Peças cerâmicas são normalmente produzidas através da aplicação de calor sobre argilas transformadas, de matérias-primas naturais ou materiais sintéticos, utilizando água e/ou outros aditivos como agentes de ligação, para formar um produto rígido, seguido por um processo de conformação. Alguns dos métodos mais comuns de conformação incluem extrusão, colagem, prensagem, colagem em fita e moldagem por injeção. No entanto, o uso de tecnologias de prototipagem rápida na fabricação de materiais cerâmicos tem aumentado nos últimos anos devido às suas muitas vantagens, porém poucos estudos foram realizados utilizando como matéria-prima a alumina em impressão 3D. Desta forma, o objetivo deste trabalho foi avaliar a influência de diferentes ligantes (PVA, PVAc e Goma Arábica) nas propriedades físicas de peças de alumina obtidas por impressão 3D por jato de tinta. Além disto, avaliar também a influência da granulometria do pó na confecção destas peças. Porosidade aparente, densidade aparente, retração após tratamento térmico, resistência mecânica e tamanho de poro foram avaliados. Os resultados obtidos demonstraram que as peças com melhor acabamento e propriedades fisicas foram as com o ligante PVA. Ainda, foi aumentado o teor de ligante de 3 para 5% em massa. Nas amostras com 3%, uma granulometria média favoreceu a obtenção de melhores resultados estruturais e de aparência, sendo, por exemplo, os valores de resistência mecânica de 47MPa, porosidade aparente média de 30% e tamanho médio de poro próximo de 21μm. Para a concentração de 5%, foi a granulometria menor que obteve os melhores resultados, onde os valores de resistência mecânica, porosidade aparente média e tamanho de poro, por exemplo, foram de 63MPa, 22% e 21 μm, respectivamente. Para todos os ligantes e granulometrias a retração volumétrica média foi de ~50%. Conclui-se desta forma, que comparativamente, as peças impressas com os resultados mais satisfatórios foram as peças da composição com 5% de ligante PVA, passante em peneira 325 ABNT. / Ceramics pieces are typically produced by the application of heat upon processed clays, natural raw materials or chemically synthetic materials, accomplished of water and/other additives as binders, to form a rigid product followed by a shape forming process. Some of the most common forming methods for ceramics include extrusion, slip casting, pressing, tape casting and injection molding. However, the use of rapid prototyping technologies in the manufacture of ceramic materials in the biomedical area has increased in recent years due to its many advantages and few studies are conducted on obtaining alumina pieces intended for biomedical applications by 3D printing. Thus, the aim of this work was to evaluate the influence of different binders (PVA, PVAc and gum arabic) on the final properties of alumina parts obtained by inkjet printing. Moreover, was evaluated the influence of particle size in manufacturing parts. Apparent porosity, apparent density, retraction after thermal treatment, mechanical strength and pore size were evaluated. The results showed that the parts with PVA binder achieved a better appearance and better final properties. Further, the binder amount of 3 was increased to 5%wt. Samples with 3%wt and a mean particle size promoted to obtain the major structural results and appearance being, which for example, the mechanical strength was 47MPa, mean apparent porosity was 30% and mean pore size of 21μm. Samples with 5%wt and the minor particle size achieved the major results, where, for example, the values of mechanical strength, mean apparent porosity and mean pore size were 63MPa, 22% and 21μm, respectively. To all binders and particle size the volumetric shrinkage was ~ 50%. It was concluded, comparatively, the printed parts with the most satisfactory results were samples with 5%wt PVA, sieved at 325 mesh.

abstract: Asphalt binder is a complex viscoelastic hydrocarbon, whose performance depends upon interaction between its physical and chemical properties, both of which are equally important to the successful understanding of the material. Researchers have proposed various models linking linear viscoelastic (LVE) and microstructural parameters. However, none of these parameters provide insight into the relationship in the non- linear viscoelastic NLVE domain. The main goals of this dissertation are two fold. The first goal is to utilize the technique of Laser Desorption Mass Spectroscopy (LDMS) to relate the molecular structure of asphalt binders to its viscoelastic properties. The second goal of the study is to utilize different NLVE characterization tools and analysis procedures to get a clear understanding of the NLVE behavior of the asphalt binders. The goals of the study are divided into four objectives; 1) Performing the LDMS test on asphalt binder to develop at the molecular weight distributions for different asphalts, 2) Characterizing LVE properties of Arizona asphalt binders, 3) Development of relationship between molecular structure and linear viscoelasticity, 4) Understanding NLVE behavior of asphalt binders through three different characterization methods and analysis techniques. In this research effort, a promising physico-chemical relationship is developed between number average molecular weight and width of relaxation spectrum by utilizing the data from LVE characterization and the