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- All Subjects: Materials Science
- Creators: Chawla, Nikhilesh
- Creators: Crozier, Peter
- Creators: Peralta, Pedro
Description
Fuel cells, particularly solid oxide fuel cells (SOFC), are important for the future of greener and more efficient energy sources. Although SOFCs have been in existence for over fifty years, they have not been deployed extensively because they need to be operated at a high temperature (∼1000 °C), are expensive, and have slow response to changes in energy demands. One important need for commercialization of SOFCs is a lowering of their operating temperature, which requires an electrolyte that can operate at lower temperatures. Doped ceria is one such candidate. For this dissertation work I have studied different types of doped ceria to understand the mechanism of oxygen vacancy diffusion through the bulk. Doped ceria is important because they have high ionic conductivities thus making them attractive candidates for the electrolytes of solid oxide fuel cells. In particular, I have studied how the ionic conductivities are improved in these doped materials by studying the oxygen-vacancy formations and migrations. In this dissertation I describe the application of density functional theory (DFT) and Kinetic Lattice Monte Carlo (KLMC) simulations to calculate the vacancy diffusion and ionic conductivities in doped ceria. The dopants used are praseodymium (Pr), gadolinium (Gd), and neodymium (Nd), all belonging to the lanthanide series. The activation energies for vacancy migration between different nearest neighbor (relative to the dopant) positions were calculated using the commercial DFT code VASP (Vienna Ab-initio Simulation Package). These activation energies were then used as inputs to the KLMC code that I co-developed. The KLMC code was run for different temperatures (673 K to 1073 K) and for different dopant concentrations (0 to 40%). These simulations have resulted in the prediction of dopant concentrations for maximum ionic conductivity at a given temperature.
ContributorsAnwar, Shahriar (Author) / Adams, James B (Thesis advisor) / Crozier, Peter (Committee member) / Krause, Stephen (Committee member) / Arizona State University (Publisher)
Created2011
Description
With the increasing focus on developing environmentally benign electronic packages, lead-free solder alloys have received a great deal of attention. Mishandling of packages, during manufacture, assembly, or by the user may cause failure of solder joint. A fundamental understanding of the behavior of lead-free solders under mechanical shock conditions is lacking. Reliable experimental and numerical analysis of lead-free solder joints in the intermediate strain rate regime need to be investigated. This dissertation mainly focuses on exploring the mechanical shock behavior of lead-free tin-rich solder alloys via multiscale modeling and numerical simulations. First, the macroscopic stress/strain behaviors of three bulk lead-free tin-rich solders were tested over a range of strain rates from 0.001/s to 30/s. Finite element analysis was conducted to determine appropriate specimen geometry that could reach a homogeneous stress/strain field and a relatively high strain rate. A novel self-consistent true stress correction method is developed to compensate the inaccuracy caused by the triaxial stress state at the post-necking stage. Then the material property of micron-scale intermetallic was examined by micro-compression test. The accuracy of this measure is systematically validated by finite element analysis, and empirical adjustments are provided. Moreover, the interfacial property of the solder/intermetallic interface is investigated, and a continuum traction-separation law of this interface is developed from an atomistic-based cohesive element method. The macroscopic stress/strain relation and microstructural properties are combined together to form a multiscale material behavior via a stochastic approach for both solder and intermetallic. As a result, solder is modeled by porous plasticity with random voids, and intermetallic is characterized as brittle material with random vulnerable region. Thereafter, the porous plasticity fracture of the solders and the brittle fracture of the intermetallics are coupled together in one finite element model. Finally, this study yields a multiscale model to understand and predict the mechanical shock behavior of lead-free tin-rich solder joints. Different fracture patterns are observed for various strain rates and/or intermetallic thicknesses. The predictions have a good agreement with the theory and experiments.
ContributorsFei, Huiyang (Author) / Jiang, Hanqing (Thesis advisor) / Chawla, Nikhilesh (Thesis advisor) / Tasooji, Amaneh (Committee member) / Mobasher, Barzin (Committee member) / Rajan, Subramaniam D. (Committee member) / Arizona State University (Publisher)
Created2011
Description
There is an inexorable link between structure and stress, both of which require study in order to truly understand the physics of thin films. To further our knowledge of thin films, the relationship between structure and stress development was examined in three separate systems in vacuum. The first was continued copper thin film growth in ultra-high vacuum after adsorption of a sub-monolayer quantity of oxygen. Results showed an increase in compressive stress generation, and theory was proposed to explain the additional compressive stress within the films. The second system explored was the adsorption of carbon monoxide on the platinum {111} surface in vacuum. The experiments displayed a correlation between known structural developments in the adsorbed carbon monoxide adlayer and the surface stress state of the system. The third system consisted of the growth and annealing stresses of ice thin films at cryogenic temperatures in vacuum. It was shown that the growth stresses are clearly linked to known morphology development from literature, with crystalline ice developing compressive and amorphous ice developing tensile stresses respectively, and that amorphous ice films develop additional tensile stresses upon annealing.
