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- Creators: Arizona State University
Description
Ordered mesoporous materials have tunable pore sizes between 2 and 50 nm and are characterized by ordered pore structures and high surface areas (~1000 m2/g). This makes them particularly favorable for a number of membrane applications such as protein separation, polymer extrusion, nanowire fabrication and membrane reactors. These membranes can be fabricated as top-layers on macroporous supports or as embedded membranes in a dense matrix. The first part of the work deals with the hydrothermal synthesis and water-vapor/oxygen separation properties of supported MCM-48 and a new Al-MCM-48 type membrane for potential use in air conditioning systems. Knudsen-type permeation is observed in these membranes. The combined effect of capillary condensation and the aluminosilicate matrix resulted in the highest separation factor (142) in Al-MCM-48 membranes, with a water vapor permeance of 6×10-8mol/m2Pas. The second part focuses on synthesis of embedded mesoporous silica membranes with helically ordered pores by a novel Counter Diffusion Self-Assembly (CDSA) method. This method is an extension of the interfacial synthesis method for fiber synthesis using tetrabutylorthosilicate (TBOS) and cetyltrimethylammonium bromide (CTAB) as the silica source and surfactant respectively. The initial part of this study determined the effect of TBOS height and humidity on fiber formation. From this study, the range of TBOS heights for best microscopic and macroscopic ordering were established. Next, the CDSA method was used to successfully synthesize membranes, which were characterized to have good support plugging and an ordered pore structure. Factors that influence membrane synthesis and plug microstructure were determined. SEM studies revealed the presence of gaps between the plugs and support pores, which occur due to shrinking of the plug on drying. Development of a novel liquid deposition method to seal these defects constituted the last part of this work. Post sealing, excess silica was removed by etching with hydrofluoric acid. Membrane quality was evaluated at each step using SEM and gas permeation measurements. After surfactant removal by liquid extraction, the membranes exhibited an O2 permeance of 1.65x10-6mol/m2.Pa.s and He/O2 selectivity of 3.30. The successful synthesis of this membrane is an exciting new development in the area of ordered mesoporous membrane technology.
ContributorsSeshadri, Shriya (Author) / Lin, Jerry Y. S. (Thesis advisor) / Dai, Lenore (Committee member) / Rege, Kaushal (Committee member) / Smith, David J. (Committee member) / Vogt, Bryan (Committee member) / Arizona State University (Publisher)
Created2011
Description
This dissertation explores the rhetorical significance of persecution claims produced by demonstrably powerful publics in contemporary American culture. This ideological criticism is driven by several related research questions. First, how do members of apparently powerful groups (men, whites, and Christians) come to see themselves as somehow unjustly marginalized, persecuted, or powerless? Second, how are these discourses related to the public sphere and counterpublicity? I argue that, despite startling similarities, these texts studied here are best understood not as counterpublicity but as a strategy of containment available to hegemonic publics. Because these rhetorics of persecution often seek to forestall movements toward pluralism and restorative justice, the analysis forwarded in this dissertation offers important contributions to ongoing theoretical discussions in the fields of public sphere theory and critical cultural theory and practical advice for progressive political activism and critical pedagogy.
ContributorsDuerringer, Christopher (Author) / Brouwer, Daniel (Thesis advisor) / Carlson, Cheree (Committee member) / McDonald, Kelly (Committee member) / Arizona State University (Publisher)
Created2011
Deviant bodies resisting online: examining the intersecting realities of women of color in Xbox Live
Description
Employing qualitative methods and drawing from an intersectional framework which focuses on the multiple identities we all embody, this dissertation focuses on oppressions and resistance strategies employed by women of color in Xbox live, an online gaming community. Ethnographic observations and narrative interviewing reveal that women of color, as deviants within the space, face intersecting oppressions in gaming as in life outside the gaming world. They are linguistically profiled within the space based off of how they sound. They have responded with various strategies to combat the discrimination they experience. Some segregate themselves from the larger gaming population and many refuse to purchase games that depict women in a hyper-sexualized manner or that present people of color stereotypically. For others, the solution is to "sit-in" on games and disrupt game flow by 'player-killing' or engage in other 'griefing' activities. I analyze this behavior in the context of Black feminist consciousness and resistance and uncover that these methods are similar to women who employ resistance strategies for survival within the real world.
