The objective of this research was to determine if mature landfill leachate could be treated to a level so that it was safe to discharge to the environment. The treatment method was an Advanced Oxidation Process. The process utilized Titanium Dioxide and UV. Three different reactor types were used, falling film, flow through and falling film + Electron Magnetic Oxygen Hydrogen (EMOH). To improve removal pre-treatment with titanium dioxide settling were conducted in conjunction with treatment in a reactor. The best removal was obtained with pre-treatment with titanium dioxide settling, followed by the falling film + EMOH reactor. In 8 hours, removal was 63% for COD, 53% for ammonia, 73% for alkalinity and 98% for calcium hardness. The kinetics found in this experiment show that full treatment times for safe discharge vary between contaminates. For complete removal of all tested contaminates to safe discharge regulations requires 185 hour of treatment. / Includes bibliography. / Thesis (M.S.)--Florida Atlantic University, 2015. / FAU Electronic Theses and Dissertations Collection

Este trabalho consiste na caracterização química, física e termoanalítica de algumas amostras de batons e dos componentes de suas formulações. O estudo termoanalítico foi desenvolvido a partir das técnicas TG/OTG sob atmosfera dinâmica de ar ou enriquecida com O2 e por DSC sob atmosfera dinâmica de N2, com razão de aquecimento de 10°C min-1 em ambos os casos. Os testes de estabilidade com exposição das amostras a 4, 25 e 43°C e à luz solar indireta permitiram avaliar as propriedades organolépticas, físicas e térmicas. Os resultados da análise de ponto de fusão obtidos pelo método convencional foram comparados àqueles encontrados por ensaios de DSC. A estabilidade térmica foi determinada pela exposição a 43°C em estufa convencional e a partir da técnica de TG no estudo da cinética de decomposição, utilizando-se os métodos dinâmico e isotérmico. Foi realizada a predição do prazo de validade de 2,4 anos para uma amostra específica de batom foi determinada por meio do estudo cinético pelo método isotérmico, aplicando-se a equação de Arrhenius. A performance de três diferentes antioxidantes quanto à estabilidade térmica de uma amostra de batom foi avaliada, verificando-se, melhor comportamento da mistura de tocoferáis aplicada a 1%. / This work consists of the chemical, physical and thermoanalytical characterization of some samples of lipsticks and the components of their formulation. The thermoanalytical study was developed by means of TG/DTG techniques under dynamic air atmosphere or air enriched with O2 and by DSC in dynamic nitrogen atmosphere, with heating rate of 10°C min-1 in both cases. The stability tests with the submitled samples at 4, 25, 43°C and sunlight allowed to evaluate the organoleptic, physical and thermal properties. The analytical results of melting point obtained from conventional methods were compared to the ones measured by DSC. The thermal stability was determined by exposition at 43°C in a conventional stove and by TG technique in the study of decomposition\'s kinetic, using dynamic and isothermal methods. A shelf-life prediction of 2.4 years for a specific sample of Iipstick was determined by means of a kinetic study, using an isothermal method and applying Arrhenius\' equation. The performance of three different antioxidants concerning the thermal stability of a Iipstick sample was evaluated, the tocopherol mix showed the better performance when applied at 1%.

The objectives of Sensor Based Fixture Design and Verification (SFDV) research are to provide the means for detecting contact failure of the workpiece with fixture locators and for preventing incorrect loading of the workpiece in a fixture. The fixtures that involve complex free-form surfaces especially in the aerospace industries face problems caused by the contact failure of the workpiece with locators. In batch and mass production defects often occur due to incorrect loading of the workpiece in a fixture by an operator due to fatigue or inadvertence. The current fixturing research is focussed on improving the fixture quality and other aspects and do not address these issues. This research is focussed on three areas, to generate algorithms for automatically foolproofing the fixtures, to build locators with embedded sensors that could be used to verify the contact and foolproof the existing fixtures, and to design and experimentally validate fixtures for free-form surfaces with sensors to verify the location. In foolproofing, workpieces were classified into different categories to identify the existence of a solution and the geometry was simplified and used to search for a solution based on symmetry/asymmetry to discover a foolproofing location. The algorithms were implemented in a CAD software and the solutions were verified in 3D space. The locators with inbuilt sensors were designed for foolproofing and location verification purposes and the sensors were used in case studies to establish credibility. A sensor based fixture design method is created for the part location of free-form surfaces using fiber optic sensors. An experimental fixture with sensors incorporated in the locators was used to determine the effects of surface curvature on the sensitivity of the sensors. A new theory on best locations for the sensor based locators by utilizing surface curvature is proposed based on the experimental results. The SFDV implementation may help realize the dream for any manufacturing sys­tem aspiring to move beyond the six sigma levels of quality and achieve zero defects.

