A rotating diffusion cell (RDC) has been used to study the kinetics of extraction of the transition metals cobalt (II), nickel (II), copper (II) and zinc (II) from sulphate solutions into either of two extractants held in n-heptane; di-(2-ethylhexyl) phosphoric acid (D2EHPA) or di-(2- ethylhexyl) dithiophosphoric acid (D2EHDTPA). The metal concentration was 10 mM and the aqueous pH was held at 4.5. The extractant concentration was varied between 0.015 to 0.4 M. In the case of cobalt extraction by D2EHPA, the metal concentration and the pH were varied Different diluents and modifiers were also studied.The rate of extraction by D2EHDTPA was found to be faster than D2EHPA. A comprehensive mathematical model, based upon established two film theory, was developed and used to describe the above experimental results. The model was also used to predict values of the important parameters. ... These values compared well with those found by other authors but using quite different experimental techniques. OS4 In the case of cobalt extraction by D2EHPA, the more polar diluents lowered the initial rate. The overall model predicts such behaviour where the rate is also dependent on the partition coefficients of the extractant. Finally, the theory of the RDC allows the prediction of the diffusion layer thicknesses, this information together with the reaction zone thickness is used to explore the influences of diffusion and chemical reaction on the overall transfer process. The diffusion processes are calculated to be the most important of the two. This is especially so for the D2EHDTPA systems.

Electrochromic iridium oxide (IrOx) and iridium-tantalum oxide (IrTaOx) thin films were prepared by reactive magnetron sputtering. Composition, density, and structure were determined using Rutherford backscattering spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and electron energy loss spectroscopy. The electronic density of states (DOS) and the solid phase chemical diffusion coefficient (D) were determined for hydrogen in IrOx and IrTaOx by potentiostatic intermittent titration technique (PITT), and electrochemical impedance spectroscopy (EIS). The complex refractive indices were determined for colored and bleached IrOx and IrTaOx by inverting transmission and reflectance, measured using spectrophotometry in the 300-2500 nm wavelength range. A very porous structure, with a stoichiometry of IrO2.2, was found for IrOx. It contained ~4 nm sized grains. The IrTaOx had a denser structure built up by ~4 nm sized grains. The composition of IrTaOx was found to vary on a nanometer scale, with an average composition of IrTa1.4O5.6. It was found that DOS can be measured using PITT and EIS in the presence of spontaneous side reactions, even for systems influenced by non-negligible charge transfer kinetics and Ohmic drops. It was found that the measured DOS is 30-50% of the theoretically calculated DOS and that D is in the 10-10 – 10-11 cm2/s range for both materials. The hydrogen diffusion mechanism was described by an anomalous diffusion model, possibly indicating percolation or diffusion paths described by a fractal network. The refractive indices were found to be ~1.3 and ~2 for IrOx and IrTaOx, respectively, and independent of coloration state, whereas the extinction coefficients were found to modulate by ~30% for IrOx and ~50% for IrTaOx, making IrTaOx more favorable for electrochromic applications. A modulation peak was found at ~660 nm for both IrOx and IrTaOx associated with the removal of intraband transitions within the Ir t2g band.

