Neste trabalho foram desenvolvidos métodos eletroanalíticos (redissolução potenciométrica e voltamétrica) para a determinação de metais (mercúrio, cobre, chumbo e zinco) em petróleo, óleo diesel, óleo lubrificante e álcool combustível. Para analisar álcool, foi também desenvolvido um método por eletroforese capilar, que possibilita a determinação de cátions (sódio, potássio e cálcio) e ânions (cloreto, sulfato e nitrato). Procedimentos envolvendo a utilização de fornos de microondas (focalizadas - que opera a pressão atmosférica - e com cavidade, que promove a digestão em frascos pressurizados) para a decomposição de petróleo, óleo diesel e óleo lubrificante são descritos. As determinações de cobre e mercúrio por redissolução potenciométrica apresentaram melhores limites de detecção do que a voltametria de redissolução de onda quadrada nas amostras digeridas, utilizando eletrodos de ouro confeccionados a partir de CDs graváveis (Cdtrodos), como eletrodo de trabalho. Para a determinação de chumbo e zinco nas mesmas amostras digeridas, os melhores resultados foram obtidos com eletrodos de filme de mercúrio e utilizando a voltametria de redissolução potenciométrica. Perdas de mercúrio por volatilização foram verificadas quando as amostras foram digeridas em fornos de microondas focalizadas. Para os demais metais, a utilização deste forno foi vantajosa por proporcionar melhores limites de detecção devido à utilização de maiores massas de amostra no processo de digestão. A utilização de um banho ultrassônico de bancada para promover a extração de cobre e chumbo de óleos lubrificantes na presença da mistura 1:1 (v/v) de HClconc. e H2O2 (30% m/v) mostrou-se eficiente. Trinta minutos de exposição à energia ultrassônica foram necessários para a extração quantitativa de ambos os metais. Nas soluções extratoras, o teor dos metais foi determinado por voltametria de redissolução anódica, usando CDtrodos. Os limites de detecção do método para a determinação de cobre e chumbo foram, respectivamente, de 23 e 67 ng g-1 de óleo, aplicando 120 s de tempo de deposição. A voltametria de redissolução anódica em eletrodo de ouro possibilitou a determinação de cobre e chumbo em álcool combustível, sem qualquer tratamento prévio das amostras. Limites de detecção de 120 e 235 ng L-1 para cobre e chumbo, respectivamente, foram obtidos aplicando 15 min de tempo de deposição. Alternativamente, a evaporação do etanol seguido da redissolução em água desionizada permitiu a determinação dos metais por análise de redissolução. Todos os resultados obtidos utilizando diferentes metodologias de decomposição de amostras foram comparados com os resultados obtidos por análises por espectrometria de absorção atômica com forno de grafite. O método envolvendo a evaporação prévia, seguida da redissolução dos íons em meio aquoso também se mostrou muito favorável para realizar a determinação de cátions e ânions por eletroforese capilar em amostras de etanol hidratado combustível. Os íons Na+, K+ e Ca2+, Cl-, NO3- e SO42- foram encontrados nas amostras analisadas. Os limites de detecção destes íons se encontram na faixa de 0,06 e 0,18 mg L-1. / In this work eletroanalytical methodologies (potentiometric stripping analysis and anodic stripping voltammetry) for the determination of metals (mercury, copper, lead, and zinc) in crude oil, lubricating oil, diesel fuel, and ethanol fuel are proposed. A capillary electrophoresis method for ethanol fuel was developed to determine cations (sodium, potassium, and calcium) and anions (chloride, sulphate, and nitrate). Microwave digestion methods using different ovens (a focused microwave oven – operating at atmospheric pressure, and a cavity microwave oven, which employs pressurized vessels) for crude oil, lubricating oil, and diesel fuel are described. The determination of copper and mercury by potentiometric stripping analysis presents better detection limits than stripping voltammetric determinations for the digested sample analysis. Loss of mercury by volatilization was verified when samples were digested in the focused microwave oven. Otherwise, this oven presented some advantages for the other metals, as the improved detection limits due to the employment of higher sample mass for the digestion process. The use of a ultrasonic bath to promote the extraction of copper and lead from lubricating oils in the presence of 1:1 (v/v) HClconc and H2O2 (30% m/v) was efficient. Thirty minutes of ultrasonic exposure were necessary for quantitative exctraction of copper and lead. Anodic stripping voltammetry using gold CDtrodes was applied for metal determination in the extracted solutions. The detection limits of the proposed method for copper and lead were 23 and 67 ng g-1, respectively, under application of 120 seconds as deposition time. Anodic stripping voltammetry at a gold electrode was used for the determination of copper and lead in ethanol fuel, without any prior sample treatment. Detection limits of 120 and 235 ng L-1 for copper and lead, respectively, were attained applying 900 s as deposition time. Alternatively, the ethanol evaporation followed by re-suspension in deionised water allowed the metals determination by stripping analysis. All results obtained for sample decomposition methods were compared with the ones obtained by electrothermal atomic absorption spectrometric determinations. The method, which employs prior ethanol evaporation followed by re-suspension in deionised water, was applied for the determination of cations and anions by capillary electrophoresis in the hydrated ethanol fuel (automotive fuel). Na+, K+, Ca2+, Cl-, NO3-, and SO42- ions were found in the analyzed samples. The detection limits for these ions were situated between 0.06 and 0.18 mg L-1.

