Pesquisas sobre aplicação de borracha de pneus descartados em pavimentação asfáltica vêm sendo desenvolvidas desde a década de 1960, especialmente nos Estados Unidos e, desde o início da década de 1990, no Brasil, como alternativa para diminuição dos problemas ambientais gerados por estes resíduos sólidos. Esta pesquisa tem por objetivo avaliar o desempenho de três misturas asfálticas do tipo concreto asfáltico usinado à quente: duas empregando teores diferentes de borracha moída e óleo de xisto (CAP 40 + 12% de borracha + 10% de óleo de xisto e CAP 40 + 20% de borracha + 15% de óleo de xisto) e uma convencional. Este estudo faz parte de um programa de pesquisa coordenado pela Escola de Engenharia de São Carlos da Universidade de São Paulo (EESC-USP), Universidade Estadual de Maringá (UEM) e Petrobrás, envolvendo a execução de misturas com borracha e óleo de xisto em trechos experimentais. Foram realizadas dosagens Marshall e ensaios de resistência à tração, módulo de resiliência e fluência por compressão uniaxial estática. Os corpos-de-prova empregados nos ensaios foram moldados no teor ótimo de cimento asfáltico referente a cada uma das misturas. Constatou-se a viabilidade técnica da adição de óleo extensor para a incorporação de borracha de pneus descartados em concreto asfáltico, permitindo a obtenção de resultados satisfatórios quanto aos projetos de dosagem das misturas pelo método Marshall. Com base nos resultados dos ensaios realizados, acredita-se ser viável a execução de trechos experimentais empregando as duas misturas modificadas. / Researches on the application of discarded tires in asphaltic pavements has been developed since 1960, mainly in the United States and since the beginning of the 90\'s in Brazil, as an alternative to the reduction of environmental problems created by this kind of solid residues. The purpose of this research is to evaluate the performance of three hot mix asphalt concrete: two using different crumb rubber and shale oil contents (CAP 40 + 12% rubber + 10% shale oil and CAP 40 + 20% rubber + 15% shale oil) and a conventional hot mix asphalt concrete. The research is part of a major program coordinated by the Universidade de São Paulo (EESC-USP), Universidade Estadual de Maringá and Petrobras, comprehending the execution of asphaltic mixtures using tire rubber and shale oil in experimental road segments. The tests performed are: Marshall test, indirect tension, resilient modulus and static creep. The samples tested were compacted in the optimum binder content of each mixture. Good results obtained in tests confirrned the technical viability of using the shale oil as extender in crumb rubber asphalt hot mixtures. The results lead to the conclusion that experimental road sections or segments may be constructed with both tested rubber-oil modified asphalt mixtures.

La réduction des émissions anthropiques de CO2 constitue actuellement un enjeu majeur. Parmi les technologies destinées à la production d'énergie, le Chemical Looping Combustion (CLC) présente un potentiel intéressant avec un faible coût de capture de CO2. Le CLC consiste à produire de l'énergie à partir de combustibles fossiles, en présence d’un transporteur d’oxygène solide qui fournit l’oxygène nécessaire à la combustion. Le matériau est ensuite régénéré sous air dans un deuxième réacteur. En sortie du réacteur de combustion, seuls les gaz CO2 et H2O sont émis et ainsi, après la condensation de l’eau, du CO2 quasiment pur est obtenu. La viabilité du procédé CLC à échelle industrielle dépend des performances et de la durée de vie des transporteurs d’oxygène utilisés. Au cours de cette thèse, les performances et le vieillissement d’un transporteur d'oxygène modèle (NiO/NiAl2O4), vis-à-vis de l’oxydation de CO ont été étudiées. Pour cela, des cycles d'oxydation-réduction dans un réacteur à lit fixe traversé ont été réalisés. Au cours de l’étude de l'influence des conditions de fonctionnement sur les performances du transporteur, il a été observé que la réactivité du transporteur augmente avec la température. De plus, le liant (NiAl2O4) participe également à la réaction d’oxydation du CO. Une évolution de la structure cristalline du liant au cours des cycles à haute température, a été mise en évidence à l’aide des techniques de caractérisation du solide (DRX, MEB-EDX, TPR,...). En parallèle à ces travaux, un outil numérique de simulation du lit fixe traversé a été développé afin de modéliser la réaction de réduction du transporteur d'oxygène avec le combustible CO. / Nowadays, the reduction of anthropogenic greenhouse gas emissions (especially CO2) constitutes an important