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Description
Metal hydride materials have been intensively studied for hydrogen storage applications. In addition to potential hydrogen economy applications, metal hydrides offer a wide variety of other interesting properties. For example, hydrogen-dominant materials, which are hydrides with the highest hydrogen content for a particular metal/semimetal composition, are predicted to display high-temperature superconductivity. On the other side of the spectrum are hydrides with small amounts of hydrogen (0.1 - 1 at.%) that are investigated as viable magnetic, thermoelectric or semiconducting materials. Research of metal hydride materials is generally important to gain fundamental understanding of metal-hydrogen interactions in materials. Hydrogenation of Zintl phases, which are defined as compounds between an active metal (alkali, alkaline earth, rare earth) and a p-block metal/semimetal, were attempted by a hot sintering method utilizing an autoclave loaded with gaseous hydrogen (< 9 MPa). Hydride formation competes with oxidative decomposition of a Zintl phase. The oxidative decomposition, which leads to a mixture of binary active metal hydride and p-block element, was observed for investigated aluminum (Al) and gallium (Ga) containing Zintl phases. However, a new phase Li2Al was discovered when Zintl phase precursors were synthesized. Using the single crystal x-ray diffraction (SCXRD), the Li2Al was found to crystallize in an orthorhombic unit cell (Cmcm) with the lattice parameters a = 4.6404(8) Å, b = 9.719(2) Å, and c = 4.4764(8) Å. Increased demand for materials with improved properties necessitates the exploration of alternative synthesis methods. Conventional metal hydride synthesis methods, like ball-milling and autoclave technique, are not responding to the demands of finding new materials. A viable alternative synthesis method is the application of high pressure for the preparation of hydrogen-dominant materials. Extreme pressures in the gigapascal ranges can open access to new metal hydrides with novel structures and properties, because of the drastically increased chemical potential of hydrogen. Pressures up to 10 GPa can be easily achieved using the multi-anvil (MA) hydrogenations while maintaining sufficient sample volume for structure and property characterization. Gigapascal MA hydrogenations using ammonia borane (BH3NH3) as an internal hydrogen source were employed in the search for new hydrogen-dominant materials. Ammonia borane has high gravimetric volume of hydrogen, and additionally the thermally activated decomposition at high pressures lead to a complete hydrogen release at reasonably low temperature. These properties make ammonia borane a desired hydrogen source material. The missing member Li2PtH6 of the series of A2PtH6 compounds (A = Na to Cs) was accessed by employing MA technique. As the known heavier analogs, the Li2PtH6 also crystallizes in a cubic K2PtCl6-type structure with a cell edge length of 6.7681(3) Å. Further gigapascal hydrogenations afforded the compounds K2SiH6 and Rb2SiH6 which are isostructural to Li2PtH6. The cubic K2SiH6 and Rb2SiH6 are built from unique hypervalent SiH62- entities with the lattice parameters of 7.8425(9) and 8.1572(4) Å, respectively. Spectroscopic analysis of hexasilicides confirmed the presence of hypervalent bonding. The Si-H stretching frequencies at 1550 cm-1 appeared considerably decreased in comparison with a normal-valent (2e2c) Si-H stretching frequencies in SiH4 at around 2200 cm-1. However, the observed stretching modes in hypervalent hexasilicides were in a reasonable agreement with Ph3SiH2- (1520 cm-1) where the hydrogen has the axial (3e4c bonded) position in the trigoal bipyramidal environment.
