京都大学 / 新制・課程博士 / 博士(農学) / 甲第23960号 / 農博第2509号 / 新制||農||1092(附属図書館) / 学位論文||R4||N5395(農学部図書室) / 京都大学大学院農学研究科地域環境科学専攻 / (主査)教授 中村 公人, 教授 星野 敏, 教授 藤原 正幸 / 学位規則第4条第1項該当 / Doctor of Agricultural Science / Kyoto University / DFAM

In all coating applications, a liquid film displaces air in contact with a dry solid substrate. At a low substrate speed a thin uniform wetting line is formed on the substrates surface, but at a high speed the wetting line becomes segmented and unsteady as air becomes entrained between the substrate and the liquid. These air bubbles affect the quality of the coated product and any means to postpone this at higher speeds without changing the specifications of the coating liquid is desirable. This research assesses the validity of a theoretically based concept developed by Blake and Rushack [1] and exploited by Cohu and Benkreira [2] for dip coating. The concept suggests that angling the wetting line by an angle ß would increase the speed at which air is entrained by a factor 1/cos ß. In practice, if achieved this is a significant increase that would result in more economical operation. This concept was tested in a fast coating operation that of curtain coating which is already enhanced by what is known as hydrodynamic assistance [2]. Here we are effectively checking an additional assistance to wetting. The work, performed on a purposed built curtain coater and a rotating die, with a range of fluids showed the concept to hold but provided the data are processed in a way that separate the effect of curtain impingement from the slanting of the wetting line.

Yes / This study examines experimentally and for the first time the effect of reduced air pressure on dynamic wetting. The purpose is to assess the role of air viscosity on dynamic wetting failure which hitherto has been speculated on but not measured. In this paper we used dip coating as the model experimental flow and report data on air entrainment velocity Vae we measured with a series of silicone oils in a range of viscosities in a vacuum chamber where the pressure can be reduced from atmospheric down to a few mbar when the mean molecular free path of air is large and air ceases to have a viscosity. To complement earlier work, we carried out the experiments with a range of substrates of varying roughness. The substrates were chosen so that for each one, their two sides differ in roughness. This enables simultaneous comparative observation of their wetting performance and reduces the experimental error in assessing the role of roughness. The data presented here capture the effects of viscosity, roughness and air pressure but the important result of this study is that Vae can be increased considerably (exponentially) when the pressure is reduced with the suggestion that Vae approaches infinity as pressure approaches zero. In other words, the role of the surrounding air viscosity is important in dynamic wetting. The data from this study have significant implication to the fundamental understanding of dynamic wetting. Indeed they form the missing data link to fully understand this phenomenon. The data presented in this work also confirm the complex role of roughness, in that it can increase or decrease the air entrainment speed depending on the value on the viscosity of the coating solution. The results presented in this paper are very useful in practice as they imply that if one chooses carefully roughness one can coat viscous formulation at unexpectedly very high speeds with a moderate vacuum (50 mbar typically).

Yes / The coating flow examined here, labelled angled dip coating, is that where a substrate enters a pool of liquid forming an angle ß with the vertical so that it intersects the liquid along a wetting line which is not perpendicular to the direction of its motion. This flow situation is distinctly different from that where the substrate, inclined in the other dimension by the so-called angle of entry ¿, intersects the liquid surface perpendicularly to its motion. Experiments were carried out with various liquids to determine the effect of ß on the substrate velocity at which air is entrained into the liquid. It was observed that as this angle departs from zero, air entrainment is delayed to higher speeds. The data show that the speed which is relevant to air entrainment is not the velocity of the substrate itself but its component normal to the wetting line. This result has important practical implications and suggests that this fundamental principle is also applicable to other coating flows.

