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Processing And Characterization Of Textured Barium Ferrite CeramicsAydogan, Eda 01 July 2012 (has links) (PDF)
Technological advances results in the fact that quite a large number of electronic equipment interacts with its environment leading to the malfunction of the devices. This brings about the necessity of using proper electromagnetic (EM) wave absorbers/shields to avoid such interactions. In order to absorb EM waves in a large frequency band from several MHz to GHz, barium hexaferrite (BaHF) ceramics which are produced as textured ceramics as well as in multilayered form can be used. Textured ceramics are processed by tape casting using templated grain growth (TGG) phenomenon. In order to obtain textured ceramics, BaHF powders and platelets are required as raw materials in such a way that during sintering small size powders are directioned by large platelet surfaces. In this study, ferrite powders were synthesized by mixed oxide technique while the platelets were produced by both molten salt synthesis (MSS) and reactive templated grain growth (RTGG) methods. In the case of platelet synthesis by MSS, effects of calcination temperature and time as well as type and composition of the flux on the formation and morphology of platelets were investigated based on the XRD and SEM results. Studies have shown that KCl flux led to the formation of sharper platelet morphology, while NaCl resulted in more round shapes. However, extent of BaHF formation in the case of NaCl was higher when compared to KCl flux due to its higher wettability characteristic, and hence faster interaction with the raw materials. Since the aspect ratio of the synthesized platelets was only ca. 2-4, these platelets were not efficient for further TGG studies. Alternatively, BiFeO3 (BiF) particles having ~30-40 &mu / m average size were synthesized as seed crystals for the synthesis of BaHF platelets by RTGG method. After the washing of these platelets with dilute HNO3, pure BaHF powders and platelets were directed by tape casting which was followed by sintering using TGG phenomenon. Degree of achieved texturing in the processed ceramics was studied using Rietveld analysis, pole figure measurement and electron backscattered diffraction (EBSD).
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A new lattice fluid equation of state for associated CO₂ + polymer and CO₂ + ionic liquid systemsHossain, Mohammad Zahid 08 June 2015 (has links)
The phase behavior of CO2 + polymer systems is of interest in polymer synthesis, flue and natural gas processing, polymer foam and nanoparticle processing, and drug delivery. Theoretical and experimental evidence suggests that CO2 is able to interact with electron donating functional groups in polymers to form weak Lewis acid – base or EDA (Electron Donor Acceptor) complexes. These complexes can have a significant effect on the phase behavior of associated CO2 + polymer systems. In spite of this, however, the phase equilibria of only a few associated CO2 + polymer systems have been measured. Some success in modeling the phase behavior of polymer solutions has been achieved by various versions of the Statistical Association Fluid Theory (SAFT), as well as by several Lattice Models. However, many of these models incorporate two to four adjustable parameters that often depend on temperature (T), pressure (P), and/or molecular weight (MW). As a result, a large amount of experimental data is required to apply these models. The goal of the present work was therefore to develop a new thermodynamic model for associating systems that would include no more than two temperature-independent adjustable parameters. The new model presented in this work is based on the Guggenheim-Huggins-Miller lattice and includes complex formation in the development of the partition function.
The EOS obtained from the resulting partition function includes two mixture parameters – the enthalpy of association or complex formation and a reference value of the equilibrium constant for complex formation . Most importantly, can be obtained from in situ Attenuated Total Reflection Fourier Transform Infrared (ATR – FTIR) measurements. This work therefore demonstrates the use of ATR – FTIR spectra to obtain molecular level information regarding the interaction of CO2 and electron donating functional groups in polymers. Unlike other studies, this work uses the bending vibration of CO2 to estimate the enthalpies of association ( ) of CO2 + polymer systems. Values of were directly incorporated in the new model and were found to lie between -7 and -12 kJ/mol for the systems investigated in this work. They increased (i.e. became more negative) in the order: CO2 + PS-co-PMMA < CO2 + PMMA <CO2 + PBMA < CO2 + PSF < CO2 + PVAc < CO2 + EVA40 < CO2 + PEG.
Values of the second parameter in the new EOS ( ) were obtained by fitting solubility data at one temperature. Both and were found to be temperature independent. The application of the new EOS was demonstrated by calculating the solubility (sorption) of CO2 in polymers, the extent of swelling of polymers due to CO2, and the solubility of polymers in CO2 (cloud points). Both sorption and cloud point behavior in CO2 + polymer systems could be calculated using a single value of for each binary system.