challenge. Among the different technologies currently studied for the CO2 capture during energy production, the Chemical Looping Combustion (CLC) shows an interesting potential with a low cost of capture. CLC consists of producing energy from fossil fuels or biomass combustion, in the presence of an oxygen carrier (generally a metal oxide) which provides the required oxygen for combustion. The material is then reoxidized with air in a different reactor. At the combustion reactor outlet only H2O and CO2 gases are emitted, therefore after condensation almost pure CO2 can be obtained. The success of a large scale CLC application depends on finding suitable oxygen carriers with good performances and long lifetime. The objective of this work is to study the performances and the ageing of a model oxygen carrier (NiO/NiAl2O4) with CO as fuel. For this, oxidation/reduction cycles have been carried out in a fixed bed reactor. The influence of the operating conditions on its performances is also investigated. From these studies, it is observed that the reactivity of the oxygen carrier increases with temperature. Moreover, the binder used in the oxygen carrier (NiAl2O4) reacts also with the fuel CO to produce CO2. An evolution on the support’s structure during cycles at high temperature is demonstrated using solid characterization techniques (DRX, MEB-EDX and TPR). After these experimental studies, a numerical model has been developed to simulate the reduction reaction of the oxygen carrier with CO in a fixed bed reactor.

Ce travail de thèse inclut deux parties : i) l'étude fondamentale de la formation de cristaux zéolithiques ; et ii) la préparation de massifs zéolithiques de taille centimétriques à porosité interparticulaire contrôlée. La première partie de ce travail est donc consacrée à l'étude de l'effet de la microstructure (propriétés physiques et texturales) et de la composition chimique du gel sur la vitesse de nucléation et la taille des cristaux formés. Les résultats de cette étude se résument par le rôle important que joue la composition du gel (plus particulièrement sa concentration en hydroxyde de cation alcalin) sur le degré de polymérisation des particules du gel, la détermination de sa microstructure et par conséquent sur la vitesse de nucléation des zéolithes et la taille des cristaux. Les connaissances acquises dans la première partie ont été utilisées dans le développement du deuxième objective. Notamment, la préparation de massifs zéolithiques de taille centimétrique de types structuraux *BEA et MFI. Le contrôle post-synthèse de la porosité interparticulaire de ces massifs était essentiel pour leur utilisation dans des applications bien précises. A cette fin, une méthode en deux étapes, comportant un assemblage de nanocristaux de zéolithes préformés (en présence ou en absence d'un liant) puis un traitement de croissance secondaire pour l'élimination de la porosité interparticulaire, a été mise en œuvre. Plusieurs traitements de croissance secondaire furent évalués selon le type de zéolithe étudié. Une attention particulière fut accordée à l'étude de l'évolution du liant au cours des processus de préparation et de calcination des massifs zéolithiques. / The present study includes two parts: i) fundamental study of zeolite nucleation-crystal growth mechanism; and ii) preparation of zeolite bodies with controlled interparticle porosity.Thus the first part of the present work deals with the study of the effect of physico-chemical characteristics of initial hydrogel on the nucleation and crystal growth kinetics of zeolite crystals. The obtained data revealed that the concentration of alkali metal hydroxide in the initial system controls the rate of polymerization of the aluminosilicate species, the size of initial gel particles, and the textural properties of the gel. Consequently, the following reaction was to great extent predetermined by the events taking place during mixing the initial reactants.The second part of this work was targeted at the preparation of centimeter-sized zeolite bodies of *BEA- and MFI-type with reduced to minimum inter-particle porosity. A preparation method consisting in assembling of zeolite nanocrystals (with or without a binder) was developed and further optimized. The preformed bodies were subjected to a hydrothermal treatrnent in a fresh zeolite synthesis solution in order to till up the inter-particle porosity. Depending onthe zeolite type, different methods of secondary growth treatrnents were employed. A particular attention has been paid on the study of the binder evolution during the calcination and secondary growth processes.

