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The use of solar energy to produce power has increased substantially in the past few decades. In an attempt to provide uninterrupted solar power, production plants may find themselves having to operate the systems at temperatures higher than the operational capacity of the materials used in many of their components,

The use of solar energy to produce power has increased substantially in the past few decades. In an attempt to provide uninterrupted solar power, production plants may find themselves having to operate the systems at temperatures higher than the operational capacity of the materials used in many of their components, which affects the microstructural and mechanical properties of those materials. Failures in components that have been exposed to these excessive temperatures have been observed during operations in the turbine used by AORA Solar Ltd. A particular component of interest was made of a material similar to the Ni-based superalloy Inconel 718 (IN 718), which was observed to have damage that is believed to have been initiated by Foreign Object Damage (FOD) and worsened by the high temperatures in the turbine. The potential links among the observed failure, FOD and the high temperatures of operation are investigated in this study.

IN718 is a precipitation hardened nickel superalloy with resistance to oxidation and ability to withstand high stresses over a wide range of temperatures. Several studies have been conducted to understand IN 718 tensile and fatigue properties at elevated temperatures (600- 950°C). However, this study focuses on understanding the behavior of IN718 with FOD induced by a stream of 50 μm Alumina particles at a velocity of 200 m/s. under high cycle fatigue at an elevated temperature of 1050 °C. Tensile tests were conducted for both as-received and heat treated (1050 °C in air for 8hrs) samples at room and high temperature. Fatigue tests were performed at heat treated samples at 1050 °C for samples with and without ablation. The test conditions were as similar as possible to the conditions in the AORA turbine. The results of the study provide an insight into tensile properties, fatigue properties and FOD. The results indicated a reduction in fatigue life for the samples with ablation damage, where crack nucleation occurred either at the edge or inside the ablation region and multisite cracking was observed under far field stresses that were the same than for pristine samples, which showed single cracks. Fracture surfaces indicate intergranular fracture, with the presence of secondary cracks and a lack of typical fatigue features, e.g., beach marks which was attributed to environmental effects and creep.
ContributorsShenoy, Sneha (Author) / Peralta, Pedro (Thesis advisor) / Solanki, Kiran (Committee member) / Sieradzki, Karl (Committee member) / Arizona State University (Publisher)
Created2017
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Description
Dealloying, the selective electrochemical dissolution of an active component from an alloy, often results in nanoscale bi-continuous solid/void morphologies. These structures are attracting attention for a wide range of applications including catalysis, sensing and actuation. The evolution of these nanoporous structures has been widely studied for the case at low

Dealloying, the selective electrochemical dissolution of an active component from an alloy, often results in nanoscale bi-continuous solid/void morphologies. These structures are attracting attention for a wide range of applications including catalysis, sensing and actuation. The evolution of these nanoporous structures has been widely studied for the case at low homologous temperature, TH, such as in Ag-Au, Cu-Au, Cu-Pt, etc. Since at low TH the solid-state mobility of the components is of order 10-30 cm2s-1 or less, percolation dissolution is the only mechanism available to support dealloying over technologically relevant time scales. Without the necessity of solid-state mass transport, percolation dissolution involves sharp transitions based on two key features, the parting limit and critical potential.

Dealloying under conditions of high TH, (or high intrinsic diffusivity of the more electrochemically reactive component) is considerably more complicated than at low TH. Since solid-state mass transport is available to support this process, a rich set of morphologies, including negative or void dendrites, Kirkendall voids and bi-continuous porous structures, can evolve. In order to study dealloying at high TH we have examined the behavior of Li-Sn and Li-Pb alloys. The intrinsic diffusivities of Li were measured in these alloys using electrochemical titration and time of flight measurements. Morphology evolution was studied with varying alloy composition, host dimension and imposed electrochemical conditions. Owing to diffusive transport, there is no parting limit for dealloying, however, there is a compositional threshold (pPD) as well as a critical potential for the operation of percolation dissolution and the formation of bi-continuous structures. Negative or void dendrite morphologies evolve at compositions below pPD and at large values of the applied electrochemical potential when the rate of dealloying is limited by solid-state mass transport. This process is isomorphic to dendrite formation in electrodeposition. Kirkendall voiding morphologies evolve below the critical potential over the entire range of alloy compositions.

We summarize our results by introducing dealloying morphology diagrams that we use to graphically illustrate the electrochemical conditions resulting in various morphologies that can form under conditions of low and high TH.
ContributorsGeng, Ke (Author) / Sieradzki, Karl (Thesis advisor) / Crozier, Peter (Committee member) / Chan, Candace (Committee member) / Jiao, Yang (Committee member) / Arizona State University (Publisher)
Created2017
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Description

Lithium ion batteries are quintessential components of modern life. They are used to power smart devices — phones, tablets, laptops, and are rapidly becoming major elements in the automotive industry. Demand projections for lithium are skyrocketing with production struggling to keep up pace. This drive is due mostly to the

Lithium ion batteries are quintessential components of modern life. They are used to power smart devices — phones, tablets, laptops, and are rapidly becoming major elements in the automotive industry. Demand projections for lithium are skyrocketing with production struggling to keep up pace. This drive is due mostly to the rapid adoption of electric vehicles; sales of electric vehicles in 2020 are more than double what they were only a year prior. With such staggering growth it is important to understand how lithium is sourced and what that means for the environment. Will production even be capable of meeting the demand as more industries make use of this valuable element? How will the environmental impact of lithium affect growth? This thesis attempts to answer these questions as the world looks to a decade of rapid growth for lithium ion batteries.

