Determinações de tensão superficial (γ) na interface ar-água e espessuras médias elipsométricas in situ (d), foram usadas para estudar as interações entre dispersões de lípides (em forma de bicamadas) e filmes de poliestireno sulfato produzidos por revestimento rotacional sobre placas de óxido de silício. A adição de NaCl para uma concentração final de 50 mM em uma dispersão de 0.2 mM de lípide catiônico sintético produziu instantaneamente uma camada de 6 nm de espessura que permaneceu estável com o tempo, indicando uma cinética de adsorção muito rápida, determinada possivelmente, pela atração hidrofóbica entre defeitos sobre a bicamada, induzidos pelo sal, e a superfície do filme. Contudo, em água a adsorção de DODAB cresceu monotonicamente alcançando no máximo uma espessura de 1.6-1.8 nm (após 15 horas de interação) em função do tempo, a qual não foi consistente com deposição de bicamada. Nos estágios iniciais em água pura, a adsorção do anfifílico aumentou linearmente com a raiz quadrada do tempo, mostrando um processo controlado por difusão de vesículas, com coeficiente de difusão(D), aproximadamente igual a 1.0 x 10-11 m22s-1 em boa aproximação com valores determinados para vesículas de outros lípides por outros autores. Medidas elipsométricas sob o ar (ex- situ) de adsorção de DODAB, DHP e PC foram difíceis de realizar devido ao aumento da espessura média do filme polimérico durante o ciclo de lavagem e secagem. Na faixa de concentração de 0.1- 1.0 mM o filme adsorvido de DODAB em ar foi mais hidrofóbico (ângulo de contato de avanço ΘA= 84° ± 3°) do que aquele para o filme puro de polímero (ΘA=71 ° ± 4°). Nenhum efeito do filme de DHP sobre a molhabilidade do filme de PSA foi observado, apenas um aumento de rugosidade revelado pela mudança em ΔΘ de 2° para 11° (tabela 3). Filmes planos de PSA são hidrofóbicos(ΘA= 86° ± 5°). Após interação com PC, as superfícies tornam-se menos hidrofóbicas (ΘA= 75° ± 3°). A tensão superficial em ar-água para uma dispersão lipídica em água pura diminuiu rapidamente sob adição de sal (7-50 mM de NaCl), sugerindo a ocorrência de fusão de vesículas, induzida por sal, com a interface ar-água.O estudo da interação entre sais de DODA e partículas poliméricas por medidas de tamanho e potencial-zeta das partículas permitiu observar deposição de bicamadas optimizada por adição de sal a baixas concentrações (0.05-5.0 mM NaCl). / Determinations of surface tension (γ) at the air--water interface, contact angles (Θ), and in and ex-situ ellipsometric mean thickness (d) were used to study the interaction between dioctadecyldimethylammonium bromide (DODAB) small vesicles and spin-coated polystyrene sulfate (PSS) films on silicon wafers. Upon the adition of NaCl (50 mM final concentration) to a 0.2 mM DODAB dispersion, adsorption from vesicles on PSS films immediatly yielded a DODAB layer 6.0 nm thick which remained stable as a function of time. However, in water, in situ DODAB adsorption monotonically increased reaching at most 1.6--1.8 nm as a function of time (from 15 mm of interaction), which were not values consistent with bilayer deposition. At early stages in pure water, DODAB adsorption linearly increased with the square root of time, indicating a vesicle difision controlled process with ca. 1.0 x 10-11 m2s-1 as the vesicle diffusion coeficient (D) in nice agreement with reported D for similar vesicles. In contrast, adding 50 mM salt, resulted in a very fast adsorption kinetics determined by the hydrophobic atraction between salt-induced defects on lhe bilayer and the film surface. Ex situ measurements of DODAB, DHP e PC adsorption were difficult because wetting/drying cycles of the polimeric fiIms increased its mean thickness. From 0.1 up to 1.0 mM DODAB, the adsorbed film in air was more hydrophobic (advancing contact angle, ΘA = 84 ± 3°) than the bare PSS film (ΘA = 71 ± 4°). No effect of DHP film on the wettability of PSA film could be observed, just a increase of rougness revealed by the change of ΔΘ from2° to 11°( table 3). Pure PSA films are hydrophobic, as revealed by the mean advancing angle ΘA = 86 ± 5°. After interaction with PC, the surfaces turn less hydrophobic with a mean ΘA = 75 ± 3°. Air-water surface tension for a DODAB dispersion in pure water rapidly decreased upon salt addition (7-50 mM NaCI), suggesting salt-induced vesicle fusion wilh the air--water interface occurred, in nice agreement with saIt-induced vesicle fusion at the hydrophobic polymer-water surface.The investigation of the interaction between DODA salts and polymeric particles from diameter and zeta- potential measurements, allowed us to detect bilayer deposition optimized by salt adition in low concentration(0.05-5.0 mM NaCl).

