abstract: This dissertation provides a fundamental understanding of the impact of bulk polymer properties on the nanometer length scale modulus. The elastic modulus of amorphous organic thin films is examined using a surface wrinkling technique. Potential correlations between thin film behavior and intrinsic properties such as flexibility and chain length are explored. Thermal properties, glass transition temperature (Tg) and the coefficient of thermal expansion, are examined along with the moduli of these thin films. It is found that the nanometer length scale behavior of flexible polymers correlates to its bulk Tg and not the polymers intrinsic size. It is also found that decreases in the modulus of ultrathin flexible films is not correlated with the observed Tg decrease in films of the same thickness. Techniques to circumvent reductions from bulk modulus were also demonstrated. However, as chain flexibility is reduced the modulus becomes thickness independent down to 10 nm. Similarly for this series minor reductions in Tg were obtained. To further understand the impact of the intrinsic size and processing conditions; this wrinkling instability was also utilized to determine the modulus of small organic electronic materials at various deposition conditions. Lastly, this wrinkling instability is exploited for development of poly furfuryl alcohol wrinkles. A two-step wrinkling process is developed via an acid catalyzed polymerization of a drop cast solution of furfuryl alcohol and photo acid generator. The ability to control the surface topology and tune the wrinkle wavelength with processing parameters such as substrate temperature and photo acid generator concentration is also demonstrated. Well-ordered linear, circular, and curvilinear patterns are also obtained by selective ultraviolet exposure and polymerization of the furfuryl alcohol film. As a carbon precursor a thorough understanding of this wrinkling instability can have applications in a wide variety of technologies. / Dissertation/Thesis / Ph.D. Chemical Engineering 2011

Two novel methods for the sulphur vulcanisation of NR, BR and EPDM rubbers using N-tert-butyl-2-benzothiazole sulphenamide (TBBS) accelerator and zinc oxide (ZnO) activator have been developed. In one method, the optimum loading of TBBS and ZnO were measured for some sulphur-filled NR, BR and EPDM rubbers. The cure systems for the NR were (S/TBBS/ZnO), (1/1.5/0.2), (2/1.5/0.3), (3/1.5/0.25), and (4/3.5/0.2), for the BR, (0.5/1.75/0.2) and (1/3/0.2), and for the EPDM, (1/1/0.075). The cure was very efficient in spite of reducing the amount of TBBS and ZnO chemicals. In another method which used a single additive component in the form of a powder (TBBS/ZnO: 350mg/1g), the loading of the powder in NR was raised increasingly from 0.63 to 5.63 phr, the scorch time was unchanged and the optimum cure time reduced at 1.25 phr powder. The rate of cure accelerated at 1.25 phr powder. The crosslink density reached its maximum value at 5.63 phr powder. This method reduced the TBBS and ZnO requirement in the cure system by 85wt%. Solid kaolin filler pre-treated with a sulphur-bearing mercaptosilane was used to reinforce NR, BR and EPDM rubbers. For NR, to react the sulphur in the silane on the kaolin surface with the rubber chains and optimise the reaction between the two, 16 phr TBBS and 0.2 phr ZnO were added to the kaolin-filled rubber. The hardness and Young s modulus increased and compression set decreased when up to 3 phr elemental sulphur was included in the kaolin-filled rubber with 16 phr TBBS and 0.2 phr ZnO. The tensile strength, elongation at break, stored energy density at break, and tear energy of the rubber vulcanisate reduced when elemental sulphur was added. Notably, the inclusion of elemental sulphur was the key factor in controlling the rubber properties. In an extended work, 60 phr silane pre-treated kaolin was mixed with NR, BR and EPDM and the rubbers were cured using the novel cure systems developed earlier. The effect of 140 phr kaolin on the properties of NR was also investigated. For NR, the hardness increased by 64% when 60 phr kaolin was added and the trend continued rising by another 28% when the loading of kaolin reached 140 phr. Similarly, the Young s modulus rose by 170% with 60 phr kaolin and then by an extra 148% when the full amount of kaolin, i.e. 140 phr, was reached. The tensile strength and tear energy were unchanged and the elongation at break and stored energy density at break deteriorated by a total of 65% and 34%, respectively with 140 phr kaolin. The compression set of the unfilled rubber was 41%, and it then rose to 64% and 71%, when 60 and 140 phr kaolin was added, respectively. For BR, the hardness increased by 23% and for EPDM, by 34%, respectively when 60 phr kaolin was incorporated in the rubbers. For BR, the tensile strength, elongation at break and Young s modulus rose by 759%, 256% and 114%, respectively. The compression set of the unfilled BR was 9.4%, and subsequently rose to 26% when 60 phr kaolin was mixed with the rubber. For EPDM, the tensile strength, elongation at break and Young s modulus improved by 964%, 332% and 71%, respectively. For BR, the stored energy density at break and tear energy were increased by 2442% and 536%, respectively and for EPDM, by 3133% and 1479%, respectively. The compression set of the unfilled EPDM was 39%, and afterward increased to 48% with 60 phr kaolin. Kaolin was found to be extending or non-reinforcing filler for the strain-induced crystallising NR and highly reinforcing for the non-crystallising BR and EPDM.

