My dissertation is an investigation into the basic Physics of phase separation fronts. Such phase-separation fronts occur in many practical applications, like the formation of immersion precipitation membranes, Temperature induced phase-separation of polymeric blends, or the formation of steel. Despite the fact that these phenomena are ubiquitous no generally acceptable theory of phase-separation front exists. I believe the reason lies in the complexity of many of these material systems where a large number of physical effects (like phase-separation, crystallization, hydrodynamics, etc) cooperate to generate these structures. As a Physicist, I was driven to develop an understanding of these systems, and we choose to start our investigation with the simplest system that would incorporate a phase-separation front. So we initially limited our study to systems with a purely diffusive dynamics. The phase-separation front is induced by a control-parameter front that is a simple step function advancing with a prescribed velocity. We investigated these systems numerically using a lattice Boltzmann method and also investigated them analytically as much as possible. Starting from a one-dimensional front moving with a constant velocity we then extended the complexity of the systems by increasing the number of dimensions, examining a variable front velocity, and finally by including hydrodynamics.

Ce travail porte sur l’élaboration de matériaux nanostructurés et le contrôle de la formation de nanocristaux d’oxyde d’étain dans une matrice de silice amorphe obtenue par voie sol-gel. Préalablement à l’étude structurale et microstructurale des xérogels, une première partie de ces travaux de thèse concerne le procédé sol-gel. Le lavage des gels par des solutions hydro-alcooliques permet d’extraire une quantité importante d’acide chlorhydrique après gélification. Ainsi si les solutions de lavage sont renouvelées, 50 % de l’acide introduit peut être retiré. Ce lavage, associé avec un séchage contrôlé, a également permis de réduire significativement la durée du séchage et d’obtenir des xérogels centimétriques non fissurés.La seconde partie de ce travail a porté sur l’étude structurale et microstructurale des xérogels réalisée au travers de mesures de diffraction des rayons X ex situ ou de diffusion centrale et diffraction des rayons X couplée in situ en fonction de la température sur des lignes de lumière situées autour de sources synchrotrons. Nous avons montré que dans des xérogels contenant 10 % d’étain, la quantité de cristaux nanométriques d'oxyde d'étain peut augmenter continuellement sans que leur taille moyenne ne s’accroisse. La taille moyenne la plus faible est obtenue après un prétraitement thermique de séparation de phases préalable à celui de cristallisation et plus ce traitement est long plus la taille des cristaux est faible. Cette étude a été complétée par des traitements thermiques effectués in situ afin de suivre simultanément la séparation de phases et la cristallisation. Ces mesures ont permis d’observer le phénomène de séparation de phases dans les xérogels contenant 10 % d’étain et dont la quantité cristallisée obtenue lors d’un traitement thermique à 350 °C est la plus importante au regard des autres températures de traitement thermique et des concentrations en étain. / This PhD work deals with the development of nanostructured oxide materials and the control of the formation of tin oxide nanocrystals in an amorphous silica matrix obtained by sol-gel process. Prior to the structural and microstructural study of xerogels, a first part of this work concerns the sol-gel process. Washing the gels with hydroalcoholic solutions allows to extract a significant quantity of hydrochloric acid after gelation. Thus, if the washing solutions are renewed, 50% of the acid introduced can be removed. This washing, combined with improvement of the drying process, allowed to reduce the drying duration and finally to obtain bulk xerogels exhibiting a centimetric size.The second part of this work focuses on the structural and microstructural evolution of xerogels through thermal treatments. The results of this second part are obtained through ex situ measurements of X-ray diffraction or coupled small angle X-ray scattering and X-ray diffraction experiments realized in situ as a function of temperature. In both cases the measurements have been performed on synchrotron beamlines. We show that in xerogels containing 10% tin, the amount of nanosized tin oxide crystals can continuously increases without increasing the average size of these crystals. The lowest average size is obtained after a phase separation thermal pretreatment before crystallization and the longer this treatment is, the smaller the size of the crystals. This study is completed by heat treatments carried out in situ in order to simultaneously evidence phase separation and crystallization. These measurements allow to observe the phenomenon of phase separation by small angle X-ray scattering in xerogels containing 10% tin and whose crystallized quantity obtained during a thermal treatment at 350 °C is the highest compared to other heat treatment temperatures and tin concentrations.

No description available.

