Die Temperaturverhältnisse beim Ziehen und Wärmebehandeln von Draht werden mit mathematisch-analytischen Methoden auf der Grundlage der FOURIERschen Wärmeleitungsgleichung eingehend untersucht. Insbesondere wird unter den spezifischen Wärmeübergangsbedingungen zwischen Draht und Ziehdüse sowie zwischen Draht und Ziehtrommel deren thermische Wechselwirkung analysiert. Ein Näherungsverfahren zur Berechnung der Drahttemperaturen in Zugfolgen unter Berücksichtigung des Ziehdüseneinflusses wird angegeben und mit einem Beispiel zum Nassziehen stark verzinkten Stahldrahts illustriert. Aus geschwindigkeitsabhängig gemessenen Änderungen des Drahtdurchmessers werden unter thermoelastischer Ziehringdurchmesserkorrektur Schmierfilmdicken bestimmt. Diffusionsgleichungen werden analysiert und ein Zusammenhang zur Reaktionskinetik wird hergestellt. Ein neues reaktionskinetisches Werkstoffmodell, das insbesondere auch im Falle stärker anisothermer Verhältnisse, also bei Kurzzeitwärmebehandlung anwendbar ist, wird vorgestellt.

Made available in DSpace on 2014-10-09T12:28:43Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:57:15Z (GMT). No. of bitstreams: 0 / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

Made available in DSpace on 2014-10-09T12:28:43Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T13:57:15Z (GMT). No. of bitstreams: 0 / Este trabalho apresenta as medidas das taxas de reação nuclear ao longo da direção radial da pastilha combustível por irradiação e posterior espectrometria gama de um fino disco de UO2 com enriquecimento de 4,3% no reator IPEN/MB- 01. A partir de sua irradiação, a taxa de captura radioativa e de fissão foram medidas em função do raio do disco utilizando um detector HPGe. Colimadores de chumbo foram utilizados para esse fim. O disco de UO2 é inserido no interior de uma vareta combustível desmontável e esta é então colocada na posição central do núcleo do reator IPEN/MB-01 e irradiada durante uma hora sob um fluxo de nêutrons de aproximadamente 9 x 108 n/cm2s. Na espectrometria gama, 10 colimadores com diâmetros diferentes foram utilizados, consequentemente, as reações nucleares de captura radioativa que ocorrem nos átomos de 238U e as fissões que ocorrem em ambos 235U e 238U são mensuradas em função de 10 regiões distintas do disco combustível. Correções de eficiência geométrica devido à introdução dos colimadores no sistema de detecção HPGe foram estimados usando o código MCNP-4C. Alguns valores calculados da taxa de reação nuclear de captura radioativa e fissão obtidos pela metodologia de Monte Carlo, utilizando o código MCNP-4C, são apresentados e comparados aos dados experimentais apresentando boa concordância. Além de taxas de reação nuclear, os índices espectrais 28ρ e 25δ foram obtidos para cada raio do disco combustível. / Dissertacao (Mestrado) / IPEN/D / Instituto de Pesquisas Energeticas e Nucleares - IPEN-CNEN/SP

