Thesis (PhD)--Stellenbosch University, 2012. / ENGLISH ABSTRACT: New methods are described for the synthesis of polymer/graphite nanocomposites using the miniemulsion polymerization process. Natural graphite was functionalized by oxidation to produce graphite oxide (GO) nanosheets. Poly(styrene-co-butyl acrylate) (poly(St-co-BA)) nanocomposite latices containing GO nanosheets were successfully synthesized using miniemulsion as a one-step nano-incorporation technique. The approach followed included expanding the GO nanosheets in situ during the miniemulsification step and then polymerizing the monomers in the presence of these expanded nanosheets. Styrene (St) and butyl acrylate (BA) were mixed with GO and then emulsified in the presence of a surfactant and a hydrophobe to afford pre-miniemulsion latex particles. The stable pre-miniemulsions were then polymerized to yield poly(St-co-BA)/GO nanocomposite latices. The polymerization proceeded with relatively high monomer conversion and produced stable nanocomposite latex particles. The nanocomposites exhibited mainly an intercalated morphology, irrespective of the percentage of GO filler loading. The synthesis of exfoliated polymer nanocomposites made with modified GO is described. GO was modified with a surfmer (reactive surfactant), 2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS), which widened the gap between the GO nanosheets and facilitated monomer intercalation between its nanogalleries. The AMPS-modified GO was used for the synthesis of poly(St-co-BA)/GO nanocomposite latices using a similar miniemulsion procedure. The obtained nanocomposites had exfoliated morphologies and the GO nanosheets were largely exfoliated (about 2–5 nm thick) in the resultant films obtained from the synthesized nanocomposite latices. The synthesized nanocomposites had enhanced thermal and mechanical properties compared to pure polymer as a result of the presence of AMPSmodified GO. Furthermore, the nanocomposites made with AMPS-modified GO had better thermal and mechanical properties than the unmodified GO. The mechanical properties of the nanocomposites depended on the AMPS-modified GO loading in the nanocomposites. The synthesis of polystyrene/GO (PS-GO) nanocomposites using the reversible additionfragmentation chain transfer (RAFT) mediated polymerization method is also described. The GO was synthesized and immobilized with a RAFT agent to afford RAFT-functionalized GO nanosheets. The RAFT-immobilized GO was used for the synthesis of PS nanocomposites in a controlled manner using miniemulsion polymerization. The molar mass and dispersity of the PS in the nanocomposites depended on the amount of RAFT-grafted GO in the system, in accordance with the features of the RAFT-mediated polymerization. X-ray diffraction and transmission electron microscopy analyses revealed that the nanocomposites had exfoliated morphology, even at relatively high GO content. The thermal stability and mechanical properties of the PS-GO nanocomposites were better than those of the neat PS polymer. Furthermore, the mechanical properties were dependent on the modified-GO content (i.e., the amount of RAFT-grafted GO). The hydrophobicity and barrier properties of the resulting films prepared from the synthesized poly(St-co-BA)/GO nanocomposite latices to water and water vapor were also investigated. The hydrophobicity of the synthesized nanocomposite films was determined using contact angle measurements. The water permeability was determined by measuring the moisture vapor transmission rate of the films. The GO in the nanocomposites was reduced to its original form (i.e., graphite), and the barrier properties of the obtained nanocomposite films were determined and compared to films containing the unmodified GO (as-prepared GO). Results showed that reduction of GO had a significant impact on the water affinity of the resultant films prepared from the synthesized nanocomposite latices. The presence of reduced-GO (RGO) instead of unmodified GO in the miniemulsion formulation significantly improved the hydrophobicity and barrier properties of the final films to water. However, the barrier properties of the nanocomposites were unaffected by the amount of RGO in the nanocomposites. / AFRIKAANSE