Dissertação(mestrado) - Universidade Federal do Rio Grande, Programa de Pós-Graduação em Engenharia Oceânica, Escola de Engenharia, 2010. / Submitted by Lilian M. Silva (lilianmadeirasilva@hotmail.com) on 2013-04-18T00:14:42Z No. of bitstreams: 1 Comportamento Dos Perfis De Cloreto Em Tetrápodes Localizados Nos Molhes Da Barra. (Rio Grande – RS –. Brasil)..pdf: 8213108 bytes, checksum: 3de71990a8d41cc4d48f12c77b892ecb (MD5) / Approved for entry into archive by Bruna Vieira(bruninha_vieira@ibest.com.br) on 2013-06-10T18:28:50Z (GMT) No. of bitstreams: 1 Comportamento Dos Perfis De Cloreto Em Tetrápodes Localizados Nos Molhes Da Barra. (Rio Grande – RS –. Brasil)..pdf: 8213108 bytes, checksum: 3de71990a8d41cc4d48f12c77b892ecb (MD5) / Made available in DSpace on 2013-06-10T18:28:50Z (GMT). No. of bitstreams: 1 Comportamento Dos Perfis De Cloreto Em Tetrápodes Localizados Nos Molhes Da Barra. (Rio Grande – RS –. Brasil)..pdf: 8213108 bytes, checksum: 3de71990a8d41cc4d48f12c77b892ecb (MD5) Previous issue date: 2010 / A vida útil de estruturas de concreto armado tem sido motivo de preocupação entre os diversos pesquisadores da área. Com o objetivo de melhor compreender o comportamento de uma estrutura de concreto armado, exposta ao ambiente marítimo, foi realizada uma avaliação dos tetrápodes dos molhes da Barra do Rio Grande à 5 anos de exposição (Guimarães, 2003) com a retirada de amostras e o traçado dos perfis de cloreto. Após essa avaliação, fora identificado um alto teor de cloretos no interior dos tetrápodes, que atribui-se a uma possível contaminação desses elementos durante a sua confecção. O presente trabalho teve com o objetivo avaliar o desempenho dos tetrápodes quanto a penetração de íons cloreto ao longo do tempo, e para tal foi realizada uma comparação entre os perfis de cloreto aos 5 anos e aos 9,5 anos. Com as equações de Cranck (1975) foi obtido um modelo no qual se considerou a variação da concentração de cloretos na superfície (Cs), pois esse parâmetro aumentou significativamente dos 5 para 9,5 anos. O referido modelo apresentou bons resultados, pois os perfis estimados demonstraram semelhança com os perfis de medição de cloreto dos tetrápodes, principalmente na idade de 9,5 anos e com o uso de keq, demonstrando a importância de sua aplicabilidade na prática. A partir do coeficiente de difusão estimado aos 9,5 anos, obteve-se os perfis de cloreto para Cs fixo de 0,588 %, aos 50 anos, aos 100 anos e aos 200 anos. De posse dos coeficientes de difusão aos 9,5 anos e com o uso de k e keq, foi estimado o grau de saturação, a partir de uma comparação com o estudo de Rodrigues (2009). Para confirmar o alto GS estimado para o ponto MLOI, foi realizado ensaio de GS dia nos tetrápodes. Os resultados foram satisfatórios e apresentaram coerência com as estimativas. Enfim, os ambientes dos tetrápodes demonstraram grande agressividade com altos teores de cloreto em profundidades consideráveis. Portanto, para o caso de uma estrutura de concreto armado, inserida em ambiente semelhante aos tetrápodes, não só as recomendações da NBR 6118/2003 são suficientes para garantir a durabilidade da estrutura, principalmente no que se refere ao cobrimento do concreto, devendo principalmente ser considerado o tipo de cimento a ser utilizado. / The useful life of structures made of reinforced concrete has been a matter of concern to researchers in this field. An evaluation of the tetrapods at the jetties located in Rio Grande, RS, was carried out after their five-year exposure to a marine environment (Guimarães, 2003)with the aim of understanding the behavior of a structure made of reinforced concrete under such conditions. Samples were collected and the chloride profiles were executed. After this evaluation, a high concentration of chloride was found in the interior of the tetrapods; this fact may be attributed to contamination during their manufacturing. This paper aims at evaluating the behavior of tetrapods regarding the penetration of chloride ions throughout some time. Therefore, a comparison between the chloride profiles at the age of 5 and at the age of 9.5 was made. Cranck’s equations (1975) led to a model in which the variation of the surface chloride concentration (CS) was taken into account, since this parameter has significantly increased from 5 year-old tetrapods to 9.5 year-old ones. This model showed good results: the estimated profiles were similar to the measurement profiles of the chloride of the tetrapods, mainly at 9.5 and with the use of keq. This is an evidence of the importance of its practical applicability. Based on the diffusion coefficient which was estimated for 9.5 year-old tetrapods, 0.588% was obtained as a fixed profile of CS at 50, 100 and 200 years old. Based on the diffusion coefficients at 9.5 and with the use of k and keq, the saturation degree (SD) was estimated after a comparison with Rodrigues’ study (2009). To confirm the high SD which was estimated for the MOIL point, a SDday test was carried out with the tetrapods. Results were satisfactory and coherent with the estimates. Finally, the environment, in which the tetrapods were, showed a high level of aggressiveness with high concentration of chloride at considerable depths. Therefore, in the case of a structure made of reinforced concrete which is an environment that is similar to the one in which tetrapods are, the NBR 6118/2003 recommendations alone are not enough to assure the durability of the structure, mainly regarding the concrete cover, i.e., the type of cement must also be chosen accordingly.

