This paper presents an approach to modeling a binary mixture near a surf ace. The approach used is based on statistical mechanics. The Cluster Variation (CV) method is used to solve an Ising-like model with a cluster size of two (neighboring lattice points). The free energy of the system is expressed in terms of the probabilities of occurrences of particular clusters. The CV method is first developed for a homogeneous system which leads to a set of three non-linear partial differential equations. The surface boundary is then introduced and the CV method is developed for this system which leads to a set of seven non-linear partial differential equations for each layer. In the calculations, the Natural Iteration (NI) method is introduced as a method of solving these non-linear partial differential equations. The steps involved in implementing the NI method are outlined. The number of layers is chosen to be 32. Concentration profiles are calculated for the binary system using the NI method and the results are discussed.

Les mélanges de toluène et de tert-butanol sont complètement miscibles dans toutes les compositions à l'échelle macroscopique. Toutefois tert-butanol forme un réseau de liaisons hydrogène à l'échelle nanométrique qui persistent même dans les mélanges liquides binaires tert-butanol/toluène. Des expériences de diffusion de neutrons ont révélé la séparation des phases du mélange dans une structure cœur-gaine sous confinement dans des solides nanoporeux hydrophiles. Le travail effectué dans cette thèse vise à comprendre le rôle joué par la concurrence des interactions intermoléculaires (liaisons hydrogène, Van der Waals) lors de la séparation de phase sous nanoconfinement. Des expériences de RMN révèlent la persistance d'un réseau de liaisons hydrogène dans ces liquides binaires confinés dans des nanopores de silice à des concentrations faibles de tert -butanol, fournissant la preuves d'un autre type de réseau de liaisons hydrogène sous confinement. Des expériences d'adsorption du mélange gazeux dans des nanopores de silice ont aidé à expliquer l'affinité plus élevée des parois de silice polaires pour tert-butanol par une modèle thermodynamique. Le remplacement de la matrice hôte par un analogue hydrophobe est associé à une inversion de la sélectivité, montrant cette fois une plus grande affinité du toluène pour la surface des pores. L'effet des interactions spécifiques avec la surface sur la dynamique d'imbibition spontanée de ces liquides binaires à travers le réseau de silice nanoporeux a également été étudié. Des expériences de radiographie de neutrons ont révélé la séparation des flux à deux composants, au sein d'une dynamique toujours gouvernée par une loi de Lucas-Washburn. / Toluene and tert-butanol mixtures are completely miscible for all compositions at the macroscopic scale. However tert-butanol forms a network of hydrogen-bonded clusters at the nanoscale which persist even in the tert-butanol-toluene binary liquid mixtures. Interpretation of neutron scattering experiments revealed phase separation of the mixture into a core-shell structure inside hydrophilic nanoporous solids, with a tert-butanol shell and a toluene core. The work carried out in this thesis is aimed at understanding the role played by competing intermolecular interactions (hydrogen-bonding, van der Waals) in driving phase separation in confinement. NMR experiments reveal the persistence of a hydrogen-bonding network in these binary liquids confined in silica nanopores even at very low concentrations of tert-butanol, providing evidence of a new kind of hydrogen bonded network under confinement. Vapour sorption isotherms of tert-butanol-toluene binary gas mixtures in silica nanopores helped explain higher affinity of polar silica walls for tert-butanol by a thermodynamic model. Replacing the host matrix by a hydrophobic analogue was found to reverse the selectivity, with toluene showing greater affinity for the pore surface. Effect of surface specific interactions was studied on spontaneous imbibition dynamics of these binary liquids through nanoporous silica network. Neutron radiography experiments revealed the separation of fluxes into a twocomponent flow, generally obeying the Lucas-Washburn law.