OPSOMMING: Nuwe metodes is beskryf vir die sintese van polimeer/grafiet nanosamestellings deur gebruik te maak van die miniemulsie polimerisasieproses. Natuurlike grafiet is gefunksionaliseer dmv oksidasie om grafietoksied (GO) nanovelle te vorm. Polistireen-ko-butielakrilaat (poli[St-ko- BA]) nanosamestellinglatekse wat GO nanovelle bevat is suksesvol gesintetiseer deur gebruik te maak van miniemulsie polimerisasie as ‘n een-stap nano-insluitingstegniek. Die benadering wat gevolg is het die uitbreiding van die GO nanovelle, in situ, gedurende die miniemulsifiseringstap behels, gevolg deur die polimerisasie van die monomere in die teenwoordigheid van hierdie uitgebreide nanovelle. Stireen (St) en butielakrilaat (BA) is met GO gemeng en daarna emulgeer in die teenwoordigheid van ‘n seepmiddel (surfactant) en ‘n hidrofoob om pre-miniemulsielateksdeeltjies te lewer. Die stabiele pre-miniemulsies is gepolimeriseer om poli(St-ko-BA)/GO nanosamestellinglatekse te vorm. Die polimerisasie het met redelike hoë monomeeromskakeling verloop en het stabiele nanosamestellinglateksdeeltjies gelewer. Hierdie nanosamestellings het hoofsaaklik geïnterkaleerde morfologie, onafhanklik van die persentasie GO vullers, getoon. Die sintese van afgeskilferde polimeernanosamestellings berei met gewysigde GO is beskryf. GO is gewysig met ‘n ‘surfmer’ (reaktiewe seepmiddel), 2-akrielamido-2-metiel-1- propaansulfoonsuur (AMPS), wat die gapings tussen die GO nanovelle vergroot het en die monomeer interkalering tusssen sy nanogange fasiliteer. Die AMPS-gewysigde GO is gebruik vir die sintese van poli(St-ko-BA)/GO nanosamestellinglatekse deur gebruik te maak van ‘n soortgelyke miniemulsie prosedure. Die nanosamestelling sό verkry het ‘n afgeskilferde morfologie getoon en die GO nanovelle was grootendeels afgeskilfer (ongeveer 2–5 nm dik) in die films wat berei is van die gesintetiseerde nanosamestellinglatekse. Laasgenoemde het verhoogde termiese en meganiese eienskappe gehad in vergelyking met die suiwer polimeer, as gevolg van die teenwoordigheid van die AMPS-gewysigde-GO. Die meganiese eienskappe van die nanosamestellings hang af van persentasie AMPS-gewysigde GO vullers in die nanosamestellings. Die sintese van PSt/GO nanosamestellings dmv die omkeerbare-addisie-fragmentasieoordrag- (OAFO-, Eng. RAFT-) bemiddelde polimerisasie metode is ook beskryf. Die GO is berei en geïmmobiliseer met ‘n RAFT verbinding om GO nanovelle met RAFT funksionaliteit te lewer. Die RAFT-geïmmobiliseerde GO is gebruik vir die sintese van PSt nanosamestellings in ‘n gekontrolleerde manier mbv miniemulsie polimerisasie. Die molêre massa en dispersie van die PSt in die nanosamestellings hang af van die hoeveelheid RAFTgeënte GO in die sisteem, in ooreenstmming met die kenmerke van RAFT-bemiddelde polimerisasie. X-straaldiffraksie en transmissie-elektronmikroskopie analises het bewys dat die nanosamestellings, selfs by relatiewe hoë GO inhoud, ‘n afgeskilferde morfologie gehad het. Die termiese stabiliteit en meganiese eienskappe van die PSt-GO nanosamestellings was beter as dié van die suiwer PSt polimeer. Verder was die meganiese eienskappe afhanklik van die gewysigde-GO-inhoud (dws, die hoeveelheid RAFT-geënte-GO). Die hidrofobisiteit en spereienskappe van die films berei vanaf die gesintetiseerde poli(St-ko- BA)/GO nanosamestellinglatekse teenoor water en waterdamp is ook ondersoek. Die hidrofobisiteit is ondersoek deur gebruik te maak van kontakhoekmeting. Die waterdeurlaatbaarheid is bepaal deur die waterdampoordragtempo van die films te bepaal. Die GO in die nanosamestellings is gereduseer tot sy eenvoudigste vorm (grafiet) en die spereienskappe van die nanosamestellingfilms is bepaal en vergelyk met die films wat die ongewysigde GO bevat het. Resultate het getoon dat reduksie van GO ‘n groot invloed gehad het op die wateraffiniteit van die films wat berei is vanaf die gesintetiseerde nanosamestellinglatekse. Die teenwoordigheid van die gereduseerde-GO (RGO) in plaas van die onveranderde GO in die miniemulsie formulasie het die hidrofobisiteit en spereienskappe van die finale films, teenoor water, baie verbeter. Die spereienskappe van die nanosamestellings is egter nie beïnvloed deur die hoeveelheid RGO in die nanosamestellings nie.