A rotating diffusion cell (RDC) has been used to study the kinetics of extraction of the transition metals cobalt (II), nickel (II), copper (II) and zinc (II) from sulphate solutions into either of two extractants held in n-heptane; di-(2-ethylhexyl) phosphoric acid (D2EHPA) or di-(2- ethylhexyl) dithiophosphoric acid (D2EHDTPA). The metal concentration was 10 mM and the aqueous pH was held at 4.5. The extractant concentration was varied between 0.015 to 0.4 M. In the case of cobalt extraction by D2EHPA, the metal concentration and the pH were varied Different diluents and modifiers were also studied.The rate of extraction by D2EHDTPA was found to be faster than D2EHPA. A comprehensive mathematical model, based upon established two film theory, was developed and used to describe the above experimental results. The model was also used to predict values of the important parameters. ... These values compared well with those found by other authors but using quite different experimental techniques. OS4 In the case of cobalt extraction by D2EHPA, the more polar diluents lowered the initial rate. The overall model predicts such behaviour where the rate is also dependent on the partition coefficients of the extractant. Finally, the theory of the RDC allows the prediction of the diffusion layer thicknesses, this information together with the reaction zone thickness is used to explore the influences of diffusion and chemical reaction on the overall transfer process. The diffusion processes are calculated to be the most important of the two. This is especially so for the D2EHDTPA systems. / University of Bradford Scholarship Award

Décrypter les mécanismes et cinétiques de croissance et dissolution des minéraux dans les liquides silicatés est indispensable à la compréhension des processus magmatiques fondamentaux. La migration transcristalline des inclusions magmatiques sous l'effet d'un gradient thermique permet de quantifier une loi cinétique de croissance et dissolution du minéral hôte dans des conditions proches de celles qui prévalent le plus souvent dans la nature. L'objectif principal de ce travail de thèse était : i) d'étudier l'effet de la composition du liquide piégé sur le processus de migration dans l'olivine et ii) d'exploiter systématiquement le processus de migration afin de quantifier les lois cinétiques pour d'autres couples minéral-liquide. Lorsqu'elles sont soumises à un gradient thermique, les inclusions siliceuses (SiO2 ≥ 60pds%) piégées dans les olivines mantelliques et les inclusions basaltiques piégées dans les clinopyroxènes volcaniques migrent à travers leur hôte en direction du point chaud de la zone de travail. La migration s'effectue à une vitesse constante et, dans les olivines, sans modification de la composition du liquide piégé ; les inclusions des clinopyroxènes subissent en revanche une rééquilibration chimique transitoire en début de migration. Les cavités, subsphériques avant la migration, évoluent vers la forme en cristal-négatif du minéral hôte en cours d'expérience. L'achèvement de l'évolution morphologique nécessite un temps caractéristique gouverné par la diffusion chimique dans le liquide. La bulle de gaz exsolvé dans les inclusions n'est pas entraînée dans la migration. Elle se sépare du liquide magmatique et donne naissance à une inclusion fluide isolée au sein du cristal hôte. Les résultats expérimentaux indiquent que la migration procède par dissolution du minéral hôte à l'avant et recristallisation à l'arrière de l'inclusion. La vitesse de migration est limitée par les mécanismes à l'interface cristal-liquide, non par la diffusion chimique. Les taux de croissance et dissolution de l'olivine et du clinopyroxène que nous obtenons sont respectivement trente et quinze fois inférieurs à ceux déterminés dans une étude antérieure à partir d'expériences de migration d'inclusions basaltiques dans des olivines volcaniques. Ils obéissent cependant à la même forme de loi cinétique, qui peut être aisément transposée à des environnements de cristallisation ou de fusion naturels, similaires ou de plus faible déséquilibre. Le taux de croissance et dissolution de l'olivine lors des migrations n'a pas de lien simple avec la composition du liquide piégé ; il est peut-être aussi en grande partie contrôlé par la densité de dislocations du cristal hôte. Le phénomène de migration n'a pas été observé dans le quartz et le plagioclase pour les durées d'expériences réalisées. Il est néanmoins probable que l'absence de migration lors des expériences ne soit qu'apparente. Notamment, la prédominance de liaisons de forte énergie dans la structure du quartz et du plagioclase est susceptible de rendre les processus interfaciaux, et donc aussi la dissolution, particulièrement lente. Au cours de ce travail de thèse, l'opportunité s'est présentée d'étudier les inclusions magmatiques piégées dans les cristaux d'olivine de la pallasite Brahin. En particulier, deux familles d'inclusions ont été identifiées. La première consiste en des plans d'inclusions secondaires contenant de nombreuses chromites et des assemblages à métal-sulfure et olivine phosphorée ; la seconde correspond à des inclusions isolées renfermant pour la plupart de la stanfieldite, une bulle de gaz et de l'olivine phosphorée. Les inclusions secondaires se seraient formées suite à un choc ayant eu lieu alors que l'assemblage minéralogique actuel de Brahin était déjà formé, ou en cours de formation. En revanche, les inclusions de stanfieldite témoigneraient d'un choc prépallasitique. / Deciphering the mechanisms and kinetics