ContributorsPuhakainen, Kati (Author) / Häussermann, Ulrich (Thesis advisor) / Seo, Dong (Thesis advisor) / Kouvetakis, John (Committee member) / Wolf, George (Committee member) / Arizona State University (Publisher)
Created2013
Description
Fibromyalgia (FM) is a chronic pain condition characterized by debilitating fatigue. This study examined the dynamic relation between interpersonal enjoyment and fatigue in 102 partnered and 74 unpartnered women with FM. Participants provided three daily ratings for 21 days. They rated their fatigue in late morning and at the end of the day. Both partnered and unpartnered participants reported their interpersonal enjoyment in the combined familial, friendship, and work domains (COMBINED domain) in the afternoon. Additionally, partnered participants reported their interpersonal enjoyment in the spousal domain. The study was guided by three hypotheses at the within-person level, based on daily diaries: (1) elevated late morning fatigue would predict diminished afternoon interpersonal enjoyment; (2) diminished interpersonal enjoyment would predict elevated end-of-day fatigue; (3) interpersonal enjoyment would mediate the late morning to end-of-day fatigue relationship. In cross-level models, the study explored whether individual differences (between-person) in late morning fatigue and afternoon interpersonal enjoyment would moderate within-person relations from late morning fatigue to afternoon interpersonal enjoyment, and from afternoon interpersonal enjoyment to end-of-day fatigue. Furthermore, it explored whether the hypothesized relationships at the within-person level would also emerge at the between-person level (between-person mediation models). Multilevel structural equation modeling and multilevel modeling were employed for model testing, separately for partnered and unpartnered participants. Within-person mediation models supported that on high fatigue mornings, afternoon interpersonal enjoyment was dampened in the spousal and combined domains in partnered and unpartnered samples. Moreover, low afternoon interpersonal enjoyment in both the spousal and combined domains predicted elevated end-of-day fatigue. Afternoon interpersonal enjoyment mediated the relationship of late morning to end-of-day fatigue in the combined domain but in not the spousal domain. Cross-level moderation analyses showed that individual differences in afternoon spousal enjoyment moderated the day-to-day relation between afternoon spousal enjoyment and end-of-day fatigue. Finally, the mediational chain was not observed at the between-person level. These findings suggest that preserving interpersonal enjoyment in non-spousal relations limits within-day increases in FM fatigue. They highlight the importance of examining domain-specificity in interpersonal enjoyment when studying fatigue, and suggest that targeting enjoyment in social relations may improve the efficacy of existing treatments.
ContributorsYeung, Wan (Author) / Aiken, Leona S. (Thesis advisor) / Davis, Mary C. (Thesis advisor) / Mackinnon, David P (Committee member) / Zautra, Alex J (Committee member) / Arizona State University (Publisher)
Created2013
Description
Past literature has indicated that the majority of people with alcohol problems never seek treatment and that this is especially true of women. Relatively few studies have investigated how different types of alcohol-related consequences longitudinally predict men and women's perceived need for treatment and their utilization of treatment services. The current study sought to expand the literature by examining whether gender moderates the links between four frequently endorsed types of consequences and perceived need for or actual utilization of treatment. Two-hundred thirty-seven adults ages 21-36 completed a battery of questionnaires at two time points five years apart. Results indicated that there were four broad types of consequences endorsed by both men and women. Multiple-group models and Wald chi square tests indicated that there were no significant relationships between consequences and treatment outcomes. No gender moderation was found but post-hoc power analyses indicated that the study was underpowered to detect moderation. Researchers need to continue to study factors that predict utilization of alcohol treatment services and the process of recovery so that treatment providers can better address the needs of people with alcohol-related consequences in the areas of referral procedures, clinical assessment, and treatment service provision and planning.
ContributorsBeltran Gonzalez, Iris (Author) / Chassin, Laurie (Thesis advisor) / Tein, Jenn-Yun (Committee member) / Corbin, William (Committee member) / Barrera, Jr., Manuel (Committee member) / Arizona State University (Publisher)
Created2013
Description
Juvenile offenders suffer from substance use disorders at higher rates than adolescents in the general public. Substance use disorders also predict an increased risk for re-offending. Therefore, it is important that these juveniles, in particular, receive the appropriate substance use disorder treatment. The present study used logistic regression to test whether race/ethnicity would moderate the match between substance use disorder diagnosis and the receipt of a substance use disorder related service in a sample of male, serious juvenile offenders. Results showed that among those with a substance use disorder diagnosis, there were no race/ethnicity differences in the receipt of the appropriate service. However, among those without a substance use disorder diagnosis, non-Hispanic Caucasians were more likely to receive substance use service than were Hispanics or African-Americans. Post-hoc analyses revealed that when using a broader definition of substance use problems, significant differences by race/ethnicity in the prediction of service receipt were only observed at low levels of substance use problems. These findings shed light on how race/ethnicity may play a role in the recommendation of substance use disorder services in the juvenile justice system.
