Ce travail vise à améliorer la description à l'échelle du nanomètre des sols argileux expansifs en utilisant la théorie de la fonctionnelle de densité (DFT). L’eau n’est plus considérée comme un solvant continu mais comme un fluide de molécules polaires individuelles. L'objectif est de reproduire les résultats issus de l'expérience ou de la modélisation numérique tels que la présence de couches d'eau discrètes dans l'espace interfolaire ou la variation de la pression de disjonction avec la distance interfolaire dans le régime de gonflement cristallin. Différents phénomènes physiques de complexité croissante sont successivement étudiés. La taille finie des molécules d'eau est tout d'abord prise en compte en modélisant l'eau comme un fluide de sphères dures traité par la théorie fondamentale de la mesure. La nature polaire du solvant est ensuite implicitement considérée en utilisant un potentiel intermoléculaire de Lennard-Jones pour reproduire les différents types d'interactions de Van der Waals. La nature dipolaire de l'eau est ensuite explicitement modélisée par un fluide dipolaire de sphères dures. Ces deux derniers modèles utilisent une approche perturbative de la théorie de la fonctionnelle de densité dans laquelle les effets de corrélation entre les molécules du fluide sont incorporés. Les ions sont finalement ajoutés afin de compléter la description de la double couche électrique. En vue d'une application au génie civil, l'expression améliorée de la pression de disjonction à l'échelle nanométrique est incluse dans une forme modifiée du principe de Terzaghi appliqué aux argiles expansives non-saturées récemment développée dans notre groupe afin de simuler numériquement le comportement hydro-mécanique des argiles gonflantes lors d’essais d'infiltration d’eau / This work aims at improving the nanoscale description of expansive clayey soils using the Density Functional Theory (DFT). Water is no longer considered as a continuous solvent but as a fluid of individual polar molecules in order to recover existing experimental and modeling results such as the presence of discrete water layers in the interplatelet space or the variation of the disjoining pressure with the interplatelet distance at low hydration level. Different physical phenomena of increasing complexity are successively considered. The finite size of the water molecules is firstly taken into account by modeling water as a Hard Sphere fluid using the Fundamental Measure Theory. The polar nature of the water solvent is then implicitly taken into account through a Lennard-Jones potential averaging the different types of Van der Waals interactions. Next the polar nature of the solvent is explicitly modelized by considering water as a Dipolar Hard Sphere fluid. These two fluid models are studied in the framework of the Density Functional Perturbation Theory in which correlation effects between the fluid molecules are incorporated. Ions are finally added in order to complete the Electrical Double Layer description at the nanoscale. With the objective of an application to civil engineering, the improved expression of the disjoining pressure at the nanoscale is included in a modified form of Terzaghi's effective stress principle for unsaturated expansive clays recently developed by our group in order to numerically simulate the hydro-mechanical behavior of expansive clays during water uptake

Ce travail de thèse inclut deux parties : i) l'étude fondamentale de la formation de cristaux zéolithiques ; et ii) la préparation de massifs zéolithiques de taille centimétriques à porosité interparticulaire contrôlée. La première partie de ce travail est donc consacrée à l'étude de l'effet de la microstructure (propriétés physiques et texturales) et de la composition chimique du gel sur la vitesse de nucléation et la taille des cristaux formés. Les résultats de cette étude se résument par le rôle important que joue la composition du gel (plus particulièrement sa concentration en hydroxyde de cation alcalin) sur le degré de polymérisation des particules du gel, la détermination de sa microstructure et par conséquent sur la vitesse de nucléation des zéolithes et la taille des cristaux. Les connaissances acquises dans la première partie ont été utilisées dans le développement du deuxième objective. Notamment, la préparation de massifs zéolithiques de taille centimétrique de types structuraux *BEA et MFI. Le contrôle post-synthèse de la porosité interparticulaire de ces massifs était essentiel pour leur utilisation dans des applications bien précises. A cette fin, une méthode en deux étapes, comportant un assemblage de nanocristaux de zéolithes préformés (en présence ou en absence d'un liant) puis un traitement de croissance secondaire pour l'élimination de la porosité interparticulaire, a été mise en œuvre. Plusieurs traitements de croissance secondaire furent évalués selon le type de zéolithe étudié. Une attention particulière fut accordée à l'étude de l'évolution du liant au cours des processus de préparation et de calcination des massifs zéolithiques. / The present study includes two parts: i) fundamental study of zeolite nucleation-crystal growth mechanism; and ii) preparation of zeolite bodies with controlled interparticle porosity.Thus the first part of the present work deals with the study of the effect of physico-chemical characteristics of initial hydrogel on the nucleation and crystal growth kinetics of zeolite crystals. The obtained data revealed that the concentration of alkali metal hydroxide in the initial system controls the rate of polymerization of the aluminosilicate species, the size of initial gel particles, and the textural properties of the gel. Consequently, the following reaction was to great extent predetermined by the events taking place during mixing the initial reactants.The second part of this work was targeted at the preparation of centimeter-sized zeolite bodies of *BEA- and MFI-type with reduced to minimum inter-particle porosity. A preparation method consisting in assembling of zeolite nanocrystals (with or without a binder) was developed and further optimized. The preformed bodies were subjected to a hydrothermal treatrnent in a fresh zeolite synthesis solution in order to till up the inter-particle porosity. Depending onthe zeolite type, different methods of secondary growth treatrnents were employed. A particular attention has been paid on the study of the binder evolution during the calcination and secondary growth processes.

