Digitized by Kansas Correctional Industries

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A thesis submitted in fulfilment of the requirements for the degree of Doctor of Philosophy in the School of Chemistry Faculty of Science, University of Witwatersrand, 2017 / Advancements in nanotechnology and nanosystems promise to extend limits of sustainable development and environment remediation in an attempt to address some of the world most challenging problems. Specifically, nanotechnology has played an important role in the design, synthesis, and characterization of various new and novel functional nanomaterials possessing extremely unique properties. For example, low dimensional nanostructures such as semiconductor nanocrystals with well controlled sizes, shapes, porosities, crystalline phases, and structures have been prepared via various synthetic methods. In addition these semiconductor nanocrystals have attracted research attention because of their fundamental role in the comprehension of the quantum size effect and great potential applications to save resources and improve the environment. Tremendous studies have established that morphological, optical, catalytic and electronic properties of semiconductor nanocrystals can be manipulated during synthesis by simply varying the growth parameters. Herein we establish the effect of different synthetic methods and several growth parameters on the properties of the as-synthesized semiconducting metal selenides nanocrystals (NixSey and InxSey) including structural, optical, electronic and catalytic properties. For example, reducing coordinating solvent oleylamine was seen to favour a particular morphologies and stoichiometries despite the duration of synthesis. In the case of InxSey nanocrystals, oleylamine favoured indium monoselenide (InSe) nanosheet formation while addition of 1-DDT as a co-surfactant to oleylamine produces In2Se3 nanowires. For NixSey nanocrystals, TOP as a co-surfactant to different ligands favoured the formation Ni3Se2 with different shapes including dots, plates, rods and wires in different solvents. Other parameters studied included the reaction time and temperature. Besides the properties, we probe the potential applications of these materials in dye sensitized solar cells as counter electrodes as well in chemical sensor as the sensing material. NixSey nanocrystals were employed as CE in DSSCs in an attempt to replace the noble expensive platinum conventionally used as CE in most DSSCs. It was established that different stoichiometry played a significant role in the catalytic reduction of I3-. Thus, different photovoltaic performance parameters were obtained with NiSe2 giving a higher PCE of 1.5 % followed Ni3Se4 then Ni3Se2. These values were however very low compared to the ones reported in literature, something that was attributed to low electron mobility, enhanced recombination and reduced catalytic performance as a result of poor device assembly and the organic ligand layer encapsulating the nanocrystal. In another scenerio, indium monoselenide nanocrystals were employed in chemiresistive sensors to detect the presence of a number of VOCs including formaldehyde, methanol, chloroform and acetone in the ambient. Indeed despite the well-known electrical, optical and structural properties previously reported in literature, metal selenides such as CdSe, PbSe and ZnSe among others present lack of investigation for gas sensing. The experimental results showed that different morphologies of InSe nanostructures interacted differently to the analyte gas suggesting difference in the electronic properties of different morphologies. The InSe nanoparticle based sensors gave a good response to HCHO and MeOH fumes and were more selective to HCHO fumes than chloroform and acetone. While those fabricated using the InSe nanosheets though responding well to HCHO recovered half way when exposed back in air and resulted in relatively high noise to signal ratio when exposed to MeOH. The operating temperature range for the InSe sensor devices were determined to be near room temperature. The sensors response was observed to decrease with increasing temperature from 30 °C to 90 °C. Evident from the results, the surface capping molecule (oleylamine) employed to stabilize the nanostructures during synthesis was responsible for the poor sensing abilities of the nanostructures. / XL2018

Thesis (Ph.D.)--University of Delaware, 2006. / Principal faculty advisor: Mary E. Galvin, Dept. of Materials Science & Engineering. Includes bibliographical references.

Thesis (Ph. D.)--University of Florida, 2001. / Title from first page of PDF file. Document formatted into pages; contains vii, 145 p.; also contains graphics. Vita. Includes bibliographical references (p. 137-144).

Thesis (Ph. D.)--Rutgers University, 2009. / "Graduate Program in Mechanical and Aerospace Engineering." Includes bibliographical references (p. 155-159).

Radiation causes performance degradation in electronics by inducing atomic displacements and ionizations. While radiation hardened components are available, non-radiation hardened electronics can be preferable because they are generally more compact, require less power, and less expensive than radiation tolerant equivalents. It is therefore important to characterize the performance of electronics, both hardened and non-hardened, to prevent costly system or mission failures. Radiation effects tests for electronics generally involve a handful of step irradiations, leading to poorly-resolved data. Step irradiations also introduce uncertainties in electrical measurements due to temperature annealing effects. This effect may be intensified if the time between exposure and measurement is significant. Induced activity in test samples also complicates data collection of step irradiated test samples. The University of Texas at Austin operates a 1.1 MW Mark II TRIGA research reactor. An in-core irradiation facility for radiation effects testing with a real-time monitoring capability has been designed for the UT TRIGA reactor. The facility is larger than any currently available non-central location in a TRIGA, supporting testing of larger electronic components as well as other in-core irradiation applications requiring significant volume such as isotope production or neutron transmutation doping of silicon. This dissertation describes the design and testing of the large in-core irradiation facility and the experimental campaign developed to test the real-time monitoring capability. This irradiation campaign was performed to test the real-time monitoring capability at various reactor power levels. The device chosen for characterization was the 4N25 general-purpose optocoupler. The current transfer ratio, which is an important electrical parameter for optocouplers, was calculated as a function of neutron fluence and gamma dose from the real-time voltage measurements. The resultant radiation effects data was seen to be repeatable and exceptionally finely-resolved. Therefore, the capability at UT TRIGA has been proven competitive with world-class effects characterization facilities. / text

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