molecular weight distribution from LDMS. The relationship states that as the molecular weight of asphalt binders increase, they require more time to relax the developed stresses. Also, NLVE characterization was carried out at intermediate and high temperatures using three different tests, time sweep fatigue test, repeated stress/strain sweep test and Multiple Stress Creep and Recovery (MSCR) test. For the intermediate temperature fatigue tests, damage characterization was conducted by applying the S-VECD model and it was found that aged binders possess greater fatigue resistance than unaged binders. Using the high temperature LAOS tests, distortion was observed in the stress-strain relationships and the data was analyzed using a Fourier transform based tool called MITlaos, which deconvolves stress strain data into harmonic constituents and aids in identification of non-linearity by detecting higher order harmonics. Using the peak intensities observed at higher harmonic orders, non-linearity was quantified through a parameter termed as “Q”, which in future applications can be used to relate to asphalt chemical parameters. Finally, the last NLVE characterization carried out was the MSCR test, where the focus was on the scrutiny of the Jnrdiff parameter. It was found that Jnrdiff is not a capable parameter to represent the stress-sensitivity of asphalt binders. The developed alternative parameter Jnrslope does a better job of not only being a representative parameter of stress sensitivity but also for temperature sensitivity. / Dissertation/Thesis / Doctoral Dissertation Civil, Environmental and Sustainable Engineering 2018

O uso de aglomerantes na pelotização a quente de minério de ferro visa cumprir duas funções: (1) aumentar a resistência da pelota antes do aquecimento (resistência a verde) e (2) evitar o colapso das pelotas durante a queima, quando a expulsão dos gases gerados pela vaporização de água e de voláteis tende a destruir a pelota. A bentonita é o aglomerante mais empregado industrialmente, e seu mecanismo de ligação no processo de ganho de resistência da pelota já foi amplamente estudado e compreendido. Várias tentativas de substituição da bentonita na pelotização de minério de ferro recorrem ao uso de aglomerantes orgânicos cuja composição apresente propriedades aglomerantes em conjunto com dispersantes. O presente trabalho visou contribuir para o melhor entendimento do mecanismo inerente ao uso de agente coloidisante na aglomeração do material particulado no processo de pelotização, por meio da avaliação da influência dos agentes coloidisantes em comparação aos aglomerantes Peridur® e bentonita no processo de pelotização de concentrado de minério de ferro. Para este fim, foram realizados ensaios de bancada visando a identificação de possíveis ações dos aglomerantes/dispersantes na viscosidade, potencial zeta e grau de dispersão das misturas, bem como a sua influência na liberação/aglomeração dos finos. Os resultados destes parâmetros foram confrontados com os resultados de caracterização das pelotas confeccionadas com os diferentes aglomerantes/ dispersantes pelos quais foi possível identificar que os dispersantes tem forte atuação sobre o conteúdo de finos do concentrado de minério de ferro. A ação principal se dá pela remoção das partículas ultrafinas que recobrem os grãos mais grosseiros presentes na amostra e as dispersam, no caso dos dispersantes, aumentando a disponibilidade do conteúdo de finos <4 µm, principalmente os finos menores que 1 µm (coloides). No caso do aglomerante orgânico, observa-se também essa ação, no entanto, os finos presentes são aglomerados na faixa entre 26 e 4 µm. / The use of binders for iron ore pelletizing is required to: (1) increase the pellet strength before heating (green strength); (2) prevent the collapse of the pellets during firing, when the gases generated by water vaporization could create cracks. Bentonite is the main binder used in industry, and its binding mechanism in iron ore pellets has been widely studied and understood. Efforts to solve the problems of using bentonite in iron ore pelletizing have focused on the use of organic binders whose composition presents dispersant properties. The objective of this study is to evaluate the influence of colloidal agents compared to binders, Peridur® and bentonite, in the pelletizing process of iron ore concentrate aiming to contribute with the understanding the action of these agents in the mechanisms of agglomeration of the pellets. With this goal, bench tests were carried out to identify possible actions of binders/dispersant in the viscosity, zeta potential and degree of dispersion of the mixtures, as well as its influence on the liberation/agglomeration of the fine particles. The results of these parameters were compared with the results of the characterization of the pellets prepared with different binders/dispersants. By this study, it was identified that the dispersant has a strong influence on the fine particle content on the iron ore concentrate. The main action takes place by the removal of ultrafine particles overlying coarser grains in the sample and the scatter, in the case of dispersants, increasing the availability of fine content <4 micrometers. In the case of the organic binder, this action is also observed; however, the fines are agglomerated in the range between 4 and 26 micrometers.

