Fibronectin/phosphorylcholine coatings on fluorocarboned surfaces: a study upon adsorption and grafting processes

Depuis ces dernières décennies, le domaine des biomatériaux a connu un essor considérable, évoluant de simples prothèses aux dispositifs les plus complexes pouvant détenir une bioactivité spécifique. Outre, le progrès en science des matériaux et une meilleure compréhension des systèmes biologiques a offert la possibilité de créer des matériaux synthétiques pouvant moduler et stimuler une réponse biologique déterminée, tout en améliorant considérablement la performance clinique des biomatériaux. En ce qui concerne les dispositifs cardiovasculaires, divers recouvrements ont été développés et étudiés dans le but de modifier les propriétés de surface et d’améliorer l’efficacité clinique des tuteurs. En effet, lorsqu’un dispositif médical est implanté dans le corps humain, son succès clinique est fortement influencé par les premières interactions que sa surface établit avec les tissus et les fluides biologiques environnants. Le recouvrement à la surface de biomatériaux par diverses molécules ayant des propriétés complémentaires constitue une approche intéressante pour atteindre différentes cibles biologiques et orienter la réponse de l’hôte. De ce fait, l’élucidation de l’interaction entre les différentes molécules composant les recouvrements est pertinente pour prédire la conservation de leurs propriétés biologiques spécifiques. Dans ce travail, des recouvrements pour des applications cardiovasculaires ont été créés, composés de deux molécules ayant des propriétés biologiques complémentaires : la fibronectine (FN) afin de promouvoir l’endothélialisation et la phosphorylcholine (PRC) pour favoriser l’hémocompatibilité. Des techniques d’adsorption et de greffage ont été appliquées pour créer différents recouvrements de ces deux biomolécules sur un polymère fluorocarboné déposé par traitement plasma sur un substrat en acier inoxydable. Dans un premier temps, des films de polytétrafluoroéthylène (PTFE) ont été utilisés en tant que surface modèle afin d’explorer l’interaction de la PRC et de la FN avec les surfaces fluorocarbonées ainsi qu’avec des cellules endothéliales et du sang. La stabilité des recouvrements de FN sur l’acier inoxydable a été étudiée par déformation, mais également par des essais statiques et dynamiques sous-flux. Les recouvrements ont été caractérisés par Spectroscopie Photoéléctronique par Rayons X, immunomarquage, angle de contact, Microscopie Électronique de Balayage, Microscopie de Force Atomique et Spectrométrie de Masse à Ionisation Secondaire à Temps de Vol (imagerie et profilage en profondeur). Des tests d’hémocompatibilité ont été effectués et l’interaction des cellules endothéliales avec les recouvrements a également été évaluée. La FN greffée a présenté des recouvrements plus denses et homogènes alors que la PRC quant à elle, a montré une meilleure homogénéité lorsqu’elle était adsorbée. La caractérisation de la surface des échantillons contenant FN/PRC a été corrélée aux propriétés biologiques et les recouvrements pour lesquels la FN a été greffée suivie de l’adsorption de la PRC ont présenté les meilleurs résultats pour des applications cardiovasculaires : la promotion de l’endothélialisation et des propriétés d’hémocompatibilité. Concernant les tests de stabilité, les recouvrements de FN greffée ont présenté une plus grande stabilité et densité que dans le cas de l’adsorption. En effet, la pertinence de présenter des investigations des essais sous-flux versus des essais statiques ainsi que la comparaison des différentes stratégies pour créer des recouvrements a été mis en évidence. D’autres expériences sont nécessaires pour étudier la stabilité des recouvrements de PRC et de mieux prédire son interaction avec des tissus in vivo.

Resistive Embedded Heating for Homogeneous Curing of Composite Damage Repair

Thesis (Ph.D.)--University of Washington, 2016-08

Motivic Decomposition of Projective Pseudo-Homogeneous Varieties

Let G be a semi-simple algebraic group over a field k. Projective G-homogeneous varieties are projective varieties over which G acts transitively. The stabilizer or the isotropy subgroup at a point on such a variety is a parabolic subgroup which is always smooth when the characteristic of k is zero. However, when k has positive characteristic, we encounter projective varieties with transitive G-action where the isotropy subgroup need not be smooth. We call these varieties projective pseudo-homogeneous varieties. To every such variety, we can associate a corresponding projective homogeneous variety. In this thesis, we extensively study the Chow motives (with coefficients from a finite connected ring) of projective pseudo-homogeneous varieties for G inner type over k and compare them to the Chow motives of the corresponding projective homogeneous varieties. This is done by proving a generic criterion for the motive of a variety to be isomorphic to the motive of a projective homogeneous variety which works for any characteristic of k. As a corollary, we give some applications and examples of Chow motives that exhibit an interesting phenomenon. We also show that the motives of projective pseudo-homogeneous varieties satisfy properties such as Rost Nilpotence and Krull-Schmidt.