Yes / This study assesses experimentally the role of gas viscosity in controlling the minimum film thickness in slot coating in both the slot over roll and tensioned web modes. The minimum film thickness here is defined with respect to the onset of air entrainment rather than rivulets, the reason being that rivulets are an extreme form of instabilities occurring at much higher speeds. The gas viscosity effects are simulated experimentally by encasing the coaters in a sealed gas chamber in which various gases can be admitted. An appropriate choice of two gases was used to compare performances: air at atmospheric pressure and helium at sub-ambient pressure (25mbar), which we establish has a significantly lower “thin film” viscosity than atmospheric air. A capacitance sensor was used to continuously measure the film thickness on the web, which was ramped up in speed at a fixed acceleration whilst visualizations of the film stability were recorded through a viewing port in the chamber. The data collected show clearly that by coating in rarefied helium rather that atmospheric air we can reduce the minimum film thickness or air/gas entrainment low-flow limit. We attribute this widening of the stable coating window to the enhancement of dynamic wetting that results when the thin film gas viscosity is reduced. These results have evident practical significance for slot coating, the coating method of choice in many new technological applications, but it is their fundamental merit which is new and one that should be followed with further data and theoretical underpinning.

No / This study assesses experimentally the role of gas dissolution in gas entrainment which hitherto has been speculated on but not measured. In this paper, we used dip coating as the model experimental flow and performed the experiments with a dip coater encased in a vacuum chamber in which we admitted various gases. An appropriate choice of gases (air, carbon dioxide and helium) coupled with low pressure conditions from atmospheric down to 75 mbar enables us to test whether gas solubility is a key determinant in gas entrainment. The data presented here track the evolution in time of the size of bubbles of gas entrained in the liquid (silicone oil) which we observed to always occur at a critical speed, immediately after the dynamic wetting line breaks from a straight line into a serrated line with tiny vees the downstream apices of which are the locations from which the bubbles stream out. The results suggest that permeability combining solubility and diffusivity as a single parameter dictates the rate of dissolution when at atmospheric pressure. Helium, despite its comparatively sluggish rate of dissolution/growth into silicone oil was observed to have a more enhanced gas entrainment speed than air and carbon dioxide. Thus, the hypothetical contention from previous work (Miyamoto and Scriven, 1982) that gas can be entrained as a thin film which breaks into bubbles before dynamic wetting failure occurs is not realised, at least not in dip coating. The data presented here reinforce recent work by Benkreira and Ikin (2010) that thin film gas viscosity is the critical factor, over-riding dissolution during gas entrainment. This finding is fundamentally important and new and provides the experimental basis needed to develop and underpin new models for gas entrainment in coating flows.

Dans le domaine de la nanophotonique, la compréhension des phénomènes optiques liés au guidage sub-longueur d'onde dans des structures pleines (nanofils) ou creuses (nanotubes) est un enjeu prioritaire. L'objectif de cette thèse a porté sur l'étude de la propagation lumineuse au sein de nouveaux guides d'onde nanométriques passifs et actifs. Pour cela, des nanofils et nanotubes à base de polymère ont été conçus et élaborés par méthode wetting template. Afin de caractériser leur comportement optique et en particulier la propagation sub-longueur d'onde, de nouveaux outils expérimentaux et numériques ont été développés. La modélisation des phénomènes propagatifs dans ces nanofibres a été effectuée par la méthode numérique FDTD. Les effets de la géométrie de ces nanofils et nanotubes, de par leurs dimensions (diamètres externe et interne pour les nanotubes) et du substrat sur le comportement propagatif et le niveau des pertes ont en particulier été déterminés. Sur le plan expérimental, deux types de nanofibres on été utilisés : - des nanofibres "passives" à base de polymère SU8 et - des nanofibres "actives" comportant un polymère guidant la lumière et un luminophore servant de source à l'échelle nanométrique. Pour l'étude des nanofibres de SU8, l'injection directe a été réalisée par le biais d'une fibre optique microlentillée. Un résultat marquant est l'évaluation des pertes optiques mesuré par la méthode cut- back autour de 1,25 dB/mm pour des nanotubes aux diamètres externes et internes respectivement de 240 nm et 120 nm. Cette évaluation de pertes optiques apparaît très compétitif comparativement à d'autres systèmes actuellement envisagés pour la nanophotonique intégrée. Concernant les nanofibres actives qui comportent des luminophores (cluster organométalliques ou polymère fluorescent PFO), nos études ont validé l'excitation du mode propre par caractérisation dans l'espace de Fourier. Nos résultats ont montré le potentiel de ces nanofibres organiques comme briques pour la nanophotonique. / In the field of nanophotonics, the understanding of optical phenomena related to sub-wavelength guiding in filled structures (nanowires) or hollow (nanotubes) is a priority. The objective of this thesis focused on the study of light propagation in new passive and active nanoscale waveguides. For this, nanowires and nanotubes based polymer has been designed and developed by template wetting method. To characterize their optical behavior and in particular the sub-wavelength propagation, new numerical and experimental tools have been developed. Modelling phenomena propagating in these nanofibers was performed by the numerical FDTD method. The effects of the geometry of these nanotubes and nanowires, by their size (outer and inner diameter for nanotubes) and propagating on the substrate and the behavior of losses have been determined in particular. Experimentally, two types of nanofibers have been used: - "passive" nanofibers based on SU8 polymer and - "active" polymer nanofibers having a waveguiding polymer and a luminophor as a source at nanoscale. To study nanofibers SU8, direct injection was performed through an microlensed optical fiber. A striking result is the assessment of optical losses measured by the cut-back around 1.25 dB/mm for nanotubes to external and internal diameters respectively 240 nm and 120 nm. This assessment of optical losses appear very competitive compared to other systems currently envisaged for integrated nanophotonics. Regarding the active nanofibers which comprise luminophors (organometallic cluster or fluorescent polymer PFO), our studies have validated the excitation of mode by characterization in Fourier space. Our results showed the potential of organic nanofibers as bricks for nanophotonics.