ContributorsMelton, John (Author) / Brian, Jennifer (Thesis director) / Karwat, Darshawn (Committee member) / Chemical Engineering Program (Contributor) / Barrett, The Honors College (Contributor)
Created2021-05
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Description
Lithium conducting garnets in the family of Li7La3Zr2O12 (LLZO) are promising lithium conductors for solid-state batteries, due to their high ionic conductivity, thermal stability, and electrochemical stability with metallic lithium. Despite these advantages, LLZO requires a large energy input to synthesize and process. Generally, LLZO is synthesized using solid-state reaction

Lithium conducting garnets in the family of Li7La3Zr2O12 (LLZO) are promising lithium conductors for solid-state batteries, due to their high ionic conductivity, thermal stability, and electrochemical stability with metallic lithium. Despite these advantages, LLZO requires a large energy input to synthesize and process. Generally, LLZO is synthesized using solid-state reaction (SSR) from oxide precursors, requiring high reaction temperatures (900-1000 °C) and producing powder with large particle sizes, necessitating high energy milling to improve sinterability. In this dissertation, two classes of advanced synthesis methods – sol-gel polymer-combustion and molten salt synthesis (MSS) – are employed to obtain LLZO submicron powders at lower temperatures. In the first case, nanopowders of LLZO are obtained in a few hours at 700 °C via a novel polymer combustion process, which can be sintered to dense electrolytes possessing ionic conductivity up to 0.67 mS cm-1 at room temperature. However, the limited throughput of this combustion process motivated the use of molten salt synthesis, wherein a salt mixture is used as a high temperature solvent, allowing faster interdiffusion of atomic species than solid-state reactions. A eutectic mixture of LiCl-KCl allows formation of submicrometer undoped, Al-doped, Ga-doped, and Ta-doped LLZO at 900 °C in 4 h, with total ionic conductivities between 0.23-0.46 mS cm-1. By using a highly basic molten salt medium, Ta-doped LLZO (LLZTO) can be obtained at temperatures as low as 550 °C, with an ionic conductivity of 0.61 mS cm-1. The formation temperature can be further reduced by using Ta-doped, La-excess pyrochlore-type lanthanum zirconate (La2Zr2O7, LZO) as a quasi-single-source precursor, which convert to LLZTO as low as 400 °C upon addition of a Li-source. Further, doped pyrochlores can be blended with a Li-source and directly sintered to a relative density up to 94.7% with high conductivity (0.53 mS cm-1). Finally, a propensity for compositional variation in LLZTO powders and sintered ceramics was observed and for the first time explored in detail. By comparing LLZTO obtained from combustion, MSS, and SSR, a correlation between increased elemental inhomogeneity and reduced ionic conductivity is observed. Implications for garnet-based solid-state batteries and strategies to mitigate elemental inhomogeneity are discussed.
ContributorsWeller, Jon Mark (Author) / Chan, Candace K (Thesis advisor) / Crozier, Peter (Committee member) / Sieradzki, Karl (Committee member) / Arizona State University (Publisher)
Created2021
Description
Current Li-ion battery technologies are limited by the low capacities of theelectrode materials and require developments to meet stringent performance demands for future energy storage devices. Electrode materials that alloy with Li, such as Si, are one of the most promising alternatives for Li-ion battery anodes due to their high capacities. Tetrel (Si,

Current Li-ion battery technologies are limited by the low capacities of theelectrode materials and require developments to meet stringent performance demands for future energy storage devices. Electrode materials that alloy with Li, such as Si, are one of the most promising alternatives for Li-ion battery anodes due to their high capacities. Tetrel (Si, Ge, Sn) clathrates are a class of host-guest crystalline structures in which Tetrel elements form a cage framework and encapsulate metal guest atoms. These structures can form with defects such as framework/guest atom substitutions and vacancies which result in a wide design space for tuning materials properties. The goal of this work is to establish structure property relationships within the context of Li-ion battery anode applications. The type I Ba 8 Al y Ge 46-y clathrates are investigated for their electrochemical reactions with Li and show high capacities indicative of alloying reactions. DFT calculations show that Li insertion into the framework vacancies is favorable, but the migration barriers are too high for room temperature diffusion. Then, guest free type I clathrates are investigated for their Li and Na migration barriers. The results show that Li migration in the clathrate frameworks have low energy barriers (0.1- 0.4 eV) which suggest the possibility for room temperature diffusion. Then, the guest free, type II Si clathrate (Na 1 Si 136 ) is synthesized and reversible Li insertion into the type II Si clathrate structure is demonstrated. Based on the reasonable capacity (230 mAh/g), low reaction voltage (0.30 V) and low volume expansion (0.21 %), the Si clathrate could be a promising insertion anode for Li-ion batteries. Next, synchrotron X-ray measurements and pair distribution function (PDF) analysis are used to investigate the lithiation pathways of Ba 8 Ge 43 , Ba 8 Al 16 Ge 30 , Ba 8 Ga 15 Sn 31 and Na 0.3 Si 136 . The results show that the Ba-clathrates undergo amorphous phase transformations which is distinct from their elemental analogues (Ge, Sn) which feature crystalline lithiation pathways. Based on the high capacities and solid-solution reaction mechanism, guest-filled clathrates could be promising precursors to form alloying anodes with novel electrochemical properties. Finally, several high temperature (300-550 °C) electrochemical synthesis methods for Na-Si and Na-Ge clathrates are demonstrated in a cell using a Na β’’-alumina solid electrolyte.
ContributorsDopilka, Andrew (Author) / Chan, Candace K (Thesis advisor) / Zhuang, Houlong (Committee member) / Peng, Xihong (Committee member) / Sieradzki, Karl (Committee member) / Arizona State University (Publisher)
Created2021