No description available.

Bien que la vulcanisation soit un procédé de réticulation très répandu dans l’industrie du caoutchouc, les mécanismes réactionnels mis en jeu, la structure du matériau formé, et en particulier les environnements chimiques du soufre restent mal connus. Sonder sélectivement les environnements chimiques du soufre par Résonance Magnétique Nucléaire (RMN) pourrait alors apporter de précieuses informations sur la structure locale du matériau. Cependant, les propriétés intrinsèques du seul isotope du soufre observable par RMN (33S) rendent l’étude de son environnement chimique très délicate et nécessitent la mise en oeuvre d’une méthodologie adaptée. Les travaux présentés dans ce manuscrit montrent que l’utilisation simultanée de très hauts champs magnétiques et de méthodes d’acquisitions appropriées peut permettre l’étude de l’environnement chimique du soufre dans les solides par RMN. Des calculs premier principe des paramètres RMN ont été menés et leur comparaison à l’expérience montre qu’il est possible de prédire avec fiabilité les paramètres RMN et d’attribuer les signaux observés à une structure chimique. Les positions et les largeurs des signaux RMN de soufre-33 correspondant à des ponts soufrés ont été calculées à partir de modèles structuraux. Pour de tels environnements, les couplages quadripolaires attendus sont particulièrement forts (CQ > 40 MHz), et donnent lieu à des signaux RMN extrêmement larges dont l’observabilité est évaluée via l’étude du soufre élémentaire. Dans le cas d’élastomères vulcanisés, les résultats de cette étude montrent que l’observation de l’ensemble des différents environnements chimiques du soufre nécessite à priori l’utilisation de très hauts champs magnétiques et de très basses températures. / Sulfur vulcanization is a widely used crosslinking process of elastomers in the rubber industry, but the involved chemical mechanisms and the structure of the crosslinked materials are still poorly understood. Nuclear Magnetic Resonance (NMR) spectroscopy, which allows selectively probing the sulfur chemical environments, can provide new information about the local structure of the crosslinked material. However, due to its intrinsic properties, the observation of the NMR active isotope of sulfur (33S) is challenging in solid materials and requires the use of a specific methodology. In this work, we show that the use of very high magnetic fields and convenient NMR methods allows studying the chemical environment of sulfur in solid materials. First principle computations of the NMR parameters have been performed and compared to experimental results. This comparison shows that the computations lead to a reliable prediction of the NMR parameters and can be used to assign the observed NMR signals to a chemical structure. The NMR parameters characteristic of sulfur atoms involved in crosslinks have been computed from structural models. For such sulfur local environments, extremely large quadrupolar coupling constants (CQ > 40 MHz) and thus ultra broad resonances are expected. The NMR detection limit of sulfur environments giving rise to such very broad lines has been investigated through the 33S NMR study of elemental sulfur. In the case of vulcanized rubbers, the results of this work suggest that the NMR observation of the distinct sulfur chemical environments present in the crosslinked networks requires the use of both ultra high magnetic field and very low temperature.

