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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

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
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ABSTRACT Recent studies indicate that top-performing companies have higher-performing work environments than average companies. They receive higher scores for worker satisfaction with their overall physical work environment as well as higher effectiveness ratings for their workspaces (Gensler, 2008; Harter et al., 2003). While these studies indicate a relationship between effective

ABSTRACT Recent studies indicate that top-performing companies have higher-performing work environments than average companies. They receive higher scores for worker satisfaction with their overall physical work environment as well as higher effectiveness ratings for their workspaces (Gensler, 2008; Harter et al., 2003). While these studies indicate a relationship between effective office design and satisfaction they have not explored which specific space types may contribute to workers' overall satisfaction with their physical work environment. Therefore, the purpose of this study is to explore the relationship between workers' overall satisfaction with their physical work environments and their perception of the effectiveness of spaces designed for Conceptual Age work including learning, focusing, collaborating, and socializing tasks. This research is designed to identify which workspace types are related to workers' satisfaction with their overall work environment and which are perceived to be most and least effective. To accomplish this two primary and four secondary research questions were developed for this study. The first primary question considers overall workers' satisfaction with their overall physical work environments (offices, workstations, hallways, common areas, reception, waiting areas, etc.) related to the effective use of work mode workspaces (learning, focusing, collaborating, socializing). The second primary research question was developed to identify which of the four work mode space types had the greatest and least relationship to workers' satisfaction with the overall physical work environment. Secondary research questions were developed to address workers' perceptions of effectiveness of each space type. This research project used data from a previous study collected from 2007 to 2012. Responses were from all staff levels of US office-based office workers and resulted in a blind sample of approximately 48,000 respondents. The data for this study were developed from SPSS data reports that included descriptive data and Pearson correlations. Findings were developed from those statistics using coefficient of determination.
ContributorsHarmon-Vaughan, Elizabeth (Author) / Kroelinger, Michael D. (Thesis advisor) / Bernardi, Jose (Committee member) / Ozel, Filiz (Committee member) / Arizona State University (Publisher)
Created2013
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Description
The electrode-electrolyte interface in electrochemical environments involves the understanding of complex processes relevant for all electrochemical applications. Some of these processes include electronic structure, charge storage, charge transfer, solvent dynamics and structure and surface adsorption. In order to engineer electrochemical systems, no matter the function, requires fundamental intuition of all

The electrode-electrolyte interface in electrochemical environments involves the understanding of complex processes relevant for all electrochemical applications. Some of these processes include electronic structure, charge storage, charge transfer, solvent dynamics and structure and surface adsorption. In order to engineer electrochemical systems, no matter the function, requires fundamental intuition of all the processes at the interface. The following work presents different systems in which the electrode-electrolyte interface is highly important. The first is a charge storage electrode utilizing percolation theory to develop an electrode architecture producing high capacities. This is followed by Zn deposition in an ionic liquid in which the deposition morphology is highly dependant on the charge transfer and surface adsorption at the interface. Electrode Architecture: A three-dimensional manganese oxide supercapacitor electrode architecture is synthesized by leveraging percolation theory to develop a hierarchically designed tri-continuous percolated network. The three percolated phases include a faradaically-active material, electrically conductive material and pore-former templated void space. The micropores create pathways for ionic conductivity, while the nanoscale electrically conducting phase provides both bulk conductivity and local electron transfer with the electrochemically active phase. Zn Electrodeposition: Zn redox in air and water stable N-ethyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide, [C2nmm][NTf2] is presented. Under various conditions, characterization of overpotential, kinetics and diffusion of Zn species and morphological evolution as a function of overpotential and Zn concentration are analyzed. The surface stress evolution during Zn deposition is examined where grain size and texturing play significant rolls in compressive stress generation. Morphological repeatability in the ILs led to a novel study of purity in ionic liquids where it is found that surface adsorption of residual amine and chloride from the organic synthesis affect growth characteristics. The drivers of this work are to understand the processes occurring at the electrode-electrolyte interface and with that knowledge, engineer systems yielding optimal performance. With this in mind, the design of a bulk supercapacitor electrode architecture with excellent composite specific capacitances, as well as develop conditions producing ideal Zn deposition morphologies was completed.
ContributorsEngstrom, Erika (Author) / Friesen, Cody (Thesis advisor) / Buttry, Daniel (Committee member) / Sieradzki, Karl (Committee member) / Arizona State University (Publisher)
Created2011
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Description
This research focuses on the stress and structure evolution observed in-situ during the earliest stages of thin film growth in Cu on Au(111)-reconstruction. For the research, an ultra high vacuum-scanning tunneling microscopy (UHV-STM) system was modified to have the additional capabilities of in-situ deposition and in-situ stress evolution monitoring. The

