Red mud is a waste product of alumina production and has an adverse effect on environment. About 90 million tonnes of red mud are produced annually throughout the world and little is recycled for useful applications. The world nickel reserves consist of approximately 30% sulphide ores and 70% oxide ores. Despite the relative abundance of oxide ores, 55% of nickel and nickel alloys produced today are derived from sulphide ores. However, with the production of nickel and its alloys from low-grade oxide ores becoming increasingly important, a major concern is high sulphur level in the resultant alloy. For this reason, desulphurization of the ferronickel becomes an important consideration. In the present study, experiments were conducted to determine if red mud could be used as a major ingredient of custom designed fluxes for the desulphurization of ferronickel alloy. Factors investigated included desulphurization rates, contact angle measurements and flux-refractory interactions.

This thesis describes the synthesis and assembly of metal and semiconductor nanoparticles (NPs). The two research topics include i) hetero-assembly of metal and semiconductor NPs, ii) effect of ionic strength on homo-assembly of gold nanorods (GNRs). First, we present hetero-assembly of GNRs and semiconductor quantum dots (QDs) in a chain using biotin-streptavidin interaction. We synthesized alloyed CdTeSe QDs and modified them with mercaptoundecanoic acid to render them water-soluble and to attach streptavidin. We synthesized GNRs by a seed-mediated method and selectively modified the ends with biotin. Hetero-assembly of QDs and GNRs depended on the size, ligands, and ratio of QDs and GNRs. Second, we controlled the rate of homo-assembly of GNRs by varying the ionic strength of the DMF/water solution. The solubility of polystyrene on the ends of GNRs depended on the ionic strength of the solution, which correlated with the rate of assembly of GNRs into chains.

Conductive anodic filament (CAF) is a failure mode in printed wiring boards (PWBs) which occurs under high humidity and high voltage gradient conditions. The filament, a copper salt, grows from anode to cathode along the epoxy-glass interface. Ready and Turbini (2000) identified this copper salt as the Cu2(OH)3Cl, atacamite compound. This work has investigated the influence of polyethylene glycol (PEG) and polyethylene propylene glycol (PEPG) fluxing agents on the chemical nature of CAF. For coupons processed with PEPG flux, with and without chloride, a copper-chloride containing compound was formed in the polymer matrix. This compound was characterized using x-ray photoelectron spectroscopy (XPS) as CuCl and an electrochemical mechanism for the formation of the chloride-containing CAF has been proposed. For PEG flux, with and without chloride, it has been shown that CAF only formed, but no copper containing compound formed in the matrix. It appears for PEG fluxed coupons, a PEG-Cu-Cl complex forms, binds the available Cu and acts as a barrier to the formation of CuCl in the polymer matrix. Meeker and Lu Valle (1995) have previously proposed that CAF failure is best represented by two competing reactions – the formation of a copper chloride corrosion compound (now identified as Cu2(OH)3Cl) and the formation of innocuous trapped chlorine compounds. Since no evidence of any trapped chloride compounds has been found, we propose that the formation of CAF is best represented by a single non-reversible reaction. For coupons processed with a high bromide-containing flux, bromide containing CAF was created and characterized using transmission electron microscopy (TEM) to be Cu2(OH)3Br. In addition, a copper-containing compound was formed in the polymer matrix and characterized using XPS as CuBr. An electrochemical mechanism for the formation of bromide-containing CAF has been proposed based on the XPS data. .

Conductive anodic filament (CAF) is a failure mode in printed wiring boards (PWBs) which occurs under high humidity and high voltage gradient conditions. The filament, a copper salt, grows from anode to cathode along the epoxy-glass interface. Ready and Turbini (2000) identified this copper salt as the Cu2(OH)3Cl, atacamite compound. This work has investigated the influence of polyethylene glycol (PEG) and polyethylene propylene glycol (PEPG) fluxing agents on the chemical nature of CAF. For coupons processed with PEPG flux, with and without chloride, a copper-chloride containing compound was formed in the polymer matrix. This compound was characterized using x-ray photoelectron spectroscopy (XPS) as CuCl and an electrochemical mechanism for the formation of the chloride-containing CAF has been proposed. For PEG flux, with and without chloride, it has been shown that CAF only formed, but no copper containing compound formed in the matrix. It appears for PEG fluxed coupons, a PEG-Cu-Cl complex forms, binds the available Cu and acts as a barrier to the formation of CuCl in the polymer matrix. Meeker and Lu Valle (1995) have previously proposed that CAF failure is best represented by two competing reactions – the formation of a copper chloride corrosion compound (now identified as Cu2(OH)3Cl) and the formation of innocuous trapped chlorine compounds. Since no evidence of any trapped chloride compounds has been found, we propose that the formation of CAF is best represented by a single non-reversible reaction. For coupons processed with a high bromide-containing flux, bromide containing CAF was created and characterized using transmission electron microscopy (TEM) to be Cu2(OH)3Br. In addition, a copper-containing compound was formed in the polymer matrix and characterized using XPS as CuBr. An electrochemical mechanism for the formation of bromide-containing CAF has been proposed based on the XPS data. .

