An experimental investigation was performed to study the confined boiling heat transfer characteristics over a saturated porous structure using distilled water as the working fluid. A thin stainless steel resistive foil stretched between two copper electrodes was used to heat a saturated porous plate with an effective pore size of 50 gm. The temperature distribution on the foil heater was measured using a high speed thermal imaging camera. The effect of the gap height between the heater and the porous plate on the heat transfer was investigated for gap heights ranging from 0 um to 1000 um and for heat fluxes ranging from 11.7 kW/m2 to 58.3 kW/m2. It was observed that the highest heat transfer rate was obtained at a gap height of approximately 600 pm. The main heat transfer mechanism is thought to be confined boiling in the small gap between the heating surface and the saturated porous structure. It was observed that the effect of the subcooled liquid temperature did not have a significant effect on the heat transfer. The effect of the pore size in the porous plate was investigated by repeating the measurements with a porous plate of 200 gm pore size. It was observed that the thermal resistance for the plate with a 200 gm pore size was significantly higher than the plate with 50 gm pores for gaps less than 300 gm. At a larger gap height of 600 gm, similar heat transfer performances were obtained for the two porous media. / Thesis / Master of Applied Science (MASc)

<p>In this work, an in-depth analysis of crystalline characteristics has been performed for a unique set of strictly monodisperse poly-ε-caprolactone (PCL) oligomers. The molecules have different sets of end groups with various degrees of bulkiness and hydrogen bonding potential, affecting their aptitude to pack in ordered crystal structures. The oligomers also have different numbers of repeating units (<em>n </em>= 2-64), affecting the degree to which end groups influence overall molecular characteristics. The presence of bulky end groups leads to an innate confinement effect on crystallisation which in turn makes it possible to utilize the set of PCL oligomers to study confined space crystallisation. Confined space crystallisation is explored as a route to gain further understanding about the early metastable phases in crystal formation.</p><p> </p><p>The monodisperse nature of the samples made it possible to collect very precise small-angle and wide-angle X-ray scattering data (SAXS and WAXS) as well as calorimetric data. Computer modeling studies were performed to support experimental findings. It was shown that end groups strongly affected crystallisation features for the shorter oligomers (<em>n </em>≤ 8) but to a lesser extend for the longer oligomers (<em>n </em>≥ 16). The presence of a bulky end group at one end of an oligomer could inhibit the formation of hydrogen bonds on the other end. Short oligomers (<em>n</em> = 8) with OH-end groups exhibited novel packing characteristics. At one isothermal crystallisation temperature the molecules exhibited not only lamellar ordering but also an additional, likely rectangular or slanted, ordering. The sample was packed in a unique structure with molecular chains lying parallel but not aligned head to head with each other. At a higher crystallisation temperature the molecules packed in a double layered structure and at an even higher temperature in a typical non-folded but tilted single-molecular layer pattern.</p><p> </p><p>Unit cell determination was performed for a short oligomer with two bulky end groups, showing the existence of a tetragonal unit cell with different dimensions than the orthorhombic unit cells previously reported for linear PCL without end groups. To gain greater insight into the earliest stages of molecular packing, in situ WAXS measurements were performed using a synchrotron radiation beam and measuring data each 12 s whilst very slowly going from melt to isothermal crystallisation. It was shown that the crystal unit cell was distorted during the first minutes of slow crystallisation, which might either represent a metastable phase or else a highly distorted orthorhombic phase.</p>