Synthesis of waterborne polyurethane-urea dispersions with chain extension step in homogeneous and heterogeneous media

Hypothesis: The possibility of tailoring the final properties of environmentally friendly waterborne polyurethane and polyurethane-urea dispersions and the films they produce makes them attractive for a wide range of applications. Both the reagents content and the synthesis route contribute to the observed final properties. Experiments: A series of polyurethane-urea and polyurethane aqueous dispersions were synthesized using 1,2-ethanediamine and/or 1,4-butanediol as chain extenders. The diamine content was varied from 0 to 4.5 wt%. Its addition was carried out either by the classical heterogeneous reaction medium (after phase inversion step), or else by the alternative homogeneous medium (prior to dispersion formation). Dispersions as well as films prepared from dispersions have been later extensively characterized. Findings: 1,2-Ethanediamine addition in heterogeneous medium leads to dispersions with high particle sizes and broad distributions whereas in homogeneous medium, lower particle sizes and narrow distributions were observed, thus leading to higher uniformity and cohesiveness among particles during film formation. Thereby, stress transfer is favored adding the diamine in a homogeneous medium; and thus the obtained films presented quite higher stress and modulus values. Furthermore, the higher uniformity of films tends to hinder water molecules transport through the film, resulting, in general, in a lower water absorption capacity.

THE STOCHASTIC NAVIER STOKES EQUATIONS FOR HEAT CONDUCTING, COMPRESSIBLE FLUIDS

This dissertation is devoted to the equations of motion governing the evolution of a fluid or gas at the macroscopic scale. The classical model is a PDE description known as the Navier-Stokes equations. The behavior of solutions is notoriously complex, leading many in the scientific community to describe fluid mechanics using a statistical language. In the physics literature, this is often done in an ad-hoc manner with limited precision about the sense in which the randomness enters the evolution equation. The stochastic PDE community has begun proposing precise models, where a random perturbation appears explicitly in the evolution equation. Although this has been an active area of study in recent years, the existing literature is almost entirely devoted to incompressible fluids. The purpose of this thesis is to take a step forward in addressing this statistical perspective in the setting of compressible fluids. In particular, we study the well posedness for the corresponding system of Stochastic Navier Stokes equations, satisfied by the density, velocity, and temperature. The evolution of the momentum involves a random forcing which is Brownian in time and colored in space. We allow for multiplicative noise, meaning that spatial correlations may depend locally on the fluid variables. Our main result is a proof of global existence of weak martingale solutions to the Cauchy problem set within a bounded domain, emanating from large initial datum. The proof involves a mix of deterministic and stochastic analysis tools. Fundamentally, the approach is based on weak compactness techniques from the deterministic theory combined with martingale methods. Four layers of approximate stochastic PDE's are built and analyzed. A careful study of the probability laws of our approximating sequences is required. We prove appropriate tightness results and appeal to a recent generalization of the Skorohod theorem. This ultimately allows us to deduce analogues of the weak compactness tools of Lions and Feireisl, appropriately interpreted in the stochastic setting.

Estudo paramétrico da recuperação de óleo no processo de drenagem gravitacional com injeção de CO2

The gas injection has become the most important IOR process in the United States. Furthermore, the year 2006 marks the first time the gas injection IOR production has surpassed that of steam injection. In Brazil, the installation of a petrochemical complex in the Northeast of Brazil (Bahia State) offers opportunities for the injection of gases in the fields located in the Recôncavo Basin. Field-scale gas injection applications have almost always been associated with design and operational difficulties. The mobility ratio, which controls the volumetric sweep, between the injected gas and displaced oil bank in gas processes, is typically unfavorable due to the relatively low viscosity of the injected gas. Furthermore, the difference between their densities results in severe gravity segregation of fluids in the reservoirs, consequently leading to poor control in the volumetric sweep. Nowadays, from the above applications of gas injection, the WAG process is most popular. However, in attempting to solve the mobility problems, the WAG process gives rise to other problems associated with increased water saturation in the reservoir including diminished gas injectivity and increased competition to the flow of oil. The low field performance of WAG floods with oil recoveries in the range of 5-10% is a clear indication of these problems. In order to find na effective alternative to WAG, the Gas Assisted Gravity Drainage (GAGD) was developed. This process is designed to take advantage of gravity force to allow vertical segregation between the injected CO2 and reservoir crude oil due to their density difference. This process consists of placing horizontal producers near the bottom of the pay zone and injecting gás through existing vertical wells in field. Homogeneous models were used in this work which can be extrapolated to commercial application for fields located in the Northeast of Brazil. The simulations were performed in a CMG simulator, the STARS 2007.11, where some parameters and their interactions were analyzed. The results have shown that the CO2 injection in GAGD process increased significantly the rate and the final recovery of oil