ZnO nanowire arrays (NWAs) and Al-doped ZnO (AZO) cathodes were applied in hybrid organic / inorganic solar cells for lower-cost solar energy. Parameters for the electrodeposition of ZnO NWAs and the fabrication of NWA-free baseline devices were systematically optimized using ITO as the cathodes. High efficiencies of up to 5.4% were achieved. Incorporation of the ZnO NWAs into the baseline devices significantly reduced their efficiencies due to possible shorting in the active layer. Devices fabricated using AZO cathodes were characterized. The AZO-based devices achieved efficiencies of up to ~4.8%, showing promising results for the application of AZO as an ITO alternative. Formation of numerous large nanoplatelets was observed during the electrodeposition of ZnO NWAs on AZO cathodes. The NWAs grown on AZO cathodes were also non-uniform. Future studies were proposed to address the issues with incorporation of ZnO NWAs in hybrid solar cells and their combination with AZO cathodes.

Environmental and economic factors demand radical advances in solar cell technologies. Organic and polymer photovoltaics emerged in the 1990's that have led to low cost per unit area, enabled in significant part by the convenient manufacturing of roll-to-roll-processible solution-cast semiconductors. Colloidal quantum dot solar cells dramatically increase the potential for solar conversion efficiency relative to organics by enabling optimal matching of a photovoltaic device's bandgap to the sun's spectrum. Infrared-absorbing colloidal quantum dot solar cells were first reported in 2005. At the outset of this study in 2007, they had been advanced to the point of achieving 1.8% solar power conversion efficiency. These devices degraded completely within a few hours’ air exposure. The origin of the extremely poor device stability was unknown and unstudied. The efficiency of these devices was speculated to be limited by poor carrier transport and passivation within the quantum dot solid, and by the limitations of the Schottky device architecture. This study sought to tackle three principal challenges facing colloidal quantum dot photovoltaics: stability; understanding; and performance. In the first part of this work, we report the first air-stable infrared colloidal quantum dot photovoltaics. Our devices have a solar power conversion efficiency of 2.1%. These devices, unencapsulated and operating in an air atmosphere, retain 90% of their original performance following 3 days’ continuous solar harvesting. The remarkable improvement in device stability originated from two new insights. First, we showed that inserting a thin LiF layer between PbS film and Al electrode blocks detrimental interfacial reactions. Second, we proposed and validated a model that explains why quantum dots having cation-rich surfaces afford dramatically improved air stability within the quantum dot solid. The success of the cation-enrichment strategy led us to a new concept: what if - rather than rely on organic ligands, as all prior quantum dot photovoltaics work had done - one could instead terminate the surface of quantum dots exclusively using inorganic materials? We termed our new materials strategy ionic passivation. The goal of the approach was to bring our nanoparticles into the closest possible contact while still maintaining quantum confinement; and at the same time achieving a maximum of passivation of the nanoparticles' surfaces. We showcase our ionic passivation strategy by building a photovoltaic device that achieves 5.8% solar power conversion efficiency. This is the highest-ever solar power conversion efficiency reported in a colloidal quantum dot device. More generally, our ionic passivation strategy breaks the past tradeoff between transport and passivation in quantum dot solids. The advance is relevant to electroluminescent and photodetection devices as well as to the record-performing photovoltaic devices reported herein.