ContributorsKennedy, Jordan (Author) / Friesen, Cody (Thesis advisor) / Sieradzki, Karl (Committee member) / Crozier, Peter (Committee member) / Arizona State University (Publisher)
Created2011
Description
ABSTRACT The behavior of the fission products, as they are released from fission events during nuclear reaction, plays an important role in nuclear fuel performance. Fission product release can occur through grain boundary (GB) at low burnups; therefore, this study simulates the mass transport of fission gases in a 2-D GB network to look into the effects of GB characteristics on this phenomenon, with emphasis on conditions that can lead to percolation. A finite element model was created based on the microstructure of a depleted UO2 sample characterized by Electron Backscattering Diffraction (EBSD). The GBs were categorized into high (D2), low (D1) and bulk diffusivity (Dbulk) based on their misorientation angles and Coincident Site Lattice (CSL) types. The simulation was run using different diffusivity ratios (D2/Dbulk) ranging from 1 to 10^8. The model was set up in three ways: constant temperature case, temperature gradient effects and window methods that mimic the environments in a Light Water Reactor (LWR). In general, the formation of percolation paths was observed at a ratio higher than 10^4 in the measured GB network, which had a 68% fraction of high diffusivity GBs. The presence of temperature gradient created an uneven concentration distribution and decreased the overall mass flux. Finally, radial temperature and fission gas concentration profiles were obtained for a fuel pellet in operation using an approximate 1-D model. The 100 µm long microstructurally explicit model was used to simulate, to the scale of a real UO2 pellet, the mass transport at different radial positions, with boundary conditions obtained from the profiles. Stronger percolation effects were observed at the intermediate and periphery position of the pellet. The results also showed that highest mass flux happens at the edge of a pellet at steady state to accommodate for the sharp concentration drop.
ContributorsLim, Harn Chyi (Author) / Peralta, Pedro (Thesis advisor) / Dey, Sandwip (Committee member) / Sieradzki, Karl (Committee member) / Arizona State University (Publisher)
Created2011
Description
Supported catalytic nanoparticles undergo rapid structural transformations faster than many transmission electron microscopes (TEMs) can track. This is the case with platinum nanoparticles supported on cerium oxide (Pt/CeO2) in a CO and O2 gaseous environment. By furthering our understanding of the structural dynamics of the Pt/CeO2 system, improved catalyst design principles may be derived to enhance the efficiency of this catalyst. Developing static models of a 2 nm Pt nanoparticle supported on CeO2 and simulating TEM images of the models was found to create similar images to those seen in experimental TEM time-resolved series of the system. Rotations of static models on a ceria support provides a way to understand the experimental samples in three dimensions, which is difficult in two dimensional TEM images. This project expands the possibilities of interpreting TEM images of catalytic systems.
ContributorsBlock, Claire (Author) / Crozier, Peter (Thesis director) / Muhich, Christopher (Committee member) / Materials Science and Engineering Program (Contributor, Contributor) / Watts College of Public Service & Community Solut (Contributor) / Barrett, The Honors College (Contributor)
Created2021-05
Description
Increasing demand for high strength powder metallurgy (PM) steels has resulted in the development of dual phase PM steels. In this work, the effects of thermal aging on the microstructure and mechanical behavior of dual phase precipitation hardened powder metallurgy (PM) stainless steels of varying ferrite-martensite content were examined. Quantitative analyses of the inherent porosity and phase fractions were conducted on the steels and no significant differences were noted with respect to aging temperature. Tensile strength, yield strength, and elongation to fracture all increased with increasing aging temperature reaching maxima at 538oC in most cases. Increased strength and decreased ductility were observed in steels of higher martensite content. Nanoindentation of the individual microconstituents was employed to obtain a fundamental understanding of the strengthening contributions. Both the ferrite and martensite hardness values increased with aging temperature and exhibited similar maxima to the bulk tensile properties. Due to the complex non-uniform stresses and strains associated with conventional nanoindentation, micropillar compression has become an attractive method to probe local mechanical behavior while limiting strain gradients and contributions from surrounding features. In this study, micropillars of ferrite and martensite were fabricated by focused ion beam (FIB) milling of dual phase precipitation hardened powder metallurgy (PM) stainless steels. Compression testing was conducted using a nanoindenter equipped with a flat punch indenter. The stress-strain curves of the individual microconstituents were calculated from the load-displacement curves less the extraneous displacements of the system. Using a rule of mixtures approach in conjunction with porosity corrections, the mechanical properties of ferrite and martensite were combined for comparison to tensile tests of the bulk material, and reasonable agreement was found for the ultimate tensile strength. Micropillar compression experiments of both as sintered and thermally aged material allowed for investigation of the effect of thermal aging.
