transformation modes include discontinuous and continuous precipitation. Discontinuous precipitation (DP) nucleates at high angle, incoherent grain boundary, grows through grain boundary diffusion, and produces a lamellar structure consisting of alternating layers of γ and γˡ (Ephler, 2004). Continuous precipitation (CP) nucleates within the grain, is controlled through volume diffusion producing, and results in a homogeneous distribution of equilibrium composition precipitates with a spherical/cuboidal morphology. Since both modes of transformation possess a chemical driving force, resulting from the supersaturation of solute, the coexistence of both DP and CP transformation in a material is possible. However, as demonstrated from past studies, the presence of a partial DP transformation in structural alloys is undesirable as detrimental effects on mechanical properties are observed. As a result, numerous studies have focused on suppressing DP all together. In 1972 Erhard Hornbogen hypothesized that a fully DP transformed material would yield superior mechanical properties, similar to pearlite formation in steel, since the lamellar structure would increase barriers to dislocation movement (Hornbogen, 1972). As a result, recent studies have redirected their focus in an effort to encourage DP transformation to completion for improved mechanical properties. Therefore, the purpose of this work was to 1) determine the aging conditions under which a complete, 100% DP transformation would be achieved in select alloys, 2) determine the conditions where optimal precipitate size via CP transformation is obtained to effectively use precipitation strengthening without the concern of over-aging, 3) experimentally compare the material and mechanical properties between 100% DP aged samples and CP aged samples consisting of the optimal precipitate size, 4) compare the mechanical properties between alloys that have undergone a complete DP transformation to commercial alloys currently used in service, and 5) provide empirical data to verify Hornbogen’s claim. The results from this work indicated that 1) a lower aging temperature promote DP transformation while a higher temperature promotes CP transformation, 2) a smaller grain size prior to aging was more favorable for DP transformation while larger grains were favorable for CP transformation, 3) a complete DP transformation was observed for Alloy 9 and Alloy 10 after aging at 500°C for 4 hours and 550°C for 4 hours, 4) Alloy 1, Alloy 3, and Alloy 5 were potentially undergoing a different type of transformation at lower DP aging temperatures, where β phase was present, 5) optimal precipitate size for effective use of precipitation strengthening (CP transformation) was achieved under CP aging conditions 700°C-1HR for Alloy 10 and 750°C-1HR for Alloy 9 and the forged stock bar, 6) a small fraction of DP consistently formed at the grain boundaries of the CP aged samples for all alloy samples, indicating that the nucleation of DP was quick, but growth was limited, 7) mechanical properties of the DP aged samples for Alloy 9, Alloy 10 and the forged bar were superior to their corresponding CP aged samples in terms of the hardness, UTS, and yield stress, but were less ductile than the CP aged samples, and 8) the mechanical properties of DP aged samples for Alloy 9, Alloy 10, and the forged bar were comparable, and at times superior, to the commercially available alloys. Due to limited prior research conducted on the mechanical properties of DP alloys, this investigation serves as a pioneering effort experimentally determine if the mechanical properties of completely DP transformed material are superior to that of CP transformed material, aged to optimal precipitate size, while collecting empirical data to verify Hornbogen’s claim.
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Title: High Energy High Power Primary Lithium Batteries with Graphite Fluoride and Functionalized Boron Nitride Cathodes
Creator: Huo, Haobin
Date: 2022
Description: The present Thesis concerns with the creation of high energy and high power batteries through the utilization of functionalized 2D materials...
Show moreThe present Thesis concerns with the creation of high energy and high power batteries through the utilization of functionalized 2D materials such as graphite fluoride (CFx) and functionalized boron nitride (FBN). The recent literature of Li-CFx batteries brings forward several methods to fabricate high energy and high power batteries. These methods include nano-architecture and porosity design, boron doping, electrolyte additives etc. The resulting batteries are capable to achieve 800-1000 Wh/kg energy density at a power density of 60-70 kW/kg. Our method is capable to achieve the same performance in a much simpler way by the application of a binder that also functions as an effective inhibitor of the growth of LiF crystals. Since LiF is the discharge product of Li-CFx batteries, it typically clogs the pores of the cathode and avoids fast discharge. Methods that increase the power density of Li-CFx batteries typically focus on the amorphization/dissolution of LiF to allow for a fast Li ion diffusion. Our solution using the effective binder appears to be well suited for a scalable production of high energy and high power Li-CFx batteries through a very small modification of existing production lines. Such high energy and high power batteries are needed for the electrification of aircraft such as unmanned aerial vehicles (UAVs), vertical take-off and landing planes (VTOLs), passenger airplanes and pulsed power sources. While Li-CFx batteries are not rechargeable this is not a problem for the above mentioned applications as current rechargeable batteries cannot provide the required energy and power densities.Li-FBN batteries may provide a rechargeable alternative to Li-CFx when fully developed. In the present thesis, we have demonstrated Li-FBN batteries with similar discharge plateaus and approximately half the capacity of Li-CFx batteries. Our Li-FBN batteries are also rechargeable to a much greater extent than Li-CFx.