A destinação final, pós-consumo, das embalagens plásticas de óleo lubrificante é um problema ambiental grave, devido às características de resistência à degradação e ao potencial de contaminação do óleo residual. A destinação final das embalagens plásticas ambientalmente adequadas é uma demanda ética e legal para as organizações. Este trabalho avalia criticamente a situação atual do programa de coleta de embalagens plásticas implantado no Estado do Rio de Janeiro, apresenta as melhores práticas em organizações que lidam com a reciclagem de embalagens plásticas, discute o uso da gestão ambiental como base para integrar os vários participantes da cadeia de produ cão e comercialização e propõe um modelo que possibilitará a destinação ambientalmente correta das embalagens plásticas pós-uso via reciclagem e reuso. A metodologia utilizada constou de pesquisa descritiva de caráter quantitativo e qualitativo para consolidação dos dados. As entrevistas realizadas mostraram que 8,2 % das embalagens plásticas pós-uso tem destino ambientalmente adequado no Estado do Rio de Janeiro. A abordagem prática com apresentação do problema atual e a proposta do modelo são as principais contribuições que esse estudo agrega á área de conhecimento e pesquisa de reciclagem e reuso de embalagens plásticas pós-uso de óleos lubrificantes / The final destination, after use, of plastic packaging with motor oil residues is one problem worldwide. The polymer resistance to biodegradability and the residual oil contamination represents a great environmental risk. The final destination of plastic packaging is an ethical and legal claim in the comp anies. This work presents a review of a waste management program implemented in the State o f Rio de Janeiro, evaluating its results and proposing improvements. This study was especially concerned about the importance of an environmental management system to integrate all stakeholders. In order to support the proposed model, best practices implemented by organizations that deal with plastic packing recycling were focused. This study presents a model that will contribute to solve practical problems regarding final destination of plastic packaging after use through recycling and or reuse, preserving soil and groundwater for future g enerations. The interviews have shown that 8,2% of plastic packaging have adequated environmental destination. The practical approach and the detailed description of the real problem structure are the main contributions of this study to the knowledge area and research of final destination, after use, of plastic packaging of lubricating oil.

A destinação final, pós-consumo, das embalagens plásticas de óleo lubrificante é um problema ambiental grave, devido às características de resistência à degradação e ao potencial de contaminação do óleo residual. A destinação final das embalagens plásticas ambientalmente adequadas é uma demanda ética e legal para as organizações. Este trabalho avalia criticamente a situação atual do programa de coleta de embalagens plásticas implantado no Estado do Rio de Janeiro, apresenta as melhores práticas em organizações que lidam com a reciclagem de embalagens plásticas, discute o uso da gestão ambiental como base para integrar os vários participantes da cadeia de produ cão e comercialização e propõe um modelo que possibilitará a destinação ambientalmente correta das embalagens plásticas pós-uso via reciclagem e reuso. A metodologia utilizada constou de pesquisa descritiva de caráter quantitativo e qualitativo para consolidação dos dados. As entrevistas realizadas mostraram que 8,2 % das embalagens plásticas pós-uso tem destino ambientalmente adequado no Estado do Rio de Janeiro. A abordagem prática com apresentação do problema atual e a proposta do modelo são as principais contribuições que esse estudo agrega á área de conhecimento e pesquisa de reciclagem e reuso de embalagens plásticas pós-uso de óleos lubrificantes / The final destination, after use, of plastic packaging with motor oil residues is one problem worldwide. The polymer resistance to biodegradability and the residual oil contamination represents a great environmental risk. The final destination of plastic packaging is an ethical and legal claim in the comp anies. This work presents a review of a waste management program implemented in the State o f Rio de Janeiro, evaluating its results and proposing improvements. This study was especially concerned about the importance of an environmental management system to integrate all stakeholders. In order to support the proposed model, best practices implemented by organizations that deal with plastic packing recycling were focused. This study presents a model that will contribute to solve practical problems regarding final destination of plastic packaging after use through recycling and or reuse, preserving soil and groundwater for future g enerations. The interviews have shown that 8,2% of plastic packaging have adequated environmental destination. The practical approach and the detailed description of the real problem structure are the main contributions of this study to the knowledge area and research of final destination, after use, of plastic packaging of lubricating oil.