ContributorsStewart, Jennifer (Author) / Chawla, Nikhilesh (Thesis advisor) / Jiang, Hanqing (Committee member) / Krause, Stephen (Committee member) / Arizona State University (Publisher)
Created2011
Description
Novel materials for Li-ion batteries is one of the principle thrust areas for current research in energy storage, more so than most, considering its widespread use in portable electronic gadgets and plug-in electric and hybrid cars. One of the major limiting factors in a Li-ion battery's energy density is the low specific capacities of the active materials in the electrodes. In the search for high-performance anode materials for Li-ion batteries, many alternatives to carbonaceous materials have been studied. Both cubic and amorphous silicon can reversibly alloy with lithium and have a theoretical capacity of 3500 mAh/g, making silicon a potential high density anode material. However, a large volume expansion of 300% occurs due to changes in the structure during lithium insertion, often leading to pulverization of the silicon. To this end, a class of silicon based cage compounds called clathrates are studied for electrochemical reactivity with lithium. Silicon-clathrates consist of silicon covalently bonded in cage structures comprised of face sharing Si20, Si24 and/or Si28 clusters with guest ions occupying the interstitial positions in the polyhedra. Prior to this, silicon clathrates have been studied primarily for their superconducting and thermoelectric properties. In this work, the synthesis and electrochemical characterization of two categories of silicon clathrates - Type-I silicon clathrate with aluminum framework substitution and barium guest ions (Ba8AlxSi46-x) and Type-II silicon clathrate with sodium guest ions (Nax Si136), are explored. The Type-I clathrate, Ba8AlxSi46-x consists of an open framework of aluminium and silicon, with barium (guest) atoms occupying the interstitial positions. X-ray diffraction studies have shown that a crystalline phase of clathrate is obtained from synthesis, which is powdered to a fine particle size to be used as the anode material in a Li-ion battery. Electrochemical measurements of these type of clathrates have shown that capacities comparable to graphite can be obtained for up to 10 cycles and lower capacities can be obtained for up to 20 cycles. Unlike bulk silicon, the clathrate structure does not undergo excessive volume change upon lithium intercalation, and therefore, the crystal structure is morphologically stable over many cycles. X-ray diffraction of the clathrate after cycling showed that crystallinity is intact, indicating that the clathrate does not collapse during reversible intercalation with lithium ions. Electrochemical potential spectroscopy obtained from the cycling data showed that there is an absence of formation of lithium-silicide, which is the product of lithium alloying with diamond cubic silicon. Type II silicon clathrate, NaxSi136, consists of silicon making up the framework structure and sodium (guest) atoms occupying the interstitial spaces. These clathrates showed very high capacities during their first intercalation cycle, in the range of 3,500 mAh/g, but then deteriorated during subsequent cycles. X-ray diffraction after one cycle showed the absence of clathrate phase and the presence of lithium-silicide, indicating the disintegration of clathrate structure. This could explain the silicon-like cycling behavior of Type II clathrates.
ContributorsRaghavan, Rahul (Author) / Chan, Candace K. (Thesis advisor) / Crozier, Peter (Committee member) / Petuskey, William T (Committee member) / Arizona State University (Publisher)
Created2013
Description
Dealloying induced stress corrosion cracking is particularly relevant in energy conversion systems (both nuclear and fossil fuel) as many failures in alloys such as austenitic stainless steel and nickel-based systems result directly from dealloying. This study provides evidence of the role of unstable dynamic fracture processes in dealloying induced stress-corrosion cracking of face-centered cubic alloys. Corrosion of such alloys often results in the formation of a brittle nanoporous layer which we hypothesize serves to nucleate a crack that owing to dynamic effects penetrates into the un-dealloyed parent phase alloy. Thus, since there is essentially a purely mechanical component of cracking, stress corrosion crack propagation rates can be significantly larger than that predicted from electrochemical parameters. The main objective of this work is to examine and test this hypothesis under conditions relevant to stress corrosion cracking. Silver-gold alloys serve as a model system for this study since hydrogen effects can be neglected on a thermodynamic basis, which allows us to focus on a single cracking mechanism. In order to study various aspects of this problem, the dynamic fracture properties of monolithic nanoporous gold (NPG) were examined in air and under electrochemical conditions relevant to stress corrosion cracking. The detailed processes associated with the crack injection phenomenon were also examined by forming dealloyed nanoporous layers of prescribed properties on un-dealloyed parent phase structures and measuring crack penetration distances. Dynamic fracture in monolithic NPG and in crack injection experiments was examined using high-speed (106 frames s-1) digital photography. The tunable set of experimental parameters included the NPG length scale (20-40 nm), thickness of the dealloyed layer (10-3000 nm) and the electrochemical potential (0.5-1.5 V). The results of crack injection experiments were characterized using the dual-beam focused ion beam/scanning electron microscopy. Together these tools allow us to very accurately examine the detailed structure and composition of dealloyed grain boundaries and compare crack injection distances to the depth of dealloying. The results of this work should provide a basis for new mathematical modeling of dealloying induced stress corrosion cracking while providing a sound physical basis for the design of new alloys that may not be susceptible to this form of cracking. Additionally, the obtained results should be of broad interest to researchers interested in the fracture properties of nano-structured materials. The findings will open up new avenues of research apart from any implications the study may have for stress corrosion cracking.
