Developments for transactinide chemistry experiments behind the gas-filled separator TASCA

Topic of this thesis is the development of experiments behind the gas-filled separator TASCA(TransActinide Separator and Chemistry Apparatus) to study the chemical properties of the transactinide elements.rnIn the first part of the thesis, the electrodepositions of short-lived isotopes of ruthenium and osmium on gold electrodes were studied as model experiments for hassium. From literature it is known that the deposition potential of single atoms differs significantly from the potential predicted by the Nernst equation. This shift of the potential depends on the adsorption enthalpy of therndeposited element on the electrode material. If the adsorption on the electrode-material is favoured over the adsorption on a surface made of the same element as the deposited atom, the electrode potential is shifted to higher potentials. This phenomenon is called underpotential deposition.rnPossibilities to automatize an electro chemistry experiment behind the gas-filled separator were explored for later studies with transactinide elements.rnThe second part of this thesis is about the in-situ synthesis of transition-metal-carbonyl complexes with nuclear reaction products. Fission products of uranium-235 and californium-249 were produced at the TRIGA Mainz reactor and thermalized in a carbon-monoxide containing atmosphere. The formed volatile metal-carbonyl complexes could be transported in a gas-stream.rnFurthermore, short-lived isotopes of tungsten, rhenium, osmium, and iridium were synthesised at the linear accelerator UNILAC at GSI Helmholtzzentrum für Schwerionenforschung, Darmstadt. The recoiling fusion products were separated from the primary beam and the transfer products in the gas-filled separator TASCA. The fusion products were stopped in the focal plane of TASCA in a recoil transfer chamber. This chamber contained a carbon-monoxide – helium gas mixture. The formed metal-carbonyl complexes could be transported in a gas stream to various experimental setups. All synthesised carbonyl complexes were identified by nuclear decay spectroscopy. Some complexes were studied with isothermal chromatography or thermochromatography methods. The chromatograms were compared with Monte Carlo Simulations to determine the adsorption enthalpyrnon silicon dioxide and on gold. These simulations based on existing codes, that were modified for the different geometries of the chromatography channels. All observed adsorption enthalpies (on silcon oxide as well as on gold) are typical for physisorption. Additionally, the thermalstability of some of the carbonyl complexes was studied. This showed that at temperatures above 200 °C therncomplexes start to decompose.rnIt was demonstrated that carbonyl-complex chemistry is a suitable method to study rutherfordium, dubnium, seaborgium, bohrium, hassium, and meitnerium. Until now, only very simple, thermally stable compounds have been synthesized in the gas-phase chemistry of the transactindes. With the synthesis of transactinide-carbonyl complexes a new compound class would be discovered. Transactinide chemistry would reach the border between inorganic and metallorganic chemistry.rnFurthermore, the in-situ synthesised carbonyl complexes would allow nuclear spectroscopy studies under low background conditions making use of chemically prepared samples.

Electrochemical surface modification of Single walled carbon nanotubes and graphene-based electrodes for (bio)sensing applications

Sensors are devices that have shown widespread use, from the detection of gas molecules to the tracking of chemical signals in biological cells. Single walled carbon nanotube (SWCNT) and graphene based electrodes have demonstrated to be an excellent material for the development of electrochemical biosensors as they display remarkable electronic properties and the ability to act as individual nanoelectrodes, display an excellent low-dimensional charge carrier transport, and promote surface electrocatalysis. The present work aims at the preparation and investigation of electrochemically modified SWCNT and graphene-based electrodes for applications in the field of biosensors. We initially studied SWCNT films and focused on their topography and surface composition, electrical and optical properties. Parallel to SWCNTs, graphene films were investigated. Higher resistance values were obtained in comparison with nanotubes films. The electrochemical surface modification of both electrodes was investigated following two routes (i) the electrografting of aryl diazonium salts, and (ii) the electrophylic addition of 1, 3-benzodithiolylium tetrafluoroborate (BDYT). Both the qualitative and quantitative characteristics of the modified electrode surfaces were studied such as the degree of functionalization and their surface composition. The combination of Raman, X-ray photoelectron spectroscopy, atomic force microscopy, electrochemistry and other techniques, has demonstrated that selected precursors could be covalently anchored to the nanotubes and graphene-based electrode surfaces through novel carbon-carbon formation.

