Mistura compactada de materiais inconsolidados das formações Serra Geral e Botucatu foram percoladas por soluções com diversas concentrações de K+, Cl- e Cu++, em testes de coluna, para a avaliar a potencialidade da sua utilização como liner. Na modelagem dos resultados adotaram-se resoluções analíticas e semi-analíticas (programa POLLUTE v6). Estudo complementar sobre o comportamento eletroquímico destes solos foi realizado pelos ensaios de titulação potenciométrica, capacidade de tamponamento, pH em água e KCI, CTC e análise mineralógica por difração de Raios-X e térmica diferencial. Os resultados mostraram uma forte influência das características da carga elétrica superficial do solo no comportamento competitivo dos íons. / A compacted mixture of soils from Serra Geral and Botucatu formations were percolated by chemical solutions with several concentrations of K+, Cu++ e Cl-, in column tests, in order to assess the potential of this mixture as a liner-building material. In the modeling procedures for the results, analytical and semi-analytical solutions (POLLUTE v.6 software) were used. Additional studies about the electrochemical behavior of these soils were performed, using potenciometric titration, soil buffer capacity, pH in water and KCI and mineralogical assessment by X-Ray Diffraction and differential thermal analysis. The results showed a very strong influence of the soil superficial charge in the competitive ion behavior.

Orientador: Serguei Popov / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Matemática Estatística e Computação Científica / Made available in DSpace on 2018-08-25T10:22:43Z (GMT). No. of bitstreams: 1 Bernardini_DiegoFernandode_D.pdf: 1410086 bytes, checksum: b77a17aefd06d547f1c5db3c5cc1a8f7 (MD5) Previous issue date: 2014 / Resumo: O modelo de entrelaçamentos aleatórios foi introduzido no sentido de se investigar originalmente o traço deixado por passeios aleatórios em grandes grafos e, basicamente, tal processo é descrito por um processo pontual de Poisson em um espaço de trajetórias duplamente infinitas de passeios aleatórios simples no reticulado d-dimensional, com dimensão d pelo menos igual a três. Neste sentido, o processo é caracterizado por um emaranhado aleatório de trajetórias deste tipo. Tal modelo possui ainda um parâmetro de intensidade, que controla, de certa forma, a quantidade de trajetórias que constituem o processo. Um problema relevante no contexto deste processo, e que tem sido amplamente estudado na literatura, diz respeito à caracterização da relação de dependência (através da covariância) entre os eventos denominados como crescentes neste modelo e suportados em subconjuntos disjuntos do reticulado, e é justamente este o problema no qual nos concentramos. Em uma primeira etapa neste trabalho, determinamos expressões explícitas para a derivada, com respeito ao parâmetro de intensidade, da probabilidade de um evento crescente e suportado em um subconjunto finito do reticulado, estabelecendo assim aquilo que denominamos como a fórmula de Russo para os entrelaçamentos aleatórios. A utilização desta denominação é justificada e motivada pelo amplamente conhecido termo original, que no contexto do modelo usual de percolação estabelece uma expressão para a derivada da probabilidade dos eventos definidos como crescentes naquele modelo. Em seguida, tentamos utilizar este resultado no sentido de estabelecer uma primeira abordagem para o problema da covariância entre os eventos crescentes, e esta investigação é baseada essencialmente em uma observação sobre o número esperado das trajetórias então denominadas como pivotais positivas para o evento de interesse. Por fim, estabelecemos uma nova abordagem para o mesmo problema, utilizando uma construção alternativa do processo de entrelaçamentos baseada na técnica dos soft local times, e investigando uma espécie de pivotalidade conjunta de coleções de excursões das trajetórias dos passeios aleatórios pelos conjuntos nos quais estão suportados os eventos de interesse. Justamente a partir desta abordagem obtemos nosso último resultado sobre a covariância. De forma geral, acreditamos que a investigação e a tentativa de obter uma caracterização cada vez mais precisa para a relação de dependência que mencionamos deve ajudar a entender o processo de entrelaçamentos e suas propriedades de forma cada vez mais clara / Abstract: The random interlacements model was originally introduced in order to investigate the trace left by random walks in large graphs and, basically, such process is described by a Poisson point process in a space of doubly infinite simple random walk trajectories in the d-dimensional lattice, with dimension d at least equal to three. In this sense, the process is characterized by a random tangle of trajectories of this kind. Such model also has an intensity parameter, which controls, in a certain sense, the quantity of trajectories that constitutes the process. A relevant issue in the context of this process, which has been largely studied in the literature, concerns the characterization of the dependence relation (through the covariance) between the so-called increasing events in this model, which are supported on disjoint subsets of the lattice, and this is precisely the issue on which we focus. In a first step in this work, we determine explicit expressions for the derivative, with respect to the intensity parameter, of the probability of an increasing event which is supported in a finite subset of the lattice, thus establishing what we call as Russo¿s formula for random interlacements. The use of this term is justified and motivated by the widely known original term, which, in the context of the usual percolation model, provides an expression for the derivative of the probability of events defined as increasing in that model. Then, we try to use this result to establish a first approach to the problem of the covariance between increasing events, and such investigation is essentially based in a fact about the expected number of the so-called positive pivotal (or plus pivotal) trajectories for the event of interest. Finally, we establish a new approach to the same problem by using an alternative construction of the interlacements process based on the technique of soft local times, and investigating a kind of joint "pivotality" of collections of excursions of the random walk trajectories, through the sets on which the events of interest are supported. From this approach we obtain our last result on the covariance. Overall, we believe that the investigation and the attempt to get an increasingly accurate characterization of the above mentioned dependence relation should help to understand the interlacements process and its properties in an increasingly clear way / Doutorado / Estatistica / Doutor em Estatística

