Processing of Bolu-Himmetoglu (Type I Kerogen) and Ankara-Beypazari (Type II Kerogen) oil shales by flotation techniques were investigated for achieving clean solid fuel substitutes. Materials characterization was done through mineralogical, XRD and FTIR analyses. Flotation responses of the samples were tested with non-ionizing and ionizing collectors of cationic and anionic types. The effects of the collector dosage and pulp pH on cleaning were determined. Other important flotation parameters, conditioning time, flotation time, pulp density, particle size and frother dosage were encountered using a statistical approach, through a full two level factorial experimental design. An advanced flotation procedure, assisted by ultrasonic application, was developed for further improvement in flotation performance. The effects of cleaning on thermal characterstics and combustion kinetics were evaluated with Differential Scanning Calorimetry and ASTM methods while the changes in the emission profiles were assessed using Effluent Gas Analysis. Himmetoglu sample was characterized as a carbonate and organic rich humic oil shale with XRD and FTIR analyses while Beypazari oil shale involved significant carbonate and clay minerals and exhibited a fulvic character with a poor organics content. Reverse flotation with amine acetates provided the most effective means of cleaning with Himmetoglu oil shale. Ash was decreased from 34.76 % to 23.52 % with a combustible recovery of 83.57 % using 800 g/ton Flotigam CA at natural pH and the calorific value increased from 4312 kcal/kg to 5010 kcal/kg. Direct flotation with amines was most effective for Beypazari oil shale cleaning. Using Armoflote 17, ash was reduced from 69.88 % to 53.10 % with 58.64 % combustible recovery using 800 g/ton Armoflote 17 at natural pulp pH and the calorific value of the sample increased from 876 kcal/kg to 2046 kcal/kg. Following optimization, ash of Himmetoglu oil shale decreased to 16.81 % with 84.10 % combustible recovery and calorific value increased to 5564 kcal/kg. For Beypazari oil shale ash decreased to % 48.42 with 59.17 % combustible recovery and the calorific value increased to 2364 kcal/kg. Ultrasonic pre-treatment before flotation further decreased the ash of Himmetoglu sample to 11.82 % with 82.66 % combustible recovery at 15 minutes pre-conditioning time and 50 % power level. For Beypazari oil shale, ash decreased to 34.76 % with 64.78 % combustible recovery after 15 minutes pre-treatment time at 70 % power level. Comparative XRD spectra and SEM analyses revealed that the extent of mineral matter removal relied on the flotation performance. The thermal indicators considerably improved after cleaning and the extent of improvement increased with a decrease in the ash of the concentrates. Kinetic analysis showed the favorable effect of inorganics removal on the effectiveness and easiness of combustion and activation energies decreased after cleaning for both oil shales. The contributions of cleaning on the effectiveness of combustion were also revealed by the increases in the emission rates and total CO2 and CO emission amounts. CO2 emissions due to mineral matter decomposition and harmful SO2 emissions apparently decreased as a consequence of the cleaning of the undesired inorganic contituents and potentially cleaning components. Results of the cleaning and thermal analysis sudies revealed that it was possible to achieve a clean energy source alternative from oil shales through flotation and a significant potential can be anticipated for future use of oil shales as a cost effective and environmental friendly solid fuel substitute in view of Turkey&amp / #8217 / s great oil shale reserves.

