Orientador: Ines Joeks / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-11T21:07:38Z (GMT). No. of bitstreams: 1 Lage_EulerMartins_D.pdf: 1438659 bytes, checksum: 1425117a8c06f2ba303a23663ae033c4 (MD5) Previous issue date: 2002 / Resumo: Neste trabalho estudou-se o transporte de CO2 através da interface água-ar e a sua difusão na água, a partir de experimentos simples e de baixo custo, em escala laboratorial. Para este estudo foram utilizadas soluções aquosas de diferentes salinidades (0, 10, 30 e 65 g/kg), a diferentes temperaturas (25 e 40 °C). Para a determinação da concentração de CO2 dissolvido, adicionou-se indicadores ácido-base. Foram obtidas imagens das soluções a diferentes tempos após o início da difusão. As imagens foram digitalizadas e tratadas com rotinas desenvolvidas utilizando-se o software Matlab. Técnicas de calibração multivariada foram usadas para construir a escala de pH x cor, a partir de curvas de calibração construídas para cada condição experimental. Construiu-se também subrotinas para o cálculo de variogramas e a partir desses calculou-se a dimensão fractal de algumas imagens. Em ensaios iniciais, provou-se que os resultados de velocidade de difusão estão de acordo com a literatura. Nos ensaios definitivos observou-se que os padrões da difusão do CO2 foram reprodutíveis. Ensaios realizados numa cuba retangular em ausência de turbulência mostraram dois padrões de difusão do CO2. Em todas as salinidades, a 40°C e a 25°C com salinidade 65g/kg, o padrão de difusão mostrou uma frente que se desloca de uma maneira regular, na forma de uma cortina. Nas outras condições, a difusão se processa na forma de viscous fingers, caótica e irregular. A salinidade de 65 g/kg proporcionou uma diminuição significativa na velocidade de difusão para ambas as temperaturas. Os resultados foram interpretados em termos da quantidade de CO2 dissolvido, que é maior no segundo caso, e em termos da viscosidade das soluções, que é menor a menor salinidade. Em outro capítulo, estudou-se o fluxo de CO2 e outros gases causadores de efeito estufa (CH4 e N2O) em amostras de pântanos, variando-se a temperatura e a concentração atmosférica de CO2. Os experimentos de medida do fluxo destes gases apresentaram como resultados mais importantes a extrema variabilidade dos valores de fluxo de CH4 e o fato de só se obter uma relação estatisticamente significante entre a produção de CO2 a concentração desse gás na atmosfera / Abstract: In this work CO2 transport through the interface water-air and its diffusion in water, using simple and low cost experiments, in laboratorial scale was studied. Aqueous solutions of different salinities (0, 10, 30 and 65 g/kg) and temperatures (25 and 40° C) had been studied. In order to determinate dissolved CO2 acid-base indicator was added to the solution. Diffusion images were recorded by VHS camera. The images had been digitalized and treated with routines developed using Matlab software. Techniques of multivaried calibration were used to elaborate the pH x color scale from constructed curves of calibration for each experimental condition. It was also constructed subrotines for the calculation of variograms and from them it was calculated the fractal dimension of some images. CO2 diffusion rates obtained in initial assays are in accordance with literature values. In the definitive assays it was observed that the diffusion pattern of CO2 had been reproducible. Assays carried out using a rectangular vessel without turbulence showed two pattern of CO2 diffusion. To all studied salinities, at 40°C and at 25°C with salinity 65 g/kg, the diffusion pattern showed a front that dislocates in a regular way, like a curtain. In the other conditions, the diffusion was chaotic and irregular presenting structures like viscous fingers. The salinity of 65 g/kg provided a significant reduction in the speed of diffusion for both temperatures. The results had been interpreted in terms of the amount of dissolved CO2, that is higher for the second pattern of diffusion and in terms of solutions viscosity, which is proportional to salinity. In another chapter, it was studied the CO2 flow and other greenhouse gases (CH4 and N2O) in wetlands samples, varying its temperature and the atmospheric CO2 concentration. The most relevant results in these measure of the gases flow are the extreme variability of values of CH4 flow. The unique achieved statistically significant obtained relationship was between CO2 production and the concentration of this gas in the atmosphere / Doutorado / Físico-Química / Doutor em Ciências