<p>Various organic reactions, including important synthetic reactions involving C–C, C–N, and C–O bond formation as well as reactions of biomolecules, are known to be accelerated when the reagents are present in confined volumes such as sprayed or levitated microdroplets or thin films. This phenomenon of reaction acceleration and the key role of interfaces played in it are of intrinsic interest and potentially of practical value as a simple, rapid method of performing small-scale synthesis. This dissertation has three focusing subtopics in the field of reaction acceleration: (1) application of reaction acceleration in levitated droplets and mass spectrometry to accelerate the reaction-analysis workflow of forced degradation of pharmaceuticals at small scale; (2) fundamental understanding of mechanisms of accelerated reactions at air/solution interfaces; (3) discovery the use of glass particles as a `green' heterogeneous catalysts in solutions and systematical study of solid(glass)/solution interfacial reaction acceleration as a superbase for synthesis and degradation using high-throughput screening.</p><p><br></p><p>Reaction acceleration in confined volumes could enhance analytical methods in industrial chemistry. Forced degradation is critical to probe the stabilities and chemical reactivities of therapeutics. Typically performed in bulk followed by LC-MS analysis, this traditional workflow of reaction/analysis sequence usually requires several days to form and measure desirable amount of degradants. I developed a new method to study chemical degradation in a shorter time frame in order to speed up both drug discovery and the drug development process. Using the Leidenfrost effect, I was able to study, over the course of seconds, degradation in levitated microdroplets over a metal dice. This two-minute reaction/analysis workflow allows major degradation pathways of both small molecules and therapeutic peptides to be studied. The reactions studied include deamidation, disulfide bond cleavage, ether cleavage, dehydration, hydrolysis, and oxidation. The method uses microdroplets as nano-reactors and only require a minimal amount of therapeutics per stress condition and the desirable amount of degradant can be readily generated in seconds by adjusting the droplet levitation time, which is highly advantageous both in the discovery and development phase. Built on my research, microdroplets can potentially be applied in therapeutics discovery and development to rapidly screen stability of therapeutics and to screen the effects of excipients in enhancing formulation stabilities.</p><p><br></p><p>My research also advanced the fundamental understanding of reaction acceleration by disentangles the factors controlling reaction rates in microdroplet reactions using constant-volume levitated droplets and Katritzky transamination as a model. The large surface-to-volume ratios of these systems results in a major contribution from reactions at the air/solution interface where reaction rates are increased. Systems with higher surface-active reactants are subject to greater acceleration, particularly at lower concentrations and higher surface-to-volume ratios. These results highlight the key role that air/solution air/solution interfaces play in Katritzky reaction acceleration. They are also consistent with the view that reaction increased rate constant is at least in part due to limited solvation of reagents at the interface.</p><p><br></p><p><br></p><p>While reaction acceleration at air/solution interfaces has been well known in microdroplets, reaction acceleration at solid/solution interfaces appears to be a new phenomenon. The Katritzky reaction in bulk solution at room temperature is accelerated significantly by the surface of a glass container compared to a plastic container. Remarkably, the reaction rate is increased by more than two orders of magnitude upon the addition of glass particles with the rate increasing linearly with increasing amounts of glass. A similar phenomenon is observed when glass particles are added to levitated droplets, where large acceleration factors are seen. Evidence shows that glass acts as a ‘green’ heterogeneous catalyst: it participates as a base in the deprotonation step and is recovered unchanged from the reaction mixture. </p><p><br></p><p>Subsequent to this study, we have systematically explored the solid/solution interfacial acceleration phenomena using our latest generation of a high-throughput screening system which is capable of screening thousands of organic reactions in a single day. Using desorption electrospray ionization mass spectrometry (DESI-MS) for automated analysis, we have found that glass promotes not only organic reactions without organic catalysts but also reactions of biomolecules without enzymes. Such reactions include Knoevenagel condensation, imine formation, elimination of hydrogen halide, ester hydrolysis and/or transesterification of acetylcholine and phospholipids, as well as oxidation of glutathione. Glass has been used as a general `green' and powerful heterogeneous catalyst.</p>

Diese Arbeit beschäftigt sich mit dem Einsatz biogener Ersatzbrennstoffe bei der motorischen Verbrennung. Zum einen wurden die laminaren Brenngeschwindigkeiten von Ethanol und iso-Butanol sowie Gemischen mit iso-Oktan bestimmt. Es konnten Messwerte für die Validierung von numerischen Mechanismen sowie Parameter für die Abbildung der Temperatur- und Druckabhängigkeit der Brenngeschwindigkeit bestimmt werden. Der Vergleich der Messverfahren zeigt eine gute Übereinstimmung. Zum anderen wurden die Auswirkungen der Beimischung von Wasserstoff auf die Abgaszusammensetzung und den Wirkungsgrad an einem Verbrennungsmotor ermittelt. Die Erhöhung des Wasserstoffanteils führt zur Erhöhung des Wirkungsgrades. Die Abgasbestanteile Kohlenstoffmonoxid, Formaldehyd und Methan werden reduziert, während Stickoxide zunehmen. Mit den begleitenden Simulationen kann gezeigt werden, dass höhere Wasserstoffanteile die Oxidation durch einen erhöhten Anteil an OH-Radikalen begünstigen. Der Grund für das verstärkte Auftreten von Stickstoffmonoxid liegt in der Verlängerung der Verweilzeit der verbrannten Gase in der Oxidationszone.

Rhenium complexes coordinated with suitable organic ligand gain increased interest in radiopharmaceutical medicine. Besides suitable radiological properties given by a metal ion itself, detailed knowledge of overall chemical properties of formed complexes, namely their exact structures, chemical stabilities and possible degradation pathways are essential pre-requisites for their clinical application. Selected rhenium complexes with pyrogallol 2,3-dihydroxynaphthalene and catechol as strongly bound ligands were prepared by a reaction of tetrabutylammonium tetrachlorooxorhenate with twofold molar excess of ligand in presence of various amount of triethylamine. The structures of formed complexes and their consequent reaction products were estimated by means of mass spectrometry with electrospray ionization. The kinetics of reactions in course of complex formation and consequent decomposition were primarily followed by UV- Vis absorption spectra measurement, complemented by single or continuous electrospray mass spectrometry analyses. Optimized HPLC and CZE procedures were utilized for monitoring of the composition of reaction mixtures in course of Re complex formation and for purity check of prepared complexes. Semi-preparative HPLC mode was succesfully utilized for isolation and final purification of...