A strongly-coupled plasma is a collection of free charged particles that interact with a Coulomb repulsion that is so strong that nearby particles do not easily move past one another. Unlike weakly-coupled plasmas, strongly-coupled plasmas exhibit a self-organization of particles into an arrangement like a solid crystalline lattice or a liquid. Dusty plasmas consist of micron-size particles of solid matter that are immersed in a plasma of electrons and ions. The dust particles gain a large electric charge and become strongly coupled. The motion of discrete particles can be tracked using a video microscopy diagnostic. Dusty plasma experiments allow a study of strongly-coupled plasma physics and an experimental simulation of condensed matter physics. Experiments are reported using a single layer of particles in the plasma to study two-dimensional (2D) physics. It is demonstrated experimentally that in addition to the solid and liquid states, a strongly-coupled dusty plasma can exist in an exotic state called a superheated solid. A 2D dusty plasma, initially self-organized in a crystalline lattice, is heated rapidly by rastered laser beams. The suspension remains in a solid lattice at a temperature well above the melting point. Shear-induced melting is studied in a 2D dusty plasma by applying shear to a crystalline lattice using a pair of oppositely-directed laser beams. Unexpectedly, coherent longitudinal waves are also excited in the resulting shear flow. In the first experiment of its kind, a suddenly-applied shear is found to produce a melting front that spreads at the transverse sound speed. The viscoelasticity of strongly-coupled plasmas in a liquid state is quantified. In the first experiment for any kind of physical system, the wavenumber-dependent viscosity, η(k), is computed from measurements of the random motion of particles. It is found that η(k) diminishes with increasing k, indicating that viscous behavior is gradually replaced by elastic behavior as the scale length is reduced. As a tool for studying transport at a microscopic level, the self-intermediate scattering function (self-ISF) is used in numerical simulations of 2D dusty plasmas. Two physical processes are studied using the self-ISF: relaxation of random motion, and melting. The wavenumber-dependence of the relaxation time in a liquid-phase strongly-coupled plasma is shown to be useful for distinguishing normal and anomalous diffusion. The self-ISF is also demonstrated to be a sensitive indicator of the melting transition. An improved image-analysis method is developed for calculating particle positions with minimal measurement errors. This development also provides an understanding of sources of error and the dependence on parameters that the experimenter can control.

Cette thèse étudie le passage liquide de Luttinger liquide de Fermi au moyen de l'application d'une pression hydrostatique dans le conducteur organique quasi unidimensionnel TMTSF2PF6. La dépendance en température de la résistivité le long the l'axe de moindre conductivité fait apparaître un régime haute température qui s'interpréter par des chaînes de Luttinger alors qu'au dessous de 100K le système évolue vers un régime de chaînes couplés avec une physique de type liquide de Fermi.Ce modèle est aussi confirmé par l'étude de l'effet Hall dans le même composé.

This study investigated the use of radon-222 as an in situ partitioning tracer for quantifying nonaqueous phase liquid (NAPL) saturations in the subsurface. Laboratory physical aquifer models (PAMs), field experiments, and numerical simulations were used to investigate radon partitioning in static (no-flow) experiments and in single-well, 'push-pull' tests conducted in non-contaminated and NAPL-contaminated aquifers. Laboratory push-pull tests in a wedge-shaped PAM and field push-pull tests in a NAPL-contaminated aquifer showed that radon was retarded in the presence of NAPL, with retardation manifested in increased dispersion of radon extraction phase breakthrough curves (BTCs). An approximate analytical solution to the governing transport equation and numerical simulations provided estimates of the radon retardation factor (R), which was used to calculate NAPL saturations (S[subscripts n]). Laboratory static and push-pull tests were conducted in a large-scale rectangular PAM before and after NAPL contamination, and after alcohol cosolvent flushing and pump-and-treat remediation. Radon concentrations in static tests were decreased due to partitioning after NAPL contamination and increased after remediation. Push-pull tests showed increased radon retardation after NAPL contamination; radon retardation generally decreased after remediation. Numerical simulations modeling radon as an injected or ex situ partitioning tracer were used to estimate retardation factors and resulted in overestimations of the likely S[subscripts n] in the PAM. Radon partitioning was sensitive to changes in S[subscripts n] in both static and push-pull tests. However, the test results were sensitive to test location, sample size, test design, and heterogeneity in S[subscripts n] distribution. Numerical simulations of hypothetical push-pull tests conducted in a NAPL-contaminated aquifer were used to investigate the influence of homogeneous and heterogeneous S[subscripts n] distributions and initial radon concentrations on radon BTCs and resulting S[subscripts n] calculations. Both of these factors were found to affect radon BTC behavior. A revised method of plotting and interpreting radon BTCs combined with numerical simulations modeling radon as an in situ partitioning tracer (incorporating initial radon concentrations into the model as a function of S[subscripts n]) were used to re-analyze laboratory and field push-pull test BTCs. This method reduced the overestimation of calculated S[subscripts n] values from laboratory tests. / Graduation date: 2003