It is undoubtable that the geological path followed by a bentonite natural occurrence, will set a birthmark in terms of grade and quality, the former being expressed in terms of mineralogical composition, smectite content and other aspects derived from the bulk sample characterization, and the latter being expressed in terms of the crystal chemistry of smectite species present and derived from the clay size fraction observations. The influence of parent rock composition, genesis mode, burial history and preservation conditions after alteration, would set the fingerprint on bentonite and inherent structural features in smectites species, which determines potential industrial and scientific uses. The following thesis aims to evaluate physicochemical properties of 12 bentonite samples, coming from the six most relevant bentonite bearing geological areas located in the Mercosur economic block (Argentina, Brazil and Uruguay)1; in order to stablish possible correlations between distinctive geological contexts, and observed characteristics from whole rock providing information regarding grade and the clay size fraction will provide information regarding quality. Mineralogical composition corroborated the tendency to be influenced by the geochemical signature of parent rock firstly, and secondly genesis mode (probably due to lack of information in this aspect). Age, on the other hand, could on the contrary, be a misleading parameter; in the sense that preservation is not necessarily time dependent. Poor grade and the presence of mixed layers and accessory clay mineral phases (mostly kaolinite but also I/S, illite and pyrophyllite) appear to be associated with hydrothermal to sedimentary alteration modes, higher grade bentonites with tendency to yield extreme relative values of physical properties, measured in layer charge, swelling and organic sorption, were found in association to diagenetic bentonites. In terms of smectite species, all members found belong to the montmorillonite-beidellite series, and rhyolitic to dacitic volcanic source, tends to alter into the montmorillonite end member of the series; and accordingly, basic precursors (basalt) to intermediary (andesite), show a tendency to alter into transitional up to beidellite Fe-rich end members of the series respectively. To evaluate implications on possible applications, crystal chemistry was evaluated over the <1 µm size fractions by XRD and XRF along with other accessory techniques (FTIR, SEM-EDS and size distribution analysis), finding a clear trend, between layer charge relative magnitude, as a function organo-sorption behavior; by simply evaluating the d-001 XRD reflections on oriented slides after first K-saturation and sequential ethylene glycol solvation, against (CTAC)-montmorillonite d001 basal reflection , being inversely proportional and resulting in a broad variety Organophilic XRD patterns, showing distinctive expandability behavior ranging from 15,2 Å To 21,68 Å. As a function of alkyl chain size and the known sorption isotherm, basically all patterns of organo-compound sorption where observed, going from lateral monolayer to paraffin type sorption behavior. / É inquestionável que o caminho geológico seguido pela ocorrência natural de bentonitas, irá indicar suas características em termos de teor e qualidade, o primeiro expressado em termos da composição mineralógica, conteúdo de esmectitas e outros aspectos derivados da caracterização da amostra cabeça, e o Segundo expressado em termos da química cristalina das espécies esmectiticas presentes e derivado das observações na fracção de tamanho de argilas. A influência da composição da rocha parental, sua gênese, o histórico de soterramento e das condições de preservação após processo de alteração, determinaria a \"impressão digital\" da bentonita e as características estruturais inerentes as espécies de esmectitas, que determina os usos potenciais e industriais. O objetivo deste trabalho é avaliar propriedades físico-químicas de 12 amostras de bentonitas, provenientes de seis áreas geológicas mais relevantes localizadas no bloco econômico do Mercosul (Argentina, Brasil e Uruguai)2; o intuito é estabelecer possíveis correlações entre contextos geológicos distintos e características observadas em rochas (teor) e fração de tamanho de argila (qualidade). A composição mineralógica corroborou a tendência de ser influenciada pela assinatura geoquímica da rocha parental em primeiro lugar, e em segundo lugar, por sua gênese (provavelmente devido à falta de informação neste aspecto). A idade, por outro lado, poderia, pelo contrário, ser um parâmetro ilusório, no sentido de que a conservação não é necessariamente dependente do tempo. Baixo teor e baixo conteúdo de esmectita, assim como a presença de camadas mistas e fases argilosas acessórias (principalmente