The Franciscan Complex forms the structurally complicated, locally chaotic basement of the Northern and Central California and southwestern Oregon Coast Ranges. It is an accretionary wedge formed during the Late- Jurassic-Tertiary subduction along the west coast of North America. In northern California, the Franciscan is subdivided into three belts, the Western, Central, and Coastal belts, which show a zonation in age, metamorphic “grade”, and structural style. Franciscan mélanges are present in the Central belt, as well as the Diablo Range --a tectonic window within the structurally overlying Great Valley Group--, and the Nacimiento Block, where the study area is located. One of the best exposures of Franciscan mélange, where contact relationships between blocks and matrix can be observed, crops out along 6 km of seacliffs near San Simeon. Boudinaged blocks of graywacke, greenstone, chert, and much rarer blueschist and graphite-schist are ix dispersed in the shale matrix. Block sizes range from 10 cm to 15 m. The discovery of interlayered blueschist and graphite-schists, and the presence of lawsonite in some graphite-schists demonstrates that these two lithologies were metamorphosed together. Graphite-schist blocks in the Franciscan have not been reported prior to this study. Two main mineral assemblages were recognized among the studied 34 mafic blueschist blocks: 1) Lws + Na-amp + Pmp + Phe + Ttn + Chl recrystallized at ~5 kbar and 200-250°C, and 2) Lws + Na-amp + Pmp + Phe + Ttn + Ep + Chl, which recrystallized under slightly higher temperatures but similar pressures (300-350°C, at 5 kbar). A pre-blueschist facies metamorphic event under greenschist facies conditions is recorded by calcic cores overprinted by Na-amp rims in about half of the blocks. Sodic amphibole rims with a higher Fe3+ content probably developed due to the breakdown of epidote during a decrease in T. These mafic blueschists followed a counterclockwise P-T path. Remnants of “actinolitic rinds”, which are reaction zones formed when the blocks were in contact with serpentine, were found associated with nine of the studied mafic blueschist blocks. Such rinds were thought to be unique to better-studied Franciscan high-T blocks. Graphite-schist blocks (30 studied) contain Qtz + Phen + Ab + Gr, and are of two types. One type has relict sedimentary textures with a weak foliation defined by graphite and pressure solution seams. The other type has a compositional layering with layers containing well recrystallized quartz. Nine of these blocks also contain lawsonite within the more graphitic layers. The geochemistry of the blueschist blocks indicates that they were derived from the MORB-like oceanic crust, and seamounts underplated during the initiation of subduction. The mainly mafic protolith contained a small volume of interlayered sediment, as indicated by the presence of associated metasedimentary graphite-schists. Blueschist facies conditions were attained at the bottom of the overriding plate during the initial states of Franciscan subduction (150-155 Ma). Mafic material continued to be underplated, and low-T dynamic blueschist-facies metamorphism continued to form until at least ~137 Ma. A model is proposed in which exhumation was facilitated by normal faulting near the surface driven by gravitational collapse driven by decrease in subduction plate dip around 80 Ma that is known to have caused the Laramide orogeny. During this time, blueschist and graphite-schist blocks were plucked from the bottom of the hanging wall, incorporated into the shaleand water-rich shear zone at the plate interface, and exhumed during the upward flow of mélange driven by the movement of the downgoing plate. Blocks were extended and boudinaged, and metasomatically altered in the cataclastic zones that developed along necks and margins of the blocks during upwelling and the dewatering that led to final compaction near the surface. / text

No description available.