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Resumo: Atualmente o aço AISI 300M tem sido amplamente empregado na fabricação de componentes estruturais para veículos automobilísticos e aeroespaciais. Este material foi introduzido como um substituto de mais alta resistência para o aço 4340. Este trabalho tem como objetivo verificar a influência da deformação plástica sobre a austenita retida, e suas conseqüências sobre a microestrutura e as propriedades mecânicas associadas. O aço foi austenitizado, em temperatura de 900°C por 20 minutos, em forno de atmosfera controlada, seguido de uma transformação isotérmica, realizada em banho de sal a 400°C, por três diferentes tempos de permanência na temperatura, 60s, 300s e 1800s. Para a identificação e quantificação da austenita retida foi aplicada a técnica heat-tinting, em que as amostras foram atacadas quimicamente com nital 2% por 15 segundos, seguido de manutenção em forno mufla, à 260°C por 9000s. Foram analisadas as regiões próxima à ruptura, afastada da ruptura e sem deformação. E, por meio dos ensaios de tração, foram medidos os níveis de resistência à tração, limite de escoamento e do alongamento em função do tempo de permanência na temperatura de transformação bainítica, objetivando o tratamento térmico otimizado que forneça a melhor relação resistência-tenacidade para o aço 300M. Por intermédio da metodologia utilizada observou-se que com o tratamento isotérmico o material teve a sua resistência aumentada em aproximadamente 40%, sem perda de ductilidade, quando comparado com o tratamento de têmpera e revenimento. Não foram observadas grandes variações no valores de resistência mecânica em função do tempo de permanência na isotérmica. / Abstract: Nowadays the steel AISI 300M has been used thoroughly in the production of structural components for aerospace vehicles and cars. This material was introduced as a substitute of higher resistance for the steel 4340. This work has as objective verifies the influence of the plastic deformation on the retained austenite, and its consequence on the microstructure and the mechanical properties of the material. The steel was austenitized in temperature of 900°C for 20 minutes, in furnace of controlled atmosphere, following by an isothermal transformation, accomplished in bath of salt to 400°C, for three different times of permanence in the temperature, 60s, 300s and 1800s. For the identification and quantification of the retained austenite was applied, specially, the heat-tinting technique, where the samples were attacked chemically with nital 2% for 15 seconds, followed by maintenance in muffle furnace, to the 260°C for 9000s. By the tensile tests, it was measured the tensile strength, yield strength and the elongation in function of the time of permanence in the temperature of bainitic transformation, looking for an optimized heat treatment that provides a better relationship strength-tenacity of the 300M steel. Through the used methodology it was observed that with the isothermal treatment the material had its resistance increased in approximately 40%, without ductility loss, when compared with the quench+temper treatment. It was not observed a great difference in the strength values in function of the time of permanence in the bainitic transformation temperature. / Orientador: Marcelo dos Santos Pereira / Coorientador: Tomaz Manabu Hashimoto / Banca: Antonio Jorge Abdalla / Banca: Rosinei Batista Ribeiro / Mestre

Orientador: Marcelo dos Santos Pereira / Banca: Tomaz Manabu Hashimoto / Banca: Alfeu Saraiva Ramos / Resumo: A redução de peso de componentes estruturais usados na fabricação de automóveis tem sido objeto de destaque na pesquisa e no desenvolvimento de novos aços. Isso devido as exigências dos principais mercados mundiais visando redução do consumo de combustíveis, ganho de energia e adequação perante as leis ambientais. Os aços bifásicos estão inseridos neste contexto por apresentarem uma combinação de boa conformabilidade associada a uma elevada resistência mecânica, justificada pela interação sinergística entre as fases ferrita e martensita, presentes na estrutura do material. Neste trabalho foi analisada a possibilidade de aplicação de três aços com médio teor de carbono, normalizados como aços 1045, 4340 e 300M, em substituição aos aços de baixo teor de carbono convencionalmente utilizados, visando a obtenção de aços com microestrutura bifásica de alta resistência. Os materiais foram tratados termicamente em diferentes temperaturas intercríticas (720oC, 740 oC e 760 oC) e por métodos convencionais de têmpera e revenimento. A caracterização mecânica foi realizada através de ensaios de tração, para estabelecer os valores de resistência e alongamento para cada condição de tratamento térmico, enquanto a caracterização microestrutural permitiu a avaliação qualitativa e quantitativa das fases presentes na estrutura. Os aços bifásicos apresentaram altos valores de resistência mecânica (acima de 1500 MPa) sem perda significativa no alongamento, e se mostraram extremamente eficientes para aplicações na fabricação de componentes estruturais usados na indústria automobilística. / Abstract: The reduction of weight of structural components used in the production of automobiles has been considered in the research and development of new steels. The demands of world markets in order to reduce consumption of fuels, due to the restrictions in the environmental laws. The dual-phase steels are inserted in this context for presenting a combination of good conformability associated to a high strength, explained by the interaction between the ferrite and martensite phases, presents in the microstructures. In this work the application of three steels with medium carbon content, or either, normalized as 1045, 4340 and 300M, in substitution to the conventional steels of low carbon steels, was analyzed aiming for the obtaining of high strength steels with dual-phase microestructure. The materials were treated in different intercritical temperatures (720°C, 740 °C and 760 °C) and for conventional methods of hardness and drawing back. The mechanical characterization was performed, using tensile tests to establish the strength values and elongation in each condition of heat treatment, while the microestructural characterization using light microscopy to quantity and quality the present phases in the structure. The results showed that the dual-phase steels presented high resistance values, reaching the higher values of strength without significant loss in the elongation, and they are shown extremely efficient for applications of several structural components used in the automotive industry. / Mestre