A numerical model for describing the kinetics of intracellular water transport during cryopreservation was developed. As ice is formed outside the cell, depleting the extracellular liquid of water, the cell will experience an osmotic pressure difference across its membrane, which causes cell dehydration and concomitant shrinkage. Although Mazur (1963) has previously modeled this phenomenon as a two-compartment system with membrane limited transport, the assumption of well-mixed compartments breaks down at large Biot numbers. Therefore, we have developed a numerical solution to this moving-boundary problem, including diffusive transport in the intracellular liquid, in addition to the osmotically driven membrane flux. Our model uses a modified Crank-Nicolson scheme with a non-uniform Eulerian-Lagrangian grid, and is able to reproduce predictions from Mazurs model at low Biot numbers, while generating novel predictions at high Biot numbers. Given that cell damage may result from excessive water loss, our model can be used to predict freezing methods that minimize the probability of cell injury during the cryopreservation process.

Conselho Nacional de Desenvolvimento Científico e Tecnológico / The study of concrete structures durability necessarily passes by the study of covercrete and by the understanding of the factors that affect the features of this superficial layer. The use of high contents of mineral addictions on the concrete influences meaningfully the resistance of the covering layer to the chemical attack and on the pores structure. This dissertation aimed to analyze, through the obtained results in the tests of capillary water absorption, according to the RILEM TC 116 PCD Recommendation, and to the diffusion of water held following the directives DAN et al (1988) presented by Isaia (1995), based on publications of CSTB, the percolation of water on concrete covering layer, besides co-relating with the resistance to 50 MPa, the total volume of intruding mercury and the critical diameter of the pores. To these analysis perform, prototypes specimens of 75 cm x 20cm x 15cm have been molded with high contents of mineral additions, 70 % of slag and 20% of fly ash, in replacement to the cement mass, with or without addition of 20% of hydrated lime, in mass, and w/cm relationships 0,3 ; 0,4 ; 0,5 besides the reference mix proportion, only with cement and w/cm relationships 0,4; 0,6 e 0,8. The tests of capillary absorption and water diffusion were held, on the 91 and 300 days to execute the comparative study between these two ages, extracted specimens of 10 cm x 20 cm, from the prototypes had been accomplished, being closed to 0, 2,5 e 5,0cm of depth from the surface. After performing the analysis, it has been noticed that the replacement of cement by mineral additions causes a strength reduction to the compression, being it more accentuated in the initial ages and eased as the time passes by. In relation to the coefficients of water absorption and diffusion of the concretes with mineral additions compared to the reference concretes in equality of w/cm and ages, being analyzed the use of additions, meaningful reductions that get to 79% in the absorption and 69% in the diffusion, on the 300 day. When analyzed considering the depth (in equality of w/cm) the layer reduction 3 (5cm) in relation to 1(0,5cm) gets to 55% in the absorption and 31% in the diffusion, on the 300 day, and in the mix proportion with addition of hydrated lime, justifiable by the fact of the hydrated lime stored water helping in the hydrating process producing a more compact matrix. In equality of 50 Mpa compressive strength, the reductions are 86% to the absorption and 70% to the diffusion. It s been noticed, as to the absorption as to the diffusion, a strong co-relation with the intruding total volume and the pores diameter on the 300 day. / O estudo da durabilidade das estruturas de concreto passa, necessariamente, pelo estudo do concreto de cobrimento e pelo entendimento dos fatores que afetam as características dessa camada superficial. O uso de altos teores de adições minerais no concreto influencia significativamente a resistência da camada de cobrimento ao ataque químico e a estrutura dos poros. Esta dissertação tem por objetivo analisar, através dos resultados obtidos nos ensaios de absorção capilar de água, conforme a norma RILEM TC-116 PCD, e de difusão de água, realizado seguindo as diretrizes de Dan et al (1988), apresentadas por Isaia (1995), baseadas em publicações de CSTB, a percolação de água na camada de cobrimento do concreto, além de correlacionar com a resistência a 50 MPa , o volume total de mercúrio intrudido e o diâmetro crítico dos poros. Para realização dessas análises, foram moldadas peças protótipos de 75 cm x 20 cm x 15 cm, que permaneceram em exposição ambiental até a data de realização dos ensaios. Os protótipos foram moldados com altos teores de escória, 70% e cinza volante 20%, em substituição à massa de cimento, com e sem adição de 20% de cal hidratada, em massa, e uma relação a/mc 0,3, 0,4, 0,5, além do traço de referência, somente com cimento e relação a/c 0,4; 0,6 e 0,8. Os ensaios de absorção capilar e de difusão de água foram realizados aos 91 e 300 dias. Para executar o estudo comparativo entre essas duas idades, foram extraídos testemunhos 10 cm x 20 cm dos protótipos sendo cerrados a 0, 2,5 e 5,0 cm de profundidade a partir da superfície. Após a realização das análises, observou-se que a substituição de cimento por adições minerais acarreta uma diminuição na resistência à compressão, sendo mais acentuada nas idades iniciais e amenizada com o passar do tempo. Em relação aos coeficientes de absorção e de difusão de água dos concretos com adições minerais, comparados com os concretos de referência, em igualdade de a/mc e idades analisadas, o uso de adições resultou em significativas reduções nesses coeficientes, que chegam a 79% na absorção e de 69% na difusão, aos 300 dias. Quando analisados em função da profundidade (em igualdade de a/mc), as reduções da camada 3 em relação à camada 1 chegam a 55% na absorção e 31% na difusão, aos 300 dias e nos traços com adição de cal hidratada. Esse comportamento é justificável pelo fato de a cal hidratada armazenar água auxiliando nos processos de hidratação, produzindo uma matriz mais compacta. Em igualdade de resistência, as reduções são de 86% para a absorção e de 70% para a difusão. Observa-se, tanto para a absorção como para a difusão, uma forte correlação com o volume total intrudido e o diâmetro dos poros aos 300 dias.