This research focuses on the stress and structure evolution observed in-situ during the earliest stages of thin film growth in Cu on Au(111)-reconstruction. For the research, an ultra high vacuum-scanning tunneling microscopy (UHV-STM) system was modified to have the additional capabilities of in-situ deposition and in-situ stress evolution monitoring. The design and fabrication processes for the modifications are explained in detail. The deposition source enabled imaging during the deposition of Cu thin films, while also being columnar enough to avoid negatively impacting the function of the microscope. It was found that the stress-induced changes in piezo voltage occurred over a substantially longer time scale and larger piezo scale than used during imaging, allowing for the deconvolution of the two sources of piezo voltage change. The intrinsic stress evolution observed at the onset of Cu growth was tensile in character and reached a maximum of 0.19 N/m at approximately 0.8ML, with an average tensile slope of 1.0GPa. As the film thickness increased beyond 0.8 ML, the stress became less tensile as the observation of disordered stripe and trigon patterns of misfit dislocations began to appear. The transport of atoms from the surface of enlarged Cu islands into the strained layer played an important role in this stage, because they effectively reduce the activation barrier for the formation of the observed surface structures. A rich array of structures were observed in the work presented here including stripe, disordered stripe and trigon patterns co-existing in a single Cu layer. Heteroepitaxial systems in existing literature showed a uniform structure in the single layer. The non-uniform structures in the single layer of this work may be attributed to the room temperature Cu growth, which can kinetically limit uniform pattern formation. The development of the UHV-STM system with additional capabilities for this work is expected to contribute to research for the stress and structure relationships of many other heteroepitaxial systems.
ContributorsNah, Jungwoo (Author) / Friesen, Cody (Thesis advisor) / Sieradzki, Karl (Committee member) / Bennett, Peter (Committee member) / Arizona State University (Publisher)
Created2012
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Description
Two-dimensional transition metal dichalcogenides (TMDCs) such as

molybdenum disulfide (MoS2), tungsten disulfide (WS2), molybdenum diselenide (MoSe2) and tungsten diselenide (WSe2) are attractive for use in biotechnology, optical and electronics devices due to their promising and tunable electrical, optical and chemical properties. To fulfill the variety of requirements for different applications, chemical

Two-dimensional transition metal dichalcogenides (TMDCs) such as

molybdenum disulfide (MoS2), tungsten disulfide (WS2), molybdenum diselenide (MoSe2) and tungsten diselenide (WSe2) are attractive for use in biotechnology, optical and electronics devices due to their promising and tunable electrical, optical and chemical properties. To fulfill the variety of requirements for different applications, chemical treatment methods are developed to tune their properties. In this dissertation, plasma treatment, chemical doping and functionalization methods have been applied to tune the properties of TMDCs. First, plasma treatment of TMDCs results in doping and generation of defects, as well as the synthesis of transition metal oxides (TMOs) with rolled layers that have increased surface-to-volume ratio and are promising for electrochemical applications. Second, chemical functionalization is another powerful approach for tuning the properties of TMDCs for use in many applications. To covalently functionalize the basal planes of TMDCs, previous reports begin with harsh treatments like lithium intercalation that disrupt the structure and lead to a phase transformation from semiconducting to metallic. Instead, this work demonstrates the direct covalent functionalization of semiconducting MoS2 using aryl diazonium salts without lithium treatments. It preserves the structure and semiconducting nature of MoS2, results in covalent C-S bonds on basal planes and enables different functional groups to be tethered to the MoS2 surface via the diazonium salts. The attachment of fluorescent proteins has been used as a demonstration and it suggests future applications in biology and biosensing. The effects of the covalent functionalization on the electronic transport properties of MoS2 were then studied using field effect transistor (FET) devices.
ContributorsChu, Ximo (Author) / Wang, Qing Hua (Thesis advisor) / Sieradzki, Karl (Committee member) / Green, Alexander (Committee member) / Chan, Candace (Committee member) / Arizona State University (Publisher)
Created2018
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Description
The 21st-century professional or knowledge worker spends much of the working day engaging others through electronic communication. The modes of communication available to knowledge workers have rapidly increased due to computerized technology advances: conference and video calls, instant messaging, e-mail, social media, podcasts, audio books, webinars, and much more. Professionals

The 21st-century professional or knowledge worker spends much of the working day engaging others through electronic communication. The modes of communication available to knowledge workers have rapidly increased due to computerized technology advances: conference and video calls, instant messaging, e-mail, social media, podcasts, audio books, webinars, and much more. Professionals who think for a living express feelings of stress about their ability to respond and fear missing critical tasks or information as they attempt to wade through all the electronic communication that floods their inboxes. Although many electronic communication tools compete for the attention of the contemporary knowledge worker, most professionals use an electronic personal information management (PIM) system, more commonly known as an e-mail application and often the ubiquitous Microsoft Outlook program. The aim of this research was to provide knowledge workers with solutions to manage the influx of electronic communication that arrives daily by studying the workers in their working environment. This dissertation represents a quest to understand the current strategies knowledge workers use to manage their e-mail, and if modification of e-mail management strategies can have an impact on productivity and stress levels for these professionals. Today’s knowledge workers rarely work entirely alone, justifying the importance of also exploring methods to improve electronic communications within teams.
ContributorsCounts, Virginia (Author) / Parrish, Kristen (Thesis advisor) / Allenby, Braden (Thesis advisor) / Landis, Amy (Committee member) / Cooke, Nancy J. (Committee member) / Arizona State University (Publisher)
Created2018
Description
Nanocrystalline (nc) thin films exhibit a wide range of enhanced mechanical properties compared to their coarse-grained counterparts. Furthermore, the mechanical behavior and microstructure of nc films is intimately related. Thus, precise control of the size, aspect ratio and spatial distribution of grains can enable the synthesis of thin films