Nanostructured materials especially, one-dimensional (1D) nanostructures have unique physical, chemical, mechanical properties and are the building blocks for a range of nanoscale devices. The procedure employed for the synthesis of nanostructures involves the use of sophisticated instruments or rigorous chemical reactions. The motivation of our work is to develop a strategy that is simple, cost effective and applicable to a host of oxide materials. Nanostructures of various oxides have been grown from the metal as the source material. 1D ZnO nanostructures have been obtained by simply heating Zn metal in ambient air at temperatures below 600 °C. The nanostructures grow on the surface of the source material and the morphology is controlled by monitoring the curvature of the source material. This technique has an added advantage that neither any catalyst nor any gas flow is required. Tetrapods of ZnO are obtained when Zn is heated above 700 °C in ambient air. It has been shown that the morphology and the aspect ratio (length-to-diameter ratio) of the tetrapods depend on the temperature and the temperature gradient. Photoluminescence studies reveal good optical quality ZnO nanostructures. The technique employed to synthesize 1D ZnO nanostructures has been checked for other oxides. The temperature required for the synthesis of Ga2O3 nanostructures is 1200 °C. Many researchers have shown that Ga2O3 emits in the blue-green region. A red emission is required to get the impression of white light which has been seen for nitrogen doped Ga2O3. As the temperature is very high and Ga is heated in ambient air, unintentional nitrogen doping of 1D Ga2O3 nanostructures is obtained which is the reason for white light emission. The morphology of Ga2O3 nanostructures has been controlled by monitoring the curvature of the starting material as is the case of ZnO. Similar technique has also been employed for the synthesis of CuO nanostructures. The morphology is temperature dependent and 1D CuO nanostructures are obtained when the synthesis temperature is between 400 and 600 C. Possible growth mechanisms have been proposed for all these oxide materials. The entire thesis is based on the results discussed above. It has been organized as follows: Chapter 1 deals with the introduction to nanostructures, importance of 1D nanostructures, the specific applications of different morphologies, materials that are widely explored in the synthesis of nanostructures and different approaches to the synthesis of nanostructures. Growth mechanisms like VLS, VS and SLS are briefly discussed. A brief review on the basic physical properties, applications and different morphologies of ZnO, Ga2O3 and CuO is outlined with emphasis to the various synthesis techniques. Finally the aim and scope of the present work is discussed. Chapter 2 describes the experimental setup used for the synthesis and the basic principles of characterization techniques like x-ray diffraction (XRD), scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), energy dispersive spectrum (EDS), electron energy loss spectroscopy (EELS), photoluminescence (PL), Raman spectroscopy, x-ray photoelectron spectroscopy (XPS), UV-Visible spectroscopy, Fourier Transform Infrared Spectroscopy (FTIR) and thermogravimetric analysis (TGA). Chapter 3 deals with the synthesis of 1D ZnO nanostructures with different morphologies such as nanoneedles, nanorods, nanobelts from Zn powder/granule. The growth process is found to be different from the conventional VS mechanism. The advantage and the versatility of the method is emphasized. In this method, neither a catalyst nor any gas flow is required for the synthesis of oxide nanostructures. Depending upon the Zn powder or Zn granules as the starting material different nanostructures of ZnO have been synthesized. The as-synthesized materials are characterized by XRD, SEM, HRTEM, EDS, TGA and Raman spectroscopy and the results are discussed. Chapter 4 describes the controlled growth of ZnO tetrapods and the influence of temperature and temperature gradient on the growth process. Though there are several methods to synthesize ZnO tetrapods and it has been established that ZnO tetrapods can be synthesized by heating Zn in air, it is advantageous to grow tetrapods of different morphologies with different lengths. The large scale synthesis of ZnO tetrapods by heating Zn in air ambient is discussed in this chapter. The key parameters that control the diameter, length, and morphology of tetrapods are identified. It is shown that the morphology and dimensions of the tetrapods depend not only on the vaporization temperature but also on the temperature gradient of the furnace. The influence of vaporization temperature and