The overall objective of this PhD thesis research is to understand and control phase separation in mixed perfluorinated fatty acid-phospholipid surfactant systems that have applications as pulmonary surfactant (PS) mixtures, with an ultimate view of controlling film composition, morphology and mechanical properties. In this context the interaction between perfluorooctadecanoic acid (C18F), 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), the major component of native PS extract, and 1,2-dipalmitoyl-sn-glycero-3-phosphoglycerol (DPPG) has been explored in Langmuir monolayers and Langmuir–Blodgett (LB) films using a combination of atomic force microscopy (AFM), fluorescence microscopy (FM) and Brewster angle microscopy (BAM) measurements. Thermodynamic and morphological studies of binary and ternary mixed films made of C18F, DPPC and DPPG indicated that both the phospholipids and C18F were miscible over a wide range of compositions. The mixed phospholipid-C18F films contained multimolecular aggregates that were highly enriched in the phospholipids. Furthermore, it was found that the magnitude of the DPPC-C18F interaction could be modulated by altering the concentration of sodium ions in the underlying subphase. Using a highly simplified lung mimic fluid (pH 7.4, 150mM NaCl), DPPC and C18F became fully immiscible. Moreover, the performance characteristics of the mixed films demonstrated the usefulness of C18F as an additive for PS formulations. The effectiveness of a PS protein mimicking peptide was evaluated against DPPC to allow comparison with previous measurements of DPPC-C18F mixed system. The mixing thermodynamics of the peptide and DPPC in Langmuir monolayer implied a repulsive interaction between the film components. The hysteresis response of the mixed monolayer films indicated that the lipid-protein mixture improved the re-spreading of DPPC films. Moreover, molecular-level organization of the mixed films explored by both FM and BAM confirmed the formation of liquid-expanded DPPC domains in the presence of minute amount of the peptide. In order to obtain a thorough understanding of the effect of the deposition process and surfactant tail polarities on the interfacial behavior of perfluorocarbon-hydrocarbon mixed monolayer films, both BAM and AFM measurements of arachidic acid (C20) with perfluorotetradecanoic acid (C14F) and palmitic acid (C16) with C18F mixed monolayer were performed. These measurements revealed that film morphology was minimally perturbed upon its deposition onto solid substrates. Coarse grained molecular dynamics (MD) simulations of films comprised of DPPC molecules with tails of various polarities suggested that the phase separation between the monolayer components could be controlled by varying surfactant tail polarities.

Electronic coarse graining is a technique improving the predictive power of molecular dynamics simulations by representing electrons via a quantum harmonic oscillator. This construction, known as a Quantum Drude Oscillator, provides all molecular long-range responses by uniting many-body dispersion, polarisation and cross interactions to all orders. To demonstrate the predictive power of electronic coarse graining and provide insights into the physics of water, a molecular model of water based on Quantum Drude Oscillators is developed. The model is parametrised to the properties of an isolated molecule and a single cut through the dimer energy surface. Such a parametrisation makes the condensed phase properties of the model a prediction rather than a fitting target. These properties are studied in four environments via two-temperature adiabatic path integral molecular dynamics: a proton ordered ice, the liquid{vapour interface, supercritical and supercooled water. In all these environments, the model predicts a condensed phase in excellent agreement with experiment, showing impressive transferability. It predicts correct densities and pressures in liquid water from 220 K to 647 K, and a correct temperature of maximum density. Furthermore, it predicts the surface tension, the liquid-vapour critical point, density of ice II, and radial distribution functions across all conditions studied. The model also provides insight into the relationship between the molecular structure of water and its condensed phase properties. An asymmetry between donor and acceptor hydrogen bonds is identified as the molecular scale mechanism responsible for the surface orientation of water molecules. The dipole moment is identified as a molecular scale signature of liquid-like and gas-like regions in supercritical water. Finally, a link between the coordination number and the anomalous thermal expansion of the second coordination shell is also presented.

No description available.