ContributorsSun, Shaofeng (Author) / Sieradzki, Karl (Thesis advisor) / Jiang, Hanqing (Committee member) / Peralta, Pedro (Committee member) / Arizona State University (Publisher)
Created2012
Description
There has been much interest in photoelectrochemical conversion of solar energy in recent years due to its potential for low-–cost, sustainable and renewable production of fuels. Despite the huge potential, there are still a number of technical barriers due to the many constraints needed in order to drive photoelectrochemical reactions such as overall water splitting and the identification of efficient and effective semiconductor materials. To this end, the search for novel semiconductors that can act as light absorbers is still needed. The copper hydroxyphosphate mineral libethenite (CHP), which has a chemical formula of Cu2(OH)PO4, has been recently shown to be active for photocatalytic degradation of methylene blue under UV-–irradiation, indicating that photo-excited electrons and holes can effectively be generated and separated in this material. However, CHP has not been well studied and many of its fundamental electrochemical and photoelectrochemical properties are still unknown. In this work, the synthesis of different morphologies of CHP using hydrothermal synthesis and precipitation methods were explored. Additionally, a preliminary investigation of the relevant fundamental characteristics such as the bandgap, flatband potential, band diagram, electrochemical and photoelectrochemical properties for CHP was performed. Better understanding of the properties of this material may lead to the development of improved catalysts and photocatalysts from natural sources.
ContributorsLi, Man (Author) / Chan, Candace K. (Thesis advisor) / O'Connell, Michael (Committee member) / Crozier, Peter (Committee member) / Arizona State University (Publisher)
Created2013
Description
The mechanical behavior of Pb-free solder alloys is important, since they must maintain mechanical integrity under thermomechanical fatigue, creep, and mechanical shock conditions. Mechanical shock, in particular, has become an increasing concern in the electronics industry, since electronic packages can be subjected to mechanical shock by mishandling during manufacture or by accidental dropping. In this study, the mechanical shock behavior of Sn and Sn-Ag-Cu alloys was systematically analyzed over the strain rate range 10-3 - 30 s-1 in bulk samples, and over 10-3 - 12 s-1 on the single solder joint level. More importantly, the influences of solder microstructure and intermetallic compounds (IMC) on mechanical shock resistance were quantified. A thorough microstructural characterization of Sn-rich alloys was conducted using synchrotron x-ray computed tomography. The three-dimensional morphology and distribution of contiguous phases and precipitates was analyzed. A multiscale approach was utilized to characterize Sn-rich phases on the microscale with x-ray tomography and focused ion beam tomography to characterize nanoscale precipitates. A high strain rate servohydraulic test system was developed in conjunction with a modified tensile specimen geometry and a high speed camera for quantifying deformation. The effect of microstructure and applied strain rate on the local strain and strain rate distributions were quantified using digital image correlation. Necking behavior was analyzed using a novel mirror fixture, and the triaxial stresses associated with necking were corrected using a self-consistent method to obtain the true stress-true strain constitutive behavior. Fracture mechanisms were quantified as a function of strain rate. Finally, the relationship between solder microstructure and intermetallic compound layer thickness with the mechanical shock resistance of Sn-3.8Ag-0.7Cu solder joints was characterized. It was found that at low strain rates the dynamic solder joint strength was controlled by the solder microstructure, while at high strain rates it was controlled by the IMC layer. The influences of solder microstructure and IMC layer thickness were then isolated using extended reflow or isothermal aging treatments. It was found that at large IMC layer thicknesses the trend described above does not hold true. The fracture mechanisms associated with the dynamic solder joint strength regimes were analyzed.
ContributorsYazzie, Kyle (Author) / Chawla, Nikhilesh (Thesis advisor) / Sane, Sandeep (Committee member) / Jiang, Hanqing (Committee member) / Krause, Stephen (Committee member) / Arizona State University (Publisher)
Created2012