L'évolution des structures poreuses du graphite et de la vermiculite expansés a été étudiée insitu sous pression uniaxiale. Les propriétés d'un matériau résultant des propriétés intrinsèques à lamatrice et de celles dues à la porosité, les études faites dans ce travail ont porté sur deux échellesdifférentes. Les évolutions structurales de la structure cristalline du graphite et de la vermiculite ontd'abord été étudiées à haute pression en cellule à enclumes de diamant. Cette partie du travail a permisd'établir les équations d'état de la vermiculite et de contribuer, de manière significative, à lacaractérisation de la phase haute pression du graphite: une nouvelle phase, le Carbone Z, a étéproposée après l'analyse des données de la spectroscopie Raman couplée aux simulations. Desdéveloppements techniques ont été particulièrement réalisés pour permettre d'étudier in situl'évolution de la porosité sous pression par diffusion aux petits angles sous pression. L'application dumodèle fractale à l'analyse des données a permis de suivre l'évolution de la dimension fractale et de lasurface spécifique apparente. Les échantillons étudiés sont des formes comprimées de graphite et devermiculite expansés dans lesquelles les plans basaux des cristallites ont une orientation préférentielle.Sous pression uniaxiale, la structure poreuse du graphite expansé comprimé évolue à travers uneffondrement irréversible des pores ou un cisaillement de la matrice suivant l'orientation de la pressionappliquée par rapport à l'orientation préférentielle des plans basaux des cristallites. Des expériencescomplémentaires de mesures électriques et de mesures de la porosité par intrusion de mercure ontpermis de confirmer ces modèles proposés. Dans la vermiculite expansée comprimée, les fissuresapparaissent, de manière générale, sous l'effet de la pression uniaxiale.

Superconductors present great potential for weight reduction and increased power delivery when compared to traditional copper power delivery systems, but current systems require cryogenic cooling systems. Traditional superconductor cooling systems consist of helium cooled by helical heat exchangers made of Oxygen Free High thermal Conductivity (OFHC) copper tube. The helium is cooled by bulky heat exchangers consisting of OFHC copper coils wrapped around a cryogenic cooler heat sink for heat transfer into the working fluid. Metal foams have recently been studied in a variety of heat transfer applications, and could greatly reduce the weight of heat exchanger modules in superconductor cooling systems while simultaneously providing increased heat transfer effectiveness. Aluminum and Copper foams have been available for several years, but more recently, graphite foams, such as PocoFoam™, have been developed which have particularly good heat transfer characteristics. Using Computational Fluid Dynamics (CFD) to model a cryogenic heat exchanger application, this study examines the effectiveness and pressure drop of several metal foam heat exchangers, and compares their performance with the traditional helical coil design for superconductor cooling applications. The CFD simulation results show that a heat exchanger with the same heat sink contact area as existing helical heat exchangers weighs up to 95 percent less and can be up to 25 percent more effective, depending on system conditions such as pressure, cryogenic cooler temperature and helium inlet temperature. Aluminum and copper foam heat exchangers had comparable weight to the PocoFoam heat exchanger, but were significantly less effective than the helical or PocoFoam heat exchanger models.

O arroz é um dos alimentos mais consumidos no mundo, caracterizando-se como a base da alimentação para mais da metade da população mundial. De acordo com a Organização Mundial da Saúde (WHO), a ingestão de alimentos contaminados é uma das principais vias de absorção de elementos potencialmente tóxicos pelo ser humano. Por esse motivo, órgãos de fiscalização têm estabelecidos limites máximos permitidos desse tipo de elemento nos alimentos. Nesse sentido, o desenvolvimento de métodos e aplicações visando à determinação de elementos com caráter tóxico, tais como o Al, As, Cd e Pb em alimentos é de suma importância. Nesse projeto, foram desenvolvidos métodos para determinações diretas de Al, As, Cd e Pb em arroz por espectrometria de absorção atômica com forno de grafite e amostragem direta de sólidos (SS-GF AAS) que tem se mostrado uma técnica promissora especialmente devido à sua elevada sensibilidade e detectabilidade, além de dispensar morosos processos de decomposição de amostra. A adequada otimização do programa de aquecimento aliado ao uso de modificadores químicos adequados possibilitou o uso de calibração aquosa. Parâmetros importantes como o tamanho de partícula, massa de amostra e segregação de analito foram investigados. Observou-se