Protein (mis)folding into highly ordered, fibrillar structures, amyloid fibrils, is a hallmark of several, mainly neurodegenerative, disorders. The mechanism of this supra-molecular self-assembly reaction, as well as its relationship to protein folding are not well understood. In particular, the molecular origin of the metastability of the soluble state of proteins with respect to the aggregated states has not been clearly established. In this dissertation, it is demonstrated, that highly accurate kinetic experiments, using a novel biosensing method, can yield fundamental insight into the dynamics of proteins in the region of the free energy landscape corresponding to protein aggregation. First, a section on Method development describes the extension and elaboration of the previously established kinetic assay relying on quartz crystal microbalance measurements for the study of amyloid fibril elongation (Chapter 3). This methodology is then applied in order to study in great detail the origin of the various contributions to the free energy barriers separating the soluble state of a protein from its aggregated state. In particular, the relative importance of residual structure, hydrophobicity (Chapter 4) and electrostatic interactions (Chapter 5) for the total free energy of activation are discussed. In the last part of this thesis (Chapter 6), it is demonstrated that this biosensing method can also be used to study the binding of small molecules to amyloid fibrils, a very useful feature in the framework of the quest for potential inhibitors of amyloid formation. In addition, it is shown that Thioflavin T, to-date the most frequently employed fluorescent label molecule for bulk solution kinetic studies, can in the presence of potential amyloid inhibitor candidates be highly unreliable as a means to quantify the effect of the inhibitor on amyloid formation kinetics. In summary, the work in this thesis contributes to both the fundamental and the applied aspects of the field of protein aggregation.

This work is focused on Density Functional Theory (DFT) calculations of oxygen vacancy diffusion barriers in mixed perovskite lead zirconate titanate and its pure counterparts. We found out that barrier heights are different in lead titanate and lead zirconate caused by the different localization of the excess electrons due to the oxygen vacancy formation. Diffusion barriers were also determined for titanium-rich mixed phases and compared to experimental values. This work contributes to clarify unusually low experimentally measured diffusion coefficients in PZT. We found out that the induced vacancy states are forming localized bonds to the lead atoms which causes the oxygen vacancies to become immobile due to the increase of the activation energy of the diffusion process.

In der vorliegenden Arbeit wurden Messtechniken zur Charakterisierung organischer Flüssigkeiten geringer Leitfähigkeit mittels Impedanzspektroskopie erprobt. Es wurden verschiedene kapazitive Elektrodenanordnungen mit dem zu untersuchenden Öl als Dielektrikum entwickelt und auf ihre Eignung zur Impedanzmessung an Schmierölen untersucht. Ausgehend von der empirischen Erfahrung, dass die Impedanzwerte in Ölen stark temperaturabhängig sind, wurde in Anlehnung an die Arrheniussche Theorie der chemischen Reaktionskinetik ein Auswerteverfahren für impedanzspektroskopische Messdaten entwickelt und getestet. So wurden die Voraussetzungen dafür geschaffen, dass für einen, in einem bestimmten Frequenzbereich relevanten Leitungsprozess, der zugehörige, auf molekularer Ebene ablaufende Vorgang mit bekannter Aktivierungsenergie angegeben werden kann.

