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- Genre: Doctoral Dissertation
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
This qualitative, action research study examines how teacher-writers' identities are constructed through the practice of revision in an extra-curriculum writing group. The writing group was designed to support the teacher-writers as they revised classroom research projects for submission for a scholarly journal. Using discourse analysis, the researcher explores how the teacher-writers' identities are constructed in the contested spaces of revision. This exploration focuses on contested issues that invariably emerge in a dynamic binary of reader/writer, issues of authority, ownership, and unstable reader and writer identities. By negotiating these contested spaces--these contact zones--the teacher-writers construct opportunities to flex their rhetorical agency. Through rhetorical agency, the teacher-writers shift their discoursal identities by discarding and acquiring a variety of discourses. As a result, the practice of revision constructs the teacher-writers identities as hybrid, as consisting of self and other.
ContributorsClark-Oates, Angela (Author) / Smith, Karen (Thesis advisor) / Roen, Duane (Thesis advisor) / Fischman, Gustavo (Committee member) / Early, Jessica (Committee member) / Arizona State University (Publisher)
Created2013
Description
Using experience, observations, data, current research, and writings in the field of volunteer management, it was determined there was a need to study the effects of leadership/management practices on the productivity outcomes of a volunteer construction workforce. A simple wood bench that would be tiled and painted was designed to test the areas of Time, Waste, Quality, Safety, and Satisfaction of different volunteer groups. The challenge was bolstered by giving the teams no power tools and limited available resources. A simple design of experiment model was used to test highs and lows in the three management techniques of Instruction, Help, and Encouragement. Each scenario was tested multiple times. Data was collected, normalized and analyzed using statistical analysis software. A few significant findings were discovered. The first; the research showed that there was no significant correlation between the management practices of the leader and the satisfaction of the volunteers. The second; the research also showed when further analyzed into specific realistic scenarios that the organizations would be better to focus on high amounts of Help and Encouragement in order to maximize the productivity of their volunteer construction workforce. This is significant as it allows NPO's and governments to focus their attention where best suited to produce results. The results were shared and the study was further validated as "significant" by conducting interviews with experts in the construction nonprofit sector.
ContributorsPrigge, Diedrich (Author) / Sullivan, Kenneth (Thesis advisor) / Wiezel, Avi (Committee member) / Badger, William (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
In this mixed-methods study, I examined the relationship between professional development based on the Common Core State Standards for Mathematics and teacher knowledge, classroom practice, and student learning. Participants were randomly assigned to experimental and control groups. The 50-hour professional development treatment was administered to the treatment group during one semester, and then a follow-up replication treatment was administered to the control group during the subsequent semester. Results revealed significant differences in teacher knowledge as a result of the treatment using two instruments. The Learning Mathematics for Teaching scales were used to detect changes in mathematical knowledge for teaching, and an online sorting task was used to detect changes in teachers' knowledge of their standards. Results also indicated differences in classroom practice between pairs of matched teachers selected to participate in classroom observations and interviews. No statistical difference was detected between the groups' student assessment scores using the district's benchmark assessment system. This efficacy study contributes to the literature in two ways. First, it provides an evidence base for a professional development model designed to promote effective implementation of the Common Core State Standards for Mathematics. Second, it addresses ways to impact and measure teachers' knowledge of curriculum in addition to their mathematical content knowledge. The treatment was designed to focus on knowledge of curriculum, but it also successfully impacted teachers' specialized content knowledge, knowledge of content and students, and knowledge of content and teaching.
ContributorsRimbey, Kimberly A (Author) / Middleton, James A. (Thesis advisor) / Sloane, Finbarr (Committee member) / Atkinson, Robert K (Committee member) / Arizona State University (Publisher)
Created2013
Description
The purpose of this study was to investigate critical literacy practices in two prehistoric exhibits in a natural history museum. Bourdieu's habitus and Bakhtin's dialogism served as theoretical frames to collect and analyze data. Data were collected and triangulated using field notes, interview transcriptions, archives, and other data sources to critically scrutinize textual meaning and participant responses. Spradley's (1979) domain analysis was used to sort and categorize data in the early stage. Glaser and Strauss's (1967) constant comparative method was used to code data. My major findings were that museum texts within this context represent embedded beliefs and values that were interwoven with curators` habitus, tastes and capital, as well as institutional policies. The texts in the two Hohokam exhibits endorse a certain viewpoint of learning. Teachers and the public were not aware of the communicative role that the museum played in the society. In addition, museum literacy/ies were still practiced in a fundamental way as current practices in the classroom, which may not support the development of critical literacy. In conclusion, the very goal for critical museum literacy is to help students and teachers develop intellectual strategies to read the word and the world in informal learning environments.