growth temperature on the morphology of the tetrapods is discussed elaborately. Chapter 5 explains the one-step synthesis of nitrogen doped Ga2O3 nanostructures of different morphologies and the different growth mechanisms. The experimental method employed for the synthesis of nanostructures is simple and is different from the other reported methods. Neither any catalyst/substrate preparation nor any gas flow is required for the synthesis of Ga2O3 nanostructures. The synthesis involves the heating of molten Ga at high temperatures. Single crystalline monoclinic phase of nitrogen-doped Ga2O3 nanorods, nanobelts and nanoneedles are obtained by this method. The morphology is controlled by monitoring the curvature of the Ga droplet which is achieved by using different substrates. Possible growth processes of different morphology have been proposed. Chapter 6 includes some surprising results on the white light emission of Ga2O3 nanorods. High synthesis temperature generates a high vapor pressure suitable for the growth of Ga2O3 nanorods, creates oxygen vacancy and incorporates nitrogen from the ambient. The oxygen vacancy is responsible for the bluish-green emission, while nitrogen is responsible for the red emission. As a consequence, white light emission is observed from Ga2O3 nanorods when irradiated with UV light. The interesting point is that neither post-treatment of the nanorods nor size control is required for white light emission. Chapter 7 describes the synthesis of CuO nanostructures by heating Cu foil in air ambient. This is an attempt to check whether the synthesis technique employed for ZnO and Ga2O3 is applicable to other oxides. The as-synthesized CuO nanostructures are characterized by XRD, SEM, HRTEM, EDS, TGA, UV-visible, FTIR and the results are discussed. Chapter 8 gives the conclusions and the overall summary of the thesis.

Made available in DSpace on 2014-07-29T16:21:17Z (GMT). No. of bitstreams: 1 TESE JULIO COLA ROVIDA.pdf: 491833 bytes, checksum: 38ea9a7ec6fd58dba6680dfa971676e6 (MD5) Previous issue date: 2011-02-18 / The current rate of extinctions observed in the entire planet has its origin in high rates of habitat loss due to human population increase. The species-area relationship may be usefull in predicting extinction threats when combined with this loss. Lists of Cerrado s tetrapods were compiled and using the species-area relationship, we predicted values of species a threat. These values were compared with the IUCN Red List. The predictions of threat in all cases were higher than the Red List, except for endemic mammals that reflect the current threat list, and endemic birds whose predictions are lower than the threat level by IUCN. A large portion of species have populations in decline according to IUCN. Part of these results can be explained by a time-lag in the response time to the degradation itself associated with the gaps of knowledge about the species. The relationship could be used as a preliminary threat assessment, and followed by the aggregation of these red lists in order to increase efficiency in conservation planning. Life history, spatial and environmental heterogeneity data, when aggregated, should increase the prediction s accuracy. Major investments in basic biology are necessary in order to achieve maximum information input about the species to be evaluated. / A atual taxa de extinções observadas em todo planeta tem sua origem nas altas taxas de perda de habitat em decorrência do aumento populacional humano. A relação espécies-área pode ser útil na predição de ameaças de extinção quando associada a essa perda. Compilamos listas de tetrápodes do Cerrado e usando a relação espécie-área, foram preditos valores (números) de espécies em ameaça. Esses valores foram comparados com a lista vermelha da IUCN. As predições de ameaça em todos os casos foram superiores às da lista vermelha, excetuando-se mamíferos endêmicos que refletem as predições da lista atual, e aves endêmicas cuja predição de ameaça é inferior ao observado pela IUCN. Uma grande parcela de espécies também possui populações em declínio segundo a IUCN. Parte desses resultados seria explicada por um time-lag no tempo de resposta à degradação associada a lacunas de conhecimento acerca das espécies. A relação poderia ser usada como forma preliminar de avaliação de ameaça, e em segundo momento a agregação dessas listas vermelhas deveria ser feita a fim de se aumentar a eficiência no planejamento da conservação. Dados de história de vida, heterogeneidade ambiental e espacial, quando agregados, aumentariam a precisão da predição. Maiores investimentos em pesquisa básica se fazem necessários a fim de se obter o máximo de informações acerca das espécies a serem avaliadas.