Neste trabalho estudou-se o comportamento reológico e morfológico da mistura polimérica imiscível de polipropileno e poliamida. Como resultado deste estudo obtiveram-se valores de tensão interfacial entre 10mN/m e 13mN/m. A tensão interfacial diminuiu em até 87% quando a mistura é compatibilizada com polipropileno maleado. A análise morfológica no regime de viscoelasticidade linear quando avaliada uma morfologia de emulsão de poliamida em polipropileno revelou diâmetro médio da fase dispersa entre 1,5µm e 20µm. O diâmetro das gotas da fase dispersa diminuiu com a adição de polipropileno maleado chegando a reduções de até 98%, mantendo-se constante a concentração da fase dispersa. No regime de viscoelasticidade não linear foram testados modelos para avaliar o comportamento da mistura em fluxos de cisalhamento e extensão, sendo que somente para os fluxos de extensão foi obtida boa correlação dos resultados experimentais com as previsões teóricas. / Rheological and morphological behaviour of polypropylene and polyamide polymer blend was studied. The values of interfacial tension were obtained between 10mN/m and 13mN/m. The interfacial tension decreased in 87% for compatibilized blend. Morphology analysis for linear viscoelastic regime shows dispersed drop diameter between 1,5µm and 20µm. The diameter of the drops decreased with the addition of maleic polypropylene reducing until 98%, keeping constant the concentration of the disperse phase. In non linear viscoelastic regime different models were tested to evaluate the behavior of the blends in shear and elongacional flows. However, only the elongacional flow results were acquired with theoretical - experimental corroboration.

Master of Science / Department of Mechanical and Nuclear Engineering / Kevin B. Lease / This research was intended to measure the interfacial shear strength between fiber/ matrix systems and to investigate the relation between structure-mechanical properties and performance of fiber/matrix systems. This work conducted a systematic study on model fiber/matrix systems to enhance the fundamental understanding on how variation of polymeric compositions (and hence, different structures), different curing conditions, and fiber surface treatments influence the interactions between the fiber and matrix. In order to measure the interfacial shear strength of fiber/matrix systems, the microdroplet technique was used. In this technique a polymer droplet was deposited on a fiber in the liquid state. Once the droplet was cured a shear force was applied to the droplet in order to detach the droplet from the fiber. The amount of the force needed to de-bond the droplet was directly related to the strength of the bonds formed between the fiber and matrix during the curing process. In addition, the micro-droplet technique was used to evaluate effects of different crosslinker ratio of fiber/ matrix system and also to see if different curing conditions affect the interfacial shear strength of fiber/ matrix system. Surface treatment was also conducted to evaluate its effects on the interfacial shear strength of the fiber/ matrix system using microdroplet technique. The interfacial shear strength of fiber/ matrix system increased along with the increase of crosslinker ratio to a limiting value, and it decreased as long as the crosslinker ratio increased. Curing condition also caused the interfacial shear strength of fiber/ matrix system to increase when it was cured at higher temperature. Fiber surface treatment exhibited a significant effect to the interfacial shear strength as well as the fiber/ matrix contact angle measurement.

The objective of this study was to characterize non-wetting fluid in multi-phase systems comprising a range of fluid and porous medium properties. Synchrotron X-ray microtomography was used to obtain high-resolution, three-dimensional images of fluids in natural porous media. Images were processed to obtain quantitative measurements of fluid distribution, morphology, and interfacial area. Column-flooding experiments were conducted with four enhanced-solubilization (ES) solutions to examine their impact on entrapped organic liquid. Mobilization caused a change in organic-liquid morphology and distribution for most experiments. The effect of ES-solution flooding on fluid-fluid interfacial area was similar to that of water flooding. Organic-liquid mobilization was observed at total trapping numbers that were smaller than expected. This was attributed to pore-scale mobilization of blobs that were re-trapped prior to being eluted from the column. Pore-scale mobilization was also observed during water-flooding experiments for which trapping numbers varied over several orders of magnitude. Water-flooding and surfactant-flooding experiments were compared to investigate the impact of interfacial tension, viscosity, and fluid velocity on entrapped organic liquid. For similar total trapping numbers, flooding at larger velocities appeared to have a greater effect on the distribution of non-wetting blobs than lowering interfacial tension or increasing the viscosity of the wetting fluid. The fluid-normalized interfacial area was generally independent of the total trapping number. Finally, the impact of fluid type on the interfacial area between different pairs of non-wetting fluids was investigated during drainage and imbibition in four natural porous media. Interfacial areas were similar among all fluid pairs for a given porous medium. They were also similar for drainage and imbibition conditions. The maximum specific interfacial area (A(m)) was determined to quantify the magnitude of interfacial area associated with a given porous medium. The value of A(m) was larger for the media with smaller median grain diameters. Therefore, physical properties of the porous medium appear to have a greater influence on the magnitude of specific total interfacial area for a given saturation than fluid properties or wetting-phase history.