ContributorsMansion, Andre (Author) / Chassin, Laurie (Thesis advisor) / Dishion, Thomas (Committee member) / Knight, George (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
Accumulating evidence implicates exposure to adverse childhood experiences in the development of hypocortisolism in the long-term, and researchers are increasingly examining individual-level mechanisms that may underlie, exacerbate or attenuate this relation among at-risk populations. The current study takes a developmentally and theoretically informed approach to examining episodic childhood stressors, inherent and voluntary self-regulation, and physiological reactivity among a longitudinal sample of youth who experienced parental divorce. Participants were drawn from a larger randomized controlled trial of a preventive intervention for children of divorce between the ages of 9 and 12. The current sample included 159 young adults (mean age = 25.5 years; 53% male; 94% Caucasian) who participated in six waves of data collection, including a 15-year follow-up study. Participants reported on exposure to negative life events (four times over a 9-month period) during childhood, and mothers rated child temperament. Six years later, youth reported on the use of active and avoidant coping strategies, and 15 years later, they participated in a standardized psychosocial stress task and provided salivary cortisol samples prior to and following the task. Path analyses within a structural equation framework revealed that a multiple mediation model best fit the data. It was found that children with better mother-rated self-regulation (i.e. low impulsivity, low negative emotionality, and high attentional focus) exhibited lower total cortisol output 15 years later. In addition, greater self-regulation in childhood predicted greater use of active coping in adolescence, whereas a greater number of negative life events predicted increased use of avoidant coping in adolescence. Finally, a greater number of negative events in childhood predicted marginally lower total cortisol output, and higher levels of active coping in adolescence were associated with greater total cortisol output in young adulthood. Findings suggest that children of divorce who exhibit better self-regulation evidence lower cortisol output during a standardized psychosocial stress task relative to those who have higher impulsivity, lower attentional focus, and/or higher negative emotionality. The conceptual significance of the current findings, including the lack of evidence for hypothesized relations, methodological issues that arose, and issues in need of future research are discussed.
ContributorsHagan, Melissa (Author) / Luecken, Linda (Thesis advisor) / MacKinnon, David (Committee member) / Wolchik, Sharlene (Committee member) / Doane, Leah (Committee member) / Arizona State University (Publisher)
Created2013
Description
The alkali activation of aluminosilicate materials as binder systems derived from industrial byproducts have been extensively studied due to the advantages they offer in terms enhanced material properties, while increasing sustainability by the reuse of industrial waste and byproducts and reducing the adverse impacts of OPC production. Fly ash and ground granulated blast furnace slag are commonly used for their content of soluble silica and aluminate species that can undergo dissolution, polymerization with the alkali, condensation on particle surfaces and solidification. The following topics are the focus of this thesis: (i) the use of microwave assisted thermal processing, in addition to heat-curing as a means of alkali activation and (ii) the relative effects of alkali cations (K or Na) in the activator (powder activators) on the mechanical properties and chemical structure of these systems. Unsuitable curing conditions instigate carbonation, which in turn lowers the pH of the system causing significant reductions in the rate of fly ash activation and mechanical strength development. This study explores the effects of sealing the samples during the curing process, which effectively traps the free water in the system, and allows for increased aluminosilicate activation. The use of microwave-curing in lieu of thermal-curing is also studied in order to reduce energy consumption and for its ability to provide fast volumetric heating. Potassium-based powder activators dry blended into the slag binder system is shown to be effective in obtaining very high compressive strengths under moist curing conditions (greater than 70 MPa), whereas sodium-based powder activation is much weaker (around 25 MPa). Compressive strength decreases when fly ash is introduced into the system. Isothermal calorimetry is used to evaluate the early hydration process, and to understand the reaction kinetics of the alkali powder activated systems. A qualitative evidence of the alkali-hydroxide concentration of the paste pore solution through the use of electrical conductivity measurements is also presented, with the results indicating the ion concentration of alkali is more prevalent in the pore solution of potassium-based systems. The use of advanced spectroscopic and thermal analysis techniques to distinguish the influence of studied parameters is also discussed.