caulinita, mas também I/S, ilita e pirofilita) parecem estar associadas aos modos de alteração hidrotermal a sedimentar, bentonita de alto teor, com tendência a produzir valores relativos extremos de propriedades físicas, medidas em carga foliar, inchamento e sorção orgânica, foram encontradas em associação com bentonitas diagenéticas. Em termos de espécies de esmectitas, todos os membros identificados como pertencentes a série montmorilonita-beidellita, e a fonte vulcânica riolítica a dacítica, tendem a se alterar para membro final da série montmorilonita, e consequentemente, os precursores básicos (basalto) e intermediário (andesito), mostram tendência a se alterar em membros transitórios e beidellita ricos em ferro, respectivamente. Para avaliar as implicações nas possíveis aplicações, a química cristalina foi avaliada nas frações abaixo de 1 µm por DRX e FRX, juntamente de outras técnicas de apoio (FTIR, MEV/EDS e distribuição granulométrica), encontrando uma tendência clara entre a magnitude relativa da carga da camada, como uma função do comportamento da organo-absorção, simplesmente avaliando as reflexões basais em d-001 a partir de lâminas orientadas após a primeira saturação em potássio e solvatação sequencial de etileno glicol, contra reflexão em d-001 da (CTAC)-montmorilonita, sendo inversamente proporcional e resultando em uma ampla variedade de padrões de DRX organofílico, mostrando um comportamento de expansibilidade distinto, variando de 15,2 Å a 21,68 Å. Como função do tamanho da cadeia carbônica e da isoterma de sorção conhecida, basicamente todos os padrões de sorção de organo-compostos foram observados, partindo do comportamento de sorção do tipo monocamada lateral para sorção tipo parafina.

Bayesian probabilistic modeling provides a powerful framework for building flexible models to incorporate latent structures through likelihood model and prior. When we specify a model, we make certain assumptions about the underlying data-generating process with respect to these latent structures. For example, the latent Dirichlet allocation (LDA) model assumes that when generating a document, we first select a latent topic and then select a word that often appears in the selected topic. We can uncover the latent structures conditioned on the observed data via posterior inference. In this dissertation, we apply the tools of probabilistic latent variable models and try to understand complex real-world data about music semantics and user behavior. We first look into the problem of automatic music tagging -- inferring the semantic tags (e.g., "jazz'', "piano'', "happy'', etc.) from the audio features. We treat music tagging as a matrix completion problem and apply the Poisson matrix factorization model jointly on the vector-quantized audio features and a "bag-of-tags'' representation. This approach exploits the shared latent structure between semantic tags and acoustic codewords. We present experimental results on the Million Song Dataset for both annotation and retrieval tasks, illustrating the steady improvement in performance as more data is used. We then move to the intersection between music semantics and user behavior: music recommendation. The leading performance in music recommendation is achieved by collaborative filtering methods which exploit the similarity patterns in user's listening history. We address the fundamental cold-start problem of collaborative filtering: it cannot recommend new songs that no one has listened to. We train a neural network on semantic tagging information as a content model and use it as a prior in a collaborative filtering model. The proposed system is evaluated on the Million Song Dataset and shows comparably better result than the collaborative filtering approaches, in addition to the favorable performance in the cold-start case. Finally, we focus on general recommender systems. We examine two different types of data: implicit and explicit feedback, and introduce the notion of user exposure (whether or not a user is exposed to an item) as part of the data-generating process, which is latent for implicit data and observed for explicit data. For implicit data, we propose a probabilistic matrix factorization model and infer the user exposure from data. In the language of causal analysis (Imbens and Rubin, 2015), user exposure has close connection to the assignment mechanism. We leverage this connection more directly for explicit data and develop a causal inference approach to recommender systems. We demonstrate that causal inference for recommender systems leads to improved generalization to new data. Exact posterior inference is generally intractable for latent variables models. Throughout this thesis, we will design specific inference procedure to tractably analyze the large-scale data encountered under each scenario.