In the thesis explicit dual parabolic-elliptic models are constructed for the Konenkov flexural edge wave and the Stoneley-type flexural interfacial wave in case of thin linearly elastic plates. These waves do not appear in an explicit form in the original equations of motion within the framework of the classical Kirchhoff plate theory. The thesis is aimed to highlight the contribution of the edge and interfacial waves into the overall displacement field by deriving specialised equations oriented to aforementioned waves only. The proposed models consist of a parabolic equation governing the wave propagation along a plate edge or plate junction along with an elliptic equation over the interior describing decay in depth. In this case the parabolicity of the one-dimensional edge and interfacial equations supports flexural wave dispersion. The methodology presented in the thesis reveals a dual nature of edge and interfacial plate waves contrasting them to bulk-type wave propagating in thin elastic structures. The thesis tackles a number of important examples of the edge and interfacial wave propagation. First, it addresses the propagation of Konenkov flexural wave in an elastic isotropic plate under prescribed edge loading. For the latter, parabolic-elliptic explicit models were constructed and thoroughly investigated. A similar problem for a semi-infinite orthotropic plate resulted in a more general dual parabolic-elliptic model. Finally, an anal- ogous model was derived and analysed for two isotropic semi-infinite Kirchhoff plates under perfect contact conditions.

The spallation of aluminum, chromium, and iron oxide scales is a chronic problem that critically impacts technological applications like aerospace, power plant operation, catalysis, petrochemical industry, and the fabrication of composite materials. The presence of interfacial impurities, mainly sulfur, has been reported to accelerate spallation, thereby promoting the high-temperature corrosion of metals and alloys. The precise mechanism for sulfur-induced destruction of oxides, however, is ambiguous. The objective of the present research is to elucidate the microscopic mechanism for the high-temperature corrosion of aluminum alloys in the presence of sulfur. Auger electron spectroscopy (AES), low energy electron diffraction (LEED), and scanning tunneling microscopy (STM) studies were conducted under ultrahigh vacuum (UHV) conditions on oxidized sulfur-free and sulfur-modified Al/Fe and Ni3Al(111). Evaporative deposition of aluminum onto a sulfur-covered iron surface results in the insertion of aluminum between the sulfur adlayer and the substrate, producing an Fe-Al-S interface. Aluminum oxidation at 300 K is retarded in the presence of sulfur. Oxide destabilization, and the formation of metallic aluminum are observed at temperatures > 600 K when sulfur is located at the Al2O3-Fe interface, while the sulfur-free interface is stable up to 900 K. In contrast, the thermal stability (up to at least 1100 K) of the Al2O3 formed on an Ni3Al(111) surface is unaffected by sulfur. Sulfur remains at the oxide-Ni3Al(111) interface after oxidation at 300 K. During annealing, aluminum segregation to the g ¢ -Al2O3-Ni3Al(111) interface occurs, coincident with the removal of sulfur from the interfacial region. A comparison of the results observed for the Al2O3/Fe and Al2O3/Ni3Al systems indicates that the high-temperature stability of Al2O3 films on aluminum alloys is connected with the concentration of aluminum in the alloy.

