The objectives of this study are to synthesize poly(dimethylsilane) (PDMS) preceramic polymer and to investigate its effect on morphology, flame retardant and mechanical properties of polypropylene (PP) based composites. There are mainly two parts in this thesis. In the first part, PDMS was synthesized by electrochemical polymerization of dichlorodimethylsilane, which was dissolved in 1,2 dimethoxyethane (DME) solvent consisting of tetrabutyl ammonium perchlorate (TBAP), as supporting electrolyte. PDMS was obtained in powder form and characterized with Fourier transform infrared, ultraviolet-visible and proton nuclear magnetic resonance spectroscopic analyses, thermogravimetric analysis (TGA) and scanning electron microscopy (SEM). Since PDMS has some impurities coming from TBAP and DME, alternatively, the PDMS synthesis was done by electrochemical reduction of dichlorodimethylsilane without using solvent and/or supporting electrolyte for seven days. PDMS was produced as pure and characterized with the same methods used for previous synthesis. In the second part of this thesis, PP based composites with additives were prepared by using a twin-screw extruder and injection molding machine and were characterized with limiting oxygen index (LOI), horizontal burning, TGA, differential scanning calorimetry (DSC), tensile and impact tests and SEM analysis. Triphenyl phosphate, boron phosphate, magnesium hydroxide, intumescent flame retardants (IFR) (melamine phosphate (MP) and pentaerythritol (PER)), antimony trioxide and poly(methylsilsesquioxane) were additives used in this study other than PDMS. According to LOI test results, the highest LOI value among the PDMS composites was obtained in 1% PDMS, 14.25% MP and 4.75% PER (w/w) containing composite as 24%, whereas the LOI value of neat PP was measured as 17.5%. It was determined that elastic moduli of all the composites studied were higher than neat PP.

This thesis described the synthesis and characterization of new perylene diimide (PDI)-based photonic and electronic materials. In the first part of this thesis, PDI-based polynorbornenes, including PDI-grafted homopolymers and block-copolymers (BCPs) were synthesized and characterized as alternative acceptors for fullerenes for organic electronics. It was found that the PDIs on the polymer side-chains affect π-π stacking with the neighboring PDIs, which has implications for the use of these materials for organic field-effect transistors (OFETs) and organic photovoltaic devices (OPVs). It should be noted that the performance of solar cell based on these materials was poor, like other similar materials. The major reasons could be the challenge in controlling the molecular alignment of the PDI-based materials, which leads to lower electron mobilities in films compared to devices with fullerene-based acceptors. One PDI-grafted BCP showed better OPV performance compared to the other BCPs and respective homepolymer blends, presumably due to favorable morphology. In the second part of this thesis, photo-induced charge-separation in blends of poly-3-hexyl-thiophene (P3HT) and various PDI derivatives have been studied. Probing of long-lived photo-generated PDI radical anions provided insight on these photo-induced processes and their use for OPVs. In the third part of this thesis, the use of photo-generated PDI radical-anion absorption was shown to be effective for optical limiting of nanosecond laser pulses between 650 - 800 nm. In Chapter 5, an effective approach for two-photon absorption (2PA)-induced optical limiting using donor-PDI dyads through which donors and acceptors can be independently chosen to maximize optical suppression at particular wavelengths has been demonstrated. In Chapter 6, conjugated polymers with PDI pendants and poly(carbazole-alt-2,7-fluorene) main-chains were synthesized for optical limiting using the photo-generated PDI radical anion via PDI aggregate excitation and/or 2PA from the polymer backbones. It was also found that nitro-phenyl group or similar derivatives could be good candidates to incorporate into those donor-conjugated polymers, which have significant overlap between their 2PA band and respective polaron absorptions for 2PA-indced optical limiting. / Thesis advisor has approved the addition of errata to this item. Corrections were made to pages 95, 98 and 101.