No description available.

No description available.

Submitted by Erika Demachki (erikademachki@gmail.com) on 2017-04-27T17:01:46Z No. of bitstreams: 2 Tese - Luis Cesar Branquinho - 2014.pdf: 6091709 bytes, checksum: 2c59441af9866c02cd7a2cc3cc667b3e (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2017-05-03T11:40:46Z (GMT) No. of bitstreams: 2 Tese - Luis Cesar Branquinho - 2014.pdf: 6091709 bytes, checksum: 2c59441af9866c02cd7a2cc3cc667b3e (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2017-05-03T11:40:46Z (GMT). No. of bitstreams: 2 Tese - Luis Cesar Branquinho - 2014.pdf: 6091709 bytes, checksum: 2c59441af9866c02cd7a2cc3cc667b3e (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2014-12-09 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Magnetic nanoparticles can generate heat when submitted to alternating magnetic fields of adequate amplitude and frequency. This phenomenon is named magnetic hyperthermia and has several therapeutic applications, as for example, in the treatment of cancer. In general, the theoretical models used to describe this neglect the effect of interparticle interaction. In this thesis we investigate the effect of magnetic dipolar interaction in the magnetothermal efficiency (named specific loss power – SLP) of bicompatible magnetic nanoparticles. Firstly, we develop a chain of magnetic particles model, where we prove that the interaction leads to a contribution to the uniaxial anisotropy. This term in the free energy density allowed us to extract from the electron magnetic resonance technique (EMR) information about the mean chain size in the colloid. Further, this additional magnetic nanoparticle anisotropy term was used to develop an analytical theoretical model that takes into account the effect of the dipolar interaction between nanoparticles to SLP, considering the case where the magnetization responds linearly to the field (Linear Response Theory). Our calculations indicate that depending on the particle parameters, specially the anisotropy, the effect can be to enhance or decrease the heat generation. Moreover, we showed that increasing the chain size (number of particles in the chain) the optimal particle size for hyperthermia can decrease up to 30% in comparison with non-interacting particles. This result has several clinical implications, which allowed us to suggest some strategies for improving the therapeutic efficacy. In order to investigate experimentally the effect, two magnetic fluids, one containing spherical nanoparticles based on manganese ferrite (MnF-citrate) in the superparamagnetic regime, and another commercial one (BNF-starch) magnetite-based with a shape of a parallellepiped and blocked, were selected and deeply characterized. We found a decrease of SLP increasing the chain size for the MnF sample, while for BNF-starch no effect was found at the same experimental conditions. The decrease of SLP in the MnF sample, within the particle concentration range, was explained considering in the model not only the effect in the anisotropy but also by an increase in the damping factor parameter, a term correlated to spin-phonon interaction. Data obtained using EMR and Monte Carlo simulations corroborate our hypothesis. The absence of concentration effect for the BNF sample was attributed to the higher anisotropy value and to the probable influence of brownian relaxation. In addition, the same chain model was used to investigate the behavior of blocked nanoparticles of Stoner-Wohlfarth type. In this case, we demonstrate that the chain formation increases the magnetic hyperthermia, as found in magnetosomes. Finally, we showed that a fluctuation of the dipolar interaction field between particles in the chain, which does not destroy the symmetry of this term, shows a Vogel-Fulcher behaviour in the weak coupling regime. / Nanopartículas magnéticas são capazes de gerar calor quando submetidas a campo magnético alternado de amplitude e frequência adequadas. Este fenômeno é conhecido como magnetohipertermia e possui aplicações terapêuticas como, por exemplo, no tratamento de câncer. Em geral, os modelos teóricos que descrevem o fenômeno não levam em conta efeitos associados à interação partícula-partícula. Nesta tese investigamos o efeito da interação dipolar magnética na eficiência magnetotérmica (SLP) de nanopartículas magnéticas biocompatíveis. Primeiramente desenvolvemos um modelo de cadeia de nanopartículas magnéticas, aonde provamos que a interação entre partículas que formam uma cadeia linear equivalem a uma contribuição uniaxial a anisotropia. Essa contribuição à densidade de energia permitiu que obtivéssemos por meio da técnica de ressonância magnética eletrônica (RME) informações acerca do tamanho médio de aglomerado na suspensão coloidal. Posteriormente utilizamos esse termo adicional da anisotropia efetiva da nanopartícula para propor um modelo teórico analítico que leve em consideração o efeito de tal interação na eficiência de aquecimento de nanopartículas magnéticas em um fluido para o caso em que a magnetização das nanopartículas responde linearmente ao campo (Teoria da Resposta Linear). Nossos cálculos indicaram que, dependendo de parâmetros da nanopartícula, em particular da anisotropia, este efeito pode aumentar ou diminuir a geração de calor. Além disso, mostramos que o aumento do número de partículas formando cadeias lineares reduz o diâmetro ótimo para hipertermia em até 30% em relação ao valor esperado para partículas isoladas. Este resultado possui fortes implicações clínicas, e permitiu que sugeríssemos algumas estratégias para aumentar a eficiência terapêutica. No intuito de investigar experimentalmente este efeito, dois fluidos magnéticos, um contendo nanopartículas esféricas de ferrita de Mn (MnF-citrato) no regime superparamagnético e outra comercial (BNF-starch) à base de magnetita com forma de nanoparalelepípedos e contendo partículas bloqueadas, foram selecionados e amplamente caracterizados. Observamos uma diminuição no SLP com o aumento de partículas na cadeia para a amostra MnF-citrato, para todos os valores de campo, enquanto que para a amostra BNF-starch não percebemos alteração do SLP. O decréscimo do SLP da amostra MnF, na faixa de concentração investigada, foi explicado incluindo não apenas o efeito na anisotropia efetiva, mas também o aumento no valor do fator de amortecimento. Dados de RME e simulação de Monte Carlo corroboraram tal hipótese. A ausência de efeito para amostra BNF-starch foi atribuída à alta anisotropia e provável influência de relaxação browniana. Adicionalmente, o modelo de cadeia foi usado para explicar o comportamento de nanopartículas bloqueadas do tipo Stoner-Wohlfarth. Neste caso demonstramos que a formação de cadeias aumenta a hipertermia magnética, como verificado em magnetossomos. Finalmente, mostramos que uma flutuação no campo dipolar interpartículas na cadeia, que não destrua a simetria desta contribuição, fornece um comportamento do tipo Vogel-Fulcher no regime fracamente interagente.