Estudo da segregação gravitacional do processo de injeção de vapor em reservátórios heterogêneos

Due to reservoirs complexity and significantly large reserves, heavy oil recovery has become one of the major oil industry challenges. Thus, thermal methods have been widely used as a strategic method to improve heavy oil recovery. These methods improve oil displacement through viscosity reduction, enabling oil production in fields which are not considered commercial by conventional recovery methods. Among the thermal processes, steam flooding is the most used today. One consequence in this process is gravity segregation, given by difference between reservoir and injected fluids density. This phenomenon may be influenced by the presence of reservoir heterogeneities. Since most of the studies are carried out in homogeneous reservoirs, more detailed studies of heterogeneities effects in the reservoirs during steam flooding are necessary, since most oil reservoirs are heterogeneous. This paper presents a study of reservoir heterogeneities and their influence in gravity segregation during steam flooding process. In this study some heterogeneous reservoirs with physical characteristics similar those found in the Brazilian Northeast Basin were analyzed. To carry out the simulations, it was used the commercial simulator STARS by CMG (Computer Modeling Group) - version 2007.11. Heterogeneities were modeled with lower permeability layers. Results showed that the presence of low permeability barriers can improve the oil recovery, and reduce the effects of gravity segregation, depending on the location of heterogeneities. The presence of these barriers have also increased the recovered fraction even with the reduction of injected steam rate

Análise paramétrica da simulação composicional do processo de Drenagem Gravitacional Assistida por Gás (GAGD)

In Brazil and around the world, oil companies are looking for, and expected development of new technologies and processes that can increase the oil recovery factor in mature reservoirs, in a simple and inexpensive way. So, the latest research has developed a new process called Gas Assisted Gravity Drainage (GAGD) which was classified as a gas injection IOR. The process, which is undergoing pilot testing in the field, is being extensively studied through physical scale models and core-floods laboratory, due to high oil recoveries in relation to other gas injection IOR. This process consists of injecting gas at the top of a reservoir through horizontal or vertical injector wells and displacing the oil, taking advantage of natural gravity segregation of fluids, to a horizontal producer well placed at the bottom of the reservoir. To study this process it was modeled a homogeneous reservoir and a model of multi-component fluid with characteristics similar to light oil Brazilian fields through a compositional simulator, to optimize the operational parameters. The model of the process was simulated in GEM (CMG, 2009.10). The operational parameters studied were the gas injection rate, the type of gas injection, the location of the injector and production well. We also studied the presence of water drive in the process. The results showed that the maximum vertical spacing between the two wells, caused the maximum recovery of oil in GAGD. Also, it was found that the largest flow injection, it obtained the largest recovery factors. This parameter controls the speed of the front of the gas injected and determined if the gravitational force dominates or not the process in the recovery of oil. Natural gas had better performance than CO2 and that the presence of aquifer in the reservoir was less influential in the process. In economic analysis found that by injecting natural gas is obtained more economically beneficial than CO2

Estudo de modelos composicionais de óleo na injeção contínua de vapor

The objective of the thermal recovery is to heat the resevoir and the oil in it to increase its recovery. In the Potiguar river basin there are located several heavy oil reservoirs whose primary recovery energy provides us with a little oil flow, which makes these reservoirs great candidates for application of a method of recovery advanced of the oil, especially the thermal. The steam injection can occur on a cyclical or continuous manner. The continuous steam injection occurs through injection wells, which in its vicinity form a zone of steam that expands itself, having as a consequence the displace of the oil with viscosity and mobility improved towards the producing wells. Another possible mechanism of displacement of oil in reservoirs subjected to continuous injection of steam is the distillation of oil by steam, which at high temperatures; their lighter fractions can be vaporized by changing the composition of the oil produced, of the oil residual or to shatter in the amount of oil produced. In this context, this paper aims to study the influence of compositional models in the continuous injection of steam through in the analysis of some parameters such as flow injection steam and temperature of injection. Were made various leading comparative analysis taking the various models of fluid, varying from a good elementary, with 03 pseudocomponents to a modeling of fluids with increasing numbers of pseudocomponents. A commercial numerical simulator was used for the study from a homogeneous reservoir model with similar features to those found in northeastern Brazil. Some conclusions as the increasing of the simulation time with increasing number of pseudocomponents, the significant influence of flow injection on cumulative production of oil and little influence of the number of pseudocomponents in the flows and cumulative production of oil were found

Spatio-temporal modeling of data imputation for daily rainfall series in homogeneous zones.

