The I-V characteristics of Tin films in the superconducting transition have been measured when ac current was applied. The experimental results suggest that the electrical response in ac is not satisfied with the I-V equation in dc. A new equation was suggested to describe the vortex motion and the vortex pair separation in the two dimensional superconducting transition with ac current, which is satisfied with our experimental results. The excess noises of Tin films in the superconducting transition have been found to depend strongly on the temperature and ac current. An empirical expression of voltage noise density in term of resistance has been used to fit the data. The peak of voltage noise density follows closely but always shifted down from dR/dT. Comparison with the dc noise measurement shows the voltage noise density with ac current is much larger than with dc current. The excess noises with ac appear earlier than the noises with dc. The difference of excess noises between ac and dc can be explained by the fluctuation of vortex pair separation process which dominates the noises generation in ac. I-V characteristics and voltage noises are measured simultaneously to reveal the nature of the excess noises. The coincidence of the excess noise and the third harmonic voltage suggests that the fluctuation of vortex pair separation process is one of the main contributions to excess noises in the two dimensional superconducting transition.

The study of excess thermodynamic properties of liquid mixtures is very important for designing the thermal separation processes, developing solution theory models and to have a better understanding of molecular structure and interactions involved in the fluid mixtures. In particular, heat of mixing or excess molar enthalpy data of binary and ternary fluid mixtures have great industrial and theoretical significance. In this connection, the experimental excess molar enthalpies for seventeen binary and nine ternary systems involving hydrocarbons, ethers and alcohol have been measured at 298.15K and atmospheric conditions for a wide range of composition by means of a flow microcalorimeter (LKB 10700-1). The binary experimental excess molar enthalpy values are correlated by means of the Redlich-Kister polynomial equations and the Liebermann - Fried solution theory model. The ternary excess molar enthalpy values are represented by means of the Tsao-Smith equation with an added ternary term and the Liebermann-Fried model was used to predict ternary excess molar enthalpy values. The Liebermann-Fried solution theory model was able to closely represent the experimental excess enthalpy data for most of the binary and ternary systems with reasonable accuracy. The correlated and predicted excess molar enthalpy data for the ternary systems are plotted in Roozeboom diagrams

In modern separation design, an important part of many phase-equilibrium calculations is the mathematical representation of pure-component and mixture enthalpies. Mixture enthalpy data are important not only for determination of heat loads, but also for the design of distillation units. Further, mixture enthalpy data, when available, are useful for extending vapor-liquid equilibria to higher (or lower) temperatures, through the use of the Gibbs-Helmholtz equation. In this connection excess molar enthalpies for several binary and ternary mixtures involving ethers and hydrocarbons have been measured at the temperature 298.15 K and atmospheric pressure, over the whole mole fraction range. Values of the excess molar enthalpies were measured by means of a modified flow microcalorimeter (LKB 10700-1) and the systems show endothermic behavior. The Redlich-Kister equation has been used to correlate experimental excess molar enthalpy data of binary mixtures. Smooth representations of the excess molar enthalpy values of ternary mixtures are accomplished by means of the Tsao-Smith equation with an added ternary contribution term and are used to construct excess enthalpy contours on Roozeboom diagrams. The values of the standard deviations indicate good agreement between experimental results and those calculated from the smoothing equations. The experimental excess enthalpy data are also correlated and predicted by means of solution theories (Flory theory and Liebermann-Fried model) for binary and ternary mixtures, respectively. These solution theories correlate the binary heats of mixing data with reasonable accuracy. The prediction of ternary excess molar enthalpy by means of the solution theories are also presented on Roozeboom diagrams. The predictions of ternary excess enthalpy data by means of these theories are reasonably reliable.

