Orientador: Maria Isabel Felisberti / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-09-27T12:44:40Z (GMT). No. of bitstreams: 1 Contar_LiviaBarbosa_M.pdf: 1831028 bytes, checksum: 9dc6aca0cd0794c653af2498ac17227d (MD5) Previous issue date: 2013 / Resumo: A incorporação de cargas em matrizes poliméricas, visando o desenvolvimento de compósitos e nanocompósitos poliméricos, tem sido foco de intensos estudos e apresentado interesse crescente na área industrial nos últimos anos em função do acréscimo conferido às suas propriedades mecânicas, térmicas e elétricas, dependendo da natureza da carga, e também devido à simplicidade, rapidez e baixo custo na obtenção destes materiais. A associação de cargas de diferentes naturezas em uma mesma matriz polimérica, além de conferir múltiplas funcionalidades ao material, pode contribuir com propriedades sinérgicas, antagônicas ou meramente aditivas. Neste trabalho, foram preparados em diferentes concentrações, compósitos binários de poliamida 6 (PA 6) com argila organicamente modificada, Cloisite® 30 B (C30B) e PA 6 com grafite puro, bem como compósitos ternários de PA 6, argila C30B e grafite, através da mistura mecânica no estado fundido, utilizando extrusora de duas roscas cônicas co-rotacionais, com o objetivo de desenvolver materiais com elevado desempenho mecânico e térmico. Corpos de prova moldados por injeção foram submetidos a ensaios para determinação de suas propriedades mecânicas (ensaios de tração e de resistência ao impacto), térmicas (DMA, TGA e DSC), morfológicas (SEM e TEM) e estruturais (XRD). Tanto os nanocompósitos de PA 6 e argila C30B, quanto os compósitos de PA 6 e grafite, apresentaram maior resistência à tração do que a PA 6 pura, assim como ocorreu com os compósitos ternários. Porém, nestes últimos, foram observados os maiores ganhos na rigidez do material, devido ao efeito co-reforçante de ambas as cargas e suas prováveis interações mútuas que favorecem a dispersão na matriz. As análises morfológicas das misturas binárias e ternárias revelaram a formação de estruturas esfoliadas e de agregados, no caso da argila, enquanto que no caso da grafite apenas se observou partículas correspondentes a agregados de multilaminas de grafeno, mesmo nos sistemas ternários. Apesar disso, contatou-se que a presença da grafite nos nanocompósitos ternários proporciona um aumento da extensão de delaminação da argila. A grafite atua como agente nucleante para a cristalização da poliamida, sem alterar a forma cristalina, no caso a forma 'alfa'. Enquanto que a argila induz a formação da fase 'gama'. / Abstract: The incorporation of fillers in polymeric matrices in order to develop polymer composites and nanocomposites has been highlighted in many works and has showed increasing interest in industrial area in the last years because of enhaced mechanical, thermal and electrical properties, depending on the filler nature, and also because of simplicity, velocity and low costs in the preparation of these materials. The association of different fillers in the same polymeric matrix, beyond multiple functionalities attributed to the material, can also contribute to synergistic, antagonistic or additive properties. In this work, binary composites of polyamide 6 (PA 6) with organic modified clay, Cloisite® 30 B (C30B), and PA 6 with pristine graphite, were prepared in different concentrations as well as ternary composites of PA 6, clay and graphite, through mechanical mixture in the molten state, using a conical co-rotational twin-screw extruder, in order to develop materials with enhaced mechanical and thermal properties. The materials were injection molded to investigate their mechanical (Tensile properties, Izod Impact resistance), thermal (DMA, TGA and DSC), morphological (SEM and TEM) and structural (XRD) properties. Both binary composites, PA 6 with C30B clay and PA 6 with graphite, showed higher tensile properties in relation to pure PA 6, and the same happened with ternary composites. But in these last one the highest gain in the material stiffness was observed, because of the co-reinforcement effect of both fillers and their mutual interations that favoured fillers dispersion. The morphological analysis of binary and ternary systems have revealed the formation of exfoliated structures and aggregates, in the case of the clay, while in the graphite case only particles refered to aggregates of graphene multi-platelets were observed even in the ternary systems. Nevertheless, it was detected that the presence of graphite in the ternary composites promotes an increase in the exfoliation degree of the organoclay. Thermal studies showed that the graphite acts as a nucleating agent for the crystallization of polyamide, without change in the crystalline 'alpha' phase, while the organoclay promotes the 'gama' phase / Mestrado / Físico-Química / Mestra em Química