The purpose of this study was to increase awareness and understanding of parental caregivers’ current support needs in order to provide direction in the development of a theory-based hope intervention. The intervention is intended to improve psychosocial and bereavement support for parental caregivers of children with life limiting (LLI) or life threatening illnesses (LTI). The number of parents who have children living with a LLI/LTI is increasing. The impact of these illnesses on parents is significant as they travel alongside their child and experience emotional, physical, and spiritual upheaval. Current empirical research reveals that this journey challenges parents’ understanding of life, faith, and certainty in the future. Many studies demonstrated that parents’ needs are not consistently met and parents often reported the need for psychosocial support. Hope has been found to be an important psychosocial concept for parents and has been shown to provide support when facing difficult circumstances. For this reason, the concept of hope provided the conceptual framework for this research. In order to develop a theory-based psychosocial hope intervention for parental caregivers, a large scale privately funded project that included a metasynthesis of current research, a Delphi survey, and focus groups was conducted. All three components of this project were developed by a research team of two doctorate nurse researchers, one pediatric palliative care specialist, one pediatric oncologist, one community member, and a graduate student. The study presented here is based on the Delphi survey only and serves as the graduate student’s master of nursing thesis. A Delphi survey consisting of three rounds of questions and controlled feedback to experts was employed. Sixty-eight experts were recruited including parental caregivers who have children diagnosed with LLIs or LTIs and those who care for them such as community members, nurses, social workers, and physicians. Based on Bally et al.’s (2013) grounded theory of Keeping Hope Possible, the survey focused on four subprocesses that were identified as essential for parental hope. Experts suggested strategies or activities for each subprocess. Answers were summarized and ranked in order of highest to lowest according to feasibility and effectiveness. The final round revealed a consensus and eight major themes emerged: organize basic needs; connect with others; prioritize self-care; obtain meaningful information; take things day by day; advocate for parental participation; manifest positivity; and celebrate milestones. The survey took place via email to allow easy access to experts and parents globally. This study identified needs of parents of children with LLIs or LTIs in order to develop a theory-based psychosocial hope intervention. Results have the potential to provide direction for a newly developing pediatric palliative care program in Western Canada.

In the production of biodiesel via the transesterification of vegetable oils, purification to international standards is challenging. A key measure of biodiesel quality is the level of free glycerol in the biodiesel. In order to remove glycerol from fatty acid methyl ester (FAME or biodiesel), a membrane separation setup was tested. The main objective of this thesis was to develop a membrane process for the separation of free glycerol dispersed in FAME after completion of the transesterification reaction and to investigate the effect of different factors on glycerol removal. These factors included membrane pore size, pressure, temperature, and methanol, soap and water content. First, a study of the effect of different materials present in the transesterification reaction, such as water, soap, and methanol, on the final free glycerol separation was performed using a modified polyacrylonitrile (PAN) membrane, with 100 kD (ultrafiltration) molecular weight cut off for all runs at 25°C. Results showed low concentrations of water had a considerable effect in removing glycerol from the FAME. The mechanism of separation of free glycerol from FAME was due to the removal of an ultrafine dispersed glycerol-rich phase present in the untreated (or raw) FAME. The size of the droplets and the free glycerol separation both increased with increasing water content of the FAME. Next, three types of polymeric membranes in the ultrafiltration range with different molecular weight cut off, were tested at three fixed operating pressures and three operating temperatures (0, 5 and 25oC) to remove the free glycerol from a biodiesel reactor effluent. The ASTM standard for free glycerol concentration was met for the experiments performed at 25°C. The results of this study indicate that glycerol could be separated from raw FAME to meet ASTM and EN standards at methanol feed concentrations of up to 3 mass%. The process was demonstrated to rely on the formation of a dynamic polar layer on the membrane surface. Ceramic membranes of different pore sizes (0.05 µm (ultrafiltration (UF) range) and 0.2 µm (microfiltration (MF) range)) were used to treat raw FAME directly using the membrane separation set up at temperatures of 0, 5 and 25°C. The results were encouraging for the 0.05 µm pore size membrane at the highest temperature (25°C). The effect of temperature on glycerol removal was evident from its relation with the concentration factor (CF). Higher temperatures promoted the achievement of the appropriate CF value sooner for faster separation. Membrane pore size was also found to affect separation performance. A subsequent study revealed the effect of different variables on the size of the glycerol droplets using dynamic light scattering (DLS). A key parameter in the use of membrane separation technology is the size of the glycerol droplets and the influence of other components such as water, methanol and soaps on that droplet size. The effect of water, methanol, soap and glycerol on the size of suspended glycerol droplets in FAME was studied using a 3-level Box-Behnken experimental design technique. Standard statistical analysis techniques revealed the significant effect of water and glycerol on increasing droplet size while methanol and soap served to reduce the droplet size. Finally, a study on the effect of trans-membrane pressure (TMP) at different water concentrations in the FAME phase on glycerol removal using UF (0.03 µm pore size, polyethersulfone (PES)) and MF (0.1 and 0.22 µm pore sizes, PES) membranes at 25, 40 and 60°C was performed. Results showed that running at 25°C for the two membrane types produced the best results for glycerol removal and exceeded the ASTM and EN standards. An enhancement of glycerol removal was found by adding small amounts of water up to the maximum solubility limit in biodiesel. An increase in temperature resulted in an increase in the solubility of water in the FAME and less effective glycerol removal. Application of cake filtration theory and a gel layer model showed that the gel layer on the membrane surface is not compressible and the specific cake resistance and gel layer concentration decrease with increasing temperature. An approximate value for the limiting (steady-state) flux was reported and it was found that the highest fluxes were obtained at the lowest initial water concentrations at fixed temperatures. In conclusion, dispersed glycerol can be successfully removed from raw FAME (untreated FAME) using a membrane separation system to meet the ASTM biodiesel fuel standards. The addition of water close to the solubility limit to the FAME mixture enables the formation of larger glycerol droplets and makes the separation of these droplets straightforward.

