O processo de proteção catódica é amplamente utilizada na indústria do petróleo e gás para a prevenção contra a corrosão. Entretanto, devido às reações catódicas induzidas pelo potencial catódico aplicado pode ocorrer a formação de depósito calcário na superfície de componentes protegidos catodicamente em água do mar. Existe certa incerteza na literatura sobre o papel do depósito calcário na absorção de hidrogênio e consequentemente na fragilização pelo hidrogênio. Assim, o presente trabalho visa investigar sua influência a fim de contribuir para o melhor entendimento da participação dessa camada nesse fenômeno. Para isso, foram realizados testes de permeação eletroquímica de hidrogênio, de tração de baixa taxa de deformação (BTD) e de cronoamperometria no aço API 5CT P110 em três soluções diferentes: água do mar sintética (AMS), água do mar sintética sem Ca2+ e Mg2+ e NaCl 3,5%. Além disso, foram aplicados dois potenciais catódicos: -1000 mVECS e -1500 mVECS. Após o ensaio de tração de BTD e de cronoamperometria as amostras foram analisadas em MEV/EDS. A partir dos resultados obtidos verificou-se que o depósito calcário formado em AMS em -1000 mVECS é formado por uma fina camada inicial rica em Mg seguida de cristais de aragonita. A formação dessa camada aparentemente diminuiu o fluxo de hidrogênio no estado estacionário em comparação com as demais soluções avaliadas nesse mesmo potencial. Todavia, essa diminuição não resultou em uma mudança significativa na fragilização do material. O depósito calcário formado em AMS em -1500 mVECS mostrou-se poroso e pulverulento, apresentando principalmente Mg em sua composição. O fluxo de hidrogênio no estado estacionário e a fragilização do material em AMS em -1500 mVECS foi maior do que nas demais soluções nesse potencial. Um possível mecanismo para explicar o efeito do depósito calcário na absorção e na fragilização pelo hidrogênio foi proposto e indica a competição entre o fator superficial ocasionado pela formação do depósito calcário e a sobretensão em hidrogênio. / The process of cathodic protection is widely used in oil & gas industry to corrosion prevention. However, the cathodic reactions induced by the applied cathodic potential can lead to the calcareous deposit formation on the cathodically protected structure surface in sea water. There is uncertainty about the role of calcareous deposit on hydrogen uptake and consequently on hydrogen embrittlement. Hydrogen electrochemical permeations, slow strain rate and chronoamperometric tests were carried out in three different solutions: artificial sea water, artificial sea water without Ca2+ and Mg2+ and 3.5% NaCl solution. Besides that, two cathodic potentials were applied: -1000 mVSCE e -1500 mVSCE. After slow strain rate and chronoamperometric tests the samples were analyzed in SEM/EDS. According to the obtained results it was observed that calcareous deposits formed in artificial sea water at -1000 mVSCE consists on a thin Mg-rich inner layer and an outer layer of aragonite crystals. The deposit formation apparently decreased hydrogen flux at steady state in comparison with other solutions evaluated at the same potential. The calcareous deposit formed in artificial sea water at -1500 mVSCE was porous, powdery and mainly composed by Mg. The hydrogen flux at steady state and the embrittlement of the material were higher in artificial sea water at -1500 mVSCE than in other solutions at the same potential. A possible mechanism to explain the calcareous deposit effect on hydrogen uptake and on hydrogen embrittlement was proposed and it indicates the competition between the surface effect induced by calcareous deposit formation and the hydrogen overpotential.

