No description available.

Electrochemical methods have been used to study electron transfer reactions at the interface between an aqueous phase of less than 1 femto liters in volume and a bulk organic phase. The small aqueous phase is formed at the end of a slightly recessed platinum electrode. When a negative potential is applied between the Pt electrode and the aqueous phase, Ru(NH3)63+ in the aqueous phase could be reduced to Ru(NH3)62+. Because the volume of the aqueous phase is very small, the electrochemically formed Ru(NH3)62+ could instantly reach the interface between the aqueous phase and the organic phase which contains 7,7,8,8-Teteracyanoquinodimethane (TCNQ), and be oxidized to form Ru(NH3)63+ by giving electrons to TCNQ at the interface. Our results showed a positive shift in the E1/2 comparing the reaction undertaken in the recessed cavity and the bulk solution.

The aim of the present thesis is to understand the phase transformation behavior of embedded alloy nanoparticles embedded in immiscible matrices. Embedded alloy inclusions have been dispersed in immiscible matrix via rapid solidification method. The present work deals with synthesis of embedded particles, evolution of microstructure, morphology and crystallographic orientation relation relationships among different phases, phase transformation and phase stability behavior of embedded alloy inclusions in different matrices. In the present investigation the systems chosen are Bi-Sn and Bi-Pb in Zn matrix and Cd-Sn in Al matrix. Chapter 1 gives the brief introduction of present work Chapter 2 gives a brief review of nanoscale materials, various synthesis techniques, microstructure evolution, solidification and melting theories. Chapter 3 discusses the processing and experimental techniques used for characterization of the different samples in the present work. Melt-spinning technique used to synthesize the rapidly solidified ribbons. The structural characterization is carried out using X-ray diffraction and transmission electron microscopy. Chapter 4 illustrates the size dependent solubility and phase transformation behavior of Sn-Cd alloy nanoparticles embedded in aluminum matrix. X-ray diffraction study shows the presence of fcc Al, bct Sn, hcp Cd solid solution and hcp Cd phases. Based on Zen’s law, the amount of Sn present Cd solid solution is estimated. Using overlapped sterograms, the orientational relationships among various phases are found. Microscopy studies reveal that majority of the alloy nano inclusions exhibit a cuboctahedral shape with 111 and 100 facets and they are bicrystalline. STEM-EDS analysis shows that both phases exhibit size dependent solubility behavior and for particles size smaller than 18 nm, single phase solid solution could only be observed. Calorimetric studies reveal a depression in eutectic melting point of bimetallic particles. In situ heating studies show that melting initiates at triple line junction corner and melt first grows into the interior of the Sn rich phase of the particle and then later the melt grows into the interior of the Cd phase of the particle. During cooling first Cd phase solidifies later Sn phase solidifies and on further cooling at low temperatures entire particle transforming into complete solid solution phase particle. Size dependent melting studies show that during heating smaller particles melted first, later bigger particles melted. During cooling first bigger particle solidified later smaller particles solidified. High resolution imaging indicates presence of steps across particle-matrix interface that may get annihilated during heating. During cooling, molten particles in the size range of 16-30 nm solidify as solid solution which for molten particles greater than 30 nm solidify as biphasic particle. Insitu heating studies indicates that for solid particles less than 15 nm get dissolved in the Al matrix at temperatures at around 135°C. Differential scanning calorimetry (DSC) studies show in the first heating cycle most of the particles melt with an onset of melting of at 166.8°C which is close to the bulk eutectic temperature of Sn-Cd alooy. The heating cycle reveals that the melting event is not sharp which can be understood from in-situ microscopy heating studies. In the second and the third cycles, the onset of melting observed at still lower temperatures 164.3°C and 158.5°C .The decrease in onset melting point in subsequent heating cycles is attributed to solid solution formation of all small particles whose size range below 30 nm during cooling. cooling cycles exhibit an undercooling of 90°C with respect to Cd liquidus temperature. Thermal cycling experiments using DSC were carried out by arresting the run at