Vertically aligned Multiwalled Carbon Nanotubes (MWCNTs) were grown in the pores of Anodized Aluminum Oxide (AAO) templates and investigated for resistive sensor applications. High Sensitivity of 23% to low concentration (100 ppm) of ammonia was observed. An equivalent circuit model was developed to understand the current flow path in the resistive sensor. This helped us in achieving high sensitivities through amorphous carbon (a-C) layer thickness tailoring by employing post-growth processing techniques like plasma etching. A simulation model in MATLAB was developed to calculate the device resistance and the change in the sensitivity as a function of device parameters. The steady state response and transient response of the model to the number of ammonia molecules and its adsorption rate were studied. Effects of oxygen plasma, argon plasma and water plasma etch on thinning of the a-C layer were studied. In order to enhance the sensitivity, the top and bottom a-C layers were replaced by a more conductive metal layer. This also helped in understanding the current flow in the device and in the estimation of the resistivity of the a-C layer.

Recent studies have demonstrated the omnipresence of antibacterial agents in the aquatic environment due to high usage and widespread applications of these compounds in medicine and agriculture, raising concerns over proliferation of antibiotic-resistant bacteria and other adverse health effects. Tetracyclines (TCs) are among the most widely used antibiotics and their fate and transformation in the soil-water environment are not yet well understood. Based on TCs' strong tendency to interact with metals, their environmental fate and transport are expected to be greatly influenced by metal species commonly present in waters and soils and thus the focus of this study. The study results show that TCs are highly susceptible to oxidative transformation mediated by dissolved Mn(II) and Cu(II) ions and manganese dioxide under environmentally relevant conditions. The oxidative transformation can occur via different TC structural moieties and reaction pathways when different metal species are involved, leading to complicated product formation patterns. It was also found that Al oxide surfaces can promote the acid-catalyzed isomeration and dehydration of TCs. To better evaluate the surface reactions of Mn oxide with TCs and other compounds, a new kinetic model was successfully developed to describe the complex reaction kinetics based on the experimental results with TCs and three other classes of antibacterial agents. Overall, this work significantly advances the fundamental understanding of the reaction mechanisms of TC compounds and provides the knowledge basis for better risk assessment of these compounds in the environment.

Mémoire (M.Eng.)--Université du Québec à Chicoutimi, 1997. / Document électronique également accessible en format PDF. CaQCU

Mémoire(M.Eng.)-- Université du Québec à Chicoutimi, 2002. / Document électronique également accessible en format PDF. CaQCU