Ionic Liquids (ILs) can also incorporate electron donating functional groups in their structure. Evidence for the interaction of such ILs with CO2 can be found in the large values of the enthalpies of absorption of CO2 in these ILs. The ALF EOS was therefore extended to CO2 + IL systems using the enthalpy of absorption as a measure of association ( ) in these systems. was again treated as an adjustable parameter in the calculation of the CO2 solubility in ILs. A single value of was sufficient to predict swelling in these systems within experimental error.
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Nitrierung von Aromaten mit SalzhydratschmelzenBok, Frank 06 July 2010 (has links) (PDF)
Gegenstand der vorliegenden Arbeit war es, die Grundlagen für ein mögliches technisches Verfahren zur Aromatennitrierung mit Salzhydratschmelzen (M(NO3)3 · n H2O, M = Fe, Cr, Bi, In, Al; n = 4 - 9) zu untersuchen. Es sollte geklärt werden, ob Toluol quantitativ zu Dinitrotoluol bzw. Benzol zu Nitrobenzol umgesetzt werden kann. In Screening-Versuchen wurden geeignete, nitrierend wirkende Salzhydrate ermittelt, sowie Wege untersucht, die Reaktivität der eingesetzten Salzhydratschmelzen durch Variation von Wasser- bzw. Säuregehalt, Durchmischung, verschiedenen Schmelzenzusätzen bzw. Reaktionstemperatur zu steigern. Das entstehende Verhältnis der Isomeren der Mono- und Dinitrierung wurde hinsichtlich einer möglichen Beeinflussung untersucht. Das Spektrum an Nebenprodukten wurde bestimmt, sowie Möglichkeiten aufgezeigt, diese zu vermeiden. Dabei konnte gezeigt werden, dass im Gegensatz zum etablierten Mischsäureverfahren beim Einsatz von Salzhydratschmelzen keine kresolischen Nebenprodukte gebildet werden. Weiterhin wurden Möglichkeiten zur Präparation wasserarmer Salzhydratschmelzen durch thermische Entwässerung bzw. Reaktion mit flüssigem N2O4 untersucht, die Löslichkeit der isomeren Zwischen- und Endprodukte in der Salzhydratschmelze bestimmt sowie das thermische Verhalten von Dinitrotoluol in Gegenwart der Salze betrachtet.
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Untersuchung von Tetrachloroaluminatschmelzen als potentielle Wärmetransportflüssigkeiten in SolarkraftwerkenAsztalos, Annifrid 06 June 2018 (has links) (PDF)
Um die Wirtschaftlichkeit von Solarkraftwerken zu verbessern, sollte geprüft werden, inwieweit eine geschmolzene Mischung aus Natriumchlorid und Aluminiumchlorid als Wärmetransportflüssigkeit in Frage kommt. Aufgrund der Hydrolyseempfindlichkeit solcher Schmelzen kommt es durch Einwirkung von Wasser zur Bildung von Chlorwasserstoff sowie Aluminiumoxidchloriden, die in einem geschlossenen System zu einem Druckanstieg bzw. Ausfällungen führen können. Der Gesamtdruck über schwach basischen NaCl-AlCl3-Schmelzen wird durch eine hohe HCl-Löslichkeit herabgesetzt, sodass aus der Bilanz heraus ein Hydrolysegrad von ca. 50 % angenommen werden kann. Für die wassermengenabhängige Verfolgung des Druckes diente eine statische Methode mit einem Drucksensor. Der Oxidgehalt wurde voltammetrisch durch Titration mit TaCl5 und die HCl-Löslichkeit durch eine Elutionsmethode ermittelt. Für Informationen zum Lösungszustand der Hydrolyseprodukte wurden 1H- und 27Al-NMR-Spektren von hydrolysierten Schmelzen aufgenommen.