In modern separation design, an important part of many phase-equilibrium calculations is the mathematical representation of pure-component and mixture enthalpies. Mixture enthalpy data are important not only for determination of heat loads, but also for the design of distillation units. Further, mixture enthalpy data, when available, are useful for extending vapor-liquid equilibria to higher (or lower) temperatures, through the use of the Gibbs-Helmholtz equation. In this connection excess molar enthalpies for several binary and ternary mixtures involving ethers and hydrocarbons have been measured at the temperature 298.15 K and atmospheric pressure, over the whole mole fraction range. Values of the excess molar enthalpies were measured by means of a modified flow microcalorimeter (LKB 10700-1) and the systems show endothermic behavior. The Redlich-Kister equation has been used to correlate experimental excess molar enthalpy data of binary mixtures. Smooth representations of the excess molar enthalpy values of ternary mixtures are accomplished by means of the Tsao-Smith equation with an added ternary contribution term and are used to construct excess enthalpy contours on Roozeboom diagrams. The values of the standard deviations indicate good agreement between experimental results and those calculated from the smoothing equations. The experimental excess enthalpy data are also correlated and predicted by means of solution theories (Flory theory and Liebermann-Fried model) for binary and ternary mixtures, respectively. These solution theories correlate the binary heats of mixing data with reasonable accuracy. The prediction of ternary excess molar enthalpy by means of the solution theories are also presented on Roozeboom diagrams. The predictions of ternary excess enthalpy data by means of these theories are reasonably reliable.

In this study, the structure sensitivity of hydrogen, oxygen and carbon monoxide adsorption was investigated by changing the metal particle size of Pt/Al2O3 catalysts. 2 % Pt/Al2O3 catalysts were prepared by incipient wetness method / the particle size of the catalysts was manipulated by calcining at different temperatures. The dispersion values for the catalysts calcined in air at 683K, 773K and 823K were measured as 0.62, 0.20 and 0.03 respectively. The differential heats of adsorption of hydrogen, carbon monoxide and oxygen were measured using a SETARAM C80 Tian-Calvet calorimeter. No structure dependency was observed for hydrogen, carbon monoxide or oxygen initial heats of adsorption. The adsorbate:metal stoichiometries at saturation systematically decreased with increasing particle size. Hydrogen chemisorption sites with low and intermediate heats were lost when the particle size increased. On the other hand, oxygen and carbon monoxide initial heats and adsorption site energy distributions did not change appreciably with the metal particle size.

This work was dedicated to quantify and distinguish the radio- and chemitoxic effects of environmentally relevant low doses of uranium on the metabolism of microorganisms and multicellular organisms by a modern and highly sensitive microcalorimetry. In such low-dose regime, lethality is low or absent. Therefore, quantitative assays based on survival curves cannot be employed, particularly for multicellular organisms. Even in the case of microbial growth, where individual cells may be killed by particle radiation, classical toxicity assessments based on colony counting are not only extremely time-consuming but also highly error-prone. Therefore, measuring the metabolic activity of the organism under such kinds of conditions would give an extremely valuable quantitative measure of viability that is based on life cell monitoring, rather than determining lethality at higher doses and extrapolating it to the low dose regime. The basic concept is simple as it relies on the metabolic heat produced by an organism during development, growth or replication as an inevitable byproduct of all biochemical processes. A metabolic effect in this concept is defined as a change in heat production over time in the presence of a stressor, such as a heavy metal. This approach appeared to be particular versatile for the low dose regime. Thus, the thesis attempted in this case to measure the enthalpy production of a bacterial population as a whole to derive novel toxicity concepts. In the following chapters, an introduction about the properties of ionizing radiation will be briefly presented, in addition to a review about the isothermal calorimetry and its application in studying the bacterial growth. Later in chapter 2, the effect of uranium on the metabolic activity of three different bacterial strains isolated form a uranium mining waste pile together with a reference strain that is genetically related to them will be investigated. Due to the lack of published dedicated calibration techniques for the interpretation of heat production of bacterial cells under the conditions of calorimetric recordings, additional experiments, thorough investigations of the effects of experimental conditions, have been carried out in order to guide the interpretation of calorimetric results. In chapter 3, the differentiation between chemi- and radiotoxicity of uranium has been addressed by isotope exchange, which was a key effort in this thesis as it opens new experimental approaches in radioecology. In chapter 4, through investigating the role of the tripeptide glutathione (GSH) in detoxifying uranium, it will be shown to which degree the intrinsically unspecific signal provided by metabolic heat can be related to highly specific metabolic pathways of an organism, when combined with genetic engineering. The demonstration of gaining molecule-specific information by life metabolic monitoring was another experimental challenge of this thesis and provides proof of principle that can be extended to many organisms. Finally in chapter 5, an attempt has been undertaken to establish a minimal food chain, in order to study the effects of the exposure of a multicellular organism to uranium through its diet.