The translational self-diffusion, the librations, and the reorientational motions of guest water molecules in the zeolite chabazite are examined by Molecular Dynamics (MD) computer simulations at different temperatures and loadings, including at room temperature, at which the experiments are carried out. Satisfactory agreement is found between the computed and measured translational self-diffusion coefficients. It is, however, furthermore found that the way in which the long-range electrostatic interactions are computed has an effect on the self-diffusion at high loadings and temperatures. The spectral densities of the librational motions of water are found to be similar to those in aqueous salt solutions. The reorientations of the water molecules, on the other hand, are much slower than in the liquids, and very anisotropic. The vector in direction of the molecular dipole moment reorients only very slowly, at the time scale of the simulations, due to the attraction to the almost immobile Ca++-ions and the walls of the zeolite. The other two vectors seem to undergo jump-reorientations rather than reorientations by a diffusion process. Hyper dynamics boost potential method has been applied to the MD simulations to estimate the self-diffusion coefficients of Ca++ ions in dehydrated chabazite. Because of our system is very complicated, the self-diffusion of Ca++ ions can only be roughly estimated. The Ca++ ions diffusion is small enough to confirm that the cation motion can be neglected in the normal MD simulation.

Aim of this study was to describe capillary water and vapor transport in shallow subsurface of Hrubá Skála sandstone in the Bohemian Paradise. I have quantified permeability of Hrubá Skála sandstone for water vapor using "wet cup" method and also capillary water absorption of sandstone drill cores. I have found out general rules of evaporation and rate of evaporation from several sandstone outcrops in real microclimate. Important part of my work was to determine whether surface crust plays some role in studied parameters. Based on my results, permeability of different types of sandstones for water vapor does not vary significantly and surface crust has no effect on rate of water vapor diffusion. Rate of capillary water absorption is reduced by surface crust. Hrubá Skála sandstone is classified as medium or highly absorbing material. I have proved that evaporation from porous medium can be approximated by exponential function. Rate of evaporation is strongly controlled by climatic conditions, especially by relative humidity. Powered by TCPDF (www.tcpdf.org)

In thesis is dealt with problematic of how the value of air permeability may be affected by properties for water vapour diffusion with regard to OSB material There were chosen two main brands of OSB at Czech trade market Two specimens of OSB with different thickness were chosen for each brand. As a first the specimens were tested for air tightness to work out a value of air permeability for each specimen. Afterwords, the testing was conducted for gaining properties of water vapour diffusion on each specimen. As a final assessment was analysed the impact of properties of water vapour diffusion on the air tightness for each specimen. The general meaning of gaining higher air tightness with higher water vapour resistance was proved . It was shown that with raising thickness is usually gotten higher value of water vapour diffusion resistance. However it could not mean getting high air tightness. The crucial parameter is the quality of the material for gaining higher resistance against water vapour diffusion as well as for higher airtightness.