YBa2Cu3O7-d (YBCO) was one of the first high temperature superconductors discovered, and its superconducting properties are strongly dependent on oxygen stoichiometry. A large amount of work has been done on the variation of stoichiometry and its effect on the superconducting properties of the material. However, in spite of all the work done, the results published in the literature are very scattered. This thesis presents a thermogravimetric study of oxygen diffusion in YBCO under isothermal and non-isothermal conditions and tries to reconcile the data available based on the results obtained and taking into account the factors that may have affected the data presented by other groups, such as the effects of the microstructure and the different diffusion coefficients measured with the techniques used. An Arrhenius expression for the chemical diffusion of oxygen has been calculated from the analysis of isothermal oxygenation data, and it has been corroborated by a study of the nonisothermal experiments carried out. This work includes the development of a macroscopic model for oxygen diffusion in YBCO based on the diffusion coefficient calculated from experimental data. The model is used to simulate for the first time oxygenations under both isothermal and non-isothermal conditions. The study of non-isothermal oxygenations has led directly to the design of novel cooling procedures that can be introduced at the end of the processing stage of YBCO samples, producing highly oxygenated specimens in shorter times than for conventional isothermal and ramped oxygenation procedures. The final section of this dissertation presents a study of the Direct Current Zoning effect. The generation of a mobile hot zone in a polycrystalline YBCO bar when passing a current across it is directly linked to the diffusion of oxygen ions in the material. A mechanism for the motion of the zone along the sample has been suggested. A computer model has been developed to reproduce this process taking into account the motion of ions due to chemical diffusion and the potential difference established. The results from this model have corroborated the mechanism suggested and give for the first time the opportunity to study this phenomenon in more detail.

<p> An investigation is reported of oxygen diffusion in monoclinic zirconia at elevated temperatures. </p> <p> A method was developed for production of solid zirconia spheres of a quality suitable for diffusion measurements. The spheres, 60μ and 90μ diameter were subsequently used for the determination of the coefficient of self-diffusion of oxygen in stoichiometric zirconia at 800°C, 850°C, 900°C, 950°C and 1000°C. Oxygen O18 isotope exchange using mass spectrometry for the gas analysis was employed for this investigation. </p> <p> The oxygen self-diffusion coefficent was found to conform to the Arrhenius equation (see online text for equation) Theoretical considerations indicate that this diffusivity represents virtually the lattice diffusion of oxygen in zirconia. </p> <p> Diffusivities of oxygen in zirconia scale calculated from zirconium oxidation studies are 104 times higher and are believed to be due to short-circuit diffusion through line defects. To substantiate this hypothesis, "slabs" of stoichiometric zirconia scale and irregular, but equiaxed particles of the same material were used for oxygen diffusion experiments employing the same method. The diffusivities for the slabs were 10^3 times higher than those for spheres, supporting the validity of the short-circuit diffusion theory for zirconia scale. </p> <p> Oxygen concentration drop across zirconia scale on metal, during its formation by parabolic kinetics was calculated for 600°C and 850°C, and was found to be 0.04 g/cm3 approximately, while the concentration drop across the interface between the oxide and the oxygen-saturated metal was about 1.07 g/cm3. </p> / Thesis / Doctor of Philosophy (PhD)

Organic materials such as polymer films surround us in many everyday applications ranging from food packaging and smartphone displays to medical purposes. One of their main usage scenarios is the thin, lightweight, and easy processable encapsulation to protect a particular target from molecular oxygen. Hence, the oxygen diffusion properties in these polymer films represent a key parameter. This work demonstrates a new method to determine and model the oxygen distribution in thin polymer films using light. It provides a significant advantage over many common methods since no vacuum machinery is needed. The working principle is based on the phosphorescent emission of an organic dopant which is quenched in the vicinity of molecular oxygen at room temperature. The model system used in this study consists of a polystyrene layer, which is doped with PtOEP (Platin(II)-2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin) and covered with a barrier layer of Ex-cevalTM. The oxygen concentration in the doped polystyrene film can be locally depleted under excitation with 365 nm UV light. To determine the oxygen diffusion coefficient, a concentration gradient is created and the time evolution of the luminescent pattern is recorded with a CCD-camera. The recorded data is reconverted to oxygen concentration equivalents and the impact of photoconsumption during the recording process is eliminated, before fitting it with a diffusion simulation. The result reveals a significant dependency on the processing conditions of the film, i.e. D = (1.49 ± 0.08) × 10−7 cm^2/s for unannealed and D = (0.71 ± 0.09) × 10−7 cm^2/s for an-nealed samples. The values lie well in the range reported in the literature.:Problem Goal Conception The physics behind the phenomenon Results More

