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- All Subjects: Materials Science
- Creators: Chan, Candace
- Member of: ASU Electronic Theses and Dissertations
Description
Dealloying, the selective dissolution of an elemental component from an alloy, is an important corrosion mechanism and a technological significant means to fabricate nanoporous structures for a variety of applications. In noble metal alloys, dealloying proceeds above a composition dependent critical potential, and bi-continuous structure evolves "simultaneously" as a result of the interplay between percolation dissolution and surface diffusion. In contrast, dealloying in alloys that show considerable solid-state mass transport at ambient temperature is largely unexplored despite its relevance to nanoparticle catalysts and Li-ion anodes. In my dissertation, I discuss the behaviors of two alloy systems in order to elucidate the role of bulk lattice diffusion in dealloying. First, Mg-Cd alloys are chosen to show that when the dealloying is controlled by bulk diffusion, a new type of porosity - negative void dendrites will form, and the process mirrors electrodeposition. Then, Li-Sn alloys are studied with respect to the composition, particle size and dealloying rate effects on the morphology evolution. Under the right condition, dealloying of Li-Sn supported by percolation dissolution results in the same bi-continuous structure as nanoporous noble metals; whereas lattice diffusion through the otherwise "passivated" surface allows for dealloying with no porosity evolution. The interactions between bulk diffusion, surface diffusion and dissolution are revealed by chronopotentiometry and linear sweep voltammetry technics. The better understanding of dealloying from these experiments enables me to construct a brief review summarizing the electrochemistry and morphology aspects of dealloying as well as offering interpretations to new observations such as critical size effect and encased voids in nanoporous gold. At the end of the dissertation, I will describe a preliminary attempt to generalize the morphology evolution "rules of dealloying" to all solid-to-solid interfacial controlled phase transition process, demonstrating that bi-continuous morphologies can evolve regardless of the nature of parent phase.
ContributorsChen, Qing (Author) / Sieradzki, Karl (Thesis advisor) / Friesen, Cody (Committee member) / Buttry, Daniel (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2013
Description
Topological insulators with conducting surface states yet insulating bulk states have generated a lot of interest amongst the physics community due to their varied characteristics and possible applications. Doped topological insulators have presented newer physical states of matter where topological order co&ndashexists; with other physical properties (like magnetic order). The electronic states of these materials are very intriguing and pose problems and the possible solutions to understanding their unique behaviors. In this work, we use Electron Energy Loss Spectroscopy (EELS) – an analytical TEM tool to study both core&ndashlevel; and valence&ndashlevel; excitations in Bi2Se3 and Cu(doped)Bi2Se3 topological insulators. We use this technique to retrieve information on the valence, bonding nature, co-ordination and lattice site occupancy of the undoped and the doped systems. Using the reference materials Cu(I)Se and Cu(II)Se we try to compare and understand the nature of doping that copper assumes in the lattice. And lastly we utilize the state of the art monochromated Nion UltraSTEM 100 to study electronic/vibrational excitations at a record energy resolution from sub-nm regions in the sample.
ContributorsSubramanian, Ganesh (Author) / Spence, John (Thesis advisor) / Jiang, Nan (Committee member) / Chen, Tingyong (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2013
Description
Recent advancements in the field of light wavefront engineering rely on complex 3D metasurfaces composed of sub-wavelength structures which, for the near infrared range, are challenging to manufacture using contemporary scalable micro- and nanomachining solutions. To address this demand, a novel parallel micromachining method, called metal-assisted electrochemical nanoimprinting (Mac-Imprint) was developed. Mac-Imprint relies on the catalysis of silicon wet etching by a gold-coated stamp enabled by mass-transport of the reactants to achieve high pattern transfer fidelity. This was realized by (i) using nanoporous catalysts to promote etching solution diffusion and (ii) semiconductor substrate pre-patterning with millimeter-scale pillars to provide etching solution storage. However, both of these approaches obstruct scaling of the process in terms of (i) surface roughness and resolution, and (ii) areal footprint of the fabricated structures. To address the first limitation, this dissertation explores fundamental mechanisms underlying the resolution limit of Mac-Imprint and correlates it to the Debye length (~0.9 nm). By synthesizing nanoporous catalytic stamps with pore size less than 10 nm, the sidewall roughness of Mac-Imprinted patterns is reduced to levels comparable to plasma-based micromachining. This improvement allows for the implementation of Mac-Imprint to fabricate Si rib waveguides with limited levels of light scattering on its sidewall. To address the second limitation, this dissertation focuses on the management of the etching solution storage by developing engineered stamps composed of highly porous polymers coated in gold. In a plate-to-plate configuration, such stamps allow for the uniform patterning of chip-scale Si substrates with hierarchical 3D antireflective and antifouling patterns. The development of a Mac-Imprint system capable of conformal patterning onto non-flat substrates becomes possible due to the flexible and stretchable nature of gold-coated porous polymer stamps. Understanding of their mechanical behavior during conformal contact allows for the first implementation of Mac-Imprint to directly micromachine 3D hierarchical patterns onto plano-convex Si lenses, paving the way towards scalable fabrication of multifunctional 3D metasurfaces for applications in advanced optics.