A numerical model for inert gas transport in the lung based on fractal airway morphology

Patients suffering from cystic fibrosis (CF) show thick secretions, mucus plugging and bronchiectasis in bronchial and alveolar ducts. This results in substantial structural changes of the airway morphology and heterogeneous ventilation. Disease progression and treatment effects are monitored by so-called gas washout tests, where the change in concentration of an inert gas is measured over a single or multiple breaths. The result of the tests based on the profile of the measured concentration is a marker for the severity of the ventilation inhomogeneity strongly affected by the airway morphology. However, it is hard to localize underlying obstructions to specific parts of the airways, especially if occurring in the lung periphery. In order to support the analysis of lung function tests (e.g. multi-breath washout), we developed a numerical model of the entire airway tree, coupling a lumped parameter model for the lung ventilation with a 4th-order accurate finite difference model of a 1D advection-diffusion equation for the transport of an inert gas. The boundary conditions for the flow problem comprise the pressure and flow profile at the mouth, which is typically known from clinical washout tests. The natural asymmetry of the lung morphology is approximated by a generic, fractal, asymmetric branching scheme which we applied for the conducting airways. A conducting airway ends when its dimension falls below a predefined limit. A model acinus is then connected to each terminal airway. The morphology of an acinus unit comprises a network of expandable cells. A regional, linear constitutive law describes the pressure-volume relation between the pleural gap and the acinus. The cyclic expansion (breathing) of each acinus unit depends on the resistance of the feeding airway and on the flow resistance and stiffness of the cells themselves. Special care was taken in the development of a conservative numerical scheme for the gas transport across bifurcations, handling spatially and temporally varying advective and diffusive fluxes over a wide range of scales. Implicit time integration was applied to account for the numerical stiffness resulting from the discretized transport equation. Local or regional modification of the airway dimension, resistance or tissue stiffness are introduced to mimic pathological airway restrictions typical for CF. This leads to a more heterogeneous ventilation of the model lung. As a result the concentration in some distal parts of the lung model remains increased for a longer duration. The inert gas concentration at the mouth towards the end of the expirations is composed of gas from regions with very different washout efficiency. This results in a steeper slope of the corresponding part of the washout profile.

Maps and acoustic profiles of free gas distribution, Western Baltic Sea and Kattgat-Skagerrak area

A shallow gas depth-contour map covering the Skagerrak-western Baltic Sea region has been constructed using a relatively dense grid of existing shallow seismic lines. The digital map is stored as an ESRI shape file in order to facilitate comparison with other data from the region. Free gas usually occurs in mud and sandy mud but is observed only when sediment thickness exceeds a certain threshold value, depending on the water depth of the area in question. Gassy sediments exist at all water depths from approx. 20 m in the coastal waters of the Kattegat to 360 m in the Skagerrak. In spite of the large difference in water depths, the depth of free gas below seabed varies only little within the region, indicating a relatively fast movement of methane in the gas phase towards the seabed compared to the rate of diffusion of dissolved methane. Seeps of old microbial methane occur in the northern Kattegat where a relatively thin cover of sandy sediments exists over shallow, glacially deformed Pleistocene marine sediments. Previous estimates of total methane escape from the area may be correct but the extrapolation of local methane seepage rate data to much larger areas on the continental shelf is probably not justified. Preliminary data on porewater chemistry were compared with the free gas depth contours in the Aarhus Bay area, which occasionally suffers from oxygen deficiency, in order to examine if acoustic gas mapping may be used for monitoring the condition of the bay.

Multi-fluid Eulerian model of an electrospray in a host gas.

