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Electrospinning of bioactive dex-PAA hydrogel fibers

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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

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.

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2011

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Creep characteristics and shear strength of recycled asphalt blends

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The trend towards using recycled materials on new construction projects is growing as the cost for construction materials are ever increasing and the awareness of the responsibility we have to be good stewards of our environment is heightened. While recycled

The trend towards using recycled materials on new construction projects is growing as the cost for construction materials are ever increasing and the awareness of the responsibility we have to be good stewards of our environment is heightened. While recycled asphalt is sometimes used in pavements, its use as structural fill has been hindered by concern that it is susceptible to large long-term deformations (creep), preventing its use for a great many geotechnical applications. While asphalt/soil blends are often proposed as an alternative to 100% recycled asphalt fill, little data is available characterizing the geotechnical properties of recycled asphalt soil blends. In this dissertation, the geotechnical properties for five different recycled asphalt soil blends are characterized. Data includes the particle size distribution, plasticity index, creep, and shear strength for each blend. Blends with 0%, 25%, 50%, 75% and 100% recycled asphalt were tested. As the recycled asphalt material used for testing had particles sizes up to 1.5 inches, a large 18 inch diameter direct shear apparatus was used to determine the shear strength and creep characteristics of the material. The results of the testing program confirm that the creep potential of recycled asphalt is a geotechnical concern when the material is subjected to loads greater than 1500 pounds per square foot (psf). In addition, the test results demonstrate that the amount of soil blended with the recycled asphalt can greatly influence the creep and shear strength behavior of the composite material. Furthermore, there appears to be an optimal blend ratio where the composite material had better properties than either the recycled asphalt or virgin soil alone with respect to shear strength.

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2011

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Synthesis and characterization of ordered mesoporous silica with controlled macroscopic morphology for membrane applications

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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,

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/m2Pas. 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.

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2011

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Community supported agriculture membership: characterizing food and sustainability behaviors

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Community Supported Agriculture programs (CSAs) have become a viable local source of fresh agricultural goods and represent a potentially new way to improve fruit and vegetable consumption among individuals and families. Studies concerning CSAs have focused mainly on characteristics of

Community Supported Agriculture programs (CSAs) have become a viable local source of fresh agricultural goods and represent a potentially new way to improve fruit and vegetable consumption among individuals and families. Studies concerning CSAs have focused mainly on characteristics of the typical CSA member and motivations and barriers to join a CSA program. The purpose of this study was to examine whether behavior and attitudinal differences existed between current CSA members and a nonmember control group. Specifically, ecological attitudes, eating out behaviors, composting frequency, and family participation in food preparation were assessed. This study utilized an online survey comprising items from previous survey research as well as newly created items. A total of 115 CSA member and 233 control survey responses were collected. CSA members were more likely to be older, have more education, and have a higher income than the control group. The majority of CSA members surveyed were female, identified as non-Hispanic and Caucasian, earned a higher income, and reported being the primary food shopper and preparer. The majority of members also noted that the amount and variety of fruits and vegetables they ate and served their family increased as a result of joining a CSA. CSA members were more ecologically minded compared to the control group. Frequency of eating out was not significantly different between groups. However, eating out behaviors were different between income categories. CSA members spent significantly more money at each meal eaten away from home and spent significantly more money on eating out each week. In both cases, controlling for income attenuated differences between groups. CSA members composted at a significantly higher rate and took part in other eco-friendly behaviors more often than the control group. Finally, no significant difference was evident between the two groups when analyzing family involvement in food preparation and meal decision-making. Overall, some significant attitudinal and behavioral differences existed between CSA members and non-CSA members. Further research is necessary to examine other distinctions between the two groups and whether these differences occur as a result of CSA membership.