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Title: EXAMINING PERFORMANCE DEGRADATION OF LI-ION BATTERIES WITH SILICON-BASED ANODE AND POSSIBLE SOLUTIONS TO IMPROVE THE SILICON ANODE BEHAVIOR
Creator: Luo, Mei
Date: 2022
Description: Si has been investigated as a promising alternative to conventional graphite because of its high specific capacity and wide operating voltage;...
Show moreSi has been investigated as a promising alternative to conventional graphite because of its high specific capacity and wide operating voltage; however, technical challenges related to volume change in the silicon anode have hampered their practical application. In this work, the effects of silicon volume change on electrochemical performance has been studied in NMC532/Si full cells. First, different area specific capacity ratios of the negative to positive electrode (N:P ratio) were investigated using three-electrode cells. With individual electrode potentials monitored by a reference electrode, different depths of lithiation/delithiation at the anode and cathode were found to play an important role on cell performance; the cell with higher N:P ratio displays superior electrochemical performance due to its smaller silicon volume change. Further, calendar-life aging and cycle-life aging of NMC532/Si cells were compared with their electrode potentials monitored using a reference electrode. The observation of larger capacity decay and impedance growth of cycle-life aging cells illustrates the important effect of silicon volume change; significant capacity decay of calendar-life aged cell was observed as well, revealing an essential role of chemical effect of ongoing side reactions at Si anode. Specially-designed silicon with different protocols and electrolyte additives were investigated to address the intrinsic challenges of Si anodes for lithium-ion batteries.
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Title: Stimulation-Responsive Materials for the Treatment of Disordered Tissues
Creator: Clutter II, Elwin Dean
Date: 2022
Description: Microenvironments offer physical and chemical cues to cells that affect their behavior. These cues can be bioactive chemicals such as drugs...
Show moreMicroenvironments offer physical and chemical cues to cells that affect their behavior. These cues can be bioactive chemicals such as drugs and cytokines, matrix cues like stiffness and composition, and electrical signals as seen in membrane potentials and epithelial wound healing. Controlling these cues can drive cell behavior toward apoptosis, proliferation, or changes in protein expression. In this thesis research, three components were used to model changes in cell behavior: the near infrared dye indocyanine green (ICG), silk fibroin (SF) from Bombyx mori silkworm cocoons, and carbon nanotubes (CNT). The mechanism of ICG photobleaching was studied for the efficacy to kill neuroblastoma cancer cells. ICG was twice as effective at killing neuroblastoma than fibroblast cells. Albumin stabilized monomeric ICG to enhance photobleaching by improving light interaction, and photodegradation of ICG into α,β-unsaturated aldehydes led to significant reduction of proliferation in neuroblastoma cells by targeting cell signaling components such as protein transcription factors. SF-ICG composite materials were developed into films and electrospun fibers. These composite materials were examined as light-activated wound coverings to control bleeding in hemorrhage, using ICG’s photothermal effect. ICG added an absorbance peak to SF at 805 nm. Irradiation decreased this peak, produced a new absorbance peak at 352 nm, and an increased fluorescence peak around 490 nm, showing photochemical changes that may be useful in sensor design. Increased heat production from irradiation of SF-ICG occurred in the films with 0.2% w/w ICG in SF during 1 min irradiation, whereas SF-ICG fibers required improvement of processing by ethanol vapor treatment (EVT) to reduce loss of ICG during preparation. EVT improved ICG retention in SF fibers during sterilization with 70% ethanol solution thus improving heat generation in the SF-ICG fibers. Heat evolved from SF-ICG 0.2% film solidified bovine blood within 42 