The first magnetization loop and the first stress–strain cycle of magnetoactive elastomers (MAEs) in a magnetic field differ considerably from the following loops and cycles, possibly due to the internal restructuring of the magnetic filler particles and the matrix polymer chains. In the present study, the irreversible magnetization processes during the first magnetization of MAEs with different filler compositions and tensile moduli of the matrix are studied by first-order reversal curve (FORC) measurements. For MAEs with mixed magnetic NdFeB/Fe fillers the FORC distributions and magnetization distributions of the first major loop reveal a complex irreversible magnetization behavior at interaction fields Hu < −50 kA m−1 due to the magnetostatic coupling between the magnetically hard NdFeB and the magnetically soft Fe particles. This coupling is enhanced either if the interparticle distance is reduced by particle motion and restructuring or by an increase in the particle densities. If the stiffness of the matrix is increased, the structuring and thus the interparticle interactions are suppressed and the magnetization reversal is dominated by domain processes in the NdFeB particles at high coercive fields of Hc > 600 kA m−1.

The first magnetization loop and the first stress–strain cycle of magnetoactive elastomers (MAEs) in a magnetic field differ considerably from the following loops and cycles, possibly due to the internal restructuring of the magnetic filler particles and the matrix polymer chains. In the present study, the irreversible magnetization processes during the first magnetization of MAEs with different filler compositions and tensile moduli of the matrix are studied by first-order reversal curve (FORC) measurements. For MAEs with mixed magnetic NdFeB/Fe fillers the FORC distributions and magnetization distributions of the first major loop reveal a complex irreversible magnetization behavior at interaction fields Hu < −50 kA m−1 due to the magnetostatic coupling between the magnetically hard NdFeB and the magnetically soft Fe particles. This coupling is enhanced either if the interparticle distance is reduced by particle motion and restructuring or by an increase in the particle densities. If the stiffness of the matrix is increased, the structuring and thus the interparticle interactions are suppressed and the magnetization reversal is dominated by domain processes in the NdFeB particles at high coercive fields of Hc > 600 kA m−1.