Submitted by Milena Rubi (milenarubi@ufscar.br) on 2017-08-16T17:03:58Z No. of bitstreams: 1 FERRO_Leticia_2016.pdf: 31138746 bytes, checksum: e2ec63a4c8fe8750b322f5f59e152466 (MD5) / Approved for entry into archive by Milena Rubi (milenarubi@ufscar.br) on 2017-08-16T17:04:05Z (GMT) No. of bitstreams: 1 FERRO_Leticia_2016.pdf: 31138746 bytes, checksum: e2ec63a4c8fe8750b322f5f59e152466 (MD5) / Approved for entry into archive by Milena Rubi (milenarubi@ufscar.br) on 2017-08-16T17:04:12Z (GMT) No. of bitstreams: 1 FERRO_Leticia_2016.pdf: 31138746 bytes, checksum: e2ec63a4c8fe8750b322f5f59e152466 (MD5) / Made available in DSpace on 2017-08-16T17:04:19Z (GMT). No. of bitstreams: 1 FERRO_Leticia_2016.pdf: 31138746 bytes, checksum: e2ec63a4c8fe8750b322f5f59e152466 (MD5) Previous issue date: 2016-03-31 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / Porous anodic alumina (PAA) has been used as platform for the manufacture of optical sensors. Itshows chemical resistance, thermal stability, hardness, biocompatibility, high surface area which facilitates interaction with the analyte and good morphological organization with the possibility to manipulate its pore size. Furthermore, PAA shows optical responses characterized by Fabry-Pérot interferences that can be obtained by photoluminescence and reflectance spectroscopy. Besides the surface of the AAP can be modified by Layer-by-Layer technique (LbL) in order to enhance optical sensors. Changes in Fabry-Pérot interferences can be monitored and analyzed as sensor responses. In this work, LbL film were deposited using hydrochloride polyallylamine (PAH) and glucose oxidase (GOx) for the purpose of manufacturing an optical biosensor for glucose detection. A protective bilayer of PAH and poly (vinyl sulfonic acid) (PVS) was assembled. The growth of the films were monitored by photoluminescence and total reflectance techniques. In addition, biosensor tests were carried out by immersing PAA in glucose solutions with different concentrations in order to check for changes in Fabry-Pérot oscillations. Analyzing the results, orderly growth of LbL film and biosensor response were verified. Results of the biosensor test were characterized by displacements of Fabry-Pérot interferences to shorter wavelengths and by multivariate analysis. Limit of detection determined by qualitative analysis of the Fabry-Pérot oscillations was 0.1 mol.L-1 to both PAA without surface modification and modified PAA. By using partial least squares (PLS) regression, it was possible to determine glucose from 0.1 mol.L-1 with PAA without modification and 0.01 mol.L-1 for PAA with LbL film. Furthermore, it was also verified the viability of using chemometrics to examine Fabry-Pérot interferences obtained with the PAA as an alternative method shown in the literature, which involves concepts of Fabry-Pérot equation. / A alumina anódica porosa (AAP) vem sendo utilizada como plataforma na fabricação de sensores ópticos por apresentar resistência química, estabilidade térmica, dureza, biocompatibilidade, grande área superficial que facilita a interação com o analito e boa organização morfológica com a possibilidade de se manipular as dimensões de seus poros. Além disso, a AAP apresenta respostas ópticas caracterizadas pelas interferências de FabryPérot, que podem ser obtidas por espectroscopia de fotoluminescência e de reflectância. A superfície da AAP ainda pode ser modificada pela técnica de deposição por camadas, Layerby-Layer (LbL), com o intuito de se aprimorar esses sensores ópticos, sendo que mudanças nas interferências de Fabry-Pérot podem ser acompanhadas e analisadas como resposta do sensor. Neste trabalho, houve a deposição de filmes LbL de polialilamina hidroclorada (PAH) e de glicose oxidase (GOx), contendo um colchão de PAH e de ácido poli(vinil sulfônico) (PVS), com a finalidade de fabricação de um biossensor óptico de glicose. O crescimento dos filmes foi acompanhado por fotoluminescência e reflectância total. Além disso, testes dos biossensores foram realizados imergindo a AAP em soluções de glicose com concentrações diferentes a fim de se verificar alterações nas oscilações apresentadas nos espectros. A partir dos resultados obtidos foram verificados o crescimento ordenado do filme LbL e a resposta do biossensor, que foi caracterizada pelo deslocamento das interferências de Fabry-Pérot para comprimentos de onda menores e por análise multivariada. O limite de detecção determinado através da análise qualitativa das oscilações de Fabry-Pérot foi de 0,1 mol.L-1 de glicose, tanto para a AAP sem modificação superficial, quanto para a modificada. Com o emprego da regressão por mínimos quadrados parciais (PLS, do inglês “partial least squares”) foi possível a determinação de glicose a partir de 0,1 mol.L-1 para a AAP sem modificação e de 0,01 mol.L-1 para a AAP com filme LbL. Além disso, foi verificada também a viabilidade de se utilizar a quimiometria para analisar as interferências de Fabry-Pérot obtidas com a AAP como um método alternativo do apresentado na literatura, que envolve conceitos da equação de Fabry-Pérot.