Dans les structures confinées, comme les silices mésoporeuses, la mobilité et l'interaction des cations avec les surfaces sont des phénomènes clés. Ils guident les propriétés d'adsorption dont découlent de nombreuses applications, en particulier pour l’extraction et la séparation. Ce travail de thèse en modélisation propose de s'intéresser aux propriétés d'interface, d'équilibre et de transport qui pilotent l'échange ou l'adsorption ionique. Il s’agit de décrire la physico-chimie du processus d’adsorption de cations alcalins à la surface de silices chargée par une approche multiéchelle ayant une base moléculaire. Pour cela une étude de la série des alcalins (Li+, Na+, K+ et Cs+) a été menée. Le cadre théorique est la théorie de Mc Millan Mayer. Celle-ci, fondamentale pour les solutions libres s’est révélée également être une méthode de choix pour les milieux confinés. Le potentiel de force moyenne de McMillan Mayer entre les ions et des sites de surface a pu être calculé par la méthode d'Umbrella Sampling associé à l’algorithme WHAM. Le phénomène qui s’est révélé le plus pertinent correspond à la présence de paires au contact (Contact Ion Pairs - CIP) entre les oxygènes de la surface et les cations, sans molécule d’eau qui les sépare. Ces CIP se traduisent dans les courbes de potentiel par un premier minimum d’intensité supérieure à l’agitation thermique. Pour les petits ions (lithium), ce complexe de surface est particulièrement stable, les constantes d’adsorption et les temps de résidence étant particulièrement élevés, ce qui rend délicat la simulation moléculaire directe de ces phénomènes. Il a été observé une inversion de sélectivité entre les sites silanolates et siloxanes. L'adsorption est différente pour un ion cosmotrope comme Li+ qui doit se déshydrater pour s'adsorber et un ion chaotrope comme Cs+ qui est moins lié au solvant. Les constantes d’adsorption de chaque site de même type ne sont pas toutes égales. L’étude des phénomènes électrocinétiques (électro-osmose et conductivité de surface) a également été menée en comparant les descriptions classiques (modèles de Poisson-Boltzmann, de Smoluchowski, et de Bikerman) aux résultats de dynamique moléculaire. Il est apparu que l'image traditionnelle en plusieurs couches des interfaces (couches de Helmholtz internes et externes, de Stern, de Gouy-Chapman, plan de cisaillement) devait être remplacée par un modèle beaucoup plus simple mais plus efficace. Du point de vue des ions, deux domaines apparaissent : les CIP, globalement fixés à la surface transmettant la force électrique au solide et pas au fluide, et les autres ions, globalement libres, transmettant la force électrique au fluide. Aucune viscosité ou constante diélectrique dépendant de la distance n’a été mise en évidence. Une diminution de la mobilité des ions à proximité de la surface a en revanche été observée. Ce phénomène peut être quantitativement compris comme un effet hydrodynamique du à la présence des surfaces qui gênent le flux en retour du solvant. Ce travail permet ainsi de mieux caractériser l'interface verre chargé-solution pour les applications en science de la séparation. Il a pu montrer comment les simulations moléculaires pouvaient non seulement prédire les paramètres des modèles macroscopiques (constantes d’adsorption, coefficients de transport, etc.) mais surtout modifier ceux-ci pour les rendre en accord avec la description moléculaire. Une telle stratégie pourra par la suite être mise en œuvre sur des systèmes plus complexes, comme des modèles de surfaces greffées. / In confined structures, such as mesoporous silica, the mobility of the cations and the surface/cations interactions are key phenomena. They drive adsorption properties, which control numerous applications, especially for extraction and separation. This modelling work describes equilibrium and transport interface properties that control ion exchange and ionic adsorption. The physical and chemical properties of adsorption processes of alkali cations at the surface of charged silica is studied thanks to a multiscale approach based on a molecular description. The systematic study of alkali serie (Li+, Na+, K+ and Cs+) has been studied to that goal. The theoretical framework is Mc Millan-Mayer theory. The latter, which is known to be of fundamental significance for bulk solutions is found to be also relevant for confined media. The mean force potential of Mc Millan-Mayer between ions and surface sites has been calculated by Umbrella Sampling associated to the WHAM algorithm. The most important phenomenon we identified corresponds to the existence of Contact Ion Pairs (CIP) between the surface oxygen and the cations, without separating solvent molecules. The CIP correspond to the first minima in the potential curves if the associated energy is more than the thermal agitation (kT). For small ions (lithium) this surface complex is especially stable, adsorption constant and residence time being particularly high so that the direct molecular simulations are very difficult. A selectivity inversion has been observed between silanolates and siloxanes. Adsorption is different for kosmotropic ions (as Li+) which has to be dehydrated to be adsorbed and chaotropic ions (as Cs+) for which the solvent bound is weaker. Adsorption constants for sites of the same nature are not equal. The study of the electrokinetic phenomena (electro-osmosis and surface conductivity) has also been performed by comparing the classical descriptions (Poisson-Boltzmann, Smoluchowski, and Bikerman models) to molecular simulations. The traditional picture of the interface with several layers (inner and outer Helmholtz, Stern and Gouy-Chapman layers, shear plane) is found to be replaced by a simpler but more efficient model. For the ions, two domains are obtained: (i) CIPs, firmly bound to the surface that transmit the electrical force to the solid (and not the fluid) (ii) other ions that are globally free that transmit the electric force to the fluid. No space dependent viscosity or dielectric constant have been obtained. On the other hand, a decrease of ion mobility in the vicinity of the surface has been observed. This phenomenon can be quantitatively understood as a hydrodynamic effect that comes from the solid surface, which hinders the backflow of the solvent. This work allows a better characterization of charged glass-solution interfaces for separation science. It shows how molecular simulations can not only predict the parameters of macroscopic models (adsorption constant, transport coefficients), but also modify the latters in order to make them in agreement with molecular descriptions. Such a strategy can be extended to more complex systems, such as models of grafted surfaces.