Neste trabalho foram desenvolvidos métodos eletroanalíticos (redissolução potenciométrica e voltamétrica) para a determinação de metais (mercúrio, cobre, chumbo e zinco) em petróleo, óleo diesel, óleo lubrificante e álcool combustível. Para analisar álcool, foi também desenvolvido um método por eletroforese capilar, que possibilita a determinação de cátions (sódio, potássio e cálcio) e ânions (cloreto, sulfato e nitrato). Procedimentos envolvendo a utilização de fornos de microondas (focalizadas - que opera a pressão atmosférica - e com cavidade, que promove a digestão em frascos pressurizados) para a decomposição de petróleo, óleo diesel e óleo lubrificante são descritos. As determinações de cobre e mercúrio por redissolução potenciométrica apresentaram melhores limites de detecção do que a voltametria de redissolução de onda quadrada nas amostras digeridas, utilizando eletrodos de ouro confeccionados a partir de CDs graváveis (Cdtrodos), como eletrodo de trabalho. Para a determinação de chumbo e zinco nas mesmas amostras digeridas, os melhores resultados foram obtidos com eletrodos de filme de mercúrio e utilizando a voltametria de redissolução potenciométrica. Perdas de mercúrio por volatilização foram verificadas quando as amostras foram digeridas em fornos de microondas focalizadas. Para os demais metais, a utilização deste forno foi vantajosa por proporcionar melhores limites de detecção devido à utilização de maiores massas de amostra no processo de digestão. A utilização de um banho ultrassônico de bancada para promover a extração de cobre e chumbo de óleos lubrificantes na presença da mistura 1:1 (v/v) de HClconc. e H2O2 (30% m/v) mostrou-se eficiente. Trinta minutos de exposição à energia ultrassônica foram necessários para a extração quantitativa de ambos os metais. Nas soluções extratoras, o teor dos metais foi determinado por voltametria de redissolução anódica, usando CDtrodos. Os limites de detecção do método para a determinação de cobre e chumbo foram, respectivamente, de 23 e 67 ng g-1 de óleo, aplicando 120 s de tempo de deposição. A voltametria de redissolução anódica em eletrodo de ouro possibilitou a determinação de cobre e chumbo em álcool combustível, sem qualquer tratamento prévio das amostras. Limites de detecção de 120 e 235 ng L-1 para cobre e chumbo, respectivamente, foram obtidos aplicando 15 min de tempo de deposição. Alternativamente, a evaporação do etanol seguido da redissolução em água desionizada permitiu a determinação dos metais por análise de redissolução. Todos os resultados obtidos utilizando diferentes metodologias de decomposição de amostras foram comparados com os resultados obtidos por análises por espectrometria de absorção atômica com forno de grafite. O método envolvendo a evaporação prévia, seguida da redissolução dos íons em meio aquoso também se mostrou muito favorável para realizar a determinação de cátions e ânions por eletroforese capilar em amostras de etanol hidratado combustível. Os íons Na+, K+ e Ca2+, Cl-, NO3- e SO42- foram encontrados nas amostras analisadas. Os limites de detecção destes íons se encontram na faixa de 0,06 e 0,18 mg L-1. / In this work eletroanalytical methodologies (potentiometric stripping analysis and anodic stripping voltammetry) for the determination of metals (mercury, copper, lead, and zinc) in crude oil, lubricating oil, diesel fuel, and ethanol fuel are proposed. A capillary electrophoresis method for ethanol fuel was developed to determine cations (sodium, potassium, and calcium) and anions (chloride, sulphate, and nitrate). Microwave digestion methods using different ovens (a focused microwave oven – operating at atmospheric pressure, and a cavity microwave oven, which employs pressurized vessels) for crude oil, lubricating oil, and diesel fuel are described. The determination of copper and mercury by potentiometric stripping analysis presents better detection limits than stripping voltammetric determinations for the digested sample analysis. Loss of mercury by volatilization was verified when samples were digested in the focused microwave oven. Otherwise, this oven presented some advantages for the other metals, as the improved detection limits due to the employment of higher sample mass for the digestion process. The use of a ultrasonic bath to promote the extraction of copper and lead from lubricating oils in the presence of 1:1 (v/v) HClconc and H2O2 (30% m/v) was efficient. Thirty minutes of ultrasonic exposure were necessary for quantitative exctraction of copper and lead. Anodic stripping voltammetry using gold CDtrodes was applied for metal determination in the extracted solutions. The detection limits of the proposed method for copper and lead were 23 and 67 ng g-1, respectively, under application of 120 seconds as deposition time. Anodic stripping voltammetry at a gold electrode was used for the determination of copper and lead in ethanol fuel, without any prior sample treatment. Detection limits of 120 and 235 ng L-1 for copper and lead, respectively, were attained applying 900 s as deposition time. Alternatively, the ethanol evaporation followed by re-suspension in deionised water allowed the metals determination by stripping analysis. All results obtained for sample decomposition methods were compared with the ones obtained by electrothermal atomic absorption spectrometric determinations. The method, which employs prior ethanol evaporation followed by re-suspension in deionised water, was applied for the determination of cations and anions by capillary electrophoresis in the hydrated ethanol fuel (automotive fuel). Na+, K+, Ca2+, Cl-, NO3-, and SO42- ions were found in the analyzed samples. The detection limits for these ions were situated between 0.06 and 0.18 mg L-1.

