Diese Arbeit berichtet über die Planung und den Aufbau eines neuen Viskosimeters und über Viskositätsuntersuchungen einiger metallischer Systeme. Diese letzteren Messungen wurden mit einem vorhandenen Viskosimeter gemacht, in dem kein besseres Vakuum als 10^(-3)mbar und keine höhere Temperatur als 1430K erreicht werden kann. Das beste Vakuum und die maximale erreichbare Temperatur in dem neuen Viskosimeter sind 10^(-6)mbar bzw. 1870K. Diese beiden Grundbedingungen ermöglichen die Viskositätsmessung metallischer Systeme, die aktive Elemente wie Al, Mg und P enthalten oder/und einen höheren Schmelzpunkt besitzen. Mit dem Drei-Zonen-Ofen erlaubt die neue Apparatur auch ein schnelleres Homogenisieren der zu untersuchenden Schmelze, besonders der monotektischen Systeme. Der Einfluß der Temperatur des Torsionsdrahtes und der Anfangsphase der Schwingung auf die Genauigkeit der Viskostätsmessung wurden analysiert und entsprechende Verbesserungen vorgeschlagen. Die untersuchten Systeme sind das Zn-Pb basierte ternäre System, die monotektischen Systeme Ag-Te und Li-Na, das Verbindungssystem Sb-Zn, die halbleitenden Cd-Te Legierungen und Schaummaterialien ZACT und ZACM. / Viscosity of metallic melts and its precise measurement This thesis reports the design and the construction of a new oscillating cup viscometer and the viscosity investigation of several metallic systems. The measurements were carried out with an existing viscometer by which one could not get better vacuum than 10^(-3)mbar or higher temperature than 1430K. With the new apparatus the best vacuum of 10^(-6)mbar and the highest temperature of 1870K can be reached. These two basic conditions permit the measurement of systems which contain active elements such as Al, Mg and P and/or have very hight melting points. The construction of the three-zone furnace in the new viscometer allows the acceleration of the homogenising process, which is especially important for monotectic systems. The influences of the temperature of the torsion thread and the initial oscillating phase on the accuracy of viscosity measurement were analysed and the corresponding solutions were put forward. The investigated systems are the Zn-Pb based ternary system, the monotectic systems Ag-Te and Li-Na, the Sb-Zn system which contains compounds in the solid phases, the semiconducting Cd-Te alloys and the foaming materials ZACT and ZACM.

The master thesis deals with comparison of atomic fluorescence spektrometry and high resolution continuum source atomic absorption spektrometry for three methods generation of volatile compounds Antimony. In both methods of atomic antimony detection, it compares the most common chemical generation of volatile compounds (hydrides) with two alternative methods - electrochemical and UV - photochemical. The values of performance parameters for the determination of Sb(III) and Sb(V) were determined for all the above combinations. In the case of chemical generation, a surprisingly almost four times higher limit of detection of Sb(III) was found in connection with AFS detection than AAS detection. The final part was devoted to UV - photochemical vapor generation, with AAS detection for Sb(III) reaching limit of detection 4,96 ppb, for Sb(V) 8,63 ppb. Although UV - photochemical generation of volatile antimony compounds did not reach such performance parameters as chemical or electrochemical generation, it was observed that the sensitivity of antimony determination increased greatly when introducing oxygen into the apparatus. The interference study also found a significant positive effect of Fe(II) on the generation efficiency, and this modification partially persisted without further introduction of these...

Ionic liquids (ILs) are able to activate elements that are insoluble in common solvents. Here, the synthesis of binary antimony compounds directly from elements was explored. The 12 elements Ti-Cu, Al, Ga, In, and Te, known to form binary compounds with Sb, were reacted with Sb in [P₆₆₆₁₄]Cl under inert conditions in a closed glass flask with vigorous stirring for 16 h at 200 °C. This was immediately successful in four cases and resulted in the formation of NiSb, InSb, Cu₂Sb and Sb₂Te3. The applied reaction temperature is several hundred degrees below the temperatures required for solvent-free conversions. Compared to reactions based on diffusion in the solid state, reaction times are much shorter. The IL is not consumed and can be recycled. Since the reaction with Cu showed almost complete conversion, the influences of reaction time, temperature and medium were further investigated. Among the tested imidazolium ILs ([BMIm]Cl, [BMIm][OAc], [BDMIm]Cl) and phosphonium ILs ([P₆₆₆₁₄]X, X=Cl⁻, [DCA]⁻, [OAc]⁻, [NTf₂]⁻), those with chloride anion yielded the best results. In a diffusion experiment, Cu₂Sb formed on the copper, which indicates that antimony forms mobile species in these ILs. Supplemental crystal structure data of (As₃S₄)[AlCl₄], which was ionothermally synthesized from As and S, are reported.