ZnO nanowire arrays (NWAs) and Al-doped ZnO (AZO) cathodes were applied in hybrid organic / inorganic solar cells for lower-cost solar energy. Parameters for the electrodeposition of ZnO NWAs and the fabrication of NWA-free baseline devices were systematically optimized using ITO as the cathodes. High efficiencies of up to 5.4% were achieved. Incorporation of the ZnO NWAs into the baseline devices significantly reduced their efficiencies due to possible shorting in the active layer. Devices fabricated using AZO cathodes were characterized. The AZO-based devices achieved efficiencies of up to ~4.8%, showing promising results for the application of AZO as an ITO alternative. Formation of numerous large nanoplatelets was observed during the electrodeposition of ZnO NWAs on AZO cathodes. The NWAs grown on AZO cathodes were also non-uniform. Future studies were proposed to address the issues with incorporation of ZnO NWAs in hybrid solar cells and their combination with AZO cathodes.

Currently the cost of solar grade silicon accounts for approximately one third of the total solar cell cost, therefore a new silicon refining process is being proposed with the goal of lowering the cost of producing solar grade silicon. In this new process, Si-Cu alloys were used as the silicon source. One to one molar ratio H2-HCl gas mixtures were used as transport agents to extract Si out from the Si-Cu alloy at about 300-700oC, with following reaction taking place: Si+3HCl(g)=HSiCl3(g)+H2(g) While at about 1000-1300oC, pure Si deposits onto a hot silicon rod according to: Si+3HCl(g)=HSiCl3(g)+H2(g) The role of the copper in the alloy was to trap impurities in the Si and catalyze the gas solid reaction. A study on determining the rate limiting step and impurity behavior was done. A possible silicon extraction reaction mechanism was also addressed.

Currently the cost of solar grade silicon accounts for approximately one third of the total solar cell cost, therefore a new silicon refining process is being proposed with the goal of lowering the cost of producing solar grade silicon. In this new process, Si-Cu alloys were used as the silicon source. One to one molar ratio H2-HCl gas mixtures were used as transport agents to extract Si out from the Si-Cu alloy at about 300-700oC, with following reaction taking place: Si+3HCl(g)=HSiCl3(g)+H2(g) While at about 1000-1300oC, pure Si deposits onto a hot silicon rod according to: Si+3HCl(g)=HSiCl3(g)+H2(g) The role of the copper in the alloy was to trap impurities in the Si and catalyze the gas solid reaction. A study on determining the rate limiting step and impurity behavior was done. A possible silicon extraction reaction mechanism was also addressed.

Xylan is one of the major hemicelluloses present in plant cell wall matrix, where it is closely associated with other cell wall components, cellulose and lignin. Xylan has enormous potential as a renewable biopolymer and recently, research in the direction of isolation and utilization of xylan is gaining lot of research attention. Extraction of xylan from the plant cell walls involves the hydrolysis of xylan and its transfer from the plant cell wall matrix to the hydrolyzing media. Current process of extraction involves prolonged heating of the biomass with the hydrolysis media at high temperature and/or pressure that leads to molecular degradation of xylan and limits its high potential polymeric applications. In this research, microwave assisted alkaline extraction of polymeric xylan from birch wood is investigated as an alternative to the time intensive conventional extraction. The hypothesis to be tested is that the microwave’s selective heating ability leads to the generation of hot spots through its interaction with the alkali present in the fibers and the resulting "explosion effect" loosen the recalcitrant fiber structure network thereby facilitating the hydrolysis of xylan and its dissolution before undergoing significant degradation. Effect of microwave extraction on the yield of xylan and wood solubilization, physico-chemical properties of wood fibers and of isolated xylan were investigated in comparison with conventional extraction. Low power input microwave (110 W) alkaline extraction was found to be an efficient alternative to the conventional extraction. FTIR and chemical composition of wood fibers after extraction demonstrated an increased removal of xylan from the wood fibre using microwave extraction. SEM, X-ray microtomography, and X-ray crystallinity studies of wood fibers demonstrated a porous and loosened fibre structure after microwave extraction confirming the hypothesis. Molecular weight of the isolated xylan using microwave extraction was found to be higher compared to the xylan isolated using conventional extraction indicating less molecular degradation. About 75% of xylan present in birch wood could be extracted using a low power input microwave heating under optimized extraction conditions of 8wt% NaOH solution, 1:8 (g:mL) solid to liquid ratio, and 25 minutes of extraction time.