ContributorsSharstniou, Aliaksandr (Author) / Azeredo, Bruno (Thesis advisor) / Chan, Candace (Committee member) / Rykaczewski, Konrad (Committee member) / Petuskey, William (Committee member) / Chen, Xiangfan (Committee member) / Arizona State University (Publisher)
Created2022
Description
This thesis presents a study of Boron Nitride (BN) and Copper (Cu)/BN multilayer thin films in terms of synthesis, chemical, structural, morphological, and mechanical properties characterization.
In this study, the influence of Ar/N₂ flow rate in synthesizing stoichiometric BN thin films via magnetron sputtering was investigated initially. Post magnetron sputtering, the crystalline nature and B:N stoichiometric ratio of deposited thin films were investigated by X-ray diffraction (XRD) and X-ray Photoelectron Spectroscopy (XPS) respectively. Thicknesses revealed by ellipsometry analysis for nearly stoichiometric B:N thin films and their corresponding deposition times were used for estimating BN interlayer deposition times during the deposition of Cu/BN multilayer thin films. To characterize the microstructure of the synthesized Cu/BN multilayer thin films, XRD and scanning electron microscopy (SEM) have been used. Finally, a comparison of nanoindentation measurements on pure Cu and Cu/BN multilayer thin films having different number of BN interlayers were used for studying the influence of BN interlayers on improving mechanical properties such as hardness and elastic modulus.
The results show that the stoichiometry of BN thin films is dependent on the Ar/N₂ flow rate during magnetron sputtering. An optimal Ar/N₂ flow rate of 13:5 during deposition was required to achieve an approximately 1:1 B:N stoichiometry. Grazing incidence and powder XRD analysis on these stoichiometric BN thin films deposited at room temperature did not reveal a phase match when compared to hexagonal boron nitride (h-BN) and cubic boron nitride (c-BN) reference XRD patterns. For a BN thin film deposition time of 5 hours, a thickness of approximately 40 nm was achieved, as revealed by ellipsometry. XRD and microstructure analysis using scanning electron microscopy (SEM) on pure Cu and Cu/BN thin films showed that the Cu grain size in Cu/BN thin films is much finer than pure Cu thin films. Interestingly, nanoindentation measurements on pure Cu and Cu/BN thin films having a similar overall thickness demonstrated that hardness and Young’s modulus of the films were improved significantly when BN interlayers are present.
ContributorsCaner, Sumeyye (Author) / Rajagopalan, Jagannathan (Thesis advisor) / Oswald, Jay (Committee member) / Solanki, Kiran (Committee member) / Arizona State University (Publisher)
Created2023
Description
This work correlates microscopic material changes to short- and long-term performance in modern, Cu-doped, CdTe-based solar cells. Past research on short- and long-term performance emphasized the device-scale impact of Cu, but neglected the microscopic impact of the other chemical species in the system (e.g., Se, Cl, Cu), their distributions, their local atomic environments, or their interactions/reactions. Additionally, technological limitations precluded nanoscale measurements of the Cu distributions in the cell, and microscale measurements of the material properties (i.e. composition, microstructure, charge transport) as the cell operates. This research aims to answer (1) what is the spatial distribution of Cu in the cell, (2) how does its distribution and local environment correlate with cell performance, and (3) how do local material properties change as the cell operates? This work employs a multi-scale, multi-modal, correlative-measurement approach to elucidate microscopic mechanisms. Several analytical techniques are used – including and especially correlative synchrotron X-ray microscopy – and a unique state-of-the-art instrument was developed to access the dynamics of microscopic mechanisms as they proceed. The work shows Cu segregates around CdTe grain boundaries, and Cu-related acceptor penetration into the CdTe layer is crucial for well-performing cells. After long-term operation, the work presents strong evidence of Se migration into the CdTe layer. This redistribution correlates with microstructural changes in the CdTe layer and limited charge transport around the metal-CdTe interface. Finally, the work correlates changes in microstructure, Cu atomic environment, and charge collection as a cell operates. The results suggest that, as the cell ages, a change to Cu local environment limits charge transport through the metal-CdTe interface, and this change could be influenced by Se migration into the CdTe layer of the cell.