Made available in DSpace on 2016-12-08T17:19:33Z (GMT). No. of bitstreams: 1 Pre-textuais.pdf: 51961 bytes, checksum: 92d8926bfc05a6edbc7684111e97a1d1 (MD5) Previous issue date: 2009-11-03 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This work presents results from an investigation on the potential use of waste vulcanized rubber scrap (WRS) particles as aggregate in construction concretes. The waste rubber scrap used in this study was obtained from the local rubber manufacturing industry. In the preparation of concretes, the Brazilian Standard was followed to achieve the required amounts of natural aggregate and WRS. For the study, mechanical properties along their durability of concrete produced with recycled aggregate were investigated and the results presented. While experimenting with hardened, concrete mixtures were prepared using WRS as the replacement of natural fine aggregate at the level 5%, 10% and 15 vol. % with water/cement ratios of 0.37, 0.45 and 0.55 (weight). The mixtures have been cured for periods of 7, 28 and 90 days. The properties of hardened recycled aggregate concrete were examined: 7-day, 28-day and 90-day compressive strength, water absorption and bulk density were carried out in specimens cured for 28 days. The analysis of the results has been carried out using analysis of variance (ANOVA). Such statistical analysis is discussed against microstructures of some selected samples which were studied using SEM/EDX. Bulk density of concrete was far lower than that of normal crushed aggregate. Although the use of waste vulcanized rubber scrap particles as replacement for the usual natural river sand, a specified 28-day compressive strength (28 MPa) can still be achieved at water/cement of 0.45 and replacement content of 15 vol. %. SEM/EDX analysis results shown that a discontinuity can be observed in the rubber-matrix interface indicating poor adhesion between the rubber particle and the cement paste. In the light of these findings, reusing waste vulcanized rubber scrap particles as aggregates in concrete production is not only a viable solution to the problem of inadequate concrete aggregates but also may help solving a vital environmental issue. / Este trabalho apresenta os resultados da investigação do uso de resíduos particulados de borracha (RPB) como substituinte parcial do agregado miúdo na produção de concretos. O resíduo foi proveniente do recorte de peças e peças com defeitos de fabricação, geradas durante as operações de moldagem, vulcanização e garantia da qualidade de uma indústria de borracha local. Por meio do método de dosagem proposto por Campiteli, foi possível definir os parâmetros de referência para a escolha dos níveis estudados. Foram preparados concretos usando RPB em níveis de 5%, 10% e 15% (em volume), em substituição ao agregado miúdo natural, com os níveis de relação água/cimento de 0,37, 0,45 e 0,55 (em massa), para diferentes traços de agregado/cimento. As misturas foram curadas por períodos de 7, 28 e 90 dias. As propriedades do concreto com RPB avaliadas foram: resistência à compressão após 7, 28 e 90 dias de cura, absorção de água e densidade aparente aos 28 dias de cura. A análise dos resultados foi feita usando ferramentas estatísticas, tais como, teste de hipóteses e análise de variância. Alguns resultados obtidos por meio da análise estatística foram confrontados com uma análise de microscopia eletrônica de varredura (MEV/EDS). A análise do ensaio de resistência a compressão mostrou que a adição de RPB diminui a resistência mecânica dos concretos em todas as idades de cura. A queda de resistência mecânica está relacionada com a microestrutura dos concretos, em conseqüência da maior porosidade na matriz cimentícia dos concretos com RPB, quando comparados aos concretos de referência. Foi possível obter concretos com resistência à compressão após 28 dias de cura de até 28 MPa, utilizando um fator água/cimento de 0,45 (em massa) e 15% em volume de RPB. Esses concretos podem ser usados na construção civil com função estrutural.

abstract: This thesis concerns the flashover issue of the substation insulators operating in a polluted environment. The outdoor insulation equipment used in the power delivery infrastructure encounter different types of pollutants due to varied environmental conditions. Various methods have been developed by manufacturers and researchers to mitigate the flashover problem. The application of Room Temperature Vulcanized (RTV) silicone rubber is one such favorable method as it can be applied over the already installed units. Field experience has already showed that the RTV silicone rubber coated insulators have a lower flashover probability than the uncoated insulators. The scope of this research is to quantify the improvement in the flashover performance. Artificial contamination tests were carried on station post insulators for assessing their performance. A factorial experiment design was used to model the flashover performance. The formulation included the severity of contamination and leakage distance of the insulator samples. Regression analysis was used to develop a mathematical model from the data obtained from the experiments. The main conclusion drawn from the study is that the RTV coated insulators withstood much higher levels of contamination even when the coating had lost its hydrophobicity. This improvement in flashover performance was found to be in the range of 20-40%. A much better flashover performance was observed when the coating recovered its hydrophobicity. It was also seen that the adhesion of coating was excellent even after many tests which involved substantial discharge activity. / Dissertation/Thesis / M.S. Electrical Engineering 2013