Increasing interest in an effciency enhancement of existing energy sources led to an extended research in the field of thermoelectrics. Especially skutterudites with their high power factor (electric conductivity times Seebeck coefficient squared) are suitable thermoelectric materials. However, a further improvement of their thermoelectric properties is necessary. The relatively high thermal conductivity can be decreased by introducing loosely bound guest ions, whereas atom substitution or nanostructuring (as thin films) could yield an increased power factor. The present work proves the feasibility to deposit single phase skutterudite thin films by MBE technique. In this regard CoSby and FeSby film series were deposited with three different methods: i) codeposition at elevated temperatures, ii) codeposition at room temperature followed by post-annealing, and iii) modulated elemental reactant method. The structural and thermoelectric properties of these films were investigated by taking the thermal stability of the film and the substrate properties into account. Compared to the stoichiometric Sb content of skutterudites of 75 at.%, a small excess of Sb is necessary for achieving single phase skutterudite films. It was found, that the deposited single phase CoSb3 films reveal bipolar conduction (and therefore a low Seebeck coefficient), whereas FeSb3 films show p-type conduction and very promising power factors at room temperature. The need of substrates with a low thermal conductivity and a suitable thermal expansion coefficient is also demonstrated. A high thermal conductivity influences the measurements of the Seebeck coefficient and the obtained values will be underestimated by thermal shortening of the film by the substrate. If the thermal expansion coefficient of film and substrate differ strongly from each other, crack formation at the film surface was observed. Furthermore, the realization of controlled doping by substitution as well as the incorporation of guest ions was successfully shown. Hence, this work is a good starting point for designing skutterudite based thin film structures. Two successful examples for such structures are given: i) a thickness series, where a strong decrease of the resistivity was observed for films with a thickness lower than 10nm, and ii) a FexCo1-xSb3 gradient film, for which the gradient was maintained even at an annealing temperature of 400°C.

(EN) The presented dissertation thesis summarizes the new results of electrochemical generation of volatile compounds usable in atomic spectral methods. The main aim of this work is to develop and to characterize new types of electrolytic flow-through cells and to examine their possibilities of determination of arsenic, selenium and antimony by using the electrochemical hydride generation technique coupled with atomic absorption spectrometry with a quartz tube atomizer. Individual electrolytic cells were designed and constructed to comply with two important requirements. The cathode chamber of the electrolytic cell should have a minimal volume and a high efficiency of analyte conversion to the volatile hydride. Constructed electrolytic cells are divided into the construction groups and described in the experimental part. Selenium was chosen as the first analyte. The relevant working parameters (such as type, concentration and flow rate of electrolytes, generation current and carrier gas flow rate) were optimized for each newly constructed electrolytic cell. Under the optimal working parameters, the basic characteristics of selenium determination were found out by using electrochemical hydride generation. The electrolytic cells were compared to each other and with the classical electrolytic cell...

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In der Umwelt vorkommende Radionuklide wurden als Tracer für Migrationsverhalten verwendet. Low-level-γ-Spektrometrie und zusätzliche Plutoniumanalysen ermöglichten den Nachweis sehr geringer Konzentrationen radioaktiver Nuklide. Der atmosphärische Eintrag wurde über Regenwasser- und Staubfilterproben gemessen. Untersuchungen an Filterstäuben ermöglichten eine nachträgliche Charakterisierung der Eintragssituation vor und nach dem Tschernobyl-Unfall im Freiberger Raum. Die Radionuklidtiefenverteilungen in Fichtenwald- und Hochmoorböden und deren weiterführende Analyse erlaubten Aussagen zum Stofftransport und zu bodenbildenden Prozessen. Die Migrationsdynamik in weitgehend ungestörten Hochmooren unterscheidet sich von der anthropogen überprägter Moore. Die Eignung verschiedener Radionuklide zur Datierung bzw. zeitlichen Markierung von Moorbodenschichten und damit zur Verwendung in der Moorstratigraphie wurde geprüft. Eine gute Übereinstimmung der Ergebnisse verschiedener Datierungs- und Markierungsmethoden zeigte sich v. a. für die Profile der ungestörten, rezent wachsenden ombrogenen Hochmoore.