Print quality demands for coated papers are steadily growing, and achieving coating uniformity is crucial for high image sharpness, colour fidelity, and print uniformity. Coating uniformity may be divided into two scales: coating thickness uniformity and coating microstructure uniformity, the latter of which includes pigment, pore and binder distributions within the coating layer. This thesis concerns the investigation of both types of coating uniformity by using an approach of quantitative microscopy.First, coating thickness uniformity was analysed by using scanning electron microscope (SEM) images of paper cross sections, and the relationships between local coating thickness variations and the variations of underlying base sheet structures were determined. Special attention was given to the effect of length scales on the coating thickness vs. base sheet structure relationships.The experimental results showed that coating thickness had a strong correlation with surface height (profile) of base sheet at a small length scale. However, at a large length scale, it was mass density of base sheet (formation) that had the strongest correlation with coating thickness. This result explains well the discrepancies found in the literature for the relationship between coating thickness variation and base sheet structure variations. The total variance of coating thickness, however, was dominated by the surface height variation in the small scale, which explained around 50% of the variation. Autocorrelation analyses were further performed for the same data set. The autocorrelation functions showed a close resemblance of the one for a random shot process with a correlation length in the order of fibre width. All these results suggest that coating thickness variations are the result of random deposition of particles with the correlation length determined by the base sheet surface textures, such as fibre width.In order to obtain fundamental understandings of the random deposition processes on a rough surface, such as in paper, a generic particle deposition model was developed, and systematic analyses were performed for the effects of particle size, coat weight (average number of particles), levelling, and system size on coating thickness variation. The results showed that coating thickness variation3grows with coat weight, but beyond a certain coat weight, it reaches a plateau value. A scaling analysis yielded a universal relationship between coating thickness variation and the above mentioned variables. The correlation length of coating thickness was found to be determined by average coat weight and the state of underlying surfaces. For a rough surface at relatively low coat weight, the correlation length was typically in the range of fibre width, as was also observed experimentally.Non-uniformities within the coating layer, such as porosity variations and binder distributions, are investigated by using a newly developed method: field emission scanning electron microscopy (FESEM) in combination with argon ion beam milling technique. The combination of these two techniques produced extremely high quality images with very few artefacts, which are particularly suited for quantitative analyses of coating structures. A new evaluation method was also developed by using marker-controlled watershed segmentation (MCWS) of the secondary electron images (SEI).The high resolution imaging revealed that binder enrichment, a long disputed subject in the area, is present in a thin layer of a 500 nm thickness both at the coating surface and at the base sheet/coating interface. It was also found that the binders almost exclusively fill up the small pores, whereas the larger pores are mainly empty or depleted of binder.

In calcium aluminate cement (CAC) systems the hydration process is different than portland cement (PC) systems. The hydration products of CAC are subjected to conversion depending on temperature, moisture, water-cement ratio, cement content, etc. Consequently, strength of CAC system can be seriously reduced. However, presence of other inorganic binders or additives may alter the hydration process and improve various properties of CAC based composites. The objective of this study is to investigate the temperature effect on the behaviour of CAC based composite binders. Throughout this research, several combinations of CAC-PC, CAC-gypsum, CAC-lime, CAC-ground granulated blast furnace slag (CAC-GGBFS) were studied. These CAC based composite binders were subjected to seven different curing regimes and their strength developments were investigated up to 210 days. In addition, the mechanism of strength development was examined by XRD analyses performed at 28 and 210 days. Finally, some empirical relationships between strength-time-curing temperatures were formulated. Experimental results revealed that the increase in ambient temperature resulted in an increase in the rate of conversion, thereby causing drastic strength reduction, particularly in pure CAC mix. It has been observed that inclusion of small amount of PC, lime, and gypsum in CAC did not induce conversion-free CAC binary systems, rather they resulted in faster conversion by enabling rapid formation of stable C3AH6 instead of metastable, high strength inducing CAH10 and C2AH8. On the other hand, in CAC-GGBFS mixes, the formation of stable straetlingite (C2ASH8) instead of calcium aluminate hydrates hindered the conversion reactions. Therefore, CAC-GGBFS mixes, where GGBFS ratio was over 40%, did not exhibit strength loss due to conversion reactions that occurred in pure CAC systems.

