O processo de conformação por prensagem uniaxial é um dos mais utilizados na indústria cerâmica devido ao seu baixo custo e alta produtividade. O entendimento e controle dos diversos fatores que interferem neste processo são cruciais, pois grande parte dos defeitos encontrados na peça final é originada nesta etapa. Este trabalho trata da avaliação da compactação de pós a base de alumina processados em spray-dryer, com diferentes composições e contendo distintos aditivos orgânicos, sendo caracterizados em relação a fluidez, densidade solta e batida, determinação da distribuição do tamanho de grânulos e morfologia. Parâmetros como umidade (10, 64 e 85%) e temperatura (5, 25 e 45°C) foram variados. O comportamento do pó foi analisado nas diferentes etapas de compactação, as quais envolvem a deformação plástica e quebra dos grânulos e também redução da porosidade intergranular e intragranular. Posteriormente foram estudadas a influência da temperatura e da umidade relativa do ar durante a compactação, sendo o efeito dos mesmos avaliados por meios de curvas de compactação. A resistência mecânica das peças também foi avaliada por meio do módulo de Weibull. Através da análise da microestrutura (MEV e porosimetria) e de curvas de compactação constatou-se que os parâmetros citados acima interferem nas características dos compactados, particularmente na resistência mecânica dos grânulos em relação à deformação e fratura. Os resultados mais importantes são que quanto maior a temperatura e umidade ocorre a redução da Tg dos ligantes, diminuindo a resistência ao esmagamento dos mesmo e que através do módulo de Weibull é possível determinar qual a melhor condição para realizar a prensagem que no caso deste estudo foi a condição intermediária. / The compaction process by uniaxial pressing is the most used in the ceramics industry due to its low cost and high productivity. The understanding and control of several factors that interfere in this process are crucial, since most of the defects found in the final piece are originated at this stage. This paper deals with compaction evaluation of alumina powders, processed by spray-dryer with different compositions and containing different organic additives, being characterized according the flow, tap and apparent density, granule size distribution and morphology. Parameters such as relative humidity (10, 64 and 85%) and temperature (5, 25 and 45°C) were varied. The powder\'s behavior was analyzed at different compaction stages, which involves plastic deformation, breakage of the granules and reduction of intergranular and intragranular porosity. The influence of temperature and relative humidity during compaction were analyzed by compaction curves. The mechanical strength of the obtained parts was evaluated using the Weibull modulus. The microstructural analysis (SEM and porosimetry) and evaluation of the compaction curves shows that these parameters affect the characteristics of compacted powder, in particular the mechanical strength of the granules in relation to the deformation and fracture. The most important results show that higher the temperature and relative humidity occurs the Tg reduction of binders, decreasing the mechanical strength of binders and by Weibull modulus it is possible to determine the best condition for pressing, in this instance the intermediate condition.

Este trabalho teve como objetivo avaliar as vantagens ou desvantagens de utilizar-se asfalto modificado com polímero em misturas densas com seixo rolado como agregado graúdo. Para o experimento foram moldados setenta e cinco corpos-de-prova com asfalto convencional (CAP-40) e setenta e cinco corpos-de-prova com asfalto modificado (BETUFLEX B 65/60) e avaliados à luz dos ensaios Marshall, fluência por compressão uniaxial estática à 40ºC, resistência à tração por compressão diametral e módulo de resiliência por compressão diametral à 25ºC. Os resultados dos ensaios Marshall e de resistência à tração acusaram um melhor desempenho das misturas com asfalto modificado. As relações MR/'sigma tal' encontradas para ambas as misturas sugerem, a princípio, um melhor comportamento para as misturas modificadas. Os resultados dos ensaios de fluência por compressão uniaxial estática, no que tange à deformação elástica, detectou também uma performance superior das misturas com asfalto modificado em três teores de ligante dos cinco teores analisados, entretanto, para as demais propriedades, deformação total, deformação viscoplástica e módulo de fluência as misturas com asfalto convencional sairam-se melhor. / This research intends to analyze the advantages of hot-mix asphalt mixtures composed by polymer modified binder and gravel in relation to those made with conventional binder. To achieve the objective, there were compacted seventy five specimens with conventional binder and seventy five specimens with SBS polymer modified binder (BETUFLEX B 65/60) and were performed Marshall tests, static creep (40oC) tests, indirect tensile strength tests and resilient modulus by indirect tensile (25oC) tests. The results of Marshall and tensile strength tests showed a better performance of the polymer modified asphalt mixes than that presented by the conventional asphalt ones. The results from the relation of resilient modulus by indirect tensile and indirect tensile strength tests probably showed that the modified asphalt mixes have the best performance. The elastic strains from static creep tests also showed a better performance of the polymer modified mixes in three of the five binder contents, however, the others properties from static creep tests like as total strain, viscoplastic strain and creep modulus showed that the conventional asphalt mixes have the best performance.