s, with visible changes after the first 6 s. SF electrospun fibers were investigated to optimize silk preparation to reduce diameters and increase alignment to mimic local native cell environments with and without CNT to add conductivity for enhancement of electrical stimulation. CNT reduced SF fiber diameters below 1% and effected alignment differently as the concentration increased. Longer degumming times decreased SF fiber diameters and alignment of the same concentration. The optimized conditions were 1 h degumming time with 1.5 ml/h flow rate at a concentration of 100 mg/ml spinning solution with 0.25% CNT to form fibers with 1.36 (± 0.09) µm diameter and 0.31 (± 0.01) a.u. alignment. Additionally, SF fibers were used as a long-term cell growth scaffold to compare with decellularized native tissue. Decellularized tissue decreased fibroblast mRNA expression of collagen type 1, lysyl oxidase-like 1 and matrix metalloproteinase 9, while all other genes expression was the same as cells on plastic. The SF fiber scaffold reduced fibroblast expression of collagen type 3 compared to growth on plastic, and both collagen types 1 and 3 increased over growth time on SF. Immunofluorescence staining showed both collagens newly deposited on the SF scaffold and improved over time. In conclusion, proteins stabilized ICG monomers to improve light interaction, efficacy of photobleaching, and heat evolution to induce apoptosis in neuroblastoma and agglutination of blood in SF composites. Irradiation of ICG enhanced changes in optical properties and may have sensor applications. The decrease of genes may be due to each scaffold having lower stiffness compared to plastic. ICG and SF are both materials with applications as biological scaffolds in pelvic organ prolapse and treatment of neuroblastoma and hemorrhage.
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Title: Effect of heat treatment on microstructure and electrochemical behavior of laser powder bed fusion hydride- dehydride ti-6al-4v alloy
Creator: Delpazir, Melody Honardan
Date: 2022
Description: In powder bed additive manufacturing, feedstock and processing have an impact onfinal microstructure and properties of 3D-printed parts. While...
Show moreIn powder bed additive manufacturing, feedstock and processing have an impact onfinal microstructure and properties of 3D-printed parts. While numerous studies have evaluated 3D-printing of spherical powder, very limited research has been carried out on the processing of the non-spherical feedstock. This study is targeted specifically to the use of non-spherical Ti-6Al-4V powders in the laser powder bed fusion (L-PBF) process. Two different post-heat-treatments including hot isostatic pressing and solution treatment are applied. The microstructure evaluation, potentiodynamic polarization, and electrochemical impedance spectroscopy methods are used to characterize L-PBF processed and post- treated specimens. Though as-built part exhibits anisotropic microstructure containing acicular α′ martensite with trace amount of β phase, the heat-treated parts are composed of α+β in which length and thickness of the α-lath depends on the treatment. The below β transus heat treatment leads to the formation of a homogenized grain structures composed of α+β. Electrochemical results show that the below β transus heat-treatment had a slight positive effect on the improvement of corrosion resistivity (corrosion rate of 4.2×10-6 mmy- 1 , which is classified as an excellent ) compared to other conditions, which would be associated to the natural excellent corrosion resistance of Ti-6Al-4V alloy. This slight improvement can be ascribed by the slightly faster formation of a passive layer and its enhanced efficiency because of the presence of the fine-structured β phase in post heat- treated L-PBF processed Ti-6Al-4V alloy.
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Title: Towards Understanding the Microstructure and Mechanical Properties of Additively Manufactured Ni-base Superalloys
Creator: Tiparti, Dhruv Reddy
Date: 2022
Description: Nickel-base superalloy components such as turbine discs typically undergo numerous manufacturing steps that contribute to increasing the cost...