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2011

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Constructing a model for small scale fish farmers

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Fish farming is a fast growing industry, which, although necessary to feed an ever growing worldwide population, has its share of negative environmental consequences, including the release of drugs and other waste into the ocean, the use of fish caught

Fish farming is a fast growing industry, which, although necessary to feed an ever growing worldwide population, has its share of negative environmental consequences, including the release of drugs and other waste into the ocean, the use of fish caught from the ocean to feed farm raised fish, and the escape of farm raised fish into natural bodies of water. However, the raising of certain types of fish, such as tilapia, seems to be an environmentally better proposition than raising other types of fish, such as salmon. This paper will explore the problems associated with fish farming, as well as offer a model, based on the literature, and interviews with fish farmers, to make small-scale fish farming both more environmentally, and more economically, sustainable. This paper culminates with a model for small-scale, specifically semi-subsistence, fish farmers. This model emphasizes education of the fish farmers, as well as educators learning from the fish farmers they interact with. The goal of this model is to help these fish farmers become both more environmentally and economically sustainable.

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2011

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Growth of gaN nanowires: a study using in situ transmission electron microscopy

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Owing to their special characteristics, group III-Nitride semiconductors have attracted special attention for their application in a wide range of optoelectronic devices. Of particular interest are their direct and wide band gaps that span from ultraviolet to the infrared wavelengths.

Owing to their special characteristics, group III-Nitride semiconductors have attracted special attention for their application in a wide range of optoelectronic devices. Of particular interest are their direct and wide band gaps that span from ultraviolet to the infrared wavelengths. In addition, their stronger bonds relative to the other compound semiconductors makes them thermally more stable, which provides devices with longer life time. However, the lattice mismatch between these semiconductors and their substrates cause the as-grown films to have high dislocation densities, reducing the life time of devices that contain these materials. One possible solution for this problem is to substitute single crystal semiconductor nanowires for epitaxial films. Due to their dimensionality, semiconductor nanowires typically have stress-free surfaces and better physical properties. In order to employ semiconductor nanowires as building blocks for nanoscale devices, a precise control of the nanowires' crystallinity, morphology, and chemistry is necessary. This control can be achieved by first developing a deeper understanding of the processes involved in the synthesis of nanowires, and then by determining the effects of temperature and pressure on their growth. This dissertation focuses on understanding of the growth processes involved in the formation of GaN nanowires. Nucleation and growth events were observed in situ and controlled in real-time using an environmental transmission electron microscope. These observations provide a satisfactory elucidation of the underlying growth mechanism during the formation of GaN nanowires. Nucleation of these nanowires appears to follow the vapor-liquid-solid mechanism. However, nanowire growth is found to follow both the vapor-liquid-solid and vapor-solid-solid mechanisms. Direct evidence of the effects of III/V ratio on nanowire growth is also reported, which provides important information for tailoring the synthesis of GaN nanowires. These findings suggest in situ electron microscopy is a powerful tool to understand the growth of GaN nanowires and also that these experimental approach can be extended to study other binary semiconductor compound such as GaP, GaAs, and InP, or even ternary compounds such as InGaN. However, further experimental work is required to fully elucidate the kinetic effects on the growth process. A better control of the growth parameters is also recommended.

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2010

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Optimization of ionic conductivity in doped ceria using density functional theory and kinetic lattice Monte Carlo

Description

Fuel cells, particularly solid oxide fuel cells (SOFC), are important for the future of greener and more efficient energy sources. Although SOFCs have been in existence for over fifty years, they have not been deployed extensively because they need to

Fuel cells, particularly solid oxide fuel cells (SOFC), are important for the future of greener and more efficient energy sources. Although SOFCs have been in existence for over fifty years, they have not been deployed extensively because they need to be operated at a high temperature (∼1000 °C), are expensive, and have slow response to changes in energy demands. One important need for commercialization of SOFCs is a lowering of their operating temperature, which requires an electrolyte that can operate at lower temperatures. Doped ceria is one such candidate. For this dissertation work I have studied different types of doped ceria to understand the mechanism of oxygen vacancy diffusion through the bulk. Doped ceria is important because they have high ionic conductivities thus making them attractive candidates for the electrolytes of solid oxide fuel cells. In particular, I have studied how the ionic conductivities are improved in these doped materials by studying the oxygen-vacancy formations and migrations. In this dissertation I describe the application of density functional theory (DFT) and Kinetic Lattice Monte Carlo (KLMC) simulations to calculate the vacancy diffusion and ionic conductivities in doped ceria. The dopants used are praseodymium (Pr), gadolinium (Gd), and neodymium (Nd), all belonging to the lanthanide series. The activation energies for vacancy migration between different nearest neighbor (relative to the dopant) positions were calculated using the commercial DFT code VASP (Vienna Ab-initio Simulation Package). These activation energies were then used as inputs to the KLMC code that I co-developed. The KLMC code was run for different temperatures (673 K to 1073 K) and for different dopant concentrations (0 to 40%). These simulations have resulted in the prediction of dopant concentrations for maximum ionic conductivity at a given temperature.