que partículas inferiores a 100 µm geravam resultados precisos. A massa mínima ideal de amostra de arroz a ser utilizada na análise foi em torno de 300 µg. A massa máxima recomendada foi 500 µg. Segregação de Al e Cd não foram observadas na amostra de arroz. A segunda parte do projeto envolveu a aplicação do método de análise desenvolvido em amostras de arroz comercializadas na cidade de São Paulo. Investigou-se também a influência dos processos de lavagem e cozimento dos grãos sobre a concentração de Al, As, Cd e Pb. Todas as 17 amostras de diversos tipos e marcas de arroz analisadas apresentaram concentrações de As, Cd e Pb abaixo dos limites estabelecidos por lei. Com relação ao Al, não há regulamentado o valor de limite máximo. As maiores concentrações desse elemento foram observadas nos grãos de arroz integral. O processo de lavagem removeu significativamente a concentração de Al e Pb na maioria das amostras, entretanto, o mesmo não foi observado para o Cd. O processo de cozimento diminuiu a concentração de Cd e Pb em parte das amostras, e um pequeno aumento na concentração do Al foi observado, o qual pode ser atribuído à contaminação pelo ambiente. O cozimento do arroz em frascos de vidro ou panelas a base de alumínio não alterou a concentração desse elemento no arroz, nem mesmo quando a panela de alumínio foi polida com palha de aço / Rice is a staple food for more than 40% of the world\'s population. Considering that the main reason of contamination by potentially toxic element occurs by food ingestion, World Health Organization (WHO) has been controlling the levels of some contaminants. In this context, development of methods and applications associated to determination of potentially toxic elements such as Al, As, Cd and Pb in food are important. In this work, methods for direct determination of Al, As, Cd and Pb in rice by solid sampling graphite furnace atomic absorption spectrometry (SS-GF AAS) were developed. Solid sampling-GF AAS has shown as a promising technique especially due to its high sensitivity and detectability and the possibility to practice direct analysis of solid samples, dismissing tedious and error prone sample preparation step. The adequate heating program optimization associated to the use of chemical modifier allowed direct rice analysis against aqueous calibration. The influence of some parameters, such as particle size, sample mass size and analyte segregation on the analytical results were investigated. Results showed that particle size smaller than 100 µm generated accurate results. The minimum sample mass size recommended for analysis was around 300 µg and the maximum sample mass size was around 500 µg. Segregation of Cd and Al was not observed in the rice sample. The second part of the work involved the analysis of 17 rice samples commercially available in São Paulo city. Influence of rice washing and cooking procedure on the Al, As, Cd and Pb concentrations was also investigated. Concentration of all analytes were lower than the maximum allowed by WHO in all samples. The highest concentrations of Al were found in coarse rice. The washing process reduced significantly the concentrations of Al and Pb in most samples, however, the same was not observed for Cd. Cooking process reduced the concentration of Cd and Pb for most samples, probably by volatilization. On the other hand, an increase in Al concentration was observed. This fact could be attributed to the sample contamination during cooking process. Rice cooked in glass or aluminum container presented the same concentration of Al, even when polished aluminum container was used. These results indicated that there is no translocation of Al from container to food

Neste trabalho foi realizada a funcionalização de grafite sem prévio tratamento em condições de Fridel-Crafts. Considerando que a grafite não possui hidrogênio em sua estrutura, não se observa uma reação de substituição eletrofílica. Por outro lado, o trabalho mostra o papel da umidade presente no grafite na reação de funcionalização. Dessa forma, foi proposto um mecanismo para a reação com a participação da água adsorvida na grafite estabilizando o carbocátion formado. O grafite funcionalizado obtido na reação foi utilizado como material eletródico. Para a reação de funcionalização, quatro moléculas foram utilizadas: ácido ferrocenomonocarboxílico, cloreto de 4-nitrobenzoíla, cloreto de 3,5-dinitrobenzoíla e ácido 3,4-dinitrobenzóico. Para o estudo das condições ótimas da reação, utilizou-se diferentes potências de radiação no reator de micro-ondas, sendo que a extensão da funcionalização mostrou-se sensível à variação deste parâmetro. Para a caracterização dos materiais, utilizou-se voltametria cíclica e análise térmica (TG e DTA). Resultados de infravermelho e Ramam são apresentados no Apêndice A. Os resultados eletroquímicos mostraram que os materiais