Um grande número de rochas de granulação grosseira tem valor agregado muito alto quando usadas como materiais de construção, as chamadas rochas exóticas. No entanto, existem problemas com a utilização desses materiais dado a sua fragilidade, que está relacionada com a sua textura muito heterogênea. No Brasil é empregado empiricamente um reforço (compósito) que utiliza resina epóxi e fibra de vidro para melhorar o desempenho mecânico de tais rochas quando empregadas como materiais de construção. Os objetivos da presente pesquisa foram estudar o reforço tradicional brasileiro (telagem) para determinar sua eficiência e, ao mesmo tempo, propor outras soluções de reforço alternativas e mais eficientes, e avaliá-las através da caracterização mecânica experimental. Foi proposto um critério denominado Declive Global para avaliar as tensões de serviço dos materiais pegmatíticos estudados, quando os reforços propostos foram aplicados. Para validar esse critério foi utilizado um sistema de correlação digital de imagem (CDI) para observar e medir o comportamento de deformação e fratura durante a realização de testes de flexão em 4 pontos. Tanto o critério proposto como a CDI mostraram que a propagação de fissuras ocorre muito antes do material atingir a carga máxima. O reforço alternativo proposto, que emprega resina epóxi e uma fibra de vidro 600 g/m² apresentou o melhor desempenho mecânico, elevando a carga de ruptura até 6x em comparação com as amostras onde nenhum reforço foi aplicado. Os resultados demonstrados pelos reforços propostos são promissores e aumentam a possibilidade de aplicar rochas exóticas frágeis como materiais de construção, além do critério proposto fornecer uma ferramenta importante para a compreensão mecânica prévia de produtos de rocha que utilizam reforços compósitos. / A great number of coarse-grained natural stones have very high added-value when used as building materials, the so called exotic stones. However, problems using these materials arise from its brittleness behavior, which are related to its very heterogeneous texture. Glass fiber-reinforced epoxy composite (GFRC) is being used to improve mechanical performance of such stones when employed as building materials. The objectives of this present investigation it were studying the Brazilian traditional reinforcement to determinate its efficiency and, at the same time, a number of alternative solutions were proposed and evaluated through experimental mechanical characterization. It was proposed a slope-based criterion to evaluate the useful service loads of pegmatitic materials when glass fiber-reinforcement is applied. To validate the proposed criterion, a digital image correlation (DIC) system was employed to observe and measure strain and fracture behavior during the realization of 4-point bending tests. Both proposed criterion and DIC show that crack propagation occurs long before the material reaches maximum load. GFRC acts as a crack inhibitor, raising the breaking load up to 6x in comparison with the specimens where no reinforcement was applied. The results from this study enhance the capability to apply such materials as building materials and provide an important tool to perform prior mechanical understanding of stone products using GFRC.

Abstract Electrostatic interactions are very important in biomolecular systems. Electrostatic forces have received a great deal of attention due to their long-range nature and the trade-off between desolvation and interaction effects. It remains a challenging task to study and to predict the effects of electrostatic interactions in biomolecular systems. Computer simulation techniques that account for such interactions are an important tool for the study of biomolecular electrostatics. This study is largely concerned with the role of electrostatic interactions in biomolecular systems and with developing novel models to estimate the strength of such interactions. First, a novel formulation based upon continuum electrostatics to compute the electrostatic potential in and around two biomolecules in a solvent with ionic strength is presented. Many, if not all, current methods rely on the (non)linear Poisson-Boltzmann equation to include ionic strength. The present formulation, however, describes ionic strength through the inclusion of explicit ions, which considerably extends its applicability and validity range. The method relies on the boundary element method (BEM) and results in two very similar coupled integral equations valid on the dielectric boundaries of two molecules, respectively. This method can be employed to estimate the total electrostatic energy of two protein molecules at a given distance and orientation in an electrolyte solution with zero to moderately high ionic strength. Secondly, to be able to study interactions between biomolecules and membranes, an alternative model partly based upon the analytical continuum electrostatics (ACE) method has been also formulated. It is desirable to develop a method for calculating the total solvation free energy that includes both electrostatic and non-polar energies. The difference between this model and other continuum methods is that instead of determining the electrostatic potential, the total electrostatic energy of the system is calculated by integrating the energy density of the electrostatic field. This novel approach is employed for the calculation of the total solvation free energy of a system consisting of two solutes, one of which could be an infinite slab representing a membrane surface.