Si-based anodes have recently received considerable attention for use in Li-ion batteries, due to their extremely high specific capacity - an order of magnitude beyond that offered by conventional graphite anode materials. However, during the lithiation process, Si-based anodes undergo extreme increases in volume, potentially by more than 300 %. The stresses produced within the electrode by these volume changes can damage the electrode binder, the active Si particles and the solid electrolyte interphase (SEI), causing the electrode to rapidly fail and lose capacity. These problems can be overcome by producing new anode materials incorporating both Si and C, which may offer a favorable combination of the best properties of both materials, and which can be designed with internal porosity, thereby buffering the high strains produced during battery charge and discharge with minimal overall volume changes. However, in order to develop useful anode materials, we must gain a thorough understanding of the structural, microstructural and chemical changes occurring within the electrode during the lithiation and delithiation process, and we must develop new processes for synthesizing composite anode particles which can survive the extreme strains produced during lithium intercalation of Si and exhibit no volume changes in spite of the volume changes in Si. In this work we have developed several novel synthesis processes for producing internally porous Si-C nanocomposite anode materials for Li-ion batteries. These nanocomposites possess excellent specific capacity, Coulombic efficiency, cycle lifetime, and rate capability. We have also investigated the influence of a range of different parameters on the electrochemical performance of these materials, including pore size and shape, carbon and silicon film thickness and microstructure, and binder chemistry.

The main purpose of this thesis was to find ways to maintain a low level of light‐induceddiscolouration at an increased addition of mechanical and chemimechanical pulps in coated highqualityfine paper and magazine paper grades. Current technology allows the production of highyieldpulps such as thermomechanical and chemimechanical pulps with properties suitable formanufacturing high‐quality paper or paperboard with a low basis weight. Coating of woodcontainingpaper will probably be necessary for photo‐stability reasons if lignin‐containing pulps areto be used as the main fibre furnish in long‐life and high‐value products.In order to find the most suitable pulp for this purpose, light‐induced discolouration of a variety ofpaper samples from unbleached and bleached softwood and hardwood pulps was studied under bothaccelerated and long‐term ambient light‐induced ageing conditions. Hardwood high‐yield pulps,especially aspen pulps, were proven to be more photo‐stable compared to softwood pulps. Hardwoodpulps should therefore be the first choice for applications where a high permanence is desirable.Evaluating ageing characteristics using the CIELAB colour system showed that accelerated ageingconditions tend to mainly increase the b* value and decrease the L* value (i.e. yellow the pulp),whereas long‐term ambient ageing also increases the a* value, which makes the pulp more reddish.A new method for studying the influence of the UV‐screening properties of coating layers on abase paper was developed, and used to investigate the effect of pigment, pigment size distribution,binder and UV‐absorbing additives. The coat weight and pigment type were found to be the mostimportant factors for reducing the transmittance of UV‐radiation. Coating colours containing kaolinpigments had a lower UV‐transmittance than calcium carbonate pigments. Of the calcium carbonates,precipitated calcium carbonates were better than ground calcium carbonates and the difference wasgreater at higher coat weights. The particle size distribution should preferable be narrow. When thebest pigment (bleached kaolin) and the best binder (styrene butadiene latex) were combined withtitanium dioxide, the UV‐transmittance could be reduced by about 90% at a coat weight of ~10 g/m2.At a coat weight close to 20 g/m2, the transmittance was close to zero. This shows that it is possible tomore or less fully protect a double coated base paper from harmful UV‐radiation, when the coatinglayer has an optimum composition for that purpose. A prerequisite to reach so far is that the coatinglayer has an even coat weight.

