<p> This thesis presents a study of the compatiblization of a hydrophobic, synthetic polymer, polydimethylsiloxane (PDMS) and a hydrophilic biopolymer, starch. The Diels- Alder adduct of cyclopentadiene and maleic anhydride, bicyclo[2.2.1]hept-5-ene-2,3- dicarboxylic-anhydride, (1), was hydrosilylated with hydride- terminated PDMS to yield α,ω-bicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic-anhydride-polydimethylsiloxane, (4) having an average molecular weight of 750 g mol^-1. This was then reacted with starch using dimethylaminopyridine as a catalyst in a dimethylsulfoxide medium at 80°C to yield a silicone-starch graft copolymer having a γ-carboxylic-ester linkage.</p> <p> In order to study the influences of the quantity of hydrophobic and hydrophilic components, a series of composites were synthesized varying the starch and silicone stoichiometry (series-1).</p> <p> In order to study the influence of the molecular weight of the silicone, 4 was redistributed with octamethylcyclotetrasiloxane (D4) via cationic polymerization to yield higher molecular weight derivatives. The products were 7 (1500 g mol^-1) and 8 (9000 g mol^-1). These were reacted with starch to give a series of composites for each molecular weight of the functionalized silicone.</p> <p> Spectroscopic and physical properties were analyzed for developing trends.</p> / Thesis / Master of Science (MSc)

<p> UV radiation disinfection technology is an advantageous method of wastewater disinfection as it avoids the formation of chemical by-products typically found from chlorination. One challenge with this technology is avoiding fouling on the quartz sleeves in which the UV lamps are housed. In this study, using a model fouling system, the roles in fouling of light, and the constitution of the fouling media, are examined. The systematic determination of fouling by various mixtures of human serum albumin, humic acid, Ca^2+, and Fe^3+ was carried out on quartz slides in the presence and absence of UV (254nm) light. Fouling was assessed by the reduction in transmission of UV light through the quartz slides over time. It was determined that the most important factors were the concentration of..iron and protein, which apparently act synergistically to foul the surface. Other contributing factors to the magnitude of fouling include the flow rate and the age of the fouling solution. Most important was the presence of UV light. In all solutions examined, fouling was observed to a lower degree when the system was exposed to light. On the other hand, XPS analysis has demonstrated differences in the nature of the fouling layer on the surface exposed to UV light compared to that in the dark. </p> <p> It is generally accepted that low energy surfaces are less easily fouled than polar surfaces. Therefore, hydrophobic modification of the quartz by a series of different silane coupling agents was undertaken. Irrespective of the nature of the coating (alkylamine, alkyl, aryl, fluorocarbon, silicone), the rate and magnitude of fouling on the surface were comparable to the unmodified quartz. However, the more hydrophobic surfaces were easier to clean. </p> / Thesis / Master of Science (MSc)

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The IAEA ICSP on Numerical Benchmarks for Multiphysics Simulation of Pressurized Heavy Water Reactor Transients was initiated in 2016 to facilitate the development of a set of open access, standardized, numerical test problems for postulated accident scenarios in a CANDU styled Reactor. The test problems include a loss of coolant accident resulting from an inlet header break, a loss of flow accident caused by a single pump trip, and a loss of regulation accident due to inadvertently withdrawn adjusters. The Benchmark was split into phases, which included stand-alone physics and thermal-hydraulics transients, coupled steady state simulations, and coupled transients. This thesis documents the results that were generated through an original TRACE/PARCS coupling methodology that was developed specifically for this work. There is a strong emphasis on development methods and step by step verification throughout the thesis, to provide a framework for future research in this area. In addition to the Benchmark results, additional studies on propagation of fundamental nuclear data uncertainty, and sensitivity analysis of coupled transients are reported in this thesis. Two Phenomena and Key Parameter Identification and Ranking Tables were generated for the loss of coolant accident scenario, to provide feedback to the Benchmark Team, and to add to the body of work on uncertainty/sensitivity analysis of CANDU style reactors. Some important results from the uncertainty analysis work relate to changes in the uncertainty of figures of merit such as integrated core power, and peak core power magnitude and time, between small and large break loss of coolant accidents. The analysis shows that the mean and standard deviation of the integrated core power and maximum integrated channel power, are very close between a 30% header break and a 60% header break, despite the peak core power being much larger in the 60% break case. Furthermore, it shows that there is a trade off between the uncertainty in the time of the peak core power, and the magnitude of the peak core power, with smaller breaks showing a smaller standard deviation in the magnitude of the peak core power, but a larger standard deviation in when this power is reached during the transient, and vice versa for larger breaks. From the results of the sensitivity analysis study, this thesis concludes that parameters related to coolant void reactivity and shutoff rod timing and effectiveness have the largest impact on loss of coolant accident progressions, while parameters that can have a large impact in other transients or reactor designs, such as fuel temperature reactivity feedback and control device incremental cross sections, are less important. / Thesis / Master of Science (MSc) / This thesis documents McMaster’s contribution to an International Atomic Energy Agency Benchmark on Pressurized Heavy Water Reactors that closely resemble the CANDU design. The Benchmark focus is on coupling of thermal-hydraulics and neutron physics codes, and simulation of postulated accident scenarios. This thesis contains some select results from the Benchmark, comparing the results generated by McMaster to other participants. This thesis also documents additional work that was performed to propagate fundamental nuclear data uncertainty through the coupled transient calculations and obtain an estimate of the uncertainty in key figures of merit. This work was beyond the scope of the Benchmark and is a unique contribution to the open literature. Finally, sensitivity studies were performed on one of the accident scenarios defined in the Benchmark, the loss of coolant accident, to determine which input parameters have the largest contribution to the variability of key figures of merit.