Show moreNickel-base superalloy components such as turbine discs typically undergo numerous manufacturing steps that contribute to increasing the cost and the waste of excess materials. With advent of fusion based additive of manufacturing (AM) techniques, such components with complex geometry can be fabricated with great efficiency. However due to characteristically high energy densities, fast cooling rate, and layer-by-layer building process associated with AM; Ni-base superalloys with higher temperature performance are difficult to be fabricated by AM due to susceptibility to composition related defect formation, which is further exacerbated by anisotropic grain structures induced by the large thermal gradients present. Crack-free material can be fabricated but, in most cases, issues such as an anisotropic microstructure will prevail, and the balance of mechanical properties achieved may not be suitable for the desired applications. Several strategies exist to mitigate the challenges posed by additive manufacturing via post-processing such as hot-isostatic processing, annealing heat treatments, application of grain refining inoculants, etc. All these strategies utilized to mitigate issues with AM of Ni-base superalloys still require further study to understand their effects on the microstructure and mechanical properties. This work aims to evaluate the use of inoculant particles, and novel heat treatments on the microstructure and mechanical properties of different superalloys. First, the effect of varying amounts of CoAl2O4 inoculant ranging from 0 to 2 wt.% on the microstructure evolution of Inconel 718(IN718) fabricated by selective laser melting (SLM) was evaluated. The findings from this study indicated that additions of CoAl2O4 only resulted in a minor degree of grain refinement with slight increase in anisotropy; in addition, a CoAl2O4 ¬content above 0.2 wt.% resulted in the formation of agglomerate inclusions; and that to effectively utilize CoAl2O4 as a grain refining inoculant, process parameters must be further optimized while considering the formation of agglomerates, and other defects. Second, the application of CoAl2¬O4 was extended towards the Direct Energy Deposition (DED) of IN718. Here findings indicated that due to the modification of the thermophysical properties of the melt pool by oxide addition, an earlier onset of large columnar extending across multiple layers occurred while counteracting conditions required for equiaxed grain formation; and these CoAl2O4 were also found to exhibit a potent Zenner pinning effect that maintained the as-built grain structure despite application of extreme high treatment condition of 1200oC for 4 hrs. Third, the tensile and fatigue properties of the DED IN718 with CoAl2O4 were evaluated. Here, it was found that the addition of CoAl2O4 leads to a minor increase in tensile strength in the as-built condition attributed primarily to the fine oxide dispersion; a more modest increase in tensile strength in the heat-treated condition due to grain refinement induced by retaining the as-built grain structure; and that despite the increase in tensile strength with CoAl2O4 a corresponding increase in fatigue life did not occur. Lastly, the processing of René 65 conducted by laser-powder bed fusion(L-PBF) was done and compared to the conventionally cast and wrought material. Here, the effect of the difference in processing route in conjunction with heat treatments was evaluated to understand the creep and stress relaxation behavior. It was found that L-PBF of René 65 led to an overall improved resistance to deformation by creep and relaxation mechanism.
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Title: SYNTHESIS AND CHARACTERIZATION OF MG, NB, TI-DOPED LINIO2 CATHODE MATERIAL FOR LI-ION BATTERIES
Creator: Tian, Yiwen
Date: 2022
Description: In this project, the influence of several metal doping on the electrochemical properties of LiNiO2 materials was analyzed. The doping method...
Show moreIn this project, the influence of several metal doping on the electrochemical properties of LiNiO2 materials was analyzed. The doping method is aiming to improve the stability of the layered structure and inhibit the mixing of nickel and lithium by enhancing the structural stability of the layered material and replacing part of Ni with other metals in the process of intercalation/deintercalation, thereby promoting the cyclic performance and reversible capacity. The LiNiO2 powder doped with Nb, Ti and Mg is denoted as Li0.96Ni0.9Nb0.06Ti0.04Mg0.02O2 or, in short, metal-doped LiNiO2. The synthesis of the metal-doped LiNiO2 powder consists of mixing the lithium and nickel sources with various metal oxides and then being subjected to high-energy ball milling for 10 hours, followed by heating for 20 h in a metallic tube furnace at 680℃ with flowing oxygen atmosphere. The undoped LiNiO2 powder synthesized using the same process and conditions was compared with the doped LiNiO2 powder. In order to understand the doping mechanism, field emission scanning electron microscopy (FESEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD) were used to analyze the morphology, composition and crystal structure of the final product. Benefiting from the Mg, Nb, and Ti doping, the doped LiNiO2 exhibited a high reversible capacity of 130.56 mAh g-1, higher than that of undoped LiNiO2 (95.02 mAh g-1) under the 0.1C charge/discharge rate in the voltage window between 2.5 and 4.2 V. Further, the doped LiNiO2 has 86% of capacity retention over 100 cycles, better than undoped LiNiO2 (only 44% of capacity retention) under the 0.5C charge/discharge rate between 2.5 and 4.2 V.
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Title: Using Niobium surface encapsulation and Rhenium to enhance the coherence of superconducting devices
Creator: Crisa, Francesco
Date: 2024
Description: In recent decades, the scientific community has grappled with escalating complexity, necessitating a more advanced tool capable of tackling...