O avanço da tecnologia do concreto permitiu o desenvolvimento de compósitos cimentícios com elevada resistência mecânica. Contudo, apesar de suas inúmeras vantagens, tais concretos estão mais suscetíveis a ocorrência de fissuração, decorrente do fenômeno da retração. Nas últimas décadas inúmeros esforços estão sendo realizados visando mitigar tal fenômeno, como a realização do procedimento de cura interna, a fim de contribuir para a redução da intensidade deste fenômeno, assim buscando a obtenção de estruturas mais duráveis. Conjuntamente, no contexto do ambiente construído, há uma crescente preocupação relacionada com o desenvolvimento sustentável da indústria da construção civil, uma vez que este setor consome grande quantidade de matérias primas não renováveis, além de gerar uma quantidade significativa de resíduos. Dentro deste contexto, o objetivo desta pesquisa foi o de contribuir para a viabilização do emprego de resíduos de construção e demolição cerâmicos como agentes de cura interna, a fim de reduzir a intensidade do fenômeno da retração por secagem em concretos, ao longo do tempo. Para tanto, avaliou-se o emprego de agregados cerâmicos miúdos e graúdos em substituição ao agregado natural, na composição dos concretos. Ensaios mecânicos (resistência à compressão e módulo de elasticidade) foram realizados nos compósitos cimentícios estudados, assim como ensaios de retração por secagem livre e restringida, buscando verificar a eficiência do agregado cerâmico como um agente mitigador do fenômeno. Conjuntamente, realizou-se uma análise da microestrutura dos concretos (por microscopia eletrônica de varredura) buscando uma avaliação do transporte entre a matriz cimentícia e o agregado cerâmico. Com os resultados obtidos verificou-se a potencialidade do emprego do agregado cerâmico na composição dos concretos estudados, uma vez que se constatou o não prejuízo das propriedades mecânicas dos compósitos cimentícios estudados, quando ocorreu a substituição do agregado natural pelo agregado cerâmico, bem como observou-se uma redução na intensidade do fenômeno da retração por secagem e uma diminuição da tendência de fissuração do material. / Advances in concrete technology have allowed the development of cementitious composites with high mechanical strength. However, even with its many advantages these kind of concrete are more susceptible to the occurrence of cracking, resulting from shrinkage phenomenon. In recent decades many efforts were made to mitigate this phenomenon, using internal curing procedures in order to contribute to the reduction of the intensity of this phenomenon, thus seeking to obtain more durable structures. On the other side, in the context of the built environment, there is growing concern related to the sustainable development of the construction industry, since this sector consumes large amount of nonrenewable raw materials, and generate a significant amount of waste. Within this context, the objective of this research was to contribute to the viability of the use of ceramic construction and demolition waste as internal curing agents, in order to reduce the intensity of the phenomenon of shrinkage in concrete over time. Therefore, we evaluated the use of ceramic fines and coarse aggregates instead of natural aggregate in the composition of concrete residue mixes. Mechanical tests (compressive strength and modulus of elasticity) were performed, as well as shrinkage tests for free and restricted drying, trying to verify the efficiency of ceramic addition as an internal curing agent. Jointly, a microstructure analysis of concrete (scanning electron microscopy) was held, seeking to analysis the transportation between the cement matrix and the ceramic aggregate. With the results obtained the potential of the ceramic aggregate employment as an internal curing agent for concrete studied was confirmed. It has been found not to harm the mechanical properties of cementitious composites studied, and there was a reduction in the intensity of the phenomenon of shrinkage by drying and a reduction in cracking tendency of the material.

Peças cerâmicas são normalmente produzidas através da aplicação de calor sobre argilas transformadas, de matérias-primas naturais ou materiais sintéticos, utilizando água e/ou outros aditivos como agentes de ligação, para formar um produto rígido, seguido por um processo de conformação. Alguns dos métodos mais comuns de conformação incluem extrusão, colagem, prensagem, colagem em fita e moldagem por injeção. No entanto, o uso de tecnologias de prototipagem rápida na fabricação de materiais cerâmicos tem aumentado nos últimos anos devido às suas muitas vantagens, porém poucos estudos foram realizados utilizando como matéria-prima a alumina em impressão 3D. Desta forma, o objetivo deste trabalho foi avaliar a influência de diferentes ligantes (PVA, PVAc e Goma Arábica) nas propriedades físicas de peças de alumina obtidas por impressão 3D por jato de tinta. Além disto, avaliar também a influência da granulometria do pó na confecção destas peças. Porosidade aparente, densidade aparente, retração após tratamento térmico, resistência mecânica e tamanho de poro foram avaliados. Os resultados obtidos demonstraram que as peças com melhor acabamento e propriedades fisicas foram as com o ligante PVA. Ainda, foi aumentado o teor de ligante de 3 para 5% em massa. Nas amostras com 3%, uma granulometria média favoreceu a obtenção de melhores resultados estruturais e de aparência, sendo, por exemplo, os valores de resistência mecânica de 47MPa, porosidade aparente média de 30% e tamanho médio de poro próximo de 21μm. Para a concentração de 5%, foi a granulometria menor que obteve os melhores resultados, onde os valores de resistência mecânica, porosidade aparente média e tamanho de poro, por exemplo, foram de 63MPa, 22% e 21 μm, respectivamente. Para todos os ligantes e granulometrias a retração volumétrica média foi de ~50%. Conclui-se desta forma, que comparativamente, as peças impressas com os resultados mais satisfatórios foram as peças da composição com 5% de ligante PVA, passante em peneira 325 ABNT. / Ceramics pieces are typically produced by the application of heat upon processed clays, natural raw materials or chemically synthetic materials, accomplished of water and/other additives as binders, to form a rigid product followed by a shape forming process. Some of the most common forming methods for ceramics include extrusion, slip casting, pressing, tape casting and injection molding. However, the use of rapid prototyping technologies in the manufacture of ceramic materials in the biomedical area has increased in recent years due to its many advantages and few studies are conducted on obtaining alumina pieces intended for biomedical applications by 3D printing. Thus, the aim of this work was to evaluate the influence of different binders (PVA, PVAc and gum arabic) on the final properties of alumina parts obtained by inkjet printing. Moreover, was evaluated the influence of particle size in manufacturing parts. Apparent porosity, apparent density, retraction after thermal treatment, mechanical strength and pore size were evaluated. The results showed that the parts with PVA binder achieved a better appearance and better final properties. Further, the binder amount of 3 was increased to 5%wt. Samples with 3%wt and a mean particle size promoted to obtain the major structural results and appearance being, which for example, the mechanical strength was 47MPa, mean apparent porosity was 30% and mean pore size of 21μm. Samples with 5%wt and the minor particle size achieved the major results, where, for example, the values of mechanical strength, mean apparent porosity and mean pore size were 63MPa, 22% and 21μm, respectively. To all binders and particle size the volumetric shrinkage was ~ 50%. It was concluded, comparatively, the printed parts with the most satisfactory results were samples with 5%wt PVA, sieved at 325 mesh.