Pigmentary titanium dioxide (TiO2) is the most important white pigment used in several industries, including those that manufacture plastic, coatings and paper. To achieve maximum efficiency in light scattering and to deliver the required opacity to the medium in which the TiO2 is present, the TiO2 particles must be fully dispersed throughout this medium. The particle dispersion in a cured, dry, or solid medium depends on the dispersion efficiency in the wet state, which depends on the effectiveness of the deagglomeration process. Based on the existing technical knowledge, the objective of this study is to investigate fundamental aspects in the dispersion process and to understand the effect of these processes on the required energy to deagglomerate pigmentary TiO2 particles in water. The fundamental aspects of particle wetting, dispersion and stability are reviewed as well as the theories of the tensile strength of agglomerates, particle roughness and liquid surface tension and viscosity. Although liquid surface tension and viscosity are the main factors that influence deagglomeration, some particle-related properties (particle radius, particle shape factor, agglomerate pore volume and specific surface area) play an important role in wetting behavior. The maximum mass of water adsorbed by the agglomerates is proportional to the liquid surface tension. The liquid adsorption rate is a function of the ratio between the liquid and solid surface tensions as well as the shape factor. In the present study, for any shape factor value, the lower the liquid surface energy is in relation to the solid surface tension, the larger the water adsorption rate. After characterizing the particles, the agglomerates and the liquid medium, and obtaining correlations between all properties and the energy to achieve maximum dispersion, a predictive model is proposed to describe the influence of liquid surface tension and the particle roughness on the energy required to produce liquid dispersions with minimum particle size. This model applies to different particles with similar surfaces and to particles with different surfaces but similar sizes. / Dióxido de titânio é o pigmento branco mais importante de diversas indústrias incluindo as de tintas, plásticos e papel. Para atingir sua máxima eficiência no espalhamento de luz, prover a opacidade requerida ao meio em que se encontra presente, as partículas devem estar completamente dispersas neste meio. A dispersão no meio sólido, seco ou curado dependerá da eficiência de dispersão no estado úmido, a eficiência da dispersão no estado úmido dependerá de quão efetivo foi o processo de desaglomeração. O objetivo deste trabalho é compreender como as propriedades do líquido e do sólido impactam a energia requerida para desaglomerar às partículas de dióxido de titânio pigmentário em um meio líquido. As teorias de umectação de partículas, dispersão e estabilidade foram revisadas assim como as teorias de tensão de coesão de aglomerados, rugosidade da partícula e viscosidade e tensão superficial de líquidos. O objetivo destas revisões foi determinar os fatores que influenciam o processo de desaglomeração e a energia requerida para que isso ocorra. Apesar das propriedades do líquido serem os principais fatores que influenciam o processo de desaglomeração (viscosidade e tensão superficial do líquido), as propriedades da partícula, ainda que sempre associadas a propriedades do líquido, desempenham um papel importante no comportamento de umectação (raio da partícula, rugosidade, volume dos poros do aglomerado e área superficial específica). Após a caracterização das propriedades das partículas, dos aglomerados e do meio, e analisar as correlações entre as propriedades e a energia necessária para atingir o máximo da dispersão um modelo preditivo foi desenvolvido para descrever a influencia da tensão superficial e da rugosidade na energia necessária para atingir o tamanho de partícula mínimo. Este modelo se aplica a diferentes partículas com superfícies similares e partículas com superfícies diferentes com tamanhos similares.