ContributorsWalker, Trumann (Author) / Bertoni, Mariana I (Thesis advisor) / Holman, Zachary (Committee member) / Chan, Candace (Committee member) / Colegrove, Eric (Committee member) / Arizona State University (Publisher)
Created2022
Description
Aromatic polymers, with benzene-like rings in their main chains, include materials such as polyurea, an amorphous elastomer capable of dissipating large amounts of energy under dynamic loading, which makes it a promising coating for defensive systems. Although computational research exists that investigates the atomic-level response of polyurea and other amorphous aromatic polymers to extreme conditions, there is little experimental work to validate these models 1) at the atomic-scale and 2) under high pressures characteristic of extreme dynamic loading. Understanding structure-property relationships at the atomic-level is important for polymers, considering many of them undergo pressure and temperature-induced structural transformations, which must be understood to formulate accurate predictive models. This work aims to gain a deeper understanding of the high-pressure structural response of aromatic polymers at the atomic-level, with emphasis into the mechanisms associated with high-pressure transformations. Hence, atomic-level structural data at high pressures was obtained in situ via multiangle energy dispersive X-ray diffraction (EDXD) experiments at the Advanced Photon Source (APS) for polyurea and another amorphous aromatic polymer, polysulfone, chosen as a reference due to its relatively simple structure. Pressures up to 6 GPa were applied using a Paris Edinburgh (PE) hydraulic press at room temperature. Select polyurea samples were also heated to 277 °C at 6 GPa. The resulting structure factors and pair distribution functions, along with molecular dynamics simulations of polyurea provided by collaborators, suggest that the structures of both polymers are stable up to 6 GPa, aside from reductions in free-volume between polymer backbones. As higher pressures (≲ 32 GPa) were applied using diamond anvils in combination with the PE press, indications of structural transformations were observed in both polymers that appear similar in nature to the sp2-sp3 hybridization in compressed carbon. The transformation occurs gradually up to at least ~ 26 GPa in PSF, while it does not progress past ~ 15 GPa in polyurea. The changes are largely reversible, especially in polysulfone, consistent with pressure-driven, reversible graphite-diamond transformations in the absence of applied temperature. These results constitute some of the first in situ observations of the mechanisms that drive pressure-induced structural transformations in aromatic polymers.
ContributorsEastmond, Tyler (Author) / Peralta, Pedro (Thesis advisor) / Hoover, Christian (Committee member) / Hrubiak, Rostislav (Committee member) / Mignolet, Marc (Committee member) / Oswald, Jay (Committee member) / Arizona State University (Publisher)
Created2022
Description
Intelligent engineering designs require an accurate understanding of material behavior, since any uncertainties or gaps in knowledge must be counterbalanced with heightened factors of safety, leading to overdesign. Therefore, building better structures and pushing the performance of new components requires an improved understanding of the thermomechanical response of advanced materials under service conditions. This dissertation provides fundamental investigations of several advanced materials: thermoset polymers, a common matrix material for fiber-reinforced composites and nanocomposites; aluminum alloy 7075-T6 (AA7075-T6), a high-performance aerospace material; and ceramic matrix composites (CMCs), an advanced composite for extreme-temperature applications. To understand matrix interactions with various interfaces and nanoinclusions at their fundamental scale, the properties of thermoset polymers are studied at the atomistic scale. An improved proximity-based molecular dynamics (MD) technique for modeling the crosslinking of thermoset polymers is carefully established, enabling realistic curing simulations through its ability to dynamically and probabilistically perform complex topology transformations. The proximity-based MD curing methodology is then used to explore damage initiation and the local anisotropic evolution of mechanical properties in thermoset polymers under uniaxial tension with an emphasis on changes in stiffness through a series of tensile loading, unloading, and reloading experiments. Aluminum alloys in aerospace applications often require a fatigue life of over 109 cycles, which is well over the number of cycles that can be practically tested using conventional fatigue testing equipment. In order to study these high-life regimes, a detailed ultrasonic cycle fatigue study is presented for AA7075-T6 under fully reversed tension-compression loading. The geometric sensitivity, frequency effects, size effects, surface roughness effects, and the corresponding failure mechanisms for ultrasonic fatigue across different fatigue regimes are investigated. Finally, because CMCs are utilized in extreme environments, oxidation plays an important role in their degradation. A multiphysics modeling methodology is thus developed to address the complex coupling between oxidation, mechanical stress, and oxygen diffusion in heterogeneous carbon fiber-reinforced CMC microstructures.