AgÃncia Nacional do PetrÃleo / O ligante asfÃltico brasileiro oriundo de petrÃleo do Campo Fazenda Alegre (CAPFA), no estado do EspÃrito Santo, foi modificado por polÃmeros (SBS e EVA) e aditivos (Ãleo extensor, cal hidratada e LCC). As principais caracterÃsticas estruturais deste ligante puro e modificado foram analisadas utilizando-se de mÃtodos espectromÃtricos (RMN e FTIR), anÃlise tÃrmica (TGA, DSC) e microscÃpica (AFM). Os polÃmeros e aditivos foram caracterizados atravÃs da termogravimetria e calorimetria exploratÃria diferencial e por espectroscopia no infravermelho. O ligante asfÃltico modificado por polÃmeros e aditivos, e os efeitos reolÃgicos resultantes desta modificaÃÃo, tambÃm foram avaliados. A metodologia aplicada foi dirigida, principalmente, para a avaliaÃÃo das propriedades constitutivas dos materiais, utilizando-se de ensaios reolÃgicos baseados em especificaÃÃes Superpave. Os parÃmetros investigados visaram a avaliaÃÃo de problemas usuais como: deformaÃÃo permanente, trincas tÃrmicas e oxidaÃÃo. O envelhecimento oxidativo dos asfaltos foi avaliado a partir da anÃlise dos espectros no infravermelho e de ressonÃncia magnÃtica nuclear, alÃm da variaÃÃo de parÃmetros reolÃgicos. A estabilidade tÃrmica do CAPFA (puro e modificado) e dos asfaltenos foi analisada atravÃs de curvas termogravimÃtricas. Esta estabilidade parece ser influenciada pelas reaÃÃes secundÃrias de decomposiÃÃo e/ou oxidaÃÃo dos produtos e resÃduos formados. Foram separadas as duas principais fraÃÃes constituintes do ligante asfÃltico: os asfaltenos (17,1%) e maltenos (82,9%). O cÃlculo da massa molar dos asfaltenos atravÃs da osmÃmetria e GPC apresentou valores muito prÃximos (5963 e 6653 g/mol). Imagens do ligante obtidas atravÃs do uso da tÃcnica de microscopia de forÃa atÃmica (AFM) mostram a coexistÃncia de uma fase rica em asfaltenos em equilÃbrio. Imagens (AFM) do ligante quando modificado por polÃmero sugerem que parte da fraÃÃo maltÃnica à absorvida pelo polÃmero. O efeito mais significativo da incorporaÃÃo de polÃmeros ao asfalto à a melhoria da elasticidade. Hà uma forte correlaÃÃo entre a resistÃncia à deformaÃÃo a alta temperatura e o G*. Para o ligante asfÃltico modificado verificou-se um aumento significativo no G* em baixas freqÃÃncias, onde a rede dos polÃmeros SBS e EVA à particularmente dominante, e um pequeno decrÃscimo no G* em freqÃÃncias mais altas. Observou-se tambÃm uma diminuiÃÃo na tan &#948; e isto indica que ocorreu a formaÃÃo de 8 uma rede polimÃrica que proporciona ao ligante um carÃter elÃstico em temperaturas mais elevadas. A adiÃÃo dos polÃmeros SBS e EVA ao CAPFA proporcionou um aumento da rigidez e da elasticidade do ligante, mas, dentre as misturas asfÃlticas produzidas, observou-se que, antes e apÃs o envelhecimento, o ligante quando modificado por EVA e cal hidratada apresentou a maior rigidez, e quando modificado por SBS apresentou a maior elasticidade. A susceptibilidade relativa à temperatura das misturas asfÃlticas medida atravÃs da energia de ativaÃÃo de fluxo, mostrou que as misturas contendo EVA se degradam menos do que aquelas que contÃm SBS, uma vez que no polÃmero EVA nÃo existem duplas ligaÃÃes butadiÃnicas que se oxidam facilmente, como no caso do SBS. Os aditivos presentes nas misturas com o polÃmero EVA tambÃm contribuÃram para esta menor sensibilidade à temperatura, uma vez que a cal hidratada reduz o envelhecimento da mistura asfÃltica atravÃs da interaÃÃo com compostos polares reativos presentes no ligante e o LCC ser um excelente antioxidante. Quanto à estabilidade à estocagem do asfalto modificado por SBS, parece ocorrer a âquebraâ da estrutura coloidal polÃmeroasfalto em freqÃÃncias elevadas. / The Brazilian asphalt binder from Fazenda Alegre oil reserve (CAPFA) in the state of EspÃrito Santo, was modified by polymers (SBS and EVA) additives (oil extensor, hydrated lime and LCC). The main structural characteristics of this pure and modified binder were analyzed using the spectroscopic methods (RMN and FTIR), thermal analysis (TGA, DSC) and through microscopy (AFM). The polymers and additives were characterized through thermogravimetry (TG), differential scanning calorimetry and infrared spectroscopy. The asphaltic binder modified by polymers and additives, and the resulting rheological effects of this modification, were also evaluated. The methodology that was applied was oriented mainly towards the evaluation of the constitutive properties of the materials, using rheological tests based on the Superpave specifications. The parameters investigated aimed the evaluation of the usual distresses such as: permanent deformation, thermal cracking and oxidation. The oxidative ageing of the asphalt was evaluated from analysis in