Dry covers can be used to limit the generation of acid mine drainage from sulphidic mine waste exposed to air and water. For the covers to act efficiently a high degree of saturation should be maintained in the cover, as the diffusion of oxygen is substantially reduced in water compared to that in air. Historically, dry covers made solely from till have been applied with varying degrees of success. To improve the performance of dry covers, a multi-layer approach can be applied incorporating a sealing layer aimed at effectively preventing oxygen ingress and an overlying protective layer. Blends of till and green liquor dregs (GLD) are thought to have advantageous properties regarding the water retention capacity and hydraulic conductivity. Subsequently, the blends should have a good ability to remain highly saturated during dry periods and be able to maintain their function as oxygen diffusion barriers over time. In this study the effective oxygen diffusion coefficient (De) in blends of till and GLD was evaluated by laboratory measurements. The oxygen diffusion coefficient of till-GLD blends was evaluated through 81 diffusion tests performed at different degrees of water saturation. The blends differed in added amounts of GLD and different types of GLD. These variables were studied as they affect the blends grain size, porosity, tortuosity, and degree of saturation, which in turn affect the De. The tests were performed in two-chamber diffusion cells and interpreted using the software Vadose/W (Geoslope, 2016) to determine the De. The results provide an initial evaluation of the variation of De that can be expected for till-GLD blends. The De was found to vary greatly for the blends (10-6 &gt; De &gt; 10-11 m2 s-1) depending on the degree of saturation. Even though the GLD contain substantial amounts of water, a high water content of the till was still required to reach a low De. A predictive model for estimating the De based on basic geotechnical soil properties was compared to the De from the interpreted diffusion tests. The model could generally predict the De to within an acceptable range (± one order of magnitude). Additionally, diffusion tests performed on materials dried in successive steps showed how the De changed over time when exposed to drying. A sharp increase in the De was found for the blends, pure GLD and pure till when exposed to drying. Thus, no clear improvement was found for the GLD-till blends compared to the pure till. These results indicate that the till-GLD layers should not be exposed to drying as loss of cover efficiency may occur. This can have implications for the use of till-GLD blends as sealing layers in terms of the design of the protective cover and the placement of covers. To validate these results, tests on larger material quantities should be performed, preferably in field conditions, and comparison to field measurements would be of high interest.