The primary objective of this research is to investigate the morphological and mechanical properties of composite materials and porous materials prepared by thermally induced phase separation. High melting crystallizable diluents were mixed with polymers so that the phase separation would be induced by the solidification of the diluents upon cooling. Theoretical phase diagrams were calculated using Flory-Huggins solution thermodynamics which show good agreement with the experimental results. Porous materials were prepared by the extraction of the crystallized diluents after cooling the mixtures (hexamethylbenzene/polyethylene and pyrene/polyethylene). Anisotropic structures show strong dependence on the identity of the diluents and the composition of the mixtures. Anisotropic crystal growth of the diluents was studied in terms of thermodynamics and kinetics using DSC, optical microscopy and SEM. Microstructures of the porous materials were explained in terms of supercooling and dendritic solidification. Dual functionality of the crystallizable diluents for composite materials was evaluated using isotactic polypropylene (iPP) and compatible diluents that crystallize upon cooling. The selected diluents form homogeneous mixtures with iPP at high temperature and lower the viscosity (improved processability), which undergo phase separation upon cooling to form solid particles that function as a toughening agent at room temperature. Tensile properties and morphology of the composites showed that organic crystalline particles have the similar effect as rigid particles to increase toughness; de-wetting between the particle and iPP matrix occurs at the early stage of deformation, followed by unhindered plastic flow that consumes significant amount of fracture energy. The effect of the diluents, however, strongly depends on the identity of the diluents that interact with the iPP during solidification step, which was demonstrated by comparing tetrabromobisphenol-A and phthalic anhydride. A simple method to prepare composite surfaces that can change the wettability in response to the temperature change was proposed and evaluated. Composite surfaces prepared by nanoporous alumina templates filled with polymers showed surface morphology and wettability that depend on temperature. This effect is attributed to the significant difference in thermal conductivity and the thermal expansion coefficient between the alumina and the polymers. The reversibility in thermal response depends on the properties of the polymers.

Co-continuous structures generated from the phase separation of polymer blends present many opportunities for practical application. Due to the large interfacial area in such structures and the incompatibility between the components, such non-equilibrium structures tend to coarsen spontaneously into larger sizes and eventually form dispersed morphologies. Here, we utilize various strategies to kinetically stabilize the co-continuous structures in polymer blend systems at nano- to micro- size scales. In the partially miscible blend of polystyrene and poly(vinyl methyl ether), we took advantage of the spinodal decomposition (SD) process upon thermal quenching, and arrested the co-continuous micro-structures by the addition of nanoparticles. In this approach, the critical factor for structural stabilization is that the nanoparticles are preferentially segregated into one phase of a polymer mixture undergoing SD and form a percolated network (colloidal gel) beyond a critical loading of nanoparticles. Once formed, this network prevents further structural coarsening and thus arrests the co-continuous structure with a characteristic length scale of several microns. Our findings indicate that a key to arresting the co-continuous blend morphology at modest volume fractions of preferentially-wetted particles is to have attractive, rather than repulsive, interactions between particles. For the immiscible blend of polystyrene and poly(2-vinyl pyridine) (PS/P2VP), we presented a strategy to compatibilize the blend by using random copolymers of styrene and 2-vinylpyridine, controlling the degree of immiscibility between PS and P2VP. Based on such compatibilization, co-continuous structured membranes, having characteristic size down to tens of nanometers, were fabricated in a facile way, via the solvent-induced macrophase separation of polymer blend thin films. The feature size was controlled by controlling the film thickness and varying the molecular weight of the PS homopolymer and the random copolymers. As the processing method (solution casting) is simple and the structures are insensitive to the solvent or substrate choices, this approach shows great potential in the large scale fabrication of co-continuous nanoscopic templates on flexible substrates via roll-to-roll processes. Moreover, we proposed a quasi-binary blend system based on the PS/P2VP pair with the addition of a common solvent. An experimentally accessible phase mixing temperature was achieved, and the co-continuous morphologies were generated via thermally induced spinodal decomposition. The addition of solid particles significantly slowed down the coarsening kinetics and, in some cases, arrested the co-continuous structures at ~6 &mum for a short period of time. This study suggests an alternative means to achieve co-continuous structures in polymer solutions and also provides better understanding of the thermodynamics and kinetics of polymer blend phase separation. Our research demonstrates several means of kinetically trapping the non-equilibrium interconnected structures at sub-micron to tens-of-nanometer size scales that are germane to several functions including active layers of photovoltaic cells and polymer-based membranes.

京都大学 / 新制・課程博士 / 博士(医学) / 甲第24134号 / 医博第4874号 / 新制||医||1060(附属図書館) / 京都大学大学院医学研究科医学専攻 / (主査)教授 竹内 理, 教授 中川 一路, 教授 髙折 晃史 / 学位規則第4条第1項該当 / Doctor of Medical Science / Kyoto University / DFAM

No description available.