It is undoubtable that the geological path followed by a bentonite natural occurrence, will set a birthmark in terms of grade and quality, the former being expressed in terms of mineralogical composition, smectite content and other aspects derived from the bulk sample characterization, and the latter being expressed in terms of the crystal chemistry of smectite species present and derived from the clay size fraction observations. The influence of parent rock composition, genesis mode, burial history and preservation conditions after alteration, would set the fingerprint on bentonite and inherent structural features in smectites species, which determines potential industrial and scientific uses. The following thesis aims to evaluate physicochemical properties of 12 bentonite samples, coming from the six most relevant bentonite bearing geological areas located in the Mercosur economic block (Argentina, Brazil and Uruguay)1; in order to stablish possible correlations between distinctive geological contexts, and observed characteristics from whole rock providing information regarding grade and the clay size fraction will provide information regarding quality. Mineralogical composition corroborated the tendency to be influenced by the geochemical signature of parent rock firstly, and secondly genesis mode (probably due to lack of information in this aspect). Age, on the other hand, could on the contrary, be a misleading parameter; in the sense that preservation is not necessarily time dependent. Poor grade and the presence of mixed layers and accessory clay mineral phases (mostly kaolinite but also I/S, illite and pyrophyllite) appear to be associated with hydrothermal to sedimentary alteration modes, higher grade bentonites with tendency to yield extreme relative values of physical properties, measured in layer charge, swelling and organic sorption, were found in association to diagenetic bentonites. In terms of smectite species, all members found belong to the montmorillonite-beidellite series, and rhyolitic to dacitic volcanic source, tends to alter into the montmorillonite end member of the series; and accordingly, basic precursors (basalt) to intermediary (andesite), show a tendency to alter into transitional up to beidellite Fe-rich end members of the series respectively. To evaluate implications on possible applications, crystal chemistry was evaluated over the <1 µm size fractions by XRD and XRF along with other accessory techniques (FTIR, SEM-EDS and size distribution analysis), finding a clear trend, between layer charge relative magnitude, as a function organo-sorption behavior; by simply evaluating the d-001 XRD reflections on oriented slides after first K-saturation and sequential ethylene glycol solvation, against (CTAC)-montmorillonite d001 basal reflection , being inversely proportional and resulting in a broad variety Organophilic XRD patterns, showing distinctive expandability behavior ranging from 15,2 Å To 21,68 Å. As a function of alkyl chain size and the known sorption isotherm, basically all patterns of organo-compound sorption where observed, going from lateral monolayer to paraffin type sorption behavior. / É inquestionável que o caminho geológico seguido pela ocorrência natural de bentonitas, irá indicar suas características em termos de teor e qualidade, o primeiro expressado em termos da composição mineralógica, conteúdo de esmectitas e outros aspectos derivados da caracterização da amostra cabeça, e o Segundo expressado em termos da química cristalina das espécies esmectiticas presentes e derivado das observações na fracção de tamanho de argilas. A influência da composição da rocha parental, sua gênese, o histórico de soterramento e das condições de preservação após