As human population increases, demand for water supplies will cause an increase in pumping rates from confined aquifers which may become unconfined after long-term pumping. Such an unconfined-confined conversion problem has not been fully investigated before and is the focus of this thesis. The objective of this thesis is to use both analytical and numerical modeling to investigate groundwater flow in an unconfined-confined aquifer including the no-flow lateral boundary effect and the regional flow influence. This study has used Girinskii’s Potential in combination with MATLAB to depict how changes in aquifer dimensions, hydraulic properties, regional flow rates, and pumping rates affect the size and shape of the unconfined-confined boundary. This study finds that the unconfined-confined conversion is quite sensitive to the distance between the piezometric surface and the upper confining bed when that distance is small, and the sensitivity lessens as that distance increases. The study shows that pumping rate is the dominating factor for controlling the size of the unconfined-confined boundary in comparison to the regional flow. It also shows that the presence of a no-flow boundary alters the normally elliptical shape of the unconfined-confined boundary.

Il est actuellement bien connu que les molécules non sphériques peuvent former des mésophases (ou cristaux liquides), c'est-à-dire des phases dont les propriétés sont intermédiaires entre celles des liquides et celles des cristaux. La mésophase la plus connue est la phase nématique. Il s'agit d'une phase caractérisée par une distribution aléatoire des centres de masse des molécules, mais dans laquelle l'orientation des molécules présente une direction préférentielle, désignée par un vecteur unité appelé le directeur du nématique. Une telle phase possède donc la fluidité d'un liquide tout en présentant, tel un cristal, une biréfringence. C'est cette dernière propriété qui est exploitée dans les applications technologiques, principalement dans les dispositifs d'affichage. Dans un tel dispositif, le liquide nématique est contenu dans une cellule (il y a une cellule par pixel), et son directeur est manipulé à l'aide d'un champ extérieur, électrique ou magnétique. Pour une bonne compréhension du fonctionnement de ce dispositif, il est essentiel de connaître le profil du directeur à travers la cellule en l'absence de champ extérieur. Dans le cadre de ce travail, nous avons étudié un nématique torsadé, c'est-à-dire dont le directeur décrit une hélice à travers la cellule. Ce profil est déterminé principalement par les propriétés d'ancrage du liquide nématique sur les parois solides de la cellule. En effet, celles-ci peuvent posséder une direction d'ancrage privilégiée, qui favorise l'alignement du directeur dans une direction particulière. Nous avons considéré ici le cas de directions d'ancrage planaires, c'est-à-dire que le directeur est dans le plan des parois. Alors que l'ajout de parois identiques dans le système induit toujours une non-uniformité spatiale dans la densité du nématique (en comparaison avec un nématique en coeur de phase), l'utilisation de directions d'ancrage différentes induit une non-uniformité orientationnelle dans le directeur du nématique; dans notre cas une torsion. C'est principalement ce profil de directeur torsadé qui nous intéresse ici. L'objectif général de ce travail consiste donc à étudier les propriétés d'ancrage d'une phase nématique confinée et torsadée, d'une part par une théorie microscopique (théorie de la fonctionnelle de la densité), et d'autre part sur le plan de simulations de Monte Carlo, en particulier dans le cas où les molécules ont la forme de disques (discotiques).

Mechanical rubbing alignment is the most common used method in the liquid crystal display manufacturing process. However, it may cause dust and electrostatic problem. In this study, we investigate effects of low surface free energy Polydimethylsiloxane (PDMS) on orientation of liquid crystal molecules in a confined structure and fabricate alignment layer using PDMS. In the present study, we show that liquid crystal molecules are arranged in consistency without rubbing process and it may be a new homogeneously aligned mode in liquid crystal display. In this thesis, liquid crystal textures were observed using polarizing optical microscopy (POM). It was found that liquid crystal molecules were homogeneously aligned in PDMS holes. In addition, this thesis indicated that how liquid crystal alignment affected by PDMS layer thickness and surface treatment. We learned that using treatment of JALS-9800 film on the bottom substrate from liquid crystal texture can obtain the arrangement of expected liquid crystal molecules. The liquid crystal device can be produced using PDMS structure. The measurement of electro-optic characteristics showed that the circular shape in the confined structure had better transmittance and contrast ratio.

PDMS has not only the characteristics of good chemical and physical properties,flexible, low surface free energy, and good optically transparent, also has the advantages of low cost, low toxicity and environmental protection. In this study we use PDMS to fabricate liquid crystal device with different micro-confined structures. We had a discussion about liquid crystal in the micro-confined structure through optical textures and measured electro-optical characteristics on our device. Through the experiment we found the liquid crystal device with micro-confined structure had not only the characteristics of wide viewing angle and contrast ratio has been up to standard in normal display. And it also demonstrated the capability in flexible liquid crystal display.