There has been much discussion about the beneficial uses of lamellar graphite iron in piston rings–cylinder liner systems, where a good combinations of both thermal and tribological properties are essential. The excellent tribological performance of lamellar iron under such sliding conditions is principally associated with lubrication behaviour of the graphite particles which are distributed as lamellas throughout the matrix. During sliding, graphite particles are extruded and smeared onto the counterfaces, act as solid lubricating agents and form a thin graphite film between the sliding surfaces. Although this process especially, during the running-in period significantly changes the sliding wear response of the components, the exact mechanism behind of this phenomenon has rarely been discussed in previous studies. It is tribologically beneficial to keep the graphite open, particularly in applications where the scuffing issues do matter. In this thesis, the main causes involved in closing the graphite lamellas are discussed, with a focus on matrix plastic deformation that occurs during sliding. In first step, the relationship between graphite lamellae orientation and plastic deformation was investigated. To do so, two piston rings, belonging to the same two-stroke marine engine operated for different periods of time, were selected and compared to the unworn sample. The worn piston rings displayed a substantial decrease in both frequency and area fraction of the graphite lamellas. Most of the lamellas were closed as a result of plastic deformation of matrix. This happening was caused mainly by the interaction between abrasive particles and metallic matrix. Additionally, it was found that graphite lamellas parallel or near-parallel to the sliding direction exhibited maximum closing tendency under sliding condition. In next step, to have a better understanding of the graphite film formation mechanism and matrix deformation role in closing the graphite lamellas, microindentation and microscratch testing were performed on typical lamellar iron. The qualitative results showed a similar mechanism involving in graphite contribution to lubricate the sliding surfaces. Moreover, microindentations made nearby the graphite lamellas demonstrated that the deformation of the matrix causes the formation of cracks in the centre of the graphite lamellas, compressing and then extruding the graphite from its natural position, irrespective of the lamellas′ size. Furthermore, it was found that subsurface graphite orientation had a large influence on the extrusion behaviour, in that, for graphite lamellas oriented towards the indenter, the effect was observed more pronounced. Furthermore, an improved fully ferritic solution strengthened compacted graphite iron was produced for future wear studies. The effects of different Si levels and section thicknesses on tensile properties and hardness were investigated as well. The influence of Si content and section thickness on mechanical properties was revealed by improving the materials strength and slightly enhancing the hardness through increasing Si content. Besides, Si addition up to 4.5 wt% significantly affected the strength and elongation to failure of cast samples. / Helios / FFI

There has been much discussion about the beneficial uses of lamellar graphite iron in piston rings–cylinder liner systems, where a good combinations of both thermal and tribological properties are essential. The excellent tribological performance of lamellar iron under such sliding conditions is principally associated with lubrication behaviour of the graphite particles which are distributed as lamellas throughout the matrix. During sliding, graphite particles are extruded and smeared onto the counterfaces, act as solid lubricating agents and form a thin graphite film between the sliding surfaces. Although this process especially, during the running-in period significantly changes the sliding wear response of the components, the exact mechanism behind of this phenomenon has rarely been discussed in previous studies. It is tribologically beneficial to keep the graphite open, particularly in applications where the scuffing issues do matter. In this thesis, the main causes involved in closing the graphite lamellas are discussed, with a focus on matrix plastic deformation that occurs during sliding. In first step, the relationship between graphite lamellae orientation and plastic deformation was investigated. To do so, two piston rings, belonging to the same two-stroke marine engine operated for different periods of time, were selected and compared to the unworn sample. The worn piston rings displayed a substantial decrease in both frequency and area fraction of the graphite lamellas. Most of the lamellas were closed as a result of plastic deformation of matrix. This happening was caused mainly by the interaction between abrasive particles and metallic matrix. Additionally, it was found that graphite lamellas parallel or near-parallel to the sliding direction exhibited maximum closing tendency under sliding condition. In next step, to have a better understanding of the graphite film formation mechanism and matrix deformation role in closing the graphite lamellas, microindentation and microscratch testing were performed on typical lamellar iron. The qualitative results showed a similar mechanism involving in graphite contribution to lubricate the sliding surfaces. Moreover, microindentations made nearby the graphite lamellas demonstrated that the deformation of the matrix causes the formation of cracks in the centre of the graphite lamellas, compressing and then extruding the graphite from its natural position, irrespective of the lamellas′ size. Furthermore, it was found that subsurface graphite orientation had a large influence on the extrusion behaviour, in that, for graphite lamellas oriented towards the indenter, the effect was observed more pronounced. Furthermore, an improved fully ferritic solution strengthened compacted graphite iron was produced for future wear studies. The effects of different Si levels and section thicknesses on tensile properties and hardness were investigated as well. The influence of Si content and section thickness on mechanical properties was revealed by improving the materials strength and slightly enhancing the hardness through increasing Si content. Besides, Si addition up to 4.5 wt% significantly affected the strength and elongation to failure of cast samples. / Helios / FFI