In the present thesis we study and compare different viscoelastic rate-type fluid models capable of describing response of geomaterials such as asphalt. Using new thermodynamic approach proposed by Rajagopal and Srinivasa (2000) we derive several classes of non-linear viscoelastic models that generalize standard Oldroyd-B and Burgers models. We show that the new models achieve better results in fitting experimental data with asphalt than the previously considered models (Oldroyd-B, Burgers, Rajagopal and Srinivasa (2000)). In particular they are able to capture the behavior of asphalt observed recently in experiments (torque overshoot and two relaxation mechanisms), which is not possible to describe by the other models. Using both the standard and the newly derived models we compute full simulations of viscoelastic flow with the finite element method in fixed domains and incorporating the Arbitrary Lagrangian-Eulerian description also in deforming domains. For example, we study rolling of asphalt or creation of ruts in the road with the real material parameters obtained by fitting the experiments. Powered by TCPDF (www.tcpdf.org)

A moldagem de pós por injeção (MPI) foi empregada neste trabalho para a fabricação de micro componentes de uma pinça de biópsia, através do desenvolvimento de misturas injetáveis. Utilizou-se a liga de aço inoxidável AISI 316L, liga reconhecidamente biocompatível, para obtenção dos micro componentes. Determinando a quantidade de 39% em volume para fração orgânica das quatro formulações de misturas injetáveis produzidas neste trabalho. Os polímeros estruturais empregados foram o PP, o PEBDL, o PEAD e o PMMA. Como material auxiliar de fluxo foi utilizada a parafina e para agente surfactante, o ácido esteárico. O desenvolvimento do sistema de extração química do polímero auxiliar de fluxo com solvente e posterior extração térmica do ligante em forno convencional e em um reator a plasma foram testados, ainda se empregou estes para testes em sinterização a temperaturas 1200°C, 1250°C e 1300°C. A extração química foi realizada com hexano atingindo 2,41% em massa de material extraído das amostras, após seis horas em um sistema aquecido entre 60°C e 70°C e uma atmosfera de vácuo. As amostras foram testadas química, física, mecânica e eletroquimicamente. Obteve-se os melhores resultados em termos de densificação de 7,05 g/cm³ para as amostras extraídas a plasma e sinterizadas a 1300 °C à vácuo em forno tubular. Isso significa uma densificação de 88,96% comparada a densidade do material comercial cuja a densidade é 7,93 g/cm³. As microdurezas encontradas nas amostras sinterizadas a 1300 °C em um forno convencional obtiveram valores de 208HV se mostrando maiores do que os 165HV obtido de um material maciço fabricado pelo extrusão e comercialmente vendido. Encontrou-se a dureza de 55HRB nas amostras processadas a 1300 °C, devido a presença de poros em componentes sinterizados. Nos componentes maciços foram medidos a dureza de 88HRB que foi maior que os resultados das amostras sinterizadas. As análises metalográficas mostraram um tamanho de grão variando entre, 30 e 50μm, se comparado ao tamanho de partícula médio do D90 de foi de 8,59 μm, se estima que este aumento foi entorno de três vezes e meia. Os testes químicos revelaram que a extração térmica em reatores a plasma melhoram significativamente os níveis de C, N, H e S quando comparados ao processo de extração térmica em forno convencional. A redução dos níveis de carbono residual, resultaram em diminuição do carboneto de cromo nas amostras, provocando uma menor corrosão. As amostras sinterizadas a 1200 °C a plasma apresentaram os melhores resultados de corrosão. / The powders injection molding (PIM) was used in this research, with objective to manufacture micro component, for application in biopsy forceps being developed injectable mixtures . It was used the powder stainless steel AISI 316L alloy, material biocompatible, to obtain the micro components. Through tests was determining the amount optimal volume in 39 % for the organic fraction of the four formulations of injectable mixtures produced in this research. The structural polymers used were PP , LLDPE , HDPE and PMMA . The paraffin was used as auxiliary material flow, the surfactant agent employed that was stearic acid . The development of chemical debiding and the thermal extraction for binder system, was used the conventional furnace and in a plasma reactor were tested also be employed for these tests sintering temperature 1200 ° C , 1250 °C and 1300 °C. Chemical extraction was performed with hexane achieving 2.41 % by extracted mass of sample material, after six hours in a heated system between 60 °C and 70 °C and a vacuum