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Études préliminaires de sûreté du réacteur à sels fondus MSFR. / Safety studies dedicated to molten salt reactors with a fast neutron spectrum and operated in the Thorium fuel cycle – Innovative concept of Molten Salt Fast ReactorBrovchenko, Mariya 25 October 2013 (has links)
Les réacteurs nucléaires de 4ème génération devront permettre une utilisation optimisée desressources naturelles. Les travaux réalisés durant cette thèse se placent ainsi dans le cadre del’étude du potentiel de déploiement d’un tel réacteur : le MSFR (Molten Salt Fast Reactor), réacteurà sels fondus à spectre neutronique rapide dans une configuration innovante et encore peuétudiée. Comme un excellent niveau de sûreté est une condition nécessaire pour le déploiementde l’énergie nucléaire, il est important de soulever la question de la sûreté de ce type de réacteurdès les premières phases de sa conception.Le MSFR a fait l’objet d’études comparatives des outils de simulations numériques dans lecadre d’un benchmark neutronique au sein du projet européen EVOL. La définition et l’analysedu benchmark neutronique statique et en évolution ont été réalisées pendant cette thèse. Lescomparaisons des différentes grandeurs physiques ont permis de conclure à un bon accord entreles différents codes et méthodes utilisés par les partenaires du projet, et ont mis en avant l’influencedu choix des bases de données nucléaires. Dans l’objectif de l’étude de sûreté du MSFR,la puissance résiduelle a aussi été étudiée en détails. Un outil de calcul de chaleur résiduellea été développé et validé, permettant ainsi d’évaluer la puissance résiduelle précise du MSFR.Les sources de chaleur de chaque localisation contenant des produits radioactifs ont alors étéquantifiées. Ceci a permis de conclure que le sel combustible et l’unité de bullage constituent lessources majeures de puissance résiduelle.Nous avons initié un travail sur la méthodologie de l’étude de sûreté. Les principes fondamentauxde sûreté sont directement transposables au MSFR, mais leurs applications concrètes nele sont pas. En effet, la spécificité du design, due à l’état liquide du combustible et aux systèmesde retraitement associés au réacteur, ainsi que l’état embryonnaire du design, font qu’un travailpréliminaire de transposition des éléments de sûreté a dû être réalisé. Ce travail a conduit entreautres à dresser une liste d’accidents propres au MSFR. Enfin, nous avons pu mener des étudesphysiques préliminaires sur les conséquences possibles de certains de ces accidents, qui serontutilisées comme base pour des études plus approfondies avec des outils plus sophistiqués. / The nuclear reactors of the 4th generation must allow an optimized use of natural resources,while performing at a high safety level. The framework of this thesis is the deployment study ofone of such a system, an innovative and still little studied Molten Salt Fast Reactor. An excellentsafety is an ultimate requirement of the nuclear energy deployment, so it is important to raisethis question at the current early stage of the MSFR concept development.This concept was the subject of a neutronic tool benchmark within a European projectEVOL. Definition, calculations and results analyses were performed during this thesis. Comparisonsof static neutronic and burn-up calculations, performed by the project participants,concluded to a good agreement between the different codes and methods used and pointed outthe sensibility of the nuclear database choice on the results. With the aim of safety analysis ofthe MSFR, the decay heat was studied in detail. The tool used for the decay heat calculationwas developed and validated, to finally evaluate the decay heat in the reactor. The decay heatsource presented in different zones was quantified, concluding to a high importance of the coolingof the fuel salt and the bubbling system enclosing a part of the fission products.The safety analysis methodology was also studied in this thesis. Even if the safety principlesare directly transposable to the MSFR, the precise recommendations are not. This is due to thespecificity of the design that relies on the liquid state of the fuel, on the reprocessing systemslocated in the reactor and the embryonic stage of the design. First, a preliminary transpositionwork of some criteria to the MSFR design was realized, resulting amongst other things in a listof accidental scenarios particular for MSFR. Finally, a preliminary physical study of some typesof accidental scenarios was performed, that can be used as a basis for further analyses with moresophisticated tools.