certain pre-determined temperatures during cooling and reheating the sample to observe the change in the melting peak position and area under the peak. The areas of these endothermic peaks give us an estimate of the fraction of the particles solidified upto the temperature when the cycling is reversed. Based on experimental observations, a thermodynamic model is developed, to understand the solubility behavior and to describe the eutectic melting transition of a binary Sn-Cd alloy particle embedded in Al matrix. Chapter 5 discusses the phase stability and phase transformation behavior of nanoscaled Bi-Sn alloys in Zn matrix. Bi-Sn alloys with eutectic composition embedded in Zn matrix using melt spinning technique. X-ray diffraction study shows the presence of rhombohedral Bi, pure BCT Sn and hcp Zn phases. In X-ray diffractogram, there are also other new peaks observed, whose peak positions (interplanar spacings) do not coincide either with rhombohedral Bi or bct Sn or hcp Zn. Assuming these new phase peaks belong to bct Sn rich solid solution(based on earlier work on Bi-Sn rapidly solidified metastable alloys) whole pattern fitting done on x-ray diffractogram using Lebail method. The new phase peaks indicated as bct M1(metastable phase1), bct M2(metastable phase2) phases. The amount of Bi present in M1, M2 solid solution is estimated using Zens law. Two sets of inclusions were found, one contains equilibrium bismuth and tin phases and the other set contains equilibrium bismuth and a metastable phase. In-situ TEM experiments suggest that as temperature increases bismuth diffuses into tin and becomes complete solid solution. Melting intiates along the matrix–particle interface leading to a core shell microstructure. During cooling the entire inclusion solidify as solid solution and decomposes at lower temperatures. High temperature XRD studies show that as temperature increases M1, M2 phases peaks merge with Sn phase peaks and Bi phase peak intensities slowly disappear and on further increasing temperature Sn solid solution phase peaks also disappear. During cooling diffraction studies show that first Sn solid solution phase peaks appear and later Bi phase peaks appear. But, the peaks belong to metstable phases not appeared while cooling. Chapter 6 presents morphology and phase transformation of nanoscaled bismuth-lead alloys with eutectic (Pb44.5-Bi55.5) and peritectic (Pb70-Bi30) compositions embedded in zinc matrix. using melt spinning technique. In alloy1[ Zn-2at%(Pb44.5-Bi55.5)] inclusions were found to be phase separated into two parts one is rhombohedral Bi and the other is hcp Pb7Bi3 phase. X-ray diffraction study shows the presence of rhombohedral Bi, hcp Pb7Bi3 and hcp Zn phases in Zn-2at%(Pb44.5-Bi55.5) melt spun sample. The morphology and orientation relationships among various phases have been found. In-situ microscpy heating studies show that melt initially spreads along the matrix–particle interface leading to a core-shell microstructure. And in the core of the core-sell particles, first Bi phase melts later Pb7Bi3 phase will melt and during cooling the whole particle solidify as biphase particle with large undercooling. In-situ heating studies carried out to study the size dependent melting and solidification behavior of biphase particles. During heating smaller particles melt melt first later bigger particle will melt. In contrast, while cooling smaller particles solidifies first, later bigger particles will solidify. Detailed high temperature x-ray diffraction studies indicate there increases first Bi phase peaks disappear later Pb7Bi3 phase peaks disappear and during cooling first Pb7Bi3 phase peaks appear and later Bi phase peaks appear. In alloy2[ Zn-2at%(Pb70-Bi30)] inclusions were found to be single phase particles. X-ray diffraction study shows the presence of hcp Pb7Bi3 and hcp Zn phases in Zn-2at%(Pb70-Bi30) melt spun sample. The crystallographic orientation relationship between hcp Pb7Bi3 and hcp Zn phases. In-situ microscpy heating studies show that melting initiates across the matrix–particle interface grows gradually into the interior of the particle. Three phase equilibrium at peritectic reaction temperature is not observed during insitu heating TEM studies. Size dependent melting point depression of single phase particles is not observed from in-situ heating studies. Detailed high temperature x-ray diffraction studies show that while heating the Pb7Bi3 phase peak intensities start decreasing after 170°C and become zero at 234°C. And during cooling Pb7Bi3 phase peaks starts appearing at 200°C and on further cooling the Pb7Bi3 phase peak intensities increase upto 150°C, below this temperature peak intensities remain constant.