This work was dedicated to quantify and distinguish the radio- and chemitoxic effects of environmentally relevant low doses of uranium on the metabolism of microorganisms and multicellular organisms by a modern and highly sensitive microcalorimetry. In such low-dose regime, lethality is low or absent. Therefore, quantitative assays based on survival curves cannot be employed, particularly for multicellular organisms. Even in the case of microbial growth, where individual cells may be killed by particle radiation, classical toxicity assessments based on colony counting are not only extremely time-consuming but also highly error-prone. Therefore, measuring the metabolic activity of the organism under such kinds of conditions would give an extremely valuable quantitative measure of viability that is based on life cell monitoring, rather than determining lethality at higher doses and extrapolating it to the low dose regime. The basic concept is simple as it relies on the metabolic heat produced by an organism during development, growth or replication as an inevitable byproduct of all biochemical processes. A metabolic effect in this concept is defined as a change in heat production over time in the presence of a stressor, such as a heavy metal. This approach appeared to be particular versatile for the low dose regime. Thus, the thesis attempted in this case to measure the enthalpy production of a bacterial population as a whole to derive novel toxicity concepts. In the following chapters, an introduction about the properties of ionizing radiation will be briefly presented, in addition to a review about the isothermal calorimetry and its application in studying the bacterial growth. Later in chapter 2, the effect of uranium on the metabolic activity of three different bacterial strains isolated form a uranium mining waste pile together with a reference strain that is genetically related to them will be investigated. Due to the lack of published dedicated calibration techniques for the interpretation of heat production of bacterial cells under the conditions of calorimetric recordings, additional experiments, thorough investigations of the effects of experimental conditions, have been carried out in order to guide the interpretation of calorimetric results. In chapter 3, the differentiation between chemi- and radiotoxicity of uranium has been addressed by isotope exchange, which was a key effort in this thesis as it opens new experimental approaches in radioecology. In chapter 4, through investigating the role of the tripeptide glutathione (GSH) in detoxifying uranium, it will be shown to which degree the intrinsically unspecific signal provided by metabolic heat can be related to highly specific metabolic pathways of an organism, when combined with genetic engineering. The demonstration of gaining molecule-specific information by life metabolic monitoring was another experimental challenge of this thesis and provides proof of principle that can be extended to many organisms. Finally in chapter 5, an attempt has been undertaken to establish a minimal food chain, in order to study the effects of the exposure of a multicellular organism to uranium through its diet.

This Master's thesis investigates a method to measure atomic nuclei with record precision using muonic atom X-ray spectroscopy. In particular, 6Li is measured experimentally. The method used is independent from the previous most precise measurement of the 6Li nuclear charge radius which uses electron scattering. Measuring low-Z elements using muonic X-ray transitions requires excellent detectors which have so far been mostly optimised for higher energies. This project investigates methods to reach precision requirements for low-Z elements which can yield insight into nuclear structure models, and uses a Silicon Drift Detector (SDD) which is here characterised in detail and found to allow for significantly improved results over previous attempts. So far, the SDD and developed calibration scheme demonstrates a 3.7 eV precision compared to the target 0.5 eV. It appears to be limited by detector resolution, which also makes curve fitting difficult for complex line structures. A new method for generating calibration lines, X-ray fluorescence, is tested and shows good promise for future use. The planned use of a Metallic Magnetic Microcalorimeter will potentially improve results significantly, having a much-improved resolution over SDD's. Preliminary experimental results find ΔEµLi-6, 2p-1s = 18780.6 ± 15.7 eV, which is a factor of 4 improvement over the previous best measurement of this transition and the world's most precise measurement to date. While the uncertainty is larger than seen in designated calibration runs, it demonstrates the ability to perform high-precision muonic atom spectroscopy. With new detector technologies, this thesis finds no immediate obstacles to the target 0.5 eV precision.