[pt] O efeito do envelhecimento em tempo real nas propriedades mecânicas, químicas e cinéticas da borracha de copolímero de copolímero etileno-propileno-dieno não conjugado (EPDM) foi quantificado, após ser exposto a condições reais de operação no sistema artificial de elevação de petróleo, do campo de Peregrino (administrado pela Equinor Brasil Ltda.). A borracha EPDM foi coletada de parte da camada de proteção mecânica (Jacket) dos cabos de alimentação elétrica das bombas eletro-submersíveis (ESP). O estudo envolve amostras de 0, 2 a 4.8 anos e com profundidades que variam de 0, 760 a 2170 m abaixo do nível do mar. O envelhecimento foi acompanhado por estudos de técnicas de espectroscopia de infravermelho por transformada de Fourier (FTIR) assistida por reflexão total atenuada (ATR), microscópio eletrônico de MEV, juntamente com espectrômetro de dispersão de energia (EDX), analisador térmico simultâneo (STA), medição da fração de reticulação, dureza (escala Shore D), testes de tração uniaxial e testes de adsorção no fluido de proteção (Parker-fluido mais safe-Scan). A estabilidade da borracha EPDM foi estudada por métodos não isotérmicos como: Kissinger-Murray-White (KMW), Ozawa-Flynn-Wall (OFW), Friedman (FR), análise cinética combinada (CKA) e correção da cinética combinada análise por isoconversão (CKA-ic). Uma oscilação de 5 por cento na energia de ativação aparente (E2 igual a 48 kJ/mol) durante a degradação térmica do material em N2, mostra uma reação que produziu uma ordem de reação (n igual a 0.93), um fator preexponencial (A igual a ln(40 /min-1)) e indica que o material não sofre ataque hidrolítico ou degradação por oxidação, comparando com os observada nos testes de envelhecimento na presença de água e compressão. Por outro lado, as propriedades do teste de tração uniaxial mostram sensibilidade à profundidade de as amostras, o que pode muito bem indicar degradação de áreas amorfas de EPDM, produto de altas temperaturas e pressões no depósito. / [en] The effect of aging in real time on the mechanical, chemical and kinetic properties of copolymer ethylene propylene diene monomer rubber (EPDM) was quantified, after being exposed to real operating conditions in the artificial petroleum lift system, from the Peregrino field. (managed by Equinor Brasil Ltda.). The EPDM rubber was collected from part of the mechanical protection cover (Jacket) of the electrical supply cables of the electro-submersible pumps (ESP). The study involves samples from 0, 2 to 4.8 years old and with depths ranging from 0, 760 to 2170 m below sea level. The aging was followed by studies of infrared spectroscopy techniques by Fourier transform (FTIR) assisted with attenuated total reflection (ATR), SEM electron microscope, along with energy dispersion X ray spectrometer (EDX), simultaneous thermal analyzer (STA), reticulation fraction measurement, hardness (Shore D scale), uniaxial traction tests and adsorption tests in the protection fluid (Parker-fluid plus safe-Scan). The stability of EPDM rubber was studied by non-isothermal methods such as: Kissinger-Murray-White (KMW), Ozawa-Flynn-Wall (OFW), Friedman (FR), combined kinetic analysis (CKA) and correction of the combined kinetics analysis by isoconversion (CKA-ic). A 5 per cent oscillation in the apparent activation energy (E equal248 kJ/mol) during the thermal degradation of the material in N2, shows a reaction that produced a reaction order (n equal 0.93), a pre-exponential factor (A equal ln(40 /min-1)) and indicates that the material does not suffer hydrolytic attack or oxidation degradation observed in aging tests in the presence of water and compression. On the other hand, the properties of the uniaxial tensile test show sensitivity to the depth of the samples, which may well indicate degradation of amorphous areas of EPDM, a product of high temperatures and pressures in the deposit.

No description available.