An Eulerian multifluid model is used to describe the evolution of an electrospray plume and the flow induced in the surrounding gas by the drag of the electrically charged spray droplets in the space between an injection electrode containing the electrospray source and a collector electrode. The spray is driven by the voltage applied between the two electrodes. Numerical computations and order-of-magnitude estimates for a quiescent gas show that the droplets begin to fly back toward the injection electrode at a certain critical value of the flux of droplets in the spray, which depends very much on the electrical conditions at the injection electrode. As the flux is increased toward its critical value, the electric field induced by the charge of the droplets partially balances the field due to the applied voltage in the vicinity of the injection electrode, leading to a spray that rapidly broadens at a distance from its origin of the order of the stopping distance at which the droplets lose their initial momentum and the effect of their inertia becomes negligible. The axial component of the electric field first changes sign in this region, causing the fly back. The flow induced in the gas significantly changes this picture in the conditions of typical experiments. A gas plume is induced by the drag of the droplets whose entrainment makes the radius of the spray away from the injection electrode smaller than in a quiescent gas, and convects the droplets across the region of negative axial electric field that appears around the origin of the spray when the flux of droplets is increased. This suppresses fly back and allows much higher fluxes to be reached than are possible in a quiescent gas. The limit of large droplet-to-gas mass ratio is discussed. Migration of satellite droplets to the shroud of the spray is reproduced by the Eulerian model, but this process is also affected by the motion of the gas. The gas flow preferentially pushes satellite droplets from the shroud to the core of the spray when the effect of the inertia of the droplets becomes negligible, and thus opposes the well-established electrostatic/inertial mechanism of segregation and may end up concentrating satellite droplets in an intermediate radial region of the spray.

Synthetic Boron-Doped Diamond Electrodes for Electrochemical Water Treatment

Boron-doped diamond electrodes have emerged as anodic material due to their high physical, chemical and electrochemical stability. These characteristics make it particularly interesting for electrochemical wastewater treatments and especially due to its high overpotential for the Oxygen Evolution Reaction. Diamond electrodes present the maximum efficiency in pollutant removal in water, just limited by diffusion-controlled electrochemical kinetics. Results are presented for the elimination of benzoic acid and for the electrochemical treatment of synthetic tannery wastewater. The results indicate that diamond electrodes exhibit the best performance for the removal of total phenols, COD, TOC, and colour.

Evidence of Intracrystalline Mesostructured Porosity in Zeolites by Advanced Gas Sorption, Electron Tomography and Rotation Electron Diffraction

The small size of micropores (typically <1 nm) in zeolites causes slow diffusion of reactant and product molecules in and out of the pores and negatively impacts the product selectivity of zeolite based catalysts, for example, fluid catalytic cracking (FCC) catalysts. Size-tailored mesoporosity was introduced into commercial zeolite Y crystals by a simple surfactant-templating post-synthetic mesostructuring process. The resulting mesoporous zeolite Y showed significantly improved product selectivity in both laboratory testing and refinery trials. Advanced characterization techniques such as electron tomography, three-dimensional rotation electron diffraction, and high resolution gas adsorption coupled with hysteresis scanning and density functional theory, unambiguously revealed the intracystalline nature and connectivity of the introduced mesopores. They can be considered as molecular highways that help reactant and product molecules diffuse quickly to and away from the catalytically active sites within the zeolite crystals and, thus, shift the selectivity to favor the production of more of the valuable liquid fuels at reduced yields of coke and unconverted feed.

Lung Structure and the Intrinsic Challenges of Gas Exchange

Structural and functional complexities of the mammalian lung evolved to meet a unique set of challenges, namely, the provision of efficient delivery of inspired air to all lung units within a confined thoracic space, to build a large gas exchange surface associated with minimal barrier thickness and a microvascular network to accommodate the entire right ventricular cardiac output while withstanding cyclic mechanical stresses that increase several folds from rest to exercise. Intricate regulatory mechanisms at every level ensure that the dynamic capacities of ventilation, perfusion, diffusion, and chemical binding to hemoglobin are commensurate with usual metabolic demands and periodic extreme needs for activity and survival. This article reviews the structural design of mammalian and human lung, its functional challenges, limitations, and potential for adaptation. We discuss (i) the evolutionary origin of alveolar lungs and its advantages and compromises, (ii) structural determinants of alveolar gas exchange, including architecture of conducting bronchovascular trees that converge in gas exchange units, (iii) the challenges of matching ventilation, perfusion, and diffusion and tissue-erythrocyte and thoracopulmonary interactions. The notion of erythrocytes as an integral component of the gas exchanger is emphasized. We further discuss the signals, sources, and limits of structural plasticity of the lung in alveolar hypoxia and following a loss of lung units, and the promise and caveats of interventions aimed at augmenting endogenous adaptive responses. Our objective is to understand how individual components are matched at multiple levels to optimize organ function in the face of physiological demands or pathological constraints. © 2016 American Physiological Society. Compr Physiol 6:827-895, 2016.