Le développement fondamental de ces thématiques est intimement lié à la nanochimie. Deux aspects importants de la nanochimie sont: la compréhension des propriétés chimiques particulières et la réactivité des nanoparticules qui contiennent un petit nombre d’atomes et les applications pour les nanotechnologies. Pour ce faire, cela nécessite le contrôle des synthèses et de la stabilité des nanoparticules individuelles, mais aussi de leurs assemblages afin de produire des nanostructures plus complexes. De plus, les recherches liées aux changements des propriétés structurales, catalytiques et physiques des nanostructures en fonction de la taille et de la forme des nanoparticules sont indispensables afin d’envisager des transferts de technologie. Les nanoparticules métalliques constituent un des états de la matière condensée. Ces systèmes présentent des propriétés spécifiques dues à leur taille, leur forme et diffèrent de celles du même matériau à l’état massif. Puisque les propriétés d’un matériau sont avant tout liées à son état de surface, on peut considérer ces nanoparticules comme des objets massifs mais délimités par les atomes formant la surface rendant donc leurs propriétés chimiques et physiques très fortement dépendantes de leur taille, leurs forme et de la présence de molécules à la surface. D’ailleurs, la versatilité des propriétés optiques, magnétiques, thermodynamiques, électrochimiques, de conductivité, de transport électronique etc., est déjà mise en évidence, non seulement pour des nanoparticules de tailles mais aussi de formes différentes. Un autre paramètre important, qui reste encore peu pris en compte aujourd’hui, est la cristallinité des nanoparticules dont le contrôle est un domaine de recherche ouvert. Aussi, malgré les problèmes de synthèse des nanocristaux de structure cristalline déterminée, de nombreuses études se sont développées ces vingt dernières années. Ces vingt dernières années, non seulement des études des propriétés chimiques et physiques d’une collection de nanoparticules ont été intensivement réalisées mais la caractérisation de leurs assemblages soit en réseau hexagonal compact (2D) soit à 3D selon une structure cristalline bien déterminée a fait l’objet de nombreuses études. Ces assemblages ont ouvert une nouvelle voie de recherche. En effet, les propriétés chimiques et physiques ne sont plus celles du nanocristal, ni même celle du même matériau à l’état massif mais sont propres à leur assemblage. Des propriétés collectives émergent. Certaines sont dues à des interactions dipolaires induites entre nanocristaux ou encore des propriétés intrinsèques dues à l’assemblage lui-même. Ces assemblages restent un immense domaine de recherche à explorer avec des propriétés chimiques et physiques qu’il est difficile de prédire. La richesse des potentialités de ces nanostructures devrait permettre d’aboutir à des applications importantes tant dans le domaine de l’énergie, de l’environnement, des transports que de la médecine. / The extensive and fundamental development of these problems was determined by nanochemistry. Nanochemistry, in turn, has two important aspects. One of these is associated with gaining insight into the peculiarities of chemical properties and the reactivity of particles comprising a small number of atoms, which lay new foundations of this science. Another aspect, correlated to nanotechnology, consists of the application of nanochemistry to the synthesis, modification, and stabilization of individual nanoparticles and also for their directed self-assembling to give more complex nanostructures. Moreover, the possibility of changing the properties of synthesized structures by regulating the sizes and shapes of original nanoparticles deserves attention. This thesis attempts to provide some answers to the many open questions to date: 1 - Is it easy to control the size and the crystal structure, called nanocrystallinity, nanoparticles of cobalt? What are the consequences for stability during the process of oxygen diffusion? 2 - Can we achieve binary assemblies involving cobalt nanocrystals of different nanocrytallinites. What are the consequences of nanocrystallinity in these assemblies? In order to answer the above two questions, this thesis is organized in four parts. The first part deals with the recent advances in Kirkendall effect, which is demonstrated to be mainly involved during the oxidation reaction of metals, and also the general view on the assembly and collective properties of binary nanoparticle superlattices. The second part deals with the oxygen diffusion through Co nanocrystals. We describe the various parameters involved in the oxygen diffusion through Co nanocrystals. We describe the influence crystalline structure of nanoparticles such as amorphous, hcp, fcc and epsilon phase of Co nanocrystals. It will be demonstrated that the TEM electron beam plays a role of the final product when Co nanocrystals are submitted to the oxygen. In the third part, we focus on the fabrication of Co nanoparticle-based binary nanoparticle superlattices. It is shown that binary superlattices of Co/Ag nanocrystals with same size, surface coating, differing by their crystallinities can be governed by Co-Co magnetic interactions. Furthermore, binary nanoparticle superlattices, which can be considered as the insertion of small nanoparticles into the nanoparticle superlattices revealed an unusual magnetic properties. Two kinds of binary nanoparticle superlattices, namely AlB2-type CoAg2 and MgZn2-type CoCo2, are produced, and their magnetic properties are studied, revealing the mesoscale doping effect on the magnetic properties of Co nanoparticle supracrystals. In the last part of this thesis is mainly focused on how to improve the nanocrystallinity of Co nanocrystals in solution and the magnetic investigation of Co nanocrystals with various crystallinities.

No description available.