The objective of this thesis was to study whether heterocyclic dicationic compounds that are minor groove binders have the ability to inhibit the digestive properties of type II restriction enzymes which bind to the major groove of the DNA. If these compounds do possess the ability to inhibit restriction enzymes, then what factors influence their ability to inhibit the restriction enzymes? The methods used to study the interactions of DNA, compounds, and enzymes are gel electrophoresis, DNA thermal melting, and circular dichroism. The results from this project reveal that the minor grove binding compounds are able to inhibition type II restriction enzymes. The inhibition is heavily influenced by compound structure and the DNA binding sequence of the enzyme.

Diamidines are a class of compounds that target the minor groove of DNA and have antiparasitic and antimicrobial properties. Their mechanism of action has not been fully elucidated, but may include changes in DNA topology. In this study we have investigated such changes using methods of gel electrophoresis including ligation ladders and cyclization assays. We found that topology changes were sequence dependent. Compounds typically caused non-anomalously migrating ATATA sequences to migrate as if they were bent, while A5 sequences that normally migrated anomalously became less so in the presence of certain diamidines. Select compounds induced changes in cyclization efficiency that were also sequence dependent; DB75 significantly abolished cyclization in A5 containing sequences but enhanced it in sequences containing ATATA sites.

DNA minor groove binding compounds have had limited therapeutic uses, in part due to problems with sequence specificity. A two-site model has been developed to enhance specificity, in which compounds bind to two short AT sites separated by one or two GC base pairs. Using thermal melting, heterocyclic dications with this capability were tested with various oligonucleotides for binding affinity and specificity. Compounds of interest were further probed using circular dichroism, mass spectrometry, biosensor-SPR, and molecular modeling. Several compounds were found to “jump” a GC base pair, binding to AT sites in the minor groove of DNA with a two-site recognition mode. One compound was also found to recognize a single intervening GC base pair. Compounds with terminal, non-polar amidine extensions were found to have increased DNA binding compared to analogs with terminal amidines. This unique, two-site DNA recognition mode offers novel design principles to recognize entirely new DNA motifs.

This dissertation covers two different topics within the area of diaza-containing aromatic five-membered rings: biimidazoles and pyrazoles. With the exception that both these subject matters are explored in the context of developing new anion binding agents, the background and research associated with these two topics are vastly different and will be treated as such. Chapter two, dealing with biimidazoles, focuses solely on expanded porphyrins, while chapter three discusses pyrazoles as potential macrocyclic building blocks and as diamidic-functionalized anion binders. The first chapter covers several different topics in order to put into perspective the diverse subject matter presented in this dissertation. It begins with an overview of some well-known expanded porphyrins. The synthesis, classical applications, and newer studies of the biimidazole synthetic efforts are then described. The third part of the introductory chapter covers the synthesis and applications of pyrazoles. The use of heterocycles with more than one heteroatom in the construction of expanded porphyrins is just beginning to be explored, and is the focus of chapter two. The synthesis of a novel expanded porphyrin is described and its applications are investigated. More specifically, chapter two covers the synthesis of several biimidazole dialdehydes and their condensation with three 3,3',4,4'-functionalized bis-[alpha]-free bipyrroles to form a series of novel macrocycles. The characterization of these new compounds has been investigated and is discussed in detail. Also presented are preliminary studies of their anion binding properties. Pyrazoles, the subject of chapter three, are another overlooked class of potential building blocks in the area of expanded porphyrins and molecular recognition chemistry. Pyrazoles have rarely been reported in the literature as being part of a larger molecular framework. Until this work, their anion binding potential had remained unexplored. Thus, the attempted incorporation of a pyrazole fragment into an expanded porphyrin framework is described. Second, and more significantly, the design, synthesis, and anion binding properties of a new series of diamidic pyrazoles are reported. / text