The goal of this thesis is to generate fundamental understandings of charge transport behaviors of composites consisting of garnet structured Al substituted Li7La3Zr2O12 (LLZO) electrolyte and LiCoO2 electrode. In order to take full advantage of all-solid-state batteries, bulk type composite electrodes should be introduced to increase energy and power density. However, the charge utilization of bulk type composite electrodes is quite low. Understanding ionic conduction behavior is, therefore, important for improving the performance of all-solid-state batteries, because ion conduction within solids depends on effective pathways. Electronic conductivity can be easily compensated by adding carbon black, but ionic conductivity can only depend on composites electrode itself. Here, we show that electronic and ionic conductivities of composites consisting of LiCoO2 and Al doped LLZO can be achieved separately. 3D reconstructed image obtained from focused ion beam-scanning electron microscope (FIB-SEM) demonstrates that porosity, percolation, and grain boundaries often play antagonistic roles in controlling the charge transport behaviors in the composite electrodes, resulting in an overall conductivity dominated by electrons. This work suggests an approach to optimize electronic and ionic conductivities for bulk type composite electrodes, which may eventually be utilized in all-solid-state batteries.

abstract: The passivity of metals is a phenomenon of vast importance as it prevents many materials in important applications from rapid deterioration by corrosion. Alloying with a sufficient quantity of passivating elements (Cr, Al, Si), typically in the range of 10% - 20%, is commonly employed to improve the corrosion resistance of elemental metals. However, the compositional criteria for enhanced corrosion resistance have been a long-standing unanswered question for alloys design. With the emerging interest in multi-principal element alloy design, a percolation model is developed herein for the initial stage of passive film formation, termed primary passivation. The successful validation of the assumptions and predictions of the model in three corrosion-resistant binary alloys, Fe-Cr, Ni-Cr, and Cu-Rh supports that the model which can be used to provide a quantitative design strategy for designing corrosion-resistant alloys. To date, this is the only model that can provide such criteria for alloy design.The model relates alloy passivation to site percolation of the passivating elements in the alloy matrix. In the initial passivation stage, Fe (Ni in Ni-Cr or Cu in Cu-Rh) is selectively dissolved, destroying the passive network built up by Cr (or Rh) oxides and undercutting isolated incipient Cr (Rh) oxide nuclei. The only way to prevent undercutting and form a stable protective passive film is if the concentration of Cr (Rh) is high enough to realize site percolation within the thickness of the passive film or the dissolution depth. This 2D-3D percolation cross-over transition explains the compositional dependent passivation of these alloys. The theoretical description of the transition and its assumptions is examined via experiments and kinetic Monte Carlo simulations. The initial passivation scenario of the dissolution selectivity is validated by the inductively coupled plasma mass spectrum (ICP-MS). The electronic effect not considered in the kinetic Monte Carlo simulations is addressed by density functional theory (DFT). Additionally, the impact of the atomic configuration parameter on alloy passivation is experimentally measured, which turns out to agree well with the model predictions developed using Monte Carlo renormalization group (MC-RNG) methods. / Dissertation/Thesis / Doctoral Dissertation Materials Science and Engineering 2020

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第21543号 / 理博第4450号 / 新制||理||1639(附属図書館) / 京都大学大学院理学研究科数学・数理解析専攻 / (主査)准教授 福島 竜輝, 教授 熊谷 隆, 教授 牧野 和久 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DFAM

Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Civil Engineering, 1982. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND ENGINEERING. / Bibliography: leaves 95-96. / by William Kensett Nuttle. / M.S.