Recently high temperature vulcanized (HTV) silicone rubber (SIR) / polymeric/composite insulators are gaining wider acceptance as overhead transmission line insulators for extra high voltage (EHV) and ultra-high voltage (UHV) systems due to some promising features like hydrophobicity recovery, light weight, ease of handling and installation, better pollution ashover performance, admirable resistance against vandalism etc. Since polymeric insula-tors are of recent origin, their long-term eld performance is yet to be understood. Owing to their organic nature, and exposure to environmental stresses like pollution, temperature, UV radiation, humidity, fog, rain etc., the insulator performance degrades over a period. The sheds/petticoats of the insulators become wettable leading to frequent ashover in humid and contaminated environment. Hence, long term reliability of the composite insulators is of foremost concern to the power utilities. The available literature on the long term eld performance of these insulators for di erent climatic conditions and under multiple environ-mental stresses for both the HTV SIR and Liquid Silicone Rubber (LSR) is scant. Also there is no reference standard for evaluation of these insulators for pollution/contamination test methods in the laboratory. However currently, CIGRE Work Group is working towards the standardization of the test methods for arti cial pollution tests for polymeric insulators. The thesis addresses some of the issues in detail. In the first part of the thesis, a new and simple pre-treatment methodology to achieve uniform contamination layer on inherently hydrophobic HTV SIR Insulator samples is presented for laboratory pollution performance evaluation. The surface water level di usion in the dipping period is found to make the insulator surface temporarily hydrophilic. Then the uniform contamination layer is applied by dipping the sample immediately in the pollution slurry. Exhaustive experiments were conducted on full scale SIR insulators as well as SIR slabs to investigate the hydrophilicity appearance on the SIR surface. A specially fabricated arrangement for assessment of Wettability Class (WC) is made as per IEC stds. The results of WC measurement and wet ashover studies support the temporary reduction in hydrophobicity of SIR due to dipping phase in the proposed pre-treatment methodology. The next part of the thesis presents the results for the effeect of long term thermal aging experimentation conducted on HTV SIR with difffeerent degrees of pollution (medium, heavy), the effeect of arid desert climate on polymeric insulators is studied. The experimental set-up consists of controlled HVAC source, temperature controlled furnace with a provision for high voltage (HV) and Leakage Current (LC) monitoring, a Digital Storage Oscilloscope (DSO), compact DAQ-9201 of National Instruments operated in LabVIEW platform etc. Two types of HTV SIR Insulators are considered for the study. Flat slabs as well as full-scale insulator samples of creepage length 725 mm are stressed simultaneously to simulate the in-service condition. The experimentation is conducted for about 575 hours with application of 21.0 kVrms at 60oC. The results of the hydrophobicity recovery for thermally aged contaminated polymeric insulators are reported. Besides, monitoring electrical and mechanical proper-ties, changes in material properties of SIR are also analyzed using Physiochemical analysis techniques like Fourier transform infrared (FTIR) spectroscopy, X-Ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM), Thermo-Gravimetric Analysis (TGA), Differential Scanning Calorimetry (DSC). Some of the key findings of the study are increased surface oxidation, surface roughness and mechanical stress due to thermal aging of polymeric insulators. Experimental investigations show that the characteristics of power frequency component of leakage current can be linked with thermal aging of SIR. Further, a unique climatic aging experimental facility is established to evaluate the long-term reliability of SIR under environmental stresses like UV, Humidity, temperature and applied electric stress. The investigations are conducted on two different types of HTV SIR and LSR at samples as well as full-scale insulator samples. The experimentation is conducted for 500 hours with 10.0 kVrms at 50oC, with 85% humidity and 1 W/m2 UV ir-radiation which is in accordance with the aging cycle specified in IEC standard. The results of the comparative studies conducted for the electrical, mechanical and material properties indicate leakage current pulses, brittleness, Salt deposition for multistress aged samples. In summary, an attempt has been made to contribute a pollution methodology with sim-ple pre-treatment technique for inherently hydrophobic HTV SIR surface to achieve better uniformity of contamination layer. Also, electro-thermal and multiple stresses investigations were conducted for long term performance on polymeric insulators.