The objectives of this work are to discuss multiscale models that are used to characterize the constitutive relations of the granular composite materials with dual functions. This is accomplished by the use of ab initio methods to obtain the constitutive relations of the structural energetic materials without conducting tests. First, it is necessary to study the quantum many body problem to quantitatively determine the internal energy of the material when subjected to different strain conditions. It is impossible to obtain an exact solution to the quantum many body problem that is modeled by the Schrödinger's equations with the current technology. It is possible to solve these equations approximately by the density functional theory which yields only energies at absolute 0ºK. Thus it becomes necessary to add both the lattice thermal contributions and electron thermal contribution. Then, resulting energy is used to bridge to the continuum level and obtain the constitutive equations. This is the procedure that is used in this work. The issues of the constitutive equations form the focus of this thesis. More specifically, the scope of the thesis is further restricted to analyze the constitutive equations of specific mixtures of nickel, aluminum with PTFE or Teflon as the binder. It is to be noted that the equations of state forms only a part of the complete constitutive relationships. This thesis presents solutions to the following problems: (1) Determination of the thermodynamically complete equation of state of the binder and the energetic material PTFE or Teflon, from ab initio methods based on the density functional theory. (2) Determination of the equations of state of the granular composite or the mixture of nickel, aluminum and PTFE from ab initio methods. (3) Determination of the complete constitutive equation of aluminum, from ab initio methods, under conditions of finite deformations, with principle of objectivity, material symmetry conditions and polyconvexity of the strain energy. All results are compared to test results whenever they are available.

The design and selection of surface treatment binders in service is currently based on specifications that only account for the penetration and ductility of emulsion residues or the penetration and viscosity of hot-applied asphalt cements. These specifications consider neither the entire range of temperatures that the binders may be subjected to during production and in service, nor long-term aging behavior. A surface performance-graded (SPG) specification for the selection of surface treatment binders was developed as part of previous Texas Department of Transportation (TxDOT) and National Cooperative Highway Research Program (NCHRP) projects. The work performed under the TxDOT Project 0-6616 was the basis for this thesis. In this project, the SPG specification, which is performance-based and takes into account the physical properties of the binder at the temperature ranges in which the material will be used, was further validated. This was accomplished by standardizing the emulsion residue recovery method through the evaluation of two warm oven methods, exploring the exclusive use of the dynamic shear rheometer (DSR) for determining performance-based properties, and further field validating the thresholds for these properties. The laboratory and field results were used to revise the SPG specification for surface treatment binders in service. Binder samples collected from chip seal projects constructed on selected highway sections in Texas in summer 2011 were tested and graded according to the existing SPG specification developed in previous research projects. Two warm oven emulsion residue recovery methods were used and compared. New DSR tests, including the multiple stress creep recovery (MSCR) test and the frequency sweep test were evaluated for developing additional criteria in the SPG specification. The SPG grades of the surface binder samples evaluated from laboratory tests were compared with the actual field performance of the highway sections one year after construction. The SPG specification was found to be functional in terms of enabling the selection of binders to ensure adequate surface treatment performance. Moreover, the results obtained from the MSCR and DSR frequency sweep tests were compared with field performance to develop additional criteria in the specification. Further validation is recommended to investigate the effects of construction and quality control processes, as this study is limited to producing a revised SPG specification for properties that address stiffness and aggregate retention in service.