Que ce soit dans l’automobile avec des contraintes thermiques ou dans l’aérospatial et lenucléaire soumis à des rayonnements ionisants, l’environnement entraîne l’apparition de fautesdans les systèmes électroniques. Ces fautes peuvent être transitoires ou permanentes et vontinduire des résultats erronés inacceptables dans certains contextes applicatifs. L’utilisation decomposants dits « rad-hard » est parfois compromise par leurs coûts élevés ou les difficultésd’approvisionnement liés aux règles d’exportation.Cette thèse propose une approche conjointe matérielle et logicielle indépendante de la technologied’intégration permettant d’utiliser des composants numériques programmables dans desenvironnements susceptibles de générer des fautes. Notre proposition comporte la définitiond’une Architecture Reconfigurable à Gros Grains (CGRA) capable d’exécuter des codes applicatifscomplets mais aussi l’ensemble des mécanismes matériels et logiciels permettant de rendrecette architecture tolérante aux fautes. Ce résultat est obtenu par l’association de redondance etde reconfiguration dynamique du CGRA en s’appuyant sur une banque de configurations généréepar une chaîne de programmation complète. Cette chaîne outillée repose sur un flot permettantde porter un code sous forme de Control and Data Flow Graph (CDFG) sur l’architecture enobtenant un grand nombre de configurations différentes et qui permet d’exploiter au mieux lepotentiel de l’architecture.Les travaux, qui ont été validés aux travers d’expériences sur des applications du domaine dutraitement du signal et de l’image, ont fait l’objet de publications en conférences internationaleset de dépôts de brevets. / Whether in automotive with heat stress or in aerospace and nuclear field subjected to cosmic,neutron and gamma radiation, the environment can lead to the development of faults in electronicsystems. These faults, which can be transient or permanent, will lead to erroneous results thatare unacceptable in some application contexts. The use of so-called rad-hard components issometimes compromised due to their high costs and supply problems associated with exportrules.This thesis proposes a joint hardware and software approach independent of integrationtechnology for using digital programmable devices in environments that generate faults. Ourapproach includes the definition of a Coarse Grained Reconfigurable Architecture (CGRA) ableto execute entire application code but also all the hardware and software mechanisms to make ittolerant to transient and permanent faults. This is achieved by the combination of redundancyand dynamic reconfiguration of the CGRA based on a library of configurations generated by acomplete conception flow. This implemented flow relies on a flow to map a code represented as aControl and Data Flow Graph (CDFG) on the CGRA architecture by obtaining directly a largenumber of different configurations and allows to exploit the full potential of architecture.This work, which has been validated through experiments with applications in the field ofsignal and image processing, has been the subject of two publications in international conferencesand of two patents.

No description available.