A crescente preocupação com a poluição ambiental nos centros urbanos tem motivado a adoção de medidas que visam a reduzir o impacto que os agentes poluidores causam. Na cidade de Curitiba, PR, esta preocupação levou os órgãos reguladores do transporte urbano a fomentar o uso do biodiesel B100 como combustível para um conjunto de 34 ônibus da frota da cidade. Entretanto, a adoção desta medida trouxe a necessidade de garantir a vida útil dos motores, o que foi feito definindo-se um plano de manutenção muito mais conservador que o usual, e que previa a troca do óleo lubrificante com o dobro da frequência normalmente praticada. A proposta deste trabalho de mestrado foi a de fazer um estudo que possa subsidiar cientificamente a definição da frequência de troca do lubrificante nos veículos abastecidos com biodiesel B100 no transporte urbano de Curitiba. Para isto, ao longo de um período de 18 meses, o lubrificante desses veículos foi periodicamente analisado, a fim de caracterizar a evolução de seu estado, bem como a degradação de seu desempenho pelo o uso em conjunto com o biodiesel B100. Para obter uma representatividade estatística, tais análises foram feitas em uma população de sete veículos, quatro dos quais eram alimentados com biodiesel B100 e três com óleo diesel convencional, sendo que estes últimos serviam como referência para comparação. As características do lubrificante que foram levadas em conta durante o estudo incluem a viscosidade, a basicidade, a acidez, a oxidação, a contaminação por fuligem, a contaminação por compostos nitrogenados, a contaminação por água, bem como os teores de ferro, chumbo, alumínio, cobre, cromo, silício e molibdênio, elementos estes que tipicamente provêm do desgaste de componentes do motor. O estudo permitiu identificar a viscosidade como a característica que mais se degrada com o envelhecimento do lubrificante pelo seu uso concomitante com o combustível B100. Assim, este parâmetro foi o fator determinante para caracterizar, com base nos resultados obtidos no estudo, que a vida útil do lubrificante deve ser de 9.900 km para o caso de veículos biarticulados, e de 13.100 km para os veículos articulados. Cumpre ressaltar que a realização deste estudo só foi possível pelo interesse e pela colaboração das empresas que juntamente com a UTFPR fizeram parte do projeto LUB-B100: Chevron Brasil Lubrificantes (fabricante de óleos lubrificantes), Volvo do Brasil (montadora de ônibus), Auto Viação Redentor (permissionária do transporte urbano de Curitiba), Nórdica Veículos S. A. (concessionária de veículos) e URBS – Urbanização de Curitiba S. A. (fiscalizadora e reguladora do transporte urbano coletivo de Curitiba). / The increasing levels of pollution in urban centers have induced the adoption of mitigating measures in order to reduce negative consequences. In Curitiba, Southern Brazil, the office that regulates urban passenger transport in the city has promoted the use of pure biodiesel (B100) as fuel for a fleet of 34 buses. However, as this measure was put into practice, concerns related to a possible reduction of engine service life were raised, thus forcing the vehicles-owner companies to adopt a conservative maintenance plan, which doubled the frequency of lubricant oil replacement. This was the opportunity for the present study, which aimed to define on a scientific basis the frequency of lubricant oil replacement in engines fueled with biodiesel B100. In order to characterize both the evolution of lubricant oil degradation, as well as the deterioration of lubricant performance due to the use of biodiesel B100, samples of engine lubricant were collected and analyzed along 18 months. Additionally, aiming to confer statistical representativeness to collected data, a population of 7 buses was considered, four of these being fueled with biodiesel B100, while the other 3 with conventional diesel fuel, thus the latter group served as a reference for comparisons. The following parameters of the lubricant oil were measured and analyzed: viscosity, basicity, acidity, oxidation, contamination by soot, contamination by nitrogenous substances, contamination by water, as well as contents of iron, lead, aluminum, copper, chrome, silicon and molybdenum, which are elements typically originated from the wear of metallic components. The conducted study allowed to point out the viscosity as the lubricant parameter that is most sensitive to concomitant use with biodiesel B100. Thus, this parameter was decisive to conclude that based on measured data the service life of the lubricant should be 9900 km for bi-articulated buses, and 13100 km for the articulated ones. It is worth mentioning that the completion of this study became possible by virtue of the collaboration with those companies that took part of the project named LUB-B100, together with the Federal University of Technology - Parana. These companies are Chevron Brasil Lubrificantes (a lubricant maker company), Volvo do Brasil (a bus manufacturer company), Auto Viação Redentor (a company that operates the passenger urban transport in Curitiba), Nórdica Veículos S. A. (a Volvo dealership company) and URBS – Urbanização de Curitiba S. A. (the office that regulates the urban passenger transport in Curitiba).