ContributorsGray, Kishonna (Author) / Anderson, Lisa M. (Thesis advisor) / Cheong, Pauline (Committee member) / Lim, Merlyna (Committee member) / Arizona State University (Publisher)
Created2011
Description
III-nitride alloys are wide band gap semiconductors with a broad range of applications in optoelectronic devices such as light emitting diodes and laser diodes. Indium gallium nitride light emitting diodes have been successfully produced over the past decade. But the progress of green emission light emitting devices has been limited by the incorporation of indium in the alloy, mainly due to phase separation. This difficulty could be addressed by studying the growth and thermodynamics of these alloys. Knowledge of thermodynamic phase stabilities and of pressure - temperature - composition phase diagrams is important for an understanding of the boundary conditions of a variety of growth techniques. In this dissertation a study of the phase separation of indium gallium nitride is conducted using a regular solution model of the ternary alloy system. Graphs of Gibbs free energy of mixing were produced for a range of temperatures. Binodal and spinodal decomposition curves show the stable and unstable regions of the alloy in equilibrium. The growth of gallium nitride and indium gallium nitride was attempted by the reaction of molten gallium - indium alloy with ammonia at atmospheric pressure. Characterization by X-ray diffraction, photoluminescence, and secondary electron microscopy show that the samples produced by this method contain only gallium nitride in the hexagonal phase. The instability of indium nitride at the temperatures required for activation of ammonia accounts for these results. The photoluminescence spectra show a correlation between the intensity of a broad green emission, related to native defects, and indium composition used in the molten alloy. A different growth method was used to grow two columnar-structured gallium nitride films using ammonium chloride and gallium as reactants and nitrogen and ammonia as carrier gasses. Investigation by X-ray diffraction and spatially-resolved cathodoluminescence shows the film grown at higher temperature to be primarily hexagonal with small quantities of cubic crystallites, while the one grown at lower temperature to be pure hexagonal. This was also confirmed by low temperature photoluminescence measurements. The results presented here show that cubic and hexagonal crystallites can coexist, with the cubic phase having a much sharper and stronger luminescence. Controlled growth of the cubic phase GaN crystallites can be of use for high efficiency light detecting and emitting devices. The ammonolysis of a precursor was used to grow InGaN powders with different indium composition. High purity hexagonal GaN and InN were obtained. XRD spectra showed complete phase separation for samples with x < 30%, with ~ 9% indium incorporation in the 30% sample. The presence of InGaN in this sample was confirmed by PL measurements, where luminescence from both GaN and InGaN band edge are observed. The growth of higher indium compositions samples proved to be difficult, with only the presence of InN in the sample. Nonetheless, by controlling parameters like temperature and time may lead to successful growth of this III-nitride alloy by this method.
ContributorsHill, Arlinda (Author) / Ponce, Fernando A. (Thesis advisor) / Chamberlin, Ralph V (Committee member) / Sankey, Otto F (Committee member) / Smith, David J. (Committee member) / Tsen, Kong-Thon (Committee member) / Arizona State University (Publisher)
Created2011
Description
In this work, a novel method is developed for making nano- and micro- fibrous hydrogels capable of preventing the rejection of implanted materials. This is achieved by either (1) mimicking the native cellular environment, to exert fine control over the cellular response or (2) acting as a protective barrier, to camouflage the foreign nature of a material and evade recognition by the immune system. Comprehensive characterization and in vitro studies described here provide a foundation for developing substrates for use in clinical applications. Hydrogel dextran and poly(acrylic acid) (PAA) fibers are formed via electrospinning, in sizes ranging from nanometers to microns in diameter. While "as-electrospun" fibers are continuous in length, sonication is used to fragment fibers into short fiber "bristles" and generate nano- and micro- fibrous surface coatings over a wide range of topographies. Dex-PAA fibrous surfaces are chemically modified, and then optimized and characterized for non-fouling and ECM-mimetic properties. The non-fouling nature of fibers is verified, and cell culture studies show differential responses dependent upon chemical, topographical and mechanical properties. Dex-PAA fibers are advantageously unique in that (1) a fine degree of control is possible over three significant parameters critical for modifying cellular response: topography, chemistry and mechanical properties, over a range emulating that of native cellular environments, (2) the innate nature of the material is non-fouling, providing an inert background for adding back specific bioactive functionality, and (3) the fibers can be applied as a surface coating or comprise the scaffold itself. This is the first reported work of dex-PAA hydrogel fibers formed via electrospinning and thermal cross-linking, and unique to this method, no toxic solvents or cross-linking agents are needed to create hydrogels or for surface attachment. This is also the first reported work of using sonication to fragment electrospun hydrogel fibers, and in which surface coatings were made via simple electrostatic interaction and dehydration. These versatile features enable fibrous surface coatings to be applied to virtually any material. Results of this research broadly impact the design of biomaterials which contact cells in the body by directing the consequent cell-material interaction.