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Développement de méthodes et d’outils numériques pour l’étude de la sûreté du réacteur à sels fondus MSFR / Development of methods and numerical tools for the study of the molten salt reactor MSFR's safetyGerardin, Delphine 04 October 2018 (has links)
Les travaux réalisés pendant cette thèse portent sur l’étude de la sûreté du Molten Salt Fast Reactor (MSFR) et incluent à la fois des méthodes d’analyse de risques et des calculs déterministes de sûreté et de design. Ce travail s’inscrit dans le cadre du projet européen SAMOFAR.Le MSFR est un réacteur régénérateur à spectre neutronique rapide qui fonctionne en cycle thorium dans sa configuration de référence, établie en début du projet SAMOFAR. Il a été sélectionné par le Forum International Génération IV pour son potentiel prometteur. Comme tout réacteur nucléaire de quatrième génération, il doit répondre à différentes contraintes dont une sûreté optimale. Celle-ci doit être étudiée dès le stade de conception afin d’être intégrée au design lors de sa définition plutôt qu’ajoutée a posteriori. En raison de ses spécificités, en particulier l’état liquide du combustible, et du stade préliminaire de son design, l’analyse de sûreté du MSFR nécessite l’utilisation de méthodologies d’analyse de sûreté adaptées et technologiquement neutres. Dans cette thèse, une telle méthodologie a été développée et une première application au MSFR réalisée. Elle a notamment permis d’identifier les évènements initiateurs d’accident de ce réacteur et d’élaborer une liste resserrée d’évènements à traiter dans la suite de l’analyse de sûreté.D’autre part, un nouveau code système a été développé pour les études de sûreté. Il est basé sur la diffusion neutronique, prend en compte le transport des précurseurs de neutrons retardés et la puissance résiduelle du combustible. Il a été utilisé pour simuler les transitoires associés à certains des évènements initiateurs et évaluer leurs conséquences pour définir, par la suite, des systèmes de protection adaptés. Ce travail a confirmé l’importance d’un dispositif spécifique au MSFR, le système de vidange d’urgence, permettant de vidanger le combustible en cas d’accident en cœur. Des études paramétriques ont été menées afin de dimensionner ce système avec pour objectif d'assurer l’évacuation de la chaleur résiduelle du combustible et sa sous-criticité en toutes circonstances.Enfin, une première ébauche de l’architecture de sûreté du réacteur a été proposée incluant l’identification des systèmes de protection et la définition des barrières de confinement. Les études de sûreté ont permis de faire des retours sur le design initialement défini. Ils incluent l’ajout de composants, des propositions de design alternatifs, et soulignent les manques de connaissances sur certains phénomènes ou procédures. L’analyse de sûreté réalisée remplit ainsi son objectif principal : guider le design du réacteur dès sa conception afin d’en améliorer la sûreté. / This PhD thesis focuses on the study of the Molten Salt Fast Reactor (MSFR) safety. It includes risk analysis methods and deterministic computations for the safety and the design of the reactor. This work was performed in the frame of the SAMOFAR European project.The MSFR is an is-breeder reactor with a fast neutron spectrum. In its reference configuration, defined at the beginning of the SAMOFAR project, it works with the thorium fuel cycle. The MSFR was selected by the Generation IV international forum for its promising features. As any fourth-generation reactor, it must fulfill several objectives including an improved safety. Thus, safety studies should be performed from the early design phases to achieve a safety that is built-in the design rather than added-on. Because of the unique characteristics of the MSFR, including a liquid circulating fuel, and its preliminary design phase, the safety assessment of the reactor should rely on adapted and technological neutral methodologies. In this PhD, such a methodology was developed and a first application to the MSFR was carried on. It allowed to identify the initiating events of the reactor and to elaborate a restricted list of events to be studied in the next steps of the safety analysis.Furthermore, a new code system was developed for the safety studies. It is based on neutronic diffusion and takes into account the movement of the delayed neutrons precursors and the production of the residual heat in the fuel. It was used to simulate the transients associated to some of the identified initiating events with the objective to evaluate their consequences and the need for adequate protection systems. This work confirmed the importance of a device that is specific to the MSFR: the emergency draining system (EDS). It allows to drain the fuel in case of accident in the core. Parametric studies were then carried on for the sizing of the EDS with the objective to ensure the evacuation of the residual heat and the sub-criticality of the system under any circumstances.Finally, a first version of the safety architecture was proposed with the identification of the protection systems and the definition of the confinement barriers. Thanks to the safety studies, feedbacks on the initial design were made to enhance the safety the reactor. They include the addition of new components, the modification of some systems and they highlight the lack of knowledge on some phenomena or procedure. In that respect, the safety analysis fulfil its main objective: to influence the design of the reactor since its conception in order to improve its safety.