of crystal growth and dissolution in silicate melts is essential for understanding the fundamental magmatic processes. When remelted and subjected to an imposed thermal gradient, melt inclusions migrate through their host, which provides a direct access to the host crystal growth / dissolution kinetics and allows to quantify the kinetic laws at very low undercoolings or overheatings, i.e. in conditions appropriate to many natural systems. The main goal of the present study was: i) to study the effect of the trapped melt composition on the migration process in olivine and ii) to extend the transcrystalline melt migration approach to quantify the kinetic law for other mineral-melt pairs. When subjected to a thermal gradient, Si-rich melt inclusions (SiO2 ≥ 60 wt%) in mantle olivines and basaltic melt inclusions in volcanic clinopyroxenes migrate through their host toward the host spot of the working zone. Migration proceeds at a constant rate and in olivine, without modification of the trapped melt composition ; melt inclusions in clinopyroxene, however, undergo a transient chemical reequilibration while they begin to migrate. While moving, the melt inclusions gradually change from subspherical to a faceted, negative-crystal shape. Completion ofthe morphological evolution requires a characteristic time that is governed by chemical diffusion. When a gas bubble is initially present, it responds to elastic forces by quickly shifting toward the cold end of the inclusion, where it soon becomes engulfed as an isolated fluid inclusion in the reprecipitated crystal. The experimental results indicate that the migration operates by progressive dissolution and recrystallistion of the host, governed by interface kinetics with no interference of chemical diffusion.The growth / dissolution rates we obtained for olivine and clinopyroxene are respectively thirty and fifteen times lower than those determined in a previous study from melt migration experiments on basaltic inclusions in volcanic olivines. Nevertheless, they obey the same form of kinetic law, which can be transposed to equally or more sluggish melting or crystallisation events in nature. Dependence of the growth / dissolution rate of olivine on trapped melt composition is not straightforward ; rates may be largely controlled by the density of dislocations in the host crystal. The melt migration phenomenon was not observed in quartz and plagioclase for the investigated experiment durations. Nonetheless, the lack of migration during experiments may only be apparent. Notably, the dominance of high-strength bonds in the quartz and plagioclase structure may render interfacial reactions, and so dissolution, particularly slow. During this research work, we had the opportunity to study the melt inclusions trapped in olivine crystals from the Brahin pallasite. In particular, two contrasted sets of melt inclusions were evidenced. The first set consists of plans of secondary inclusions containing abundant chromite and assemblies of metal, sulfide, and phosphoran olivine ; the second set corresponds to isolated inclusions consisting for the most part of stanfieldite, a gas bubble, and phosphoran olivine. Secondary inclusions may have formed during a shock event that took place while the current stony-iron assembly of the Brahin pallasite was already formed, or was created by this shock. However, stanfieldite inclusions may originate from a pre-pallasitic shock event.

Prestressed concrete is a popular construction material for highway bridges. A variety of girder span values, cross-sectional shapes, and prestressing strand layouts has been used in bridges across the United States. A major concern for such bridges is the possibility of corrosion damage in the prestressing strands or reinforcing bars, which is commonly caused by the use of deicing salts on the deck or saltwater spray in coastal regions. The present study aims at establishing analytical tools for the accurate simulation of chloride ingress, corrosion and mechanical damage (cracking) in the concrete, and for the evaluation of the impact of corrosion on the flexural and shear strength of bridge girders. First, an efficient and accurate analytical scheme is formulated to enable the calculation of the load-carrying capacity of corrosion-damaged girders. The analyses rely on two types of models, namely, beam models and nonlinear truss models. The latter are deemed necessary to obtain reliable estimates of the shear capacity, as beam models are not well-tailored for capturing shear failures. A procedure to account for the reduction in area and deformability of corroded strands, based on visually observed corrosion damage, is proposed and implemented. The models are calibrated and validated with the results of experimental tests on prestressed girders which exhibited varying levels of corrosion damage. Further analyses allow the comparison of the capacity of corrosion-damaged girders to that of their undamaged counterparts. The accuracy of a simplified procedure, using equations in the AASHTO code to determine the flexural and shear capacity of the damaged girders, is also determined. Subsequently, a computation scheme was proposed to describe the intrusion of chloride ions in prestressed bridge girder sections. The approach accounts for multiple, coupled processes, i.e., heat transfer, moisture transport, and chloride advective and diffusive transport. The constitutive models for moisture and chloride transport rely on previous pertinent work, with several necessary enhancements. The modeling scheme