<p>Zr-based materials have found their main application in the nuclear field having high corrosion resistance and low neutron absorption cross-section. The oxide layer that is formed on the surface of these alloys is meant to be the barrier between the metal and the corrosive environment. The deterioration of this protective layer limits the lifetime of these alloys. A better understanding of the transport phenomena, which take place in the oxide layer during oxidation, could be beneficial for the development of more resistant alloys.</p><p>In the present study, oxygen and hydrogen transport through the zirconia layer during oxidation of Zr-based materials at temperatures around 400C have been investigated using the isotope-monitoring techniques Gas Phase Analysis and Secondary Ion Mass Spectrometry. The processes, which take place at oxide/gas and oxide/metal interface, in the bulk oxide and metal, have to be considered in the investigation of the mechanism of hydration and oxidation. Inward transport of oxygen and hydrogen species can be influenced by modification of the surface properties. We found that CO molecules adsorbed on Zr surface can block the surface reaction centers for H₂ dissociation, and as a result, hydrogen uptake in Zr is reduced. On the other hand, coating the Zr surface with Pt, resulted in increased oxygen dissociation rate at the oxide/gas interface. This generated enhanced oxygen transport towards the oxide/metal interface and formation of thicker oxides. Our results show that at temperatures relevant for the nuclear industry, oxygen dissociation efficiency decreases in the order: Pt > Zr₂Fe > Zr₂Ni > ZrCr₂ ≥ Zircaloy-2.</p><p>Porosity development in the oxide scales generates easy diffusion pathways for molecules across the oxide layer during oxidation. A novel method for evaluation of the gas diffusion, gas concentration and effective pore size of oxide scales is presented in this study. Effective pore sizes in the nanometer range were found for pretransition oxides on Zircaloy-2.</p><p>A mechanism for densification of oxide scales by obtaining a better balance between inward oxygen and outward metal transport is suggested. Outward Zr transport can be influenced by the presence of hydrogen in the oxide/metal substrate. Inward oxygen transport can be promoted by oxygen dissociating elements such as Fe-containing second phase particles. The results suggest furthermore that a proper choice of the second-phase particle composition and size distribution can lead to the formation of dense oxides, which are characterized by low oxygen and hydrogen uptake rates during oxidation.</p>

Fluorescent proteins are valuable tools as biochemical markers for studying cellular processes. Red fluorescent proteins (RFPs) are highly desirable for in vivo applications because they absorb and emit light in the red region of the spectrum where cellular autofluorescence is low. The naturally occurring fluorescent proteins with emission peaks in this region of the spectrum occur in dimeric or tetrameric forms. The development of mutant monomeric variants of RFPs has resulted in several novel FPs known as mFruits. Though oxygen is required for maturation of the chromophore, it is known that photobleaching of FPs is oxygen sensitive, and oxygen-free conditions result in improved photostabilities. Therefore, understanding oxygen diffusion pathways in FPs is important for both photostabilites and maturation of the chromophores. We used molecular dynamics calculations to investigate the protein barrel fluctuations in mCherry, which is one of the most useful monomeric mFruit variants, and its GFP homolog citrine. We employed implicit ligand sampling and locally enhanced sampling to determine oxygen pathways from the bulk solvent into the mCherry chromophore in the interior of the protein. The pathway contains several oxygen hosting pockets, which were identified by the amino acid residues that form the pocket. We calculated the free-energy of an oxygen molecule at points along the path. We also investigated an RFP variant known to be significantly less photostable than mCherry and find much easier oxygen access in this variant. We showed that oxygen pathways can be blocked or altered, and barrel fluctuations can be reduced by strategic amino acid substitutions. The results provide a better understanding of the mechanism of molecular oxygen access into the fully folded mCherry protein barrel and provide insight into the photobleaching process in these proteins.