Radon-222 gas has unique properties allowing it to be used as an indicator for the presence of organic phase liquids in the saturated zone. It naturally occurs in soils. It is radioactive, making quantitative detection straight forward. A noble gas, it is chemically inert and does not react with aquifer media. Finally, radon has an affinity to concentrate in nonaqueous phase liquids. A proposed linear equilibrium partitioning model was tested by batch equilibration with the pore fluid to establish the deficit in aqueous radon concentrations that results from its partitioning into the residual saturation of the organic phase (Soltrol-220). Five sets of experiments were run on columns with 0.0, 1.0, 2.5, 5.0, and 8.0 percent residual soltrol fractions. The model was found to accurately represent the partitioning process. A one-dimensional physical model was run to see if the data from the partitioning experiments could be successfully applied to predict the aqueous radon concentrations in a more complex situation. The results indicate that radon-222 has great potential to be used as a means of detecting and quantifying the presence of residual organic phase liquids in the saturated zone. / Graduation date: 1995

The needs for sustainable energy generation, but also a sustainable chemistry display the basic motivation of the current thesis. By different single investigated cases, which are all related to the element carbon, the work can be devided into two major topics. At first, the sustainable synthesis of “useful” carbon materials employing the process of hydrothermal carbonisation (HC) is described. In the second part, the synthesis of heteroatom - containing carbon materials for electrochemical and fuel cell applications employing ionic liquid precursors is presented. On base of a thorough review of the literature on hydrothermolysis and hydrothermal carbonisation of sugars in addition to the chemistry of hydroxymethylfurfural, mechanistic considerations of the formation of hydrothermal carbon are proposed. On the base of these reaction schemes, the mineral borax, is introduced as an additive for the hydrothermal carbonisation of glucose. It was found to be a highly active catalyst, resulting in decreased reaction times and increased carbon yields. The chemical impact of borax, in the following is exploited for the modification of the micro- and nanostructure of hydrothermal carbon. From the borax - mediated aggregation of those primary species, widely applicable, low density, pure hydrothermal carbon aerogels with high porosities and specific surface areas are produced. To conclude the first section of the thesis, a short series of experiments is carried out, for the purpose of demonstrating the applicability of the HC model to “real” biowaste i.e. watermelon waste as feedstock for the production of useful materials. In part two cyano - containing ionic liquids are employed as precursors for the synthesis of high - performance, heteroatom - containing carbon materials. By varying the ionic liquid precursor and the carbonisation conditions, it was possible to design highly active non - metal electrocatalyst for the reduction of oxygen. In the direct reduction of oxygen to water (like used in polymer electrolyte fuel cells), compared to commercial platinum catalysts, astonishing activities