is calibrated with data from previous experimental tests on concrete cylindrical and prismatic specimens. The calibrated models are then validated using data from chloride titration tests conducted on girders removed from two bridges in Virginia after 34 and 49 years of service. The results indicate that the proposed framework can accurately reproduce the experimentally measured chloride content. The modeling approach also allows the evaluation of the accuracy of simplified, design-oriented tools for estimating the evolution of chloride content with time. The multi-physics simulation scheme is further refined to account for the corrosion-induced mechanical damage (cracking), by incorporating a phenomenological description of the electrochemical reaction kinetics, generation of expansive corrosion products, and subsequent development of tensile stresses and cracking in the surrounding concrete. The impact of cracking on the chloride and moisture transport mechanisms is also taken into account. The last part of this dissertation pursues the quantification of the uncertainty governing the chloride ingress in bridge girders, through the use of a stochastic collocation approach. The focus is on understanding how the inherent uncertainty in the value of input parameters (e.g., material transport parameters, ambient conditions etc.) is propagated, leading to uncertainty in the evolution of chloride content and the expected corrosion initiation time for a given bridge. / Doctor of Philosophy / Prestressed concrete is widely utilized in the construction of highway bridges in the United States. A significant concern arises regarding potential corrosion damage in the prestressing strands or reinforcing bars, which is commonly attributed to the application of deicing salts on the deck or exposure to saltwater spray in coastal regions. This study aims to develop analytical tools that can accurately simulate the intrusion of corrosive agents (namely chloride ions), and subsequent damage (cracking) in concrete. Furthermore, the research seeks to assess the impact of corrosion on the bearing capacity of bridge girders. Two different classes of analytical approaches are pursued. The first class employs purely mechanical (stress/deformation) models for capturing the strength, deformability and failure modes of girders with visual corrosion damage. These models rely on two approaches to capture the flexural and shear capacity of specimens, namely, beam-based models and truss-based models. The impact of corrosion is established through appropriate modification of the model parameters, based on the extent of visually observed corrosion damage. The analytical approaches are validated through a series of experimental tests previously conducted on corrosion-damaged girders. The second class of analytical approaches employs multi-physics models, to describe the mechanisms leading to corrosion-induced damage. The models account for heat transfer, moisture transport, and chloride transport in prestressed beam sections. Model parameters are calibrated with experimental tests in literature. The computational scheme is used to quantitatively describe the chloride ingress on bridge girders decommissioned from two different bridges in Virginia, after 34 and 49 years of service. The analysis results are found capable of capturing the actual chloride content at various depths from the exposure surface, as determined by chloride titration tests. The temporal evolution of chloride on the surface of prestressing strands indicates that corrosion has been taking place over a period of time for the two bridges. The multi-physics simulation approach is further enhanced to account for the corrosion-induced mechanical damage (cracking), by explicitly incorporating a description of the reaction kinetics, generation of expansive corrosion products and subsequent development of cracking in the surrounding concrete. The last part of this dissertation pursues the quantification of the uncertainty in the expected service life of prestressed concrete bridge structures. Given the inherent uncertainty to key values of model parameters, a parametric study is employed to investigate the propagation of uncertainty to the time history of chloride content at particular locations of the section and the probability of corrosion initiation at specific age values.

Title: Diffusion of native defects and impurities in CdTe/CdZnTe. Author: Lukáš Šedivý Author's e-mail address: luky.sedivy@seznam.cz Department: Institute of Physics of Charles University Supervisor: Doc. Ing. Eduard Belas, CSc. Supervisor's e-mail address: belas@karlov.mff.cuni.cz Abstract: In this thesis, the influence of structural defects on the electrical and de- tection characteristics of CdTe material was investigated. The performed research fo- cused on the reduction of structural defects in the material by annealing in Cd or Te vapor, while preserving acceptable features for X-ray and γ-ray detection. The mate- rial was characterized by measurement of the electrical resistivity and concentration and mobility of free carriers. Tellurium and cadmium inclusions were studied using infrared microscope. The static and dynamic properties of defect structures at high temperatures and de- fined Cd pressures was investigated, as well, and chemical diffusion coeficients describing the dynamic properties of these defects were experimentally determined. Keywords: monocrystal CdTe, structural defects in semiconductors, annealing in Cd or Te, chemical diffusion coefficient, γ-ray detectors. 1