Show moreIn recent decades, the scientific community has grappled with escalating complexity, necessitating a more advanced tool capable of tackling increasingly intricate simulations beyond the capabilities of classical computers. This tool, known as a quantum computer, features processors composed of individual units termed qubits. While various methods exist for constructing qubits, superconducting circuits have emerged as a leading approach, owing to their parallels with semiconductor technology.In recent years, significant strides have been made in optimizing the geometry and design of qubits. However, the current bottleneck in the performance of superconducting qubits lies in the presence of defects and impurities within the materials used. Niobium, owing to its desirable properties, such as high critical temperature and low kinetic inductance, stands out as the most prevalent superconducting material. Nonetheless, it is encumbered by a relatively thick oxide layer (approximately 5 nm) exhibiting three distinct oxidation states: NbO, NbO$_2$, and Nb$_2$O$_5$. The primary challenge with niobium lies in the multitude of defects localized within the highly disordered Nb$_2$O$_5$ layer and at the interfaces between the different oxides. In this study, I present an encapsulation strategy aimed at restraining surface oxide growth by depositing a thin layer (5 to 10 nm) of another material in vacuum atop the Nb thin film. This approach exploits the superconducting proximity effect, and it was successfully employed in the development of Josephson junction devices on Nb during the 1980s.In the past two years, tantalum and titanium nitride have emerged as promising alternative materials, with breakthrough qubit publications showcasing coherence times five to ten times superior to those achieved in Nb. The focus will be on the fabrication and RF testing of Nb-based qubits with Ta and Au capping layers. With Ta capping, we have achieved the best T1 (not average) decay time of nearly 600 us, which is more than a factor of 10 improvements over the bare Nb. This establishes the unique capping layer approach as a significant new direction for the development of superconducting qubits.Concurrently with the exploration of materials for encapsulation strategies, identifying materials conducive to enhancing the performance of superconducting qubits is imperative. Ideal candidates should exhibit a thin, low-loss surface oxide and establish a clean interface with the substrate, thereby minimizing defects and potential sources of losses. Rhenium, characterized by an extremely thin surface oxide (less than 1 nm) and nearly perfect crystal structure alignment with commonly used substrates such as sapphire, emerges as a promising material platform poised to elevate the performance of superconducting qubits.
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Title: Improving Niobium Superconducting Radio-Frequency Cavities by Studying Tantalum
Creator: Helfrich, Halle
Date: 2023
Description: Niobium superconducting radio-frequency (SRF) cavities are widely used accelerating structures. Improvements in both quality factor, Q0, and...
Show moreNiobium superconducting radio-frequency (SRF) cavities are widely used accelerating structures. Improvements in both quality factor, Q0, and maximum accelerating gradient, Eacc, have been made to SRF cavities by introducing new processing techniques. These breakthroughs include processes such as nitrogen doping(N-Doping) and infusion, electrochemical polishing (EP) and High Pressure Rinsing (HPR). [1] There is still abundant opportunity to improve the cavities or, rather, the material they’re primarily composed of: niobium. A focus here is the role the native oxide of Nb plays in SRF cavity performance. The values of interest in a given cavity are its quality factor Q0, maximum accelerating gradient Eacc and surface resistance Rs . This work characterizes Nb and Ta foils prepared under identical conditions using X-ray photoelectron spectroscopy (XPS) to compare surface oxides and better understand RF loss mechanisms in Nb SRF cavities and qubits. It is well established that Ta qubits experience much longer coherence times than Nb qubits, which is probably due to the larger RF losses in Nb oxide. By studying Tantalum, an element similar to Niobium, the mechanisms of the losses that originate in the oxide and suboxide layers present on the surface of Nb cavities might finally be unlocked. We find noticeable differences in the oxides of Nb and Ta formed by air exposure of clean foils. In particular, Ta does not display the TaO2 suboxide in XPS, while Nb commonly shows NbO2. This suggests that suboxides are an additional contributor of RF losses. We also suggest that thin Ta film coatings of Nb SRF cavities may be a way of increasing Q0. It is in the interest of the accelerator community to fully understand the surface impurities present in Nb SRF cavities so that strategies for mitigating the effects can be proposed.
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Title: Laser Powder Bed Fusion Of Cost-Effective Non-Spherical Ti-6Al-4V Powder
Creator: Asherloo, Mohammadreza
Date: 2023
Description: This comprehensive research delves into the intricate dynamics of Laser Powder Bed Fusion (L-PBF) of Ti-6Al-4V powders, emphasizing the...
