The goal of this work is to increase the current understanding of Controlled Radical Polymerizations (CRPs) in two areas. Progressing closer towards employing an aqueous system, specifically miniemulsion, to produce poly(vinyl acetate) via reversible addition fragmentation chain transfer (RAFT) chemistry constitutes the first part of this goal. Presented are the results of miniemulsion polymerizations using both water and oil-soluble initiators. Limiting conversions in both are examined and explained in terms of radical loss. The second part of the goal is to further the understanding of the nature of the RAFT/miniemulsion system when employed in continuous tubular reactors. The development of the recipe using mixed surfactants, the results of styrene homopolymerizations in batch and tube, and the results of a chain extension experiment demonstrating the living nature of the chains formed in the tubular reactor are presented. Kinetic anomalies are addressed, as well as polydispersity (PDI) differences between batch and tube. Flow phenomenon and their influence on residence time distribution and by implication the polydispersity of the polymer formed are offered as explanations for the variance in PDI and are subsequently quantified. A model of RAFT in laminar flow is presented and the results and implications are discussed in general terms. The flow profile of the reactor is examined using a tracer technique developed specifically for this system. Experiments are presented directly relating the residence time distribution to the polydispersity of the polymer. Transient behavior of the reactor in isolated plug flow is explained in terms of initiator loss. Both experimental data and a model are used to support this hypothesis. Finally, conclusions and implications are presented and unanswered questions and the ideas for future work that they generated are addressed.

New environmental regulations enforce the electronic industry to replace Pb-Sn solder due to Pb could contaminate our environment. Pure Sn has good material properties such as solderability, conductivity and anti-corrosion. Pure Sn is a good candidate to replace Pb-Sn solder. One of the disadvantages of pure Sn is the whisker growth phenomenon. Whisker problem has become a major concern in electronic industry due to the trend toward component miniaturization and pitch reduction. It is well understood that the root cause for tin whisker growth is the compressive stress within the tin layer. In the literature, the main stress sources are, (1) the intermetallic layer induced interface stress, (2) the difference of thermal expansion coefficient between Sn layer and substrate and (3) the mechanical residual stress from trim-form operation after tin plating. In our study, we used the electrochemical electrolysis method and Cross-section Polisher (CP) to examine the tin whisker growth mechanism. In the result, we can clearly show the Cu6Sn5 phase grow up in the tin grain boundary regions and demonstrate that the Cu6Sn5 phase formation is the main cause of the tin whisker growth. We also discuss the relationship of tin whisker growth and tin-plating process parameters that include the temperature effect; Ni underlay effect and tin-plating bath effect. For the temperature effect, the Cu6Sn5 is the major phase at 150¢XC aging. The mechanism behind its growth mechanism was grain boundary diffusion at the earlier stage and then the bulk diffusion in the later stage. The application of 150¢XC post-heat treatment could drive the bulk diffusion and form a layer type Cu6Sn5 phase to eliminate the whisker growth. For the Ni underlay effect, the Ni underlay can block the Cu atom diffusion to the tin layer and changed the tin layer stress state from compressive to tensile. Therefore, the tin whisker can be eliminated. For the tin-plating bath effect, in the sulfuric acid base and uses Triton X-100 as the surface active agent, may transform the whisker type to particular tin grain type. Thus, this tin-plating solution can restrain the tin whisker growth.

published_or_final_version / Chemistry / Doctoral / Doctor of Philosophy

A major factor complicating the cleanup at many sites is co-contamination by both organic compounds and heavy metals. Whereas much research has focused on the removal of either organic compounds or metals, relatively few studies have investigated simultaneous removal of organic and inorganic pollutants from soil. / The studies reported in this thesis have evaluated a novel technique for the simultaneous mobilization of polychlorinated biphenyl (PCB) compounds and heavy metals (HMs) from a field contaminated soil. Soil extraction with washing aids {surfactants/cyclodextrin in combination with chelating reagent(s)} was optimized for mobilization efficiency, recovery/recycle of washing additives, and in parallel detoxification of mobilized contaminants. PCB extraction efficiencies were determined with a method that converted all the PCB congeners to dicyclohexyl by hydrogenation over palladium. Studies demonstrated that 10 minutes of ultrasonic mixing of field contaminated soil with a combination of surfactant (30 mL L-1) or cyclodextrin (100 g L-1) and a sparing quantity (2 mmoles) of EDTA, simultaneously mobilized appreciable quantities of PCBs and most analyte metals (Cd, Cu, Mn, Pb, Zn, Ni, Cr). / Relative to individual reagents, combinations of surfactant (Brij 98, Triton X-301, or Triton XQS-20) or cyclodextrin (RAMEB or HPCD) with EDTA did not influence PCB extraction efficiencies perceptibly. The presence of surfactant or cyclodextrin in admixture with EDTA did not appreciably change the efficiency of mobilization of most heavy metals (Al, Cd, Cr, Fe, Mn, Ni, and Zn) but did increase the recovery of Cu and Pb with nonionic surfactant and cyclodextrin. When coupled with PCB removal by hexane back-extraction and precipitation of the HMs (mediated by hydrolysis of zero-valent magnesium (Mg0)}, aqueous washing suspension was regenerated and recycled twice to mobilize more contaminants from the soil. Three sonication-washes with the same charge of reagent mobilized appreciable quantities of PCBs (68 - 83%) and virtually all of the available Cd, Cu, Mn, and Pb and lesser amounts of the Zn (56%), Ni (59%), and Cr (50%) but only small quantities of Al (28%) and Fe (30%). / The release of EDTA from heavy metals complexes was efficient for most metals (99%) but was influenced by the nature of surfactant. EDTA recovery (62-65%) post three cycles of soil washing, hexane back-extraction, and Mg 0 treatment was similar for all reagent combinations. Among surfactants and cyclodextrin, only anionic surfactants suffered losses to Mg0 treatment.