Cette thèse correspond à une étude comparative détaillée de trois gisements aurifères birimiens (~ 2 Ga) du craton ouest africain (Syama, Tabakoroni et Tellem), situés sur la ceinture de Bagoé au Mali. La minéralisation se concentre dans les roches où les structures de déformation fragile sont les plus développées (basaltes et métasédiments bréchifiés, microgranite à Tellem) et se développe préférentiellement en bordure des veines. Les sulfures majeurs (pyrite à Syama et pyrite + arsénopyrite à Tabakoroni et Tellem) sont zonés avec : i) un cœur arsénifère riche en inclusions d'albite, d'ankérite et de rutile (accessoirement pyrrhotite); ii) une bordure limpide, globalement moins arsénifère que le coeur mais présentant une fine zonation avec des alternances de zones riches en As et de zones pauvres en As. L'or se présente sous forme d'or invisible inclus dans le réseau cristallin des sulfures, de petits grains individualisés en inclusion dans les sulfures, souvent accompagnés de sulfoantimoniures, notamment la tétraédrite et la chalcostibite, et d'or libre associé au quartz. Les pyrites arsénifères et les arsénopyrites des gisements de la ceinture de Bagoé sont parmi les plus riches en or invisible de tous les gisements d'or de l'Afrique de l'Ouest et tout à fait comparables à ceux de la ceinture d'Ashanti au Ghana. / This thesis presents a comparative study of the Syama, Tabakoroni and Tellem gold deposits, located in the N-S trending Bagoé greenstone belt of Mali. Mineralization is found preferentially along the edges of millimetre- to centimetre-sized quartz, quartz-albite, quartz-ankerite, dolomite-quartz veins developed in tension gaps that formed during brittle deformation. Gold mineralization is mostly associated with pyrite in the three deposits, and also with arsenopyrite at Tabakoroni and Tellem. These sulphides are zoned with (i) an arsenic-rich core containing several albite, ankerite and rutile inclusions (less commonly, pyrrhotite) and (ii) a clear border of finely alternating As-rich and As-poor bands. Gold occurs in the form of i) invisible gold included in their crystal lattices, ii) small individual grains bound to these sulphides, frequently accompanied by sulphoantimonides, mainly tetrahedrite and chalcostibite and iii) free gold associated with quartz. The arseniferous pyrites and arsenopyrites of the Bagoé belt deposits are among the richest in invisible gold in all gold deposits in West Africa and are quite comparable to those of the Ashanti Belt in Ghana.

The aim of the thesis is to analyse legal aspects of the position of the municipality in the role of a public guardian and on a practical example introduce the issue of establishing a municipality as a public guardian. Furthermore, using a quantitative survey to find a possible alternative of a financing public guardianship, which would be positively accepted by municipalities. The issue of public guardianship is currently becoming a much debated topic not only because of the lack of legislation governing the institute of public guardianship, but also because the financing of this agenda towards municipalities acting as public guardian is insufficient and unsatisfactory for municipalities.