Show moreThis comprehensive research delves into the intricate dynamics of Laser Powder Bed Fusion (L-PBF) of Ti-6Al-4V powders, emphasizing the potential of non-spherical, hydride-dehydride (HDH) powders as a cost-efficient alternative to traditional spherical powders. The study systematically explores the interplay between powder morphology, granulometry, and various post-processing treatments in shaping the resultant microstructure, porosity, and mechanical properties of L-PBF fabricated Ti-6Al-4V components.Initial investigations focused on the flowability, packing density, and resultant density of L-PBF parts using HDH powders with varying size distributions. Through meticulous optimization of laser parameters, parts with a relative density exceeding 99.5% were achieved, even at production rates 1.5–2 times higher than conventional LPBF processes. Dynamic synchrotron X-ray imaging provided insights into laser-powder interactions, revealing key mechanisms of porosity formation associated with HDH powders. Further microstructural examinations highlighted the formation of columnar β grains with acicular α/α′ phases in the as-built condition. Mechanical tests, including fatigue assessments under fully-reversed tension-compression conditions, revealed the critical role of surface roughness in fatigue performance. Notably, mechanical grinding significantly improved fatigue strength, especially in the high cycle fatigue region, by eliminating surface micro-notches. X-ray diffraction analyses further elucidated the stress and micro-strain profiles, offering insights into the material's deformation mechanisms. A pivotal discovery was the presence of α/α′ on prior β/β grain boundaries, challenging the prevailing notion that high cooling rates in L-PBF preclude β/β grain boundary variant selection. Electron backscatter diffraction and synchrotron X-ray imaging illuminated the role of powder characteristics in locally modulating cooling rates, leading to β/β grain boundary α′ lath growth. Lastly, the research underscored the multifaceted interdependencies among contouring, powder granulometry, Hot Isostatic Pressing (HIP), and mechanical surface treatments. A pronounced increase in sub-surface porosities was identified when contouring was combined with fine powder granulometry. However, post-HIP treatments induced a phase transformation from martensitic α′ to a basket-weave α+β microstructure, enhancing the material's fatigue resistance to levels comparable to wrought Ti-6Al-4V. In summation, this doctoral research offers a holistic understanding of the L-PBF process for Ti-6Al-4V, emphasizing the viability of non-spherical HDH powders and providing a roadmap for parameter optimization, defect minimization, and mechanical property enhancement in L-PBF-fabricated Ti-6Al-4V structures.
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Title: Investigation of Electrochemical Properties and Fabrication of Lithium- and Sodium-ion Batteries
Creator: Chen, Changlong
Date: 2023
Description: Since the successful commercialization of Li-ion battery, the opportunity in creating a sustainable world with evenly-distributed energy...
Show moreSince the successful commercialization of Li-ion battery, the opportunity in creating a sustainable world with evenly-distributed energy supply and less environmental concerns has been significantly increased. This triggered tremendous efforts from both academy and industry in building better Li-ion batteries. Along the research and development over past 30 years, the performance of current Li-ion batteries has met some basic needs in our daily life, such as powering electronic devices and electric vehicles for a short time, while superior capabilities, like extended operating life, stable function under extreme circumstances, is always pursued. Under the pressure from these ever-growing demands, the corresponding Li-ion battery production is faced with a lot of new challenges. Regarding the battery production, the present Li-ion battery manufacturing heavily relies on the use of certain repo-toxic solvent, N-methyl-2-pyrrolidone (NMP), which arouses safety concerns to human health. In the pursuit of a higher energy density, silicon anode, bearing ten times the gravimetric capacity of commercially-dominating graphite anode, is intensively studied as the anode material for next-generation Li-ion batteries. However, its degradation mechanism is not completely revealed yet, which makes the methods of effective optimizations hard to be developed. In terms of the cost control, Na-ion batteries have been revisited and have received extra attention in the past decade owing to the abundance in raw materials and the high compatibility with state-of-art Li-ion industry while blank space in understanding primary electrochemical properties, such as impedance signals, has not been totally filled. This will also cause the misunderstandings in such interpretation and, thereby, postpone the pace of relevant advancement. Targeting these proposed issues, this thesis provides a series of feasible solutions via careful investigation and rational analysis with the aid of various advanced (non)electrochemical techniques, which offers a few unique perspectives in studying Li- and Na-ion batteries, and further facilitates the following research and development in the corresponding communities.
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Title: First-principles study on the stability, electrochemical property, and degradation mechanism of ceramic electrode materials
Creator: Wei, Jialiang
Date: 2023
Description: First-principles studies demonstrate the capability to rapidly and accurately calculate desired properties in battery materials. This thesis...