No description available.

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.

L'électrolyse de la vapeur d'eau à haute température et sous pression avec des électrolytes à conduction protonique est un moyen envisagé pour produire massivement de l'hydrogène à un coût compétitif. Pour être fonctionnelle, une cellule d'électrolyse doit être hermétique vis-à-vis de l'extérieur et entre le compartiment anodique (O2 et H2O) et le compartiment cathodique (H2). Ainsi, la réalisation de liaisons céramique-métal est nécessaire, soit pour l'intégration de l'électrolyte (liaison perovskite-métal), soit pour l'intégration d'alimentations électriques (liaison alumine-métal). Compte-tenu des conditions de fonctionnement de la cellule (600°C, 50 bars, vapeur d'eau), seul un procédé de brasage est envisageable pour réaliser des jonctions résistantes mécaniquement et hermétiques. L'expertise des processus de corrosion sous vapeur d'eau a permis de définir la partie métallique et la brasure pour cette application et a montré que des alliages spécifiques étaient requis. L'étude de métallisation des céramiques par PVD pour permettre le mouillage de la brasure au moment du brasage a montré que la présence d'une barrière de diffusion était nécessaire, pour éviter la dissolution du dépôt lors du passage à l'état liquide de la brasure. Après une étude de mouillabilité à chaud de la brasure sélectionnée sur les céramiques métallisées et les substrats métalliques, les liaisons ont été optimisées en appliquant la méthodologie des plans d'expériences sur des éprouvettes normalisées. L'ensemble des résultats a ainsi conduit au développement de liaisons céramique-métal possédant de bonnes propriétés mécaniques (Rm = 60 MPa à 20°C) et hermétiques. / Steam electrolysis at high temperature and under pressure with protonic conduction electrolyte is a way to produce hydrogen massively at low cost. To operate, an electrolysis cell must be hermetic especially between the anodic compartment (O2 and H2O) and the cathodic one (H2). Thus, ceramic to metal assemblies are needed, either to insert the electrolyte (perovskite-metal junction) or to realize power supply (alumina-metal junction).Considering the operating conditions (873°K, 725 PSI, steam), only a brazing process is possible to realize strong and hermetic junctions.The evaluation of corrosion process under steam pressure has enabled to select a metallic component and a brazing alloy for this application, and has shown that specific alloys are needed.The studies of ceramics metallization by PVD to assure the brazing alloy wetting throughout the brazing process have shown that a barrier diffusion was necessary to avoid the dissolution of coatings when the brazing alloy become liquid.After wetting experimentations of the chosen brazing alloy over the metalized ceramics and the metallic substrate, ceramic to metal assemblies have been optimized in applying the experimental design methodology on standard samples (ASTM).The whole results have enabled to develop hermetic ceramic to metal assemblies having good mechanical properties (Rm = 8700 PSI at 300°K).