Concrete, the second most used material in the world, presents great performance and economic benefits. Yet, it is often characterized by a brittle behaviour, low tensile strength, and toughness. Fibers are usually added to concrete to counteract its brittle behaviour, increasing ductility and toughness, controlling crack propagation and delaying concrete failure. However, their addition significantly worsens the fresh state performance of the material. To improve fresh state of the so-called Fiber Reinforced Concrete (FRC), conventional mix-design methods recommend the use of high paste content, which results in a significant increase of Portland cement (PC) content and raises the carbon footprint of the material. The latter is responsible for 8% of the global annual carbon dioxide (CO2) anthropogenic emissions. Given the current worldwide concerns on global warming, the construction industry is in a need to lessen the demand, and thus production of PC. Recent studies have been focusing on the use of advanced mix-design techniques (i.e. particle packing models- PPMs) along with Inert Fillers (IF) as an alternative to reduce PC content in concrete. However, the latter was not applied to conventional FRC. In this work, advanced mix design techniques (i.e. PPMs) are used to overcome the aforementioned issues and mix-proportion eco-efficient FRC with low cement content (< 300 kg/m3). Fresh (i.e. VeBe time, slump, rheological behaviour) and hardened (i.e. compressive strength, and flexural behaviour) state tests were performed on the proposed mixtures and compared with control high PC content (375 kg/m3) FRC mixes. Results show that PPM designed mixes presented higher minimum torque (yield stress) but quite comparable apparent viscositiy when compared to conventionally designed mixtures. Moreover, the flowability (i.e. VeBe time, and slump) tends to decrease as fiber content, length, and/or as the amount of fillers increase in the mixtures. In addition, PPM mixes exhibited a shear thinning behaviour following the Herschel-Bulkley model, which enables the design of FRC PPM mix-proportioned mixtures for applications requiring high torque regimes such as vibrated and/or pumped concrete. Finally, results show that the use of PPMs to mix proportion eco-efficient low cement FRC mixtures produced improved hardened (i.e. compressive strength, and flexural performance) state behaviour with lower environmental impact than conventional ACI designed FRC mixtures.

<p> A detailed petrographic study of the Pleistocene Key Largo Limestone Formation, Key Largo, Florida, was undertaken observing three units of varying ages. From oldest to youngest, these are: Q4A (age unknown); Q4B, (180,000 years B.P.), and Q5, (125, 000 years B.P.). Fifty thin sections from four cored wells were point counted. Porosity remained constant for all three units at 28.5% as did total cements at 27.5%. These are still very porous rocks relative to ancient carbonates, which generally show 0-2% porosity. Q5 is diagenetically less mature than Q4B and Q4A, with the persistence of aragonite (which is being leached) and solution-enhanced interparticle porosity. Q5 has been exposed to a vadose environment. Multiple generation cements in Q4B indicate two periods of vadose exposure coincident with known Pleistocene eustatic sea level fluctuations. Moldic porosity is predominant in Q4B. Vague horizons of macroscopic vuggy porosity act as pathways of directed flow for percolating fluids precipitating late stage cements and stains rich in iron. Q4A has been interpreted as a beachrock in part, deposited at pH's greater than 9, resulting in dissolution of quartz grains. Of special interest in Q4A is the probable exploitation of a quartz substrate by endolithic borers. </p> / Thesis / Bachelor of Science (BSc)

Объектом данного исследования является феррожидкость. В работе определено влияние полидисперсности на термодинамические и магнитные свойства феррожидкостей. В первой главе данной работы построена теория, описывающая термодинамические свойства бидисперсной системы дипольных твердых сфер. Разработан программный комплекс, позволяющий численно определить ряд термодинамических характеристик бидисперсной феррожидкости. Проведено сравнение теории и результатов компьютерного моделирования. Во второй главе рассмотрена полидисперсная модель дипольных твердых сфер. Вычислено дополнительное слагаемое в существующем приближении начальной магнитной восприимчивости полидисперсных феррожидкостей. Проведено сравнение теории и результатов компьютерного моделирования, известных в литературе. Определены условия работоспособности нового приближения начальной магнитной восприимчивости. / The object of this study is ferrofluid. In the study the effect of polydispersity on the thermodynamic and magnetic properties of ferrofluids was investigated. In the first chapter of this paper we construct theory describing the thermodynamic properties of the bidisperse system of dipolar hard spheres. Computer program was developed that allows numerically to identify the thermodynamic characteristics of bidisperse ferrofluid. A comparison between theory and computer simulation was performed. In the second chapter the polydisperse model of dipolar hard spheres was considered. Additional new term in the existing approximation of the initial magnetic susceptibility of polydisperse ferrofluid was calculated. A comparison between theory and computer simulations was performed. The conditions for the availability of the new approach were defined.