the infrared and nuclear magnetic resonance, as well as the variations of the rheological parameters. The thermal stability of the CAPFA (pure and modified) and of the asphaltenic was analysed through the TG curves. This stability looks as if it is influenced by the secondary reactions of decomposition and/or oxidation of the products and residuals that have been formed. The two main constituent fractions of the asphaltic binder were separated: the asphaltenic (17,1%) and maltenic (82,9%). The calculation of the molar mass of the asphaltenic by osmometry and GPC demonstrated very similar values (5963 and 6653 g/mol). Images of the binders obtained through the use of atomic force microscopy (AFM) show the coexistence of a rich phase in asphaltenic in equilibrium. Images (AFM) of the binder while modified by a polymer suggest that part of the maltenic fraction is absorbed by the polymer. The most significant effect of the polymer incorporation to the asphalt was the improvement of the elasticity. There is a strong correlation between the deformation resistance at high temperature and G*. For the modified asphalt binder, a significant increase was noted in G* in lower frequencies, where a network of the polymers SBS and EVA are particularly dominant, and a small decrease on G* in higher frequencies. It was also observed a decrease in the tan &#948; and this indicates that the formation of a 10 polymeric network, which gives the binder an elastic stability at higher temperatures, has occurred. The addition of SBS and EVA to the CAPFA lead to an increase of the hardness and the elasticity of the asphalt binder, but among the asphaltic mixtures produced, it was observed, before and after ageing, that the binder modified by the EVA and the hydrated lime demonstrated a higher stiffness and the binder modified by the SBS demonstrated a higher elasticity. The susceptibility relative to the temperature of the asphalt mixtures measured through the flow activated energy, demonstrated that the mixtures containing EVA degrade themselves less than those that contain SBS. This happens due to the fact that there is no butadiene double bond in the polymer EVA that easily oxidizes, like in the case of the SBS. The additives present in the mixtures with the EVA polymer also contributed to a lower sensitivity to the temperature, once the hydrated lime reduces the ageing of the asphalt mixture through the interaction with the reactive polar molecules present in the asphalt binder and CNSL it is an excellent antioxidant. In regards to the stability of the storage of the modified asphalt by SBS, apparently occurs a âbreakâ of the colloidal polymer-asphalt structure in higher frequencies.

CoordenaÃÃo de AperfeiÃoamento de Pessoal de NÃvel Superior / O CAP 50/70 (Petrobras - LUBNOR) puro e modificado por poli (Ãcido fosfÃrico) (PPA) foram analisados quanto as suas principais caracterÃsticas utilizando-se de ensaios reolÃgicos (viscosidade e DSR), anÃlise tÃrmica (TGA e DSC), mÃtodos espectromÃtricos (RMN e FTIR) e cromatogrÃficos (TLC-FID e GPC). A interaÃÃo do CAP com o PPA foi investigada a partir das reaÃÃes de suas fraÃÃes (aromÃticos, resinas e asfaltenos) com o PPA. Os espectros de RMN 31P indicaram que a reaÃÃo ocorre preferencialmente com as resinas e os asfaltenos. Os parÃmetros G* e tan &#948;, obtidos atravÃs dos ensaios reolÃgicos, mostraram que o PPA promoveu uma melhoria no desempenho do CAP em relaÃÃo à rigidez e elasticidade, tornando o ligante modificado com PPA mais resistente à deformaÃÃo permanente e ao trincamento por fadiga. O CAP modificado com PPA apresentou um aumento na viscosidade, na temperatura de usinagem e compactaÃÃo (TUC) e tambÃm a suscetibilidade tÃrmica em relaÃÃo ao CAP puro. Na tentativa de reduzir esses efeitos - que elevam o gasto energÃtico de modo substancial durante o processamento, foi incorporado um novo aditivo â o lÃquido da casca da castanha de caju (LCC) ao CAP + PPA. Os efeitos da adiÃÃo do LCC ao CAP + PPA foram: reduÃÃo na viscosidade, na temperatura de compactaÃÃo e usinagem (TCU) e na suscetibilidade tÃrmica, portanto, o LCC apresenta-se como aditivo Ãtil para melhorar o desempenho do CAP + PPA em relaÃÃo a essas propriedades. Para efeito comparativo, as propriedades do LCC como aditivo modificador do CAP puro tambÃm foram analisadas. A modificaÃÃo do CAP com PPA, com LCC e com os dois aditivos combinados (PPA + LCC) foi analisada atravÃs das curvas mestras: provocou um aumento significativo no mÃdulo complexo G*, principalmente em baixas frequÃncias (altas temperaturas), tornando esses ligantes mais resistentes à deformaÃÃo permanente em temperaturas mais elevadas. Todos os modificadores promoveram uma diminuiÃÃo no valor da tangente