Embankment dams are made from soil materials of varying sizes and widely used all over the world.When constructing these, knowing the hydraulic conductivity (K) of the soil materials is a keyparameter in order to construct safe embankment dams. A knowledge gap regarding K measurementsin coarse grained soils has been identified. This thesis aims to provide a theoretical overview ofpresent day state-of-the-art methods for measuring hydraulic conductivity and the controllingcharacteristics for K. Coarse grained soils refers to a soil with the coarsest grain fraction being > 20mm and/or have a K > 10-4m/s.   It was found that the fixed wall permeameter is the most suitable laboratory method. In the field, itis possible to estimate K using tracer methods, these however show more potential for leakagepathway detection. Common for all K measurement methods are the controlling characteristics of K,grain size distribution, pore geometry, degree of compaction, particle movement and flow regime.These need to be considered when testing to produce useful measurements. If the relationshipbetween flow velocity and hydraulic head is non-linear, Darcy's law is not valid for calculating K. / Fyllnadsdammar är uppbyggda av jord och sprängsten av olika storlekar och finns över hela världen.Att känna till den hydrauliska konduktiviteten (K) av de olika lagren är viktigt för att kunna byggadessa på ett säkert och hållbart sätt. Det har identifierats en bristande kunskap angående K mätningar igrovkorniga jord- och stenmaterial. Målet med denna uppsats är att presentera en teoretisk översikt avden senaste kunskapen inom K mätningar i grovkorniga jord- och stenmaterial och vilka egenskapersom avgör ett materials K. Grovkorniga jord- och stenmaterial syftar till material där den grövstakornstorleken är > 20 mm och/eller har ett K > 10-4m/s.   För laboratorie mätningar är en permeameter med en solid vägg den mest lämpliga metoden. Förfältmätningar är det möjligt att mäta K med hjälp av spårämnen, men dessa har mer potential för attupptäcka läckage vägar i fyllnadsdammar. De faktorer som avgör ett materials K ärkornstorleksfördelningen, geometrin av porerna, graden av kompaktering, partikelrörelse ochflödestyp. För att producera mätningar som är användbara behöver dessa faktorer kontrolleras. Omsambandet mellan hydrauliskt huvud och flödeshastighet är icke linjärt kan K inte beräknas genomDarcy´s lag.

<p>A thermodynamically consistent coarsed-grained phase field model was developed to find the conditions under which a heterogeneous porous electrode can be treated as homogeneous in the description of Lithium-ions in rechargeable batteries. Four regimes of behavior under which the transport phenomena can be homogenized to describe porous LIBs were identied: regime (a), where the model is inaccurate, for physically accessible particle packings of aspect ratios smaller than c/a = 0.5 and electrode porosities between 0.34 to 0.45; regime (b), where the model is valid, for particles of aspect ratios greater than c/a = 0.7 and electrode porosities greater than 0.35; regime (c), where the model is valid, but the microstructures are physically inaccessible, and correspond to particles with aspect ratios greater than c/a = 0.7 and electrode porosities smaller than 0.34; and regime (d), where the model is invalid and the porous microstructures are physically inaccessible, and correspond to particles with aspect ratios smaller than c/a = 1 and electrode porosities smaller than 0.34.</p> <p>The developed formulation was applied to the graphite | LixNi1/3Mn1/3Co1/3O2 system to analyze the effect of microstructure and coarsed-grained long-range chemomechanical effects on the electrochemical behavior. Specically, quantiable lithium distribution populations in the cathode, as a result of long range interactions of the diffuse interface, charge effects and mechanical stresses were identified: i) diffusion limited population due to negligible composition gradients, ii) stress-induced population as a result of chemically induced stresses, and iii) lithiation-induced population, as a consequence of the electrochemical potential gradients.</p>

Sandstone bodies of the Lower and Middle Turonian well exposed in the northwestern part of the Bohemian Cretaceous Basin represent deposits of the coarse-grained deltas. Aim of this paper is to interpret the architectures, stratigraphy and depositional regime of these bodies. The main architectural elements are clinoforms which show intermediate dip 4ř to 5ř of the delta slope and the direction of the progradation of the delta to the west-southwest. Correlation of the lithological profiles with the well - log data provided the stratigraphic classification of the outcrops in the studied area mostly to the genetic sequence TUR2. Correlations in one of the two stratigraphic cross - sections revealed the existence of the second delta body prograding into the basin from Most - Teplice Palaeohigh during TUR1. Detailed study of the sedimentary structures in the outcrops show high degree of reworking of foresets by tidal generated current. Two main directions of the paleocurrents results from the analysis - dominant current to the NW and subordinate current to the SE - SSE.