Esta dissertação relê aspectos da relação entre as artes plásticas e as poéticas do espaço urbano a partir da trajetória e da obra fotográfica de Gyula Halász, conhecido como Brassaï. Além da referida reflexão, cujo objetivo implica na observação de um corpus estrito, este estudo evidencia algumas problemáticas que se inserem em contextos mais amplos. De um lado, permite apreender, através de sua singularidade, aspectos históricos, econômicos, técnico-científicos e socioculturais que são relevantes para a temática da modernidade. Por outro lado, esses aspectos relacionam-se à investigação das dinâmicas criativas, processos de conhecimento, culturas urbanas e mobilidade, que estão presentes no desenvolvimento das imensas aglomerações urbanas que se espalharam pelo globo a partir do fim da Segunda Guerra Mundial. Embora a importância de todos esses objetos de estudos seja incontestável na atualidade do mundo globalizado, sua relação com o passado recente é menos nítida. Dividida em quatro capítulos, esta dissertação está organizada em quatro partes que correspondem a aspectos particulares, ainda que não isolados, da obra de Brassaï artista. No primeiro capítulo exploro a relação entre a imigração e a transição para uma nova perspectiva artística de Brassaï, transformando-o naquilo que o escritor Henry Miller descreveu como o olho de P ris. O segundo capítulo se concentra na estética noturna pela qual Brassaï apresenta Paris, bem como os aspectos culturais de sua leitura sobre a noturnidade. O terceiro capítulo prende-se aos aspectos do fazer artístico de Brassaï, da exploração da cidade e, particularmente, das técnicas visuais que o fotógrafo usava para narrar os acontecimentos em um espaço urbano iluminado pela noite. Já no quatro e último capítulo, que funciona como considerações finais da pesquisa, traço um paralelo entre da Paris dos anos 1920 à Paris contemporânea, onde a flânerie tornou possível a Brassaï o encontro com os graffitti, que capta simultaneamente as paredes tatuadas da cidade e as inscrições da luz fotográfica, estabelecendo com uma humanidade noturna uma fraternidade que a câmera transfigura e eterniza. / This dissertation reviews aspects of the relation between plastic arts and the poetics of urban space reflecting on the trajectory and the photographic work of Gyula Halász, also known as Brassaï. Further than the referred reflection, whose objective implies the observation of a strict corpus, this study makes evident some issues inserted in wider contexts. From one side, it makes possible to grasp, by means of its singularity, the historical, economic, techno-scientific and social-cultural aspects that are relevant to the theme of modernity. From another side, these aspects are related to the investigation of creative dynamics, knowledge processes, urban cultures and mobility, which are present in the development of huge urban agglomerations that spread in the globe from the end of Second World War. Although the importance of all these objects of study were incontestable, its relations with recent past are not fully clear. Being presented in three chapters, this dissertation is organized in three parts which correspond to particular aspects of the artistic work of Brassaï. In the first chapter, I explore the relation between immigration nd Br ss ïs tr nsition to a new artistic perspective that transformed him in what Henry Miller described as the eye of P ris. The second chapter leads with the nocturnal esthetics by which Brassaï presented Paris, as much as with the cultural aspects of his lecture of the nocturne. The third chapter is linked with the exploration of the city and, particularly, with the technical approaches Brassaï used to describe events in an urban space illuminated by night. In the fourth and final chapter, which serves as final considerations of the research, we draw a parallel between the Paris of the 1920s to contemporary Paris, where dawdling made it possible to Brassaï the meeting with graffitti, which simultaneously captures the tattooed city walls and the inscriptions of the photographic light setting with a night humanity a fraternity that the camera transfigures and perpetuates.

Several methods of increasing railgun barrel performance and lifetime are investigated. These include two different barrel-projectile interface coatings: a solid graphite coating and a liquid eutectic indium-gallium alloy coating. These coatings are characterized and their usability in a railgun application is evaluated. A new type of projectile, in which the electrical conductivity varies as a function of position in order to condition current flow, is proposed and simulated with FEA software. The graphite coating was found to measurably reduce the forces of friction inside the bore but was so thin that it did not improve contact. The added contact resistance of the graphite was measured and gauged to not be problematic on larger scale railguns. The liquid metal was found to greatly improve contact and not introduce extra resistance but its hazardous nature and tremendous cost detracted from its usability. The simulated resistivity augmented projectiles were able to mitigate harmful current build-up on the back of a projectile using different conductivity gradients. Within the range of conductivity of aluminum alloys no simulated gradient was able to fully level the current density, however, once the range was expanded to include the lower conductivity of titanium, nearly uniform current density was achieved.