are observed. In another example the selective and very cost efficient electrochemical synthesis of hydrogen peroxide is presented. In a last example the synthesis of graphitic boron carbon nitrides from the ionic liquid 1 - Ethyl - 3 - methylimidazolium - tetracyanoborate is investigated in detail. Due to the employment of unreactive salts as a new tool to generate high surface area these materials were first time shown to be another class of non - precious metal oxygen reduction electrocatalyst. / Die Notwendigkeit einer nachhaltigen Energiewirtschaft, sowie der nachhaltigen Chemie stellen die Motivation der vorgelegten Arbeit. Auf Grundlage separater Untersuchungen, die jeweils in engem Bezug zum Element Kohlenstoff stehen, kann die Arbeit in zwei Themenfelder geordnet werden. Der erste Teil behandelt die nachhaltige Herstellung nützlicher Kohlenmaterialien mit Hilfe des Verfahrens der hydrothermalen Carbonisierung. Im zweiten Teil wird die Synthese von Bor und Stickstoff angereicherten Kohlen aus ionischen Flüssigkeiten für elektrochemische Anwendungen abgehandelt. Insbesondere geht es um die Anwendung in Wasserstoff-Brennstoffzellen. Als Ergebnis einer sorgfältigen Literatur¬zusammenfassung der Bereiche Hydrothermolyse, hydrothermale Carbonisierung und Chemie des Hydroxymethylfurfurals wird ein chemisch-mechanistisches Modell zur Entstehung der Hydrothemalkohle vorgestellt. Auf der Basis dieses Modells wird ein neues Additiv zur hydrothermalen Carbonisierung von Zuckern vorgestellt. Die Verwendung des einfachen Additivs, genauer Borax, erlaubt eine wesentlich verkürzte und zu niedrigeren Temperaturen hin verschobene Prozessführung mit höheren Ausbeuten. Anhand des mechanistischen Modells wird ein Einfluss auf die Reaktion von Zuckern mit der reaktiven Kohlenvorstufe (Hydroxymethylfurfural) identifiziert. Die chemische Wirkung des Minerals Borax in der hydrothermalen Carbonisierung wird im Folgenden zur Herstellung vielfältig anwendbarer, hochporöser Kohlen mit einstellbarer Partikelgröße genutzt. Zum Abschluss des ersten Teils ist in einer Serie einfacher Experimente die Anwendbarkeit des mechanischen Modells auf die Verwendung „echter“ Biomasse in Form von Wassermelonenabfall gezeigt. Im zweiten Teil werden verschiedene cyano-haltige ionische Flüssigkeiten zur ionothermalen Synthese von Hochleistungskohlen verwendet. Durch Variation der ionischen Flüssigkeiten und Verwendung unterschiedlicher Synthesebedingungen wird die Herstellung hochaktiver, metallfreier Katalysatoren für die elektrochemische Reduktion von Sauerstoff erreicht. In der direkten Reduktion von Sauerstoff zu Wasser (wie sie in Brennstoffzellen Anwendung findet) werden, verglichen zu konventionellen Platin-basierten elektrochemischen Katalysatoren, erstaunliche Aktivitäten erreicht. In einem anderen Beispiel wird die selektive Herstellung von Wasserstoffperoxid zu sehr geringen Kosten vorgestellt. Abschließend wird anhand der Verwendung der ionischen Flüssigkeit 1-Ethyl-3-methylimidazolium-tetracyanoborat eine detaillierte Betrachtung zur Herstellung von graphitischem Borcarbonitrid vorgestellt. Unter Verwendung unreaktiver Salze, als einfaches Werkzeug zur Einführung großer inneren Oberflächen wird erstmals die elektrokatalytische Aktivität eines solchen Materials in der elektrochemischen Sauerstoffreduktion gezeigt.