The first part of this dissertation deals with the application of a luminescence quenching method to measure diffusion and permeation coefficients of oxygen in polymers. Most luminescence oxygen sensors do not follow linearity of the Stern-Volmer (SV) equation due to heterogeneity of luminophore in the polymer matrix, thus the complexity of data analysis is increased. To circumvent this limitation, inverted fluorescence microscopy is utilized in this work to investigate the SV response of the sensors at the micron-scale. In these diffusion experiments, oxygen concentration is measured by luminescence changes in regions with high SV constants and good linearity. Thus, we avoid numerical complexity of combining nonlinear SV equation with a diffusion model. This technique allows us to measure oxygen diffusion properties in different type of polymers like transparent, opaque, free-standing polymers and polymers that cannot be cast into free standing films and polymer composites. In the second part of this thesis, we have explored the effect of Ag-Cu alloy nanoparticles on the emission intensity of luminophores at their close proximity. Alloy nanoparticles offer additional degrees of freedom for tuning their optical properties by altering atomic composition and atomic arrangement and thus can be an attractive option for manipulating signal of a wide range of luminophores. In this work, surface plasmon resonance spectrum of Ag-Cu alloy nanoparticles deposited by sputtering was easily tuned in wide wavelength range by varying one experimental condition- annealing temperature. Large metal enhanced luminescence for different luminophores viz Alexa Fluor 594 and Alexa Fluor 488 were achieved at the vicinity of Ag-Cu nanoparticles when maximum spectral overlap between SPR spectra of Ag-Cu nanoparticles and the emission and absorption spectra of the luminophores occur. We also studied the effect of composition of Ag-Cu nanoparticles synthesized by the polyol process on the luminescence of low quantum yield dye Cy3. In the third part of this thesis, quenching effect of Cu nanoparticles on CdSe/ZnS nanocrystal quantum dots has been explored. As Cu nanoparticles have comparable dielectric properties with gold nanoparticles, they are expected to show similar quenching effects. It was found that Cu is an efficient quencher of fluorescence from CdSe/ZnS quantum dots and the quenching effect is due to resonance energy transfer from quantum dots to Cu nanoparticles.

Zr-based materials have found their main application in the nuclear field having high corrosion resistance and low neutron absorption cross-section. The oxide layer that is formed on the surface of these alloys is meant to be the barrier between the metal and the corrosive environment. The deterioration of this protective layer limits the lifetime of these alloys. A better understanding of the transport phenomena, which take place in the oxide layer during oxidation, could be beneficial for the development of more resistant alloys. In the present study, oxygen and hydrogen transport through the zirconia layer during oxidation of Zr-based materials at temperatures around 400C have been investigated using the isotope-monitoring techniques Gas Phase Analysis and Secondary Ion Mass Spectrometry. The processes, which take place at oxide/gas and oxide/metal interface, in the bulk oxide and metal, have to be considered in the investigation of the mechanism of hydration and oxidation. Inward transport of oxygen and hydrogen species can be influenced by modification of the surface properties. We found that CO molecules adsorbed on Zr surface can block the surface reaction centers for H2 dissociation, and as a result, hydrogen uptake in Zr is reduced. On the other hand, coating the Zr surface with Pt, resulted in increased oxygen dissociation rate at the oxide/gas interface. This generated enhanced oxygen transport towards the oxide/metal interface and formation of thicker oxides. Our results show that at temperatures relevant for the nuclear industry, oxygen dissociation efficiency decreases in the order: Pt &gt; Zr2Fe &gt; Zr2Ni &gt; ZrCr2 ≥ Zircaloy-2. Porosity development in the oxide scales generates easy diffusion pathways for molecules across the oxide layer during oxidation. A novel method for evaluation of the gas diffusion, gas concentration and effective pore size of oxide scales is presented in this study. Effective pore sizes in the nanometer range were found for pretransition oxides on Zircaloy-2. A mechanism for densification of oxide scales by obtaining a better balance between inward oxygen and outward metal transport is suggested. Outward Zr transport can be influenced by the presence of hydrogen in the oxide/metal substrate. Inward oxygen transport can be promoted by oxygen dissociating elements such as Fe-containing second phase particles. The results suggest furthermore that a proper choice of the second-phase particle composition and size distribution can lead to the formation of dense oxides, which are characterized by low oxygen and hydrogen uptake rates during oxidation.