An in-depth study has been carried out to investigate refractory degradation during continuous steel casting processes. Slag/refractory interactions have been investigated through a study of the wetting behaviour and gas generation phenomena at the slag/refractory interface at 1550oC using sessile drop experiments. The influence of carbon content and slag composition was investigated. Two different steel casting slags (slag1: MnO 50%, SiO2 25%, Al2O3 25%; and slag2: MnO 40%, SiO2 60%) have been studied along with yttria stabilized zirconia refractory substrates respectively containing 10%, 15% and 20% carbon. The gas generation has been measured using the Infrared gas analyser, and its influence has also been investigated by taking optical images at varying times. The total amount of gases emitted has shown the dependence on the compositions of refractory substrates and the existence of casting slags. Under the investigation of zirconia-carbon refractory, a new phenomenon that the gas generated can push the liquid slags away and minimise the contact of slags and refractory substrates has been proven.

Dans un souci de réduction du volume de déchets nucléaires et de revalorisation des matières combustibles, une stratégie de gestion du combustible des réacteurs à haute température (HTR) est développée dans cette étude. La réduction de volume passe par la séparation des particules TRISO hautement radioactives et du graphite faiblement radioactif (les deux étant réunis dans un assemblage de combustible appelé "compact") tandis que le recyclage total nécessite la séparation du coeur de la particule, valorisable, et de sa gangue, déchet ultime. Les méthodes de séparation doivent préserver l'intégrité des TRISO afin d'empêcher la fuite des radioéléments. Ainsi, le traitement de choc thermique entre l'azote liquide et l'eau chaude permet une division partielle des compacts mais ne permet de récupérer que peu de particules. L'érosion du graphite par jet d'eau à haute pression présente le risque de fracturer les particules. La combustion totale du carbone libère toutes les billes. Le traitement des compacts par les ultrasons dans l'eau érode le graphite en fonction de l'intensité de travail, des direction et distance d'attaque, de la température et du gaz de saturation, nettoyant les particules. L'attaque acide des compacts par un mélange H2O2 + H2SO4 provoque l'intercalation du graphite par l'acide, faisant gonfler la structure et libérant ainsi les billes intactes. Les TRISO d'une part et leurs gangues d'autre part ont ensuite été vitrifiées par frittage de manière à obtenir une forte densité, jusqu'à un taux de 25% vol. Enfin, la lixiviation des composites dans l'eau ultrapure à 90°C montre de fortes propriétés de confinement.

La formation de H2 dans le milieu interstellaire, à partir de deux atomes H, est une question essentielle en astrophysique. Cette réaction exothermique qui a lieu à la surface d'un grain de poussière interstellaire est la première étape d'une suite de réactions primordiales pour la physico-chimie. Dans les nuages diffus et les régions de photodissociation, on invoque pour mécanisme de formation une réaction de catalyse hétérogène Eley Rideal, un des atomes étant chimisorbé. Les grains sont principalement carbonés et constitués notamment de graphite. Les travaux théoriques antérieurs effectués en géométrie réduite n'ont pas permis d'expliquer la formation de H2 dans les états rovibrationnels observés (v<5). Pour prendre en compte les degrés de liberté de tous les atomes, nous avons conçu à partir du potentiel de Brenner, un nouveau potentiel pour modéliser le système graphène-H-H avec lequel nous avons réalisé une étude de dynamique moléculaire classique de la formation de H2. Cette étude a été effectuée pour des énergies de collision d'atomes H incidents de 0.015eV à 0.2eV et pour des surfaces à 0, 10 et 30K. Un des résultats principaux est que la section efficace de réaction est directement reliée à l'allure du potentiel que voit l'atome H incident. De plus, il a été mis en évidence que la distribution rovibrationnelle obtenue en autorisant la relaxation de la surface correspond mieux à celle observée par les astrophysiciens (v < 6), la surface absorbant ~25% de l'énergie disponible. Des travaux étudiant l'influence de la présence d'un atome H supplémentaire sur la surface ou d'une possible structure poreuse des grains, sur la formation de H2, sont présentés en annexe.

Dans cette thèse le magnétotransport à basse température (T = 10 mK) et l'effet de Haas-van Alphen sont examinés pour le graphite naturel et le graphite HOPG. Dans la première partie, le magnétotransport au champ magnétique jusqu'à B = 11 T est présenté. Une analyse de Fourier du signal après soustraction du fond de magnétorésistance montre que le transport électrique dans le graphite est dominé par deux types de porteurs avec des fréquences et phases en accord avec le modèle SWM. Nous confirmons la validité du modèle SWM par des calculs détaillés de la structure de bande en champ magnétique. Le mouvement de l'énergie de Fermi pour B > 2 T est calculé d'une manière auto-cohérente en supposant que la somme des concentrations des électrons et des trous est constante. Des mesures sous champs magnétiques intenses (0 < B < 28 T) sont employées pour étudier l'effet Zeeman et la phase de l'onde de densité de charge. En ce qui concerne l'effet Zeeman, les calculs SWM incluant le mouvement de l'énergie de Fermi nécessitent un facteur de Lande g = 2.5 pour reproduire la séparation de spin des motifs dans les données. Les mesures de l'onde de charge de densité confirment que le champ magnétique auquel l'onde de charge de densité apparait est lie a la température par une formule de type Bardeen-Cooper-Schrieffer (BCS). Des mesures de l'effet de Haas-van Alphen confirment les résultats obtenus par de magnétotransport à bas champ.