ContributorsLouie, Katherine BoYook (Author) / Massia, Stephen P (Thesis advisor) / Bennett, Kevin (Committee member) / Garcia, Antonio (Committee member) / Pauken, Christine (Committee member) / Vernon, Brent (Committee member) / Arizona State University (Publisher)
Created2011
Description
The current study is the first qualitative investigation aimed solely at understanding what it means to communicate conditional forgiveness in serious romantic relationships. Conditional forgiveness is forgiveness that has been offered with the stipulation that the errant behavior cease. It is a provocative topic because some argue genuine forgiveness is not conditional, but recent discoveries that have associated its use with severe transgressions and relational deterioration suggest it is a critical site for investigation. This inductive analysis of open-ended data from 201 anonymous surveys identified both distinctions between and intersections of conditional forgiveness, forgiveness, and reconciliation. A relational dialectics analysis also revealed that reconcilable-irreconcilable was the overarching tension for conditional forgivers and six additional tensions also were also discovered: individual identity-couple identity, safety-risk, certainty-uncertainty, mercy-justice, heart-mind, and expression-suppression. Of particular intrigue, the current analysis supports the previous discovery of implicit conditional forgiveness--suppressing conditions, sometimes in response to physical and substance abuse. Ultimately, the current analysis contributes to the enduring conversation aimed at understanding the communication and pursuit of forgiveness and reconciliation. It addresses one of the basic instincts and paradoxes of existing with others--the balance between vulnerability and protection.
ContributorsKloeber, Dayna Noel (Author) / Waldron, Vincent R. (Thesis advisor) / Kelley, Douglas L. (Committee member) / Kassing, Jeffrey W. (Committee member) / Fisher, Carla L. (Committee member) / Arizona State University (Publisher)
Created2011
Description
Ge1-ySny alloys represent a new class of photonic materials for integrated optoelectronics on Si. In this work, the electrical and optical properties of Ge1-ySny alloy films grown on Si, with concentrations in the range 0 ≤ y ≤ 0.04, are studied via a variety of methods. The first microelectronic devices from GeSn films were fabricated using newly developed CMOS-compatible protocols, and the devices were characterized with respect to their electrical properties and optical response. The detectors were found to have a detection range that extends into the near-IR, and the detection edge is found to shift to longer wavelengths with increasing Sn content, mainly due to the compositional dependence of the direct band gap E0. With only 2 % Sn, all of the telecommunication bands are covered by a single detector. Room temperature photoluminescence was observed from GeSn films with Sn content up to 4 %. The peak wavelength of the emission was found to shift to lower energies with increasing Sn content, corresponding to the decrease in the direct band gap E0 of the material. An additional peak in the spectrum was assigned to the indirect band gap. The separation between the direct and indirect peaks was found to decrease with increasing Sn concentration, as expected. Electroluminescence was also observed from Ge/Si and Ge0.98Sn0.02 photodiodes under forward bias, and the luminescence spectra were found to match well with the observed photoluminescence spectra. A theoretical expression was developed for the luminescence due to the direct band gap and fit to the data.
ContributorsMathews, Jay (Author) / Menéndez, Jose (Thesis advisor) / Kouvetakis, John (Thesis advisor) / Drucker, Jeffery (Committee member) / Chizmeshya, Andrew (Committee member) / Ponce, Fernando (Committee member) / Arizona State University (Publisher)
Created2011
Description
This thesis seeks to answer the question: "What do artistic representations add to the dialogue about the U.S.-Mexico border and immigration beyond political rhetoric and popular media portrayals?" Drawing on political communications (as put forth by Edelman and Altheide), socio-political construction (particularly the White Racial Frame put forth by Feagin), and collective memory theory (especially those of Halbwachs and Pollak), this thesis uses a dual-coding, content analysis to examine the linguistic and visual messages disseminated through news media. Then, interviews with and the work of six immigrant artists are examined for their contribution to the information put forth in the news media. This study finds that news reporting bias falls along a continuum from pro-immigration to extreme anti-immigration (labeled "fearful" reporting). The news media skew strongly toward anti-immigration to fearful in bias, and there is no opposite pro-immigration bias. Through observations of artists' work, the study concludes that artistic representations of the border can fill this strongly pro-immigration void on this bias continuum.