The implementation of energy storage systems in the current electrical grid will increase the grid's reliability and e ciency. Room temperature sodium batteries are seen as potential technology, especially to assist renewable energy generation sources. Currently, suggested negative electrode materials, however, are still not satisfactory for practical use in terms of fabrication costs, gravimetric /volumetric energy densities, cyclability, and irreversible capacity losses occur at the rst cycle. The literature describes various strategies that enhance the specific capacity and/or the cyclability of negative electrode materials but all involve increasing the fabrication costs due to the chosen synthesis or the complexity of the electrode's design. Furthermore, strategies, that reduce the irreversible capacity loss at first cycle, are not discussed. In this present experimental research work, presodiating bulk metallic negative electrode materials prior to cycling, prepared via a simple, cheap and easy-to-scaleup synthesis route, is introduced as a new strategy to improve the cyclability and to effectively reduce the first cycle irreversible capacity loss. Electrochemical and structural experiments were carried out to investigate sodiumtin-antimony powders. Presodiating mechanically bulk Sn-Sb negative electrode materials e ectively reduces the irreversible capacity loss at first cycle and enhances the specific capacity when compared to the non-presodiated powder, while the proper choice of electrode composite and electrolyte formulation improves the cycle life of the electrodes. The enhancement of the electrochemical properties of the presodiated NaSnSb powder, composed of the ternary phase Na5Sb3Sn and an unknown ternary phase crystallising in a hexagonal setting P6, is associated with the stabilisation of the SnSb as desodiation product. Presodiating bulk SnSb negative electrode material is a viable strategy to reduce the first cycle irreversible capacity loss, alleviating the volume changes. With an optimised system, this approach may be extended to other negative electrode materials, reducing the fabrication costs of high capacity negative electrode materials for room temperature sodium batteries. Presodiated NaSnSb negative electrode material may be combined with non-sodiated positive electrode material, such as sulphur to develop competitive room temperature sodium-sulphur batteries. / Die Implementierung von Energiespeichersystemen im bereits bestehenden Stromnetz ist eine der Lösungen, um die Zuverlässigkeit und die Effizienz des Netzes zu nutzen. Raumtemperatur Natrium-Batterien gelten als erfolgsversprechende Technologie insbesondere zur Unterstützung erneuerbarer Energieerzeugungsquellen. Jedoch sind die naheliegenden negativen Elektrodenmaterialien für eine praktische Anwendung hinsichtlich Herstellungskosten, gravimetrischer oder volumetrischer Energiedichte, Zyklenfestigkeit und irreversiblen Kapazitätsverlusten im ersten Zyklus noch nicht zufriedenstellend. Die Literatur beschreibt verschiedene Strategien, die die spezifische Kapazität und / oder die Zyklenfestigkeit von negativen Elektrodenmaterialien verbessern. Diese führen jedoch alle zu einer Erhöhung der Herstellungskosten aufgrund der gewählten Synthese oder des Designs der komplexierten Elektrode. Darüber hinaus werden Strategien zur Reduzierung des irreversiblen Kapazitätsverlusts im ersten Zyklus nicht erörtert. Diese experimentelle Forschungsarbeit präsentiert mit Natrium angereicherte metallische negative Elektrodenmaterialien vor der Wechselbeanspruchung/dem periodischen Durchlaufen, die durch einen schlichten, billigen und einfach zu skalierenden Syntheseweg hergestellt wurden, als eine neue Strategie zur Verbesserung der Zyklenfestigkeit und zur wirksamen Verringerung des irreversiblen Kapazitätsverlusts im ersten Zyklus. Elektrochemische und strukturelle Experimente wurden durchgeführt, um mit Natrium angereichertes Zinn-Antimon-Pulver zu untersuchen. Die mechanischen mit Natrium angereichertes Sn-Sb-negativen Elektrodenmaterialien verringert effektiv den irreversiblen Kapazitätsverlust im ersten Zyklus und erhöht die spezische Kapazität im Vergleich zu dem ohne Natrium angereicherte Pulver, während die richtige Wahl der Elektrodenzusammensetzung und der Elektrolytformulierung die Lebenszyklus der Elektroden verbessert. Die Verbesserung der elektrochemischen Eigenschaften des mit Natrium angereicherten NaSnSb-Pulvers, bestehend aus der ternären Phase Na5Sb3Sn und einer unbekannten ternären Phase, die in einer hexagonalen Aufbau P6 kristallisiert, ist mit der Stabilisierung des Enddesodiationsproduktes beim periodischen Zyklus verbunden, wobei das intermetallische SnSb nach Rekristallisation vorliegt. Mit Natrium angereicherte SnSb negativen Elektrodenmaterialien sind eine tragfähige Strategie zur Verringerung des irreversiblen Kapazitätsverlustes im ersten Zyklus, die Volumenänderungen abschwächen. Mit einem optimierten System kann dieser Ansatz auf andere negative Elektrodenmaterialien erweitert werden um die Herstellungskosten von negativen Elektrodenmaterialien mit hoher Kapazität für Raumtemperatur-Natrium-Batterien zu verringern. Mit Natrium angereichertes NaSnSb-negatives Elektrodenmaterial kann mit nicht mit Natrium versetztem positivem Elektrodenmaterial wie Schwefel kombiniert werden, um realisierbare Raumtemperatur Natrium-Schwefel-Batterien zu entwickeln.