processo de alteração, determinaria a \"impressão digital\" da bentonita e as características estruturais inerentes as espécies de esmectitas, que determina os usos potenciais e industriais. O objetivo deste trabalho é avaliar propriedades físico-químicas de 12 amostras de bentonitas, provenientes de seis áreas geológicas mais relevantes localizadas no bloco econômico do Mercosul (Argentina, Brasil e Uruguai)2; o intuito é estabelecer possíveis correlações entre contextos geológicos distintos e características observadas em rochas (teor) e fração de tamanho de argila (qualidade). A composição mineralógica corroborou a tendência de ser influenciada pela assinatura geoquímica da rocha parental em primeiro lugar, e em segundo lugar, por sua gênese (provavelmente devido à falta de informação neste aspecto). A idade, por outro lado, poderia, pelo contrário, ser um parâmetro ilusório, no sentido de que a conservação não é necessariamente dependente do tempo. Baixo teor e baixo conteúdo de esmectita, assim como a presença de camadas mistas e fases argilosas acessórias (principalmente caulinita, mas também I/S, ilita e pirofilita) parecem estar associadas aos modos de alteração hidrotermal a sedimentar, bentonita de alto teor, com tendência a produzir valores relativos extremos de propriedades físicas, medidas em carga foliar, inchamento e sorção orgânica, foram encontradas em associação com bentonitas diagenéticas. Em termos de espécies de esmectitas, todos os membros identificados como pertencentes a série montmorilonita-beidellita, e a fonte vulcânica riolítica a dacítica, tendem a se alterar para membro final da série montmorilonita, e consequentemente, os precursores básicos (basalto) e intermediário (andesito), mostram tendência a se alterar em membros transitórios e beidellita ricos em ferro, respectivamente. Para avaliar as implicações nas possíveis aplicações, a química cristalina foi avaliada nas frações abaixo de 1 µm por DRX e FRX, juntamente de outras técnicas de apoio (FTIR, MEV/EDS e distribuição granulométrica), encontrando uma tendência clara entre a magnitude relativa da carga da camada, como uma função do comportamento da organo-absorção, simplesmente avaliando as reflexões basais em d-001 a partir de lâminas orientadas após a primeira saturação em potássio e solvatação sequencial de etileno glicol, contra reflexão em d-001 da (CTAC)-montmorilonita, sendo inversamente proporcional e resultando em uma ampla variedade de padrões de DRX organofílico, mostrando um comportamento de expansibilidade distinto, variando de 15,2 Å a 21,68 Å. Como função do tamanho da cadeia carbônica e da isoterma de sorção conhecida, basicamente todos os padrões de sorção de organo-compostos foram observados, partindo do comportamento de sorção do tipo monocamada lateral para sorção tipo parafina.

This study investigates the research on current self escape practices, the need for training on emergency evacuation procedures and the use of virtual reality simulations for the purposes of training. Thus, this project focuses on the advantages of using virtual reality as an educational tool and follows the development and design aspects of the tool. It includes each phase in development of the tool, including current research on self escape practices, training needs analyses and the actual design phases of the simulation. The design phase focuses on the objects and animations required to be implemented in order to create a realistic virtual mine. The programming logic of the simulation tool is also examined. Moreover, the final simulation is evaluated and proved to be an appropriate form of assessment and efficient learning environment for the trainee. Furthermore, recommendations are made for future developments.