Made available in DSpace on 2014-12-17T15:42:26Z (GMT). No. of bitstreams: 1 ZilvamMS_TESE_reduzido.pdf: 9108618 bytes, checksum: 613dad3fd1a359dce84e2af73b067934 (MD5) Previous issue date: 2013-02-22 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / Surfactant-polymer interactions are widely used when required rheological properties for specific applications, such as the production of fluids for oil exploration. Studies of the interactions of chitosan with cationic surfactants has attracted attention by being able to cause changes in rheological parameters of the systems making room for new applications. The commercial chitosan represents an interesting alternative to these systems, since it is obtained from partial deacetylation of chitin: the residues sites acetylated can then be used for the polymer-surfactant interactions. Alkyl ethoxylated surfactants can be used in this system, since these non-ionic surfactants can interact with hydrophobic sites of chitosan, modifying the rheology of solutions or emulsions resultants, which depends on the relaxation phenomenon occurring in these systems. In this work, first, inverse emulsions were prepared from chitosan solution as the dispersed phase and cyclohexane as the continuous phase were, using CTAB as a surfactant. The rheological analysis of these emulsions showed pronounced pseudoplastic behavior. This behavior was attributed to interaction of "loops" of chitosan chains. Creep tests were also performed and gave further support to these discussions. Subsequently, in order to obtain more information about the interaction of chitosan with non-ionic surfactants, solutions of chitosan were mixed with C12E8 and and carried out rheological analysis and dynamic light scattering. The systems showed marked pseudoplastic behavior, which became less evident when the concentration of surfactant was increased. Arrhenius and KWW equations were used to obtain parameters of the apparent activation energy and relaxation rate distribution, respectively, to which were connected to the content of surfactant and temperature used in this work / As intera??es tensoativo-pol?mero s?o amplamente usadas quando s?o necess?rias propriedades reol?gicas para aplica??es espec?ficas, como a produ??o de fluidos para explora??o do petr?leo. Estudos das intera??es de quitosana com tensoativos cati?nicos tem chamado aten??o por serem capazes de causar mudan?as nos par?metros reol?gicos dos sistemas abrindo espa?o para novas aplica??es. A quitosana comercial representa uma alternativa interessante para estes sistemas, uma vez que ela ? obtida a partir da desacetila??o parcial da quitina: os s?tos acetilados residuais podem, ent?o, ser usados para as intera??es pol?mero-tensoativo. Tensoativos alquil etoxilados podem ser utilizados neste sistema, pois estes tensoativos n?o i?nicos podem interagir com s?tios hidrof?bicos da quitosana, modificando a reologia de solu??es ou emuls?es resultantes, os quais dependem do fen?meno de relaxa??o ocorrendo nestes sistemas. Neste trabalho, primeiramente, foram preparadas emuls?es inversas de solu??o de quitosana como fase dispersa e cicloexano como fase cont?nua usando CTAB como tensoativo. A an?lise reol?gica destas emuls?es mostrou pronunciado comportamento pseudopl?stico. Esta pseudoplasticidade foi atribu?da ? intera??o por la?os loops de cadeias de quitosana. Ensaios de flu?ncia tamb?m foram executados e deram maior suporte a estas discuss?es. Em seguida, a fim de se obter maiores informa??es sobre as intera??es da quitosana com tensoativos n?o i?nicos, solu??es de quitosana foram misturadas com C12E8 e levadas ?s an?lises reol?gica e de espalhamento din?mico de luz. Os sistemas tiveram elevado comportamento pseudopl?stico, o qual se tornava menos evidente, quando o teor de tensoativo foi aumentado. Equa??es de Arrhenius e de KWW foram usadas para obter par?metros de energia de ativa??o aparente e de distribui??o da taxa de relaxa??o, respectivamente, aos quais foram relacionados em fun??o do teor de tensoativo e da temperatura, usados neste trabalho

Dünne Schichten aus hydrogenisiertem amorphem Silizium a-Si:H spielen für die Photovoltaik eine wichtige Rolle. Einerseits kommt für die Dünnschicht-Photovoltaik unterschiedlich dotiertes a-Si:H in den Schichten einer p-i-n-Solarzelle zur Anwendung, andererseits stellen Heterokontakt-Solarzellen aus amorphem und kristallinem Silizium (a-Si:H/c-Si) wegen ihres hohen Wirkungsgrades derzeit ein sehr aktuelles Forschungsthema dar. Die Abscheidung der a-Si:H-Schichten im Rahmen dieser Arbeit erfolgt mit der Methode des Magnetronsputterns (Kathodenzerstäubung). Dieses für die in-line-Beschichtung etablierte Verfahren wird speziell für die Photovoltaik noch nicht in industriellem Maßstab eingesetzt (lediglich für transparente leitfähige Oxide TCO). Insbesondere existiert nur eine geringe Zahl von Veröffentlichungen zu Heterokontakten, welche mittels Magnetronsputtern hergestellt wurden. Ein Schwerpunkt der vorliegenden Arbeit ist daher die Herstellung sowie Charakterisierung solcher Heterokontakte unter dem Aspekt variierter Abscheide- und Prozessparameter (Substrattemperatur, Wasserstoffflussrate, Ionenbeschuss). Das für das Sputtern erforderliche Plasma wird mit einer im Mittelfrequenzbereich gepulsten Gleichspannung angeregt. Ein dadurch mehr oder weniger ausgeprägter Ionenbeschuss der wachsenden Schichten in Abhängigkeit der Pulsparameter wird hier analysiert. Die Charakterisierung der Heterokontakte erfolgt hauptsächlich anhand deren Strom-Spannung-Kennlinien, welche auch bei variierter Temperatur gemessen werden. Erzielte Gleichrichtungsverhältnisse um 10000:1 sowie Diodenidealitätsfaktoren η ≈ 1,3 kennzeichnen (p)a-Si:H/(n)c-Si-Heterokontakte mit den besten halbleiterphysikalischen Eigenschaften. Bei zu schwacher Schichthydrogenisierung wurde ein Ladungstransportmechanismus nachgewiesen, welcher in der Literatur als multi-tunneling capture-emission MTCE bekannt ist. Eine erhöhte Hydrogenisierung unterdrückt diesen Mechanismus nahezu vollständig. Durch Abscheidung unterschiedlich stark bordotierter a-Si:H-Schichten wird außerdem die Dotiereffizienz beurteilt. Hohe Werte sind bei amorphen Halbleitern im Allgemeinen schwer zu erreichen. Die mit stärkerer Dotierung erhöhte Gleichrichterwirkung lieferte hier ein Indiz für eine nachweisbare Dotiereffizienz.