[pt] A utilização de compósitos de matriz ferrosa com pré-forma cerâmica oferece a possibilidade de redução do desgaste abrasivo em aplicações onde as ligas usuais não são efetivas. Nesta tese, foi desenvolvido um estudo voltado para a obtenção de um compósito de matriz metálica com ênfase na caracterização e previsão da infiltração espontânea de um ferro fundido nodular através de uma préforma granulada porosa de óxido de alumínio. O processo de infiltração de pré-forma porosa constituída de óxido de alumínio, em três granulometrias distintas (12#, 16# e 42#), por um ferro fundido nodular de composição eutética (3,9 graus Celsius) foi realizado em três temperaturas de vazamento diferentes (1403 graus Celsius, 1299 graus Celsius e 1250 graus Celsius), desde a elaboração das pré-formas passando pela infiltração do metal, até a caracterização microestrutural. Os resultados dos ensaios de compressão com as pré-formas foram processados por análise fatorial e mostraram que, dentro dos níveis estudados, o percentual utilizado de ligante (silicato de sódio) e o tempo de cura influenciam positivamente e de forma mais significativa do que a granulometria do óxido de alumínio. A microestrutura da matriz foi afetada pelos grãos cerâmicos da préforma, fato este caracterizado pela presença de veios de grafita no lugar de nódulos em uma extensão variável entre 10 micrômetros e 60 micrômetros a partir da superfície do grão. Após a permeabilidade da pré-forma cerâmica ter sido estimada por processamento digital de imagens em 3D, foi desenvolvido um modelo matemático voltado para a identificação da penetração máxima da fase metálica levando em consideração as temperaturas de vazamento e de solidificação do ferro fundido. As curvas do modelo mostraram boa correlação quando comparados com os resultados experimentais. / [en] Iron metal matrix composites in aluminium oxide offers an outstanding possibility to reduce abrasive wear where usual alloys are not working well. For the present study the composite was obtained by carrying out an spontaneous infiltration of an eutectic (3,9 degrees Celsius) nodular iron in a preform made with three aluminiun oxide granulometries (#12, #16 and #42), in three different pouring temperatures (1403 degrees Celsius, 1299 degrees Celsius e 1250 degrees Celsius). The preforms compression tests results were processed by factorial analysis and showed a greater influence of the sodium silicate amount and the curing time over the aluminium oxide granulometry. After the estimation of the ceramic phase permeability by 3D image digital processing it was developed a mathematical model to predict the maximum infiltration of the ferrous melt through the ceramic phase. It was based on the pouring and alloy solidification temperatures and produced a good agreement with the experimental results. The matrix microstructure was affected by the ceramic grains. This was characterized by the presence of lamellar graphite instead of the expected nodules in an extension between 10 micrometers and 60 micrometers from the border of the composite.

O estudo teve o objetivo de avaliar a resistência adesiva e a degradação da interface entre uma cerâmica tratada com laser e cimentos resinosos. Sessenta e quatro blocos cerâmicos foram distribuídos em 16 grupos distribuídos de acordo com os fatores em estudo: tratamento da superfície interna da cerâmica: Oxido de Alumínio (Ox), Rocatec (R), Laser de Nd:YAG 141,54 J/cm2 (Nd) e Laser de Nd:YAG + Rocatec (NdR); cimentos resinosos: Panavia F (Kuraray) e Relyx Unicem (3M ESPE); e método de envelhecimento: água destilada (W) e hipoclorito de sódio 10% (H). Após os procedimentos de cimentação e corte dos blocos, metade dos palitos foi armazenada em solução de hipoclorito de sódio 10% para simular envelhecimento in vitro. A resistência de união foi avaliada através do ensaio de microtração (0,5 mm/min) e os padrões de fratura foram classificados em adesivo, coesivo ou misto. Blocos cerâmicos adionciais foram confeccionados e analisados em Microscopia Eletrônica de Varredura e em Microscópio de Força Atômica para verificação dos padrões gerados pelos tratamentos. Os grupos tratados com laser de Nd:YAG apresentaram os maiores valores de resistência de união. Para os grupos cimentados com Panavia F, os valores de resistência de união foram: OxW: 27,71±6,3; RW: 35,67±5,13; NdW: 42,49±6,8; NdRW: 37,41±4,76; OxH: 22,27±6,05; RH: 27,49±8,83; NdH: 32,24±6,94; NdRH: 31,75±7,77. Para os grupos com RelyX Unicem: OxW: 26,74±6,34; RW: 35,07±6,02; NdW: 41,05±7,71; NdRW: 33,85±6,03; OxH: 22,77±7,37; RH: 27,84±6,26; NdH: 36,42±5,08; NdRH: 27,6±5,8. Pode-se concluir que o laser de Nd:YAG foi o tratamento mais efetivo, seguido da associação entre o laser de Nd:YAG+Rocatec, Rocatec e jateamento com Al2O3. Os cimentos testados apresentam comportamentos similares. O envelhecimento in vitro com hipoclorito de sódio diminuiu os valores de resistência de união. / The aim of this study was to evaluate the influence of different surface treatments on resistance to degradation between In-Ceram Alumina and two resin-based cements. Sixteen experimental groups were formed according to ceramic treatment: Sandblasting (S), Rocatec System (R), Nd:YAG Laser (Nd), Nd:YAG Laser plus Rocatec System (NR); luting cement: Panavia F (Kuraray) or Relyx Unicem (3M ESPE); and aging method: water (W) or sodium hypochlorite (H). Sixty four In-Ceram Alumina blocks (10x10x6mm) received four surface treatments: Al2O3 sandblasting; Al2O3 sandblasting + Rocatec Plus; Al2O3 sandblasting + Nd:YAG Lase; Al2O3 sandblasting + Nd:YAG Laser + Rocatec Plus. Each conditioned ceramic block was bonded to a composite block using a resin cement system. After 24h storage time, the blocks were sectioned to obtain sticks with cross-sectional area of 1.0mm2. The specimens were loaded to failure in a universal testing machine at a crosshead speed of 0.5mm/min. The fractured surface morphology of the debonded specimens was observed (40X) to evaluate the fracture pattern. Failure modes were classified as adhesive, cohesive in ceramic, cohesive in resin cement and mixed. The ceramic treatment and the aging method significantly affected the microtensile bond strength. Nd:YAG surface treatment resulted in the best bond strength values. To groups luted with Panavia F cement the microtensile bond strength values were: SW: 27,71±6,3; RW: 35,67±5,13; NdW: 42,49±6,8; NdRW: 37,41±4,76; SH: 22,27±6,05; RH: 27,49±8,83; NdH: 32,24±6,94; NdRH: 31,75±7,77. To groups luted with RelyX cement: SW: 26,74±6,34; RW: 35,07±6,02; NdW: 41,05±7,71; NdRW: 33,85±6,03; SH: 22,77±7,37; RH: 27,84±6,26; NdH: 36,42±5,08; NdRH: 27,6±5,8. Nd:YAG laser was the most effective surface treatment, followed by Nd:YAG+Rocatec, Rocatec and Al2O3 sandblasting. Resin cements presented similar behaviors in spite of aging. NaOCl 12h-immersion decreased Bond strength values.