funcionalizados em maiores potências apresentaram maior corrente Faradaica, mas ao mesmo tempo, o material obtido foi mais resistivo. A diferença de potencial relacionada ao processo redox do ferroceno aumentou conforme a extensão da funcionalização, uma vez que um sobrepotencial é necessário devido ao fluxo iônico (para a manutenção da eletroneutralidade) relativo ao número de espécies envolvidas. Os resultados eletroquímicos também indicaram que a funcionalização do grafite com os nitro compostos foi baixa. A análise térmica evidenciou que a reação de funcionalização do grafite com o ferroceno resultou em materiais com 15% a 20% (m/m) de material ligado ao grafite. Os materiais funcionalizados a maiores potências apresentaram maior massa ligada ao grafite. A funcionalização com os nitro compostos resultou em materiais com menos de 3% (m/m) de composto ligado ao grafite. Os resultados das duas técnicas mostraram coerência na análise da extensão da funcionalização. O material funcionalizado com o ácido ferrocenomonocarboxilico foi o que apresentou os melhores resultados e propõe-se uma explicação para tal baseado no mecanismo de reação sugerido. Com o objetivo de melhor elucidar o mecanismo da reação, foram realizadas algumas reações na ausência de alguns reagentes. Por exemplo, quando tenta-se funcionalizar o material sem a presença de cloreto de alumínio ou sem a umidade natural do grafite, a reação não ocorre. / In this work natural graphite functionalization in Fridel-Crafts conditions is performed using a one-step microwave assisted reaction. Since there is no hydrogen in graphite structure, it is not possible to observe electrophilic substitution. On the other hand this work shows the role of the moisture present on graphite in the functionalization reaction under this condition. Therefore, a reaction mechanism with the participation of the water naturally adsorbed on graphite stabilizing the formed carbocation has been suggested. After the reaction, the functionalized graphite was used as electrode material. Four molecules were used to functionalize graphite: Ferrocene monocarboxylic acid, 4-nitrobenzoyl chloride, 3,5-dinitrobenzoyl chloride and 3,4-dinitrobenzoic acid. To study the optimal conditions of the reaction, the microwave radiation power was varied and the extent of the functionalization on graphite was sensitive to this parameter. Two techniques were used to characterize the materials, cyclic voltammetry and thermal analysis (TG and DTA). IR and Raman data are shown in appendix A. Electrochemical results have shown that the materials functionalized at higher microwave radiation power have higher Faradaic current, but are more resistive. The potential difference between the peaks of the redox process of ferrocene increased with the extent of functionalization. This occurs because an overpotencial is needed to compensate the ionic flux (in order to maintain the electroneutrality) related to the number of species involved. The electrochemical results also indicated that the extent of functionalization of graphite with the nitro compounds was low. The thermal analysis have shown that the functionalization of graphite with ferrocene lead to values between 15% to 20% (m/m) of compound in the material. The materials functionalized at higher microwave radiation power presented higher relative mass in the material. The reaction with the nitro compounds lead to less than 3% (m/m) of compound in the final material. The results of both techniques were coherent about the extent of functionalization. The material functionalized with ferrocene monocarboxylic acid showed the best results, and an explanation for that based on the reaction mechanism is suggested. In order to elucidate the reaction mechanism, some experiments were realized in absent of some reagents. When the reaction were carried out without aluminum chloride or with dried graphite, the reaction has not occurred.

Uma parte significativa das perdas por atrito num motor automotivo resulta da ação de partículas abrasivas. Dentre as fontes possíveis, podem ser citados o próprio meio ambiente - partículas que passam pelo filtro de ar - o desgaste de partes metálicas do motor ou mesmo resíduos de combustão. Essas partículas podem ficar encrustadas em anéis do pistão, ou ficar na interface entre pistão e bloco ou camisa, e são responsáveis por sulcos axiais, na direção do movimento do pistão, observáveis em motores usados. O objetivo deste trabalho foi obter um melhor entendimento dos mecanismos de desgaste relacionados com o sulcamento de camisa/bloco e identificar conjuntos de testes laboratoriais capazes de reproduzi-los sob condições controladas. Amostras de ferro fundido cinzento (FoFo) e de aço AISI 1070 com dureza de matriz próxima daquela encontrada em FoFo (?200HV30) foram submetidas a ensaios de riscamento em tribômetros. Verificou-se