Since the past decade, use of electro-osmotic flow (EOF) as an alternative flow mechanism in microdevices is becoming more popular due to its less bulky and low maintenance system design. However, one of the biggest shortcomings for its usage in mainstream applications is that it requires the concerned liquid to be electrically conductive. One idea can be to use the flow of conductive fluids to transport non-conductive liquids passively via interfacial shear transfer. Such an idea can has numerous applications in a wide range of fields like bio-chemical processing (e.g. lab-on-a-chip reactors, mixers, etc.), to oil extraction from porous rock formations. One of the significant characteristics of micro-scale flows is high surface to volume ratio, which significantly highlights the role of multi-phase interfaces in such dynamics. The presence of a fluid-fluid interface in an EOF necessitates the characterization of the parameters responsible for hydrodynamic instability of such systems. The present work focuses on the role of steady and time-dependent electric stress (Maxwell stress), capillary force and disjoining pressure on fluid-fluid interfacial instability. A linear stability analysis of interfacial perturbation was performed for a thin film of electrolyte under DC and AC electric fields. Through long wave asymptotic analysis of the Orr-Sommerfeld equations, parametric stability thresholds of a thin aqueous film explored. Further, a set of experiments were performed in order to characterize the EOF in a rectangular microchannel. With the help of a Particle Tracking Velocimetry analysis, velocity distributions were obtained which agreed well to the theoretical values. This was further used to estimate PDMS zeta potential, which was found to be within the reported values in the existing literature. Liquid-liquid interfacial deformation was also explored under a time-periodic EOF and a wide range of the magnitudes of capillary force, and diffusive and convective transport.

We propose a hypothesis and a numerical model for the formation of branching plagioclase textures visible at both macroscopic (∼cm to ∼m) and microscopic scale within melagabbro of the Isle of Rum, Scotland, based on macroscopic, microscopic observations and relevant geological history. The plagioclase crystals are typically linked as twins and form meshes of planar stellate structures (m-scale) with a large range in geometrical organization from patchy to radiating. Evidence of macroscopic crystal aggregation and alignment is attributed to interfacial free energy minimization at the microscopic scale during growth. Accordingly, a binary immiscible Lattice Boltzmann model was developed to simulate diffusion of simplified plagioclase in the melt phase. Isothermal phase transitions modelled via first order chemical reactions are subsequently coupled with stochastic dynamics at the crystal growth front to simulate energy minimization processes including twinning during crystallization in an igneous environment. The solid phase and the liquid phase are coupled with a temporal flexibility that sets the overall ratio between the rate of diffusion and chemical enrichment in the liquid state and the rate of crystallization. The parameter space of the model is explored extensively, followed by a reasonable transcription of physical parameters and an estimation of other parameters to construct realistic simulation scenarios yielding synthetic plagioclase stellates. The results are presented, analyzed and discussed. They appear to be in reasonable qualitative agreement with observations, and several aspects of the natural stellates such as the stellate spacing and long continuous stretches of plagioclase with epitaxial junctions seem to be in reasonable quantitative agreement with observations.

We propose a hypothesis and a numerical model for the formation of branching plagioclase textures visible at both macroscopic (∼cm to ∼m) and microscopic scale within melagabbro of the Isle of Rum, Scotland, based on macroscopic, microscopic observations and relevant geological history. The plagioclase crystals are typically linked as twins and form meshes of planar stellate structures (m-scale) with a large range in geometrical organization from patchy to radiating. Evidence of macroscopic crystal aggregation and alignment is attributed to interfacial free energy minimization at the microscopic scale during growth. Accordingly, a binary immiscible Lattice Boltzmann model was developed to simulate diffusion of simplified plagioclase in the melt phase. Isothermal phase transitions modelled via first order chemical reactions are subsequently coupled with stochastic dynamics at the crystal growth front to simulate energy minimization processes including twinning during crystallization in an igneous environment. The solid phase and the liquid phase are coupled with a temporal flexibility that sets the overall ratio between the rate of diffusion and chemical enrichment in the liquid state and the rate of crystallization. The parameter space of the model is explored extensively, followed by a reasonable transcription of physical parameters and an estimation of other parameters to construct realistic simulation scenarios yielding synthetic plagioclase stellates. The results are presented, analyzed and discussed. They appear to be in reasonable qualitative agreement with observations, and several aspects of the natural stellates such as the stellate spacing and long continuous stretches of plagioclase with epitaxial junctions seem to be in reasonable quantitative agreement with observations.