atmosphere. The samples were tested analysis by chemical , physical , mechanical and electrochemical.If it obtained the best results in terms of densification of 7.05g/cm ³ for plasma samples extracted and sintering at 1300 °C in vacuum tube furnace . This means densification of 88.96 % compared to the density of commercial material whose density is 7.93 g/cm ³ . The microhardness found in the samples sintered at 1300°C in a conventional furnace obtained 208HV microhardness showing larger than the commercial 165HV. Found that the HRB hardness of 55 in the samples processed at 1300 °C, due to the presence of pores in sintered parts. In the extruded components were measured hardness of 88HRB which was higher than the results of the sintered samples. The metallographic analysis showing a grain size ranging between 30 and 50μm , compared to the average particle size D90 was 8,59 microns is estimated that this increase was around three and half times . The chemical tests revealed that the thermal plasma extraction reactor significantly improve the levels of C, N , H and S compared to the process heat extraction in a conventional furnace . The residual carbon levels significantly improved, which helps to avoid the formation of chromium carbides , which aumnetou corrosion resistance . The best results in terms of corrosion were found for the samples sintered at 1200 ° C the plasma.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / The given work presents the development and usage of a device (DEC Device for Extraction and Collection) capable of generate and collect fumes produced by the heating of asphalt cement samples. The DEC was elaborated aiming its employment on laboratory bench. The heating of the asphalt binder in a closed system generates the fumes. This process occurs under controlled temperature and non-oxidizing atmosphere with hot argon gas as carrier. The fumes are then extracted from small portions of asphalt binder. The developed system was applied on the generation and collection of asphalt binder fumes commercially available in Brazil. The levels of some polycyclic aromatic hydrocarbons (PAH) for the collected fumes were determined. According to the World Health Organization, these compounds must be monitored, regarding their carcinogenic potential. The DEC can operate over a wide temperature range that covers all usual asphalt application temperatures, without any significant losses of the components and without risk of ignition, due to the inert atmosphere. Besides, the present device may operate using different solvents for extraction or even no solvents, through the heating of the sample in question. In addition, the effect of the asphalt cement mass temperature on the PAH levels was discussed in this work. The DEC allows the fume collection either straight from the liquid phase (absorbent solutions) or in solid phase (adsorbent solids). The analysis of the collected fumes using the DEC reported 14 out of the 16 PAH considered high priority by the EPA (Environmental Protection Agency). / O presente trabalho trata da construção e utilização de um dispositivo (DEC-Dispositivo de Extracão e Coleta) capaz de gerar e coletar fumos produzidos pelo aquecimento de amostras de cimento asfáltico. O DEC foi desenvolvido para utilização em bancada de laboratório, e a geração dos fumos se da através do aquecimento do ligante asfáltico em sistema fechado, com temperatura controlada em atmosfera não oxidante utilizando-se para isso argônio aquecido como gás de arraste. As extrações dos fumos são feitas a partir de pequenas massas de ligante asfáltico. O sistema desenvolvido foi aplicado na geração e coleta de fumos de ligantes asfálticos comercializados no Brasil. Os fumos coletados foram analisados quanto aos teores de alguns hidrocarbonetos policíclicos aromáticos (HPA) cujo monitoramento é recomendado pela Organização Mundial da Saúde devido ao seu potencial carcinogênico. O DEC pode ser operado numa ampla faixa de temperaturas que cobre todas as temperaturas usuais de aplicação de asfalto, sem perdas significativas dos analitos e sem risco de ignição em virtude da atmosfera inerte presente. O dispositivo pode operar com diferentes solventes em contato com a massa de cimento asfáltico, e também sem a presença destes solventes, pelo aquecimento direto da amostra. A influencia do efeito da temperatura da massa de cimento asfáltico sobre o teor de HPA observado, foi discutido neste trabalho. O DEC permite a coleta dos fumos tanto diretamente em fase liquida (soluções absorventes) quanto em fase solida (adsorventes sólidos). Na análise dos fumos coletados no DEC foram encontrados 14 dos 16 HPA considerados prioritários pela EPA (Environmental Protection agency).