Show moreFirst-principles studies demonstrate the capability to rapidly and accurately calculate desired properties in battery materials. This thesis focuses on the examination of layered NaCrO2 as a case study to assess the impact of various calculation methods. Additionally, a microscopic analysis is conducted to investigate the failure mode of NaCrO2. Lastly, a successful first-principles based high-throughput screening of electrode materials is performed to identify stable compounds that enable easy Li migration.The layered O3 NaCrO2 compound exhibits promising characteristics as a Na-ion cathode material, including good thermal stability and specific capacity. However, it suffers from poor rate capability. To address this limitation and develop high-rate Na-ion cathodes, we conducted a first-principles study that focused on the stability and Na diffusion in pure and doped NaCrO2. The study utilized various functionals, including those explicitly incorporating van der Waals (vdW) interactions. By including vdW interactions, we observed a significant reduction in interlayer distances within partially desodiated NaCrO2, which directly impacted the prediction of Na diffusion barriers. We established a linear relationship between interlayer distance and diffusion barrier using different functionals. Notably, the increased diffusion barriers were mainly due to the reduced interlayer distances predicted by the vdW-inclusive functionals, rather than the inclusion of vdW interactions in the transition state calculations. Other factors, such as the charge density change introduced by different dopants, also influenced the Na diffusion barriers. Metal doping (Al, Zn, Mn, and Co) at low concentrations in NaCrO2 had minor effects on its thermodynamic stability but significantly promoted Na diffusivity. Among the doped NaCrO2 compounds, Co-doped NaCrO2 exhibited the lowest Na diffusion barriers and emerged as a potential candidate for high-rate Na-ion cathode materials. This study highlights the significance of vdW interactions in layered transition metal oxides and provides strategies to enhance first-principles predictions for such structures.Then, TM migration usually occurs at highly charged states in layered Na transition metal oxide, leading to a deterioration in capacity and reversibility. Furthermore, the formation of hybrid phases, characterized by the intergrowth of octahedral and prismatic Na layers, is known to take place at highly charged states. These hybrid phases often exhibit greater stability compared to simple O3 or P3 stacking configurations. However, there is limited understanding regarding the mechanism and impact of TM migration in these hybrid phases. To address this gap, we conducted a comparative first-principles study to elucidate the connection between structural changes and Cr migration in layered O3 and hybrid-phased NaCrO2. We observed that the hybrid-phased NaCrO2 experienced more significant layer shrinkage than the O3 phase after Cr migration. Three factors were found to affect the Cr migration energy: the Na concentration, local 3D configuration, and 2D in-plane geometry. Low Na concentration and specific 3D configurations facilitated Cr migration. Furthermore, the Cr migration barriers in both O3 and hybrid-phased NaCrO2 were found to be positively correlated with Cr migration energy. Lastly, we surveyed the Cr migration of 17 doped O3 and hybrid-phased NaCrO2 compounds. A uniform distribution of Cr-O bond length usually indicated suppressed Cr migration. We identified optimal dopants for Cr migration suppression by considering both Cr and dopant migration energy. This comparative study on Cr migration in O3 and hybrid-phased NaCrO2 highlights the significant role of hybrid phases in the application of layered cathode materials.Moving from the calculations of single material system, we last conduct a first-principles high-throughput screening of multicomponent transition metal sulfides (TMS) as fast Li-ion intercalation compounds. We compared two representative TMS frameworks, pyrite and spinel, with regard to their selectivity in forming stable disordered TMS. To quantify the ability to form entropy stabilized disordered TMS, we examined the effects of cation permutation on the formation enthalpy range. Although low energy-above-hull (Ehull) is a preliminary requirement for the formation of stable TMS, a narrow formation enthalpy range can also lead to entropy stabilized TMS, as only a small amount of excess energy is required to stabilize the metastable configurations. Among the 70 pyrite and spinel frameworks studied, we selected 13 spinel compounds based on their low Ehull and narrow Ef range. Additionally, these spinel compounds exhibited greater stability compared to their pyrite counterparts. We found that early transition metal elements such as Ti and V were less favorable for the formation of pyrite TMS, while late TM elements, especially Cu, strongly destabilized spinel TMS. The spinel (CrMnCoNi)S2 TMS demonstrated the most promising characteristics with a narrow Ef range. Finally, we calculated and ranked the Li migration barriers in the 13 stable spinel TMS using a bond valence-based method, which allowed for quick screening of ion migration. High oxidation state TM elements, such as Mn4+ and Cr3+, located nearest to the Li migration path, increased the Li migration barrier. (CrMnCoNi)S2 exhibited the lowest Li migration barrier, positioning it as a promising entropy-stabilized spinel intercalation compound.