Spatio-temporal modelling is an area of increasing importance in which models and methods have often been developed to deal with specific applications. In this study, a spatio-temporal model was used to estimate daily rainfall data. Rainfall records from several weather stations, obtained from the Agritempo system for two climatic homogeneous zones, were used. Rainfall values obtained for two fixed dates (January 1 and May 1, 2012) using the spatio-temporal model were compared with the geostatisticals techniques of ordinary kriging and ordinary cokriging with altitude as auxiliary variable. The spatio-temporal model was more than 17% better at producing estimates of daily precipitation compared to kriging and cokriging in the first zone and more than 18% in the second zone. The spatio-temporal model proved to be a versatile technique, adapting to different seasons and dates.

3D-form metrology of arbitrary optical surfaces by absorption in fluids

We present an imaging technique for the 3D-form metrology of optical surfaces. It is based on the optical absorption in fluids situated between the surface and a reference. An improved setup with a bi-chromatic light source is fundamental to obtain reliable topographic maps. It is able to measure any surface finish (rough or polished), form and slope and independently of scale. We present results focused on flat and spherical optical surfaces, arrays of lenses and with different surface finish (rough-polished). We achieve form accuracies from several nanometers to sub-lambda for sag departures from tens to hundred of microns. Therefore, it seems suitable for the quality control in the production of precision aspheric, freeform lenses and other complex shapes on transparent substrates, independently of the surface finish.

Numerical simulation of fresh SCC flow in wall and beam elements using flow dynamics models

Abstract : Recently, there is a great interest to study the flow characteristics of suspensions in different environmental and industrial applications, such as snow avalanches, debris flows, hydrotransport systems, and material casting processes. Regarding rheological aspects, the majority of these suspensions, such as fresh concrete, behave mostly as non-Newtonian fluids. Concrete is the most widely used construction material in the world. Due to the limitations that exist in terms of workability and formwork filling abilities of normal concrete, a new class of concrete that is able to flow under its own weight, especially through narrow gaps in the congested areas of the formwork was developed. Accordingly, self-consolidating concrete (SCC) is a novel construction material that is gaining market acceptance in various applications. Higher fluidity characteristics of SCC enable it to be used in a number of special applications, such as densely reinforced sections. However, higher flowability of SCC makes it more sensitive to segregation of coarse particles during flow (i.e., dynamic segregation) and thereafter at rest (i.e., static segregation). Dynamic segregation can increase when SCC flows over a long distance or in the presence of obstacles. Therefore, there is always a need to establish a trade-off between the flowability, passing ability, and stability properties of SCC suspensions. This should be taken into consideration to design the casting process and the mixture proportioning of SCC. This is called “workability design” of SCC. An efficient and non-expensive workability design approach consists of the prediction and optimization of the workability of the concrete mixtures for the selected construction processes, such as transportation, pumping, casting, compaction, and finishing. Indeed, the mixture proportioning of SCC should ensure the construction quality demands, such as demanded levels of flowability, passing ability, filling ability, and stability (dynamic and static). This is necessary to develop some theoretical tools to assess under what conditions the construction quality demands are satisfied. Accordingly, this thesis is dedicated to carry out analytical and numerical simulations to predict flow performance of SCC under different casting processes, such as pumping and tremie applications, or casting using buckets. The L-Box and T-Box set-ups can evaluate flow performance properties of SCC (e.g., flowability, passing ability, filling ability, shear-induced and gravitational dynamic segregation) in casting process of wall and beam elements. The specific objective of the study consists of relating numerical results of flow simulation of SCC in L-Box and T-Box test set-ups, reported in this thesis, to the flow performance properties of SCC during casting. Accordingly, the SCC is modeled as a heterogeneous material. Furthermore, an analytical model is proposed to predict flow performance of SCC in L-Box set-up using the Dam Break Theory. On the other hand, results of the numerical simulation of SCC casting in a reinforced beam are verified by experimental free surface profiles. The results of numerical simulations of SCC casting (modeled as a single homogeneous fluid), are used to determine the critical zones corresponding to the higher risks of segregation and blocking. The effects of rheological parameters, density, particle contents, distribution of reinforcing bars, and particle-bar interactions on flow performance of SCC are evaluated using CFD simulations of SCC flow in L-Box and T-box test set-ups (modeled as a heterogeneous material). Two new approaches are proposed to classify the SCC mixtures based on filling ability and performability properties, as a contribution of flowability, passing ability, and dynamic stability of SCC.

One-dimensional Model for Fluids of Third-grade in Tubes with Constant Radius

Our goal in this paper is to extend previous results obtained for Newtonian and secondgrade fluids to third-grade fluids in the case of an axisymmetric, straight, rigid and impermeable tube with constant cross-section using a one-dimensional hierarchical model based on the Cosserat theory related to fluid dynamics. In this way we can reduce the full threedimensional system of equations for the axisymmetric unsteady motion of a non-Newtonian incompressible third-grade fluid to a system of equations depending on time and on a single spatial variable. Some numerical simulations for the volume flow rate and the the wall shear stress are presented.