ContributorsChowdhury, Ussala (Author) / Neithalath, Narayanan (Thesis advisor) / Rajan, Subramanium D. (Committee member) / Mobasher, Barzin (Committee member) / Arizona State University (Publisher)
Created2013
Description
The thesis studies new methods to fabricate optoelectronic Ge1-ySny/Si(100) alloys and investigate their photoluminescence (PL) properties for possible applications in Si-based photonics including IR lasers. The work initially investigated the origin of the difference between the PL spectrum of bulk Ge, dominated by indirect gap emission, and the PL spectrum of Ge-on-Si films, dominated by direct gap emission. It was found that the difference is due to the supression of self-absorption effects in Ge films, combined with a deviation from quasi-equilibrium conditions in the conduction band of undoped films. The latter is confirmed by a model suggesting that the deviation is caused by the shorter recombination lifetime in the films relative to bulk Ge. The knowledge acquired from this work was then utilized to study the PL properties of n-type Ge1-ySny/Si (y=0.004-0.04) samples grown via chemical vapor deposition of Ge2H6/SnD4/P(GeH3)3. It was found that the emission intensity (I) of these samples is at least 10x stronger than observed in un-doped counterparts and that the Idir/Iind ratio of direct over indirect gap emission increases for high-Sn contents due to the reduced gamma-L valley separation, as expected. Next the PL investigation was expanded to samples with y=0.05-0.09 grown via a new method using the more reactive Ge3H8 in place of Ge2H6. Optical quality, 1-um thick Ge1-ySny/Si(100) layers were produced using Ge3H10/SnD4 and found to exhibit strong, tunable PL near the threshold of the direct-indirect bandgap crossover. A byproduct of this study was the development of an enhanced process to produce Ge3H8, Ge4H10, and Ge5H12 analogs for application in ultra-low temperature deposition of Group-IV semiconductors. The thesis also studies synthesis routes of an entirely new class of semiconductor compounds and alloys described by Si5-2y(III-V)y (III=Al, V= As, P) comprising of specifically designed diamond-like structures based on a Si parent lattice incorporating isolated III-V units. The common theme of the two thesis topics is the development of new mono-crystalline materials on ubiquitous silicon platforms with the objective of enhancing the optoelectronic performance of Si and Ge semiconductors, potentially leading to the design of next generation optical devices including lasers, detectors and solar cells.
ContributorsGrzybowski, Gordon (Author) / Kouvetakis, John (Thesis advisor) / Chizmeshya, Andrew (Committee member) / Menéndez, Jose (Committee member) / Arizona State University (Publisher)
Created2013
Description
Nitrate is the most prevalent water pollutant limiting the use of groundwater as a potable water source. The overarching goal of this dissertation was to leverage advances in nanotechnology to improve nitrate photocatalysis and transition treatment to the full-scale. The research objectives were to (1) examine commercial and synthesized photocatalysts, (2) determine the effect of water quality parameters (e.g., pH), (3) conduct responsible engineering by ensuring detection methods were in place for novel materials, and (4) develop a conceptual framework for designing nitrate-specific photocatalysts. The key issues for implementing photocatalysis for nitrate drinking water treatment were efficient nitrate removal at neutral pH and by-product selectivity toward nitrogen gases, rather than by-products that pose a human health concern (e.g., nitrite). Photocatalytic nitrate reduction was found to follow a series of proton-coupled electron transfers. The nitrate reduction rate was limited by the electron-hole recombination rate, and the addition of an electron donor (e.g., formate) was necessary to reduce the recombination rate and achieve efficient nitrate removal. Nano-sized photocatalysts with high surface areas mitigated the negative effects of competing aqueous anions. The key water quality parameter impacting by-product selectivity was pH. For pH < 4, the by-product selectivity was mostly N-gas with some NH4+, but this shifted to NO2- above pH = 4, which suggests the need for proton localization to move beyond NO2-. Co-catalysts that form a Schottky barrier, allowing for localization of electrons, were best for nitrate reduction. Silver was optimal in heterogeneous systems because of its ability to improve nitrate reduction activity and N-gas by-product selectivity, and graphene was optimal in two-electrode systems because of its ability to shuttle electrons to the working electrode. "Environmentally responsible use of nanomaterials" is to ensure that detection methods are in place for the nanomaterials tested. While methods exist for the metals and metal oxides examined, there are currently none for carbon nanotubes (CNTs) and graphene. Acknowledging that risk assessment encompasses dose-response and exposure, new analytical methods were developed for extracting and detecting CNTs and graphene in complex organic environmental (e.g., urban air) and biological matrices (e.g. rat lungs).
ContributorsDoudrick, Kyle (Author) / Westerhoff, Paul (Thesis advisor) / Halden, Rolf (Committee member) / Hristovski, Kiril (Committee member) / Arizona State University (Publisher)
Created2013
Description
This study examined the relationship that gender in interaction with interpersonal problem type has with outcome in psychotherapy. A sample of 200 individuals, who sought psychotherapy at a counselor training facility, completed the Outcome Questionnaire-45(OQ-45) and the reduced version of the Inventory of Interpersonal Problems (IIP-32). This study was aimed at examining whether gender (male and female), was related to treatment outcome, and whether this relationship was moderated by two interpersonal distress dimensions: dominance and affiliation. A hierarchical regression analyses was performed and indicated that gender did not predict psychotherapy treatment outcome, and neither dominance nor affiliation were moderators of the relationship between gender and outcome in psychotherapy.
ContributorsHoffmann, Nicole (Author) / Tracey, Terence (Thesis advisor) / Kinnier, Richard (Committee member) / Homer, Judith (Committee member) / Arizona State University (Publisher)
Created2013