Medidas de Termoluminescência (TL), Luminescência Opticamente Estimulada (LOE), EPR (Ressonância Paramagnética de Elétron) e RL (Radioluminescência) foram obtidas de amostras de óxido de alumínio e óxido de alumínio dopado com magnésio. As amostras foram calcinadas em três diferentes temperaturas (1100, 1350 e 1600°C) para observar a variação do comportamento das propriedades luminescentes. Ao final, constatou-se que a temperatura de calcinação é um parâmetro de grande importância para a produção de materiais dosimétricos, pois a amostra com melhores resultados LOE foi o material sem dopante tratada a 1600°C. Em trabalhos anteriores, a composição de óxido de alumínio dopado com magnésio havia apresentado nanoestruturas de aluminato de magnésio, observadas através de Microscopia Eletrônica de Transmissão (MET), que influenciaram a sensibilidade do material à radiação. Amostras de aluminato de magnésio puro e dopado com terras raras foram obtidas na forma de pó e calcinadas a 1100, 1350 e 1600°C. Medidas de TL e LOE de amostras irradiadas com fonte de partículas foram analisadas e comparadas com resultados de EPR e Difração de Raios-X (DRX). Como resultado, foi concluído que, nas condições trabalhadas, somente o elemento gadolínio proporcionou aumento de emissão LOE e TL no espectro visível. DRX indicou a formação dos compostos Al5Er3O12 e Al5Yb3O12; gadolínio e európio também formaram estruturas secundárias que não puderam ser determinadas. A partir do óxido de alumínio em pó, foram produzidos alvos para deposição de filmes finos empregando um sistema de sputtering magnetron e lâminas de silício monocristalino (100) tipo P para substrato. Parâmetros de deposição e de tratamento térmico foram variados de modo a produzir amostras com diferentes características. Curvas de TL foram levantadas e analisadas com relação aos resultados de DRX. Imagens de Microscopia Eletrônica de Varredura (MEV) foram obtidas de algumas amostras para visualizar o estado dos filmes depositados após tratamentos térmicos de 500 e 1100°C. Resultados mostraram a formação de picos de difração de a-Al2O3 em algumas das amostras espessas. Medidas de TL de amostras expostas à radiação ambiente exibiram picos de emissão em posições que variaram de acordo com a composição e espessura do filme depositado. / Thermoluminecent (TL), Optically Stimulated Luminescence (OSL), EPR (Electron spin Resonance) and Radioluminescence (RL) measurements were obtained from aluminum oxide and magnesium doped aluminum oxide samples. The samples were calcinated at three different temperatures (1100, 1350 and 1600°C) in order to observe variation of luminescent properties. As results, it was found that the calcination temperature is of great importance in the production of dosimetric materials, since the undoped sample calcinated at 1600°C showed the highest sensibility. In early works, magnesium doped aluminum oxide samples exhibited the formation of nanostructured layer composed by magnesium aluminate, observed using Transmission Electron Microscopy (TEM), which induced an increase of the luminescent properties. Samples of undoped and rare-earths doped magnesium aluminate, calcinated at 1100, 1350 and 1600°C, were produced. TL and OSL measurements were obtained from irradiated aliquots, analyzed and compared to EPR and XRD results. Results showed that, under the parameters used in this work, only gadolinium doped samples exhibited increase in TL and OSL emissions. XRD indicated the formation of Al5Er3O12 and Al5Yb3O12 structures in doped samples; gadolinium and europium doped samples also showed new structures, which couldnt be identified. Powder aluminum oxide was used to produce deposition targets, which were employed in the deposition of thin films over P type monocrystalline silicon (100) wafers. Variations of deposition parameters and heat treatment induced the formation of thin films with different characteristics, observed by XRD and luminescent analysis (TL). XRD results indicated the occurrence of alpha-Al2O3 in some of the thick films. Samples exposed to natural radiation produced TL emission in the visible spectrum.