A crescente preocupação com a poluição ambiental nos centros urbanos tem motivado a adoção de medidas que visam a reduzir o impacto que os agentes poluidores causam. Na cidade de Curitiba, PR, esta preocupação levou os órgãos reguladores do transporte urbano a fomentar o uso do biodiesel B100 como combustível para um conjunto de 34 ônibus da frota da cidade. Entretanto, a adoção desta medida trouxe a necessidade de garantir a vida útil dos motores, o que foi feito definindo-se um plano de manutenção muito mais conservador que o usual, e que previa a troca do óleo lubrificante com o dobro da frequência normalmente praticada. A proposta deste trabalho de mestrado foi a de fazer um estudo que possa subsidiar cientificamente a definição da frequência de troca do lubrificante nos veículos abastecidos com biodiesel B100 no transporte urbano de Curitiba. Para isto, ao longo de um período de 18 meses, o lubrificante desses veículos foi periodicamente analisado, a fim de caracterizar a evolução de seu estado, bem como a degradação de seu desempenho pelo o uso em conjunto com o biodiesel B100. Para obter uma representatividade estatística, tais análises foram feitas em uma população de sete veículos, quatro dos quais eram alimentados com biodiesel B100 e três com óleo diesel convencional, sendo que estes últimos serviam como referência para comparação. As características do lubrificante que foram levadas em conta durante o estudo incluem a viscosidade, a basicidade, a acidez, a oxidação, a contaminação por fuligem, a contaminação por compostos nitrogenados, a contaminação por água, bem como os teores de ferro, chumbo, alumínio, cobre, cromo, silício e molibdênio, elementos estes que tipicamente provêm do desgaste de componentes do motor. O estudo permitiu identificar a viscosidade como a característica que mais se degrada com o envelhecimento do lubrificante pelo seu uso concomitante com o combustível B100. Assim, este parâmetro foi o fator determinante para caracterizar, com base nos resultados obtidos no estudo, que a vida útil do lubrificante deve ser de 9.900 km para o caso de veículos biarticulados, e de 13.100 km para os veículos articulados. Cumpre ressaltar que a realização deste estudo só foi possível pelo interesse e pela colaboração das empresas que juntamente com a UTFPR fizeram parte do projeto LUB-B100: Chevron Brasil Lubrificantes (fabricante de óleos lubrificantes), Volvo do Brasil (montadora de ônibus), Auto Viação Redentor (permissionária do transporte urbano de Curitiba), Nórdica Veículos S. A. (concessionária de veículos) e URBS – Urbanização de Curitiba S. A. (fiscalizadora e reguladora do transporte urbano coletivo de Curitiba). / The increasing levels of pollution in urban centers have induced the adoption of mitigating measures in order to reduce negative consequences. In Curitiba, Southern Brazil, the office that regulates urban passenger transport in the city has promoted the use of pure biodiesel (B100) as fuel for a fleet of 34 buses. However, as this measure was put into practice, concerns related to a possible reduction of engine service life were raised, thus forcing the vehicles-owner companies to adopt a conservative maintenance plan, which doubled the frequency of lubricant oil replacement. This was the opportunity for the present study, which aimed to define on a scientific basis the frequency of lubricant oil replacement in engines fueled with biodiesel B100. In order to characterize both the evolution of lubricant oil degradation, as well as the deterioration of lubricant performance due to the use of biodiesel B100, samples of engine lubricant were collected and analyzed along 18 months. Additionally, aiming to confer statistical representativeness to collected data, a population of 7 buses was considered, four of these being fueled with biodiesel B100, while the other 3 with conventional diesel fuel, thus the latter group served as a reference for comparisons. The following parameters of the lubricant oil were measured and analyzed: viscosity, basicity, acidity, oxidation, contamination by soot, contamination by nitrogenous substances, contamination by water, as well as contents of iron, lead, aluminum, copper, chrome, silicon and molybdenum, which are elements typically originated from the wear of metallic components. The conducted study allowed to point out the viscosity as the lubricant parameter that is most sensitive to concomitant use with biodiesel B100. Thus, this parameter was decisive to conclude that based on measured data the service life of the lubricant should be 9900 km for bi-articulated buses, and 13100 km for the articulated ones. It is worth mentioning that the completion of this study became possible by virtue of the collaboration with those companies that took part of the project named LUB-B100, together with the Federal University of Technology - Parana. These companies are Chevron Brasil Lubrificantes (a lubricant maker company), Volvo do Brasil (a bus manufacturer company), Auto Viação Redentor (a company that operates the passenger urban transport in Curitiba), Nórdica Veículos S. A. (a Volvo dealership company) and URBS – Urbanização de Curitiba S. A. (the office that regulates the urban passenger transport in Curitiba).