de delta (tan &#61540;), o que significa que esses aditivos proporcionam maior elasticidade ao ligante asfÃltico. Os efeitos da combinaÃÃo dos modificadores PPA + LCC, resultaram em valores intermediÃrios de viscosidade, energia de ativaÃÃo de fluxo e TUC quando comparados aos efeitos provocados pelos dois aditivos isoladamente. O CAP + PPA + LCC ainda apresentou os menores valores do Ãndice de envelhecimento, indicando uma maior resistÃncia ao envelhecimento. Em relaÃÃo aos estudos de estabilidade à estocagem, os aditivos demostraram boa compatibilidade com o ligante, sendo que a amostra com LCC apresentou menores valores do Ãndice de separaÃÃo (Is) e, portanto, melhor resultado. Os valores da temperatura de transiÃÃo vÃtrea (Tg) medidos atravÃs das curvas de DSC foram menores para os ligantes modificados, sugerindo que os mesmos podem ser utilizados em temperaturas mais baixas que o ligante de origem. Dados cromatogrÃficos relativos à composiÃÃo SARA (saturados, aromÃticos, resinas e asfaltenos) mostraram uma mudanÃa na composiÃÃo dos ligantes apÃs o processo de envelhecimento das amostras, no entanto, todos os ligantes (puro e modificados) foram classificados como ligantes do tipo GEL. Os resultados de GPC mostraram que os valores de massa molar das fraÃÃes I (asfaltenos) e II (maltenos) dos ligantes estudados aumentaram apÃs do processo de envelhecimento. Os ensaios mecÃnicos dos corpos de prova das misturas asfÃlticas trabalhadas (ligantes + agregados) mostraram que a adiÃÃo de PPA, bem como a de LCC, melhoram as propriedades mecÃnicas e a adesividade das misturas. / The AC with 50/70 penetration grade (Petrobras - LUBNOR), pure and modified by polyphosphoric acid (PPA), was analyzed by rheological tests (viscosity and DSR), thermal analysis (TGA and DSC), spectrometric (NMR and FTIR) and chromatographic (TLC-FID and GPC) methods. The interaction of AC with PPA was investigated from the reactions of its fractions (aromatics, resins and asphaltenes) with the PPA. The 31P NMR spectra indicated that the reaction occurs preferentially with the resins and asphaltenes. The parameters G * and tan &#948;, obtained from the rheological tests showed that the PPA has promoted an improvement in the performance of the AC in relation to the stiffness and elasticity, making the binder modified with PPA more resistant to permanent deformation and fatigue cracking. The results show that modification with PPA increased the viscosity of the binder, the mixing and compaction temperatures, as well as the thermal susceptibility. In an attempt to reduce these effects - which increase energy cost substantially during processing, we have incorporated a new additive - the cashew nut shell liquid (CNSL) to the AC / PPA. The effects of the CNSL addition of AC + PPA were: reduction in viscosity, mixing and compaction temperature and thermal susceptibility, so the LCC presents useful as an additive to improve the performance of the regarding AC + PPA to these properties. For comparison, the properties of the LCC as an additive modifier pure AC were also analyzed. The modification of the AC + PPA with LCC and the two combined additives (PPA + LCC) was analyzed using the master curves, caused a significant increase in complex modulus G *, especially at low frequencies (high temperatures), making these binders resistant to permanent deformation at higher temperatures. All modifiers lead to a decrease in the value of tan &#948;, which means that these additives provide greater elasticity to the asphalt binder. The effects of the combination of PPA + CNSL modifiers, resulted in intermediate values of viscosity, flow activation energy and TUC compared to the effects caused by the two additives alone. The AC + PPA + CNSL also had the lowest aging index values, indicating a greater resistance to aging. Regarding storage stability, the additives showed good compatibility with the binder, and the CNSL showed lower values of the separation index and, therefore, the best result. The values of glass transition temperature as measured by the DSC curves were lower for the modified binders, suggesting that they may be used at temperatures lower than the binder source. Chromatographic data on the composition SARA (saturates, aromatics, resins and 19 asphaltenes) showed a change in the composition of the binders after the aging process of the samples. However, all the binders (pure and modified) were classified as gel-type. The GPC results showed that the values of molar mass fractions I (asphaltenes) and II (maltene) of all the binders studied increased after the aging process. The mechanical tests showed that the addition of PPA and the CNSL improves the mechanical properties and adhesiveness of mixtures.