<p align="justify">This work is a theoretical contribution to the study of thermo-hydrodynamic instabilities in fluids submitted to surface-tension (Marangoni) and buoyancy (Rayleigh) effects in layered (Benard) configurations. The driving constraint consists in a thermal (or a concentrational) gradient orthogonal to the plane of the layer(s).</p><p><p align="justify">Linear, weakly nonlinear as well as strongly nonlinear analyses are carried out, with emphasis on high Prandtl (or Schmidt) number fluids, although some results are also given for low-Prandtl number liquid metals. Attention is mostly devoted to the mechanisms responsible for the onset of complex spatio-temporal behaviours in these systems, as well as to the theoretical explanation of some existing experimental results. </p><p><p align="justify">As far as linear stability analyses (of the diffusive reference state) are concerned, a number of different effects are studied, such as Benard convection in two layers coupled at an interface (for which a general classification of instability modes is proposed), surface deformation effects and phase-change effects (non-equilibrium evaporation). Moreover, a number of different monotonous and oscillatory instability modes (leading respectively to patterns and waves in the nonlinear regime) are identified. In the case of oscillatory modes in a liquid layer with deformable interface heated from above, our analysis generalises and clarifies earlier works on the subject. A new Rayleigh-Marangoni oscillatory mode is also described for a liquid layer with an undeformable interface heated from above (coupling between internal and surface waves).</p><p><p align="justify">Weakly nonlinear analyses are then presented, first for monotonous modes in a 3D system. Emphasis is placed on the derivation of amplitude (Ginzburg-Landau) equations, with universal structure determined by the general symmetry properties of the physical system considered. These equations are thus valid outside the context of hydrodynamic instabilities, although they generally depend on a certain number of numerical coefficients which are calculated for the specific convective systems studied. The nonlinear competitions of patterns such as convective rolls, hexagons and squares is studied, showing the preference for hexagons with upflow at the centre in the surface-tension-driven case (and moderate Prandtl number), and of rolls in the buoyancy-induced case.</p><p><p align="justify">A transition to square patterns recently observed in experiments is also explained by amplitude equation analysis. The role of several fluid properties and of heat transfer conditions at the free interface is examined, for one-layer and two-layer systems. We also analyse modulation effects (spatial variation of the envelope of the patterns) in hexagonal patterns, leading to the description of secondary instabilities of supercritical hexagons (Busse balloon) in terms of phase diffusion equations, and of pentagon-heptagon defects in the hexagonal structures. In the frame of a general non-variational system of amplitude equations, we show that the pentagon-heptagon defects are generally not motionless, and may even lead to complex spatio-temporal dynamics (via a process of multiplication of defects in hexagonal structures).</p> <p><p align="justify">The onset of waves is also studied in weakly nonlinear 2D situations. The competition between travelling and standing waves is first analysed in a two-layer Rayleigh-Benard system (competition between thermal and mechanical coupling of the layers), in the vicinity of special values of the parameters for which a multiple (Takens-Bogdanov) bifurcation occurs. The behaviours in the vicinity of this point are numerically explored. Then, the interaction between waves and steady patterns with different wavenumbers is analysed. Spatially quasiperiodic (mixed) states are found to be stable in some range when the interaction between waves and patterns is non-resonant, while several transitions to chaotic dynamics (among which an infinite sequence of homoclinic bifurcations) occur when it is resonant. Some of these results have quite general validity, because they are shown to be entirely determined by quadratic interactions in amplitude equations.</p><p><p align="justify">Finally, models of strongly nonlinear surface-tension-driven convection are derived and analysed, which are thought to be representative of the transitions to thermal turbulence occurring at very high driving gradient. The role of the fastest growing modes (intrinsic length scale) is discussed, as well as scalings of steady regimes and their secondary instabilities (due to instability of the thermal boundary layer), leading to chaotic spatio-temporal dynamics whose preliminary analysis (energy spectrum) reveals features characteristic of hydrodynamic turbulence. Some of the (2D and 3D) results presented are in qualitative agreement with experiments (interfacial turbulence).</p><p><p><p> / Doctorat en sciences appliquées / info:eu-repo/semantics/nonPublished