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2011

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Operationalizing neighborhood resiliency: a grass-roots approach

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This research addresses the ability for neighborhoods to assess resiliency as it applies to their respective local areas. Two demographically and economically contrasting neighborhoods in Glendale, Arizona were studied to understand what residents' value and how those values link to

This research addresses the ability for neighborhoods to assess resiliency as it applies to their respective local areas. Two demographically and economically contrasting neighborhoods in Glendale, Arizona were studied to understand what residents' value and how those values link to key principles of resiliency. Through this exploratory research, a community-focused process was created to use these values in order to link them to key principles of resiliency and potential measureable indicators. A literature review was conducted to first assess definitions and key principles of resiliency. Second, it explored cases of neighborhoods or communities that faced a pressure or disaster and responded resiliently based on these general principles. Each case study demonstrated that resiliency at the neighborhood level was important to its ability to survive its respective pressure and emerge stronger. The Heart of Glendale and Thunderbird Palms were the two neighborhoods chosen to test the ability to operationalize neighborhood resiliency in the form of indicators. First, an in-depth interview was conducted with a neighborhood expert to understand each area's strengths and weaknesses and get a context for the neighborhood and how it has developed. Second, a visioning session was conducted with each neighborhood consisting of seven participants to discuss its values and how they relate to key principles of resiliency. The values were analyzed and used to shape locally relevant indicators. The results of this study found that the process of identifying participants' values and linking them to key principles of resiliency is a viable methodology for measuring neighborhood resiliency. It also found that indicators and values differed between the Heart of Glendale, a more economically vulnerable yet ethnically diverse area, than Thunderbird Palms, a more racially homogenous, middle income neighborhood. The Heart of Glendale valued the development of social capital more than Thunderbird Palms which placed a higher value on the condition of the built environment as a vehicle for stimulating vibrancy and resiliency in the neighborhood. However, both neighborhoods highly valued public education and providing opportunities for children to be future leaders in their local communities.

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2011

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Community food resource assessment in Central City South, Phoenix: a study of community capacity building

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Many studies have shown that access to healthy food in the US is unevenly distributed and that supermarkets and other fresh food retailers are less likely to be located in low-income minority communities, where convenience and dollar stores are more

Many studies have shown that access to healthy food in the US is unevenly distributed and that supermarkets and other fresh food retailers are less likely to be located in low-income minority communities, where convenience and dollar stores are more prevalent grocery options. I formed a partnership with Phoenix Revitalization Corporation, a local community development organization engaged in Central City South, Phoenix, to enhance the community's capacity to meet its community health goals by improving access to healthy food. I used a community-based participatory approach that blended qualitative and quantitative elements to accommodate collaboration between both academic and non-academic partners. Utilizing stakeholder interviews, Nutrition Environment Measures Surveys (NEMS), and mapping to analyze the community's food resources, research revealed that the community lacks adequate access to affordable, nutritious food. Community food stores (n=14) scored an average of 10.9 out of a possible 54 points using the NEMS scoring protocol. The community food assessment is an essential step in improving access to healthy food for CCS residents and provides a baseline for tracking progress to improve residents' food access. Recommendations were drafted by the research partnership to equip and empower the community with strategic, community-specific interventions based on the research findings.

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2011

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Growth, characterization, and thermodynamics of III-nitride semiconductors

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

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.

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2011