Vinyltrialkoxysilanes are grafted onto polyolefins via a radical mechanism; in a subsequent step, the pendant alkoxysilanes hydrolyze and condense upon exposure to water, resulting formation of crosslinks. Straight chain hydrocarbons were used as model compounds to investigate the regioselectivity of vinyltrimethoxysilane grafting. To stabilize the water-sensitive grafted products, the methoxy groups were substituted using phenyllithium. It was found that this reaction must be carried out for a minimum of three days to ensure full substitution. The grafted products were then separated on a weight basis using semi-preparative HPLC. Analysis of the di-grafted fraction using edited HSQC and HSQC-TOCSY NMR showed that radical propagation occurs via 1,4- and 1,5-intramolecular hydrogen shifts along the hydrocarbon backbone, resulting in multiple grafts per backbone. Post-combustion carbon capture targets CO₂ emissions from large point sources for capture and sequestration. A new class of potential carbon capture agents known as reversible ionic liquids (RevILs) has been synthesized and evaluated in terms of potential performance parameters (e.g. CO₂ capacity, viscosity, enthalpy of regeneration). These RevILs are silylated amines, which react with CO₂ to form a salt comprising an ammonium cation and a carbamate anion that is liquid at room temperature. Structural modifications of the basic silylamine skeleton result in drastic differences in the performance of the resulting RevIL. Systematic variation of the silylated amines allowed determination of a structure-property relationship, and continued iterations will allow development of an ideal candidate for scale-up. The properties and potential applications of gold nanoparticles (AuNP) are highly dependent on their size and shape. These properties are commonly controlled during liquid-phase synthesis through the use of capping agents, which must be removed following synthesis. Reverse micelles can also be used to control the morphology of AuNP during their synthesis. When RevILs are used in the formation of these reverse micelles, either as the disperse phase or as the surfactant, the built-in switch can be used to release the nanoparticles following their synthesis. This release on command could decrease the post-synthetic steps required to clean and purify AuNP prior to use. We have successfully synthesized AuNP using a number of different RevILs.

As feature sizes in semiconductor devices become smaller and newer materials are incorporated, current methods for photoresist and post plasma etch residue removal face several challenges. A cleaning process should be environmentally benign, compatible with dielectric materials and copper, and provide residue removal from narrow and high aspect ratio features. In this work, sub-critical CO2 based mixtures have been developed to remove the etch residues; these mixtures satisfy the above requirements and can potentially replace the two step residue removal process currently used in the integrated circuit (IC) industry. Based on the chemical nature of the residue being removed, additives or co-solvents to CO2 have been identified that can remove the residues without damaging the dielectric layers. Using the phase behavior of these additives as a guide, the composition of the co-solvent was altered to achieve a single liquid phase at moderate pressures without compromising cleaning ability. The extent of residue removal has been analyzed primarily by x-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Various techniques such as attenuated total reflection - Fourier transform infrared (ATR-FTIR) spectroscopy, angle-resolved XPS (ARXPS), and interferometry were used to probe the interaction of cleaning fluids with residues. Model films of photoresists and plasma deposited residues were used to assist in understanding the mechanism of residue removal. From these studies, it was concluded that residue removal takes place primarily by attack of the interface between the residue and the substrate; a solvent rinse then lifts these residues from the wafer. It has been shown that transport of the additives to the interface is enhanced in the presence of CO2. From positronium annihilation lifetime spectroscopy (PALS) studies on a porous dielectric film, it has been shown that these high pressure fluids do not cause significant changes to the pore sizes or the bonding structure of the film. Hence, this method can be used to remove post etch residues from low-k dielectric films.

Gas Metal Arc Welding (GMAW) is one of the main methods used to join structural members. One of the largest challenges involved in production of welds is ensuring the quality of the weld. One of the main factors attributing to weld quality is penetration depth. Automatic control of the welding process requires non-contact, non-destructive sensors that can operate in the presence of high temperatures and electrical noise found in the welding environment. Inspection using laser generation and electromagnetic acoustic transducer (EMAT) reception of ultrasound was found to satisfy these conditions. Using this technique, the time of flight of the ultrasonic wave is measured and used to calculate penetration depth. Previous works have shown that penetration depth measurement performance is drastically reduced when performed during welding. This work seeks to realize in-process penetration depth measurement by compensating for errors caused by elevated temperature. Neuro-fuzzy models are developed that predict penetration depth based on in-process time of flight measurements and the welding process input. Two scenarios are considered in which destructive penetration depth measurements are or are not available for model training. Results show the two scenarios are successful. When destructive measurements are unavailable, model error is comparable to that of offline ultrasonic measurements. When destructive measurements are available, measurement error is reduced by 50% compared to offline ultrasonic measurements. The two models can be effectively applied to permit in-process penetration depth measurements for the purpose of real-time monitoring and control. This will reduce material, production time, and labor costs and increase the quality of welded parts.