The theory describing the scaling properties of quantum field theory is introduced. The symmetry principles behind scale and conformal transformations are reviewed together with the renormalisation group. A method for improving perturbative calculations of physical quantities in the infra-red limit is developed using general analyticity properties valid for all unitary quantum field theories. The infra-red limit of a physical quantity is shown to equal the limiting value of the Borel transform in a complex scale parameter, where the order of the Borel transform is related to the domain of analyticity. It is shown how this general result can be used to improve perturbative calculations in the infra-red limit. First, the infra-red central charge of a perturbed conformal field theory is considered, and for the unitary minimal models perturbed by ɸ(1,3) the developed approximation is shown to be very close to the exact results by improving only a one loop perturbation. The other example is the infra-red limit of the critical exponents of x(^4) theory in three dimensions, where our approximation is within the limits of other approximations. The exact renormalisation group equation is studied for a theory with exponential interactions and a background charge. It is shown how to incorporate the background charge, and using the operator product expansion together with the equivalence between the quantum group restricted sine-Gordon model and the unitary minimal models perturbed by ɸ(1,3), the equation obtained is argued to describe the flow between unitary minimal models. Finally, a semi-classical approximation of the low energy limit of a bosonic membrane is studied where the action is taken to be the world-volume together with an Einstein-Hilbert term. A solution to the linearized equations of motion is determined describing a membrane oscillating around a flat torus.