Thesis (M.S.)--Massachusetts Institute of Technology, Dept. of Civil Engineering, 1980. / MICROFICHE COPY AVAILABLE IN ARCHIVES AND ENGINEERING. / Bibliography: leaves 163-166. / by Theodore von Rosenvinge IV. / M.S.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第19470号 / 理博第4130号 / 新制||理||1594(附属図書館) / 32506 / 京都大学大学院理学研究科数学・数理解析専攻 / (主査)教授 熊谷 隆, 教授 岡本 久, 教授 小野 薫 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DFAM

Biofuel additives have been designed to reduce vehicular emissions to the atmosphere to limit the effects of greenhouse gases on global climate change. The chemical properties of common biofuel additives exhibit ideal characteristics for use in gasoline and diesel, while limiting emissions from exhaust. As biofuel additives begin to be administered regularly to gasoline and fuel sources, the compounds will appear in spill sites, posing a risk to groundwater sources. The interactions that occur between common biofuel additives and trapped gases below the water table were analyzed in this work to further understand the potential consequences on quasi-saturated groundwater zones. The behaviour of trapped gases contaminated with different biofuel additives were analyzed in laboratory experiments conducted in a two-dimensional flow cell to demonstrate the mechanisms of gas flow through a capillary barrier resulting from modified interfacial properties in the presence of a chemical surfactant. Contamination of gas-fluid interfaces by applied biofuel additives at the pore scale resulted in the breakthrough of gas through the capillary barrier. Gas migration terminated at a critical pool height proportional to the reduction in interfacial tension induced by the administered biofuel additives. To further demonstrate the relationship between interfacial tension and critical gas pool height, an interfacial tension-macroscopic invasion percolation model was developed to simulate the transport mechanisms and behaviours of gas flow when an immobile pool is contaminated with 1-Butanol. The findings in this study provide a fundamental understanding of the mechanisms and behaviours of gas mobilization in the presence of common biofuel additives. / Thesis / Master of Science (MSc) / The use of biofuel additives in gasoline and diesel fuels has become an attractive alternative to fully petroleum-based fuels to reduce the release of vehicular greenhouse gases to the atmosphere. As fuel spills and storage tank leaks continue to be a primary source of groundwater contamination, the appearance of biofuel additives in contaminated systems will appear below the subsurface as they continue to be administered to modern gasoline and diesel fuels. This work investigated the consequences of biofuel contamination of groundwater systems containing gas trapped within pore spaces through the use of laboratory experiments and numerical modelling. Contamination of these systems with different biofuel additives displayed a similar response, in which gas had mobilized from within pore spaces and released to the atmosphere. Mobilization of trapped gas in groundwater can alter the primary hydraulic properties that characterize a particular hydrogeologic system.

Increasing human populations are placing greater strain on water resources, prompting the use of treated wastewater effluent for irrigation in some areas, including the desert regions of the Western United States. To determine the potential effects of using secondary effluent for irrigation, we applied wastewater effluent and irrigation waters to natural and artificially constructed calcareous soils in greenhouse and field lysimeters, and in soil columns. The leachate from one field lysimeter contained increased fecal coliform counts than the effluent. Leachate coliform counts were decreased or not significantly changed in two field lysimeters. Electrical conductivity (EC), sodium adsorption ratio (SAR), chloride and nitrate concentrations also increased significantly in the leachate of the three field lysimeters however. Samples collected from the greenhouse lysimeters showed a significant decrease in all categories except EC, was not significantly changed. Soil column drainage samples showed a decrease in coliform counts, and increase in EC and chloride levels while SAR and nitrate levels varied with clay content. Preferential flow of coliform bacteria and high EC and SAR values could indicate long term effects that may affect the sustainability of the practice.