Les recherches actuelles dans le domaine des composites montrent l'utilisation croissante de matrices biodégradables et/ou de renforts fibreux naturels issus de ressources renouvelables. Néanmoins, une étape de compatibilisation fibres/matrice est très souvent nécessaire. Dans cette thèse, nous avons exploré une méthode physique : le traitement corona. Son impact sur les propriétés physicochimiques de différentes fibres a été étudié par XPS, mesure d'angle de contact et MEB. Il ressort qu'il entraîne principalement une oxydation de surface et une augmentation de sa rugosité. Nous avons évalué le comportement mécanique de composites, préparés par extrusion à partir de fibres de chanvre ou miscanthus et de matrices polypropylène (PP) ou acide polylactique (PLA). L'incorporation de renforts accroît la rigidité des matériaux et le transfert de contrainte et leur traitement permet d'obtenir des caractéristiques encore supérieures en raison d'un ancrage mécanique accru. Les valeurs optimales sont obtenues pour un taux massique de fibres de l'ordre de 20%. Les propriétés thermiques et thermomécaniques des composites ont été caractérisées par ATG, DMA et DSC. La stabilité thermique des matériaux est abaissée après incorporation de renforts bruts mais très largement améliorée (+ 15-20°C) après traitement des fibres. Dans certaines conditions, les fibres agissent comme des agents nucléants qui influent sur le processus de cristallisation et le taux de cristallinité. Le traitement des fibres par corona ne permet pas de retarder la dégradation des matériaux au cours d'un vieillissement accéléré en milieu humide et l'évolution des propriétés thermomécaniques est plus prononcée pour les matériaux à base de PLA plus hydrophile / The field of composites materials shows increasing use of biodegradable matrices and / or natural reinforcements from renewable resources. Nevertheless, a compatibilization step between fiber and matrix is necessary. In this PhD study, we have explored a physical method: corona treatment. Its impact on the physicochemical properties of different fibres has been studied by XPS, contact angle measurement and SEM. It appears that it mainly involves surface oxidation and roughness increase. We have also evaluated the mechanical behaviour of composites, prepared by extrusion from hemp or miscanthus fibres and polypropylene (PP) or polylactic acid (PLA) matrices. The incorporation of raw reinforcements increases the stiffness and the stress transfer. Composites based on treated fibres show better mechanical performances, resulting from an enhanced mechanical anchorage. The optimum values are obtained for 20% (wt) fibres content. The thermal and thermomechanical properties of composites have been characterized by TGA, DMA and DSC. The thermal stability of materials is reduced after incorporation of raw reinforcements but very much improved (+ 15 - 20 ° C) after treatment of fibres. Under certain conditions, the fibres act as nucleating agents that affect the crystallization process and crystallinity rate. The corona treatment of fibres does not delay the degradation of materials during an accelerated aging in humid environment and the evolution of the thermomechanical properties is more pronounced for PLA based materials because of its hydrophilic character.

UA Open Access Publishing Fund / Molecular diagnostics offers quick access to information but fails to operate at a speed required for clinical decision-making. Our novel methodology, droplet-on-thermocouple silhouette real-time polymerase chain reaction (DOTS qPCR), uses interfacial effects for droplet actuation, inhibition relief, and amplification sensing. DOTS qPCR has sample-to-answer times as short as 3 min 30 s. In infective endocarditis diagnosis, DOTS qPCR demonstrates reproducibility, differentiation of antibiotic susceptibility, subpicogram limit of detection, and thermocycling speeds of up to 28 s/cycle in the presence of tissue contaminants. Langmuir and Gibbs adsorption isotherms are used to describe the decreasing interfacial tension upon amplification. Moreover, a log-linear relationship with low threshold cycles is presented for real-time quantification by imaging the droplet-on-thermocouple silhouette with a smartphone. DOTS qPCR resolves several limitations of commercially available real-time PCR systems, which rely on fluorescence detection, have substantially higher threshold cycles, and require expensive optical components and extensive sample preparation. Due to the advantages of low threshold cycle detection, we anticipate extending this technology to biological research applications such as single cell, single nucleus, and single DNA molecule analyses. Our work is the first demonstrated use of interfacial effects for sensing reaction progress, and it will enable point-of-care molecular diagnosis of infections.

Although the leading-order motion of waves is periodic - in other words backwards and forwards - many types of waves including those driven by gravity induce a mean flow as a higher-order effect. It is the induced mean flow of three types of gravity waves that this thesis examines: surface (part I), internal (part II) and interfacial gravity waves (part III). In particular, this thesis examines wave groups. Because they transport energy, momentum and other tracers, wave-induced mean flows have important consequences for climate, environment, air traffic, fisheries, offshore oil and other industries. In this thesis perturbation methods are used to develop a simplified understanding of the physics of the induced mean flow for each of these three types of gravity wave groups. Leading-order estimates of different transport quantities are developed. For surface gravity wave groups (part I), the induced mean flow consists of two compo- nents: the Stokes drift dominant near the surface and the Eulerian return flow acting in the opposite direction and dominant at depth. By considering subsequent orders in a separation of scales expansion and by comparing to the Fourier-space solutions of Longuet-Higgins and Stewart (1962), this thesis shows that the effects of frequency dis- persion can be ignored for deep-water waves with realistic bandwidths. An approximate depth scale is developed and validated above which the Stokes drift is dominant and below which the return flow wins: the transition depth. Results are extended to include the effects of finite depth and directional spreading. Internal gravity wave groups (part II) do not display Stokes drift, but a quantity analogous to Stokes transport for surface gravity waves can still be developed, termed the “divergent- flux induced flow” herein. The divergent-flux induced flow it itself a divergent flow and induces a response. In a three-dimensional geometry, the divergent-flux induced flow and the return flow form a balanced circulation in the horizontal plane with the former transporting fluid through the centre of the group and the latter acting in the opposite direction around the group. In a two-dimensional geometry, stratification inhibits a balanced circulation and a second type of waves are generated that travel far ahead and in the lee of the wave group. The results in the seminal work of Bretherton (1969b) are thus validated, explicit expressions for the response and return flow are developed and compared to numerical simulations in the two-dimensional case. Finally, for interfacial wave groups (part III) the induced mean flow is shown to behave analogously to the surface wave problem of part I. Exploring both pure interfacial waves in a channel with a closed lid and interacting surface and interfacial waves, expressions for the Stokes drift and return flow are found for different configurations with the mean set-up or set-down of the interface playing an important role.