Submitted by Arnolfo Coelho (arnolfo.menezes@grupomoura.com) on 2018-07-30T21:05:37Z No. of bitstreams: 1 TA MPGC Arnolfo Menezes Versão Final R1.pdf: 1141674 bytes, checksum: e87c994b8339b250e34e46111cc83222 (MD5) / Approved for entry into archive by Simone de Andrade Lopes Pires (simone.lopes@fgv.br) on 2018-07-31T17:38:31Z (GMT) No. of bitstreams: 1 TA MPGC Arnolfo Menezes Versão Final R1.pdf: 1141674 bytes, checksum: e87c994b8339b250e34e46111cc83222 (MD5) / Approved for entry into archive by Suzane Guimarães (suzane.guimaraes@fgv.br) on 2018-07-31T17:51:27Z (GMT) No. of bitstreams: 1 TA MPGC Arnolfo Menezes Versão Final R1.pdf: 1141674 bytes, checksum: e87c994b8339b250e34e46111cc83222 (MD5) / Made available in DSpace on 2018-07-31T17:51:27Z (GMT). No. of bitstreams: 1 TA MPGC Arnolfo Menezes Versão Final R1.pdf: 1141674 bytes, checksum: e87c994b8339b250e34e46111cc83222 (MD5) Previous issue date: 2018-06-29 / As modalidades insustentáveis de produção e consumo praticadas têm sido ponto de discussões ambientais que influenciam a sociedade e, consequentemente, aspectos legais e de produção. Portanto, a gestão ambientalmente racional dos resíduos foi incluída entre as questões de maior importância para a manutenção da qualidade do ambiente natural e para o atingimento de um modelo mais sustentável de desenvolvimento. Em adição aos argumentos supramencionados, sabe-se que o aumento populacional em diversas partes do mundo, e o consequente incremento no consumo, facilmente influenciam as organizações a aumentarem sua produção, o que também aumenta tanto o consumo de matéria-prima quanto a geração de resíduos. Uma maneira de mitigar a pegada ecológica – e, inclusive, de gerar valor para a organização – está em utilizar os recursos de maneira mais sustentável, dando prioridade a processos de reuso, reaproveitamento e reciclagem de matérias-primas. E a logística reversa é um conceito que cresce em importância, já que permite às organizações, de maneira estruturada, ter acesso ao resíduo de seu produto e/ou de produtos de terceiros após o uso pelo consumidor, tornando este resíduo (em parte ou no todo) uma nova entrada no processo produtivo como matéria-prima ou insumo, ao invés de ser direcionado a lixões ou aterros sanitários. Diante desta problemática, e face à criação, no Brasil, da Política Nacional de Resíduos Sólidos, este estudo tem como objetivo descrever, analisar e comparar as práticas de logística reversa pós-consumo de três setores distintos: baterias chumbo-ácido, embalagens de óleo lubrificante e pneus. Foram verificados os modelos de funcionamento e os resultados ambientais da implementação dos sistemas de logística reversa. Para a realização do estudo, foram entrevistados representantes dos setores afim de estudar as entidades gestoras: IBER, Instituto Jogue Limpo e RECICLANIP, responsáveis pela gestão dos sistemas de logística reversa de baterias chumbo-ácido, embalagens de óleo lubrificante e pneus, respectivamente. / The unsustainable modalities of production and consumption have been the point of environmental discussions that influence society and, consequently, legal and production aspects. Sustainable waste management has been included as one of the most important issues for maintaining the quality of the natural environment and for achieving a more sustainable model of development. In addition to the above arguments, it is known that the population increases in several parts of the world, and the consequent increase in consumption, easily influence the organizations to increase their production, which also increases both the consumption of raw material and the generation of waste. One way to mitigate the ecological footprint - and even to generate value for the organization - is to use resources in a more sustainable way, giving priority to processes of reuse and recycling of raw materials. Reverse logistics is a concept that grows in importance, since it allows the organization, in a structured way, to have access to the residue of its product after the use by the consumer, making this residue (in part or in whole) a new entry in the process as raw material or input, rather than being directed to landfills. In view of this problem, and in view of the creation in Brazil of the National Solid Waste Policy, this study aims to describe, analyze and compare the postconsumption reverse logistics practices of three different sectors: lead-acid batteries, lubricating oil and tires. The operating models and the environmental performance of the sectors were verified before and after the implementation of the reverse logistics systems. In order to carry out the study, were interviewed representatives of three sectors in order to study the entities: IBER, Jogue Limpo Institute and RECICLANIP, responsible for the management of reverse logistics systems for lead-acid batteries, lubricating oil packing and tires, respectively.