A commercial GC-AFS instrument has been developed and optimised for the speciation of organomercury. This instrument couples a GC oven to a modified atomic fluorescence detector via a ceramic pyrolyser. Organomercury compounds in dichloromethane solvent were directly injected through a Programmable Temperature Vaporiser Injector onto a DBl Megabore column. Once separated, the compounds eluted from the column and were atomised in the pyrolyser then detected by AFS. The direct injection technique, ceramic pyrolysis design and argon purged detector have improved previous instrument designs by enhancing and maintaining sensitivity. The instrumental limit of detection was determined to be 0.25 pg Hg absolute. Methods were developed for the extraction of methylmercury from a variety of marine samples. The techniques were validated using mussel homogenate and dogfish liver (IAEA 142, SRM 8044 and DOLT-2) certified reference materials. An interlaboratory comparision exercise was participated in and a method was developed for the detemination of methylmercury in Fucus sea plant (IAEA 140). A concentration of 0.63 ± 0.006 ng g-1 was reported. The material is now certified at 0.626 +0.139 ng g-1. Of all the participating laboratories, this was the closest result to the certified value. The instrument and methods were also applied to soil and sediment samples. Once again validation was performed with a CRM sediment, IAEA 356. Although this material has been reported to give positive artifact formation when using a steam distillation sample preparation procedure, good agreement and no artifects were observed upon analysis. A further contaminated land, an uncontaminated soil and sediment sample were also studied. For all the samples studied by GC-AFS total mercury measurements were also made following an appropriate digestion procedure and CV-AFS. A gas chromatograph was also coupled with ICP-MS and HPLC was coupled to CV-AFS as comparative techniques. Both approaches were optimised and validated with CRM's. The GC-ICP-MS had the advantage of providing additional element information and confirmed the presence of methylmercury bromide in the final mussel homogenate extract. The HPLC approach found to be much less sensitive than the GC techniques and also suffered from vapour generation interferences. The PTV injector was considered for large volume injection and thermal desorption techniques. Injector breakdown problems were overcome by optimising the conditions and solid phase adsorbent for cold splitless injection. A recovery of 70% was achieved for a 50 ul large volume injection of methylmercury chloride in DCM. This technique indicated the possibility that LVI may in the future offer increased method sensitivity.

Consider two Markovian N-policy queueing models in discrete time, one with batch arrival, the other with batch service. In this paper the transient behaviour of both models is studied and the analogous continuous time results are achieved by a limiting process. The steady state solution for the model with batch arrival is derived. (author's abstract) / Series: Forschungsberichte / Institut für Statistik

Clinical management of esophageal adenocarcinoma (EAC) relies on radiation therapy, yet radioresistance is a pervasive challenge in this disease. The mechanisms of EAC radioresistance remain largely unknown due to a paucity of validated preclinical models. The present studies report on the development of seven primary xenograft models established from patient tumours. These models are used to interrogate the range of radiosensitivities and mechanisms of radioresistance in EAC tumours. We found that radiation enriches the tumour-initiating cell population in two xenograft lines tested. Furthermore, three tested xenograft lines respond to irradiation by upregulating Hedgehog transcripts, a pathway involved in stem cell maintenance and proliferation. Upregulation occurs in autocrine and paracrine patterns simultaneously, suggesting that Hedgehog signalling may have a complex role in the radioresponse of EAC tumours. These findings suggest that inhibiting stem cell pathways in combination with radiotherapy may have an important role in the clinical management of EAC.

Mobile boom cranes are used throughout the world to perform important and dangerous manipulation tasks. Given their mobility, these types of cranes can quickly be moved into position. Generally, their base is then fixed and stabilized before they start lifting heavy materials. The usefulness of these cranes can be greatly improved if they can utilize their mobile base during the lifting and transferring phases of operation. This ability greatly expands the workspace by combining base motion with the rotation, lifting, and luffing motions. Of course, the cranes lose some stability margin when a payload is attached. The stability is further degraded when the payload swings. This Master's Thesis presents a stability study of such cranes. As a first step, a static stability analysis of a boom crane is conducted in order to provide basic insights into the effects of the payload weight and crane configuration. Then, a semi-dynamic method is used to take the payload swing into account. As a final step, the results of a dynamic stability analysis obtained by using a multi-body simulation of the boom crane are compared to the outcomes of the previous approaches. This provides conclusions for the practical application of stability analysis. A control method that limits payload swing, and thereby improves stability, is also presented.