que riscos executados com um endentador cônico submetido a cargas na faixa de 20 a 50 mN eram similares aos sulcos observados em camisas ou blocos. Ensaios com outros materiais, como alumínio e latão e mesmo aço de diferentes durezas contribuíram para melhorar o entendimento dos resultados. Não foi observada transição brusca entre mecanismos de abrasão. O cálculo do fator de remoção de material, fab, a partir de perfilometria óptica resultou em valores com dispersão elevada; não foi possível associa-los aos diferentes mecanismos de abrasão observados. Valores obtidos para o coeficiente de atrito no riscamento permitiram fazer uma estimativa inicial de energia gasta nos processos abrasivos do motor. / A significant part of the friction losses in an automotive engine results from the abrasive action of particles. Among possible sources of such particles one can mention the environment - particles that were not retained by the filters - metallic residues from worn parts or even combustion residues. They may be picked up by piston rings and become part of their surfaces or stay loose in the piston/liner interface. Those particles are responsible for axial grooves that are observed in the liners of used engines. The objective of this work was to get a better understanding of the wear mechanisms related to liner/bore grooving and to identify a laboratory testing setup that might reproduce them under controlled conditions. Specimens of Gray Cast Iron (GCI) and of AISI 1070 steel with matrix hardness close to that found in GCI (?200HV30) were submitted to scratch tests in a tribometer. It was found that scratches performed under 20-50 mN indenter load (conical tip) were similar to grooves observed in cylinder liners. Tests with other materials such as aluminum, brass and even steel with different hardness values contributed to a better understanding of the results. No sharp transition between abrasion mechanisms was observed. Calculation of material removal factor fab from optical profilometry resulted in values with a large dispersion; they could not be associated with different abrasion mechanisms. Friction coefficient values obtained from the tests were used to make preliminary estimates of energy consumption due to abrasive processes in the engine.

Reflexo de um modo de vida que exige locomoção rápida e com um mínimo de conforto, atualmente, nas grandes metrópoles, há um grande número de veículos em circulação que emitem gases poluentes (hidrocarbonetos, CO e óxidos de nitrogênio - NOx). Para minimizar a emissão desses gases, os carros atuais são dotados de conversores catalíticos, formados pelos metais do grupo da platina, com a finalidade de converter gases nocivos em gases menos agressivos ao ambiente e ao homem. Porém, esses elementos constituintes dos conversores catalíticos podem ser expelidos para o ambiente, na forma de materiais particulados em suspensão, por volatilização ou junto com os gases da combustão. Desta forma, esses elementos podem acumular-se nos mais diversos ambientes. A utilização de amostras biológicas, tal como sangue, na investigação e no controle à exposição de elementos nos seres humanos vem sendo praticada há muito tempo. Estudos com materiais biológicos apontam que as concentrações de metais do grupo da Platina estão na ordem de ng/kg. Tais níveis de concentração representam um grande desafio para a Química Analítica, pois são muito baixos para que se tenham resultados com boa precisão e exatidão nas análises, mesmo utilizando técnicas muito sensíveis. Como alternativa para contornar os problemas, nas determinações destas baixas concentrações, etapas prévias de pré-concentração, com posterior determinação, vem sendo propostas com sucesso. Nessa pesquisa, para a pré-concentração dos analito, extração em ponto nuvem foi empregada com determinação por espectrometria de absorção atômica por forno de grafite. O procedimento da extração em ponto nuvem consiste em derivatizar os analitos em espécies hidrofóbicas por meio de um agente complexante, e extrair por micelas formadas a partir de um surfactante não iônico, induzidas por mudança de temperatura. Essa extração se baseia no fenômeno que ocorre com a formação de agregados micelares, quais apresentam caráter hidrofóbico. Foram estudados diferentes ligantes, e o melhor resultado para a extração foi obtido empregando-se o APDC (pirrolidina ditiocarbamato de amônio). Os parâmetros da extração em ponto nuvem otimizados para o melhor ligante foram: pH=7; 3,0x10-2 mol L-1 de APDC; 0,5 % m v-1 de Triton X-114; 60ºC durante 10 min de banho, 10 min de centrifugação e 50 mg L-1 Cu(II) como modificador químico. O método apresentou fator de enriquecimento de 24 vezes, mas o LOD (0,24 µg L-1) ficou muito acima dos valores apresentados em amostras de indivíduos expostos e não expostos. Adições de 1, 5 e 10 µg L-1 foram realizadas para