In dieser Arbeit wurde die Möglichkeit untersucht, Bortrihalogenide mit Wasserstoff unter milden Bedingungen (T < 100 °C, p(H2) < 50 bar) zu hydrieren. Um eine Triebkraft für die thermodynamisch ungünstige Reaktion zu erhalten, wurden Amine als Hilfsbasen zugesetzt, welche den bei der Reaktion entstehenden Halogenwasserstoff als Ammoniumsalz binden und damit das Reaktionsgleichgewicht in Richtung der Produkte verschieben. Es wurden dafür verschiedene Amin-Boran bzw. Amin-HCl Addukte synthetisiert und mittels IR, NMR und DSC charakterisiert. Bei den anschließenden Hydrierungsversuchen wurden verschiedene Katalysatoren auf ihre Eignung getestet und weiterentwickelt. Unterstützt wurden die experimentellen Arbeiten durch Berechnungen mit Gaussian 03. IR- und NMR-Spektren vieler Addukte wurden berechnet und freie Reaktionsenthalpien der Hydrierung in Abhängigkeit des verwendeten Amins und Borhalogenids bestimmt. Mögliche Übergangszustände wurden diskutiert und ihre Aktivierungsenergien ermittelt.

Ce travail présente le développement d’un banc de mesure thermique, pour la mesure : de réseaux I (V), d’impédance basse fréquence et de bruit basse fréquence des composants semi-conducteurs. Le banc de mesure de bruit BF est composé d’un amplificateur de tension faible bruit, d’un amplificateur transimpédance, d’un analyseur FFT et d’un support thermique. Ce banc a permis d’extraire les sources de bruit en courants équivalentes aux accès du transistor pour différentes densités de courant et à différentes températures. Dans le but de calculer l’énergie d’activation et la section de capture des pièges grâce à la localisation des fréquences de coupures de bruit GR dans la technologie du TBH InGaP/GaAs. Dans un deuxième temps, nous avons étudié le bruit basse fréquence dans le transistor InGaP/GaAs et les jonctions base émetteur, base collecteur et la résistance TLM par le moyen de simulation physique et de mesure de densité spectrale de puissance de bruit basse fréquence. Grâce à ces mesures, nous avons pu extraire les sources de bruit internes locales commandées et non commandées. Cette extraction nous a permis de calculer les énergies d’activations, les sections de capture et de valider la simulation physique. / This work presents the development of a thermal test bench for I(V) characteristics, for low frequency impedance and for low frequency noise of semiconductor components. This thermal bench for low frequency noise measurement is composed of a low-noise voltage amplifier, a low-noise transimpedance amplifier, an FFT vector signal analyzer and a thermal chuck. This measurement bench has allowed to extract the current noise sources equivalent to the access transistor at different current densities and at different temperatures. In order to calculate the activation energy and the capture cross section of traps thanks to the localization of the cutoff frequency of GR noise in HBT InGaP / GaAs technology. Secondly, we studied the low frequency noise in the transistor InGaP / GaAs and the differents junctions: emitter base, collector base and the base represented by the TLM resistance using physical simulations and measurements of low-frequency noise power spectrum density. Using this measurements, we extract the controlled and not controlled local internal noise sources. The extraction has allowed us to calculate the activation energy, the capture cross sections and validate the physical simulation.