Made available in DSpace on 2014-06-11T19:30:26Z (GMT). No. of bitstreams: 0 Previous issue date: 2010-06-05Bitstream added on 2014-06-13T20:40:23Z : No. of bitstreams: 1 arroyogarcia_r_dr_botfca.pdf: 1117377 bytes, checksum: 640c0531b51ae26f4c6122ba741bb333 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / O manejo inadequado do solo ocasiona a formação de camadas compactadas que prejudicam o desenvolvimento radicular das plantas, diminuindo a disponibilidade de água e nutrientes, enquanto que o acúmulo de carbono pode melhorar a qualidade do solo. Em sistemas com semeadura direta (SSD), com a menor mobilização do solo, pode-se usar, em rotação, plantas com sistema radicular vigoroso, capaz de crescer em condições adversas. Este trabalho teve como objetivo avaliar a ação de espécies de cobertura, gramíneas e uma leguminosa, em rotação com a cultura da soja, nos atributos físicos de um Latossolo, no acúmulo de carbono, nas diferentes frações da matéria orgânica e na produção da soja, em semeadura direta, ao longo de três anos. O experimento foi conduzido em um Latossolo Vermelho distroférrico de textura argilosa, na Fazenda Experimental Lageado, Unesp/Botucatu, nos anos agrícolas de 2006/2007, 2007/2008 e 2008/2009. No outonoinverno foram estabelecidas parcelas com braquiária (Brachiaria ruziziensis), sorgo granífero (Sorghum bicolor) e sorgo consorciado com braquiária. Na primavera, foram cultivados, em subparcelas, milheto (Pennisetum glaucum), cober crop [Sorghum bicolor (L.) Moench x Sorghum sudanense Piper Stapf], crotalária (Crotalaria juncea) ou pousio. A soja foi cultivada como safra de verão. Em março do primeiro ano foram retiradas amostras para caracterização da área experimental. Após o manejo das espécies cultivadas na primavera, no primeiro e terceiro ano, foram retiradas amostras indeformadas nas camadas de 0-5; 7,5-12,5; 15-20; 27,5-32,5 e 47,5-52,5 cm para determinação da densidade do solo, porosidade e curva de retenção de água no solo. Nas mesmas épocas, a estabilidade de agregados foi avaliada em amostras coletadas nas camadas de 0-5 e 5-10 cm. No terceiro ano do experimento, o intervalo hídrico ótimo (IHO) foi determinado... / Compacted layers resulting from inappropriate soil management may impair root growth, thus decreasing water and nutrient acquisition by crops. Conversely, soil quality is improved with soil carbon accumulation. In areas under no-till, crop rotation with plants with vigorous root systems may alleviate soil compaction, as well as increase soil carbon. In this experiment the effects of cover crops on soil physical properties, carbon accumulation, organic matter quality and soybean production under no-till in a compacted soil were studied for three years. The experiment was conducted on a clayey Rhodic Ferralsol, Lageado Experimental Farm, Unesp/Botucatu, in 2006/2007, 2007/2008 and 2008/2009. Congo grass (Brachiaria ruziziensis), grain sorghum (Sorghum bicolor) and a mix of both were cropped during fall-winter. Then, in the spring, pear millet (Pennisetum glaucum), cober crop [Sorghum bicolor (L.) Moench x Sorghum sudanense Piper Stapf] and indian hemp (Crotalaria juncea) were cropped and a treatment under fallow was set on sub-plots. Soybean was cropped as a summer crop. In March of the first year, samples were taken for characterization of the area. Right after spring crops were chemically desiccated in 2006 and 2008, undisturbed soil samples were taken from the layers 0-5; 7.5-12.5; 15-20; 27.5-32.5 and 47.5-52.5 cm to determine bulk density, porosity and water retention curve. At the same time, samples taken from the depths 0-5 and 5-10 cm were used to determine aggregate stability. In the third year, least limiting water range (LLWR) was evaluated in the 7.5-12.5 and 27.5-32.5 cm soil layers. Organic matter characterization was done in the third year, in the depths of 0-5 and 5-10 cm. Roots of spring crops were sampled in the layers 0-5; 5-10; 10-20; 20-40 and 40- 60 cm, one day before chemical desiccation in all growing seasons. Soybean roots were sampled in the same depths at R2 each... (Complete abstract click electronic access below)