The objective of this study was to modify the asphalt binder (LA) with 50/70 penetration by incorporating SBS (3, 4 and 4.5%) and the cashew nut shell liquid (CNSL) (1% w/w). The studies were directed towards assessing and analyzing the rheological master curves obtained from tests on a dynamic-shear rheometer (DSR). In addition, we assessed the effects of additives in relation to the viscosity, storage stability, and oxidative aging simulated at the RTFOT. The results indicated that the addition of SBS increases the stiffness and the elastic response of the binder at high temperatures. The master curves showed improvements in the rheological parameters at intermediate and high temperatures, where the process of permanent deformation occurs. Samples with SBS contents 3, 4 and 4.5% were tested for storage stability for 48 hours. The sample with 3% SBS showed no phase separation when stored under the conditions investigated, however, samples with 4 and 4.5% of SBS showed phase separation. In these samples (4 and 4.5%), the addition of CNSL embedded in the modified binder by SBS show the potential to estabilize the binder-polymer mixture, avoiding phase separation. The CNSL, therefore, proved to be potentially useful to prevent phase separation of the LAs with the polymer. The results also indicate that the presence of CNSL promoted a reduction in viscosity and flow activation energy of the binder modified by SBS, contributing thus to improve the thermal susceptibility of the modified binder. Tests of resilient modulus (MR) and tensile strength (RT) in asphalt mixtures containing modified binder suggest that the presence of SBS makes the mixture less susceptible to deformation and failure than mixtures with pure LA. However, the asphalt mixture containing the binder modified by SBS with the addition of CNSL presents an even greater hardening when compared to the SBS blend containing no additive. It is likely that the presence of polymerized CNSL has contributed to the hardening of the sample. / O objetivo deste trabalho foi modificar o ligante asfÃltico (LA) com penetraÃÃo 50/70 pela incorporaÃÃo de SBS (3, 4 e 4,5% m/m) e do lÃquido da castanha do caju (LCC) (1% m/m). Os estudos foram dirigidos para avaliaÃÃo dos parÃmetros reolÃgicos e anÃlise das curvas mestras obtidas atravÃs de ensaios realizados em um reÃmetro de cisalhamento dinÃminco (DSR). AlÃm disso, foram avaliados os efeitos da presenÃa dos aditivos em relaÃÃo à viscosidade, estabilidade à estocagem e envelhecimento oxidativo simulado em estufa RTFOT. Os resultados indicaram que a adiÃÃo de SBS aumenta a rigidez e a resposta elÃstica do ligante em altas temperaturas. As curvas mestras mostraram melhorias nos parÃmetros reolÃgicos em temperaturas intermediÃrias e altas, onde ocorre o processo de deformaÃÃo permanente. As amostras com teores de 3, 4 e 4,5% foram testadas quanto à estabilidade a estocagem por 48h. A amostra com teor de 3% SBS nÃo apresentou separaÃÃo de fases quando estocada nas condiÃÃes trabalhadas, no entanto, as amostras com teores de 4 e 4,5% apresentaram separaÃÃo de fases. Nessas amostras (4 e 4,5%), a adiÃÃo do LCC incorporado ao ligante modificado por SBS demonstrou estabilizar a mistura ligante-polÃmero, evitando a separaÃÃo de fases. O LCC, portanto, mostrou-se potencialmente Ãtil para prevenir a separaÃÃo de fases dos LAs modificados com o polÃmero. Os resultados tambÃm indicam que a presenÃa do LCC promoveu uma reduÃÃo na viscosidade e na energia de ativaÃÃo de fluxo do ligante modificado por SBS, contribuindo, portanto, para melhorar a susceptibilidade tÃrmica do ligante modificado. Os ensaios de mÃdulo de resiliÃncia (MR) e reistÃncia a traÃÃo (RT) nas misturas asfÃlticas contendo os ligantes modificados sugerem que a presenÃa do SBS torna a mistura menos susceptÃvel à deformaÃÃo do que as misturas com o LA puro. No entanto, a mistura asfÃltica contendo o ligante modificado por SBS com adiÃÃo de LCC apresenta um endurecimento ainda maior quando comparada a mistura que contÃm o SBS sem o aditivo. à provÃvel que a presenÃa de LCC polimerizado tenha contribuÃdo para o endurecimento da amostra.