Sites contaminated with polyaromatic hydrocarbons (PAHs) pose serious health and safety risks to the surrounding environment due to their toxicity, persistence and accumulation in the environment. Because certain members of this class have been demonstrated to be both carcinogenic and mutagenic, PAHs are considered as environmental priority pollutants (US EPA). The studies in this thesis provide an efficient, economical and environmentally benign technique for the remediation of PAH contaminated soil/sediment by means of PAH mobilization with surfactant followed with a catalytic hydrogenation in supercritical carbon dioxide (scCO2). / Catalytic hydrogenation of naphthalene, acenaphthylene, ancenaphthene, anthracene, phenanthrene, chrysene and benzo[a]pyrene over alumina supported palladium (5% Pd0/gammaAl2O3) commercial catalyst were investigated in either a batch reaction mode or a continuous reaction system in H2-scCO2 (∼5% v/v). The hydrocarbon compounds were efficiently reduced to their corresponding fully saturated polycyclic hydrocarbon homologs with mild conditions of temperature (90°C) and pressure (60 psi H2 or 3000 psi H2-scCO2). The bacterial reverse mutation assay demonstrated that both the fully and partially hydrogenated products of chrysene and benzo[a]pyrene were devoid of mutagenic activity. / A laboratory study was conducted on the surfactant-assisted mobilization of PAH compounds combined with reagent regeneration and detoxification steps to generate innocuous products. Five minutes of ultrasonication of field contaminated soil with a 3% (w/v) surfactant suspension mobilized appreciable quantities of all PAH compounds. Formulating the Brij 98 surfactant in 0.1 M phosphate buffer (pH 8.0) mobilized the largest quantities of PAH compounds and the recovery of surfactant (>90%) but soil residues exceeded permissible maxima for five- and six-ring analytes. Five successive washes were required to reduce the residual fraction to permissible levels. The mobilized PAH compounds were then detoxified at line by catalytic hydrogenation in a 5% H2-scCO2 (v/v) atmosphere. / New palladium hydrogenation catalysts were fabricated in the laboratory with specific processes on various supports. The hydrogenation of phenanthrene and benzo[a]pyrene in a fixed bed micro reactor demonstrated that the catalyst that was fabricated from organosoluble precursor loaded on aluminum oxide (2.5% Pd0/gammaAl2O3) was four times more efficient than the commercial catalyst that was used for PAH hydrogenations.

Ligand I- along with nonionic surfactant, Triton X-100 or anionic surfactant, sodium dodecyl sulfate (SDS) were applied as soil washing agents to desorb Cd from both naturally and artificially contaminated soils. After seven consecutive washings, up to 90% of Cd was desorbed from both soils. Triton X-100 with I- showed a higher capacity to desorbing Cd than did SDS with I-. The increase of ligand concentration was a critical factor for increasing leaching capacity. Without the ligand, surfactant alone could not desorb Cd effectively from either soil. After seven consecutive washings, a sequential extraction experiment was performed for soil residuals to define the soil fraction of Cd removed by the washing agent. Among the washing agents, only Triton X-100/I- could remove Cd from the exchangeable fraction of both soils. / Various ligands including I-, SCN-, and I-/SCN- in combination with Triton X-100 were tested for their efficacy in desorbing heavy metals such as Cd, Zn, Cu, and Pb from a field contaminated soil. Cadmium was preferentially desorbed by Triton X-100/I- whereas Zn and Cu were preferentially desorbed by Triton X-100/SCN-. The mixture of I- and SCN- with Triton X-100 desorbed the most Cd and Cu, but not for Zn, as I- inhibited Zn desorption. Sequential extraction experiments after seven washings showed that metals held in the exchangeable fraction can be desorbed only by a combination of ligand and surfactant. / Nonionic surfactants having different alkyl chain lengths in combination with ligand I- were tested for the desorption of Cd and PCBs from soil. Cadmium desorption was increased at the lower surfactant concentration and higher ligand concentration. The increase in the hydrophilic alkyl chain length of the surfactant adversely affected Cd desorption. Up to 100% of PCBs were successfully removed by most of surfactant-ligand combinations and the desorption was less dependent, compared to heavy metals, on the concentration of washing agents and length of alkyl chain. The linear relationships between number of washings and Cd desorption, and between alkyl chain length and Cd desorption was defined. (Abstract shortened by UMI.)

Thesis (Ph. D.)--West Virginia University, 2007. / Title from document title page. Document formatted into pages; contains xv, 145 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 138-145).

Thesis (M.Sc.(Tech.))--University of Waikato, 2006. / Includes bibliographical references (leaves 221-230) Also available via the World Wide Web.

Thesis (PhD) - Swinburne University of Technology, Faculty of Engineering and Industrial Sciences, Centre for Micro-Photonics, 2005. / A thesis submitted in fulfillment of the requirements for the degree of Doctor of Philosophy, Centre for Micro-Photonics, Faculty of Engineering and Industrial Sciences, Swinburne University of Technology, 2005. Typescript. Bibliography: p. 201-210. Also available on cd-rom.

Thesis (M.S.)--University of Alabama at Birmingham, 2008. / Additional advisors: Marion Nipper, Robert A. Angus, Addison L. Lawrence. Description based on contents viewed May 30, 2008; title from title screen. Includes bibliographical references.