Nanotechnology is the science and technology of manipulating materials at atomic and molecular scale with properties different from bulk. Semiconductor QDs are important class of nanomaterials with unique physical and chemical properties owing to the quantum confinement effect. Size dependent optical properties make research on semiconductor QDs more attractive in the field of nanotechnology. Semiconductor QDs are usually composed of combination of elements from groups II–VI, III–V, or IV–VI of the periodic table. Group II-VI semiconductor QDs (ZnS, ZnSe, ZnO, CdSe, CdS) are most extensively studied systems, having bandgap which can be engineered through the variation of the material composition and size. Most common QDs are made of CdE (E=S, Se, Te) which are toxic. Recent environmental regulations restrict the use of toxic metals and therefore QDs containing nontoxic metals such as Zn are of great importance. The chemical synthesis of QDs involves different methods. Usually high temperature thermal decomposition of organometallic compounds in high boiling point organic solvents is used which needs long reaction time and involves complex synthesis procedures. New simpler and efficient synthetic routes with alternative solvents are required. Recently the synthesis of non-toxic QDs using green chemical routes is a promising approach receiving increasing attention. The aim of this Thesis is to develop novel routes for synthesis of semiconductor QDs employing green nanomaterial synthesis techniques. Therefore, in this work, we developed different green chemical routes mainly for the synthesis Zn-based QDs. Low temperature synthesis routes were developed for the synthesis of ZnS and ZnO QDs. Microwave irradiation was also used as efficient heating source which creates numerous nucleation sites in the solution, leading to the formation of homogeneous nanoparticles with small size and narrow size distribution. Different polar solvents with high MW absorption were used for synthesis of ZnS QDs. We also introduced ionic liquids as solvents in the synthesis of ZnS QDs using microwave heating. ILs are excellent reaction media for absorbing microwaves and are recognized as ‘green’ alternative to volatile and toxic organic solvents. For ZnS systems, the QDs produced by different methods were less than 5 nm in size as characterized by high-resolution transmission electron microscopy (HR-TEM). Selected area electron diffraction (SAED) patterns revealed that ZnS QDs synthesized by low temperature synthesis technique using conventional heating are of cubic crystalline phase while the QDs synthesized by using MW heating are of wurtzite phase. The optical properties were investigated by UV-Vis absorption spectrum and show a blue shift in absorption as compared to bulk due to quantum confinement effect. The photoluminescence (PL) spectra of ZnS QDs show different defect states related emission peaks and depend on different synthesis methods, high bandedge related emission is observed for ZnS QDs synthesized by using ionic liquids. ZnO QDs synthesized by low temperature route were found to be less than 4 nm in size and also show a blue shift in their absorption. The PL spectrum show bandedge related emission which is blue shifted compared with bulk with no emission originating from surface defect levels. The results show that QDs are of high crystalline quality with narrow size distribution. A comparative study of using conventional and MW heating in the synthesis of CdSe QDs was performed. The reactions involving microwave heating showed enhanced rates and higher yields. The developed methods involve all principles for green nanomaterials synthesis i.e. design of safer nanomaterials, reduced environmental impact, waste reduction, process safety, materials and energy efficiency. / <p>QC 20121115</p>

No description available.

The work conducted in this thesis is two-fold. First, binary vapor liquid equilibria of several solvent/CO2 systems are measured at 40 ?? The systems analyzed are all gas-expanded liquids (GXLs) characterized with a Jerguson Cell apparatus. A Jerguson cell is a windowed pressure vessel that allows one to measure the height of the condensed liquid. Using this height and the known overall contents in the cell, one can calculate the liquid composition without using any external sampling. Secondly, this same setup is attached to a sampling system, and solid solubility (fractional crystallization) is measured for various GXL systems. The CO2 acts as an antisolvent in what is commonly known as a gaseous antisolvent (GAS) system. Essentially, this work shows that expansion of the tested solvents with CO2 will cause the precipitation of the solid solute. This work also analyzes the affect two solutes have on each other in a quaternary GAS system. Gas-expanded liquids combine desirable gaseous properties and liquid properties to yield a very useful solvent for many applications. An advantage of GXLs is that a relatively small change in pressure or temperature can greatly affect the solvation properties. The tunability of GXLs increases as the amount of the gas (usually CO2) increases in the liquid phase. With the benign chemical nature and environmental impact of CO2 processing, GXLs and supercritical fluids (SCFs) have garnered a lot of attention for industry and academia. Supercritical fluids in this work refer to pure CO2 above its critical temperature and pressure.