In this work a manufacturing method for UN, ZrN and (U,Zr)N pellets was established at the nuclear fuel laboratory at KTH Stockholm/Sweden, which consists of the production of nitride powders and their sintering into pellets by spark plasma sintering. The nitride powders were produced by the hydriding-nitriding route using pure metal as starting material. This synthesis was performed in a stream of the particular reaction gas. A synthesis control and monitoring system was developed, which can follow the reactions in real time by measuring the gas flow difference before and after the reaction chamber. With the help of this system the hydriding and nitriding reactions of uranium and zirconium were studied in detail. Fine nitride powders were obtained; however, the production of zirconium nitride involved one milling step of the brittle zirconium hydride. Additionally uranium and zirconium alloys with different zirconium contents were produced and synthesized to nitride powders. It was found that also the alloys could be reduced to fine powder, but only by cyclic hydriding-dehydriding. Pellets were sintered out of uranium nitrides, zirconium nitrides, mixed nitrides and alloy nitrides. These experiments showed that relative densities of more than 90% can easily be achieved for all those powders. Pellets sintered from mechanically mixed nitride powders were found to still consist of two separate nitride phases, while nitride produced from alloy was demonstrated to be a monophasic solid solution both as powder and as sintered pellets.

L’objectif de ce travail est de remplacer les catalyseurs organométalliques à base d’étain et de mercure utilisés lors de la synthèse de polyuréthane via la réaction isocyanate – alcool. Une étude bibliographique a montré que la basicité et la nucléophilie d’un catalyseur organique gouvernent son activité et le mécanisme réactionnel qu’il induit. Pour les catalyseurs organométalliques, ces propriétés catalytiques s’expliquent par des considérations électroniques ainsi que par le principe HSAB. D’autre part, une étude approfondie du catalyseur organomercuriel a été menée. Elle a révélé l’intérêt d’ajouter à l’espèce catalytique organométallique un acide carboxylique, de préférence à longue chaîne carbonée. Celui-ci ralentit l’hydrolyse du catalyseur tout en augmentant sa sélectivité envers la réaction isocyanate – alcool. De nouveaux catalyseurs ou systèmes catalytiques originaux ont ensuite été évalués grâce à un test simplifié. Trois catalyseurs organométalliques ont ainsi été sélectionnés pour de nouveaux essais dans des conditions plus proches de celles rencontrées dans l’industrie. Ils se sont tous révélés actifs, mais seul le -dicétonate de zinc II permet d’obtenir un prépolymère incolore et transparent, deux critères essentiels pour les applications visées. Il pourrait donc remplacer le catalyseur organostannique. Enfin, l’étude de la sélectivité de systèmes catalytiques impliquant un catalyseur commercial en présence d’acide néodécanoïque a confirmé le rôle protecteur de ce dernier. La sélectivité du complexe de zinc retenu précédemment a par ailleurs été évaluée et apparaît 2,5 fois supérieure à celle du complexe organomercuriel à remplacer. / The aim of this work is to replace organotin and organomercury catalysts used for the synthesis of polyurethane via the isocyanate – alcohol reaction. A bibliographic review revealed that basicity and nucleophilicity of an organic catalyst affect its activity and the reaction mechanism it induces. For organometallic catalysts, these catalytic properties can be explained by electronic considerations and by the HSAB principle. On the other hand, a comprehensive study of the organomercury catalyst highlighted the benefit to combine it with a carboxylic acid, preferably with a long carbon backbone. This slows down hydrolysis of the catalyst while increasing its selectivity toward the isocyanate – alcohol reaction. New original catalysts or catalytic systems were then evaluated using a simplified experiment. Three organometallic catalysts were selected for further testing in conditions closer to industrial ones. They all showed appropriate catalytic activity, but the zinc II -diketonate is the only one to provide a colorless and transparent prepolymer, two essential criteria for the intended applications. This complex could therefore replace the organotin catalyst. Finally, the study of the selectivity of catalytic systems involving a commercial catalyst in the presence of neodecanoic acid confirmed its protective role toward hydrolysis. The previously retained zinc complex was also evaluated and revealed a selectivity 2.5 times greater than that of the organomercurial complex to replace.

This thesis deals with the methods of Terahertz (THz) spectroscopy to observe the kinetics of haemostatic materials used for supporting the native mechanism of haemostasis. The theoretical part follows the physical principles of THz time-domain spectroscopy (THz TDS), mentions the advantages and limitations of this method and its application possibilities for the characterization of biomedical materials. Further, there are specified properties of actual haemostats, described principles of their function and usage in practice, including their interaction with the living tissue. There were performed experiments monitoring the kinetics of physiologic reaction of the tissue adhesive based on the cyanoacrylates and absorbable haemostats. The mechanisms of monitored reactions were explained based on the physical-chemical principles that are used also for the kinetic models’ derivation. Modelling of the measured data results in the estimation of the parameters characterizing the observed samples. The most interesting parameter is the time constant of the reaction because of the possibility to compare reaction rates of different types of haemostats. The detailed analysis of this parameter is performed using the means of statistical methods. Tissue adhesive samples were measured by other spectroscopic and microscopic methods to compare the findings with the experimental results of the THz TDS. Data were processed using algorithms designed especially for this experiment and analysed using mathematical methods.

No description available.