ContributorsMcCarty, Kelly Erin (Author) / Téllez, Michelle (Thesis advisor) / Stancliff, Michael (Committee member) / Segura, Joseph (Committee member) / Arizona State University (Publisher)
Created2011
Description
Separation from a loved one is a highly stressful event. The range and intensity of emotions accompanying such a separation arguably are amplified when one's spouse deploys. This thesis examines at-home spouses (AHSs) of deployed military and how emotion, marital satisfaction, and communication are impacted throughout the deployment cycle. Additionally, I explore technology as a possible coping mechanism to help AHSs adapt and overcome stressfulness of deployment. One hundred sixty-six married females with a partner currently deployed, anticipating deployment, or recently returned from deployment completed an on-line survey. It was predicted AHSs would experience specific emotions during each phase, categorized as "anticipatory," (e.g., anger, worry) "absence" (e.g., lonely, sad) or "post" (e.g., happiness, relief); marital satisfaction also was predicted to be higher among spouses whose partner recently returned from deployment versus was deployed or anticipating deployment. Data showed AHSs whose partner was anticipating or currently deployed reported more "anticipatory" and "absence" emotions than AHSs with a recently returned partner. The former two groups did not differ in these emotions. AHSs with a recently returned partner reported more "post" emotions than the other two groups. Marital satisfaction did not differ based on deployment status. It was also predicted that among AHSs with a currently deployed partner, less negative emotion upon deployment would be associated with more frequent communication during deployment. Data showed AHSs who reported less negative emotion upon deployment engaged in more frequent communication with their deployed partner. Lastly, I predicted AHSs whose partners are currently deployed and who prefer modes of communication allowing direct contact (e.g., Skype) will experience less negative emotions than AHSs who prefer indirect contact (e.g., e-mail). Data showed reports of negative emotion did not differ based on preference for direct versus indirect communication. Therefore, negative emotions may develop and persist before and during deployment, but when the partner returns home, spouses do experience a rebound of positive emotions. Additionally, emotions at the time of deployment may be useful in predicting spouses' communication frequency during deployment. Findings aim to provide knowledge of family life during separation and explore technology as a possible coping mechanism for AHSs.
ContributorsPowell, Katrina D (Author) / Roberts, Nicole A. (Thesis advisor) / Burleson, Mary H. (Committee member) / Hall, Deborah (Committee member) / Arizona State University (Publisher)
Created2011
Description
In this work, a new method, "Nanobonding" [1,2] is conceived and researched to bond Si-based surfaces, via nucleation and growth of a 2 D silicon oxide SiOxHx interphase connecting the surfaces at the nanoscale across macroscopic domains. Nanobonding cross-bridges two smooth surfaces put into mechanical contact in an O2/H2O mixed ambient below T <200 °C via arrays of SiOxHx molecules connecting into a continuous macroscopic bonding interphase. Nano-scale surface planarization via wet chemical processing and new spin technology are compared via Tapping Mode Atomic Force Microscopy (TMAFM) , before and after nano-bonding. Nanobonding uses precursor phases, 2D nano-films of beta-cristobalite (beta-c) SiO2, nucleated on Si(100) via the Herbots-Atluri (H-A) method [1]. beta-c SiO2 on Si(100) is ordered and flat with atomic terraces over 20 nm wide, well above 2 nm found in native oxides. When contacted with SiO2 this ultra-smooth nanophase can nucleate and grow domains with cross-bridging molecular strands of hydroxylated SiOx, instead of point contacts. The high density of molecular bonds across extended terraces forms a strong bond between Si-based substrates, nano- bonding [2] the Si and silica. A new model of beta-cristobalite SiO2 with its <110> axis aligned along Si[100] direction is simulated via ab-initio methods in a nano-bonded stack with beta-c SiO2 in contact with amorphous SiO2 (a-SiO2), modelling cross-bridging molecular bonds between beta-c SiO2 on Si(100) and a-SiO2 as during nanobonding. Computed total energies are compared with those found for Si(100) and a-SiO2 and show that the presence of two lattice cells of !-c SiO2 on Si(100) and a-SiO2 lowers energy when compared to Si(100)/ a-SiO2 Shadow cone calculations on three models of beta-c SiO2 on Si(100) are compared with Ion Beam Analysis of H-A processed Si(100). Total surface energy measurements via 3 liquid contact angle analysis of Si(100) after H-A method processing are also compared. By combining nanobonding experiments, TMAFM results, surface energy data, and ab-initio calculations, an atomistic model is derived and nanobonding is optimized. [1] US Patent 6,613,677 (9/2/03), 7,851,365 (12/14/10), [2] Patent Filed: 4/30/09, 10/1/2011
ContributorsWhaley, Shawn D (Author) / Culbertson, Robert J. (Thesis advisor) / Herbots, Nicole (Committee member) / Rez, Peter (Committee member) / Marzke, Robert F (Committee member) / Lindsay, Stuart (Committee member) / Chamberlin, Ralph V (Committee member) / Arizona State University (Publisher)
Created2011