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Hydrogenolysis of lignin in ZnCl₂ and KCl as an inorganic molten salt mediumAppelt, Jörn, Gohrbandt, Anne, Peters, Jana, Bremer, Martina, Fischer, Steffen 23 June 2020 (has links)
Lignin can be converted into monomeric products with the aid of molten salt media. Molten zinc chloride (ZnCl₂)/potassium chloride (KCl) mixtures are suitable for this purpose. The application of an eutectic mixture with low melting points leads to similar main products as are obtained by pyrolysis. The hydrogenolysis of an organosolv lignin in molten salts of ZnCl₂/KCl was investigated as a function of reaction temperature, residence time, and lignin concentration, and the composition of liquid products and monophenols was analyzed by gas chromatography-mass spectrometry (GC-MS). The yields can be optimized by the proper selection of the reaction temperature. A longer residence time and higher lignin concentrations lead to increased formation of solid residues and gaseous products. The liquid products mainly consist of substituted phenols derived from lignins. Polymeric products are the result of condensation reactions (i.e., the formation of new C-C linkages in the course of secondary reactions).
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Studium chování jaderného reaktoru chlazeného tekutými solemi / Reseach of Molten Salt Cooled Nuclear Reactor BehaviorKostečka, Jan January 2018 (has links)
The master ‘s thesis deals with the studying behavior of nuclear reactors cooled by liquid salts and with application of liquid salts for IV. Generation of nuclear reactors. For the use of liquid salts, it’s necessary to change the concept of the structure of nuclear reactors. There are new ways to use new fuel in a liquid state. Each salt compound or a set thereof is original in its nature. Therefore, it is necessary to consider a suitable compound for the purposes employed. These points are discussed in the theoretical part. The thesis examines particularly chloride salts, with which there is not much experience. The practical part monitors and verifies the nuclear properties of chloride salts, in our case it is a solid-state chloride sodium chloride’s compound. In addition to the experimental measurement, the MCNP simulation program is used also.
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Experimentální a výpočetní výzkum vlastností solí pro jaderné reaktory typu MSR z pohledu jaderných dat / Experimental and calculational salts' properties investigation for MSR reactors from nuclear data point-of-viewBurian, Jiří January 2021 (has links)
Nowadays there is research into molten salt reactors. The use of chlorine-based salts, which would be more available than known fluoride salts, is envisaged. The subject of research is not only the chemical and physical properties of chloride salts, but also their behavior in the neutron field and the influence of neutron balance inside the reactor. Many properties can also be determined using calculations that draw information from scientific nuclear libraries (endf). The purpose of this work is to compare important nuclear libraries with each other, and also to compare the reaction rates calculated from the library data with the reaction rates obtained by self-measurement. The preview will include a description of the necessary activities associated with the preparation of measurements, instructions for compiling the computer program NJOY and the process of the measurement itself. At the end of the work will be summarized the results and statements of which nuclear library is the closest in its values to the results of experiments.
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Nitrierung von Aromaten mit SalzhydratschmelzenBok, Frank 18 June 2010 (has links)
Gegenstand der vorliegenden Arbeit war es, die Grundlagen für ein mögliches technisches Verfahren zur Aromatennitrierung mit Salzhydratschmelzen (M(NO3)3 · n H2O, M = Fe, Cr, Bi, In, Al; n = 4 - 9) zu untersuchen. Es sollte geklärt werden, ob Toluol quantitativ zu Dinitrotoluol bzw. Benzol zu Nitrobenzol umgesetzt werden kann. In Screening-Versuchen wurden geeignete, nitrierend wirkende Salzhydrate ermittelt, sowie Wege untersucht, die Reaktivität der eingesetzten Salzhydratschmelzen durch Variation von Wasser- bzw. Säuregehalt, Durchmischung, verschiedenen Schmelzenzusätzen bzw. Reaktionstemperatur zu steigern. Das entstehende Verhältnis der Isomeren der Mono- und Dinitrierung wurde hinsichtlich einer möglichen Beeinflussung untersucht. Das Spektrum an Nebenprodukten wurde bestimmt, sowie Möglichkeiten aufgezeigt, diese zu vermeiden. Dabei konnte gezeigt werden, dass im Gegensatz zum etablierten Mischsäureverfahren beim Einsatz von Salzhydratschmelzen keine kresolischen Nebenprodukte gebildet werden. Weiterhin wurden Möglichkeiten zur Präparation wasserarmer Salzhydratschmelzen durch thermische Entwässerung bzw. Reaktion mit flüssigem N2O4 untersucht, die Löslichkeit der isomeren Zwischen- und Endprodukte in der Salzhydratschmelze bestimmt sowie das thermische Verhalten von Dinitrotoluol in Gegenwart der Salze betrachtet.
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