Dans cette thèse le magnétotransport à basse température (T = 10 mK) et l'effet de Haas-van Alphen sont examinés pour le graphite naturel et le graphite HOPG. Dans la première partie, le magnétotransport au champ magnétique jusqu'à B = 11 T est présenté. Une analyse de Fourier du signal après soustraction du fond de magnétorésistance montre que le transport électrique dans le graphite est dominé par deux types de porteurs avec des fréquences et phases en accord avec le modèle SWM. Nous confirmons la validité du modèle SWM par des calculs détaillés de la structure de bande en champ magnétique. Le mouvement de l'énergie de Fermi pour B > 2 T est calculé d'une manière auto-cohérente en supposant que la somme des concentrations des électrons et des trous est constante. Des mesures sous champs magnétiques intenses (0 < B < 28 T) sont employées pour étudier l'effet Zeeman et la phase de l'onde de densité de charge. En ce qui concerne l'effet Zeeman, les calculs SWM incluant le mouvement de l'énergie de Fermi nécessitent un facteur de Lande g = 2.5 pour reproduire la séparation de spin des motifs dans les données. Les mesures de l'onde de charge de densité confirment que le champ magnétique auquel l'onde de charge de densité apparait est lie a la température par une formule de type Bardeen-Cooper-Schrieffer (BCS). Des mesures de l'effet de Haas-van Alphen confirment les résultats obtenus par de magnétotransport à bas champ.

<p>The formation of surface films on electrodes in contact with non-aqueous electrolytes in lithium-ion batteries has a vital impact on battery performance. A basic understanding of such films is essential to the development of next-generation power sources. The surface chemistry, morphology and thermal stability of two typical anode and cathode materials, graphite and LiNi_0.8Co_0.2O₂, have here been evaluated by X-ray photoelectron spectroscopy (XPS), X-ray diffraction, scanning electron microscopy and differential scanning calorimetry, and placed in relation to the electrochemical performance of the electrodes. </p><p>Chemical and morphological information on electrochemically formed graphite surface films has been obtained accurately by combining XPS measurements with Ar⁺ ion etching. An improved picture of the spatial organisation, including thickness determination of the surface film and characterisation of individual component species, has been established by a novel sputtering calibration procedure. The stability of the surface films has been shown to depend strongly on temperature and choice of lithium salt. Decomposition products from elevated-temperature storage in different electrolyte systems were identified and coupled to effects such as capacity loss and increase in electrode resistance. Different decomposition mechanisms are proposed for surface films formed in electrolytes containing LiBF₄, LiPF₆, LiN(SO₂CF₃)₂ and LiCF₃SO₃ salts.</p><p>Surface film formation due to electrolyte decomposition has been confirmed on LiNi_0.8Co_0.2O₂ positive electrodes. An overall surface-layer increase with temperature has been identified and provides an explanation for the impedance increase the material experiences on elevated-temperature storage. </p><p>Surface phenomena are clearly major factors to consider in selecting materials for practical Li-ion batteries.</p>

Several methods have been developed previously for estimating cumulative energy production and plutonium production from graphite-moderated reactors. The Graphite Isotope Ratio Method (GIRM) is one well-known technique. This method is based on the measurement of trace isotopes in the reactor’s graphite matrix to determine the change in their isotopic ratios due to burnup. These measurements are then coupled with reactor calculations to determine the total plutonium and energy production of the reactor. To facilitate sensitivity analysis of these methods, a one-group cross section and fission product yield library for the fuel and graphite activation products has been developed for MAGNOX-style reactors. This library is intended for use in the ORIGEN computer code, which calculates the buildup, decay, and processing of radioactive materials. The library was developed using a fuel cell model in Monteburns. This model consisted of a single fuel rod including natural uranium metal fuel, magnesium cladding, carbon dioxide coolant, and Grade A United Kingdom (UK) graphite. Using this library a complete sensitivity analysis can be performed for GIRM and other techniques. The sensitivity analysis conducted in this study assessed various input parameters including 235U and 238U cross section values, aluminum alloy concentration in the fuel, and initial concentrations of trace elements in the graphite moderator. The results of the analysis yield insight into the GIRM method and the isotopic ratios the method uses as well as the level of uncertainty that may be found in the system results.