Capability of a prototype of miniature collection device based on a strip of the molybdenum foil for collecting hydride forming elements (As, Se, Sb and Bi) was studied. The device was combined with a miniature hydrogen diffusion flame for detection by atomic absorption spectrometry. The conditions for trapping and subsequent vaporization of analytes of interest were optimized. A twin-channel hydride generation system was used for study of mutual interference effects of co-generated hydride forming elements. The influence of modification of the molybdenum surface with noble metals - Rh, Pt and Ir on trapping and vaporization processes was also studied and changes of microstructure of the foil surface after modification were investigated using scanning electron microscope equipped with energy dispersive x-ray analyzer and electron backscattered diffraction system. Complementary radiotracer and radiography experiments were performed in order to determine trapping efficiency and to assess the spatial distribution of collected analytes within the device. Practical application of the method was demonstrated on determination of antimony in water samples at trace level. Possibility of multi-element analysis was demonstrated by combining the collection device with atomization and excitation of the analyte in microwave induced plasma and with detection by atomic emission spectrometry method. The results of the experiments proved that tested miniature collection device is capable of trapping analytes that form volatile hydrides. This device can be coupled to various types of atomizers, typically used in spectrometry methods. Thus, very sensitive and specific detection of hydride forming elements can be performed.

Diese Arbeit berichtet über die Planung und den Aufbau eines neuen Viskosimeters und über Viskositätsuntersuchungen einiger metallischer Systeme. Diese letzteren Messungen wurden mit einem vorhandenen Viskosimeter gemacht, in dem kein besseres Vakuum als 10^(-3)mbar und keine höhere Temperatur als 1430K erreicht werden kann. Das beste Vakuum und die maximale erreichbare Temperatur in dem neuen Viskosimeter sind 10^(-6)mbar bzw. 1870K. Diese beiden Grundbedingungen ermöglichen die Viskositätsmessung metallischer Systeme, die aktive Elemente wie Al, Mg und P enthalten oder/und einen höheren Schmelzpunkt besitzen. Mit dem Drei-Zonen-Ofen erlaubt die neue Apparatur auch ein schnelleres Homogenisieren der zu untersuchenden Schmelze, besonders der monotektischen Systeme. Der Einfluß der Temperatur des Torsionsdrahtes und der Anfangsphase der Schwingung auf die Genauigkeit der Viskostätsmessung wurden analysiert und entsprechende Verbesserungen vorgeschlagen. Die untersuchten Systeme sind das Zn-Pb basierte ternäre System, die monotektischen Systeme Ag-Te und Li-Na, das Verbindungssystem Sb-Zn, die halbleitenden Cd-Te Legierungen und Schaummaterialien ZACT und ZACM. / Viscosity of metallic melts and its precise measurement This thesis reports the design and the construction of a new oscillating cup viscometer and the viscosity investigation of several metallic systems. The measurements were carried out with an existing viscometer by which one could not get better vacuum than 10^(-3)mbar or higher temperature than 1430K. With the new apparatus the best vacuum of 10^(-6)mbar and the highest temperature of 1870K can be reached. These two basic conditions permit the measurement of systems which contain active elements such as Al, Mg and P and/or have very hight melting points. The construction of the three-zone furnace in the new viscometer allows the acceleration of the homogenising process, which is especially important for monotectic systems. The influences of the temperature of the torsion thread and the initial oscillating phase on the accuracy of viscosity measurement were analysed and the corresponding solutions were put forward. The investigated systems are the Zn-Pb based ternary system, the monotectic systems Ag-Te and Li-Na, the Sb-Zn system which contains compounds in the solid phases, the semiconducting Cd-Te alloys and the foaming materials ZACT and ZACM.