The techniques mostly used to decontaminate air as well as water pollutants have drawbacks in terms of higher costs, require secondary treatment, and some methods are very slow. So, emphasis has been given to water though the use of photocatalysts, which break organic pollutants to water and carbon dioxide and leave no trace of by-products at the end. Photocatalytic remediation aligns with the waste and wastewater industries’ zero waste schemes with lower cost, eco-friendly and sustainable treatment technology. The commonly used photocatalysts such as titanium oxide (TiO2), zinc oxide (ZnO), tungsten oxide (WO3) have band gap of nearly 3.2 eV. The lower energy band-gap of a semiconductor makes it a better photocatalyst. The major drawbacks of photocatalysts are its inefficiency to work under visible light and high photocorrosion which limits its uses. These limitations can be mitigated through dopants and the formation of varying morphologies like nanowires, nanoparticles, nanotubes etc. Several organic pollutants are insoluble in water, which inhibits the pollutant (insoluble) to come in contact with photocatalytic material thus hindering remediation characteristic of a photocatalyst. Binder material used to immobilize the photocatalytic material tends to decompose due to oxidative and reduction reactions around the photocatalyst which causes the loss of photocatalytic material. This investigation displays the advantage of organic remediation in visible radiation using graphene (G) doped TiO2 nanoparticles and nanowires. The nanostructured G-TiO2 nanoparticles and G-TiO2 nanowires were synthesized using sol-gel and hydrothermal methods. The nanostructured materials were characterized using scanning electron microscopy (SEM), Transmission electron microscopy (TEM), X-ray diffraction (XRD), UV-visible spectroscopy (UV-vis), Fourier transform infrared spectroscopy (FTIR) and particle analyser procedures. The remediation of organic compounds (methyl orange) in water was achieved under visible radiation using graphene doped nanostructured photocatalytic materials. The sol-gel synthesized G-TiO2 nanoparticles has shown complete remediation of methyl orange (MO) in less than four hours, thus displaying enhanced photocatalytic activity achieved through graphene doping on TiO2 nanostructures The dopant and structure introduced in zinc oxide (ZnO) nanomaterials bring foundation for enhanced photocatalytic activity due to lowering of the band gap, and decreasing of photocorrosion through delaying of electron-hole recombination. The challenge to synthesize both nanowire and nanoparticle structures of ZnO doped with graphene (G) are carried out by simple and cost effective hydrothermal as well as super saturation precipitation techniques, respectively. Various nanostructures of ZnO have been synthesized using precipitation and hydrothermal methods are ZnO nanoparticles, G doped ZnO nanoparticles, ZnO nanowires, G doped ZnO nanowires, TiO2 seeded ZnO nanowires and G doped TiO2 seeded ZnO nanowires The synthesized ZnO based nanostructures were characterized using SEM, TEM, XRD, UV-vis, FTIR and particle analyser methods respectively. The standard organic pollutant methyl orange (MO) dye was employed in the water to understand the effective remediation using ZnO nanostructured materials under visible light radiation. The G-ZnO NW structure has shown effective remediation of MO in water in three hours compared to other synthesized nanostructured ZnO materials. The petroleum compounds were photocatalytically remediated from water using G- TiO2 nanoparticles material in visible light radiation. The G-TiO2 nanoparticle was synthesized using sol-gel technique and used on various petroleum-based chemicals (toluene, naphthalene and diesel) were remediated, and samples were analysed using optical and gas chromatography (GC) techniques. The importance of pollutant to come in contact with photocatalyst have been demonstrated by employing surfactant along with G-TiO2 nanoparticles to remediate naphthalene. Earlier studies in this investigation have shown that graphene (G) doping in both titanium oxide (TiO2) and zinc oxide (ZnO), has brought about a reduction in photocorrosion, and an increase in the photocatalytic efficiency for remediation of organics under visible light (λ > 400nm). However, the graphene doped photocatalysts have proven to be hard to coat on a surface, due to the strong hydrophobic nature of graphene. So, attempts have been made to use polyaniline (PANI), a conducting polymer, as a binder material by insitu polymerization of aniline over G-TiO2 nanoparticles (G-TiO2 NP) and G-ZnO nanowires (G-ZnO NW) & characterized using SEM, XRD, UV-vis and FTIR techniques. The photocatalytic, as well as photoelectrochemical catalytic performance of PANI:G-TiO2 NP and PANI:G-ZnO NW, were investigated. The standard MO in water was used for both PANI:G-TiO2 NP and PANI:G-ZnO NW electrodes on conducting substrates. 1:1 PANI:G-TiO2 NP shows an increase of 31% in the remediation of MO in water at potential of +1000 mV, and with the ease in coating PANI:G-TiO2 NP and PANI:G-ZnO NW on various substrates, on top of the visible light remediation allows for the use of these materials and process to be used for practical applications of remediation of organics from water.

In this thesis, drill bit buttons with cobalt, nickel and iron binders in different compositions have been tested against granite and sandstone and the wear and friction have been measured. Furthermore, the wear and degradation of the buttons have been categorized. Buttons with cobalt binder were tested against granite and sandstone and buttons with alternative binders (Ni, Fe, Co) were tested against granite. Cobalt buttons were used as a reference and the wear and friction of the alternative binders was compared to the reference. The amount of worn rock was also measured. Furthermore, post treated drill bit buttons with a composition of Fe-Ni-Co were compared to buttons with the same composition that had not been post treated The results show that buttons with an alternative composition of Fe-Co-Ni and Fe- Ni wears less than the cobalt reference. The post treatment process does not decrease the wear of the drill bit but lowers the deviation from the mean wear. The amount of worn rock does not differ between the samples except for between the post treated and not post treated buttons with a composition of Fe-Ni-Co. The post treated buttons produces more rock debris than the not post treated. No apparent difference could be seen on the surface of the tested buttons after the test. However, composition specific cracks could be found underneath the surface of the samples. EDS-analysis showed signals of oxygen inside of all of the investigated cracks. For some compositions at depths of 20 micrometers. The curves of friction shows similar appearance but the values of the coefficient of friction differs. No apparent correlation was found between the wear and friction of the samples. Furthermore, no apparent correlation was found between the hardness and the wear of the buttons.