ContributorsSchichtel, Jacob (Author) / Chattopadhyay, Aditi (Thesis advisor) / Dai, Lenore (Committee member) / Ghoshal, Anindya (Committee member) / Huang, Huei-Ping (Committee member) / Jiao, Yang (Committee member) / Oswald, Jay (Committee member) / Arizona State University (Publisher)
Created2022
Description
This research seeks to answer the question if there is a singular relationship between stishovite nucleation and the atomistic structure of the preshocked amorphous SiO$_2$. To do this a stishovite manufacturing method is developed in which 1,152 samples were produced. The majority of these samples did crystallize. The method was produced through two rounds of experiments and fine-tuning with the pressure damp, temperature damp, shock pressure using an NPHug fix, and sample origin. A new random atomic insertion method was used to generate a new and different SiO$_2$ amorphous structure not before seen within the research literature. The optimal values for shock were found to be 60~GPa for randomly atom insertion samples and 55~GPa for quartz origin samples. Temperature damp appeared to have a slight effect optimizing at 0.05~ps and the pressure damp had no visible effect, testing was done with temperature damp from 0.05 to 0.5~ps and pressure damp from 0.1 to 10.0~ps. There appeared to be significant randomness in crystallization behavior. The preshocked and postnucleated samples were transformed into Gaussian fields of crystal, mass, and charge. These fields were divided and classified using a cut-off method taking the number of crystals produced in portions of each simulation and classifying each potion as nucleated or non-nucleated. Data in which some nucleation but not a critical amount was present was removed constituting 2.6\% to 20.3\% of data in all tests. A max method was also used which takes only the maximum portions of each simulation to classify as nucleating. There are three other variables tested within this work, a sample size of 18,000 or 72,728~atoms, Gaussian variance of 1 or 4~\AA, and Convolutional neural network (CNN) architecture of a garden verity or all convolution along with the portioning classification method, sample origination, and Gaussian field type. In total 64 tests were performed to try every combination of variable. No significant classifications were made by the CNNs to nucleation or non-nucleation portions. The results clearly confirmed that the data was not abstracting to atomistic structure and was random by all classifications of the CNNs. The all convolution CNN testing did show smoother outcomes in training with less fluctuations. 59\% of all validation accuracy was held at 0.5 for a random state and 84\% was within $\pm0.02$ of 0.5. It is conclusive that prenucleation structure is not the sole predictor of nucleation behavior. It is not conclusive if prenucleation structure is a partial or non-factor within nucleation of stishovite from amorphous SiO$_2$.