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Title: Effect of Phosphorus Additions on Polycrystalline Ni-base Superalloys
Creator: Li, Linhan
Date: 2020
Description: In recent years, advanced polycrystalline Ni-base superalloys have been developed with elevated levels of γ′ forming elements and high level...
Show moreIn recent years, advanced polycrystalline Ni-base superalloys have been developed with elevated levels of γ′ forming elements and high level of refractory elements as solid-solution strengtheners in an effort to extend the temperature capability. Moreover, the properties of the grain boundaries become more important and this necessitates the need to study of effects of minor additions of interstitial P for grain structure optimization. Due to the increased level of refractory elements employed, powder-processed Ni-base superalloys tend to have a high propensity to form Topologically Close-Packed (TCP) phases, which was found to be further promoted by the addition of P. A systematic study of the phase stability of high refractory content powder-processed Ni-base superalloys with three levels of P additions revealed an increased tendency to form Laves phase as a function of P additions. Additions of P were discovered to not only depress the incipient melting temperature to stabilize the eutectic Laves phase, but also promote Laves phase formation during the aging heat treatment and the following isothermal exposure. During the thermal exposure, excessive formation of Laves phase promoted the formation of a basket-weave structure comprised of an intertwined mixture of Laves and Sigma phase. The stabilization of the Laves phase structure due to P additions was found to be consistent with Density Functional Theory (DFT) calculations and could be rationalized through structure maps that relate the valence electron concentration and relative size differences. Additionally, a variation of grain structure obtained via either a sub-solvus or super-solvus solution heat treatment was noted to some extent vary the P segregation level at high-angle grain boundaries, thereby affecting the phase stability. For a sub-solvus solutioned grain structure that possessed a high length density of high-angle grain boundaries, the Laves phase formation was depressed for alloys with a low level of P addition. However, the phase stability variation associated with Laves phase formation was moderate when high concentrations of P were present. The effect of P addition on the γ′ microstructure variation is limited, which was confirmed by microstructure observations as well as through the short-term 0.6%-strain stress relaxation tests at high temperature. Heat treatment variations to modify the secondary and tertiary γ′ microstructures were discovered to exert a much more significant influence on the 0.6%-strain stress relaxation behavior. When a higher initial strain of 2% was applied, the stress relaxation behavior of the powder-processed Ni-base superalloys was found to be microstructure independent. The creep ductility of Waspaloy was determined to be notably reduced by the P additions due to the enhanced precipitation of M23C6 carbide at the grain boundaries. Excessive precipitation of M23C6 carbide increased the likelihood of brittle fracture when tested under low temperature/high stress creep conditions. However, the P addition as well as the excessive precipitation of M23C6 carbide did not impact the creep behavior as the dominant deformation was transgranular in nature when tested under high temperature/low stress conditions.
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Title: Developing Advanced Materials for Carbon Dioxide Electroreduction to Value-Added Chemicals and Fuels
Creator: Esmaeilirad, Mohammadreza
Date: 2023
Description: Developing highly efficient electrocatalysts for the carbon dioxide reductionreaction (CO2RR) to value-added fuels and chemicals offers a...
Show moreDeveloping highly efficient electrocatalysts for the carbon dioxide reductionreaction (CO2RR) to value-added fuels and chemicals offers a feasible pathway for renewable energy storage and could help mitigate the ever-increasing carbon dioxide (CO2) emissions from human activities. Different catalysts are known to catalyze CO2RR in aqueous solutions. Most known catalysts are only capable of transferring 2 electrons with needed protons to CO2 producing either carbon monoxide (CO) or formic acid (HCOOH). Copper (Cu) is the only electrocatalytic material that converts CO2 into different types of hydrocarbon products. Additionally, owing to Cu’s natural abundance and low cost, it has been intensively studied for CO2RR for decades. However, the required high input energy (overpotential), low product selectivity towards valuable fuel products, and the lack of long-term stability remain major challenges for Cu-based catalysts. This work aims to develop new materials that produce hydrocarbons at lower overpotentials with higher rates and greater selectivity than current copper catalysts. By implementing a process referred to as the electrocatalyst discovery cycle iterations between predications, catalyst testing, and active site characterization allow for the rational design and discovery of new and improved electrocatalysts for CO2RR. This methodology led to the discovery of different heteroatomic catalysts as low overpotential catalysts for electroreduction of CO2 high energy density hydrocarbon products.
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