avaliar a exatidão do método e apresentaram recuperações média de 91%. / Reflecting a way of life that requires fast displacement with a minimum of comfort, currently in big cities, there are a large number of vehicles that produce a large amount of waste gases (hydrocarbons, CO and nitrogen oxides - NOx) to atmosphere. To minimize the emission of these gases, current cars are equipped with catalytic converter, made of platinum group metals, which has the purpose of converting the noxious gases into less harmful gases to environment and man. However, these constituents of the catalytic converter can be expelled to the environment in form of particulates in suspension, or by volatilization along with the combustion gases. Thus, these elements can accumulate. Biological samples such as blood, urine, hair, nail, have been used for a long time in studies and control of human exposition to elements. Studies of biological materials indicate that the concentrations of platinum group metals are the order of ng/kg. Such concentration levels means a huge challenge for analytical chemistry, as they are too low to provide the necessary results with good precision and accuracy in the analysis, even using very sensitive techniques. As an alternative to overcome the problems in the provisions of these low concentrations, preconcentration methods, with subsequent determination has been proposed successfully. Cloud point extraction (CPE) was proposed in this work for pre-concentration of the analytes. CPE procedure consists in derivatizing the analytes into hydrophobic species by a complexing agent and extracts them trapped inside micelles formed from a nonionic surfactant, induced by temperature change. The cloud point extraction is based on the phenomenon that occurs with the formation of these hydrophobics aggregates by those micelles. Dithizone, DBTC, DMG, DDTC and APDC ligands were studied. The optimized parameters of cloud point extraction were: pH=7; 3,0x10-2 mol L-1 APDC; 0,5% m v-1 Triton X-114; 60 ºC while 10 min of termal bath and 10 min of centrifugation time. A Cu (II) 50 mg L-1 solution was used as a chemical modifier. The method was evaluated after optimized cloud point extraction\'s parameters conditions. It showed enrichment factor of 24-fold, but the limit of detection (0.24 µg L-1) was higher than the values expected to samples of exposed and non exposed individuals. A recovery test was done and a satisfactory recovery result was provided, up to 91%.

O presente projeto avaliou uma célula combustível microbiana (CCM) composta de um reator combinado (anaeróbio e aeróbio), operada em fluxo contínuo com tempo de detenção hidráulico de 12 horas, alimentada com esgoto sintético (487 \'+ OU -\' 115 mg DQO/L) e esgoto sanitário (631 \'+ OU -\' 213 mg DQO/L). A estabilidade da CCM variou conforme as características do substrato aplicado. A eficiência de remoção de DQO ficou em 61 \'+ OU -\' 17; 67 \'+ OU -\' 26%, para esgoto sintético e sanitário respectivamente. Em média tensão obtida com o esgoto sintético foi de 76 mV com picos - 112,5 e 409 mV, enquanto que com o esgoto sanitário foi possível obter 52,1 mV na média e pico de geração em 325 mV. A potência variou de 10-150 mW/\'M POT.2\' com resistências entre 50-650 \'ômega\'. A geração de energia elétrica não apresentou relação linear com a DQO consumida em nenhum dos casos. A aplicação de barras de grafite como eletrodos se mostrou satisfatória na condução da corrente elétrica, o fator limitante foi a transferência de massa, principalmente a transferência de prótons do anodo para o catodo e a difusão de oxigênio para o anodo. Contudo os resultados obtidos demonstraram que é possível gerar eletricidade e, simultaneamente, tratar esgoto sanitário. / This project evaluated a microbial fuel cell (MFC) consisting of combined reactor (anaerobic and aerobic), operated in continuous flow with hydraulic detention time of 12 hours, fed with synthetic wastewater (487 \'+ OR -\' 115 mg COD/L) and wastewater (631 \'+ OR -\' 213 mg COD/L). The stability of the CCM varied according to the characteristics of the substrate applied. The efficiency of COD removal was at 61 \'+ OR -\' 17; 67 \'+ OR -\' 26 for synthetic wastewater and sawage respectively. On a average voltage obtained with synthetic wastewater was 76 mV with peaks - 112.5 and 409 mV, while the wastewater was obtained 52.1 mV on average peaks generation at 325 power was varied from 10-150 mW/\'M POT.2\' with resistances between 50-650 \'ômega\'. The power generation showed no liner relationship with the COD consumed in any case. The application of graphite rods as electrodes were satisfactory in the conduction of electrical of protons from the anode to the cathode and the diffusion of oxygen to the anode. However the results showed that it is possible to generate electricity while simultaneously treating sewage.