Microcalorimetric measurements and contact angle measurements were conducted to study the surface chemistry of powdered minerals. The contact angle measurements were conducted on both flat and powdered talc samples, and the results were used to determine the surface free energy components using Van Oss-Chaudhury-Good (OCG) equation. It was found that the surface hydrophobicity of talc increases with decreasing particle size. At the same time, both the Lifshitz-van der Waals (gSLW) and the Lewis acid-base (gSAB) components (and, hence, the total surface free energy (gS)) decrease with decreasing particle size. The increase in the surface hydrophobicity and the decrease in surface free energy (gS) can be attributed to preferential breakage of the mineral along the basal plane, resulting in the exposure of more basal plane surfaces to the aqueous phase. Heats of immersion measurements were conducted using a flow microcalorimeter on a number of powdered talc samples. The results were then used to calculate the contact angles using a rigorous thermodynamic relation. The measured heat of immersion values in water and calculated contact angles showed that the surface hydrophobicity of talc samples increase with decreasing particle size, which agrees with the direct contact angle measurements. A relationship between advancing water contact angle qa, and the heat of immersion (-DHi) and surface free energies was established. It was found that the value of -DHi decrease as qa increases. The microcalorimetric and direct contact angle measurements showed that acid-base interactions play a crucial role in the interaction between talc and liquid. Using the Van Oss-Chaudhury-Good's surface free energy components model, various talc powders were characterized in terms of their acidic and basic properties. It was found that the magnitude of the Lewis electron donor, gS-, and the Lewis electron acceptor, gS+, components of surface free energy is directly related to the particle size. The gS- of talc surface increased with decreasing particle size, while the gS+ slightly decreased. It was also found that the Lewis electron-donor component on talc surface is much higher than the Lewis electron-acceptor component, suggesting that the basal surface of talc is basic. The heats of adsorption of butanol on various talc samples from n-heptane solution were also determined using a flow microcalorimeter. The heats of adsorption values were used to estimate % hydrophilicity and hydrophobicity and the areal ratios of the various talc samples. In addition, contact angle and heat of butanol adsorption measurements were conducted on a run-of-mine talc sample that has been ground to two different particle size fractions, i.e., d50=12.5 mm and d50=3.0 mm, respectively. The results were used to estimate the surface free energy components at the basal and edge surfaces of talc. It was found that the total surface free energy (gS) at the basal plane surface of talc is much lower than the total surface free energy at the edge surface. The results suggest also that the basal surface of talc is monopolar basic, while the edge surface is monopolar acidic. The results explain why the basicity of talc surface increases with decreasing particle size as shown in the contact angle and microcalorimetric measurements. Furthermore, the effects of the surface free energies of solids during separation from each other by flotation and selective flocculation were studied. In the present work, a kaolin clay sample from east Georgia was used for the beneficiation tests. First, the crude kaolin was subjected to flotation and selective flocculation experiments to remove discoloring impurities (i.e., anatase (TiO2) and iron oxides) and produce high-brightness clay with GE brightness higher than 90%. The results showed that a clay product with +90% brightness could be obtained with recoveries (or yields) higher than 80% using selective flocculation technique. It was also found that a proper control of surface hydrophobicity of anatase is crucially important for a successful flotation and selective flocculation process. Heats of immersion, heats of adsorption and contact angle measurements were conducted on pure anatase surface to determine the changes in the surface free energies as a function of the surfactant dosage (e.g. hydroxamate) used for the surface treatment. The results showed that the magnitude of the contact angle and, hence, the surface free energy and its components on anatase surface varies significantly with the amount of surfactant used for the surface treatment. / Ph. D.