ContributorsLiang, Sheau-yann (Author) / Mccarty, Teresa (Thesis advisor) / Marsh, Josephine (Committee member) / Blumenfeld-Jones, Donald (Committee member) / Welsh, Peter (Committee member) / Arizona State University (Publisher)
Created2013
Description
An integral part of teacher development are teacher observations. Many teachers are observed once or twice a year to evaluate their performance and hold them accountable for meeting standards. Instructional coaches, however, observe and work with teachers to help them reflect on their performance, with the goal of improving their practice. Video-based evidence has long been used in connection with teacher reflection and as the technology necessary to record video has become more readily available, video recordings have found an increasing presence in teacher observations. In addition, more and more schools are turning to mobile technology to help record evidence during teacher observations. Several mobile applications have been developed, which are designed to help instructional coaches, administrators, and teachers make the most of teacher observations. This study looked at the use of the DataCapture mobile application to record video-based evidence in teacher observations as part of an instructional coaching program in a large public school district in the Southwestern United States. Six instructional coaches and two teachers participated in interviews at the end of the study period. Additional data was collected from the DataCapture mobile application and from a survey of instructional coaches conducted by the school district in connection with its Title I programs. Results show that instructional coaches feel that using video-based evidence for teacher reflection is effective in a number of ways. Teachers who have experienced seeing themselves on video also felt that video-based evidence is effective at improving teacher reflection, while teachers who have not yet experienced seeing themselves on video displayed extreme apprehensiveness about being video recorded in the classroom. Instructional coaches felt the DataCapture mobile application was beneficial in teacher evaluation, but there were several issues that impacted the use of the mobile application and video-based evidence, including logistics, time requirements, and administrative support. The discussion focuses on recommendations for successfully using video-based evidence in an instructional coaching context, as well as some suggestions for other researchers attempting to study how video-based evidence impacts teachers' ability to reflect on their own teaching.
ContributorsShewell, Justin Reed (Author) / Bitter, Gary (Thesis advisor) / Dawson, Edwin (Committee member) / Blair, Heidi (Committee member) / Arizona State University (Publisher)
Created2013
Description
Growing popularity of alternatively certifying teachers has created challenges for teacher preparation programs. Many non-traditional routes into classroom include no full-time mentor teacher. Absence of a mentor teacher in the classroom leaves teachers with a deficit. This study follows ten teachers on the intern certificate enrolled in both an alternative certification teacher preparation program and the Teach for America organization as they pursue a master's degree in education and state teaching certification from a large southwestern university. The five randomly chosen for the treatment group and the control group contained 1 male and 4 female teachers, some of whom teach at public schools and others at charter schools. All were secondary education language arts teachers ranging in age from 22- 29. The treatment used in this study is a job-embedded, professional development, software tool designed to help teachers track their classroom practices called MyiLOGS. The purpose of this action research project was to study the effect using MyiLOGS had on six of the nine areas evaluated by a modified version of the Teacher Advancement Program evaluation rubric, alignment with Opportunity To Learn constructs, and the tool's influence on the efficacy of these first year teachers. The data generated from this study indicate that the MyiLOGS tool did have a positive effect on the teachers' TAP evaluation performances. Also, the MyiLOGS tool had a large impact on the teachers' instruction as measured by the constructs of Opportunity to Learn and their teaching self-efficacy. Implications suggested the tool was an asset to these teachers because they tracked their data, became more reflective, and self-sufficient.
ContributorsRoggeman, Pamela (Author) / Puckett, Kathleen (Thesis advisor) / Kurz, Alexander (Committee member) / Mathur, Sarup (Committee member) / Arizona State University (Publisher)
Created2013
Description
The overall objective of this project is to optimize the development of magnetic ferrite thin films targeted for enabling low-loss broadband communication devices, miniaturized low-microwave inductors and electromagnetic noise suppressors. The focus of this objective is to design and build a reactor and improve the spin-spray process. Each film is then characterized and optimized to have a high permeability and high frequency in the range of 500 MHz - 3 GHz. Films produced by the µ-droplet deposition regime yields a higher Snoek's product than the continuous liquid layer regime. The highest Snoek's product occurs when it is deposited at an oxidant pH of 8.28. The Ni-Zn-Co ferrite magnetic domains were imaged using the Lorentz TEM in which multi-grain domains are experimentally observed for the first time.
ContributorsRay, Nicole M (Author) / Petuskey, William T. (Thesis advisor) / Diaz, Rodolfo E. (Committee member) / Chamberlin, Ralph V. (Committee member) / Arizona State University (Publisher)
Created2013