Les nuages sont essentiels dans le cycle de l'eau et dans le budget climatique mais certains aspects de leur formation sont encore incompris. La théorie de Köhler prédit que les surfactants devraient favoriser l'activation des particules en goutte de nuage alors que les modèles actuels les considèrent comme négligeables. Au début de ce travail de thèse, quelques études commençaient à démontrer le contraire mais des preuves du rôle de ces composés dans l'atmosphère étaient encore manquantes, d'où l'objectif de ce travail de thèse. Le développement d'une méthode pour déterminer la concentration en surfactants dans les aérosols a conduit aux premières courbes de tension de surface de surfactants atmosphériques dans des aérosols PM2.5 côtiers (Suède), et à l'identification du ratio C/CMC comme paramètre clé contrôlant l'efficacité des aérosols à former des nuages. Une seconde étude a révélé des corrélations fortes entre la présence de nuages et les propriétés intrinsèques des surfactants dans des aérosols PM1 boréaux (Finlande), démontrant pour la première fois le rôle des surfactants dans la formation des gouttes de nuage à partir d'observations directes dans l'atmosphère. Les résultats prédisent un nombre de noyaux de condensation en moyenne quatre fois plus important que lorsque les effets des surfactants étaient négligés, montrant l‘importance d'inclure l'effet des surfactants dans les modèles prédictifs. Cette importance a été confirmée en laboratoire par des expériences sur des gouttes individuelles microniques par l'augmentation de leur taille en présence de surfactants. Enfin, les observations à partir des différentes études indiquent une origine biologique des surfactants dans les aérosols atmosphériques / Clouds are essential components of the Earth’s hydrological system and climate but some aspects of their formation are still not completely understood. In particular, although Köhler theory predicts that surfactants should enhance cloud droplet activation, current models consider this role negligible. At the time of this PhD work, a few studies had started to demonstrate the contrary but atmospheric evidence for the role of these compounds was still missing and very little was known about their atmospheric concentrations, sources, and mechanism of action. The objective of this PhD work was to investigate these aspects. A method was developed to quantify surfactant concentrations in aerosols. Its application led to the first absolute atmospheric surfactants’ surface tension curves, in coastal PM2.5 aerosols in Sweden, and to the identification of the ratio C/CMC as the key parameter controlling the cloud-forming efficiency of aerosols. A second study revealed strong correlations between cloud occurrence and intrinsic surfactant properties in boreal PM1 aerosols in Finland, demonstrating for the first time the role of surfactants in cloud formation from direct atmospheric observations. The results predicted Cloud Condensation Nuclei numbers four times larger on average than when neglecting surfactant effects, showing the importance of including surfactant effects in cloud predictions models. The role of surfactants inferred from macroscopic measurements was confirmed by laboratory experiments on individual micron-sized droplets showing an increase of droplet growth in the presence of surfactants. Finally, observations from the different field studies indicated a biological origin for the surfactants present in atmospheric aerosols

Ces travaux de thèse portent sur l'étude expérimentale des propriétés physiques et de la biomécanique des agrégats cellulaires embryonnaires. Le but de cette thèse était d'une part de mieux comprendre l'origine biologique de la viscosité et de la tension de surface tissulaire, d'autre part d'étudier quantitativement en détail l'élasticité cellulaire par des nouvelles mesures de rhéologie en cisaillement. Un premier chapitre concerne les mesures de tension de surface tissulaire par la méthode de compression et de viscosité tissulaire par analyse de la cinétique de fusion de deux agrégats en faisant varier comme paramètre principal la contractilité cellulaire que certains suspectent comme étant la principale origine biologique de ces paramètres. Nous utilisons le formalisme du DITH (Haris, 1976: Differential Interfacial Tension Hypothesis) pour interpréter les données. Le deuxième chapitre concerne les mesures rhéologiques en cisaillement à l'aide d'un rhéomètre commercial plan-plan sur plusieurs centaines ou milliers d'agrégats cisaillés ensembles. Nous montrons que les cellules deviennent moins rigides pour une déformation minimale d'environ 4%, mais sur l'échelle de l'heure les cellules sont capables de se rigidifier à nouveau. Ces expériences sont analysées à l'aide d'un modèle de ressorts qui cassent sous contrainte puis se ressoudent à contrainte nulle / This thesis focuses on the experimental study of physical properties and biomechanics of embryonic cell aggregates. The aim of this thesis was on one hand to better understand the biological origin of tissue viscosity and tissue surface tension, and on the other hand to study quantitatively in detail cell elasticity by means of new rheological measurements in shear. A first chapter deals with measurements of tissue surface tension by tissue compression method and tissue viscosity by analysis of the fusion kinetics of two aggregates. We vary key parameters such as cell contractility that some people suspect to be the main biological origin of these parameters. We use the formalism of DITH (Haris, 1976: Differential Interfacial Tension Hypothesis) to interpret the data. The second chapter deals with rheological measurements in shear using a commercial plate-plate rheometer over several hundred of aggregates. We showed that cells become softer after a minimal deformation of 4% is reached, and can harden again on the timescale of hour. These experiences are analyzed using a model of springs that break under stress and then reattach at zero strain