Nanocrystalline (nc) thin films exhibit a wide range of enhanced mechanical properties compared to their coarse-grained counterparts. Furthermore, the mechanical behavior and microstructure of nc films is intimately related. Thus, precise control of the size, aspect ratio and spatial distribution of grains can enable the synthesis of thin films with exceptional mechanical properties. However, conventional bottom-up techniques for synthesizing thin films are incapable of achieving the microstructural control required to explicitly tune their properties. This dissertation focuses on developing a novel technique to synthesize metallic alloy thin films with precisely controlled microstructures and subsequently characterizing their mechanical properties using in situ transmission electron microscopy (TEM). Control over the grain size and distribution was achieved by controlling the recrystallization process of amorphous films by the use of thin crystalline seed layers. The novel technique was used to manipulate the microstructure of structural (TiAl) and functional (NiTi) thin films thereby exhibiting its capability and versatility. Following the synthesis of thin films with tailored microstructures, in situ TEM techniques were employed to probe their mechanical properties. Firstly, a novel technique was developed to measure local atomic level elastic strains in metallic glass thin films during in situ TEM straining. This technique was used to detect structural changes and anelastic deformation in metallic glass thin films. Finally, as the electron beam (e-beam) in TEMs is known to cause radiation damage to specimen, systematic experiments were carried out to quantify the effect of the e-beam on the stress-strain response of nc metals. Experiments conducted on Al and Au films revealed that the e-beam enhances dislocation activity leading to stress relaxation.
ContributorsSarkar, Rohit (Author) / Rajagopalan, Jagannathan (Thesis advisor) / Peralta, Pedro (Committee member) / Sieradzki, Karl (Committee member) / Crozier, Peter (Committee member) / Arizona State University (Publisher)
Created2017
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Description
Traditionally nanoporous gold is created by selective dissolution of silver or copper from a binary silver-gold or copper-gold alloy. These alloys serve as prototypical model systems for a phenomenon referred to as stress-corrosion cracking. Stress-corrosion cracking is the brittle failure of a normally ductile material occurring in a

Traditionally nanoporous gold is created by selective dissolution of silver or copper from a binary silver-gold or copper-gold alloy. These alloys serve as prototypical model systems for a phenomenon referred to as stress-corrosion cracking. Stress-corrosion cracking is the brittle failure of a normally ductile material occurring in a corrosive environment under a tensile stress. Silver-gold can experience this type of brittle fracture for a range of compositions. The corrosion process in this alloy results in a bicontinuous nanoscale morphology composed of gold-rich ligaments and voids often referred to as nanoporous gold. Experiments have shown that monolithic nanoporous gold can sustain high speed cracks which can then be injected into parent-phase alloy. This work compares nanoporous gold created from ordered and disordered copper-gold using digital image analysis and electron backscatter diffraction. Nanoporous gold from both disordered copper-gold and silver-gold, and ordered copper-gold show that grain orientation and shape remain largely unchanged by the dealloying process. Comparing the morphology of the nanoporous gold from ordered and disordered copper-gold with digital image analysis, minimal differences are found between the two and it is concluded that they are not statistically significant. This reveals the robust nature of nanoporous gold morphology against small variations in surface diffusion and parent-phase crystal structure.
Then the corrosion penetration down the grain boundary is compared to the depth of crack injections in polycrystal silver-gold. Based on statistical comparison, the crack-injections penetrate into the parent-phase grain boundary beyond the corrosion-induced porosity. To compare crack injections to stress-corrosion cracking, single crystal silver-gold samples are employed. Due to the cleavage-like nature of the fracture surfaces, electron backscatter diffraction is possible and employed to compare the crystallography of stress-corrosion crack surfaces and crack-injection surfaces. From the crystallographic similarities of these fracture surfaces, it is concluded that stress-corrosion can occur via a series of crack-injection events. This relationship between crack injections and stress corrosion cracking is further examined using electrochemical data from polycrystal silver-gold samples during stress-corrosion cracking. The results support the idea that crack injection is a mechanism for stress-corrosion cracking.
ContributorsKarasz, Erin (Author) / Sieradzki, Karl (Thesis advisor) / Chawla, Nikhilesh (Committee member) / Peralta, Pedro (Committee member) / Rajagopalan, Jagannathan (Committee member) / Arizona State University (Publisher)
Created2020