This study is an investigation of the chemical vapor deposition (CVD) of aluminum and copper on fluoropolymer surfaces and the subsequent interfacial interactions.

Les mousses aqueuses sont des fluides complexes constitués de dispersions concentrées de bulles de gaz dans une solution de tensioactifs. A l'instar d'autres fluides complexes comme les émulsions ou les pâtes, une mousse se comporte comme un solide viscoélastique lorsque la fraction volumique de la phase continue est suffisamment faible pour que l'empilement des bulles soit bloqué. Ses propriétés mécaniques résultent de couplages entre processus se produisant à plusieurs échelles de temps et d'espace : celles des tensioactifs adsorbés aux interfaces liquide-gaz, celles d'une bulle de gaz ou de mouvements collectifs à une échelle mésoscopique. A partir de trois expériences, nous avons mis en évidence l'impact du désordre de leur structure d'une part, et celui des tensioactifs d'autre part, sur les propriétés viscoélastiques des mousses. Nous avons mis au point un rhéomètre oscillatoire qui permet de mesurer la relation contrainte-déformation-fréquence d'une monocouche de bulles confinées entre deux parois planes parallèles tout en contrôlant sa pression osmotique. Nous avons montré que les relaxations de ces mousses de structure modèle sont pilotées par la rhéologie interfaciale de cisaillement que nous avons caractérisée indépendamment. Nous proposons un modèle quantitatif de ce couplage. Dans une deuxième expérience, nous avons sondé la réponse viscoélastique des mousses de structure 3D désordonnées. Nos résultats montrent que selon la rigidité des interfaces, le facteur de perte d'une mousse est décrit par une loi d'échelle en fréquence. Son évolution avec la taille des bulles et la viscosité du liquide permet de déterminer le mécanisme à l'origine de la dissipation. Dans une troisième expérience, Nous avons élaboré des mousses monodisperses de structure 3D ordonnées et de pression osmotique contrôlée. De manière remarquable, la variation de leur facteur de perte en fonction de la fréquence est similaire à celle des mousses désordonnées de même composition chimique. Ces résultats démontrent que le désordre de l'empilement des bulles n'est pas à l'origine des relaxations viscoélastiques linéaires des mousses, comme l'avaient suggéré plusieurs modèles théoriques, et ouvrent la voie à une modélisation quantitative du lien entre la viscoélasticité des interfaces et celle des mousses 3D / Aqueous foams are constituted of concentrated gas bubble dispersions in a surfactant solution. Like other complex fluids, such as emulsions or pastes, foam behaves as a viscoelastic solid if the volume fraction of the continuous phase is sufficiently small for the bubble packing to be jammed. The mechanical properties of the foam are due to couplings between processes at a wide range of time and length scales: The ones of the surfactant molecules that are adsorbed to the gas-liquid interfaces, the ones of the bubbles or collective motions at a mesoscopic scale. On the basis of three experiments, we have evidenced the impact of structural disorder and surfactant properties on foam viscoelasticity. We have constructed an oscillatory rheometer to measure the frequency and strain dependent stress response of a bubble monolayer confined between two parallel plates, subjected to an imposed osmotic pressure. We have shown that the relaxation of these model foams are governed by the interfacial shear rheology which we have probed in independent experiments and, we present a quantitative model of this coupling. In a second experiment, we have probed the viscoelastic response of disordered 3D foams. Our results show that, depending on interfacial rigidity, the mechanical loss factor of a foam is described by a scaling law depending on frequency. Its dependence on bubble size and liquid viscosity helps to determine the origin of the dissipation. In our third experiment, we have produced monodispersed ordered foams, subjected to a controlled osmotic pressure. Remarkably, the frequency scaling of their loss factor is similar to the one of disordered foams of the same chemical composition. These results demonstrate that the linear viscoelastic response of foams is not the consequence of disorder on the bubble scale as suggested by several previous theories, and they thus open the way for quantitative models linking the viscoelasticity of the interfaces to that of 3D foams