This thesis explores the topic of flow of two immiscible liquids in horizontal pipeline. For this purpose, the experimental apparatus has been set up, that allows to observe the flow of mixture through the transparent pipe. Moderately viscous oil and water (viscosity ratio: 52,81, density ratio: 0.86, interfacial tension: 41,64 mN/m) have been chosen for the experiment. Both fluids were introduced into the pipe through a T-junction. At the end of the apparatus, a mixture of liquids flowed into the separation tank, where both phases were separated. The separated oil was then reused for further measurements. The oil and water flow rates could be individually changed by use control valves, that led to identification of different flow regimes. These varied from stratified flows to fully dispersed ones as the mixture speed increased. All observed flow regimes were plotted in the flow map, that is a function of the inlet velocities of both fluids. For further analysis, a second type of flow map has been created that displays rates as a function of mixture velocity and phase volume fraction. Selected regime was also simulated using software ANSYS FLUENT. The VOF method was used to simulate multiphase flow. This thesis critically evaluates the results of the study and shows the direction for further research in the field of immiscible liquids flow.

Dans le domaine des plastiques biodégradables, les produits se doivent d’être de plus en plus compétitifs. Ces travaux, menés entre le laboratoire IMP@UJM et la société LCI ont eu pour objectif principal l’augmentation de la part en matières d’origines renouvelables dans le mélange de polymères biodégradable poly(butylène adipate-co-téréphtalate) (PBAT)/TPF (farine thermoplastique), sans diminuer ses propriétés mécaniques. Ce mélange est obtenu par extrusion en une seule étape, comprenant la plastification de la farine et le mélange avec le polyester. L’enjeu scientifique était donc en premier lieu de comprendre les relations entre la mise en oeuvre, l’établissement de la morphologie du mélange, la concentration en chacun des polymères et les propriétés mécaniques. Dans un second temps, ces résultats ont été exploités en vue de l’augmentation des propriétés mécaniques du mélange. L’influence de la concentration en TPF et du rapport de viscosité entre les phases a donc été mise en évidence sur toute la gamme de concentration, mettant en lumière l’importance de contrôler la tension interfaciale du mélange. Des mécanismes d’établissement de la morphologie et des interprétations quant à son effet sur les propriétés mécaniques du mélange sont proposés. L’étude d’une modification par extrusion réactive du PBAT est ensuite présentée. L’évolution de la structure du polyester est caractérisée par chromatographie d’exclusion stérique en fonction de différents paramètres, dont le temps de mélange. Enfin, différentes modifications du mélange PBAT/TPF sont testées. L’influence de la modification du PBAT, de la modification de la phase TPF ou de la modification de l’interface via des agents compatibilisants est étudiée sur les propriétés rhéologiques, morphologiques et mécaniques du mélange / Biodegradable plastics need to be more and more competitive. This work, conducted between IMP@UJM laboratory and LCI company had the main objective of increasing the content of renewable materials in the biodegradable blend of poly(butylene adipate-co-terephthalate) (PBAT)/ thermoplastic flour (TPF), without decreasing its mechanical properties. The blend was obtained by a single step extrusion, including flour thermoplastification and blending with the polyester. The scientific challenge was to understand the relationship between processing parameters, the morphology establishment, the concentration of each phase of the blend and its mechanical properties. Then, these results were exploited in order to increase the mechanical properties of the mixture. The influence of the concentration of TPF and the viscosity ratio between the phases was highlighted over the entire concentration range. This highlighted the importance of controlling the interfacial tension of the blend. Mechanisms of the morphology establishment were proposed, as well as interpretations about its effect on the mechanical properties of the blend. Then, a study of the PBAT modification by reactive extrusion was proposed. The evolution of the polyester structure was characterized by size exclusion chromatography, according to various parameters including the mixing time. Finally, various modifications of PBAT/TPF mixture were tested. Modifying the PBAT, the TPF phase or the interface via the compatibilizers were studied in order to tailor the rheological, morphological and mechanical properties