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In industrial use of paint systems a swift processing is crucial. Another very important issue is to improve the quality of the final coating. This report investigates the film formation process of powder coatings, specially the spreading of individual powder particles. The obtained results can be used to understand and control the film formation process. In this way the desired levelling can be achieved and thus the desired gloss or other surface characteristics that may be required. This means that the method could be used when evaluating different polymer and additive combinations that could be used to change film formation behaviour or curing time for powder coating systems to suit various substrates. It makes it possible to avoid and minimize different surface defects as orange peel or cratering in the powder coated film. We used a reflection optical microscope to better understand the film formation process and especially the spreading of a powder melt on surfaces with various surface energies. The obtained data were: the particle diameter, the area, area ratio and the contact angle of the powder particle as a function of time and temperature. This information can be used to derive the surface tension of any powder melt. In this report we evaluate the dependencies of temperature, heat rate and surface energy for powder coatings on different substrates. The method provides information that can be used to optimize the film formation of a specific powder coating/substrate combination. This method can be used to evaluate the powder spreading and levelling on different substrates from a surface tension point of view. We found, as expected, that the powder flows out on a hydrophilic surface and is inhibited by a hydrophobic. The increase of the area ratio on a hydrophilic surface was about five times as the initial area coverage and on a hydrophobic surface only two times the initial area coverage. The contact angle between the melted powder particle on the different surface types could be calculated. The melt surface tension could be calculated since three substrates surfaces with various surface energies were used. The melt surface tension was found to be about 18.5 mN/m. / Sammanfattning Vid industriell användning av ett färgsystem är det viktigt med en snabb och smidig målningsprocess. En viktig del är att förbättra kvaliteten på den färdiga ytan. Denna rapport undersöker filmbildningsprocessen för pulverfärg, närmare bestämt spridningen av individuella pulverpartiklar. Resultaten från utvärderingen av denna metod kan användas för att bättre förstå och få kontroll över filmbildningsprocessen. Med denna undersökningsmetod kan den önskade utslätningen uppnås och därmed den önskade glansen eller annan yteffekt som kan vara önskvärd. Metoden kan användas för att utvärdera olika polymer- och additivkombinationer som kan användas för att ändra filmbildningens uppförande eller bestämma härdningstiden för en pulverfärg att passa ett visst substrat. Metoden gör det möjligt att förhindra och minska olika ytdefekter såsom apelsinskals- eller kratereffekter i pulverfärgens yta. Ett optiskt reflectionsmikroskop användes för att bättre kunna förstå filmbildningsprocessen och särskilt spridningen av smält pulver på substrat med olika ytenergier. De mätdata vi fick var partikeldiameter, area, areaförändring och kontaktvinkeln för pulverpartiklar som funktion av tid och temperatur. Ur denna information kunde pulversmältans ytenergier härledas. I denna rapport utvärderas pulvrets beroende av temperatur, uppvärmning och ytenergi på olika substrat. Denna metod ger information som kan användas för att optimera filmbildningen av en specifik kombination av pulverfärg och substrat. Denna metod kan också användas för att utvärdera pulverspridning och utjämning av färgfilmen på olika substrat med avseende på ytenergierna. Som förväntat flyter pulvret ut på hydrofila ytor och utflytningen ändras på en hydrofob yta. På en hydrofil yta sprider sig partikeln till fem gånger den ursprungliga arean över substratet och motsvarande två gånger för en hydrofob yta. Kontaktvinkeln mellan en smält pulverpartikel på olika sorters substrat från utförda mätningar beräknas utifrån utförda mätningar. Kontaktvinklar mellan pulver och olika substrat kan användas för att beräkna smältans ytspänning. Smältans ytspänning kan beräknas då experiment gjorts på tre sorters ytor med olika kända ytenergier. Smältans ytspänning var 18,5 mN/m. Slutsatsen är att det går att observera och utvärdera resultaten av utsmältningsförloppet för pulverfärg med denna metod.