The effect of species diffusion and heat conduction on nonequilibrium flows behind strong shocks. Contract no. NASr-119.

Mode of access: Internet.

Effects of adsorbed phase on diffusion of subcritical hydrocarbons in activated carbon at low pressures

Diffusions of free and adsorbed molecules of subcritical hydrocarbons in activated carbon were investigated to study the influence of adsorbed molecules on both diffusion processes at low pressures. A collision reflection factor, defined as the fraction of molecules undergoing collision to the solid surface over reflection from the surface, is incorporated into Knudsen diffusivity and surface diffusivity in meso/macropores. Since the porous structure of activated carbon is bimodal in nature, the diffusion of adsorbed molecules is contributed by that of weakly adsorbed molecules on the meso/macropore surfaces and that of strongly adsorbed molecules in the small confinement of micropores. The mobility of adsorbed molecules on the meso/macropore surface is characterized by the surface diffusivity D-mu 2, while that in the micropore is characterized by D-mu 1. In our study with subcritical hydrocarbons, we have found that the former increases almost linearly with pressure, while the latter exhibits a sharp increase at a very low-pressure region and then decreases beyond a critical pressure. This critical pressure is identified as a pressure at which the micropores are saturated.

Preparation and anode property of Pt-CeO2 electrodes supported on carbon black for direct methanol fuel cell applications

A platinum (Pt) on pure ceria (CeO2) supported by carbon black (CB) anode was synthesized using a combined process of precipitation and coimpregnation methods. The electrochemical activity of methanol oxidation reaction on synthesized Pt-CeO2/CB anodes was investigated by cyclic voltammetry and chronoamperometry experimentation. To improve the anode property on Pt-CeO2/CB, the influence of particle morphology and particle size on anode properties was examined. The morphology and particle size of the pure CeO2 particles could be controlled by changing the preparation conditions. The anode properties (i.e., peak current density and onset potential for methanol oxidation) were improved by using nanosize CeO2 particles. This indicates that a larger surface area and higher activity on the surface of CeO2 improve the anode properties. The influence of particle morphology of CeO2 on anode properties was not very large. The onset potential for methanol oxidation reaction on Pt-CeO2/CB, which consisted of CeO2 with a high surface area, was shifted to a lower potential compared with that on the anodes, which consisted of CeO2 with a low surface area. The onset potential on Pt-CeO2/CB at 60 degrees C became similar to that on the commercially available Pt-Ru/carbon anode. We suggest that the rate-determining steps of the methanol oxidation reaction on Pt-CeO2/CB and commercially available Pt-Ru/carbon anodes are different, which accounts for the difference in performance. In the reaction mechanism on Pt-CeO2/CB, we conclude that the released oxygen species from the surface of CeO2 particles contribute to oxidation of adsorbed CO species on the Pt surface. This suggests that the anode performance of the Pt-CeO2/CB anode would lead to improvements in the operation of direct methanol fuel cells at 80 degrees C by the enhancement of diffusion of oxygen species created from the surface of nanosized CeO2 particles. Therefore, we conclude that fabrication of nanosized CeO2 with a high surface area is a key factor for development of a high-quality Pt-CeO2/CB anode in direct methanol fuel cells.

A micro gas turbines for UK domestic combined heat and power

Various micro-radial compressor configurations were investigated using one-dimensional meanline and computational fluid dynamics (CFD) techniques for use in a micro gas turbine (MGT) domestic combined heat and power (DCHP) application. Blade backsweep, shaft speed, and blade height were varied at a constant pressure ratio. Shaft speeds were limited to 220 000 r/min, to enable the use of a turbocharger bearing platform. Off-design compressor performance was established and used to determine the MGT performance envelope; this in turn was used to assess potential cost and environmental savings in a heat-led DCHP operating scenario within the target market of a detached family home. A low target-stage pressure ratio provided an opportunity to reduce diffusion within the impeller. Critically for DCHP, this produced very regular flow, which improved impeller performance for a wider operating envelope. The best performing impeller was a low-speed, 170 000 r/min, low-backsweep, 15° configuration producing 71.76 per cent stage efficiency at a pressure ratio of 2.20. This produced an MGT design point system efficiency of 14.85 per cent at 993 W, matching prime movers in the latest commercial DCHP units. Cost and CO2 savings were 10.7 per cent and 6.3 per cent, respectively, for annual power demands of 17.4 MWht and 6.1 MWhe compared to a standard condensing boiler (with grid) installation. The maximum cost saving (on design point) was 14.2 per cent for annual power demands of 22.62 MWht and 6.1 MWhe corresponding to an 8.1 per cent CO2 saving. When sizing, maximum savings were found with larger heat demands. When sized, maximum savings could be made by encouraging more electricity export either by reducing household electricity consumption or by increasing machine efficiency.