Artigos de couro estão associados com tendências de moda e sofisticação em produtos de consumo. No processamento do couro, a fase de acabamento consiste de um conjunto de operações e tratamentos, essencialmente de superfície, que conferem características finais ao produto. Os objetivos do acabamento são reduzir defeitos visíveis, modificar as propriedades superficiais e melhorar os atributos de uso. Nesta fase final, são aplicadas, dentre outros produtos, resinas, geralmente, poliacrilatos e poliuretanos, e algumas vezes caseínas e outros polímeros que formam filmes de recobrimento protetores sobre o couro. Nesse contexto, este trabalho visa a uma avaliação dos filmes formados com resinas comerciais utilizadas industrialmente no acabamento de couros, relacionando a composição destes materiais com características sensoriais, com resistência mecânica, através de testes de tração, com estabilidade à água ou a solvente orgânico, com análise de dureza, e através de caracterizações por infravermelho e DSC. Ensaios de tração mostraram que as resinas poliuretânicas, no geral, apresentam uma maior resistência à tração quando comparadas com resinas acrílicas, assim como os valores de tenacidade, indicando que esses filmes suportam um maior impacto para levar o material à ruptura. A adição de pigmentos diminui essa resistência, tanto em resinas acrílicas quanto em resinas poliuretânicas, enquanto que a produção de filmes compactos apresenta características intermediárias com relação aos componentes puros. Todos os filmes acrílicos testados apresentaram uma maior capacidade de alongamento. Com relação à dureza, as resinas que se mostraram mais flexíveis e com maior alongamento, foram as que apresentaram menor dureza. A estabilidade dos filmes com relação à água e solventes mostrou que os componentes solúveis em água e em solvente aumentam com a presença de pigmento e que a absorção de água é maior e de solvente é menor em filmes com pigmento, tanto para acrilatos quanto para poliuretanos. As caracterizações a partir de análise por FTIR e DSC indicaram os grupamentos químicos e picos de temperaturas característicos dos acrilatos e poliuretanos, respectivamente. / Leather goods are associated with fashion trends and sophistication in consumer products. In the leather processing, the finishing phase consists of a series of operations and treatments, essentially in surface, conferring its final characteristics. The objectives are to reduce visible defects, modify surface properties and improve the usage attributes In this final stage are applied, among other products, resins, generally polyacrylates and polyurethanes, sometimes casein and other polymers, which form protective coating films on leather. In this context, this paper evaluates the films formed with commercial polymeric resins used industrially in finishing leather, relating the composition of these materials with their sensory characteristics, with their strength by tensile testing, with its stability to water or organic solvent, with analysis of hardness and characterizations by IR and DSC. Tensile tests showed that the polyurethane resins in general have a higher tensile strength when compared with acrylic resins, as well as the toughness values, indicating that these films support a greater impact to bring the material to rupture. The addition of pigments decreases this resistance, for acrylic resins and polyurethane resins, while the production of compact film has intermediate characteristics with respect to the pure components. All acrylic films tested had a higher elongation. With respect to hardness, the resins that were more flexible and more stretching, showed the lowest hardness. The stability of the films with respect to water and solvents has shown that water soluble solvent components increased by the presence of pigment and the water absorption is higher and the solvent is lower in pigmented films to acrylates and polyurethanes. The characterizations from IR and DSC analysis indicated the chemical groups and characteristic temperatures peaks of acrylates and polyurethanes, respectively.

abstract: The application of fibers and other materials in asphalt mixes has been studied and applied over the past five decades in order to improve pavement performance around the world. This thesis highlights the characteristics and performance properties of modified asphalt mixes using a blend of polypropylene and aramid fibers, The main objective of this study was to evaluate the effect of adding different fiber dosages on the laboratory performance of both asphalt binder and mixture. The laboratory study was conducted on sixteen different dosages and blends of the fibers, with various combinations of polypropylene and aramid, using binder tests as well as hot mix asphalt tests. The binder tests included: penetration, softing point, and Brookfield viscosity tests. The asphalt mixture tests included the dynamic modulus, and indirect tensile strength. The binder test results indicated that the best viscosity - temperature susceptibility performance would be from the blend of three dosages of polypropylene and one dosage of aramid, the dynamic modulus test results also confirmed this finding. Overall, in almost every case, the addition of fibers resulted in an increase in mixture stiffness regardless of fiber content. From the indirect tensile strength results, the polypropylene fibers had less of an effect on post peak failure than the aramid fibers. Overall, the aramid fibers yielded better results than the polypropylene fibers. This study has important implications for the future of pavement design and the prospect of using optimal dosages of polypropylene and aramid fibers in further research to further determine their long-term performance and characteristics used in real world applications. / Dissertation/Thesis / M.S. Civil and Environmental Engineering 2012