L'objectif de la thèse concerne l'analyse du système matières organiques (carbone)-uranium-sulfure qui contrôle la formation du gisement d'uranium de type de roll-front au Zoovch Ovoo (Mongolie). La formation Cénomanienne du Sainshand est constituée de sédiments continentaux silicoclastiques déposés dans des milieux fluvio-lacustres. Le système global est en début de diagénèse et n'a pas été affecté par un enfouissement significatif, estimé à moins de 600 m pour une température maximale de 40°C. Le réservoir se caractérise par des sables non consolidés et des argiles silteuses. Parfois, certains lits de grès d’épaisseur décimétriques sont cimentés par des carbonates et disposés au sein de faciès silicoclastiques non consolidés. L’étude systématique des grès à ciment carbonaté a révélé la présence exclusive de dolomite. Quatre types de dolomite différents ont été reconnus. Tous ont été formés par des eaux d'origine météorique et présentent des caractéristiques isotopiques (C, O) semblables. Ils sont génétiquement liés les uns aux autres, avec de possibles épisodes de recristallisation impliquant une réincorporation progressivement moindre des éléments en traces comme les terres rares et le manganèse. Le premier type de dolomite est contrôlé par les conditions de sédimentation, tandis que les trois suivants sont contrôlés par diagenèse. Le troisième type de dolomite n'a été trouvé que dans des échantillons ayant été affectés par le roll-front alors que le quatrième est postérieur aux porteurs d'uranium. La matière organique détritique est très abondante et joue un rôle majeur dans le piégeage de l’uranium aux côtés de la pyrite. L'étude en pétrographie organique a montré que toute est d'origine végétale supérieure et immature, comme l'ont montré les mesures de réflectance de la vitrinite (<0,4%). Elle est exclusivement présente sous forme de particules détritiques et sa distribution est donc régie par l’évolution des conditions de dépôt sédimentaires. Huit générations de pyrite ont été identifiées sur la base textures et des associations minérales, avec trois types majeurs : les pyrites framboidales en sphérolites isolés, les surcroissances automorphes, et les pyrites de remplacement (épigénie). L'étude isotopique du δ34S de la pyrite a montré qu’une grande parties des pyrites s‘est formée par bio-réduction des sulfates. Les porteurs de l’uranium sont la pechblende et dans une moindre mesure la phospho-coffinite. La pechblende cimente et remplace la matière organique mais aussi les pyrites automorphes corrodées ce qui indique que l’enrichissement ou l’introduction massive de l’uranium s’est produit assez tardivement. La matière organique a piégé l’uranium de manière diffuse à des fortes concentrations, sous une forme minéralogique non accessible au MEB. Il peut s’agir de nanophases de pechblende de taille inférieure à la centaine de nanomètres. Pour expliquer ces concentrations, une préconcentration ne peut pas être totalement exclue ou un processus de diffusion piégeage lors du stade de minéralisation. La considération de l’ensemble des données indique que l’aquifère principal a été le siège probable d’activité microbienne subcontinue, qui est attestée par la formation à différentes stades de l’histoire du bassin de pyrites dont les caractéristiques isotopiques indiquent des processus complexes de fractionnement. La présence de matière organique en quantité significative et des pyrites peut expliquer l’efficacité du piège redox pour la réduction de l’uranium. Le modèle métallogénique présenté est celui d’un système mixte où un processus de type roll-front lié aux caractéristiques sédimentologiques de cette zone se superpose à un piège redox particulier dont la chimie C-S-U est assistée par les bactéries. / The objective of the PhD thesis concerns the analysis of the processes governing the carbon-uranium-sulfide system in the aquifers of the roll-front type Zoovch Ovoo uranium-deposit (Mongolia). The Cenomanian Sainshand Formation hosting the ore deposit contains reservoirs made of silicoclastic sediments deposited in fluvio-lacustrine settings mostly characterized by unconsolidated silty clays and sands ranging from arenite to sub-arkose. Occasionally some decimetres thick sandstone beds are dolomite cemented. Four different dolomite fabrics are recognized and classified according to their crystal boundaries and geochemistry. Isotopic analysis indicates that they were formed from meteoric waters with the carbon source being probably the detrital material itself issued from basement rock erosion. Dolomites are genetically related to each other with possible recrystallization episodes that are indicated by gradual depletion in REE and Mn. The first dolomite type was depositionally controlled, while the next three parageneses are diagenetic. The third dolomite type is found only in samples that have experienced roll-front waters, whereas the fourth post-dates uranium formation. As a result the dolomite cements paragenetic evolution is used as reference to document the whole burial history of the deposit. Organic matter particles, pyrite and uranium are very intimately related. Organic matter present in clay, silt and sand is always represented by poorly preserved detrital elements of higher plant origin and is very immature (peat stage; vitrinite reflectance <0.4%). At the scale of the sedimentary particles, organic matter complexes U(VI). However, despite a systematic association to UO2, it cannot be considered as directly involved in the reduction mechanism of uranium because of the low burial temperatures (max 50°C) and hence very limited diagenesis. Nevertheless, the investigation reveals that organic matter is the most important element in the U trapping process. Indeed, it acts as a substrate sustaining and focusing bacterial activity into specific sedimentary layers. In turn the microbial communities catalyze the reduction of sulfur, iron and especially uranium leading to two major consequences: 1) the precipitation of UO2 onto organic matter particles and 2) the formation of pyrite which acts as an additional reducer for U(VI). It appears that the uranium ore deposit at Zoovch Ovoo is primarily controlled by the distribution of the detrital organic matter in the sedimentary system as well as by the permeability network allowing the input of S, U and micro-organisms. The rather shallow aquifers probably underwent a nearly continuous bacterial activity which is responsible of many chemical features and processes controlling the U and sulfide precipitation. However, main uranium deposition events occur since the beginning of exhumation when enhanced fluid movement sustains roll-front activity. The latter displaces and combines the ingredients of the biochemical trap, allowing progressive enrichment in uranium through time.

This dissertation investigates the influence of surface heterogeneities on colloid deposition. First, deposition of colloidal particles on a nanofiltration membrane during cross flow membrane filtration was studied under different operating pressures and solution chemistries. An atomic force microscope (AFM) was then used to observe the deposit morphology formed on the membrane. At the initial stages of fouling, more particles preferentially accumulate near the peaks than in the valleys of the rough nanofiltration membrane surface. This study demonstrates that it is difficult to isolate, correlate and assess the effects that physical (roughness) heterogeneity and chemical heterogeneity has on colloid deposition based on experiments involving surfaces where the physical and chemical heterogeneities are uncorrelated or randomly distributed. In the second phase of the study, the deposition of model colloidal particles onto patterned charge-heterogeneous surfaces was studied both experimentally and theoretically. Controlled charge heterogeneity was created experimentally employing self assembled monolayers of alkanethiols patterned onto gold substrates using a soft lithographic technique. Model colloidal particles and fluorescent nanoparticles were sequentially deposited onto the patterned substrate under no flow (quiescent) conditions, and the deposited structures and the micro-patterns were imaged in situ using a combination of phase contrast and fluorescence microscopy. This study indicates that particles tend to preferentially deposit at the edges of the chemically favourable stripes. The theoretical investigation involved the formulation of a mathematical model based on Random Sequential Adsorption (RSA). This study showed that a simple binary probability distribution assumed in the model is able to predict the experimental deposit morphology adequately, particularly the periodicity of the underlying patterns on the substrate. Furthermore, the effect of charge heterogeneity on the electrostatic double layer interaction between a particle and a charge heterogeneous planar surface was studied numerically employing a 3D finite element model. In this system, significant lateral forces at close separation distances were observed, and found to be appreciably higher when the particle is near the edge of a heterogeneous region of the substrate. From the above studies, it can be concluded that by altering/controlling the chemical heterogeneity of the substrate, it is possible to achieve significant control on the resulting deposit morphology.