Anomalously high groundwater salinities exist within the syn-impact sediment of the Chesapeake Bay impact crater, including an unexplained brine. This brine may be the result of phase-separation of seawater that occurred within the syn-impact sediments as underlying deformed and possibly melted basement rock cooled following impact. The 85 km wide crater has been described as a complex peak-ring crater; created 35.8 million years ago in the then submerged unconsolidated sediments of the Atlantic Coastal Plain and now completely buried by post-impact sediments. An annular trough with relatively undisturbed basement surrounds a ~38 km diameter inner basin with a peak ring and central uplift. The basement surface within the inner basin was modified by the impact and is projected to be approximately 1.6 km below sea level. Geothermometry and advective and conductive heat flow modeling was performed to characterize a possible post-impact hydrothermal system. Thermal maturity and radiogenic techniques were used to estimate the temperature history of the crater sediments. Core samples from one borehole just outside the crater, two within the annular trough, and one shallow borehole within the inner basin were examined. Numerical heat and fluid flow models were developed using a range of likely sediment parameters and basal heat flow values to determine if phase-separation temperatures were likely to have occurred, and to evaluate what affect, if any, lithostatic overpressures may have had on post-impact cooling. Geothermometry results indicate that no detectable thermal anomaly exists within the syn or post-impact sediments at these boreholes; however, no data are available within the deep inner basin where temperatures were likely to have been higher. Samples from existing boreholes suggest that sediment are organically immature and likely were never heated above ~40°C for a geologically significant period of time. These results support apatite He (U/Th) and previously published apatite fission track radiogenic ages indicating no Cenozoic resetting. Heat flow simulations indicate that a high temperature (>400°C) hydrothermal system could have existed within the inner basin and not caused any measurable effect on thermal maturity in the annular trough and shallow portion of the inner basin. Results also indicate that phase-separation could have occurred in the syn-impact sediments using reasonable estimates of basal heat flow, permeability, thermal conductivity, and porosity values, and that overpressures resulting from rapid deposition of syn-impact sediments dissipate within a few thousand years and are not an important heat transport mechanism. / Master of Science

Phase-redistribution and full-phase separation data were generated for two-phase (air-water) flow splitting at an equal-sided impacting tee junction with a horizontal inlet and inclined outlets. The flow loop incorporated a tee junction machined in an acrylic block with the three sided having an equal diameter of 13.5 ± 0.1 mm I.D. Both sets of experiments were conducted at a nominal pressure (Ps) of 200 kPa (abs) and near-ambient temperature (Ts). The operating conditions for the phase-redistribution experiments were as follows: inlet superficial liquid velocities (JL1) ranging from 0.01 to 0.18 m/s, inlet qualities (x1) ranging from 0.1 to 0.9, mass split ratios (W3/W1) from 0 to 1.0, and outlet inclination angles ranging from horizontal to vertical. These inlet conditions corresponded to inlet flow regimes of stratified, wavy, and annular. Phase-redistribution data revealed that the redistribution of phases depended on the inlet conditions, the mass split ratio at the junction, and the inclination angle of the outlets. The magnitude of the inclination effect was dependent on the inlet flow regime. The phase redistribution in stratified flow was very sensitive to the outlet angle and full separation could be achieved at angles as low as 0.7°. Wavy flow was less sensitive to the outlet angle and annular flow was even less sensitive to the outlet angle. The capability of a single impacting tee junction to perform as a full phase separator has been examined. Experimental data were obtained for the limiting inlet conditions under which full separation was attainable at various outlet inclinations (θ) of 2.5°, 7.5°, 15°, 30°, 60°, 75°, and 90°. Full separation data have shown that a single impacting tee junction can perform as a full-phase separator for some inlet conditions. Flow phenomena near the limiting conditions were observed and a simple correlation based on the similarity between these flow phenomena and the phenomenon of liquid entrainment in small upward branches was developed. This correlation was capable of accurate prediction of the data in terms of magnitude and trend.

Phase-redistribution and full-phase separation data were generated for two-phase (air-water) flow splitting at an equal-sided impacting tee junction with a horizontal inlet and inclined outlets. The flow loop incorporated a tee junction machined in an acrylic block with the three sided having an equal diameter of 13.5 ± 0.1 mm I.D. Both sets of experiments were conducted at a nominal pressure (Ps) of 200 kPa (abs) and near-ambient temperature (Ts). The operating conditions for the phase-redistribution experiments were as follows: inlet superficial liquid velocities (JL1) ranging from 0.01 to 0.18 m/s, inlet qualities (x1) ranging from 0.1 to 0.9, mass split ratios (W3/W1) from 0 to 1.0, and outlet inclination angles ranging from horizontal to vertical. These inlet conditions corresponded to inlet flow regimes of stratified, wavy, and annular. Phase-redistribution data revealed that the redistribution of phases depended on the inlet conditions, the mass split ratio at the junction, and the inclination angle of the outlets. The magnitude of the inclination effect was dependent on the inlet flow regime. The phase redistribution in stratified flow was very sensitive to the outlet angle and full separation could be achieved at angles as low as 0.7°. Wavy flow was less sensitive to the outlet angle and annular flow was even less sensitive to the outlet angle. The capability of a single impacting tee junction to perform as a full phase separator has been examined. Experimental data were obtained for the limiting inlet conditions under which full separation was attainable at various outlet inclinations (θ) of 2.5°, 7.5°, 15°, 30°, 60°, 75°, and 90°. Full separation data have shown that a single impacting tee junction can perform as a full-phase separator for some inlet conditions. Flow phenomena near the limiting conditions were observed and a simple correlation based on the similarity between these flow phenomena and the phenomenon of liquid entrainment in small upward branches was developed. This correlation was capable of accurate prediction of the data in terms of magnitude and trend.