A total of 17 samples were collected for OSL dating from a Swift Creek archaeological site, known as Harrison Ring, which lies on the Tyndall Air force peninsula in northwest Florida. High-resolution vertical sampling conducted at 10 cm intervals from the surface was performed in order to determine the timing of occupation at the site, and to look for patterns in radiation dosimetry and post-depositional disturbance that can compromise OSL results. We find OSL ages determined using both 0.5 mm aliquots and single grains at the archaeological levels (approximately 1751 ± 339 years ago) to be consistent with the timing of early Swift Creek cultures on the Florida Gulf Coast. The ages we report are both consistent with radiocarbon dates taken at Harrison Ring, and those taken at other Swift Creek sites on the Gulf Coast. In general, we find OSL equivalent doses that show high overdispersion and skewness that we attribute to beta-microdosimetry and possible bioturbation in the profiles. We also present results from a test with a novel dosimetric technique employing Al2O3:C chips. By using Al2O3:C dosimeters, we find that large variability in beta dose rates exist in the sedimentary profile at Harrison Ring. By testing a combination of dosimetric techniques in a site with a well-constrained age, we find that the best agreement with independent age control exists when calculating ages using a beta dose rate from NAA/DNC and gamma dose rate from Al2O3:C dosimetry. / Thesis / Master of Science (MSc)

Ultra-thin films (UTFs) are important in many applications, seen in the semiconductor industry, in chromatography, in sensing, in microfluidics, in aerospace, and in robotics. They also protect materials from corrosion, change surface energies, limit water intrusion into materials, allow material self-cleaning and self-healing, provide scratch resistance, and impart other specific chemical properties. In many cases, UTFs drastically alter surface properties and therefore their applications. It is imperative that proper and consistent characterization be performed on coatings to confirm and understand their desired properties. In Chapter two, Al oxidation under MgF2 protective layers is studied using real time X-ray photoelectron spectroscopy (XPS), and spectroscopic ellipsometry (SE). These tools allowed me to monitor Al oxidation for both short (hours) and long (months) periods of time. XPS revealed the chemical changes that took place in these materials as a function of time, and these changes were verified with SE. These studies help increase an understanding of aluminum changes under MgF2 protective layers. The third chapter demonstrates ab initio calculations guided X-ray photoelectron spectroscopy (XPS) analysis of surfaces functionalized with fluorinated silanes. This study addresses deficiencies in the literature where CF2:CF3 ratios from experimental XPS data do not match theoretical CF2:CF3 ratios. In a systematic approach, I developed semi-empirical models directed both by ab initio calculations and adjustable, empirical parameters. These models were effective in describing the raw data and exceeded fitting methods used in literature. In Chapter four, SiO2 UTFs with variable thicknesses deposited on Eagle XG® glass substrates are characterized. Challenges associated with this work consisted of similar optical functions of the film and substrate as well as backside reflections from the substrate. These obstacles were met using a multi-sample analysis (MSA), a variable angle spectroscopic ellipsometric approach, and mechanical abrasion/roughening of the substrate backside. With these approaches, I developed a model that precisely fit the data collected from all the samples and gave the correct optical function of the material along with thickness values for each film. Surface characterization represents a commitment of resources. It takes time to make measurements, and it takes time to analyze and understand the results. As presented in this work, I increase understanding of ultra-thin films at interfaces using both a multi-tool approach as well as using multiple analytical methods on data collected from each tool.