Microcalorimetric measurements and contact angle measurements were conducted to study the surface chemistry of powdered minerals. The contact angle measurements were conducted on both flat and powdered talc samples, and the results were used to determine the surface free energy components using Van Oss-Chaudhury-Good (OCG) equation. It was found that the surface hydrophobicity of talc increases with decreasing particle size. At the same time, both the Lifshitz-van der Waals (gSLW) and the Lewis acid-base (gSAB) components (and, hence, the total surface free energy (gS)) decrease with decreasing particle size. The increase in the surface hydrophobicity and the decrease in surface free energy (gS) can be attributed to preferential breakage of the mineral along the basal plane, resulting in the exposure of more basal plane surfaces to the aqueous phase. Heats of immersion measurements were conducted using a flow microcalorimeter on a number of powdered talc samples. The results were then used to calculate the contact angles using a rigorous thermodynamic relation. The measured heat of immersion values in water and calculated contact angles showed that the surface hydrophobicity of talc samples increase with decreasing particle size, which agrees with the direct contact angle measurements. A relationship between advancing water contact angle qa, and the heat of immersion (-DHi) and surface free energies was established. It was found that the value of -DHi decrease as qa increases. The microcalorimetric and direct contact angle measurements showed that acid-base interactions play a crucial role in the interaction between talc and liquid. Using the Van Oss-Chaudhury-Good's surface free energy components model, various talc powders were characterized in terms of their acidic and basic properties. It was found that the magnitude of the Lewis electron donor, gS-, and the Lewis electron acceptor, gS+, components of surface free energy is directly related to the particle size. The gS- of talc surface increased with decreasing particle size, while the gS+ slightly decreased. It was also found that the Lewis electron-donor component on talc surface is much higher than the Lewis electron-acceptor component, suggesting that the basal surface of talc is basic. The heats of adsorption of butanol on various talc samples from n-heptane solution were also determined using a flow microcalorimeter. The heats of adsorption values were used to estimate % hydrophilicity and hydrophobicity and the areal ratios of the various talc samples. In addition, contact angle and heat of butanol adsorption measurements were conducted on a run-of-mine talc sample that has been ground to two different particle size fractions, i.e., d50=12.5 mm and d50=3.0 mm, respectively. The results were used to estimate the surface free energy components at the basal and edge surfaces of talc. It was found that the total surface free energy (gS) at the basal plane surface of talc is much lower than the total surface free energy at the edge surface. The results suggest also that the basal surface of talc is monopolar basic, while the edge surface is monopolar acidic. The results explain why the basicity of talc surface increases with decreasing particle size as shown in the contact angle and microcalorimetric measurements. Furthermore, the effects of the surface free energies of solids during separation from each other by flotation and selective flocculation were studied. In the present work, a kaolin clay sample from east Georgia was used for the beneficiation tests. First, the crude kaolin was subjected to flotation and selective flocculation experiments to remove discoloring impurities (i.e., anatase (TiO2) and iron oxides) and produce high-brightness clay with GE brightness higher than 90%. The results showed that a clay product with +90% brightness could be obtained with recoveries (or yields) higher than 80% using selective flocculation technique. It was also found that a proper control of surface hydrophobicity of anatase is crucially important for a successful flotation and selective flocculation process. Heats of immersion, heats of adsorption and contact angle measurements were conducted on pure anatase surface to determine the changes in the surface free energies as a function of the surfactant dosage (e.g. hydroxamate) used for the surface treatment. The results showed that the magnitude of the contact angle and, hence, the surface free energy and its components on anatase surface varies significantly with the amount of surfactant used for the surface treatment. / Ph. D.