Sootblowing is a process in which supersonic steam jets are used to periodically blast deposits off heat transfer tubes in kraft recovery boilers. However, sootblowing significantly consumes the valuable high pressure steam generated by the boiler, hence it should be optimized. A recovery boiler consists of three convective sections - superheater, generating bank and economizer. The tube arrangement in these sections, particularly the tube spacing is different from each other. Moreover, tubes in an economizer are finned. A sootblower jet will interact differently with these tube arrangements, potentially affecting its strength, and hence deposit removal capability. The objective of this work was to characterize jet/tube interaction in the three sections of a recovery boiler. Lab-scale experiments were conducted in which these interactions were visualized using the schlieren technique coupled with high-speed video, and were quantified by pitot pressure measurements. This work is the first to visualize the interactions. The offset between the jet and tube centrelines, the nozzle exit diameter relative to the tube diameter, and the distance between the nozzle and tube were varied to examine their effects on jet/tube interaction. Results showed that due to the very low spreading rate of a supersonic jet, a jet (primary jet) stops interacting with a superheater platen when the jet is only a small distance away from it. When the jet impinges on a tube, the jet deflects at an angle, giving rise to a weaker ‘secondary’ jet. Due to the large inter-platen spacing, a secondary jet has an insignificant impact in a superheater. In a generating bank, the primary jet weakens between the closely spaced tubes due to increased mixing. However, a secondary jet impinges on the adjacent tubes exerting a high impact pressure on those tubes. The primary jet also weakens between finned economizer tubes, but remains stronger for a greater distance than in a generating bank. As in the case inside a generating bank, a secondary jet also impinges on adjacent rows of tubes in an economizer. The results imply that in a superheater, a sootblower jet must be directed close to the platens to yield useful jet/deposit interactions, and to avoid wasting steam by blowing between the platens. In a generating bank, deposits beyond the first few tubes of a row experience a weaker sootblower jet, and thus may not be removed effectively. However, secondary jets may contribute to removing deposits from the first few adjacent tubes. They may also induce erosion-corrosion of those tubes. Secondary jets may also help remove deposits from adjacent rows in a finned tube economizer. In an economizer, the strength and hence, the deposit removal capability of a sootblower jet diminish only slightly beyond the supersonic portion of the jet. A mathematical model was also developed to determine the feasibility of using inclined sootblower nozzles in recovery boiler superheaters, and suggests that it may be possible to clean superheater platens more effectively with slightly inclined nozzles.

Sootblowing is a process in which supersonic steam jets are used to periodically blast deposits off heat transfer tubes in kraft recovery boilers. However, sootblowing significantly consumes the valuable high pressure steam generated by the boiler, hence it should be optimized. A recovery boiler consists of three convective sections - superheater, generating bank and economizer. The tube arrangement in these sections, particularly the tube spacing is different from each other. Moreover, tubes in an economizer are finned. A sootblower jet will interact differently with these tube arrangements, potentially affecting its strength, and hence deposit removal capability. The objective of this work was to characterize jet/tube interaction in the three sections of a recovery boiler. Lab-scale experiments were conducted in which these interactions were visualized using the schlieren technique coupled with high-speed video, and were quantified by pitot pressure measurements. This work is the first to visualize the interactions. The offset between the jet and tube centrelines, the nozzle exit diameter relative to the tube diameter, and the distance between the nozzle and tube were varied to examine their effects on jet/tube interaction. Results showed that due to the very low spreading rate of a supersonic jet, a jet (primary jet) stops interacting with a superheater platen when the jet is only a small distance away from it. When the jet impinges on a tube, the jet deflects at an angle, giving rise to a weaker ‘secondary’ jet. Due to the large inter-platen spacing, a secondary jet has an insignificant impact in a superheater. In a generating bank, the primary jet weakens between the closely spaced tubes due to increased mixing. However, a secondary jet impinges on the adjacent tubes exerting a high impact pressure on those tubes. The primary jet also weakens between finned economizer tubes, but remains stronger for a greater distance than in a generating bank. As in the case inside a generating bank, a secondary jet also impinges on adjacent rows of tubes in an economizer. The results imply that in a superheater, a sootblower jet must be directed close to the platens to yield useful jet/deposit interactions, and to avoid wasting steam by blowing between the platens. In a generating bank, deposits beyond the first few tubes of a row experience a weaker sootblower jet, and thus may not be removed effectively. However, secondary jets may contribute to removing deposits from the first few adjacent tubes. They may also induce erosion-corrosion of those tubes. Secondary jets may also help remove deposits from adjacent rows in a finned tube economizer. In an economizer, the strength and hence, the deposit removal capability of a sootblower jet diminish only slightly beyond the supersonic portion of the jet. A mathematical model was also developed to determine the feasibility of using inclined sootblower nozzles in recovery boiler superheaters, and suggests that it may be possible to clean superheater platens more effectively with slightly inclined nozzles.