Experiments were performed with naphthalene and a-naphthol to compare the processes involved in the sorption of a polycyclic aromatic hydrocarbon (PAH) and its metabolite, respectively, and to assess the bioavailability of these two compounds adsorbed to two sandy soils with different organic carbon contents. Adsorption conditions were varied to estimate the extent that biologically-mediated and chemically-induced oxidative coupling, and rate-limited diffusive processes contributed to the apparent irreversible adsorption of these compounds. The purposes of this research were to: (1) investigate the processes which cause the irreversible adsorption of organic contaminants to soil~ (2) gauge the impact that these different adsorption processes have on the bioavailability of sorbed contaminants; and, (3) evaluate the environmental significance of these processes in soils and the subsurface. This dissertation has been prepared as three separate articles for publication in peer reviewed journals. The first article serves as a literature review in evaluating the significance of oxidative coupling reactions in soil and subsurface environments. This review concludes that oxidative coupling of organic contaminants may be important in soils and could be stimulated as a viable remediation strategy. For subsurface systems oxidative coupling appears much more limited, however, engineered systems could be developed to enhance this process. The second article presents experimental results used to quantify the individual processes involved in the irreversible adsorption of naphthalene and a-naphthol. This article concludes that both biological and chemical catalysts are important in promoting irreversible adsorption reactions, and that once the partial oxidation of a PAH occurs, oxidative coupling can become a significant process affecting contaminant fate. The third and final article examines the effect of different adsorption processes on the subsequent bioavailability of sorbed naphthalene and anaphthol, and concludes that the biodegradation of naphthalene and α-naphthol adsorbed to both the soils tested was controlled by the rate of desorption and the reversibility of the adsorption process. / Ph. D.

The earth's ionosphere-thermosphere region is a coupled environment which is governed by interactions between the overlapping neutral constituents and ionospheric plasma. The mid-latitude thermosphere-ionosphere system is very complex owing to its sensitivity to both the polar and equatorial processes. The mid-latitudes is also a relatively unexplored and less understood region primarily due to the paucity of observing instruments that have traditionally been available. However, the past 9 years of mid-latitude expansion of the Super Dual Auroral Radar Network (SuperDARN) has provided new access to continuous large-scale observations of the sub-auroral ionosphere. On the other hand, the past 3 years of mid-latitude expansion of the North American Thermosphere Ionosphere Observation Network (NATION) Fabry-Perot interferometer array, has created a critical resource for measuring the thermospheric neutral winds. The overlap of these two observing networks in the mid-east North American sector has resulted in a strong ground-based large-scale platform for co-located study of mid-latitude thermosphere-ionosphere dynamics for the first time. The coupling between ions and neutrals is a very important process for controlling the thermospheric dynamics. Ion-neutral coupling at high latitudes has been studied in many previous papers, but there have been very few studies focused on the mid-latitude region. Hence, in this work we have studied the ion-neutral coupling mechanisms and timescales at mid-latitudes during disturbed geomagnetic conditions by using the co-located observations from the SuperDARN-NATION array. The study has focused on the main phase as well as the late recovery phase of a geomagnetic storm which occurred on October 2-3, 2013. Ion drag is known to drive the neutral circulation during the main phase of storm at auroral latitudes, while the neutral wind disturbance dynamo mechanism is known to generate ionospheric electric fields and currents during the recovery phase. By using the methods of ion-neutral momentum exchange theory and time lagged correlation analysis, we analyzed the timescales at which the ion-neutral coupling operates. The ions are observed to drive the neutral winds on a timescale of ~ 84 minutes in the storm main phase which is significantly faster than expected from the driving due to local ion-drag alone (~ 124 minutes). This suggests that along with ion-drag, other local and non-local storm-time influences like Joule heating are also playing an important part in driving the neutral winds. On the other hand, in the late recovery phase, the neutral winds are found to be strongly coupled with the ions and maintain the ion convection without any significant time delay which is consistent with effect of the 'disturbance dynamo' or 'neutral-flywheel' persisting well into the late recovery phase. The timescales and underlying physics understood through this work serve as an important contribution to our knowledge of ion-neutral coupling processes at the middle latitudes. Looking forward, the expansion of co-located SuperDARN-NATION coverage at mid-latitudes, and developments in the tools of large-scale visualization through FPI wind field mapping and SuperDARN convection maps, has created a very strong basis for using the results and analysis tools developed in this work for large-scale ion-neutral coupling characterization in future. / Master of Science