<p dir="ltr">Positive displacement machines are used in various industries spanning the power spectrum, from industrial robotics to heavy construction equipment to aviation. These machines should be highly efficient, compact, and reliable. It is very advantageous for designers to use virtual simulations to design and improve the performance of these units as they significantly reduce cost and downtime. The recent trends of electrification and the goal to increase power density force these units to work at higher pressures and higher rotational speeds while maintaining their efficiencies and reliability. This push means that the simulation models need to advance to account for various aspects during the operation of these machines. </p><p dir="ltr">These machines typically have several bodies in relative motion with each other. Quantifying these motions and solving for their effect on the fluid enclosed are vital as they influence the machine's performance. The push towards higher rotational speeds introduces unwanted cavitation and aeration in these units. To model these effects, keeping the design evaluation time low is key for a designer. The lumped parameter approach offers the benefit of computational speed, but a major drawback that comes along with it is that it typically assumes fluid inertia to be negligible. These effects cannot be ignored, as quantifying and making design considerations to negate these effects can be beneficial. Therefore, this thesis addresses these key challenges of cavitation dynamics, body dynamics, and accounting for fluid inertia effects using a lumped parameter formulation.</p><p dir="ltr">To account for dynamics features related to cavitation, this thesis proposes a novel approach combining the two types of cavitation, i.e., gaseous and vaporous, by considering that both vapor and undissolved gas co-occupy a spherical bubble. The size of the spherical bubble is solved using the Rayleigh-Plesset equation, and the transfer of gas through the bubble interface is solved using Henry's Law and diffusion of the dissolved gas in the liquid. These equations are coupled with a novel pressure derivative equation. To account for body dynamics, this thesis introduces a novel approach for solving the positions of the bodies of a hydraulic machine while introducing new methods to solve contact dynamics and the application of Elasto Hydrodynamic Lubrication (EHL) friction at those contact locations. This thesis also proposes strategies to account for fluid inertia effects in a lumped parameter-based approach, taking as a reference an External Gear Machine. This thesis proposes a method to study the effects of fluid inertia on the pressurization and depressurization of the tooth space volumes of these units. The approach is based on considering the fluid inertia in the pressurization grooves and inside the control volumes with a peculiar sub-division. Further, frequency-dependent friction is also modeled to provide realistic damping of the fluid inside these channels.</p><p dir="ltr">To show the validity of the proposed dynamic cavitation model, the instantaneous pressure of a closed fluid volume undergoing expansion/compression is compared with multiple experimental sources, showing an improvement in accuracy compared to existing models. This modeling is then further applied to a gerotor machine and validated with experiments. Integrating this modeling technique with current displacement chamber simulation can further improve the understanding of cavitation in hydraulic systems. Formulations for body dynamics are tested on a prototype Gerotor and Vane unit. For both gerotor and vane units, comparisons of simulation results to experimental results for various dynamic quantities, such as pressure ripple, volumetric, and hydromechanical efficiency for multiple operating conditions, have been done. Extensive validation is performed for the case of gerotors where shaft torque ripple and the motion of the outer gear is experimentally validated. The thesis also comments on the distribution of the different torque loss contributions. The model for fluid inertia effects has been validated by comparing the lumped parameter model with a full three-dimensional Navier Stokes solver. The quantities compared, such as tooth space volume pressures and outlet volumetric flow rate, show a good match between the two approaches for varying operating speeds. A comparison with the experiments supports the modeling approach as well. The thesis also discusses which operating conditions and geometries play a significant role that governs the necessity to model such fluid inertia effects in the first place.</p>