ContributorsChristen, Jonathan Scorr (Author) / Oswald, Jay (Thesis advisor) / Muhich, Christopher (Committee member) / Zhuang, Houlong (Committee member) / Arizona State University (Publisher)
Created2021
Description
The current Li-ion batteries with organic liquid electrolytes are limited by their safety and energy density. Therefore, ceramic electrolytes are proposed in developing next-generation, energy-dense Li-metal batteries by replacing organic liquid electrolytes to improve safety and performance. Among numerous ceramic Li-ion conductors, garnet-based solid electrolyte c-Li7La3Zr2O12 (c-LLZO) is considered one of the most promising candidates to enable Li metal batteries due to its high ionic conductivity, chemical stability, and wide electrochemical stability window against Li metal. However, synthesis and processing of c-LLZO through conventional solid-sate reaction methods requires long periods of calcination (> 6 h) at high reaction temperatures (> 1000 °C). The need for high reaction temperature results to attain cubic-LLZO phase results in large aggerated LLZO particles and causes Li-loss from the garnet structure, making them unfavorable to process further as bulk pellets or thin films. To overcome processing challenges with solid-state reaction method, two novel facile synthesis approaches molten salt (flux growth method), and solution combustion are employed to produce submicron-sized LLZO powders at low reaction temperatures (< 1000 °C) in a short time. In the first case, molten salt synthesis method with LiCl-KCl eutectic mixture is employed to produce sub-micron sized Ta-doped LLZO (LLZTO) powders at low temperatures (900 °C, 4 h). In addition, a detailed investigation on effect of sintering medium and sintering additives on the structural, microstructural, chemical, and Li-ion transport behavior of the LLZTO pellets are investigated. Sintered LLZTO pellets prepared using molten salt synthesis route exhibited high Li-ion conductivity up to 0.6 mS cm-1 and high relative density (> 95 %) using Pt-crucible. In the second case, a facile solution-combustion technique using an amide-based fuel source CH6N4O is utilized to produce submicron-sized Al-doped LLZO (Al-LLZO) powders at low reaction temperatures 600-800 °C in a short duration of 4 h. In addition, effect of fuel to oxidizer ratio on phase purity, particle growth size, and formation mechanism of conductive Al-LLZO are reported and discussed. The Al-LLZO pellets sintered at 1100 °C/ 6 h exhibited high Li-ion conductivity up to 0.45 mS cm-1 with relative densities (> 90 %).
ContributorsBadami, Pavan Pramod (Author) / Kannan, Arunachalandar Mada (Thesis advisor) / Chan, Candace (Thesis advisor) / Song, Kenan (Committee member) / Arizona State University (Publisher)
Created2021
Description
Hydrogen is considered one of the most potential fuels due to its highest gravimetric energy density with no pollutant emission during the energy cycle. Among several techniques for hydrogen generation, the promising photoelectrochemical water oxidation is considered a long-term solar pathway by splitting water. The system contains a photoanode and a cathode immersed in an aqueous electrolyte where charge separation takes place in the bulk of the semiconducting material on light absorption, leading to water oxidation/reduction at the surface of the photoelectrodes/cathode. It is imperative to develop materials that demonstrate high light absorption in the wide spectrum along with photoelectrochemical stability. N-type Monoclinic scheelite bismuth vanadate (BiVO4) is selected due to its incredible light absorption capabilities, direct bandgap (Eg ∼ 2.4-2.5 eV) and relatively better photoelectrochemical stability. However, BiVO4 encounters huge electron-hole recombination due to smaller diffusion lengths and positive conduction bands that cause slow charge dynamics and sluggish water oxidation kinetics. In order to improve the illustrated drawbacks, four strategies were discussed. Chapter 1 describe the fundamental understanding of photoelectrochemical cell and BiVO4. Chapter 2 illustrates details of the experimental procedure and state-of-the-art material characterization. Chapter 3 provide the impact of alkali metal placement in the crystal structure of BiVO4 systematically that exhibited ~20 times more performance than intrinsic BiVO4, almost complete bulk charge separation and enhancement in the diffusion length. Detailed characterization determined that the alkali metal getting placed in the interstitial void of BiVO4 lattice and multiple interbands formation enhanced the charge dynamics. Chapter 4 contains stoichiometric doping of Y3+ or Er3+ or Yb3+ at the Bi3+ site, leading to an extended absorption region, whereas non-stoichiometric W6+ doping at the V5+ site minimizes defects and increased charge carriers. To further enhance the performance, type-II heterojunction with WO3 along p-n junction with Fe:NiO enhance light absorption and charge dynamics close to the theoretical performance. Chapter 5 provides a comprehensive study of a uniquely developed sulfur modified Bi2O3 interface layer to facilitate charge dynamics and carrier lifetime improvement by effectively passivating the WO3/BiVO4 heterojunction interface. Finally, chapter 6 summarized the major findings, conclusion and outlook in developing BiVO4 as an efficient photoanode material.
ContributorsPrasad, Umesh (Author) / Kannan, Arunachala Mada (Thesis advisor) / Azeredo, Bruno (Committee member) / Chan, Candace (Committee member) / Segura, Sergio Garcia (Committee member) / Arizona State University (Publisher)
Created2021