Self-assembled SnO2 micro- and nanosphere-based gas sensor thick films from an alkoxide-derived high purity aqueous colloid precursor

Tin oxide is considered to be one of the most promising semiconductor oxide materials for use as a gas sensor. However, a simple route for the controllable build-up of nanostructured, sufficiently pure and hierarchical SnO2 structures for gas sensor applications is still a challenge. In the current work, an aqueous SnO2 nanoparticulate precursor sol, which is free of organic contaminants and sorbed ions and is fully stable over time, was prepared in a highly reproducible manner from an alkoxide Sn(OR)4 just by mixing it with a large excess of pure neutral water. The precursor is formed as a separate liquid phase. The structure and purity of the precursor is revealed using XRD, SAXS, EXAFS, HRTEM imaging, FTIR, and XRF analysis. An unconventional approach for the estimation of the particle size based on the quantification of the Sn-Sn contacts in the structure was developed using EXAFS spectroscopy and verified using HRTEM. To construct sensors with a hierarchical 3D structure, we employed an unusual emulsification technique not involving any additives or surfactants, using simply the extraction of the liquid phase, water, with the help of dry butanol under ambient conditions. The originally generated crystalline but yet highly reactive nanoparticles form relatively uniform spheres through self-assembly and solidify instantly. The spheres floating in butanol were left to deposit on the surface of quartz plates bearing sputtered gold electrodes, producing ready-for-use gas sensors in the form of ca. 50 μm thick sphere-based-films. The films were dried for 24 h and calcined at 300°C in air before use. The gas sensitivity of the structures was tested in the temperature range of 150-400°C. The materials showed a very quickly emerging and reversible (20-30 times) increase in electrical conductivity as a response to exposure to air containing 100 ppm of H2 or CO and short (10 s) recovery times when the gas flow was stopped.

Design of a low power - high temperature heated ceramic sensor to detect halogen gases

The design, construction and optimization of a low power-high temperature heated ceramic sensor to detect leaking of halogen gases in refrigeration systems are presented. The manufacturing process was done with microelectronic assembly and the Low Temperature Cofire Ceramic (LTCC) technique. Four basic sensor materials were fabricated and tested: Li2SiO3, Na2SiO3, K2SiO3, and CaSiO 3. The evaluation of the sensor material, sensor size, operating temperature, bias voltage, electrodes size, firing temperature, gas flow, and sensor life was done. All sensors responded to the gas showing stability and reproducibility. Before exposing the sensor to the gas, the sensor was modeled like a resistor in series and the calculations obtained were in agreement with the experimental values. The sensor response to the gas was divided in surface diffusion and bulk diffusion; both were analyzed showing agreement between the calculations and the experimental values. The sensor with 51.5%CaSiO3 + 48.5%Li 2SiO3 shows the best results, including a stable current and response to the gas. ^

Design of a Low Power – High Temperature Heated Ceramic Sensor to Detect Halogen Gases

The design, construction and optimization of a low power-high temperature heated ceramic sensor to detect leaking of halogen gases in refrigeration systems are presented. The manufacturing process was done with microelectronic assembly and the Low Temperature Cofire Ceramic (LTCC) technique. Four basic sensor materials were fabricated and tested: Li2SiO3, Na2SiO3, K2SiO3, and CaSiO3. The evaluation of the sensor material, sensor size, operating temperature, bias voltage, electrodes size, firing temperature, gas flow, and sensor life was done. All sensors responded to the gas showing stability and reproducibility. Before exposing the sensor to the gas, the sensor was modeled like a resistor in series and the calculations obtained were in agreement with the experimental values. The sensor response to the gas was divided in surface diffusion and bulk diffusion; both were analyzed showing agreement between the calculations and the experimental values. The sensor with 51.5%CaSiO3 + 48.5%Li2SiO3 shows the best results, including a stable current and response to the gas.