No description available.

Magistro baigiamajame darbe išanalizuoti ir susisteminti įvairių Lietuvos ir užsienio autorių namų ūkių biudžeto bei finansinių įsipareigojimų aspektai. Atsižvelgus į literatūros šaltiniuose autorių siūlomą problemos tyrimo metodologiją, būsto paskolų įmokų poveikio namų ūkių biudžetų lygio įvertinimui sukuriamas scenarijų modelis. Darbe išsamiai analizuojami skirtingų tipų šalies namų ūkių finansiniai duomenys ir jų dinamika, taikant santykinių rodiklių analizę kiekybiškai įvertinamas šalies namų ūkių įsiskolinimo lygis. Taikant scenarijų modelį, įvertinamas būsto paskolų įmokų poveikis namų ūkių biudžetų lygiui. Iš dalies patvirtinama autoriaus suformuluota mokslinio tyrimo hipotezė, kad didėjančios būsto paskolų įmokos didina nemokių namų ūkių skaičių. / Various Lithuanian and foreign authors’ household budget and financial obligations aspects have been analysed and systematized in the final Master’s work. Considering to the authors’ suggested methodology of problem investigation which is given in literature source, scenarios model has been created for the reason of influence of home loans deposits’ to the level evaluation of households’ budgets. Different types of country household financial data, their dynamic have been properly analysing in the work and applying analysis of comparative indexes indebtedness level of country households is evaluated quantitatively. Applying scenarios model, deposits influence of home loans has been evaluated to determine budget level of households. Partly the author’s formulated hypothesis of scientific research has been confirmed that growing deposits of home loans increase the number of insolvent households.

A prominent landslide deposit in the Slope Basin seaward of the Megasplay Fault in the Nankai Trough was emplaced by a high-mobility landslide based on analysis of physical properties and seismic geomorphology. Slide acceleration is a critical variable that determines amplitude of slide-generated tsunami but is many times a variable with large uncertainty. In recent controlled laboratory experiments, the ratio of the shear stress to yield strength (defined as the Flow Factor) controls a wide spectrum of mass movement styles from slow, retrogressive failure to rapid, liquefied flows. Here, we apply this laboratory Flow Factor approach to a natural landslide in the Nankai Trough by constraining pre-failure particle size analysis and porosity. Several mass transport deposits (MTDs), were drilled and cored at Site C0021 in the Nankai Trough during International Ocean Discovery Program (IODP) Expedition 338. The largest, MTD B, occurs at 133-176 meters below seafloor and occurred approximately 0.87 Mya. Slide volume is 2 km3, transport distance is 5 km, and average deposit thickness is 50 m (maximum 180 m). Pre-failure water content was estimated from shallow sediments at Site C0018 (82%). The average grain size distribution is 37% clay-sized, 60% silt-sized, and 3% sand-size particles as determined by hydrometer analyses of the MTD. Together, the water content and clay fraction predict a Flow Factor of 3.5, which predicts a relatively high mobility slide. We interpret that the landslide that created MTD B was a single event that transported the slide mass relatively rapidly as opposed to a slow, episodic landslide event. This is supported by the observation of a completely evacuated source area with no remnant blocks or retrogressive headscarp and an internally chaotic seismic facies with large entrained blocks. This approach can be extended to other field settings characterized by fine-grained siliciclastics and where water content and clay percentages are known.