This study investigates the changes due to crosslinking treatment in stiffness, permeability, and glycosaminoglycan (GAG) content of bovine intervertebral discs. The objective of this study was to determine the mechanical and biochemical effects of crosslinking treatment on lumbar bovine tissue. Previous studies have found that crosslinking can increase stiffness and permeability in the intervertebral disc. These changes have not yet been investigated by confined compression, stress-relaxation tests of young bovine tissue. Eleven lumbar motion segments were harvested from calf spines and soaked in a saline solution or one of four crosslinking treatments (genipin, methylglyoxal, proanthrocyanidin, and EDC). Five mm diameter samples were removed from the midannulus region at anterior / anterior-lateral locations, confined in a saline bath, swelled to equilibrium, and tested in confined compression stress-relaxation to 15% strain in 5% increments. Radial samples were also harvested, treated with saline solution and EDC, and tested in the same manner. The aggregate modulus and hydraulic permeability were calculated using the nonlinear biphasic theory. Swelling pressure was calculated as the load at swelling equilibrium. GAG content was measured using the dimethylmethylene blue assay. Differences with P value < 0.05 were considered significant. In the axial orientation, all crosslinking treatments except methyglyoxal at least doubled the aggregate modulus relative to soaked controls (P less than 0.05). Genipin treatment resulted in 78% lower axial permeability, proanthrocyanidin (PA) 50% lower, and EDC treatment 84% lower relative to soaked controls (P &lt; 0.05). GAG content measured in the methyglyoxal treatment group was 25% lower than in soaked control group. Genipin (G), proanthrocyanidin (PA), and EDC treatment increased the swelling pressure by at least 65% (P less than 0.05). In the radial orientation, EDC treatment increased the stiffness by 75%, and did not significantly affect the permeability or swelling pressure. Some crosslinking treatments proved effective in increasing the stiffness and swelling pressure of the disc. The increased swelling pressure in G, PA, and EDC treatment groups relative to soaked controls suggests reduced GAG leaching during soaking treatment, further confirmed by the reduction in permeability in these groups.

As human population increases, demand for water supplies will cause an increase in pumping rates from confined aquifers which may become unconfined after long-term pumping. Such an unconfined-confined conversion problem has not been fully investigated before and is the focus of this thesis. The objective of this thesis is to use both analytical and numerical modeling to investigate groundwater flow in an unconfined-confined aquifer including the no-flow lateral boundary effect and the regional flow influence. This study has used Girinskii’s Potential in combination with MATLAB to depict how changes in aquifer dimensions, hydraulic properties, regional flow rates, and pumping rates affect the size and shape of the unconfined-confined boundary. This study finds that the unconfined-confined conversion is quite sensitive to the distance between the piezometric surface and the upper confining bed when that distance is small, and the sensitivity lessens as that distance increases. The study shows that pumping rate is the dominating factor for controlling the size of the unconfined-confined boundary in comparison to the regional flow. It also shows that the presence of a no-flow boundary alters the normally elliptical shape of the unconfined-confined boundary.

Orientador: Aguinaldo Robinson de Souza / Banca: Nelson Henrique Morgon / Banca: Francisco Carlos Lavarda / O Programa de Pós-Graduação em Ciência e Tecnologia de Materiais, PosMat, tem caráter institucional e integra as atividades de pesquisa em materiais de diversos campi da Unesp / Resumo: Esse trabalho tem por objetivo estudar moléculas confinadas via método de Hartree-Fock, de modo a determinar a energia de ligação e do raio de ligação. Estudamos as moléculas de H- 'H POT. +' e HE- 'H POT. +' incluindo os efeitos de blindagem através da modificação da energia de repulsão nuclear. Essa modificação ocorreu pela introdução do "fator de blindagem" que, ao ser sucessivamente modificado, permitiu um estudo comparativo do comportamento da energia de ligação e do raio de ligação. A relevância desse trabalho para a área de Ciências e Tecnologia de Materiais deve-se ao fato de que a compreensão e o desenvolvimento de materiais e técnicas dependem não somente das espécies químicas, mas também das ligações químicas, pois ambas determinam as características e as propriedades do material. / Abstract: The main objective of this work was to study the chemical and physical properties, as the bond distance and energy, of confined atoms via Hartree-Fock method. We studied the H- 'H POT. +' e HE- 'H POT. +' molecules introducing the screening effects via modification of the nuclear repulsion energy between atoms allowing thus to understanding the effects in the bond length and energy. The relevance of this work is of prime importance in material science due to many technological applications as molecules confined to surfaces, in liquid helium, neutral plasma and catalysis. All this applications has a common background of knowledge: the influence of the material physical and chemical properties with the distance and energy between the atoms in the chemical composition of the material. / Mestre